KR101298485B1 - Chemical and organic electroric element using the same, terminal thererof - Google Patents

Chemical and organic electroric element using the same, terminal thererof Download PDF

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KR101298485B1
KR101298485B1 KR1020110018801A KR20110018801A KR101298485B1 KR 101298485 B1 KR101298485 B1 KR 101298485B1 KR 1020110018801 A KR1020110018801 A KR 1020110018801A KR 20110018801 A KR20110018801 A KR 20110018801A KR 101298485 B1 KR101298485 B1 KR 101298485B1
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KR20120100123A (en
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김동하
문성윤
박정철
주진욱
백장열
김원삼
박성진
김은경
최대혁
박정환
홍철광
유한성
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덕산하이메탈(주)
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D209/56—Ring systems containing three or more rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
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    • H05B33/00—Electroluminescent light sources
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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]
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
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    • 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
    • H—ELECTRICITY
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    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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Abstract

본 발명은 신규한 화합물 및 이를 이용한 유기전기소자, 그 단말을 제공한다.The present invention provides a novel compound, an organic electric device using the same, and a terminal thereof.

Description

화합물 및 이를 이용한 유기전기소자, 그 단말{CHEMICAL AND ORGANIC ELECTRORIC ELEMENT USING THE SAME, TERMINAL THEREROF}Compound and organic electric device using same, terminal thereof {CHEMICAL AND ORGANIC ELECTRORIC ELEMENT USING THE SAME, TERMINAL THEREROF}

본 발명은 화합물 및 이를 이용한 유기전기소자, 그 단말에 관한 것이다.The present invention relates to a compound, an organic electric element using the same, and a terminal 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 emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer may have a multi-layer structure composed of different materials, and may be formed 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, 전자주입 재료 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 depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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. 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.On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자내 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 forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

상술한 배경기술의 문제점을 해결하기 위한 본 발명의 실시예는, 신규한 화합물을 밝혀내었으며, 또한 이 화합물을 유기전기소자에 적용시 소자의 효율 상승, 구동전압 하강, 수명 상승 및 안정성 상승 효과를 나타낼 수 있다는 사실을 밝혀내었다.Embodiments of the present invention to solve the problems of the above-described background, the discovery of a novel compound, and also when the compound applied to the organic electronic device, the efficiency of the device, the driving voltage drop, the lifetime increase and the stability increase effect It turned out that it can represent.

이에 본 발명은 신규한 화합물 및 이를 이용한 유기전기소자, 그 전자장치 또는 단말을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a novel compound and an organic electric device using the same, an electronic device or a terminal thereof.

일 측면에서, 본 발명은 하기 화학식의 화합물을 제공한다.In one aspect, the present invention provides a compound of the formula:

Figure 112011015280967-pat00001
Figure 112011015280967-pat00001

본 발명은 신규한 화합물로서 유기 전자 소자에서정공 주입, 정공수송, 전자 주입, 전자 수송, 발광 물질 및 패시베이션(케핑) 물질로 사용될 수 있고, 특히 단독으로 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다.The present invention is a novel compound which can be used as hole injection, hole transport, electron injection, electron transport, light emitting material and passivation (kepping) material in organic electronic devices, in particular a host or a dopant in the light emitting material and host / dopant alone It can be used as a hole injection, hole injection layer can be used as a hole transport layer.

또한, 본 발명은 상기의 화학식을 가지는 화합물을 이용한 유기 전자 소자 및 이 유기 전자 소자를 포함하는 전자 장치 또는 단말을 제공한다.The present invention also provides an organic electronic device using the compound having the above formula, and an electronic device or terminal including the organic electronic device.

본 발명은 신규한 화합물로서 유기 전자 소자에서정공 주입, 정공수송, 전자 주입, 전자 수송, 발광 물질 및 패시베이션(케핑) 물질로 사용될 수 있고, 특히 단독으로 발광물질 및 호스트/도판트에서 호스트 또는 도판트로 사용될 수 있으며, 정공 주입, 정공수송층으로 사용될 수 있다.The present invention is a novel compound which can be used as hole injection, hole transport, electron injection, electron transport, light emitting material and passivation (kepping) material in organic electronic devices, in particular a host or a dopant in the light emitting material and host / dopant alone It can be used as a hole injection, hole injection layer can be used as a hole transport layer.

이 화합물을 유기전기소자 및 이 유기 전자 소자를 포함하는 전자 장치 또는 단말에 적용시 소자의 효율 상승, 구동전압 하강, 수명 상승 및 안정성 상승 효과를 나타낼 수 있다When the compound is applied to an organic electronic device and an electronic device or a terminal including the organic electronic device, the efficiency of the device may be increased, the driving voltage may be decreased, the lifetime may be increased, and the stability may be increased.

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. 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.Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. 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 the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

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 describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

본 발명은 하기 화학식 1의 화합물을 제공한다. The present invention provides a compound of Formula 1 below.

Figure 112011015280967-pat00002
Figure 112011015280967-pat00002

화학식1에서, Cz기는 하기 화학식2로 표시될 수 있는 될 수 치환 또는 비치환된 카바졸 유도체일 수 있으나 이에 제한되지 않는다.In Chemical Formula 1, the Cz group may be a substituted or unsubstituted carbazole derivative which may be represented by the following Chemical Formula 2, but is not limited thereto.

Figure 112011015280967-pat00003
Figure 112011015280967-pat00003

이때 화학식2에서 카바졸의 탄소원자에 치환될 수 있는 R3-R7는 서로 같거나 상이할 수 있으면 각각 독립적으로 수소원자, 중소수, 삼중수소; 치환 또는 비치환된 핵 탄소수 5~60의 아릴기, S, N, O, P 및 Si를 적어도 하나 이상의 헤테로 원자를 포함하는 치환 또는 비치환된 핵 탄소수 5~60의 헤테로 아릴기, 치환 또는 비치환된 탄소수 1~60의 알킬기, 치환 또는 비치환된 탄소수 1~60의 알콕시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴옥시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴싸이오기, 치환 또는 비치환된 핵 탄소수 5~60의 알콕시카보닐기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴기로 치환된 아미노기, 할로겐 원자, 사이아노기, 나이트로기, 하이드록실기 또는 카복실기 등으로 이루어진 군으로부터 선택될 수 있으나 이에 제한되지 않는다. 한편, R3-R7는인접한 기끼리 서로 결합하여 고리(환)를 형성할 수도 있다. In this case, R 3 -R 7 which may be substituted on the carbon atom of carbazole in Formula 2 may be the same or different from each other independently hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one hetero atom, substituted or unsubstituted A substituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted nuclear C5-C60 aryloxy group, a substituted or unsubstituted C5-C60 aryl cy Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be selected from the group consisting of, but not limited thereto. In addition, R <3> -R <7> may combine with adjacent groups, and may form the ring (ring).

한편, X는 R3-R7와 동일할 수 있으나 이에 제한되지 않는다. m은 1~3의 정수일 수 있으나 이에 제한되지 않는다. On the other hand, X may be the same as R 3 -R 7 but is not limited thereto. m may be an integer of 1 to 3, but is not limited thereto.

또한, 화학식 1에서 Ar1~Ar3은 서로 같거나 상이할 수 있으며 각각 독립적으로 치환 또는 비치환된 핵원자수 1~60의 아릴기, 또는 S, N, O, P 및 Si를 적어도 하나 이상의 헤테로 원자를 포함하는 치환 또는 비치환된 핵 원자수 4~ 60의 헤테로아릴기 이며, 치환 또는 비치환된 알킬기일 수 있으나 이에 제한되지 않는다. 이때 Ar1~Ar3은 인접한 기끼리 서로 결합하여 고리(환)를 형성할 수도 있다. 한편, Ar1~Ar3은 구체적으로 치환 또는 비치환된 페닐기, 비페닐기, 1-나프틸기, 2-나프틸기, 플루오렌기, 티오펜기, 피롤기, 퓨란기, 피리딜기로 이뤄진 군에서 선택될 수 있으나 이에 제한되지 않는다. In addition, in Formula 1, Ar 1 to Ar 3 may be the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 1 to 60 nuclear atoms, or at least one of S, N, O, P, and Si. Substituted or unsubstituted heteroaryl group having 4 to 60 nuclear atoms including a hetero atom, and may be a substituted or unsubstituted alkyl group, but is not limited thereto. At this time, Ar 1 ~ Ar 3 may be bonded to each other adjacent groups to form a ring (ring). Meanwhile, Ar 1 to Ar 3 are specifically substituted or unsubstituted phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, fluorene group, thiophene group, pyrrole group, furan group, pyridyl group in the group consisting of May be selected but is not limited thereto.

한편, 화학식 1에서 R1 및 R2, R'및 R''는 서로 같거나 상이할 수 있으며 각각 독립적으로 수소원자, 중소수, 삼중수소; 치환 또는 비치환된 핵 탄소수 5~60의 아릴기, S, N, O, P 및 Si를 적어도 하나 이상의 헤테로 원자를 포함하는 치환 또는 비치환된 핵 탄소수 5~60의 헤테로 아릴기, 치환 또는 비치환된 탄소수 1~60의 알킬기, 치환 또는 비치환된 탄소수 1~60의 알콕시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴옥시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴싸이오기, 치환 또는 비치환된 핵 탄소수 5~60의 알콕시카보닐기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴기로 치환된 아미노기, 할로겐 원자, 사이아노기, 나이트로기, 하이드록실기 또는 카복실기 등으로 이루어진 군으로부터 선택될 수 있으나 이에 제한되지 않는다. 또한, R1 및 R2, R'및 R''는 인접한 기끼리 서로 결합하여 고리를 형성할 수도 있다.Meanwhile, in Chemical Formula 1, R 1 and R 2 , R ′, and R ″ may be the same as or different from each other, and each independently hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one hetero atom, substituted or unsubstituted A substituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted nuclear C5-C60 aryloxy group, a substituted or unsubstituted C5-C60 aryl cy Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be selected from the group consisting of, but not limited thereto. In addition, R 1 and R 2 , R ', and R''may combine with each other to form a ring.

위 화학식 1의 X, R3-R7 , R1 및 R2, R'및 R''의 치환기들은 치환 또는 비치환될 수 있은데 치환된 경우 수소원자, 중소수, 삼중수소; 치환 또는 비치환된 핵 탄소수 5~60의 아릴기, S, N, O, P 및 Si를 적어도 하나 이상의 헤테로 원자를 포함하는 치환 또는 비치환된 핵 탄소수 5~60의 헤테로 아릴기, 치환 또는 비치환된 탄소수 1~60의 알킬기, 치환 또는 비치환된 탄소수 1~60의 알콕시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴옥시기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴싸이오기, 치환 또는 비치환된 핵 탄소수 5~60의 알콕시카보닐기, 치환 또는 비치환된 핵 탄소수 5~60의 아릴기로 치환된 아미노기, 할로겐 원자, 사이아노기, 나이트로기, 하이드록실기 또는 카복실기 등으로 이루어진 군으로부터 선택된 하나로 치환될 수 있다.
Substituents of X, R 3 -R 7 , R 1, and R 2 , R ', and R''of Formula 1 may be substituted or unsubstituted, and when substituted, hydrogen atom, deuterium, tritium; Substituted or unsubstituted aryl group having 5 to 60 carbon atoms, S, N, O, P and Si Substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms containing at least one hetero atom, substituted or unsubstituted A substituted C1-C60 alkyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted nuclear C5-C60 aryloxy group, a substituted or unsubstituted C5-C60 aryl cy Amino, substituted or unsubstituted alkoxycarbonyl groups having 5 to 60 carbon atoms, substituted or unsubstituted aryl groups having 5 to 60 carbon atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups or carboxyl groups It may be substituted with one selected from the group consisting of groups and the like.

