KR20120072785A - Spiro compound and organic electroluminescent devices comprising the same - Google Patents

Spiro compound and organic electroluminescent devices comprising the same Download PDF

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KR20120072785A
KR20120072785A KR1020100134674A KR20100134674A KR20120072785A KR 20120072785 A KR20120072785 A KR 20120072785A KR 1020100134674 A KR1020100134674 A KR 1020100134674A KR 20100134674 A KR20100134674 A KR 20100134674A KR 20120072785 A KR20120072785 A KR 20120072785A
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제종태
정성욱
박석배
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에스에프씨 주식회사
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Abstract

PURPOSE: A spiro compound and an organic electro luminescence device including thereof are provided to enhance luminance, color purity, and lifetime property of the organic electro luminescence device by having high triplet energy and high thermal stability. CONSTITUTION: A spiro compound is represented by chemical formula 1 or chemical formula 2. Here, R1 - R20 are respectively selected from hydrogen, deuterium, halogen, substituted or non-substituted C6-40 arylamino group, substituted or non-substituted C3-40 aryloxy group, substituted or non-substituted C6-40 aryl, substituted or non-substituted C3-40 heteroaryl, substituted or non-substituted germanium, and substituted or non-substituted phosphorous, and substituted or non-substituted boron. A1 or A2 is selected from substituted or non-substituted C6-40 aryl group and substituted or non-substituted C3-40 heteroaryl group.

Description

스피로 화합물 및 이를 포함하는 유기전계발광소자{SPIRO COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME}Spiro compounds and organic electroluminescent devices comprising same {SPIRO COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICES COMPRISING THE SAME}

본 발명은 스피로 화합물 및 이를 포함하는 유기전계발광소자에 관한 것으로서, 보다 상세하게는, 휘도, 색순도 및 수명 특성이 우수한 스피로 화합물 및 이를 포함하는 유기전계발광소자에 관한 것이다.The present invention relates to a spiro compound and an organic light emitting device including the same, and more particularly, to a spiro compound having excellent brightness, color purity and life characteristics and an organic light emitting device comprising the same.

최근 표시장치의 대형화에 따라 공간 점유가 작은 평면표시소자의 요구가 증대되고 있는데, 대표적인 평면표시소자인 액정 디스플레이는 기존의 CRT(cathode ray tube)에 비해 경량화가 가능하다는 장점은 있으나, 시야각(viewing angle)이 제한되고 배면 광(back light)이 반드시 필요하다는 등의 단점을 갖고 있다. 이에 반하여, 새로운 평면표시소자인 유기전계발광소자(organic light emitting diode; OLED)는 자기 발광 현상을 이용한 디스플레이로서, 시야각이 크고, 액정 디스플레이에 비해 경박, 단소해질 수 있으며, 빠른 응답 속도 등의 장점을 가지고 있으며, 최근에는 풀-컬러(full-color) 디스플레이 또는 조명으로의 응용이 기대되고 있다.Recently, as the size of the display device increases, the demand for a flat display device having a small space is increasing. A liquid crystal display, which is a typical flat display device, has a merit of being lighter than a conventional cathode ray tube (CRT). The disadvantage is that the angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, the application to full-color display or lighting is expected.

일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다.In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

유기 발광 현상을 이용하는 유기전계발광소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기전계발광소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기전계발광소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. 이러한 유기전계발광소자는 자발광, 고휘도, 고효율, 낮은 구동전압, 넓은 시야각, 높은 콘트라스트, 고속 응답성 등의 특성을 갖는 것으로 알려져 있다.An organic light emitting display device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows. Such an organic electroluminescent device is known to have properties such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

유기전계발광소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. 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 light emitting device may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . 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 호스트보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이 때, 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 shifts to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

유기전계발광소자가 전술한 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전계발광소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서, 당 기술분야에서는 새로운 재료의 개발이 계속 요구되고 있는 실정이다.In order for the organic electroluminescent device to fully exhibit the above-mentioned excellent features, the organic layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. is supported by a stable and efficient material Although this should be preceded, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet. Therefore, the development of new materials in the art continues to be required.

본 발명이 이루고자 하는 기술적 과제는 녹색 인광의 휘도, 색순도가 우수하며, 장수명의 스피로 화합물을 제공하는 것이다.The technical problem to be achieved by the present invention is to provide a spiro compound having excellent luminance and color purity of green phosphorescence and long life.

본 발명이 이루고자 하는 두 번째 기술적 과제는 상기 스피로 화합물을 포함하는 유기전계발광소자를 제공하는 것이다.The second technical problem to be achieved by the present invention is to provide an organic light emitting device comprising the spiro compound.

상기 첫 번째 기술적 과제를 달성하기 위해서, 본 발명은 하기 [화학식 1] 또는 [화학식 2]로 표시되는 스피로 화합물을 제공한다.In order to achieve the first technical problem, the present invention provides a spiro compound represented by the following [Formula 1] or [Formula 2].

Figure pat00001
(1)
Figure pat00001
(One)

Figure pat00002
(2)
Figure pat00002
(2)

상기 화학식에서,In the above formulas,

R1 내지 R20은 각각 독립적으로 수소 원자, 중수소 원자, 할로겐 원자, 치환 또는 비치환의 탄소수 6 내지 40의 아릴아미노기, 치환 또는 비치환의 탄소수 3 내지 40의 아릴옥시기, 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기, 치환 또는 비치환의 게르마늄기, 치환 또는 비치환의 인, 치환 또는 비치환의 보론으로부터 선택되고, 상기 R1 내지 R20 중 인접하는 기는 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있으며,R 1 to R 20 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted carbon atom 6 to A aryl group of 40, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, a substituted or unsubstituted boron, and the adjacent groups of R 1 to R 20 are selected from Combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring,

A1 또는 A2는 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 및 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기로부터 선택되고, A 1 or A 2 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

상기 A1은 R6 또는 R7, A2는 R14 또는 R15와 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있다.A 1 is R 6 or R 7 , A 2 may be bonded to R 14 or R 15 to each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring.

본 발명에 있어서, 상기 R1 내지 R20, A1 또는 A2는 각각 독립적으로 중수소 원자, 시아노기, 할로겐 원자, 히드록시기, 니트로기, 탄소수 1 내지 40의 알킬기, 탄소수 1 내지 40의 알콕시기, 탄소수 1 내지 40의 알킬아미노기, 탄소수 6 내지 40의 아릴아미노기,　탄소수 3 내지 40의 헤테로아릴아미노기, 탄소수 1 내지 40의 알킬실릴기, 탄소수 6 내지 40의 아릴실릴기, 탄소수 6 내지 40의 아릴기, 탄소수 3 내지 40의 아릴옥시기, 탄소수 3 내지 40의 헤테로아릴기, 게르마늄기, 인 및 보론으로 이루어진 군으로부터 선택된 하나 이상의 치환기에 의해서 치환될 수 있고, 상기 치환기에 의해 추가로 치환될 수 있으며, 상기 치환기는 서로 결합하여 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있다.In the present invention, the R 1 to R 20 , A 1 or A 2 are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms , May be substituted by one or more substituents selected from the group consisting of an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron, and may be further substituted by the substituents. , The substituents may be bonded to each other to form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic.

상기 두 번째 기술적 과제를 해결하기 위하여, 본 발명은 애노드; 캐소드; 및 상기 애노드 및 캐소드 사이에 개재되며, 상기 화학식 (1) 또는 (2)로 표시되는 스피로 화합물을 포함하는 층을 구비한 유기전계발광소자를 제공한다.In order to solve the second technical problem, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, there is provided an organic electroluminescent device having a layer comprising a spiro compound represented by the formula (1) or (2).

본 발명에 따른 화학식 (1) 또는 (2)로 표시되는 스피로 화합물은 높은 삼중항 에너지(T1)와 높은 열적안정성을 가지는 화합물이기 때문에 상기화합물을 포함하는 유기전계발광소자는 휘도, 색순도, 수명특성이 우수해져 디스플레이 및 조명 등에 유용하게 사용될 수 있다.Since the spiro compound represented by the formula (1) or (2) according to the present invention is a compound having high triplet energy (T1) and high thermal stability, the organic light emitting device including the compound has luminance, color purity, and lifetime characteristics. This is excellent and can be usefully used for display and lighting.

도 1a 내지 1e는 본 발명의 실시예에 따른 유기전계발광소자의 구조를 보여주는 단면도이다.
도 2은 본 발명의 실시예에 따른 화학식 81의 TGA 및 DSC 그래프이다.
도 3은 본 발명의 실시예에 따른 화학식 86의 TGA 및 DSC 그래프이다.
도 4는 본 발명의 실시예에 따른 화학식 86의 EL스펙트럼을 나타낸 도면이다.1A to 1E are cross-sectional views illustrating a structure of an organic light emitting display device according to an embodiment of the present invention.
2 is a TGA and DSC graph of Formula 81 according to an embodiment of the present invention.
3 is a TGA and DSC graph of Formula 86 according to an embodiment of the present invention.
4 is a view showing an EL spectrum of the formula 86 according to an embodiment of the present invention.

이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따른 스피로 화합물은 하기 [화학식 1] 또는 [화학식 2]로 표시되는 것을 특징으로 한다.The spiro compound according to the present invention is characterized by being represented by the following [Formula 1] or [Formula 2].

Figure pat00003
(1)
Figure pat00003
(One)

Figure pat00004
(2)
Figure pat00004
(2)

상기 화학식에서,In the above formulas,

R1 내지 R20은 각각 독립적으로 수소 원자, 중수소 원자, 할로겐 원자, 치환 또는 비치환의 탄소수 6 내지 40의 아릴아미노기, 치환 또는 비치환의 탄소수 3 내지 40의 아릴옥시기, 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기, 치환 또는 비치환의 게르마늄기, 치환 또는 비치환의 인, 치환 또는 비치환의 보론으로부터 선택되고, 상기 R1 내지 R20 중 인접하는 기는 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있으며,R 1 to R 20 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted carbon atom 6 to A aryl group of 40, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, a substituted or unsubstituted boron, and the adjacent groups of R 1 to R 20 are selected from Combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring,

A1 또는 A2는 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 및 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기로부터 선택되고, A 1 or A 2 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms,

상기 A1은 R6 또는 R7, A2는 R14 또는 R15와 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있다.A 1 is R 6 or R 7 , A 2 may be bonded to R 14 or R 15 to each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring.

본 발명에 있어서, 상기 R1 내지 R20, A1 또는 A2는 각각 독립적으로 중수소 원자, 시아노기, 할로겐 원자, 히드록시기, 니트로기, 탄소수 1 내지 40의 알킬기, 탄소수 1 내지 40의 알콕시기, 탄소수 1 내지 40의 알킬아미노기, 탄소수 6 내지 40의 아릴아미노기,　탄소수 3 내지 40의 헤테로아릴아미노기, 탄소수 1 내지 40의 알킬실릴기, 탄소수 6 내지 40의 아릴실릴기, 탄소수 6 내지 40의 아릴기, 탄소수 3 내지 40의 아릴옥시기, 탄소수 3 내지 40의 헤테로아릴기, 게르마늄기, 인 및 보론으로 이루어진 군으로부터 선택된 하나 이상의 치환기에 의해서 치환될 수 있고, 상기 치환기에 의해 추가로 치환될 수 있으며, 상기 치환기는 서로 결합하여 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있다.In the present invention, the R 1 to R 20 , A 1 or A 2 are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, An alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms , May be substituted by one or more substituents selected from the group consisting of an aryloxy group having 3 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron, and may be further substituted by the substituents. , The substituents may be bonded to each other to form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic.

본 발명에서 사용되는 치환기인 알킬기의 구체적인 예로는 메틸기, 에틸기, 프로필기, 이소부틸기, sec-부틸기, tert-부틸기, 펜틸기, iso-아밀기, 헥실기, 헵틸기, 옥틸기, 스테아릴기, 트리클로로메틸기, 트리플루오르메틸기 등을 들 수 있으며, 상기 알킬기 중 하나 이상의 수소 원자는 중수소 원자, 할로겐 원자, 히드록시기, 니트로기, 시아노기, 트리플루오로메틸기, 실릴기(이 경우 "알킬실릴기"라 함), 치환 또는 비치환된 아미노기(-NH2, -NH(R), -N(R')(R''), 여기서 R, R' 및 R"은 각각 독립적으로 탄소수 1 내지 24의 알킬기임(이 경우 "알킬아미노기"라 함)), 아미디노기, 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, 탄소수 1 내지 24의 알킬기, 탄소수 1 내지 24의 할로겐화된 알킬기, 탄소수 2 내지 24의 알케닐기, 탄소수 2 내지 24의 알키닐기, 탄소수 1 내지 24의 헤테로알킬기, 탄소수 5 내지 24의 아릴기, 탄소수 6 내지 24의 아릴알킬기, 탄소수 3 내지 24의 헤테로아릴기 또는 탄소수 3 내지 24의 헤테로아릴알킬기로 치환될 수 있다.Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, A stearyl group, a trichloromethyl group, a trifluoromethyl group, and the like, and at least one hydrogen atom of the alkyl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, or a silyl group (in this case, Alkylsilyl groups ", substituted or unsubstituted amino groups (-NH 2 , -NH (R), -N (R ') (R''), wherein R, R' and R" are each independently carbon atoms An alkyl group of 1 to 24 (in this case referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group of 1 to 24 carbon atoms, a halogenated alkyl group of 1 to 24 carbon atoms , Alkenyl group having 2 to 24 carbon atoms, alkynyl group having 2 to 24 carbon atoms, 1 carbon atom It may be substituted with a heteroalkyl group of 24 to 24, an aryl group of 5 to 24 carbon atoms, an arylalkyl group of 6 to 24 carbon atoms, a heteroaryl group of 3 to 24 carbon atoms or a heteroarylalkyl group of 3 to 24 carbon atoms.