이 화학식 1로 표시되는 화합물들은 아래 화학식 3으로 표시되는 화합물들 중 하나일 수 있으나 이에 제한되지 않는다. 이때 화학식1로 표시되는 화합물들은 화학식1의 X, R3-R7 , R1 및 R2, R'및 R''의 치환 또는 비치환된 치환기들은 광범위한 관계로 모든 화합물들을 예시하는 것은 현실적으로 어려우므로 대표적인 화합물들을 예시적으로 설명하나 화학식 3에 설명하지 않은 화학식 1로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다.Compounds represented by Formula 1 may be one of compounds represented by Formula 3 below, but is not limited thereto. In this case, the compounds represented by Formula 1 may be difficult to exemplify all the compounds in the broad relationship between the substituted or unsubstituted substituents of X, R 3 -R 7 , R 1 and R 2 , R ′ and R ″ of Formula 1 Therefore, exemplary compounds are exemplarily described, but the compounds represented by Formula 1, which are not described in Formula 3, may also form part of the present specification.

Figure 112011015280967-pat00004
Figure 112011015280967-pat00004

Figure 112011015280967-pat00005
Figure 112011015280967-pat00005

Figure 112011015280967-pat00006
Figure 112011015280967-pat00006

Figure 112011015280967-pat00007
Figure 112011015280967-pat00007

Figure 112011015280967-pat00008
Figure 112011015280967-pat00008

Figure 112011015280967-pat00009
Figure 112011015280967-pat00009

Figure 112011015280967-pat00010
Figure 112011015280967-pat00010

Figure 112011015280967-pat00011
Figure 112011015280967-pat00011

Figure 112011015280967-pat00012
Figure 112011015280967-pat00012

Figure 112011015280967-pat00013
Figure 112011015280967-pat00013

Figure 112011015280967-pat00014
Figure 112011015280967-pat00014

Figure 112011015280967-pat00015
Figure 112011015280967-pat00015

Figure 112011015280967-pat00016
Figure 112011015280967-pat00016

Figure 112011015280967-pat00017
Figure 112011015280967-pat00017

Figure 112011015280967-pat00018
Figure 112011015280967-pat00018

Figure 112011015280967-pat00019
Figure 112011015280967-pat00019

Figure 112011015280967-pat00020
Figure 112011015280967-pat00020

Figure 112011015280967-pat00021
Figure 112011015280967-pat00021

Figure 112011015280967-pat00022
Figure 112011015280967-pat00022

Figure 112011015280967-pat00023
Figure 112011015280967-pat00023

Figure 112011015280967-pat00024
Figure 112011015280967-pat00024

Figure 112011015280967-pat00025
Figure 112011015280967-pat00025

Figure 112011015280967-pat00026
Figure 112011015280967-pat00026

Figure 112011015280967-pat00027
Figure 112011015280967-pat00027

Figure 112011015280967-pat00028
Figure 112011015280967-pat00028

Figure 112011015280967-pat00029
Figure 112011015280967-pat00029

Figure 112011015280967-pat00030
Figure 112011015280967-pat00030

Figure 112011015280967-pat00031
Figure 112011015280967-pat00031

Figure 112011015280967-pat00032
Figure 112011015280967-pat00032

Figure 112011015280967-pat00033
Figure 112011015280967-pat00033

Figure 112011015280967-pat00034
Figure 112011015280967-pat00034

Figure 112011015280967-pat00035
Figure 112011015280967-pat00035

Figure 112011015280967-pat00036
Figure 112011015280967-pat00036

Figure 112011015280967-pat00037
Figure 112011015280967-pat00037

Figure 112011015280967-pat00038
Figure 112011015280967-pat00038

Figure 112011015280967-pat00039
Figure 112011015280967-pat00039

Figure 112011015280967-pat00040
Figure 112011015280967-pat00040

Figure 112011015280967-pat00041
Figure 112011015280967-pat00041

Figure 112011015280967-pat00042
Figure 112011015280967-pat00042

Figure 112011015280967-pat00043
Figure 112011015280967-pat00043

Figure 112011015280967-pat00044
Figure 112011015280967-pat00044

Figure 112011015280967-pat00045
Figure 112011015280967-pat00045

Figure 112011015280967-pat00046
Figure 112011015280967-pat00046

Figure 112011015280967-pat00047
Figure 112011015280967-pat00047

Figure 112011015280967-pat00048
Figure 112011015280967-pat00048

Figure 112011015280967-pat00049
Figure 112011015280967-pat00049

Figure 112011015280967-pat00050
Figure 112011015280967-pat00050

아울러 화학식 1 내지 3에서 치환체들은 위에서 언급하지 않은 경우라도 다시 치환되거나 비치환될 수도 있어, 치환체가 다시 치환될 수도 있다.In addition, the substituents in Chemical Formulas 1 to 3 may be substituted or unsubstituted again even if not mentioned above, and the substituents may be substituted again.

화학식 1 내지 3를 참조하여 설명한 화합물들이 유기물층으로 사용되는 다양한 유기전기소자들이 존재한다. 화학식 1 내지 3를 참조하여 설명한 화합물들이 사용될 수 있는 유기전기소자는 예를 들어, 유기전계발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 등이 있다.Various organic electric devices exist in which the compounds described with reference to Chemical Formulas 1 to 3 are used as the organic material layer. Examples of the organic electronic device in which the compounds described with reference to Chemical Formulas 1 to 3 may be used include an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, and an organic transistor (organic TFT). .

화학식 1 내지 3를 참조하여 설명한 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 described with reference to Formulas 1 to 3 can be applied, an organic light emitting diode (OLED) will be described. However, the present invention is not limited thereto, and the compounds described above 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 상기 화학식 1 내지 3의 화합물들을 포함하는 유기전계발광소자를 제공한다.Another embodiment of the present invention is an organic electric 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 of the organic electric field comprising the compounds of Formulas 1 to 3 Provided is a light emitting device.

예를 들어, 제 1 전극, 제 2 전극, 및 상기 제 1 전극과 제 2 전극 사이에 배치된 1층 이상의 유기물 층을 포함하는 유기 전기 소자로서, 상기 유기물층 중 1층 이상은 화학식1 내지 3로 표시되는 화합물을 포함하는 유기전계발광소자를 제공한다.For example, an organic electric device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers is represented by Chemical Formulas 1 to 3 It provides an organic electroluminescent device comprising the compound represented.

상기 유기물층은 정공 주입층, 정공 수송층, 및 정공 주입 및 정공 수송을 동시에 하는 층 중 1층 이상의 층을 포함하고, 상기 층 중 하나의 층이 화학식1 내지 3로 표시되는 화합물을 포함할 수 있다.  The organic layer may include one or more layers of a hole injection layer, a hole transport layer, and a layer simultaneously performing hole injection and hole transport, and one of the layers may include a compound represented by Chemical Formulas 1 to 3.

다른 측면으로, 상기 유기물층은 정공 주입층, 정공 수송층, 및 정공 주입 및 정공 수송을 동시에 하는 층 중 1층 이상의 층을 포함하고, 상기 층 중 하나의 층이 화학식1 내지 3로 표시되는 화합물을 포함할 수도 있다. In another aspect, the organic material layer includes at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein one of the layers includes a compound represented by Chemical Formulas 1 to 3 You may.

구체적으로, 상기 유기물층은 발광층을 포함하고, 상기 발광층이 화학식1 내지 3로 표시되는 화합물을 포함할 수 있다. Specifically, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formulas 1 to 3.

또한, 상기 유기물층은 전자 수송층을 포함하고, 상기 전자 수송층이 화학식1 내지 3로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formulas 1 to 3.

또한, 상기 유기물층은 발광보조층을 포함하고, 상기 발광 보조층이 화학식1 내지 3로 표시되는 화합물을 포함할 수 있다.
In addition, the organic material layer may include a light emitting auxiliary layer, and the light emitting auxiliary layer may include a compound represented by Chemical Formulas 1 to 3.

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 상기 화학식 1 내지 3의 화합물들을 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, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer And a structure known in the art using conventional manufacturing methods and materials in the art, except that at least one layer of the organic material layer including the electron injection layer is formed to include the compounds of Formulas 1 to 3. It can be prepared as.

본 발명에 다른 실시예에 따른 유기전계발광소자의 구조는 도 1 내지 6에 예시되어 있으나, 이들 구조에만 한정된 것은 아니다. 이때, 도면번호 101은 기판, 102는 양극, 103는 정공주입층(HIL), 104는 정공수송층(HTL), 105는 발광층(EML), 106은 전자주입층(EIL), 107은 전자수송층(ETL), 108은 음극을 나타낸다. 미도시하였지만, 이러한 유기전계발광소자는 정공의 이동을 저지하는 정공저지층(HBL), 전자의 이동을 저지하는 전자저지층(EBL) 및 보호층이 더 위치할 수도 있다. 보호층의 경우 최상위층에서 유기물층을 보호하거나 음극을 보호하도록 형성될 수 있다.The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

이때, 화학식 1 내지 3를 참조하여 설명한 화합물은 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물층 중 하나 이상에 포함될 수 있다. 구체적으로, 화학식 1 내지 3를 참조하여 설명한 화합물은 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 정공저지층, 전자저지층, 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.In this case, the compound described with reference to Chemical Formulas 1 to 3 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. Specifically, the compounds described with reference to Chemical Formulas 1 to 3 may be used instead 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 protective layer. It may be used to form a layer. Of course, the organic layer may be used not only in one layer but also in two or more layers.

특히, 화학식 1 내지 3를 참조하여 설명한 화합물에 따라서 정공주입 재료, 정공수송 재료, 전자주입 재료, 전자수송 재료, 발광 재료 및 패시베이션(케핑) 재료로 사용될 수 있고, 특히 단독으로 발광 재료 및 호스트 또는 도판트로 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 light emitting material and a passivation (kepping) material according to the compound described with reference to the formulas (1) to 3, in particular a light emitting material and a host or It can be used as a dopant.