본 발명의 화합물에서 사용되는 치환기인 알콕시기의 구체적인 예로는 메톡시기, 에톡시기, 프로폭시기, 이소부틸옥시기, sec-부틸옥시기, 펜틸옥시기, iso-아밀옥시기, 헥실옥시기 등을 들 수 있으며, 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group and the like. These can be mentioned and can substitute by the same substituent as the case of the said alkyl group.

본 발명의 화합물에서 사용되는 치환기인 할로겐기의 구체적인 예로는 플루오르(F), 클로린(Cl), 브롬(Br) 등을 들 수 있다.Specific examples of the halogen group which is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br) and the like.

본 발명의 화합물에서 사용되는 치환기인 아릴기의 구체적인 예로는 페닐기, 2-메틸페닐기, 3-메틸페닐기, 4-메틸페닐기, 4-에틸페닐기, o-비페닐기, m-비페닐기, p-비페닐기, 4-메틸비페닐기, 4-에틸비페닐기, o-터페닐기, m-터페닐기, p-터페닐기, 1-나프틸기, 2-나프틸기, 1-메틸나프틸기, 2-메틸나프틸기, 안트릴기, 페난트릴기, 피레닐기, 플루오레닐기, 테트라히드로나프틸기 등과 같은 방향족 그룹을 들 수 있으며, 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the aryl group which is a substituent used in the compound of the present invention are phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-ratio Phenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group And an aromatic group such as an anthryl group, a phenanthryl group, a pyrenyl group, a fluorenyl group, a tetrahydronaphthyl group, and the like, and may be substituted with the same substituent as in the alkyl group.

본 발명의 화합물에서 사용되는 치환기인 헤테로아릴기의 구체적인 예로는 피리디닐기, 피리미디닐기, 트리아지닐기, 인돌리닐기, 퀴놀린닐기, 피롤리디닐기, 피페리디닐기, 모폴리디닐기, 피페라디닐기, 카바졸릴기, 옥사졸릴기, 옥사디아졸릴기, 벤조옥사졸릴기, 치아졸릴기, 치아디아졸릴기, 벤조치아졸릴기, 트리아졸릴기, 이미다졸릴기, 벤조이미다졸기 등이 있으며, 상기 헤테로아릴기 중 하나 이상의 수소 원자는 상기 알킬기의 경우와 동일한 치환기로 치환가능하다.Specific examples of the heteroaryl group which is a substituent used in the compound of the present invention include pyridinyl group, pyrimidinyl group, triazinyl group, indolinyl group, quinolinyl group, pyrrolidinyl group, piperidinyl group, morpholidinyl group, pipepe Radiinyl, carbazolyl, oxazolyl, oxdiazolyl, benzooxazolyl, chiazolyl, thiadiazolyl, benzothiazolyl, triazolyl, imidazolyl and benzoimidazole At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the alkyl group.

본 발명에 있어서, "치환 또는 비치환된"이라는 용어는 중수소, 할로겐기, 알킬기, 알케닐기, 알콕시기, 아릴기, 아릴알킬기, 아릴알케닐기, 헤테로아릴기, 카바졸릴기, 플루오레닐기, 니트릴기 및 아세틸렌기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되는 것을 의미한다.In the present invention, the term "substituted or unsubstituted" is deuterium, halogen, alkyl, alkenyl, alkoxy, aryl, arylalkyl, arylalkenyl, heteroaryl, carbazolyl, fluorenyl, Substituted or unsubstituted with one or more substituents selected from the group consisting of a nitrile group and an acetylene group.

구체적으로, 본 발명에 따른 스피로 화합물은 하기 [화학식 3] 내지 [화학식 242]로 표시되는 화합물 중 어느 하나일 수 있다.
Specifically, the spiro compound according to the present invention may be any one of the compounds represented by the following [Formula 3] to [Formula 242].

Figure pat00005
Figure pat00005

[화학식 3] [화학식 4] [화학식 5] [화학식 6] [Formula 3] [Formula 4] [Formula 5] [Formula 6]

Figure pat00006
Figure pat00006

[화학식 7] [화학식 8] [화학식 9] [화학식 10][Formula 7] [Formula 8] [Formula 9] [Formula 10]

Figure pat00007
Figure pat00007

[화학식 11] [화학식 12] [화학식 13] [화학식 14][Formula 11] [Formula 12] [Formula 13] [Formula 14]

Figure pat00008
Figure pat00008

[화학식 15] [화학식 16] [화학식 17] [화학식 18][Formula 15] [Formula 16] [Formula 17] [Formula 18]

Figure pat00009
Figure pat00009

[화학식 19] [화학식 20] [화학식 21] [화학식 22][Formula 19] [Formula 20] [Formula 21] [Formula 22]

Figure pat00010
Figure pat00010

[화학식 23] [화학식 24] [화학식 25] [화학식 26][Formula 23] [Formula 24] [Formula 25] [Formula 26]

Figure pat00011
Figure pat00011

[화학식 27] [화학식 28] [화학식 29] [화학식 30][Formula 27] [Formula 28] [Formula 29] [Formula 30]

Figure pat00012
Figure pat00012

[화학식 31] [화학식 32] [화학식 33] [화학식 34][Formula 31] [Formula 32] [Formula 33] [Formula 34]

Figure pat00013
Figure pat00013

[화학식 35] [화학식 36] [화학식 37] [화학식 38][Formula 35] [Formula 36] [Formula 37] [Formula 38]

Figure pat00014
Figure pat00014

[화학식 39] [화학식 40] [화학식 41] [화학식 42][Formula 39] [Formula 40] [Formula 41] [Formula 42]

Figure pat00015
Figure pat00015

[화학식 43] [화학식 44] [화학식 45] [화학식 46][Formula 43] [Formula 44] [Formula 45] [Formula 46]

Figure pat00016
Figure pat00016

[화학식 47] [화학식 48] [화학식 49] [화학식 50][Formula 47] [Formula 48] [Formula 49] [Formula 50]

Figure pat00017
Figure pat00017

[화학식 51] [화학식 52] [화학식 53] [화학식 54][Formula 51] [Formula 52] [Formula 53] [Formula 54]

Figure pat00018
Figure pat00018

[화학식 55] [화학식 56] [화학식 57] [화학식 58][Formula 55] [Formula 56] [Formula 57] [Formula 58]

Figure pat00019
Figure pat00019

[화학식 59] [화학식 60] [화학식 61] [화학식 62][Formula 59] [Formula 60] [Formula 61] [Formula 62]

Figure pat00020
Figure pat00020

[화학식 63] [화학식 64] [화학식 65] [화학식 66][Formula 63] [Formula 64] [Formula 65] [Formula 66]

Figure pat00021
Figure pat00021

[화학식 67] [화학식 68] [화학식 69] [화학식 70][Formula 67] [Formula 68] [Formula 69] [Formula 70]

Figure pat00022
Figure pat00022

[화학식 71] [화학식 72] [화학식 73] [화학식 74][Formula 71] [Formula 72] [Formula 73] [Formula 74]

Figure pat00023
Figure pat00023

[화학식 75] [화학식 76] [화학식 77] [화학식 78]
[Formula 75] [Formula 76] [Formula 77] [Formula 78]

Figure pat00024
Figure pat00024

[화학식 79] [화학식 80] [화학식 81] [화학식 82][Formula 79] [Formula 80] [Formula 81] [Formula 82]

Figure pat00025
Figure pat00025

[화학식 83] [화학식 84] [화학식 85] [화학식 86][Formula 83] [Formula 84] [Formula 85] [Formula 86]

Figure pat00026
Figure pat00026

[화학식 87] [화학식 88] [화학식 89] [화학식 90][Formula 87] [Formula 88] [Formula 89] [Formula 90]

Figure pat00027
Figure pat00027

[화학식 91] [화학식 92] [화학식 93] [화학식 94][Formula 91] [Formula 92] [Formula 93] [Formula 94]

Figure pat00028
Figure pat00028

[화학식 95] [화학식 96] [화학식 97] [화학식 98][Formula 95] [Formula 96] [Formula 97] [Formula 98]

Figure pat00029
Figure pat00029

[화학식 99] [화학식 100] [화학식 101] [화학식 102][Formula 99] [Formula 100] [Formula 101] [Formula 102]

Figure pat00030
Figure pat00030

[화학식 103] [화학식 104] [화학식 105] [화학식 106][Formula 103] [Formula 104] [Formula 105] [Formula 106]

Figure pat00031
Figure pat00031

[화학식 107] [화학식 108] [화학식 109] [화학식 110][Formula 107] [Formula 108] [Formula 109] [Formula 110]

Figure pat00032
Figure pat00032

[화학식 111] [화학식 112] [화학식 113] [화학식 114][Formula 111] [Formula 112] [Formula 113] [Formula 114]

Figure pat00033
Figure pat00033

[화학식 115] [화학식 116] [화학식 117] [화학식 118][Formula 115] [Formula 116] [Formula 117] [Formula 118]

Figure pat00034
Figure pat00034

[화학식 119] [화학식 120] [화학식 121] [화학식 122][Formula 119] [Formula 120] [Formula 121] [Formula 122]

Figure pat00035
Figure pat00035

[화학식 123] [화학식 124] [화학식 125] [화학식 126][Formula 123] [Formula 124] [Formula 125] [Formula 126]

Figure pat00036
Figure pat00036

[화학식 127] [화학식 128] [화학식 129] [화학식 130][Formula 127] [Formula 128] [Formula 129] [Formula 130]

Figure pat00037
Figure pat00037

[화학식 131] [화학식 132] [화학식 133] [화학식 134][Formula 131] [Formula 132] [Formula 133] [Formula 134]

Figure pat00038
Figure pat00038

[화학식 135] [화학식 136] [화학식 137] [화학식 138][Formula 135] [Formula 136] [Formula 137] [Formula 138]

Figure pat00039
Figure pat00039

[화학식 139] [화학식 140] [화학식 141] [화학식 142][Formula 139] [Formula 140] [Formula 141] [Formula 142]

Figure pat00040
Figure pat00040

[화학식 143] [화학식 144] [화학식 145] [화학식 146][Formula 143] [Formula 144] [Formula 145] [Formula 146]

Figure pat00041
Figure pat00041

[화학식 147] [화학식 148] [화학식 149] [화학식 150][Formula 147] [Formula 148] [Formula 149] [Formula 150]

Figure pat00042
Figure pat00042

[화학식 151] [화학식 152] [화학식 153] [화학식 154][Formula 151] [Formula 152] [Formula 153] [Formula 154]

Figure pat00043
Figure pat00043

[화학식 155] [화학식 156] [화학식 157] [화학식 158][Formula 155] [Formula 156] [Formula 157] [Formula 158]

Figure pat00044
Figure pat00044

[화학식 159] [화학식 160] [화학식 161] [화학식 162][Formula 159] [Formula 160] [Formula 161] [Formula 162]

Figure pat00045
Figure pat00045

[화학식 163] [화학식 164] [화학식 165] [화학식 166][Formula 163] [Formula 164] [Formula 165] [Formula 166]

Figure pat00046
Figure pat00046

[화학식 167] [화학식 168] [화학식 169] [화학식 170][Formula 167] [Formula 168] [Formula 169] [Formula 170]

Figure pat00047
Figure pat00047

[화학식 171] [화학식 172] [화학식 173] [화학식 174][Formula 171] [Formula 172] [Formula 173] [Formula 174]

Figure pat00048
Figure pat00048

[화학식 175] [화학식 176] [화학식 177] [화학식 178][Formula 175] [Formula 176] [Formula 177] [Formula 178]

Figure pat00049
Figure pat00049

[화학식 179] [화학식 180] [화학식 181] [화학식 182][Formula 179] [Formula 180] [Formula 181] [Formula 182]

Figure pat00050
Figure pat00050

[화학식 183] [화학식 184] [화학식 185] [화학식 186][Formula 183] [Formula 184] [Formula 185] [Formula 186]

Figure pat00051
Figure pat00051

[화학식 187] [화학식 188] [화학식 189] [화학식 190][Formula 187] [Formula 188] [Formula 189] [Formula 190]

Figure pat00052
Figure pat00052

[화학식 191] [화학식 192] [화학식 193] [화학식 194][Formula 191] [Formula 192] [Formula 193] [Formula 194]

Figure pat00053
Figure pat00053

[화학식 195] [화학식 196] [화학식 197] [화학식 198][Formula 195] [Formula 196] [Formula 197] [Formula 198]

Figure pat00054
Figure pat00054

[화학식 199] [화학식 200] [화학식 201] [화학식 202][Formula 199] [Formula 200] [Formula 201] [Formula 202]

Figure pat00055
Figure pat00055

[화학식 203] [화학식 204] [화학식 205] [화학식 206][Formula 203] [Formula 204] [Formula 205] [Formula 206]

Figure pat00056
Figure pat00056

[화학식 207] [화학식 208] [화학식 209] [화학식 210][Formula 207] [Formula 208] [Formula 209] [Formula 210]

Figure pat00057
Figure pat00057

[화학식 211] [화학식 212] [화학식 213] [화학식 214][Formula 211] [Formula 212] [Formula 213] [Formula 214]

[화학식 215] [화학식 216] [화학식 217] [화학식 218][Formula 215] [Formula 216] [Formula 217] [Formula 218]

Figure pat00059
Figure pat00059

[화학식 219] [화학식 220] [화학식 221] [화학식 222][Formula 219] [Formula 220] [Formula 221] [Formula 222]

Figure pat00060
Figure pat00060

[화학식 223] [화학식 224] [화학식 225] [화학식 226][Formula 223] [Formula 224] [Formula 225] [Formula 226]

Figure pat00061
Figure pat00061

[화학식 227] [화학식 228] [화학식 229] [화학식 230][Formula 227] [Formula 228] [Formula 229] [Formula 230]

Figure pat00062
Figure pat00062

[화학식 231] [화학식 232] [화학식 233] [화학식 234][Formula 231] [Formula 232] [Formula 233] [Formula 234]

Figure pat00063
Figure pat00063

[화학식 235] [화학식 236] [화학식 237] [화학식 238][Formula 235] [Formula 236] [Formula 237] [Formula 238]

Figure pat00064
Figure pat00064

[화학식 239] [화학식 240] [화학식 241] [화학식 242]
[Formula 239] [Formula 240] [Formula 241] [Formula 242]

본 발명에 따른 스피로 화합물의 제조방법은 후술하는 실시예에 구체적으로 나타내었다.The method for preparing the spiro compound according to the present invention is shown in detail in the Examples to be described later.

또한, 본 발명은 애노드; 캐소드; 및 상기 애노드 및 캐소드 사이에 개재되며, 상기 [화학식 1] 또는 [화학식 2]로 표시되는 스피로 화합물을 포함하는 층을 구비한 유기전계발광소자를 제공한다.In addition, the present invention is an anode; Cathode; And it is interposed between the anode and the cathode, and provides an organic light emitting device having a layer comprising a spiro compound represented by the above [Formula 1] or [Formula 2].

이 때, 상기 스피로 화합물이 함유된 층은 상기 애노드 및 캐소드 사이의 발광층인 것이 바람직하며, 애노드 및 캐소드 사이에는 정공주입층, 정공수송층, 전자저지층, 정공저지층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택된 하나 이상의 층을 더 포함할 수 있다.At this time, the layer containing the spiro compound is preferably a light emitting layer between the anode and the cathode, and between the anode and the cathode as a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer It may further comprise one or more layers selected from the group consisting of.

또한, 본 발명의 다른 일실시예에 의하면, 상기 발광층의 두께는 0.5nm 내지 500nm인 것이 바람직하며, 상기 발광층은 하기 구조식의 Ir(ppy)3을 추가로 포함할 수 있다.In addition, according to another embodiment of the present invention, the thickness of the light emitting layer is preferably 0.5nm to 500nm, the light emitting layer may further include Ir (ppy) 3 of the following structural formula.

[Ir(ppy)3][Ir (ppy) 3 ]

Figure pat00065
Figure pat00065

구체적인 예로서, 정공수송층(HTL: Hole Transport Layer)이 추가로 적층되어 있고, 상기 캐소드와 상기 유기발광층 사이에 전자수송층(ETL: Electron Transport Layer)이 추가로 적층되어 있는 것일 수 있는데, 상기 정공수송층은 애노드로부터 정공을 주입하기 쉽게 하기 위하여 적층되는 것으로서, 상기 정공수송층의 재료로는 이온화 포텐셜이 작은 전자공여성 분자가 사용되는데, 주로 트리페닐아민을 기본 골격으로 하는 디아민, 트리아민 또는 테트라아민 유도체가 많이 사용되고 있다.As a specific example, a hole transport layer (HTL) may be further stacked, and an electron transport layer (ETL) may be further stacked between the cathode and the organic light emitting layer. The silver is stacked to facilitate the injection of holes from the anode, and the electron transport molecule having a small ionization potential is used as the material of the hole transport layer. A diamine, triamine or tetraamine derivative mainly based on triphenylamine is used. It is used a lot.

본 발명에서도 상기 정공수송층의 재료로서 당업계에 통상적으로 사용되는 것인 한 특별히 제한되지 않으며, 예를 들어, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'- 디아민(TPD) 또는 N,N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(a-NPD) 등을 사용할 수 있다.The present invention is not particularly limited as long as it is commonly used in the art as a material of the hole transport layer. For example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1 , 1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (a-NPD) and the like can be used.

상기 정공수송층의 하부에는 정공주입층(HIL: Hole Injecting Layer)을 추가적으로 더 적층할 수 있는데, 상기 정공주입층 재료 역시 당업계에서 통상적으로 사용되는 것인 한 특별히 제한되지 않고 사용할 수 있으며, 예를 들어 CuPc(copper phthalocyanine) 또는 스타버스트(Starburst)형 아민류인 TCTA(4,4',4"-tri(N-carbazolyl) triphenyl-amine), m-MTDATA(4,4',4"-tris-(3-methylphenylphenylamino)triphenylamine) 등을 사용할 수 있다.A hole injection layer (HIL) may be further stacked on the lower portion of the hole transport layer. The hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. TCP (4,4 ', 4 "-tri (N-carbazolyl) triphenyl-amine), for example, copper phthalocyanine (CuPc) or starburst amines, m-MTDATA (4,4', 4" -tris- (3-methylphenylphenylamino) triphenylamine) etc. can be used.

또한, 본 발명에 따른 유기전계발광소자에 사용되는 상기 전자수송층은 캐소드로부터 공급된 전자를 유기발광층으로 원활히 수송하고 상기 유기발광층에서 결합하지 못한 정공의 이동을 억제함으로써 발광층 내에서 재결합할 수 있는 기회를 증가시키는 역할을 한다. 상기 전자수송층 재료로는 당 기술분야에서 통상적으로 사용되는 것이면 특별히 제한되지 않고 사용할 수 있음은 물론이며, 예를 들어 옥사디아졸 유도체인 PBD, BMD, BND 또는 Alq3 등을 사용할 수 있다.In addition, the electron transport layer used in the organic electroluminescent device according to the present invention has the opportunity to recombine in the light emitting layer by smoothly transporting the electrons supplied from the cathode to the organic light emitting layer and suppressing the movement of holes not bonded in the organic light emitting layer. Serves to increase. The electron transport layer material may be used without particular limitation as long as it is commonly used in the art, and for example, oxadiazole derivatives such as PBD, BMD, BND or Alq 3 may be used.

한편, 상기 전자수송층의 상부에는 캐소드로부터의 전자 주입을 용이하게 해주어 궁극적으로 파워효율을 개선 시키는 기능을 수행하는 전자주입층(EIL: Electron Injecting Layer)을 더 적층시킬 수도 있는데, 상기 전자주입층 재료 역시 당 기술분야에서 통상적으로 사용되는 것이면 특별한 제한없이 사용할 수 있으며, 예를 들어, LiF, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다.Meanwhile, an electron injection layer (EIL) may be further stacked on the electron transport layer to facilitate electron injection from the cathode and ultimately improve power efficiency. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li 2 O, BaO.

본 발명에 따른 유기전계발광소자는 표시소자, 디스플레이 소자 및 단색 또는 백색 조명용 소자 등에 사용될 수 있다.The organic light emitting display device according to the present invention can be used for a display device, a display device and a monochrome or white lighting device.

도 1은 본 발명의 유기전계발광소자의 구조를 나타내는 단면도이다. 본 발명에 따른 유기전계발광소자는 애노드(20), 정공수송층(40), 유기발광층(50), 전자수송층(60) 및 캐소드(80)을 포함하며, 필요에 따라 정공주입층(30)과 전자주입층(70)을 더 포함할 수 있으며, 그 이외에도 1층 또는 2층의 중간층을 더 형성하는 것도 가능하며, 정공저지층 또는 전자저지층을 더 형성시킬 수도 있다.1 is a cross-sectional view showing the structure of an organic light emitting display device according to the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, the hole injection layer 30 and The electron injection layer 70 may be further included. In addition, an intermediate layer of one or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

도 1을 참조하여 본 발명의 유기전계발광소자 및 그 제조방법에 대하여 살펴보면, 다음과 같다. 먼저 기판(10) 상부에 애노드 전극용 물질을 코팅하여 애노드(20)를 형성한다. 여기에서 기판(10)으로는 통상적인 유기 EL 소자에서 사용되는 기판을 사용하는데 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유기 기판 또는 투명 플라스틱 기판이 바람직하다. 그리고, 애노드 전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용한다.Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention, as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used.

상기 애노드(20) 전극 상부에 정공 주입층 물질을 진공열 증착, 또는 스핀 코팅하여 정공주입층(30)을 형성한다. 그 다음으로 상기 정공주입층(30)의 상부에 정공수송층 물질을 진공 열증착 또는 스핀 코팅하여 정공수송층(40)을 형성한다. 이어서, 상기 정공수송층(40)의 상부에 유기발광층(50)을 적층하고 상기 유기발광층(50)의 상부에 선택적으로 정공저지층(미도시)을 진공 증착 방법, 또는 스핀 코팅 방법으로서 박막을 형성할 수 있다. 상기 정공저지층은 정공이 유기발광층을 통과하여 캐소드로 유입되는 경우에는 소자의 수명과 효율이 감소되기 때문에 HOMO(Highest Occupied Molecular Orbital) 레벨이 매우 낮은 물질을 사용함으로써 이러한 문제를 방지하는 역할을 한다. 이 때, 사용되는 정공 저지 물질은 특별히 제한되지는 않으나 전자수송능력을 가지면서 발광 화합물보다 높은 이온화 포텐셜을 가져야 하며 대표적으로 BAlq, BCP, TPBI 등이 사용될 수 있다.The hole injection layer 30 is formed by vacuum-heat deposition or spin coating of the hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30. Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level because when the hole is introduced into the cathode through the organic light emitting layer is reduced the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

이러한 정공저지층 위에 전자수송층(60)을 진공 증착 방법, 또는 스핀 코팅 방법을 통해 증착한 후에 전자주입층(70)을 형성하고 상기 전자주입층(70)의 상부에 캐소드 형성용 금속을 진공 열증착하여 캐소드(80) 전극을 형성함으로써 유기 EL 소자가 완성된다. 여기에서 캐소드 형성용 금속으로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리듐(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등을 사용할 수 있으며, 전면 발광 소자를 얻기 위해서는 ITO, IZO를 사용한 투과형 캐소드를 사용할 수 있다.After the electron transport layer 60 is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed and a cathode forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form a cathode 80 electrode. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lidium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag), and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

또한, 본 발명의 다른 일실시예에 의하면, 상기 정공주입층, 정공수송층, 전자저지층, 발광층, 정공저지층, 전자수송층 및 전자주입층으로부터 선택된 하나 이상의 층은 단분자 증착방식 또는 용액공정에 의하여 형성될 수 있으며, 본 발명에 따른 유기전계발광소자는 표시소자, 디스플레이 소자 및 단색 또는 백색 조명용 소자에 사용될 수 있다.According to another embodiment of the present invention, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer is a single molecule deposition method or a solution process The organic light emitting display device according to the present invention may be used in display devices, display devices, and monochrome or white lighting devices.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

<< 합성예Synthetic example 1> 화학식  1> chemical formula 30로30 표시되는 화합물의 제조 Preparation of the Compounds Displayed

1) 화학식 1-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 1-a

하기 반응식 1에 의하여 화학식 1-a로 표시되는 화합물을 합성하였다.A compound represented by Chemical Formula 1-a was synthesized according to Scheme 1 below.

<반응식 1><Scheme 1>

Figure pat00066
Figure pat00066

[화학식 1-a]                                         [Formula 1-a]

100mL 둥근 바닥 플라스크에 1,10-페안스로린 10.0g(0.0505mol), 초산 60mL을 넣고 교반한 후 30% 과산화수소수 6mL을 천천히 가한 다음 70℃ 에서 3시간 동안 교반한다. 다시 30% 과산화수소수 6mL을 가한 다음 같은 온도에서 3시간 동안 교반한다. 반응물을 감압 농축한 다음 메탄올을 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 화학식 1-a로 표시되는 화합물을 7.6g(70%) 얻었다.Into a 100 mL round bottom flask, 10.0 g (0.0505 mol) of 1,10-feanthroline and 60 mL of acetic acid were added. After stirring, 6 mL of 30% hydrogen peroxide solution was added slowly, followed by stirring at 70 ° C. for 3 hours. Again, 6 mL of 30% hydrogen peroxide solution was added and stirred at the same temperature for 3 hours. The reaction product was concentrated under reduced pressure, and methanol was used as a developing solvent to separate the residue by column chromatography to obtain 7.6 g (70%) of the compound represented by Chemical Formula 1-a.

2) 화학식 1-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Chemical Formula 1-b

하기 반응식 2에 의하여 화학식 1-b로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 1-b was synthesized by Reaction Scheme 2 below.

<반응식 2><Reaction Scheme 2>

Figure pat00067
Figure pat00067

[화학식 1-b]                      [Formula 1-b]

100mL 둥근 바닥 플라스크에 반응식 1로부터 얻은 화학식 1-a 3.0g(0.0148mol), 시안화칼륨 3.0g, 물 50mL 넣고 교반시킨 후 벤졸클로라이드 3mL을 천천히 가한 다음 15분 동안 교반한다. 고형물을 거른 다음 물로 세척 후 고체를 건조하여 화학식 1-b로 표시되는 화합물을 2.2g(71%) 얻었다.In a 100 mL round bottom flask, 3.0 g (0.0148 mol) of Chemical Formula 1-a obtained from Scheme 1, 3.0 g of potassium cyanide, and 50 mL of water were stirred, and then slowly added 3 mL of benzol chloride, followed by stirring for 15 minutes. The solid was filtered off, washed with water, and dried to obtain 2.2 g (71%) of a compound represented by Chemical Formula 1-b.