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

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 물질이 바람직하다. 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. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

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 사이인 것이 바람직하다. 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.As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic 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 재료가 바람직하다. 이와 같은 조건을 만족하는 물질들로는 NPD(혹은 NPB라 함), 스피로-아릴아민계화합물, 페릴렌-아릴아민계화합물, 아자시클로헵타트리엔화합물, 비스(디페닐비닐페닐)안트라센, 실리콘게르마늄옥사이드화합물, 실리콘계아릴아민화합물 등이 될 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, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, 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 물질이 바람직하다. 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 a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

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)-phenol lithium 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. 잉크젯프린팅, 롤코팅, 스핀코팅 등의 공정을 사용하여 발광층을 형성할 경우에, 폴리페닐렌비닐렌(PPV) 계통의 고분자나 폴리 플로렌(poly 플루오렌(fluorene)) 등의 고분자를 유기발광층에 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) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(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. 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. 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.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 containing Alq 3 ; 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 금속착제 화합물, 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 weight material containing boron compounds 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 금속이 보다 바람직하다. 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. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable 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, an electrode 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, 화학식 1 내지 3를 참조하여 설명한 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, the hole injection material, the hole transport material, the light emitting material, the electron transport material and the electron injection material suitable for the fluorescent and phosphorescent devices of all colors, such as red, green, blue and white, according to the compounds described with reference to the formulas (1) to (3) 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.

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 Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

제조예1Preparation Example 1

이하, 화학식 1 내지 3에 속하는 화합물들에 대한 제조예 또는 합성예를 설명한다. 다만, 화학식 1 내지 3에 속하는 화합물들의 수가 많기 때문에 화학식 1 내지 3에 속하는 화합물 중 하나 또는 둘을 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, the preparation or synthesis examples of the compounds belonging to formulas (1) to (3). However, since the number of compounds belonging to the general formula (1) to 3 is large, one or two of the compounds belonging to the general formula (1) to 3 will be exemplarily described. 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.

다시 말해 반응식1를 통해 알 수 있는 바와 같이, 중간체4와 중간체2를 반응하여 최종적으로 화학식 1 내지 3로 표시되는 화합물들을 합성할 수 있다. 이때 중간체 4는 반응식1에서 화합물3을 통해서 합성되고, 중간체2는 화합물1 및 2를 통해 합성될 수 있다. 이들에 대한 자세한 설명은 아래에서 구체적으로 설명한다.In other words, as can be seen through Scheme 1, the intermediate 4 and the intermediate 2 may be reacted to finally synthesize the compounds represented by Chemical Formulas 1 to 3. In this case, intermediate 4 may be synthesized through compound 3 in Scheme 1, and intermediate 2 may be synthesized through compounds 1 and 2. Detailed description thereof will be described below in detail.

[반응식 1] [Reaction Scheme 1]

Figure 112011015280967-pat00051

Figure 112011015280967-pat00051

중간체 4의 합성Synthesis of Intermediate 4

4a-1(9-4a-1 (9- PhenylcarbazolePhenylcarbazole )의 합성 ) Synthesis of

[반응식 2] [Reaction Scheme 2]

Figure 112011015280967-pat00052
Figure 112011015280967-pat00052

500 mL 반응 플라스크에 9-페닐 카바졸 (20 g, 82.2 mmol), NBS (15.36 g, 86.31 mmol), 메틸렌클로라이드 (200 mL) 을 넣고 상온에서 5시간동안 반응을 진행시킨다. 반응이 완료되면 메틸렌클로라이드와 Na2CO3 수용액으로 추출하고 MgSO4로 건조하여 농축한 후 생성된 화합물을 short phase Column (메틸렌클로라이드 : 헥산 = 1:1 ) 한 후에 메틸렌클로라이드와 헥산으로 재결정하여 23 g (87 %)을 얻었다.
9-phenyl carbazole (20 g, 82.2 mmol), NBS (15.36 g, 86.31 mmol) and methylene chloride (200 mL) were added to a 500 mL reaction flask, and the reaction was performed at room temperature for 5 hours. When the reaction is completed, methylene chloride and Na 2 CO 3 The mixture was extracted with an aqueous solution, dried over MgSO 4 , concentrated, and the resulting compound was short phase column (methylene chloride: hexane = 1: 1) and recrystallized with methylene chloride and hexane to obtain 23 g (87%).

4a-2(2-4a-2 (2- bromobromo -9--9- phenylphenyl carbazolecarbazole )의 합성 ) Synthesis of

단계1)Step 1)

[반응식 3] Scheme 3

Figure 112011015280967-pat00053
Figure 112011015280967-pat00053

500 mL 둥근바닥플라스크에 toluene (250 mL), phenyl boronic acid (10 g, 82 mmol), 2,5-dibromonitrobenzene (23.1 g, 82.3 mmol), Pd(PPh3)4 (2.8 g, 2.5 mmol), 2M Na2CO3 수용액 (124 mL)을 넣는다. 그런 후에 90℃ 상태에서 6시간 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시킨다. 그런후에 메틸렌클로라이드와 물로 추출하고 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column (메틸렌클로라이드 : 헥산=1:1)하여 19.2 g (84.2 %) 의 생성물을 얻었다.
Toluene (250 mL), phenyl boronic acid (10 g, 82 mmol), 2,5-dibromonitrobenzene (23.1 g, 82.3 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.5 mmol) in a 500 mL round bottom flask, Add 2M Na 2 CO 3 aqueous solution (124 mL). Thereafter, the mixture was heated to reflux for 6 hours at 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was silicagel column (methylene chloride: hexane = 1: 1) to give 19.2 g (84.2%) of the product.

단계2)Step 2)

[반응식 4] [Reaction Scheme 4]

Figure 112011015280967-pat00054
Figure 112011015280967-pat00054

250 mL 둥근바닥플라스크에 4-Bromo-2-nitrobenzene (19.2 g, 69.04 mmol), triehtyl phosphate (84 mL, 483.28 mmol)을 넣고 160℃~165℃ 상태에서14시간 동안 가열 환류시킨다. 반응이 완료되면 감압증류로 남은 triehtyl phosphite을 제거하고, MeOH : H2O = 1:1 혼합용매로 희석시킨 후 생성된 고체를 여과한다. 얻어진 고체를 MeOH : H2O = 1:1 혼합용매와 petroleum ether로 씻어준다. 상기 고체를 메틸렌클로라이드에 녹인후에 MgSO4로 건조하여 농축하고silicagel column 한다. (petroleum ether : methylene chloride = 2:1) 10.2 g (60 %)의 생성물을 얻는다.
4-Bromo-2-nitrobenzene (19.2 g, 69.04 mmol) and triehtyl phosphate (84 mL, 483.28 mmol) were added to a 250 mL round bottom flask, and the mixture was heated and refluxed at 160 ° C. to 165 ° C. for 14 hours. After the reaction is completed, the remaining triehtyl phosphite is removed by distillation under reduced pressure, diluted with MeOH: H 2 O = 1: 1 mixed solvent, and the resulting solid is filtered. The resulting solid is washed with MeOH: H 2 O = 1: 1 mixed solvent and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO 4 , concentrated and silica gel column. (petroleum ether: methylene chloride = 2: 1) 10.2 g (60%) of product is obtained.

단계3)Step 3)

[반응식 5] Scheme 5

Figure 112011015280967-pat00055
Figure 112011015280967-pat00055

250 mL 둥근바닥플라스크에 2-Bromocarbazole (6 g, 24.38 mmol), iodobenzene (9.95 g, 48.76 mmol), K2CO3 (10.11 g, 73.14 mmol), Cu powder (1.55 g, 24.38 mmol), 18-crown-6 (3.22 g, 12.19 mmol), o-dichlorobenzene (150 mL)을 넣고 24시간 동안 가열 환류시킨다. 반응이 완료되면 메틸렌클로라이드와 물로 추출하고 얻어진 유기층을 5% 염산, brine으로 씻어준다. 유기층을 MgSO4로 건조하여 농축한 후 화합물을 silicagel column (ethyl acetate : hexane =1:1)하여 5.5 g (70 %) 의 생성물을 얻었다.
2-Bromocarbazole (6 g, 24.38 mmol), iodobenzene (9.95 g, 48.76 mmol), K 2 CO 3 (10.11 g, 73.14 mmol), Cu powder (1.55 g, 24.38 mmol), 18- in a 250 mL round bottom flask. Add crown-6 (3.22 g, 12.19 mmol) and o-dichlorobenzene (150 mL) and reflux for 24 hours. After the reaction was completed, the mixture was extracted with methylene chloride and water, and the obtained organic layer was washed with 5% hydrochloric acid and brine. The organic layer was dried over MgSO 4, concentrated, and the compound was purified by silicagel column (ethyl acetate: hexane = 1: 1) to give 5.5 g (70%) of the product.

출발물질 2의 합성 Synthesis of starting material 2

[반응식 6] [Reaction Scheme 6]

Figure 112011015280967-pat00056
Figure 112011015280967-pat00056

2-1의 합성법(1-1과 1-2과 동일할 경우) Synthesis of 2-1 (if same as 1-1 and 1-2)

반응식5를 통해 알 수 있는 바와 같이 둥근바닥플라스크에 1번의 화합물 (1당량), 아민화합물 (2당량), Pd2(dba)3 (0.06~0.1 mmol),PPh3 (0.2당량), NaOt-Bu (6당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 얻었다.
As can be seen from Scheme 5, 1 round compound (1 equivalent), amine compound (2 equivalents), Pd 2 (dba) 3 (0.06 ~ 0.1 mmol), PPh 3 (0.2 equivalents), NaOt- After adding Bu (6 equivalents) and toluene (10.5 mL / 1 mmol), the reaction is performed at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain a product.

2-2의 합성법(1-1과 1-2과 다를 경우) Synthesis of 2-2 (if different from 1-1 and 1-2)

반응식5를 통해 알 수 있는 바와 같이 둥근바닥플라스크에 1번의 화합물 (1당량), 아민화합물 1-1 (1당량), Pd2(dba)3 (0.05eq), PPh3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 얻었다.As can be seen from Scheme 5, 1 round compound (1 equivalent), amine compound 1-1 (1 equivalent), Pd 2 (dba) 3 (0.05eq), PPh 3 (0.1 equivalent), NaOt -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added, followed by reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain a product.

얻어진 생성물(1eq), 아민화합물 1-2 (1당량), Pd2(dba)3 (0.05eq), PPh3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 얻었다.
Obtained product (1eq), amine compound 1-2 (1 equiv), Pd 2 (dba) 3 (0.05eq), PPh 3 (0.1 equiv), NaOt-Bu (3 equiv), toluene (10.5 mL / 1 mmol) After adding the reaction proceeds at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain a product.

5- Bromo - N1 -(9,9- dimethyl -9H- fluoren -2- yl )- N1 , N3 , N3 - triphenylbenzene -1,3-diamine

Figure 112011015280967-pat00057
의 합성 5- Bromo - N1 - (9,9- dimethyl -9H- fluoren -2- yl) - N1, N3, N3 - triphenylbenzene -1,3-diamine
Figure 112011015280967-pat00057
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 반응식5의 상기 2-2의 합성법(이하, '2-2의 합성법'이라 함)을 사용하여 19.44g (수율 : 64%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was synthesized according to the above Synthesis 2-2 of Scheme 5 ( Hereinafter, 19.44 g (yield: 64%) of the product was obtained using 'synthesis method of 2-2').

2- Bbromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 1 , N 4 - triphenylbenzene -1,4-diamine

Figure 112011015280967-pat00058
의 합성 2- Bbromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 1, N 4 - triphenylbenzene -1,4-diamine
Figure 112011015280967-pat00058
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluore1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluore

n-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd2(dba)3 n-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd 2 (dba) 3

(4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 18.23 g (수율 : 60 %)의 생성물을 얻었다
(4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was obtained using 18.23 g (yield: 60) using the synthesis method of 2-2. Product)

5- Bromo - N1 -(9,9- diphenyl -9H- fluoren -2- yl )- N1 , N3 , N3 - triphenylbenzene -1,3-diamine

Figure 112011015280967-pat00059
의 합성 5- Bromo - N1 - (9,9- diphenyl -9H- fluoren -2- yl) - N1, N3, N3 - triphenylbenzene -1,3-diamine
Figure 112011015280967-pat00059
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 22.68g (수율 : 62%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd 2 ( dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) using 22.68 g ( Yield: 62%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 1 , N 3 , N 3 - triphenylbenzene -1,3-diamine

Figure 112011015280967-pat00060
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 1 , N 3 , N 3 - triphenylbenzene -1,3-diamine
Figure 112011015280967-pat00060
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine (20.38g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.72 g (수율 : 65%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) using 23.72 synthesis g (yield: 65%) of product was obtained.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 - phenyl - N 1 , N 3 -di( pyridin -2-yl)benzene-1,3-Diamine

Figure 112011015280967-pat00061
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - phenyl - N 1, N 3 -di (pyridin -2-yl) benzene-1,3-Diamine
Figure 112011015280967-pat00061
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl)

pyridin-2-amine (14.32g, 50 mmol), N-phenylpyridin-2-amine (8.51 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 18.90 g (수율 : 62%)의 생성물을 얻었다.
pyridin-2-amine (14.32g, 50 mmol), N-phenylpyridin-2-amine (8.51 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol ), NaOt-Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to give 18.90 g (yield: 62%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 - phenyl - N 1 , N 3 -di( thiophen -2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00062
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - phenyl - N 1, N 3 -di (thiophen -2-yl) benzene-1,3-diamine
Figure 112011015280967-pat00062
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)thiophen-2-amine(14.57 g, 50 mmol), N-phenylthiophen-2-amine (8.76 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.52 g (수율 : 63%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N-phenylthiophen-2 -amine (8.76 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) The product of 19.52 g (yield: 63%) was obtained using the synthesis method of 2-2.

5- Bromo - N 1 , N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 - diphenylbenzene -1,3-diamine

Figure 112011015280967-pat00063
의 합성 5- Bromo - N 1, N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 - diphenylbenzene -1,3-diamine
Figure 112011015280967-pat00063
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (28.54g, 100 mmol), Pd2(dba)3 (2.3 g, 2.5 mmol), PPh3 (1.31 g, 5 mmol), NaOt-Bu (14.42 g, 150 mmol), toluene (525 mL) 을 반응식5의 상기 2-1의 합성법(이하 '2-1의 합성법이라 함)을 사용하여 24.25 g (수율 : 67%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (28.54g, 100 mmol), Pd 2 (dba) 3 (2.3 g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaOt-Bu (14.42 g, 150 mmol), toluene (525 mL) were synthesized according to the above Synthesis 2-1 of Scheme 5 (hereinafter referred to as 'synthesis of 2-1'). ) Gave 24.25 g (yield: 67%) of product.

2- Bromo - N 1 , N 4 - bis (9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 4 - diphenylbenzene -1,4-diamine

Figure 112011015280967-pat00064
의 합성 2- Bromo - N 1, N 4 - bis (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 4 - diphenylbenzene -1,4-diamine
Figure 112011015280967-pat00064
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd2(dba)3 1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), diphenylamine (8.46 g, 50 mmol), Pd 2 (dba) 3

(4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-1의 합성법을 사용하여 23.16 g (수율 : 64 %)의 생성물을 얻었다
(4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were obtained using 23.16 g (yield: 64) using the synthesis method of 2-1. Product)

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(9,9- diphenyl -9H- fluoren -2-yl)-N 1 ,N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00065
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - (9,9- diphenyl -9H- fluoren -2-yl) -N 1, N 3 -diphenylbenzene- 1,3-diamine
Figure 112011015280967-pat00065
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine 1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine

(20.48 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 26.28 g (수율 : 62%)의 생성물을 얻었다
(20.48 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 ( 2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to give 26.28 g (yield: 62%) of product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -(9,9- dimethyl -9H- fluoren -2-yl)-N 1 ,N 3 -diphenyl benzene -1,3- diamine

Figure 112011015280967-pat00066
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- (9,9- dimethyl- 9H- fluoren- 2-yl) -N 1 , N 3 -diphenyl benzene -1,3- diamine
Figure 112011015280967-pat00066
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 26.22 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 9,9-dimethyl-N-phenyl- 9H-fluoren-2-amine (14.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), Toluene (1050 mL) was obtained by 26.22 g (yield: 62%) of the product using the above synthesis method.

5- Bromo - N 1 , N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 -di( pyridin -2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00067
의 합성 5- Bromo - N 1, N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 -di (pyridin -2-yl) benzene-1,3-diamine
Figure 112011015280967-pat00067
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (28.64 g, 100 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-1의 합성법을 사용하여 23.59 g (수율 : 65 %)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (28.64 g, 100 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared using 23.59 g (yield: 65%) of the product

5- Bromo - N 1 , N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 -di( thiophen -2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00068
의 합성 5- Bromo - N 1, N 3 - bis (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 -di (thiophen -2-yl) benzene-1,3-diamine
Figure 112011015280967-pat00068
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)thiphen-2-amine (29.14 g, 100 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-1의 합성법을 사용하여 23.18g (수율 : 63 %)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiphen-2-amine (29.14 g, 100 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were prepared using 23.18 g (yield: 63%) of the product

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 - diphenyl - N3 -p-tolylbenzene-1,3-diamine

Figure 112011015280967-pat00069
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 - diphenyl - N3 -p-tolylbenzene-1,3-diamine
Figure 112011015280967-pat00069
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.58 g (수율 : 63%)의 생성물을 얻었다
amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt- Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using 19.58 g (yield: 63%) of the product using the above synthesis method.

2- Bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 4 - diphenyl - N1 -p-tolylbenzene-1,4-diamine

Figure 112011015280967-pat00070
의 합성 2- Bromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 4 - diphenyl - N1 -p-tolylbenzene-1,4-diamine
Figure 112011015280967-pat00070
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.89 g (수율 : 64 %)의 생성물을 얻었다
1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. Using the synthesis method of 19.89 g (yield: 64%) product

5- Bromo - N 1 -(9,9- diphenyl -9H- fluoren -2- yl )- N 1 , N 3 - diphenyl - N 3 -p-tolylbenzene-1,3-diamine

Figure 112011015280967-pat00071
의 합성 5- Bromo - N 1 - (9,9- diphenyl -9H- fluoren -2- yl) - N 1, N 3 - diphenyl - N 3 -p-tolylbenzene-1,3-diamine
Figure 112011015280967-pat00071
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.12 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. To give 23.12 g (yield: 62%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 1 , N 3 - diphenyl - N 3 -p-tolylbenzene-1,3-diamine

Figure 112011015280967-pat00072
의 합성 N 1 - (9,9'- spirobi [fluorene ] -2- yl) -5- bromo - N 1, N 3 - diphenyl - N 3 -p-tolylbenzene-1,3-diamine
Figure 112011015280967-pat00072
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.06 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-methyl-N-phenylaniline (9.16 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 23.06 g (yield: 62%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 - di ( pyridin -2- yl )- N 3 -p-tolylbenzene-1,3-diamine

Figure 112011015280967-pat00073
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 - di (pyridin -2- yl) - N 3 -p-tolylbenzene-1,3-diamine
Figure 112011015280967-pat00073
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl)

pyridin-2-amine (14.32g, 50 mmol), N-p-tolylpyridin-2-amine (9.21 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.64 g (수율 : 63%)의 생성물을 얻었다.
pyridin-2-amine (14.32g, 50 mmol), Np-tolylpyridin-2-amine (9.21 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol ), NaOt-Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to obtain 19.64 g (yield: 63%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 - di ( thiophen -2- yl )- N 3 -p-tolylbenzene-1,3-diamine

Figure 112011015280967-pat00074
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 - di (thiophen -2- yl) - N 3 -p-tolylbenzene-1,3-diamine
Figure 112011015280967-pat00074
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-l)thiophen-1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-

2-amine(14.57 g, 50 mmol), N-p-tolylthiophen-2-amine (9.46 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.00 g (수율 : 60%)의 생성물을 얻었다.
2-amine (14.57 g, 50 mmol), Np-tolylthiophen-2-amine (9.46 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to obtain 19.00 g (yield: 60%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- methoxyphenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00075
의 합성 5- Bromo - N 1- (9,9- dimethyl -9H- fluoren -2- yl ) -N 3- (4- methoxyphenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00075
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 20.72 g (수율 : 65%)의 생성물을 얻었다
amine (14.27 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt- Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 to obtain 20.72 g (yield: 65%) of product.

2- Bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 -(4- methoxyphenyl )- N 1 , N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00076
의 합성 2- Bromo - N 4- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 1- (4- methoxyphenyl ) -N 1 , N 4 -diphenylbenzene-1,4-diamine
Figure 112011015280967-pat00076
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.45 g (수율 : 61%)의 생성물을 얻었다
1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis was carried out to give 19.45 g (yield: 61%) of the product.

5- Bromo - N 1 -(9,9- diphenyl -9H- fluoren -2- yl )- N 3 -(4- methoxyphenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00077
의 합성 5- Bromo - N 1- (9,9- diphenyl -9H- fluoren -2- yl ) -N 3- (4- methoxyphenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00077
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.23 g (수율 : 61%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. To give 23.23 g (yield: 61%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -(4- methoxyphenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00078
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- (4- methoxyphenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00078
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g, 50 mmol), Pd2(dba)3 (4.58 g,5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 23.06 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-methoxy-N-phenylaniline (9.96 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 23.06 g (yield: 62%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- methoxyphenyl )- N 1 , N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00079
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- (4- methoxyphenyl ) -N 1 , N 3 -di (pyridin-2-yl) benzene-1, 3-diamine
Figure 112011015280967-pat00079
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(4-methoxyphenyl)pyridin-2-amine (10.01 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.19 g (수율 : 60%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (4- methoxyphenyl) pyridin-2-amine (10.01 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), Toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.19 g (yield: 60%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- methoxyphenyl )- N 1 , N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00080
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- (4- methoxyphenyl ) -N 1 , N 3 -di (thiophen-2-yl) benzene-1, 3-diamine
Figure 112011015280967-pat00080
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-l)thiophen-2-amine(14.57 g, 50 mmol), N-(4-methoxyphenyl)thiophen-2-amine (10.26 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol),toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.81 g (수율 : 61%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (4- methoxyphenyl) thiophen-2-amine (10.26 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), Toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.81 g (yield: 61%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- fluorophenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00081
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- (4- fluorophenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00081
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 18.77 g (수율 : 60%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis was carried out to give 18.77 g (yield: 60%) of the product.

2- Bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 -(4- fluorophenyl )- N 1 , N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00082
의 합성 2- Bromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1 - (4- fluorophenyl) - N 1, N 4 -diphenylbenzene-1,4-diamine
Figure 112011015280967-pat00082
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 18.14g (수율 : 58%)의 생성물을 얻었다
amine (14.27 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt- Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using 18.14 g (yield: 58%) of the product using the above synthesis method.

5- Bromo - N 1 -(9,9- diphenyl -9H- fluoren -2- yl )- N 3 -(4- fluorophenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00083
의 합성 5- Bromo - N 1- (9,9- diphenyl -9H- fluoren -2- yl ) -N 3- (4- fluorophenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00083
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 22.12 g (수율 : 59%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. Obtained 22.12 g (yield: 59%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -(4- fluorophenyl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00084
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- (4- fluorophenyl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00084
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 21.31 g (수율 : 57%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), 4-fluoro-N-phenylaniline (9.36 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis was carried out to give 21.31 g (yield: 57%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- fluorophenyl )- N 1 , N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00085
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- (4- fluorophenyl ) -N 1 , N 3 -di (pyridin-2-yl) benzene-1, 3-diamine
Figure 112011015280967-pat00085
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(4-fluorophenyl)pyridin-2-amine (9.41 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 18.20 g (수율 : 58%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (4- fluorophenyl) pyridin-2-amine (9.41 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), Toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 18.20 g (yield: 58%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -(4- fluorophenyl )- N 1 , N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00086
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- (4- fluorophenyl ) -N 1 , N 3 -di (thiophen-2-yl) benzene-1, 3-diamine
Figure 112011015280967-pat00086
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-l)thiophen-2-amine(14.57 g, 50 mmol), N-(4-fluorophenyl)thiophen-2-amine (9.66 g, 50 mmol),Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol),toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 19.13 g (수율 : 60%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (4- fluorophenyl) thiophen-2-amine (9.66 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), Toluene (1050 mL) was obtained using the synthesis method of 2-2 to obtain 19.13 g (yield: 60%) of product.

N 1 -( biphenyl -4- yl )-5- bromo - N 3 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00087
의 합성 N 1 - (biphenyl -4- yl) -5- bromo - N 3 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00087
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.25 g (수율 : 68%)의 생성물을 얻었다
amine (14.27 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt- Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2, to obtain 23.25 g (yield: 68%) of product.

N 1 -( biphenyl -4- yl )-2- bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00088
의 합성 N 1 - (biphenyl -4- yl) -2- bromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 4 -diphenylbenzene-1,4-diamine
Figure 112011015280967-pat00088
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.88 g (수율 : 64%)의 생성물을 얻었다
amine (14.27 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt- Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to give 21.88 g (yield: 64%) of product.

N 1 -( biphenyl -4- yl )-5- bromo - N 3 -(9,9- diphenyl -9H- fluoren -2- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00089
의 합성 N 1 - (biphenyl -4- yl) -5- bromo - N 3 - (9,9- diphenyl -9H- fluoren -2- yl) - N 1, N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00089
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 25.45 g (수율 : 63%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. To give 25.45 g (yield 63%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )- N 3 -( biphenyl -4- yl )-5- bromo - N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00090
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -N 3- ( biphenyl -4- yl ) -5- bromo - N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00090
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 25.79 g (수율 : 64%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N-phenylbiphenyl-4-amine (12.27 g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis was carried out to give 25.79 g (yield: 64%) of the product.

N 1 -( biphenyl -4- yl )-5- bromo - N 3 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00091
의 합성 N 1 - (biphenyl -4- yl) -5- bromo - N 3 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 -di (pyridin-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00091
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(biphenyl-4-yl)pyridin-2-amine (12.32 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.26 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (biphenyl- 4-yl) pyridin-2-amine (12.32 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol ), toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 21.26 g (yield: 62%) of product.

N 1 -( biphenyl -4- yl )-5- bromo - N 3 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 , N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00092
의 합성 N 1 - (biphenyl -4- yl) -5- bromo - N 3 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1, N 3 -di (thiophen-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00092
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-l)thiophen-2-amine(14.57 g, 50 mmol), N-(biphenyl-4-yl)thiophen-2-amine (12.57 g, 50 mmol),Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.57 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-l) thiophen-2-amine (14.57 g, 50 mmol), N- (biphenyl- 4-yl) thiophen-2-amine (12.57 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol ), toluene (1050 mL) was obtained using the synthesis method in the above 2-2 to obtain 21.57 g (yield: 62%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -1- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00093
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - (naphthalen -1- yl) - N 1, N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00093
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 22.03 g (수율 : 67%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 22.03 g (yield 67%) of the product.

2- Bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 -( naphthalen -1- yl )- N 1 , N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00094
의 합성 2- Bromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1 - (naphthalen -1- yl) - N 1, N 4 -diphenylbenzene-1,4-diamine
Figure 112011015280967-pat00094
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.37 g (수율 : 65%)의 생성물을 얻었다.
1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 21.37 g (yield: 65%) of the product.

5- Bromo - N 1 -(9,9- diphenyl -9H- fluoren -2- yl )- N 3 -( naphthalen -1- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00095
의 합성 5- Bromo - N 1- (9,9- diphenyl- 9H- fluoren -2- yl ) -N 3- ( naphthalen -1- yl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00095
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 24.63 g (수율 : 63%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. 24.63 g (yield 63%) of the product were obtained.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -( naphthalen -1- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00096
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- ( naphthalen -1- yl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00096
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 25.34 g (수율 : 65%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N-phenylnaphthalen-1-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis was carried out to give 25.34 g (yield: 65%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -1- yl )- N 1 , N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00097
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- ( naphthalen -1- yl ) -N 1 , N 3 -di (pyridin-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00097
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(naphthalen-1-yl)pyridin-2-amine (11.01 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.11 g (수율 : 64%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (naphthalen- 1-yl) pyridin-2-amine (11.01 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol ), toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 21.11 g (yield: 64%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -1- yl )- N 1 , N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00098
의 합성 5- Bromo - N 1- (9,9- dimethyl -9H- fluoren -2- yl ) -N 3- ( naphthalen -1- yl ) -N 1 , N 3 -di (thiophen-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00098
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)thiophen-2-amine(14.57 g, 50 mmol), N-(naphthalen-1-yl)thiophen-2-amine (11.27 g, 50mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 20.43 g (수율 : 61%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (naphthalen- 1-yl) thiophen-2-amine (11.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 20.43 g (yield: 61%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -2- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00099
의 합성 5- Bromo - N 1- (9,9- dimethyl- 9H- fluoren -2- yl ) -N 3- ( naphthalen -2- yl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00099
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.70 g (수율 : 66%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 21.70 g (yield: 66%) of the product.

2- Bromo - N 4 -(9,9- dimethyl -9H- fluoren -2- yl )- N 1 -( naphthalen -2- yl )- N 1 , N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00100
의 합성 2- Bromo - N 4 - (9,9- dimethyl -9H- fluoren -2- yl) - N 1 - (naphthalen -2- yl) - N 1, N 4 -diphenylbenzene-1,4-diamine
Figure 112011015280967-pat00100
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.04 g (수율 : 64%)의 생성물을 얻었다.
1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 21.04 g (yield: 64%) of the product.

5- Bromo - N 1 -(9,9- diphenyl -9H- fluoren -2- yl )- N 3 -( naphthalen -2- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00101
의 합성 5- Bromo - N 1- (9,9- diphenyl -9H- fluoren -2- yl ) -N 3- ( naphthalen -2- yl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00101
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 25.41 g (수율 : 65%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) were synthesized in 2-2. Obtained 25.41 g (yield: 65%) of the product.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -( naphthalen -2- yl )- N 1 , N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00102
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- ( naphthalen -2- yl ) -N 1 , N 3 -diphenylbenzene-1,3-diamine
Figure 112011015280967-pat00102
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g, 50 mmol), Pd2(dba)3 (4.58 g,5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 24.56 g (수율 : 63%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N-phenylnaphthalen-2-amine (10.96g , 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) was prepared in 2-2. The synthesis method of yielded 24.56 g (yield: 63%) of the product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -2- yl )- N 1 , N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00103
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - (naphthalen -2- yl) - N 1, N 3 -di (pyridin-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00103
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(naphthalen-2-yl)pyridin-2-amine (11.01 g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.11 g (수율 : 64%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (naphthalen- 2-yl) pyridin-2-amine (11.01 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol ), toluene (1050 mL) was obtained using the synthesis method of 2-2 to give 21.11 g (yield: 64%) of product.

5- Bromo - N 1 -(9,9- dimethyl -9H- fluoren -2- yl )- N 3 -( naphthalen -2- yl )- N 1 , N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00104
의 합성 5- Bromo - N 1 - (9,9- dimethyl -9H- fluoren -2- yl) - N 3 - (naphthalen -2- yl) - N 1, N 3 -di (thiophen-2-yl) benzene- 1,3-diamine
Figure 112011015280967-pat00104
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)thiophen-2-amine(14.57 g, 50 mmol), N-(naphthalen-2-yl)thiophen-2-amine (11.27 g, 50mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 20.76 g (수율 : 62%)의 생성물을 얻었다
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (naphthalen- 2-yl) thiophen-2-amine (11.27 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol) , toluene (1050 mL) was obtained using the synthesis method of 2-2 to yield 20.76 g (yield: 62%) of product.

5- Bromo - N 1 -( dibenzo [b,d]thiophen-2- yl )- N 3 -(9,9- dimethyl -9H- fluoren -2-yl)-N 1 ,N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00105
의 합성 5- Bromo - N 1 - (dibenzo [b, d] thiophen-2- yl) - N 3 - (9,9- dimethyl -9H- fluoren -2-yl) -N 1, N 3 -diphenylbenzene-1, 3-diamine
Figure 112011015280967-pat00105
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-1,3,5-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-

amine (14.27 g, 50 mmol), N-phenyldibenzo[b,d]thiophen-2-amine (13.77g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 23.20 g (수율 : 65%)의 생성물을 얻었다.
amine (14.27 g, 50 mmol), N-phenyldibenzo [b, d] thiophen-2-amine (13.77 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to obtain 23.20 g (yield: 65%) of product.

2- Bromo - N 1 -( dibenzo [b,d]thiophen-2- yl )- N 4 -(9,9- dimethyl -9H- fluoren -2-yl)-N 1 ,N 4 -diphenylbenzene-1,4-diamine

Figure 112011015280967-pat00106
의 합성 2- Bromo - N 1 - (dibenzo [b, d] thiophen-2- yl) - N 4 - (9,9- dimethyl -9H- fluoren -2-yl) -N 1, N 4 -diphenylbenzene-1, 4-diamine
Figure 112011015280967-pat00106
Synthesis of

1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenyldibenzo[b,d]thiophen-2-amine (13.77g, 50 mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 22.48 g (수율 : 63%)의 생성물을 얻었다.
1,2,4-tribromobenzene (15.74 g, 50 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (14.27 g, 50 mmol), N-phenyldibenzo [b, d] thiophen- 2-amine (13.77g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL ) Was obtained using the synthesis method of 2-2 above to obtain 22.48 g (yield: 63%) of the product.