3) 화학식 1-c로 표시되는 화합물의 합성3) Synthesis of Compound Represented by Chemical Formula 1-c

하기 반응식 3에 의하여 화학식 1-c로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 1-c was synthesized by Reaction Scheme 3 below.

<반응식 3><Scheme 3>

Figure pat00068
Figure pat00068

[화학식 1-c][Formula 1-c]

250mL 둥근 바닥 플라스크에 반응식 2로부터 얻은 화학식 1-b로 표시되는 화합물 2.2g(0.0107mol)을 톨루엔 60mL에 녹인 후 반응물의 온도를 -78℃까지 내리고 페닐리튬 38.5g(0.0632mol)을 천천히 적가시켰다. 온도를 상온으로 올린 다음 12시간 동안 교반 후 물을 천천히 가한 다음 염화메틸렌을 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에틸아세테이트와 헥산 전개용매를 이용하여 컬럼크로마토그래피로 분리하여 화학식 1-c로 표시되는 0.8g(21.3%)를 얻었다.In a 250 mL round bottom flask, 2.2 g (0.0107 mol) of the compound represented by Chemical Formula 1-b obtained in Scheme 2 was dissolved in 60 mL of toluene, and then the temperature of the reaction was lowered to -78 ° C and 38.5 g (0.0632 mol) of phenyllithium was slowly added dropwise. . After raising the temperature to room temperature and stirring for 12 hours, water was slowly added, the organic layer was separated using methylene chloride, concentrated under reduced pressure, and the resulting solid was separated by column chromatography using ethyl acetate and hexane developing solvent to obtain a chemical formula (1). 0.8 g (21.3%) indicated by -c was obtained.

4) 화학식 1-d로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Chemical Formula 1-d

하기 반응식 4에 의하여 화학식 1-d로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 1-d was synthesized by Reaction Scheme 4 below.

<반응식 4><Reaction Scheme 4>

Figure pat00069
Figure pat00069

[화학식 1-d]                                           [Formula 1-d]

2L 둥근 바닥 플라스크에 디페닐아민 50.0g(0.295mol)과 브로모메틸메틸 에테르 38.10mL(0.443mol)를 테트라하이드로퓨란 1L에 녹인 후 트리에틸아민 44.85g(0.443mol)을 천천히 적가시키고, 질소 기류하에서 5시간 교반 후 물과 테트라하이드로퓨란을 이용하여 유기층을 분리하고 감압 농축한 후 헥산과 테트라하이드로퓨란을 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 53.3g(84.6%)을 얻었다.In a 2 L round bottom flask, 50.0 g (0.295 mol) of diphenylamine and 38.10 mL (0.443 mol) of bromomethylmethyl ether were dissolved in 1 L of tetrahydrofuran, and 44.85 g (0.443 mol) of triethylamine was slowly added dropwise, followed by nitrogen stream. After stirring for 5 hours, the organic layer was separated using water and tetrahydrofuran, concentrated under reduced pressure, and separated by column chromatography using hexane and tetrahydrofuran as a developing solvent to obtain 53.3 g (84.6%).

5) 화학식 1-e로 표시되는 화합물의 합성5) Synthesis of Compound Represented by Chemical Formula 1-e

하기 반응식 5에 의하여 화학식 1-e로 표시되는 화합물을 합성하였다.A compound represented by Chemical Formula 1-e was synthesized by Reaction Scheme 5 below.

<반응식 5>Scheme 5

Figure pat00070
Figure pat00070

[화학식 1-e][Formula 1-e]

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 0.8g(0.002mol)을 테트라하이드로퓨란 15mL에 녹인 후 질소 상태하에서 10분간 교반을 시키고 반응물의 온도를 -78℃까지 내리고 1.6몰 헥산 용액의 노르말 뷰틸리튬 1.1g(0.003mol)을 10분 동안 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 상기 반응식 4로부터 얻은 화학식 1-d로 표시되는 화합물 0.4g(0.002mol)를 테트라히드로퓨란 5mL에 녹이고 천천히 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 실온으로 온도를 올리고 5시간 동안 교반 후 염화암모늄 수용액과 에틸에테르 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에탄올을 이용해 씻어주고 건조시켰다. 건조된 물질을 아세트산 20mL에 분산시키고 진한 황산 1mL를 천천히 적가한 후 5시간 동안 환류시켰다. 생성된 고체를 감압여과 후 물과 에탄올을 이용해 씻어준 후 에탄올을 이용해 재결정을 실시하고 얻은 고체를 건조하여 0.9g(87.5%)를 얻었다.In a 100 mL round bottom flask, 0.8 g (0.002 mol) of the compound represented by Chemical Formula 1-c obtained in Scheme 3 was dissolved in 15 mL of tetrahydrofuran, stirred for 10 minutes under nitrogen, and the reaction temperature was lowered to -78 ° C and 1.6 mol. 1.1 g (0.003 mol) of normal butyllithium in a hexane solution was added dropwise for 10 minutes. After stirring at the same temperature for 1 hour, 0.4 g (0.002 mol) of the compound represented by Chemical Formula 1-d obtained in Scheme 4 was dissolved in 5 mL of tetrahydrofuran and slowly added dropwise thereto. After stirring for 1 hour at the same temperature, the temperature was raised to room temperature, and after stirring for 5 hours, the organic layer was separated using an aqueous ammonium chloride solution and ethyl ether, concentrated under reduced pressure, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 20 mL of acetic acid, slowly added dropwise 1 mL of concentrated sulfuric acid, and refluxed for 5 hours. The resulting solid was filtered under reduced pressure, washed with water and ethanol, and then recrystallized with ethanol, and dried to obtain 0.9g (87.5%).

6) 화학식 1-f로 표시되는 화합물의 합성6) Synthesis of Compound Represented by Chemical Formula 1-f

하기 반응식 6에 의하여 화학식 1-f로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 1-f was synthesized by Reaction Scheme 6 below.

<반응식 6><Scheme 6>

Figure pat00071
Figure pat00071

[화학식 1-f][Formula 1-f]

5L 둥근 바닥 플라스크에 디벤조사이오펜 200g, 클로로름 2L 넣고 교반시키면서 0℃로낮추었다. 브로민 170.8g을 클로로름 512ml에 녹인 후 천천히 적가 시켰다. 완료 후 상온에서 12 시간 교반시켰다. 반응이 종결된 후 쇼듐사이오설패이트를 녹인 물로 추출한 뒤 유기층을 모아 농축 후 에탄올로 고체를 생성시켰다. 고체를 여과하고 디클로로메탄와 에탄올로 재결정하여 1-f로 표시되는 화합물을 142g(50.5%) 얻었다.200 g of dibenzothiophene and 2 L of chloromum were added to a 5 L round bottom flask, and the mixture was lowered to 0 ° C while stirring. 170.8 g bromine was dissolved in 512 ml of chlorom and slowly added dropwise. After completion, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, sodium thiosulphate was extracted with dissolved water, and then the organic layers were collected and concentrated to produce a solid with ethanol. The solid was filtered and recrystallized with dichloromethane and ethanol to give 142 g (50.5%) of the compound represented by 1-f.

7) 화학식 1-g로 표시되는 화합물의 합성7) Synthesis of Compound Represented by Chemical Formula 1-g

하기 반응식 7에 의하여 화학식 1-g로 표시되는 화합물을 합성하였다.A compound represented by Chemical Formula 1-g was synthesized according to Reaction Scheme 7 below.

<반응식 7><Reaction Scheme 7>

Figure pat00072
Figure pat00072

[화학식 1-g][Formula 1-g]

2L 둥근 바닥 플라스크에 마그네슘 15.8g(0.652mol)을 테트라히드로퓨란 700mL에 넣고 교반한다. 상기 반응식 6으로부터 얻은 화학식 1-f로 표시되는 화합물 143g(0.543mol)을 테트라히드로퓨란 200mL에 녹인 후 천천히 적가한 다음 2시간 동안 환류 교반시켰다. 5L 둥근 바닥 플라스크에 2,4,6-클로로-1,3,5-트리아진 47.7g(0.258mol), 테트라히드로퓨란 500mL을 넣고 상기 화합물을 천천히 가한 후 상온에서 4시간 동안 교반하였다. 4M 염산 500 mL에 붓고 톨루엔으로 추출하였다. 유기층을 황산 마그네슘으로 수분 제거하고, 감압 농축시키고, 헥산으로 재결정하여 화학식 1-g로 표시되는 화합물을 101.5g(82%) 얻었다.Into a 2 L round bottom flask, 15.8 g (0.652 mol) of magnesium was added to 700 mL of tetrahydrofuran and stirred. 143 g (0.543 mol) of the compound represented by Chemical Formula 1-f obtained in Scheme 6 was dissolved in 200 mL of tetrahydrofuran, and slowly added dropwise thereto, followed by stirring under reflux for 2 hours. 47.7g (0.258mol) of 2,4,6-chloro-1,3,5-triazine and tetrahydrofuran 500mL were added to a 5L round bottom flask, and the compound was slowly added thereto, followed by stirring at room temperature for 4 hours. Poured into 500 mL of 4M hydrochloric acid and extracted with toluene. The organic layer was evaporated with magnesium sulfate, concentrated under reduced pressure, and recrystallized with hexane to obtain 101.5 g (82%) of the compound represented by Chemical Formula 1-g.

8) 화학식 30로 표시되는 화합물의 합성8) Synthesis of Compound Represented by Chemical Formula 30

하기 반응식 8에 의하여 화학식 30로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 30 was synthesized according to Scheme 8 below.

<반응식 8><Reaction Scheme 8>

Figure pat00073
Figure pat00073

[화학식 30](30)

50mL 둥근 바닥 플라스크에 수소화나트륨 0.08g(0.0032mol)을 N,N-디메틸포름아마이드 10mL에 녹인 후 온도를 0℃ 이하로 내린 다음 상기 반응식 5으로부터 얻은 화학식 1-e로 표시되는 화합물 0.9g(0.0018mol)을 N,N-디메틸포름아마이드 20mL에 녹여 천천히 적가한 다음 1시간 동안 교반시켰다. 상기 반응식 7으로부터 얻은 화학식 1-g로 표시되는 화합물 1.3g(0.0027mol)을 N,N-디메틸포름아마이드 20mL에 녹여 상기 반응물에 천천히 가한 후 상온에서 8시간 동안 교반하였다. 생성된 고체는 여과한 후 메탄올로 세척한 다음 테트라히드로퓨란과 에틸아세테이트으로 재결정하여 화학식 30로 표시되는 화합물을 1.3g(76%) 얻었다.In a 50 mL round bottom flask, 0.08 g (0.0032 mol) of sodium hydride was dissolved in 10 mL of N, N-dimethylformamide, and the temperature was lowered to 0 ° C or lower, and 0.9 g (0.0018) of the compound represented by Chemical Formula 1-e obtained from Scheme 5 above. mol) was dissolved in 20 mL of N, N-dimethylformamide, slowly added dropwise, and stirred for 1 hour. 1.3 g (0.0027 mol) of the compound represented by Chemical Formula 1-g obtained in Scheme 7 was dissolved in 20 mL of N, N-dimethylformamide, and slowly added to the reactant, followed by stirring at room temperature for 8 hours. The resulting solid was filtered and washed with methanol and then recrystallized with tetrahydrofuran and ethyl acetate to obtain 1.3 g (76%) of the compound represented by the formula (30).

MS: m/z calcd 954.26 ; found 954. Anal. Calcd. for C64H38N6S2: C, 80.48; H, 4.01; N, 8.80; S, 6.71. Found: C, 80.84; H, 3.93; N, 8.57.
MS: m / z calcd 954.26; found 954. Anal. Calcd. for C 64 H 38 N 6 S 2 : C, 80.48; H, 4.01; N, 8.80; S, 6.71. Found: C, 80.84; H, 3.93; N, 8.57.

<< 합성예Synthetic example 2> 화학식 75 표시되는 화합물의 제조 2> Preparation of the Compound of Formula 75

1) 화학식 2-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 2-a

하기 반응식 9에 의하여 화학식 2-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 2-a was synthesized by Reaction Scheme 9 below.

<반응식 9><Reaction Scheme 9>

Figure pat00074
Figure pat00074

[화학식 2-a]                            [Formula 2-a]

500mL 둥근 바닥 플라스크에 다이페닐아민 30g(0.18mol)에 브로모아이오도벤젠 60g(0.21mol), 팔라듐아세테이트 0.79g(0.0035mol), 쇼듐털트뷰톡사이드34g(0.35mol), 트리털트뷰틸포스핀 8.9ml, 톨루엔 300mL 넣고 12시간 환류시켰다. 반응 종료 후 상온으로 온도를 내리고 추출한 뒤 유기층을 감압 농축 후 에틸아세테이트와 헥산을 사용하여 컬럼크로마토그래피로 분리하고 고체를 건조하여 화학식 2-a로 표시되는 화합물을 25g(43.5%) 얻었다.In a 500 mL round bottom flask, 30 g (0.18 mol) of diphenylamine, 60 g (0.21 mol) of bromoiodobenzene, 0.79 g (0.0035 mol) of palladium acetate, 34 g (0.35 mol) of sodium butyl butoxide, 8.9 ml of tributyl butyl phosphine Toluene was added 300mL and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted, and the organic layer was concentrated under reduced pressure, separated by column chromatography using ethyl acetate and hexane, and dried to obtain 25 g (43.5%) of the compound represented by the formula 2-a.

2) 화학식 75 표시되는 화합물의 합성2) Synthesis of Compound Represented by Formula 75

하기 반응식 10에 의하여 화학식 75 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 75 was synthesized by Reaction Scheme 10 below.

<반응식 10><Reaction formula 10>

Figure pat00075
Figure pat00075

[화학식 75](75)

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 2g(0.0055mol)을 테트라히드로퓨란 10mL에 녹인 후 질소 상태하에서 30분간 교반을 시키고 반응물의 온도를 -78℃까지 내리고 2.5몰 헥산 용액의 노말 뷰틸리튬 1.8g(0.0067mL)을 20분 동안 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 반응식 9로부터 얻은 화학식 2-a로 표시되는 화합물 1.8g(0.0067mol)를 테트라히드로퓨란 20mL에 녹이고 천천히 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 실온으로 온도를 올리고 5시간 동안 교반 후 암모늄 클로라이드 수용액과 에틸에테르 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에탈올을 이용해 씻어주고 건조시켰다. 건조된 물질을 아세트산 30mL 분산시키고 진한 염산 4mL를 천천히 적가한 후 5시간 동안 환류시켰다. 생성된 고체를 감압여과 후 물과 에탄올을 이용해 씻어준 후 에탄올을 이용해 재결정을 실시하고 얻은 고체를 건조하여 화학식 75로 표시되는 화합물 2.7g(83%)을 얻었다.In a 100 mL round bottom flask, 2 g (0.0055 mol) of the compound represented by Chemical Formula 1-c obtained from Scheme 3 was dissolved in 10 mL of tetrahydrofuran, stirred for 30 minutes under nitrogen, and the reaction temperature was lowered to -78 ° C and 2.5 mol hexane. 1.8 g (0.0067 mL) of normal butyllithium of the solution was added dropwise for 20 minutes. After stirring at the same temperature for 1 hour, 1.8 g (0.0067 mol) of the compound represented by Chemical Formula 9 obtained from Scheme 9 was dissolved in 20 mL of tetrahydrofuran and slowly added dropwise thereto. After stirring for 1 hour at the same temperature, the temperature was raised to room temperature, and after stirring for 5 hours, the organic layer was separated using an aqueous ammonium chloride solution and ethyl ether, concentrated under reduced pressure, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 30 mL of acetic acid and slowly added dropwise 4 mL of concentrated hydrochloric acid, followed by reflux for 5 hours. The resulting solid was filtered under reduced pressure, washed with water and ethanol, recrystallized with ethanol, and dried to obtain 2.7 g (83%) of the compound represented by Chemical Formula 75.

MS: m/z calcd 587.24 ; found 587. Anal. Calcd. for C43H29N3: C, 87.88; H, 4.97; N, 7.15. Found: C, 87.76; H, 4.85; N, 6.92.
MS: m / z calcd 587.24; found 587.Anal. Calcd. for C 43 H 29 N 3 : C, 87.88; H, 4.97; N, 7.15. Found: C, 87.76; H, 4. 85; N, 6.92.

<< 합성예Synthetic example 3> 화학식 79로 표시되는 화합물의 제조 3> Preparation of the compound represented by Formula 79

1) 화학식 3-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Formula 3-a

하기 반응식 11에 의하여 화학식 3-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 3-a was synthesized according to Scheme 11 below.

<반응식 11><Reaction Scheme 11>

Figure pat00076
Figure pat00076

[화학식 3-a]                         [Formula 3-a]

상기 합성예 2의 화학식 2-a에서 디페닐아민 대신 카바졸을 사용한 것을 제외하고 동일한 방법으로 화학식 3-a, 30.0g(78%)을 얻었다.Except for using carbazole instead of diphenylamine in Formula 2-a of Synthesis Example 2 to obtain a compound 3-a, 30.0g (78%).

2) 화학식 79로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Formula 79

하기 반응식 12에 의하여 화학식 79로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 79 was synthesized by Reaction Scheme 12 below.

<반응식 12><Reaction Scheme 12>

Figure pat00077
Figure pat00077

[화학식 75]                          (75)

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 2g(0.0055mol), 반응식 11로부터 얻은 화학식 3-a로부터 얻은 화합물 2.2g(0.0067mol)을 가지고 반응식 10과 같은 방법으로 화학식 79로 표시되는 화합물을 2.6g(81%) 얻었다. In a 100 mL round bottom flask, 2 g (0.0055 mol) of the compound represented by Formula 1-c obtained from Scheme 3 and 2.2 g (0.0067 mol) of the compound obtained from Formula 3-a obtained from Scheme 11 were prepared in the same manner as in Scheme 10 2.6g (81%) of compounds obtained were obtained.

MS: m/z calcd 585.22 ; found 585. Anal. Calcd. for C43H27N3: C, 88.18; H, 4.65; N, 7.17. Found: C, 87.97; H, 4.47; N, 6.93.
MS: m / z calcd 585.22; found 585.Anal. Calcd. for C 43 H 27 N 3 : C, 88.18; H, 4.65; N, 7.17. Found: C, 87.97; H, 4. 47; N, 6.93.

<< 합성예Synthetic example 4> 화학식 81로 표시되는 화합물의 제조 4> Preparation of a compound represented by Formula 81

1) 화학식 4-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 4-a

하기 반응식 13에 의하여 화학식 4-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 4-a was synthesized according to Scheme 13 below.

<반응식 13><Reaction Scheme 13>

Figure pat00078
Figure pat00078

[화학식 4-a][Formula 4-a]

5L 둥근 바닥 플라스크에 디벤조사이오펜 200g(1.085mol), 클로로름 2L 넣고 교반시키면서 0℃로 낮추었다. 브로민 170.8g(1.0678mol)을 클로로름 512mL에 녹인 후 천천히 적가 시켰다. 완료 후 상온에서 12 시간 교반시켰다. 반응이 종결된 후 쇼듐사이오설패이트를 녹인 물로 추출한 뒤 유기층을 모아 농축 후 에탄올로 고체를 생성시켰다. 고체를 여과하고 염화메틸렌과 에탄올로 재결정하여 4-a로 표시되는 화합물을 142g(50.5%) 얻었다.200 g (1.085 mol) of dibenzothiophene and 2 L of chloromum were added to a 5 L round bottom flask, and the mixture was lowered to 0 ° C. while stirring. 170.8 g (1.0678 mol) of bromine was dissolved in 512 mL of chlorom and slowly added dropwise. After completion, the mixture was stirred at room temperature for 12 hours. After the reaction was completed, sodium thiosulphate was extracted with dissolved water, and then the organic layers were collected and concentrated to produce a solid with ethanol. The solid was filtered and recrystallized with methylene chloride and ethanol to obtain 142 g (50.5%) of the compound represented by 4-a.

2) 화학식 4-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Formula 4-b

하기 반응식 14에 의하여 화학식 4-b로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 4-b was synthesized according to Scheme 14 below.

<반응식 14>Scheme 14

Figure pat00079
Figure pat00079

[화학식 4-b][Formula 4-b]

2L 둥근 바닥 플라스크에 상기 반응식 13으로부터 얻은 화학식 4-a로 표시되는 화합물 143g(0.544mol), 비스피나콜디보론 152g(0.598mol), 비스디페닐포스피노페로센디클로로팔라듐 8.8g(0.01mol), 칼륨 아세테이트 107g(2.02mol), 톨루엔 1440mL를 넣고, 6시간 환류시켰다. 반응이 종결되면, 뜨거운 상태에서 여과하고 톨루엔과 물을 사용하여 추출하였다. 유기층을 황산 마그네슘으로 수분 제거하고, 감압 농축시키고, 염화메틸렌와 헥산으로 컬럼크로마토그래피로 분리하여 화학식 4-b로 표시되는 화합물을 161g(95%) 얻었다.143 g (0.544 mol) of the compound represented by the formula (4-a) obtained from Scheme 13, 152 g (0.598 mol) of bispinacol diborone, 8.8 g (0.01 mol) of bisdiphenylphosphinoferrocene dichloropalladium, in a 2 L round bottom flask, 107 g (2.02 mol) of potassium acetate and 1440 mL of toluene were added and refluxed for 6 hours. After the reaction was completed, the mixture was filtered while hot and extracted using toluene and water. The organic layer was removed with magnesium sulfate, concentrated under reduced pressure, and separated by methylene chloride and hexane by column chromatography to obtain 161 g (95%) of the compound represented by the formula (4-b).

3) 화학식 4-c로 표시되는 화합물의 합성3) Synthesis of Compound Represented by Chemical Formula 4-c

하기 반응식 15 의하여 화학식 4-c 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 4-c was synthesized by Reaction Scheme 15 below.

<반응식 15>Scheme 15

Figure pat00080
Figure pat00080

[화학식 4-c][Formula 4-c]

2L 둥근 바닥 플라스크에 상기 반응식 14으로부터 얻은 화학식 4-b로 표시되는 화합물 158.4g(0.51mol), 브로모나이트로벤젠 86g(0.0.426mol), 테트라키스트리페닐포스핀팔라듐 9.8g(0.008mol), 탄산칼륨 118g(0.852mol), 테트라하이드로퓨란 430mL, 다이옥산 430mL, 물 172mL를 넣고 12시간 환류시켰다. 반응이 종결되면, 상온으로 냉각시키고, 에틸 아세테이트와 물로 추출하였다. 유기층을 황산 마그네슘으로 수분 제거하고, 감압 농축하여 결정을 얻고 염화메틸렌와 헥산으로 재결정하여 화학식 4-c로 표시되는 화합물을 62g(93%) 얻었다.158.4 g (0.51 mol) of the compound represented by the formula (4-b) obtained from Scheme 14, 86 g (0.0.426 mol) of bromonite benzene, and 9.8 g (0.008 mol) of tetrakistriphenylphosphine palladium in a 2 L round bottom flask 118 g (0.852 mol) of potassium carbonate, 430 mL of tetrahydrofuran, 430 mL of dioxane, and 172 mL of water were added thereto, and the mixture was refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was removed with magnesium sulfate, concentrated under reduced pressure to obtain crystals, and recrystallized with methylene chloride and hexane to give 62 g (93%) of the compound represented by the formula (4-c).

4) 화학식 4-d로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Chemical Formula 4-d

하기 반응식 16의하여 화학식 4-d 표시되는 화합물을 합성하였다.The compound represented by formula 4-d was synthesized according to Scheme 16 below.

<반응식 16>Scheme 16

Figure pat00081
Figure pat00081

[화학식 4-d][Formula 4-d]

500mL 둥근 바닥 플라스크에 디클로로벤젠 200mL 넣고 끓인 후 나이트로페닐디벤조사이오펜 20g(0.0654mol)와 트리페닐포스핀 42.8g을 넣고 12시간 환류시켰다. 반응 종료 후 디클로로벤젠을 증류로 제거한 뒤 에틸아세테이트와 헥산을 사용하여 컬럼크로마토그래피로 분리하고 고체를 건조하여 화학식 4-d로 표시되는 화합물을 16.6g(93.1%)을 얻었다.200 mL of dichlorobenzene was added to a 500 mL round bottom flask, which was then boiled, and 20 g (0.0654 mol) of nitrophenyl dibenzocyphene and 42.8 g of triphenylphosphine were added and refluxed for 12 hours. After the completion of the reaction, dichlorobenzene was distilled off, and then separated by column chromatography using ethyl acetate and hexane, and the solid was dried to obtain 16.6 g (93.1%) of the compound represented by Chemical Formula 4-d.

5) 화학식 4-e로 표시되는 화합물의 합성5) Synthesis of Compound Represented by Formula 4-e

하기 반응식 17에 의하여 화학식 4-e로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 4-e was synthesized according to Scheme 17 below.

<반응식 17>Scheme 17

Figure pat00082
Figure pat00082

[화학식 4-e][Formula 4-e]

500mL 둥근 바닥 플라스크에 상기 반응식 17 으로부터 얻은 화학식 4-d로 표시되는 화합물 17.4g(0.0636mol)과 브로모아이오도벤젠 26.8g(0.0954mol), 탄산칼륨 35.2g(0.254mol), 구리 10.2g(0.159mol) 및 디클로로벤젠 348ml을 넣고 24시간 동안 환류시켰다. 반응 종료 후 디클로로벤젠을 증류로 제거한 뒤 물과 에틸아세테이트 이용하여 유기층을 분리하고 감압 농축한 후 헥산과 에틸아세테이트를 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 얻은 고체를 건조하여 화학식 4-e로 표시되는 화합물을 22.8g(83.1%) 얻었다.In a 500 mL round bottom flask, 17.4 g (0.0636 mol) of the compound represented by the formula (4-d) obtained from Scheme 17, 26.8 g (0.0954 mol) of bromoiodobenzene, 35.2 g (0.254 mol) of potassium carbonate, and 10.2 g (0.159) of copper mol) and 348 ml of dichlorobenzene were added and refluxed for 24 hours. After the completion of the reaction, dichlorobenzene was removed by distillation, the organic layer was separated using water and ethyl acetate, concentrated under reduced pressure, and the solid obtained by column chromatography using hexane and ethyl acetate as a developing solvent was dried to formula 4-e. 22.8g (83.1%) of obtained compounds were obtained.

6) 화학식 81로 표시되는 화합물의 합성6) Synthesis of Compound Represented by Chemical Formula 81

하기 반응식 18에 의하여 화학식 81로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 81 was synthesized by Reaction Scheme 18 below.

<반응식 18>Scheme 18

Figure pat00083
Figure pat00083

[화학식 81]                          [Formula 81]

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 2g(0.0055mol), 반응식 17로부터 얻은 화학식 4-e로부터 얻은 화합물 2.2g(0.0067mol)을 가지고 반응식 10과 같은 방법으로 화학식 81로 표시되는 화합물을 2.8g(74%) 얻었다. In a 100 mL round bottom flask, 2 g (0.0055 mol) of the compound represented by Formula 1-c obtained from Scheme 3 and 2.2 g (0.0067 mol) of the compound obtained from Formula 4-e obtained from Scheme 17 were prepared in the same manner as in Scheme 10. 2.8g (74%) of compounds obtained by this were obtained.