5- Bromo - N 1 -( dibenzo [b,d]thiophen-2- yl )- N 3 -(9,9- diphenyl -9H- fluoren -2-yl)-N 1 ,N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00107
의 합성 5- Bromo - N 1 - (dibenzo [b, d] thiophen-2- yl) - N 3 - (9,9- diphenyl -9H- fluoren -2-yl) -N 1, N 3 -diphenylbenzene-1, 3-diamine
Figure 112011015280967-pat00107
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N,9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenyldibenzo[b,d]thiophen-2-amine (13.77g, 50 mmol),Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 28.07 g (수율 : 67%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N, 9,9-triphenyl-9H-fluoren-2-amine (20.48 g, 50 mmol), N-phenyldibenzo [b, d] thiophen-2- amine (13.77 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) Using the synthesis method of 2-2, 28.07 g (yield: 67%) of the product were obtained.

N 1 -(9,9'- spirobi [ fluorene ]-2- yl )-5- bromo - N 3 -( dibenzo [b,d]thiophen-2-yl)-N 1 ,N 3 -diphenylbenzene-1,3-diamine

Figure 112011015280967-pat00108
의 합성 N 1- (9,9'- spirobi [ fluorene ] -2- yl ) -5- bromo - N 3- ( dibenzo [b, d] thiophen-2-yl) -N 1 , N 3 -diphenylbenzene-1, 3-diamine
Figure 112011015280967-pat00108
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi[fluoren]-2-amine(20.38 g, 50 mmol), N-phenyldibenzo[b,d]thiophen-2-amine (13.77g, 50 mmol),Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2 의 합성법을 사용하여 27.17 g (수율 : 65%)의 생성물을
1,3,5-tribromobenzene (15.74 g, 50 mmol), N-phenyl-9,9'-spirobi [fluoren] -2-amine (20.38 g, 50 mmol), N-phenyldibenzo [b, d] thiophen- 2-amine (13.77g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL ) To 27.17 g (yield: 65%) of the product using the synthesis method of 2-2.

5- Bromo - N 1 -( dibenzo [b,d]thiophen-2- yl )- N 3 -(9,9- dimethyl -9H- fluoren -2-yl)-N 1 ,N 3 -di(pyridin-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00109
의 합성 5- Bromo - N 1 - (dibenzo [b, d] thiophen-2- yl) - N 3 - (9,9- dimethyl -9H- fluoren -2-yl) -N 1, N 3 -di (pyridin- 2-yl) benzene-1,3-diamine
Figure 112011015280967-pat00109
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)pyridin-2-amine (14.32g, 50 mmol), N-(dibenzo[b,d]thiophen-2-yl)pyridin-2-amine (13.82 g, 50mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 21.47 g (수율 : 60%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) pyridin-2-amine (14.32g, 50 mmol), N- (dibenzo [ b, d] thiophen-2-yl) pyridin-2-amine (13.82 g, 50 mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu ( 28.84 g, 300 mmol) and toluene (1050 mL) were obtained using the synthesis method of 2-2 above to give 21.47 g (yield: 60%) of product.

5- Bromo - N 1 -( dibenzo [b,d]thiophen-2- yl )- N 3 -(9,9- dimethyl -9H- fluoren -2-yl)-N 1 ,N 3 -di(thiophen-2-yl)benzene-1,3-diamine

Figure 112011015280967-pat00110
의 합성 5- Bromo - N 1 - (dibenzo [b, d] thiophen-2- yl) - N 3 - (9,9- dimethyl -9H- fluoren -2-yl) -N 1, N 3 -di (thiophen- 2-yl) benzene-1,3-diamine
Figure 112011015280967-pat00110
Synthesis of

1,3,5-tribromobenzene (15.74 g, 50 mmol), N-(9,9-dimethyl-9H-fluoren-2-yl)thiophen-2-amine(14.57 g, 50 mmol), N-(thiophen-2-yl)dibenzo[b,d]thiophen-2-amine (14.07g, 50mmol), Pd2(dba)3 (4.58 g, 5 mmol), PPh3 (2.62 g, 10 mmol), NaOt-Bu (28.84 g, 300 mmol), toluene (1050 mL) 을 상기 2-2의 합성법을 사용하여 22.86 g (수율 : 63%)의 생성물을 얻었다.
1,3,5-tribromobenzene (15.74 g, 50 mmol), N- (9,9-dimethyl-9H-fluoren-2-yl) thiophen-2-amine (14.57 g, 50 mmol), N- (thiophen- 2-yl) dibenzo [b, d] thiophen-2-amine (14.07g, 50mmol), Pd 2 (dba) 3 (4.58 g, 5 mmol), PPh 3 (2.62 g, 10 mmol), NaOt-Bu ( 28.84 g, 300 mmol) and toluene (1050 mL) were obtained using 22.86 g (yield: 63%) of the product using the above synthesis method.

최종화합물의 합성방법Synthesis of Final Compound

[반응식 7] [Reaction Scheme 7]

Figure 112011015280967-pat00111
Figure 112011015280967-pat00111

반응식6을 통해 알 수 있는 바와 같이, 둥근 바닥플라스크에 4의 화합물 (1당량), 2화합물 (1.1당량), Pd(PPh3)4 (0.03~0.05당량),NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1mmol)을 넣는다. As can be seen from Scheme 6, Compound 4 (1 equiv), 2 compounds (1.1 equiv), Pd (PPh 3 ) 4 (0.03-0.05 equiv), NaOH (3 equiv), THF ( 3 mL / 1 mmol) and water (1.5 mL / 1 mmol).

그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시킨다. 그런 후에 메틸렌클로라이드와 물로 추출하고 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 얻었으며 아래 표1과 같이 FD-MS로 생성물을 확인하였다. After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, and the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain a product. The product was confirmed by FD-MS as shown in Table 1 below.

일반적으로 최종화합물들은 핵자기공명(NMR), 질량분석(Mass) 등으로 구조를 분석할 수 있다. 그런데 전술한 최종화합물들은 많은 aromatic 구조를 가지고 있어서 핵자기공명(NMR) 보다는 주로 질량분석(Mass)을 사용하여 구조를 분석하였다. In general, the final compounds can be analyzed by nuclear magnetic resonance (NMR), mass spectrometry (Mass). However, the above-mentioned final compounds have many aromatic structures, so the structure was analyzed by mass spectrometry (Mass) rather than nuclear magnetic resonance (NMR).

이때 FD-MS는 질량분석기를 의미하고 질량분석기로 질량분석을 하면 최종화합물들이 깨지면서 여러개의 피크가 나타나는데 m/z는 그 피크를 의미한다. 다시 말해서 m/z는 전술한 최종화합물들의 질량분석 주요 피크(main peck)를 의미한다. 이를 통해 화합물들의 존재를 확인할 수 있다.In this case, FD-MS refers to a mass spectrometer. When mass spectrometry is performed on a mass spectrometer, several peaks appear as the final compounds are broken, and m / z refers to the peak. In other words, m / z means the mass spectrometry main peck of the above-mentioned final compounds. This can confirm the presence of the compounds.

Figure 112011015280967-pat00112
Figure 112011015280967-pat00112

Figure 112011015280967-pat00113
Figure 112011015280967-pat00113

Figure 112011015280967-pat00114
Figure 112011015280967-pat00114

이때 화학식1로 표시되는 화합물들은 화학식1의 X, R3-R7 , R1 및 R2, R'및 R''의 치환 또는 비치환된 치환기들은 광범위한 관계로 화학식 3으로 표시한 화합물들의 합성예를 예시적으로 설명하였으나 합성예로 예시적으로 설명하지 않은 화학식 1로 표시되는 화합물들도 본 명세서의 일부를 구성할 수 있다.
In this case, the compounds represented by the formula (1) are X, R 3 -R 7 , R 1 and R 2 , R 'and R''substituted or unsubstituted substituents of the formula 1 in a wide range of synthesis of the compound represented by the formula (3) Examples are described by way of example, but the compounds represented by Formula 1, which are not described by way of example as synthetic examples, may also form part of the present specification.

유기 EL 소자의 제조 평가Manufacturing evaluation of organic electroluminescent element

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, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 4,4’,4"-트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민 (이하 2T-NATA로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter 2T-NATA) as a hole injection layer on the ITO layer (anode) formed on the glass substrate first The film was vacuum deposited to form a thickness of 10 nm.

이어서, 정공수송 화합물로서 화학식1 내지 3로 표시되는 화합물들 중 하나를 30 nm의 두께로 진공증착하여 홀 수송층을 형성하였다. 홀 수송층을 형성한 후, 개발한 물질을 홀 수송층으로 측정할 시에는 이 홀 수송층 상부에 45nm두께의 BD-052X(Idemitus사)가 7% 도핑된 발광층 (이때, BD-052X는 청색 형광 도펀트이고, 발광 호스트 물질로는 9,10-다이(나프탈렌-2-안트라센(AND))을 사용하였다.Subsequently, one of the compounds represented by Chemical Formulas 1 to 3 as the hole transport compound was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After the formation of the hole transport layer, when the developed material was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X was a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material.

홀 저지층으로 (1,1' 비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 의 두께로 진공증착하고, 이어서 전자주입층으로 트리스(8-퀴놀리놀)알루미늄 (이하 Alq3로 약칭함)을 40 nm의 두께로 성막하였다. 이 후, 할로젠화 알칼리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 사용함으로서 유기전계 발광소자를 제조하였다.
(1,1 'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm in a hole blocking layer, followed by electron Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq 3 ) was formed into an injection layer to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

비교실험예1Comparative Experimental Example 1

본 발명의 화합물들을 정공수송층으로 측정 했을 경우, 비교를 위해 본 발명의 화합물 대신에 하기식으로 표시되는 화합물(이하 NPB로 약기함)를 정공수송 물질로 사용하여 실험예와 동일한 구조의 유기전계발광소자를 제작하였다.When the compounds of the present invention were measured by the hole transport layer, an organic electroluminescent light emitting device having the same structure as in the experimental example was prepared by using a compound represented by the following formula (hereinafter abbreviated as NPB) as a hole transport material instead of the compound of the present invention for comparison. The device was produced.