MS: m/z calcd 691.21 ; found 691. Anal. Calcd. for C49H29N3S: C, 85.07; H, 4.23; N, 6.07. Found: C, 85.11; H, 4.04; N, 5.79.
MS: m / z calcd 691.21; found 691.Anal. Calcd. for C 49 H 29 N 3 S: C, 85.07; H, 4. 23; N, 6.07. Found: C, 85.11; H, 4.04; N, 5.79.

<< 합성예Synthetic example 5> 화학식  5> chemical formula 86로To 86 표시되는 화합물의 제조 Preparation of the Compounds Displayed

1) 화학식 5-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 5-a

하기 반응식 19에 의하여 화학식 5-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 5-a was synthesized according to Reaction Scheme 19 below.

<반응식 19>Scheme 19

Figure pat00084
Figure pat00084

[화학식 5-a][Formula 5-a]

2L 둥근 바닥 플라스크에 2-브로모아릴린 51.6g(0.304mol), 2-아이오도-9,9-디메틸플로렌 81.0g(0.253mol), 비스디페닐포스피노바이나프탈렌 6.3g(0.010mol) 비스디벤질덴아세톤팔라듐 4.6g(0.0051mol), 쇼듐털트뷰톡사이드 36.5g(0.379mol), 다이옥안 810mL 넣고 12시간 환류 교반시켰다. 반응 종료 후 상온으로 온도를 내리고 추출한 뒤 유기층을 감압 농축 후 염화메틸렌과 헥산을 사용하여 컬럼크로마토그래피로 분리하여 화학식 5-a로 표시되는 화합물을 62.6g(68%) 얻었다.51.6 g (0.304 mol) of 2-bromoaryline, 81.0 g (0.253 mol) of 2-iodo-9,9-dimethylfluorene, 6.3 g (0.010 mol) of bisdiphenylphosphinovanaphthalene in a 2 L round bottom flask Dibenzylideneacetone palladium 4.6g (0.0051mol), sodium butylbutoxide 36.5g (0.379mol), 810 mL dioxane was put, it was stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted, and the organic layer was concentrated under reduced pressure, separated by column chromatography using methylene chloride and hexane, thereby obtaining 62.6 g (68%) of a compound represented by Chemical Formula 5-a.

2) 화학식 5-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Chemical Formula 5-b

하기 반응식 20에 의하여 화학식 5-b로 표시되는 화합물을 합성하였다.A compound represented by Chemical Formula 5-b was synthesized by Reaction Scheme 20 below.

<반응식 20>Scheme 20

Figure pat00085
Figure pat00085

[화학식 5-b][Formula 5-b]

2L 둥근 바닥 플라스크에 반응식 19으로부터 얻은 화학식 5-a 59.0g(0.162mol), 트리시클로헥실포스핀 테트라플로루보레이트 1.2g(0.003mol), 팔라듐아세테이트 0.4g(0.002mol), 탄산칼륨 44.8g(0.324mol), N,N-디메틸아세터아마이드 700mL 넣고 130℃에서 15시간 교반시켰다. 상온으로 온도를 내리고 추출한 뒤 유기층을 감압 농축 후 염화메틸렌과 헥산을 사용하여 컬럼크로마토그래피로 분리하여 화학식 5-b로 표시되는 화합물을 34.0g(74.1%) 얻었다.59.0 g (0.162 mol) of formula 5-a, 1.2 g (0.003 mol) of tricyclohexylphosphine tetrafluoroborate, 0.4 g (0.002 mol) of palladium acetate, 44.8 g of potassium carbonate 0.324 mol) and 700 mL of N, N-dimethylaceteramide were added and stirred at 130 ° C. for 15 hours. The mixture was cooled to room temperature, extracted, and the organic layer was concentrated under reduced pressure and separated by column chromatography using methylene chloride and hexane to obtain 34.0 g (74.1%) of the compound represented by Chemical Formula 5-b.

3) 화학식 5-c로 표시되는 화합물의 합성3) Synthesis of Compound Represented by Chemical Formula 5-c

하기 반응식 21에 의하여 화학식 5-c로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 5-c was synthesized by Reaction Scheme 21 below.

<반응식 21>Scheme 21

Figure pat00086
Figure pat00086

[화학식 5-c][Formula 5-c]

500mL 둥근 바닥 플라스크에 상기 반응식 20로부터 얻은 화학식 5-b로 표시되는 화합물 18.0g(0.0636mol)과 브로모아이오도벤젠 26.8g(0.0954mol), 탄산칼륨 35.2g(0.254mol), 구리 10.2g(0.159mol) 및 디클로로벤젠 348mL을 넣고 24시간 동안 환류시켰다. 반응 종료 후 디클로로벤젠을 증류로 제거한 뒤 물과 에틸아세테이트 이용하여 유기층을 분리하고 감압 농축한 후 헥산과 에틸아세테이트를 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 얻은 고체를 건조하여 화학식 4-e로 표시되는 화합물을 22.1g(79.2%) 얻었다.In a 500 mL round bottom flask, 18.0 g (0.0636 mol) of a compound represented by the formula (5-b) obtained from Scheme 20, 26.8 g (0.0954 mol) of bromoiodobenzene, 35.2 g (0.254 mol) of potassium carbonate, and 10.2 g (0.159) of copper mol) and 348 mL of dichlorobenzene were added and refluxed for 24 hours. After the completion of the reaction, dichlorobenzene was removed by distillation, the organic layer was separated using water and ethyl acetate, concentrated under reduced pressure, and the solid obtained by column chromatography using hexane and ethyl acetate as a developing solvent was dried to formula 4-e. 22.1 g (79.2%) of obtained compounds were obtained.

4) 화학식 86로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Formula 86

하기 반응식 22에 의하여 화학식 86로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 86 was synthesized according to Scheme 22 below.

<반응식 22>Scheme 22

Figure pat00087
Figure pat00087

[화학식 86]&Lt; EMI ID =

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 2g(0.0055mol), 반응식 21로부터 얻은 화학식 5-c로부터 얻은 화합물 4.7g(0.0067mol)을 가지고 반응식 10과 같은 방법으로 화학식 75로 표시되는 화합물을 2.7g(69.3%) 얻었다. In a 100 mL round bottom flask, 2 g (0.0055 mol) of the compound represented by Formula 1-c obtained from Scheme 3, and 4.7 g (0.0067 mol) of the compound obtained from Formula 5-c obtained by Scheme 21 were prepared in the same manner as in Scheme 10. 2.7g (69.3%) of compounds represented by the above were obtained.

MS: m/z calcd 701.28 ; found 701. Anal. Calcd. for C52H35N3: C, 88.99; H, 5.03; N, 5.99. Found: C, 88.53; H, 4.92; N, 5.98.
MS: m / z calcd 701.28; found 701. Anal. Calcd. for C 52 H 35 N 3 : C, 88.99; H, 5.03; N, 5.99. Found: C, 88.53; H, 4.92; N, 5.98.

<< 합성예Synthetic example 6> 화학식 107로 표시되는 화합물의 제조 6> Preparation of the compound represented by Chemical Formula 107

1) 화학식 6-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 6-a

하기 반응식 23에 의하여 화학식 6-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 6-a was synthesized according to Scheme 23 below.

<반응식 23>Scheme 23

Figure pat00088
Figure pat00088

[화학식 6-a][Formula 6-a]

500mL의 둥근 바닥 플라스크에 3-브로모카바졸 22.9g(0.093mol), 페닐보론산 13.5g(0.111mol), 테트라키스트리페닐포스핀팔라듐 2.2g (1.86mmol), 탄산칼륨 25.8g(0.186mol), 테트라히드로퓨란 300mL, 물 60mL를 넣고 12시간 동안 환류 교반시켰다. 상기 용액을 상온으로 냉각하고 유기층을 분리하여 감압농축한 후, 헥산과 염화메틸렌을 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 얻은 고체를 건조하여 화학식 6-a로 표시되는 19.9g(88.1%)을 제조하였다.In a 500 mL round bottom flask, 22.9 g (0.093 mol) of 3-bromocarbazole, 13.5 g (0.111 mol) of phenylboronic acid, 2.2 g (1.86 mmol) of tetrakistriphenylphosphinepalladium, 25.8 g (0.186 mol) of potassium carbonate 300 mL of tetrahydrofuran and 60 mL of water were added thereto, and the mixture was stirred under reflux for 12 hours. The solution was cooled to room temperature, the organic layer was separated, concentrated under reduced pressure, and the solid obtained by column chromatography using hexane and methylene chloride as a developing solvent was dried to give 19.9 g (88.1%) represented by Chemical Formula 6-a. Was prepared.

2) 화학식 6-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Chemical Formula 6-b

하기 반응식 24에 의하여 화학식 6-b로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 6-b was synthesized according to Scheme 24 below.

<반응식 24>Scheme 24

Figure pat00089
Figure pat00089

[화학식 6-b][Formula 6-b]

500mL 둥근 바닥 플라스크에 상기 반응식 23로부터 얻은 화학식 6-a로 표시되는 화합물 15.5g(0.0636mol)과 브로모아이오도벤젠 26.8g(0.0954mol), 탄산칼륨 35.2g(0.254mol), 구리 10.2g(0.159mol) 및 디클로로벤젠 348mL을 넣고 24시간 동안 환류시켰다. 반응 종료 후 디클로로벤젠을 증류로 제거한 뒤 물과 에틸아세테이트 이용하여 유기층을 분리하고 감압 농축한 후 헥산과 에틸아세테이트를 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 얻은 고체를 건조하여 화학식 6-b로 표시되는 화합물을 19.6g(77.5%) 얻었다.In a 500 mL round bottom flask, 15.5 g (0.0636 mol) of the compound represented by Chemical Formula 6-a obtained from Scheme 23, 26.8 g (0.0954 mol) of bromoiodobenzene, 35.2 g (0.254 mol) of potassium carbonate, and 10.2 g (0.159) of copper mol) and 348 mL of dichlorobenzene were added and refluxed for 24 hours. After the completion of the reaction, dichlorobenzene was distilled off, the organic layer was separated using water and ethyl acetate, concentrated under reduced pressure, and the solid obtained by column chromatography using hexane and ethyl acetate as a developing solvent was dried to formula 6-b. 19.6g (77.5%) of obtained compounds were obtained.

3) 화학식 107표시되는 화합물의 합성3) Synthesis of Compound Represented by Formula (107)

하기 반응식 25에 의하여 화학식 107로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 107 was synthesized by Reaction Scheme 25 below.

<반응식 25>Scheme 25

Figure pat00090
Figure pat00090

[화학식 107]&Lt; EMI ID =

100mL 둥근 바닥 플라스크에 반응식 3로부터 얻은 화학식 1-c로 표시되는 화합물 2g(0.0055mol), 반응식 24로부터 얻은 화학식 6-b로부터 얻은 화합물 2.7g(0.0067mol)을 가지고 반응식 10과 같은 방법으로 화학식 107로 표시되는 화합물을 2.7g(69.3%) 얻었다. In a 100 mL round bottom flask, 2 g (0.0055 mol) of the compound represented by Formula 1-c obtained from Scheme 3 and 2.7 g (0.0067 mol) of the compound obtained from Formula 6-b obtained from Scheme 24 were prepared in the same manner as in Scheme 10 2.7g (69.3%) of compounds represented by the above were obtained.

MS: m/z calcd 661.79 ; found 662. Anal. Calcd. for C49H31N3: C, 88.93; H, 4.72; N, 6.35. Found: C, 87.21; H, 4.69; N, 6.15.
MS: m / z calcd 661.79; found 662.Anal. Calcd. for C 49 H 31 N 3 : C, 88.93; H, 4.72; N, 6.35. Found: C, 87.21; H, 4.69; N, 6.15.

<< 합성예Synthetic example 7> 화학식  7> chemical formula 190로190 with 표시되는 화합물의 제조 Preparation of the Compounds Displayed

1) 화학식 7-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 7-a

하기 반응식 26에 의하여 화학식 7-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 7-a was synthesized according to Scheme 26 below.

<반응식 26>Scheme 26

Figure pat00091
Figure pat00091

[화학식 7-a][Formula 7-a]

100mL 둥근 바닥 플라스크에 4,7-디페닐-1,10-페안스로린 16.8g(0.0505mol), 초산 60mL을 넣고 교반한 후 30% 과산화수소수 6mL을 천천히 가한 다음 70℃ 에서 3시간 동안 교반한다. 다시 30% 과산화수소수 6mL을 가한 다음 같은 온도에서 3시간 동안 교반한다. 반응물을 감압 농축한 다음 메탄올을 전개용매로 사용하여 컬럼크로마토그래피로 분리하여 화학식 7-a로 표시되는 화합물을 9.1g(52%) 얻었다.Into a 100 mL round bottom flask, add 16.8 g (0.0505 mol) of 4,7-diphenyl-1,10-pheanthroline and 60 mL of acetic acid, stir, and slowly add 6 mL of 30% hydrogen peroxide solution, and then stir at 70 ° C. for 3 hours. . Again, 6 mL of 30% hydrogen peroxide solution was added and stirred at the same temperature for 3 hours. The reaction product was concentrated under reduced pressure, and methanol was used as a developing solvent to separate the product by column chromatography to obtain 9.1 g (52%) of a compound represented by Chemical Formula 7-a.

2) 화학식 7-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Chemical Formula 7-b

하기 반응식 27에 의하여 화학식 7-b로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 7-b was synthesized by Reaction Scheme 27 below.