Figure 112011015280967-pat00115
Figure 112011015280967-pat00115

정공 수송
재료Hole transport
material 전압
( V )Voltage
(V) 전류밀도
( mA/cm2 )Current density
(mA / cm 2 ) 발광효율
( cd/A )Luminous efficiency
(cd / A) 색도좌표
( x, y )Chromaticity coordinates
(x, y) 실시예 1Example 1 화합물 A-1 Compound A-1 5.65.6 12.6712.67 8.48.4 ( 0.15, 0.14 )(0.15, 0.14) 실시예 2Example 2 화합물 A-2 Compound A-2 6.06.0 12.8912.89 8.28.2 ( 0.15, 0.14 )(0.15, 0.14) 실시예 3Example 3 화합물 A-3 Compound A-3 5.75.7 12.7312.73 8.58.5 ( 0.15, 0.14 )(0.15, 0.14) 실시예 4Example 4 화합물 A-4 Compound A-4 5.75.7 12.7112.71 8.78.7 ( 0.15, 0.14 )(0.15, 0.14) 실시예 5Example 5 화합물 A-5 Compound A-5 5.85.8 12.7712.77 8.98.9 ( 0.15, 0.14 )(0.15, 0.14) 실시예 6Example 6 화합물 A-14 Compound a -14 6.26.2 12.9112.91 8.18.1 ( 0.15, 0.13 )(0.15, 0.13) 실시예 7Example 7 화합물 A-19 Compound a -19 4.94.9 12.0912.09 8.88.8 ( 0.15, 0.14 )(0.15, 0.14) 실시예 8Example 8 화합물 A-20 Compound A-20 5.15.1 12.1212.12 8.78.7 ( 0.15, 0.13 )(0.15, 0.13) 실시예 9Example 9 화합물 A-21 Compound a -21 5.05.0 12.0912.09 8.88.8 ( 0.15, 0.14 )(0.15, 0.14) 실시예 10Example 10 화합물 A-22 Compound a -22 5.05.0 12.3012.30 8.68.6 ( 0.15, 0.15 )(0.15, 0.15) 실시예 11Example 11 화합물 A-23 Compound a -23 5.15.1 12.2812.28 8.68.6 ( 0.15, 0.14 )(0.15, 0.14) 실시예 12Example 12 화합물 A-27 Compound a -27 6.46.4 12.9312.93 8.18.1 ( 0.15, 0.14 )(0.15, 0.14) 실시예 13Example 13 화합물 A-35 Compound A-35 6.76.7 12.8912.89 8.28.2 ( 0.15, 0.12 )(0.15, 0.12) 실시예 14Example 14 화합물 A-55 Compound a -55 5.85.8 12.7412.74 8.58.5 ( 0.15, 0.14 )(0.15, 0.14) 실시예 12Example 12 화합물 A-91 Compound a -91 5.65.6 12.6812.68 8.58.5 ( 0.15, 0.14 )(0.15, 0.14) 실시예 13Example 13 화합물 A-92 Compound a -92 6.06.0 12.7912.79 8.68.6 ( 0.15, 0.13 )(0.15, 0.13) 실시예 14Example 14 화합물 A-93 Compound a -93 5.75.7 12.6812.68 8.38.3 ( 0.15, 0.14 )(0.15, 0.14) 실시예 15Example 15 화합물 A-109 Compound a -109 5.65.6 12.7512.75 8.78.7 ( 0.15, 0.14 )(0.15, 0.14) 실시예 16Example 16 화합물 A-110 Compound a -110 5.85.8 12.8112.81 8.68.6 ( 0.15, 0.13 )(0.15, 0.13) 실시예 17Example 17 화합물 A-127 Compound a -127 5.85.8 12.7612.76 8.88.8 ( 0.15, 0.13 )(0.15, 0.13) 실시예 18Example 18 화합물 A-128 Compound a -128 6.16.1 12.8812.88 8.58.5 ( 0.15, 0.14 )(0.15, 0.14) 실시예 19Example 19 화합물 A-145 Compound A-145 6.36.3 12.8612.86 8.68.6 ( 0.15, 0.14 )(0.15, 0.14) 비교예 1Comparative Example 1 NPBNPB 7.27.2 13.3513.35 7.57.5 ( 0.15, 0.15 )(0.15, 0.15)

상기 표2의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 고효율이면서 색순도가 향상될 뿐만 아니라 장수명인 청색 발광이 얻어지므로 유기전계발광소자의 정공수송재료로 사용되어 낮은 구동전압과 높은 발광효율 및 수명을 현저히 개선시킬 수 있다. As can be seen from the results of Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity but also blue light emission with long life is obtained as a hole transporting material of the organic light emitting device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.

본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 정공수송층 뿐만 아니라 발광층, 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole transport layer as well as a light emitting layer, 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. .

이때 화학식1로 표시되는 화합물들은 화학식1의 X, R3-R7 , R1 및 R2, R'및 R''의 치환 또는 비치환된 치환기들은 광범위한 관계로 화학식 3으로 표시한 화합물들 중 일부의 비교실시예를 예시적으로 설명하였으나 비교실시예로 예시적으로 설명하지 않은 화학식 1로 표시되는 화합물들도 전술한 화학식 1의 모핵 구조를 가지는 이유로 전술한 비교실시예들과 동일한 효과를 나타내는 것으로 확인할 수 있으며 그 결과는 본 명세서의 일부를 구성할 수 있다.
In this case, the compounds represented by Formula 1 may be substituted or unsubstituted substituents of X, R 3 -R 7 , R 1 and R 2 , R ′ and R ″ of Formula 1 in a broad range of compounds represented by Formula 3 Some comparative examples have been described by way of example, but the compounds represented by the formula (1), which are not illustratively described as comparative examples, also exhibit the same effects as the above-described comparative examples because of the parent nucleus structure of the formula (1). The results may form part of the specification.

제조예2Production Example 2

이하, 중수소, 삼중수소를 포함하고 있는 화학식 1 내지 3에 속하는 화합물에 대한 제조예 또는 합성예를 설명한다. 다만, 중수소, 삼중수소를 포함하고 있는 화학식 1 내지 3에 속하는 화합물들의 수가 많기 때문에 중수소, 삼중수소를 포함하고 있는 화학식 1 내지 3에 속하는 화합물 중 하나 또는 둘을 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, the preparation or synthesis examples of the compound belonging to the formulas (1) to (3) containing deuterium and tritium will be described. However, since the number of compounds belonging to the formulas 1 to 3 containing deuterium and tritium is large, one or two of the compounds belonging to formulas 1 to 3 including deuterium and tritium will be described. 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.

다시 말해 반응식 7을 통해 알 수 있는 바와 같이, 중간체1) 내지 중간체5)를 합성한 후 이 중간체들을 이용하여 본 발명의 실시예들(B-1 내지 B-8, C-1 내지 C-8)의 화합물들을 합성할 수 있다. 이들에 대한 자세한 설명은 아래에서 구체적으로 설명한다.In other words, as shown in Scheme 7, intermediates 1) to intermediates 5) were synthesized and then used in the embodiments of the present invention using the intermediates (B-1 to B-8, C-1 to C-8). ) Compounds can be synthesized. Detailed description thereof will be described below in detail.

[반응식 7][Reaction Scheme 7]

Figure 112011015280967-pat00116
Figure 112011015280967-pat00116

중간체들의 합성Synthesis of Intermediates

중간체 1)의 합성 Synthesis of Intermediate 1)

1L 둥근바닥플라스크에 9-phenyl-9H-carbazole (20 g, 82.203 mmol), NBS (48.84 g, 172.63 mmol), BPO (1.99 g, 8.22 mmol) 을 순서대로 넣은 후 methylene chloride (246 mL)을 넣고 상온에서 5~7시간 교반 한다. 반응이 완료되면 methylene chloride 와 물을 사용하여 추출 후 유기층을 MgSO4로 건조 시킨 후 유기용매를 제거한다. silicagel column 한 후에 다이클로로메탄과 헥산으로 재결정하여 고체의 표제 화합물을 28.7 g 얻었다. 수율 : 87 % , FD-MS : m/z=398.93(C18H11Br2N=401.09)
9-phenyl-9H-carbazole (20 g, 82.203 mmol), NBS (48.84 g, 172.63 mmol) and BPO (1.99 g, 8.22 mmol) were added to the 1L round bottom flask, followed by methylene chloride (246 mL). Stir at room temperature for 5-7 hours. After the reaction is completed, the organic layer is extracted with methylene chloride and water, dried over MgSO 4 and the organic solvent is removed. After silicagel column, recrystallized with dichloromethane and hexane to give 28.7 g of the title compound as a solid. Yield: 87%, FD-MS: m / z = 398.93 (C 18 H 11 Br 2 N = 401.09)

중간체 2)의 합성 Synthesis of Intermediate 2)

1L 둥근바닥플라스크에 합성식 1 (28.7 g, 71.56 mmol)을 넣고 무수 THF 200mL에 녹인 후에 -78℃로 온도를 낮춘 후 n-BuLi (2.5M in hexane, 34.35 mL, 85.9 mmol)을 넣고 1시간 동안 교반한다. 그런 후에 D2O (2.14 g, 107.15 mmol)을 넣고, 상온으로 승온 시킨 후에 1시간 동안 교반한다. 상온에서 H2O (48 mL) 을 넣고 교반 후 유기층을 추출하여 분리하였다. 유기층을 MgSO4로 건조 시킨 후 유기용매를 제거한다. silicagel column 한 후에 다이클로로메탄과 헥산으로 재결정하여 고체의 표제 화합물을 11.56 g 얻었다. 수율 : 50 % , FD-MS : m/z=322.02(C18H11DBrN=323.20)
In a 1L round bottom flask, add Formula 1 (28.7 g, 71.56 mmol) to 200 mL of anhydrous THF, lower the temperature to -78 ° C, and add n-BuLi (2.5M in hexane, 34.35 mL, 85.9 mmol) for 1 hour. While stirring. Then add D2O (2.14 g, 107.15 mmol), warm to room temperature and stir for 1 hour. H2O (48 mL) was added at room temperature, and after stirring, the organic layer was extracted and separated. The organic layer is dried over MgSO 4 and the organic solvent is removed. After silicagel column, recrystallized with dichloromethane and hexane to give 11.56 g of the title compound as a solid. Yield: 50%, FD-MS: m / z = 322.02 (C 18 H 11 DBrN = 323.20)

중간체 3)의 합성Synthesis of Intermediate 3)

합성식 2 (11.56 g, 35.77 mmol)을 넣고 무수 THF 110 mL에 녹인 후에 -78℃ 로 온도를 낮춘다. 그런 다음 n-BuLi (2.5M in hexane, 40.2 mL, 37.56 mmol)을 천천히 적가한다. -78℃ 에서 1.5 시 간 교반한다. triisopropyl borate (24.7 mL, 107.31 mmol)을 천천히 적가한다. 천천히 상온으로 온도를 올린 후에 상온에서 overnight 한다. 반응 종료 후 10% HCl 수용액을 첨가한다. 생성된 고체를 여과하여 hexane 으로 washing 한 후 고체의 표제 화합물을 6.7 g 얻었다. 수율 : 65 %, FD-MS : m/z=288.12(C18H13DBNO2=288.13)
Add Formula 2 (11.56 g, 35.77 mmol) and dissolve in 110 mL of anhydrous THF and lower the temperature to -78 ° C. Then slowly add dropwise n-BuLi (2.5M in hexane, 40.2 mL, 37.56 mmol). Stir at -78 ° C for 1.5 hours. triisopropyl borate (24.7 mL, 107.31 mmol) is slowly added dropwise. Slowly raise the temperature to room temperature and overnight at room temperature. 10% HCl aqueous solution is added after completion of the reaction. The resulting solid was filtered and washed with hexane to give 6.7 g of the title compound as a solid. Yield: 65%, FD-MS: m / z = 288.12 (C 18 H 13 DBNO 2 = 288.13)

중간체 4) 및 5)의 합성Synthesis of Intermediates 4) and 5)

중간체 4) 및 5)는 D2O 대신에 T2O를 사용한 것을 제외하고는 전술한 중간체들의 합성방방법과 동일하게 최종 물질을 얻었다.
Intermediates 4) and 5) obtained the final material in the same manner as the synthesis method of the above-described intermediates except that T2O was used instead of D2O.

최종화합물의 합성방법Synthesis of Final Compound

[반응식 8][Reaction Scheme 8]

Figure 112011015280967-pat00117
Figure 112011015280967-pat00117

둥근바닥플라스크에4의 화합물 (1당량), 2화합물 (1.1당량), Pd(PPh3)4 (0.03~0.05당량),NaOH (3당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1mmol)을 넣는다. Compound (1 equiv), 2 compounds (1.1 equiv), Pd (PPh 3 ) 4 (0.03-0.05 equiv), NaOH (3 equiv), THF (3 mL / 1 mmol), water (1.5) in a round bottom flask mL / 1 mmol).

그런 후에 80℃~90℃ 상태에서 가열 환류 시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시킨다. 그런 후에 메틸렌클로라이드와 물로 추출하고 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물을 얻었으며 아래 표 3와 같이 FD-MS로 생성물(실시예들(B-1 내지 B-8, C-1 내지 C-8)의 화합물들)을 확인하였다. After that, the mixture is heated to reflux at 80 ° C to 90 ° C. After the reaction is completed, distilled water is diluted at room temperature. Thereafter, the mixture was extracted with methylene chloride and water, and the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product by FD-MS as shown in Table 3 below. B-8, C-1 to C-8) compounds) were identified.

[표 3][Table 3]

Figure 112011015280967-pat00118
Figure 112011015280967-pat00118

유기 EL 소자의 제조 평가Manufacturing evaluation of organic electroluminescent element

합성을 통해 얻은 여러 화합물을 각각 발광층의 발광 호스트 물질이나 정공 수송층으로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 4,4',4''-트리스(N-(2-나프틸)-N-페닐아미노)-트리페닐아민 (이하 2T-NATA로 약기함)막을 진공증착하여 10 nm 두께로 형성하였다. 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. First, 4,4 ', 4' '-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter 2T-) as a hole injection layer on the ITO layer (anode) formed on the glass substrate. Abbreviated as NATA) film was vacuum deposited to form a thickness of 10 nm.

이어서, 정공수송 화합물로서 본 발명의 실시예들(B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C-8)의 화합물들 중 하나를 30 nm의 두께로 진공증착하여 홀 수송층을 형성하였다. 홀 수송층을 형성한 후, 개발한 물질을 홀 수송층으로 측정할 시에는 이 홀 수송층 상부에 45nm두께의 BD-052X(Idemitus사)가 7% 도핑된 발광층 (이때, BD-052X는 청색 형광 도펀트이고, 발광 호스트 물질로는 9,10-다이(나프탈렌-2-안트라센(AND))을 사용하였다.Subsequently, embodiments of the present invention as a hole transport compound (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C One of the compounds of -8) was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After the formation of the hole transport layer, when the developed material was measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X was a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material.

홀 저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 의 두께로 진공증착하고, 이어서 전자주입층으로 트리스(8-퀴놀리놀) 알루미늄 (이하 Alq3로 약칭함)을 40 nm의 두께로 성막하였다. 이 후, 할로젠화 알칼리 금속인 LiF를 0.2 nm의 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 이 Al/LiF를 음극으로 사용함으로서 유기전계 발광소자를 제조하였다.
(1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited to an electron injection layer at a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

비교실험예2Comparative Experiment 2

본 발명의 실시예들(B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C-8)의 화합물들 중 하나를 정공수송층으로 측정했을 경우, 비교를 위해 본 발명의 실시예들(B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C-8)의 화합물들 중 하나 대신에 하기식으로 표시되는 화합물(이하 NPB로 약기함)를 정공수송 물질로 사용하여 실험 예와 동일한 구조의 유기전계발광소자를 제작하였다. Compounds of Embodiments of the Invention (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C-4, C-5, C-8) When one of the measured by the hole transport layer, embodiments of the present invention (B-1, B-2, B-4, B-5, B-8, C-1, C-2, C- for comparison) 4, C-5, C-8) instead of one of the compounds represented by the following formula (hereinafter abbreviated as NPB) was used as a hole transport material to fabricate an organic EL device having the same structure as the experimental example .

Figure 112011015280967-pat00119
Figure 112011015280967-pat00119

[표 4][Table 4]

Figure 112011015280967-pat00120
Figure 112011015280967-pat00120

상기 표2의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 이용한 유기전계발광소자는 고효율이면서 색순도가 향상될 뿐만 아니라 장수명인 청색 발광이 얻어지므로 유기전계발광소자의 정공수송재료로 사용되어 낮은 구동전압과 높은 발광효율 및 수명을 현저히 개선시킬 수 있다. As can be seen from the results of Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity but also blue light emission with long life is obtained as a hole transporting material of the organic light emitting device Can be used to significantly improve the low driving voltage, high luminous efficiency and lifetime.

본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 정공수송층 뿐만 아니라 발광층, 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.
Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a hole transport layer as well as a light emitting layer, 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. .

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. While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments.

본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

Claims (11)

하기 화학식 1로 표시되는 화합물.
화학식 1 화학식 2
Figure 112013032074936-pat00131
Figure 112013032074936-pat00132

(상기 화학식 1에서,
Cz기는 상기 화학식 2로 표시될 수 있는 치환 또는 비치환된 카바졸 유도체이고,
R1 및 R2는 ⅰ) 서로 독립적으로 탄소수 1~60의 알킬기; 및 핵 탄소수 6~60의 아릴기;로 이루어진 군에서 선택되거나, 또는 ⅱ) 서로 결합하여 고리를 형성할 수 있고,
Ar1 내지 Ar3는 서로 독립적으로 핵 탄소수 6~60의 아릴기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 핵 탄소수 4~60의 헤테로아릴기;로 이루어진 군에서 선택되며, 여기서 아릴기인 경우 탄소수 1~20의 알킬기; 탄소수 1~20의 알콕시기; 및 할로겐;으로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,
상기 화학식 2에서,
R3 내지 R6은 서로 독립적으로 수소; 중수소; 및 삼중수소;로 이루어진 군에서 선택되고(단, R3 내지 R6이 모두 수소로 되는 경우는 제외한다),
R7은 탄소수 1~20의 알킬기로 치환되거나 비치환된 핵 탄소수 6~60의 아릴기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 핵 탄소수 4~60의 헤테로아릴기;로 이루어진 군에서 선택될 수 있다)A compound represented by the following formula (1).
Formula 1 Formula 2
Figure 112013032074936-pat00131
Figure 112013032074936-pat00132

(In Formula 1,
Cz group is a substituted or unsubstituted carbazole derivative may be represented by Formula 2,
R 1 and R 2 are each independently iii) an alkyl group having 1 to 60 carbon atoms; And aryl group having 6 to 60 nuclear carbon atoms; or ii) may be combined with each other to form a ring,
Ar 1 to Ar 3 are each independently an aryl group having 6 to 60 nuclear carbon atoms; And a heteroaryl group having 4 to 60 nuclear carbon atoms including at least one hetero atom of O, N, S, Si, and P; wherein the aryl group is an alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; And halogen; may be substituted with one or more substituents selected from the group consisting of,
In Formula 2,
R 3 to R 6 are each independently hydrogen; heavy hydrogen; And tritium; selected from the group consisting of (except when R 3 to R 6 are all hydrogen),
R 7 is an aryl group having 6 to 60 nuclear carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; And a heteroaryl group having 4 to 60 nuclear carbon atoms including at least one heteroatom of O, N, S, Si, and P). 삭제delete 제1항에 있어서,
상기 Ar1 내지 Ar3은 서로 독립적으로 알킬기, 알콕시기 및 할로겐으로 이루어진 군에서 선택된 하나의 작용기로 치환되거나 비치환된 페닐기; 비페닐기; 1-나프틸기; 2-나프틸기; 메틸기로 치환되거나 비치환된 플루오렌일기; 티오펜기; 및 피리딜기로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.The method of claim 1,
Ar 1 to Ar 3 are each independently a phenyl group unsubstituted or substituted with one functional group selected from the group consisting of an alkyl group, an alkoxy group and a halogen; Biphenyl group; 1-naphthyl group; 2-naphthyl group; A fluorenyl group unsubstituted or substituted with a methyl group; Thiophene group; And pyridyl groups. 제1항에 있어서,
상기 화학식1로 표시되는 화합물을 아래 화학식3으로 표시되는 화합물들 중 하나인 것을 특징으로 하는 화합물.
화학식3
Figure 112011015280967-pat00123

Figure 112011015280967-pat00124

The method of claim 1,
A compound represented by Chemical Formula 1 is one of the compounds represented by Chemical Formula 3 below.
Formula 3
Figure 112011015280967-pat00123

Figure 112011015280967-pat00124

 제1항, 제3항 및 제4항 중 어느 한 항의 화합물을 함유하는 1층 이상의 유기물층을 포함하는 유기전기소자.An organic electric device comprising at least one organic material layer containing the compound of any one of claims 1, 3 and 4. 제5항에 있어서,
상기 화합물을 용액 공정(soluble process)에 의해 상기 유기물층을 형성하는 것을 특징으로 하는 유기전기소자.The method of claim 5,
The organic electroluminescent device according to claim 1, wherein the organic layer is formed by a solution process. 제5항에 있어서,
상기 유기전기소자는 제1 전극, 상기 1층 이상의 유기물층 및 제2 전극을 순차적으로 적층된 형태로 포함하는 유기전계발광소자인 것을 특징으로 하는 유기전기소자.The method of claim 5,
The organic electroluminescent device is an organic electroluminescent device comprising a first electrode, the at least one organic material layer and the second electrode in a stacked form sequentially. 제7항에 있어서,
상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나인 것을 특징으로 하는 유기전기소자.The method of claim 7, wherein
The organic material layer is an organic electric element, characterized in that any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. 제7항에 있어서,
상기 유기물층은 발광층을 포함하며,
상기 발광층에서 상기 화합물이 호스트 또는 도판트 물질로 사용되는 것을 특징으로 하는 유기전기소자.The method of claim 7, wherein
The organic material layer includes a light emitting layer,
In the light emitting layer, the compound is used as a host or a dopant material. 제7항의 유기전기소자를 포함하는 디스플레이장치와;
상기 디스플레이장치를 구동하는 제어부를 포함하는 단말.A display device comprising the organic electric element of claim 7;
And a control unit for driving the display device. 제10항에 있어서,
상기 유기전기소자는 유기전계발광소자(OLED), 유기태양전지, 유기감광체(OPC) 드럼, 유기트랜지스트(유기 TFT) 중 하나인 것을 특징으로 하는 단말.
The method of claim 10,
The organic electroluminescent device is an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) drum, characterized in that one of the organic transistor (organic TFT).
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