<반응식 27>Scheme 27

Figure pat00092
Figure pat00092

[화학식 7-b]                        [Formula 7-b]

100mL 둥근 바닥 플라스크에 반응식 26로부터 얻은 화학식 7-a 9.0g(0.0258mol), 시안화칼륨 6.0g, 물 50mL 넣고 교반시킨 후 벤졸클로라이드 5mL을 천천히 가한 다음 15분 동안 교반한다. 고형물을 거른 다음 물로 세척 후 고체를 건조하여 화학식 7-b로 표시되는 화합물을 6.4g(69.1%) 얻었다.Into a 100 mL round bottom flask was added 9.0 g (0.0258 mol) of Chemical Formula 7-a, 6.0 g of potassium cyanide, and 50 mL of water, followed by stirring, and slowly adding 5 mL of benzol chloride, followed by stirring for 15 minutes. The solid was filtered off, washed with water, and dried to obtain 6.4 g (69.1%) of a compound represented by Chemical Formula 7-b.

3) 화학식 7-c로 표시되는 화합물의 합성3) Synthesis of Compound Represented by Chemical Formula 7-c

하기 반응식 28에 의하여 화학식 7-c로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 7-c was synthesized according to Scheme 28 below.

<반응식 28>Scheme 28

Figure pat00093
Figure pat00093

[화학식 7-c][Formula 7-c]

250mL 둥근 바닥 플라스크에 반응식 27로부터 얻은 화학식 7-b로 표시되는 화합물 6.0g(0.0168mol)을 톨루엔 100mL에 녹인 후 반응물의 온도를 -78℃까지 내리고 페닐리튬 46.7g(0.1007mol)을 천천히 적가시켰다. 온도를 상온으로 올린 다음 12시간 동안 교반 후 물을 천천히 가한 다음 염화메틸렌을 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에틸아세테이트와 헥산 전개용매를 이용하여 컬럼크로마토그래피로 분리하여 화학식 7-c로 표시되는 1.9g(22.5%)를 얻었다.In a 250 mL round bottom flask, 6.0 g (0.0168 mol) of the compound represented by Chemical Formula 7-b obtained in Scheme 27 was dissolved in 100 mL of toluene, and then the temperature of the reaction was lowered to -78 ° C and 46.7 g (0.1007 mol) of phenyllithium were slowly added dropwise. . After raising the temperature to room temperature and stirring for 12 hours, water was slowly added, the organic layer was separated using methylene chloride, concentrated under reduced pressure, and the resulting solid was separated by column chromatography using ethyl acetate and hexane developing solvent to obtain a chemical formula (7). 1.9 g (22.5%) indicated by -c were obtained.

4) 화학식 190로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Formula 190

하기 반응식 28에 의하여 화학식 190로 표시되는 화합물을 합성하였다.The compound represented by Formula 190 was synthesized according to Scheme 28 below.

<반응식 28>Scheme 28

Figure pat00094
Figure pat00094

[화학식 190][Formula 190]

100mL 둥근 바닥 플라스크에 반응식 28로부터 얻은 화학식 7-c로 표시되는 화합물 2.8g(0.0055mol), 반응식 21로부터 얻은 화학식 5-c로부터 얻은 화합물 2.9g(0.0067mol)을 가지고 반응식 10과 같은 방법으로 화학식 190로 표시되는 화합물을 2.9g(61.9%) 얻었다. In a 100 mL round bottom flask, 2.8 g (0.0055 mol) of the compound represented by Formula 7-c obtained from Scheme 28 and 2.9 g (0.0067 mol) of the compound obtained from Formula 5-c obtained by Scheme 21 were prepared in the same manner as in Scheme 10 2.9 g (61.9%) of the compound represented by 190 was obtained.

MS: m/z calcd 853.35 ; found 853. Anal. Calcd. for C64H43N3: C, 90.01; H, 5.07; N, 4.92. Found: C, 89.60; H, 5.05; N, 4.92.
MS: m / z calcd 853.35; found 853.Anal. Calcd. for C 64 H 43 N 3 : C, 90.01; H, 5.07; N, 4.92. Found: C, 89.60; H, 5.05; N, 4.92.

<< 합성예Synthetic example 8> 화학식  8> chemical formula 216로With 216 표시되는 화합물의 제조 Preparation of the Compounds Displayed

1) 화학식 8-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 8-a

하기 반응식 29에 의하여 화학식 8-a로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 8-a was synthesized according to Reaction Scheme 29 below.

<반응식 29>Scheme 29

Figure pat00095
Figure pat00095

[화학식 8-a][Formula 8-a]

500mL 둥근 바닥 플라스크에 2,9-디메틸-1,10-페안스노린 15g(0.072mol)다이옥산 1L을 넣고 교반 후 상온에서 셀레니늄옥사드 40g(0.360mol)을 가한 다음 2시간 동안 환류 교반시켰다. 온도를 실온으로 내리고 고형물을 거른 다음 여액을 감압 농축한 후 디에틸에테르로 세척하여 화학식 8-a로 표시되는 화합물을 10.9g(64%) 얻었다.15 g (0.072 mol) dioxane 1L was added to a 500 mL round bottom flask, and after stirring, 40 g (0.360 mol) of selenium oxide was added at room temperature, followed by stirring under reflux for 2 hours. The temperature was lowered to room temperature, the solid was filtered off, and the filtrate was concentrated under reduced pressure and washed with diethyl ether to obtain 10.9 g (64%) of a compound represented by Chemical Formula 8-a.

2) 화학식 8-b로 표시되는 화합물의 합성2) Synthesis of Compound Represented by Chemical Formula 8-b

하기 반응식 30에 의하여 화학식 8-b로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 8-b was synthesized by Reaction Scheme 30 below.

<반응식 30>Scheme 30

Figure pat00096
Figure pat00096

[화학식 8-b][Formula 8-b]

250mL 둥근 바닥 플라스크에 반응식 29로부터 얻은 화학식 8-a로 표시되는 화합물 10.0g(0.0423mol), 질산 1L을 넣고 2시간 동안 환류 교반시켰다. 온도를 상온으로 내리고 0℃에서 물 500mL을 천천히 가하면 고형물이 생성된다. 이 고형물을 거르고 디에틸에테르로 세척하여 화학식 8-b로 표시되는 화합물을 8.6g(76%) 얻었다.Into a 250 mL round bottom flask, 10.0 g (0.0423 mol) of a compound represented by Chemical Formula 8-a obtained from Scheme 29 and 1 L of nitric acid were added and stirred under reflux for 2 hours. Lowering the temperature to room temperature and slowly adding 500 mL of water at 0 ° C produces a solid. The solid was filtered and washed with diethyl ether to give 8.6 g (76%) of the compound represented by the formula (8-b).

3) 화학식 8-c로 표시되는 화합물의 합성3) Synthesis of Compound Represented by Chemical Formula 8-c

하기 반응식 31에 의하여 화학식 8-c로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 8-c was synthesized by Reaction Scheme 31 below.

<반응식 31>Scheme 31

Figure pat00097
Figure pat00097

[화학식 8-c][Formula 8-c]

500mL 둥근 바닥 플라스크에 반응식 30로부터 얻은 화학식 8-b로 표시되는 화합물 8.6g(0.0321mol)과 티오닐클로라이드 100mL을 넣고 6시간 동안 환류 교반시켰다. 온도를 상온으로 내리고 티오닐클로라이드를 감압하에서 제거하여 화학식 8-c로 표시되는 화합물을 9.7g(99%) 얻었다.In a 500 mL round bottom flask, 8.6 g (0.0321 mol) of the compound represented by Chemical Formula 8-b obtained from Scheme 30 and 100 mL of thionyl chloride were added thereto, and the mixture was stirred under reflux for 6 hours. The temperature was lowered to room temperature, and thionyl chloride was removed under reduced pressure to obtain 9.7 g (99%) of the compound represented by Chemical Formula 8-c.

4) 화학식 8-d로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Chemical Formula 8-d

하기 반응식 32에 의하여 화학식 8-d로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 8-d was synthesized according to Scheme 32 below.

<반응식 32>Scheme 32

Figure pat00098
Figure pat00098

[화학식 8-d][Formula 8-d]

500ml 둥근 바닥 플라스크에 반응식 31로부터 얻은 화학식 8-c로 표시되는 화합물 8.0g(0.0262mol), 염화메틸렌 250mL을 넣고 교반한 후 피롤리딘 18.7g(0.262mol)을 천천히 가한 다음 상온에서 24시간 동안 교반시켰다. 탄산나트륨과 클로로포름으로 추출한 다음 감압 농축 후 톨루엔으로 재결정하여 화학식 8-d로 표시되는 화합물을 8.3g(85%) 얻었다.Into a 500 ml round bottom flask, 8.0 g (0.0262 mol) of the compound represented by Chemical Formula 8-c obtained from Scheme 31 and 250 mL of methylene chloride were added thereto, followed by stirring. Then, 18.7 g (0.262 mol) of pyrrolidine was slowly added thereto, and then stirred at room temperature for 24 hours. Stirred. Extraction with sodium carbonate and chloroform, followed by concentration under reduced pressure and recrystallization with toluene yielded 8.3 g (85%) of the compound represented by formula 8-d.

5) 화학식 8-e로 표시되는 화합물의 합성5) Synthesis of Compound Represented by Chemical Formula 8-e

하기 반응식 33에 의하여 화학식 8-e로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 8-e was synthesized by Reaction Scheme 33 below.

<반응식 33>Scheme 33

Figure pat00099
Figure pat00099

[화학식 8-e][Formula 8-e]

500mL 둥근 바닥 플라스크에 반응식 32로부터 얻은 화학식 8-d로 표시되는 화합물 8.0g(0.0214mol)을 테트라히드로퓨란 300mL에 녹인 후 반응물의 온도를 -78℃까지 내리고 페닐리튬 21.8g(0.0471mol)을 천천히 적가시켰다. 온도를 상온으로 올린 다음 12시간 동안 교반 후 포화 염화암모늄 수용액을 천천히 가한 다음 에틸아세테이트을 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에틸아세테이트와 헥산 전개용매를 이용하여 컬럼크로마토그래피로 분리하여 화학식 8-e로 표시되는 7.4g(89%)를 얻었다.In a 500 mL round bottom flask, 8.0 g (0.0214 mol) of the compound represented by Chemical Formula 8-d obtained in Scheme 32 was dissolved in 300 mL of tetrahydrofuran, and the temperature of the reaction was lowered to -78 ° C and 21.8 g (0.0471 mol) of phenyllithium was slowly added. I dropped it. After raising the temperature to room temperature and stirring for 12 hours, saturated aqueous ammonium chloride solution was slowly added, the organic layer was separated using ethyl acetate, concentrated under reduced pressure, and the resulting solid was separated by column chromatography using ethyl acetate and hexane developing solvent. 7.4 g (89%) represented by Chemical Formula 8-e was obtained.

4) 화학식 216로 표시되는 화합물의 합성4) Synthesis of Compound Represented by Chemical Formula 216

하기 반응식 34에 의하여 화학식 216로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 216 was synthesized according to Scheme 34 below.

<반응식 34>Scheme 34

Figure pat00100
Figure pat00100

[화학식 216]Formula 216

100mL 둥근 바닥 플라스크에 반응식 33로부터 얻은 화학식 8-e로 표시되는 화합물 2.1g(0.0055mol)을 테트라히드로퓨란 10mL에 녹인 후 질소 상태하에서 30분간 교반을 시키고 반응물의 온도를 -78℃까지 내리고 2.5몰 헥산 용액의 노말 뷰틸리튬 3.7g(0.0132mol)을 20분 동안 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 반응식 11로부터 얻은 화학식 3-a로 표시되는 화합물 4.4g(0.0138mol)를 테트라히드로퓨란 20mL에 녹이고 천천히 적가시켰다. 동일한 온도에서 1시간 동안 교반 후 실온으로 온도를 올리고 5시간 동안 교반 후 암모늄 클로라이드 수용액과 에틸에테르 이용하여 유기층을 분리하고 감압 농축한 후 생성된 고체를 에탈올을 이용해 씻어주고 건조시켰다. 건조된 물질을 아세트산 30mL 분산시키고 진한 염산 4mL를 천천히 적가한 후 5시간 동안 환류시켰다. 생성된 고체를 감압여과 후 물과 에탄올을 이용해 씻어준 후 에탄올을 이용해 재결정을 실시하고 얻은 고체를 건조하여 화학식 216로 표시되는 화합물 3.3g(72.5%)을 얻었다.In a 100 mL round bottom flask, 2.1 g (0.0055 mol) of the compound represented by Chemical Formula 8-e obtained in Scheme 33 was dissolved in 10 mL of tetrahydrofuran, stirred for 30 minutes under nitrogen, and the reaction temperature was lowered to -78 ° C and 2.5 mol. 3.7 g (0.0132 mol) of normal butyllithium in the hexane solution was added dropwise for 20 minutes. After stirring at the same temperature for 1 hour, 4.4 g (0.0138 mol) of the compound represented by Chemical Formula 11 obtained from Scheme 11 was dissolved in 20 mL of tetrahydrofuran and slowly added dropwise thereto. After stirring for 1 hour at the same temperature, the temperature was raised to room temperature, and after stirring for 5 hours, the organic layer was separated using an aqueous ammonium chloride solution and ethyl ether, concentrated under reduced pressure, and the resulting solid was washed with ethanol and dried. The dried material was dispersed in 30 mL of acetic acid and slowly added dropwise 4 mL of concentrated hydrochloric acid, followed by reflux for 5 hours. The resulting solid was filtered under reduced pressure, washed with water and ethanol, recrystallized with ethanol, and dried to obtain 3.3 g (72.5%) of the compound represented by Chemical Formula 216.

MS: m/z calcd 838.31 ; found 838. Anal. Calcd. for C62H38N4: C, 88.76; H, 4.57; N, 6.68. Found: C, 89.68; H, 5.03; N, 6.65.
MS: m / z calcd 838.31; found 838. Anal. Calcd. for C 62 H 38 N 4 : C, 88.76; H, 4.57; N, 6.68. Found: C, 89.68; H, 5.03; N, 6.65.

<< 합성예Synthetic example 9> 화학식 225로 표시되는 화합물의 제조 9> Preparation of the compound represented by Chemical Formula 225

1) 화학식 8-a로 표시되는 화합물의 합성1) Synthesis of Compound Represented by Chemical Formula 8-a

하기 반응식 35에 의하여 화학식 225로 표시되는 화합물을 합성하였다.The compound represented by Chemical Formula 225 was synthesized by Reaction Scheme 35 below.

<반응식 35>Scheme 35

Figure pat00101
Figure pat00101

[화학식 225]Formula 225

100mL 둥근 바닥 플라스크에 반응식 33로부터 얻은 화학식 8-e로 표시되는 화합물 2.1g(0.0055mol), 반응식 21로부터 얻은 화학식 5-c로부터 얻은 화합물 6.0g(0.0138mol)을 가지고 반응식 34과 같은 방법으로 화학식 225로 표시되는 화합물을 4.4g(75.2%) 얻었다. In a 100 mL round bottom flask, 2.1 g (0.0055 mol) of the compound represented by Formula 8-e obtained from Scheme 33 and 6.0 g (0.0138 mol) of the compound obtained from Formula 5-c obtained from Scheme 21 were prepared in the same manner as in Scheme 34. 4.4 g (75.2%) of the compound represented by 225 was obtained.

MS: m/z calcd 1070.43 ; found 1070. Anal. Calcd. for C80H54N4: C, 89.63; H, 5.08; N, 5.23. Found: C, 88.49; H, 5.48; N, 5.10.MS: m / z calcd 1070.43; found 1070. Anal. Calcd. for C 80 H 54 N 4 : C, 89.63; H, 5.08; N, 5.23. Found: C, 88.49; H, 5. 48; N, 5.10.

<실시예 1 ~ 9> 유기전계발광소자의 제조<Examples 1 to 9> Fabrication of the organic light emitting device

ITO 글래스의 발광 면적이 2mm × 2mm 크기가 되도록 패터닝한 후 세정하였다. 기판을 진공 챔버에 장착한 후 베이스 압력이 1 × 10-6 torr가 되도록 한 후 유기물을 상기 ITO 위에 DNTPD(700Å), NPD(300Å), 본 발명에 의해 제조된 화합물 + Ir(ppy)3(10%)(300Å), Alq3(350Å), LiF(5Å), Al(1,000Å)의 순서로 성막하였으며, 0.4mA에서 측정을 하였다.The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 -6 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), the compound + Ir (ppy) 3 (prepared by the present invention) 10%) (300 mW), Alq 3 (350 mW), LiF (5 mW), and Al (1,000 mW) were formed in this order and measured at 0.4 mA.

[DNTPD][DNTPD]

Figure pat00102
Figure pat00102

[NPD][NPD]

Figure pat00103
Figure pat00103

[Ir(ppy)3][Ir (ppy) 3 ]

Figure pat00104
Figure pat00104

[Alq3][Alq 3 ]

Figure pat00105

Figure pat00105

비교예Comparative example 1 One

비교예를 위한 유기전계발광소자는 상기 실시예 1 ~ 9의 소자 구조에서 발명에 의해 제조된 화합물 대신 하기 구조식의 CBP를 사용한 점을 제외하고 동일하게 제작하였다.The organic light emitting display device for the Comparative Example was prepared in the same manner except for using the CBP of the following structural formula instead of the compound prepared by the invention in the device structure of Examples 1 to 9.

[CBP][CBP]

Figure pat00106

Figure pat00106

구분division 호스트Host 도펀트Dopant 도핑농도(%)Doping Concentration (%) ETLETL VV Cd/ACd / A CIExCIEx CIEyCIEy 비교예 1Comparative Example 1 CBPCBP Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 8.208.20 38.8138.81 0.290.29 0.620.62 실시예 1Example 1 화합물 30Compound 30 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 6.186.18 47.2747.27 0.310.31 0.620.62 실시예 2Example 2 화합물 75Compound 75 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 5.875.87 49.4549.45 0.290.29 0.630.63 실시예 3Example 3 화합물 79Compound 79 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 5.195.19 52.6752.67 0.320.32 0.630.63 실시예 4Example 4 화합물 81Compound 81 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 5.525.52 52.1152.11 0.310.31 0.640.64 실시예 5Example 5 화합물 86Compound 86 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 4.974.97 58.2458.24 0.330.33 0.630.63 실시예 6Example 6 화합물107Compound107 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 5.395.39 49.7249.72 0.300.30 0.630.63 실시예 7Example 7 화합물190Compound190 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 5.275.27 55.9055.90 0.310.31 0.630.63 실시예 8Example 8 화합물216Compound216 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 6.016.01 49.5549.55 0.320.32 0.640.64 실시예 9Example 9 화합물225Compound 225 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 6.216.21 43.1743.17 0.330.33 0.640.64

상기 실시예와 비교예 및 표 1의 결과로부터, 본 발명에 따른 화학식 (1) 또는 (2)로 표시되는 화합물은 인광발광재료로 많이 쓰이는 CBP에 비하여 열적특성 및 발광효율 등이 우수한 특성을 보이므로, 표시소자, 디스플레이 소자 및 조명 등에 유용하게 사용될 수 있음을 알 수 있다.From the results of the above Examples, Comparative Examples and Table 1, the compound represented by the formula (1) or (2) according to the present invention shows excellent thermal properties and luminous efficiency, etc. compared to CBP which is used as a phosphorescent material Therefore, it can be seen that it can be usefully used for a display element, a display element and lighting.

Claims (6)

하기 [화학식 1] 또는 [화학식 2]로 표시되는 스피로 화합물:
[화학식 1]
Figure pat00107

[화학식 2]
Figure pat00108

상기 [화학식 1] 또는 [화학식 2]에서,
R1 내지 R20은 각각 독립적으로 수소 원자, 중수소 원자, 할로겐 원자, 치환 또는 비치환의 탄소수 6 내지 40의 아릴아미노기, 치환 또는 비치환의 탄소수 3 내지 40의 아릴옥시기, 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기, 치환 또는 비치환의 게르마늄기, 치환 또는 비치환의 인, 치환 또는 비치환의 보론으로부터 선택되고, 상기 R1 내지 R20 중 인접하는 기는 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있으며,
A1 또는 A2는 치환 또는 비치환의 탄소수 6 내지 40의 아릴기, 및 치환 또는 비치환의 탄소수 3 내지 40의 헤테로아릴기로부터 선택되고, 상기 A1은 R6 또는 R7, A2는 R14 또는 R15와 서로 결합하여 치환 또는 비치환의 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성할 수 있다.Spiro compounds represented by the following [Formula 1] or [Formula 2]:
[Formula 1]
Figure pat00107

(2)
Figure pat00108

In [Formula 1] or [Formula 2],
R 1 to R 20 are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted arylamino group having 6 to 40 carbon atoms, a substituted or unsubstituted aryloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted carbon atom 6 to A aryl group of 40, a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted phosphorus, a substituted or unsubstituted boron, and the adjacent groups of R 1 to R 20 are selected from Combine with each other to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring,
A 1 or A 2 is selected from a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms, wherein A 1 is R 6 or R 7 , and A 2 is R 14 Or may be combined with R 15 to form a substituted or unsubstituted aliphatic, aromatic, heteroaliphatic or heteroaromatic condensed ring. 제1항에 있어서,
상기 R1 내지 R20, A1 또는 A2는 각각 독립적으로 중수소 원자, 시아노기, 할로겐 원자, 히드록시기, 니트로기, 탄소수 1 내지 40의 알킬기, 탄소수 1 내지 40의 알콕시기, 탄소수 1 내지 40의 알킬아미노기, 탄소수 6 내지 40의 아릴아미노기,　탄소수 3 내지 40의 헤테로아릴아미노기, 탄소수 1 내지 40의 알킬실릴기, 탄소수 6 내지 40의 아릴실릴기, 탄소수 6 내지 40의 아릴기, 탄소수 3 내지 40의 아릴옥시기, 탄소수 3 내지 40의 헤테로아릴기, 게르마늄기, 인 및 보론으로 이루어진 군으로부터 선택된 하나 이상의 치환기에 의해서 치환될 수 있고, 상기 치환기에 의해 추가로 치환될 수 있으며, 상기 치환기는 서로 결합하여 지방족, 방향족, 헤테로지방족 또는 헤테로방향족의 축합고리를 형성하는 것을 특징으로 하는 스피로 화합물.The method of claim 1,
R 1 to R 20 , A 1 or A 2 are each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or an alkyl group having 1 to 40 carbon atoms. Alkylamino group, C6-C40 arylamino group, C3-C40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 It may be substituted by one or more substituents selected from the group consisting of an aryloxy group, a heteroaryl group having 3 to 40 carbon atoms, a germanium group, phosphorus and boron, and may be further substituted by the substituents, the substituents Spiro compound, characterized in that by combining to form a condensed ring of aliphatic, aromatic, heteroaliphatic or heteroaromatic. 제1항에 있어서,
하기 [화학식 3] 또는 [화학식 242]로 표시되는 화합물 중에서 선택된 어느 하나인 것을 특징으로 하는 스피로 화합물:
Figure pat00109

[화학식 3] [화학식 4] [화학식 5] [화학식 6]
Figure pat00110

[화학식 7] [화학식 8] [화학식 9] [화학식 10]
Figure pat00111

[화학식 11] [화학식 12] [화학식 13] [화학식 14]
Figure pat00112

[화학식 15] [화학식 16] [화학식 17] [화학식 18]
Figure pat00113

[화학식 19] [화학식 20] [화학식 21] [화학식 22]
Figure pat00114

[화학식 23] [화학식 24] [화학식 25] [화학식 26]
Figure pat00115

[화학식 27] [화학식 28] [화학식 29] [화학식 30]
Figure pat00116

[화학식 31] [화학식 32] [화학식 33] [화학식 34]
Figure pat00117

[화학식 35] [화학식 36] [화학식 37] [화학식 38]
Figure pat00118

[화학식 39] [화학식 40] [화학식 41] [화학식 42]
Figure pat00119

[화학식 43] [화학식 44] [화학식 45] [화학식 46]
Figure pat00120

[화학식 47] [화학식 48] [화학식 49] [화학식 50]
Figure pat00121

[화학식 51] [화학식 52] [화학식 53] [화학식 54]
Figure pat00122

[화학식 55] [화학식 56] [화학식 57] [화학식 58]
Figure pat00123

[화학식 59] [화학식 60] [화학식 61] [화학식 62]
Figure pat00124

[화학식 63] [화학식 64] [화학식 65] [화학식 66]
Figure pat00125

[화학식 67] [화학식 68] [화학식 69] [화학식 70]
Figure pat00126

[화학식 71] [화학식 72] [화학식 73] [화학식 74]
Figure pat00127

[화학식 75] [화학식 76] [화학식 77] [화학식 78]

Figure pat00128

[화학식 79] [화학식 80] [화학식 81] [화학식 82]
Figure pat00129

[화학식 83] [화학식 84] [화학식 85] [화학식 86]
Figure pat00130

[화학식 87] [화학식 88] [화학식 89] [화학식 90]
Figure pat00131

[화학식 91] [화학식 92] [화학식 93] [화학식 94]
Figure pat00132

[화학식 95] [화학식 96] [화학식 97] [화학식 98]
Figure pat00133

[화학식 99] [화학식 100] [화학식 101] [화학식 102]
Figure pat00134

[화학식 103] [화학식 104] [화학식 105] [화학식 106]
Figure pat00135

[화학식 107] [화학식 108] [화학식 109] [화학식 110]
Figure pat00136

[화학식 111] [화학식 112] [화학식 113] [화학식 114]
Figure pat00137

[화학식 115] [화학식 116] [화학식 117] [화학식 118]
Figure pat00138

[화학식 119] [화학식 120] [화학식 121] [화학식 122]
Figure pat00139

[화학식 123] [화학식 124] [화학식 125] [화학식 126]
Figure pat00140

[화학식 127] [화학식 128] [화학식 129] [화학식 130]
Figure pat00141

[화학식 131] [화학식 132] [화학식 133] [화학식 134]
Figure pat00142

[화학식 135] [화학식 136] [화학식 137] [화학식 138]
Figure pat00143

[화학식 139] [화학식 140] [화학식 141] [화학식 142]
Figure pat00144

[화학식 143] [화학식 144] [화학식 145] [화학식 146]
Figure pat00145

[화학식 147] [화학식 148] [화학식 149] [화학식 150]
Figure pat00146

[화학식 151] [화학식 152] [화학식 153] [화학식 154]
Figure pat00147

[화학식 155] [화학식 156] [화학식 157] [화학식 158]
Figure pat00148

[화학식 159] [화학식 160] [화학식 161] [화학식 162]
Figure pat00149

[화학식 163] [화학식 164] [화학식 165] [화학식 166]
Figure pat00150

[화학식 167] [화학식 168] [화학식 169] [화학식 170]
Figure pat00151

[화학식 171] [화학식 172] [화학식 173] [화학식 174]
Figure pat00152

[화학식 175] [화학식 176] [화학식 177] [화학식 178]
Figure pat00153

[화학식 179] [화학식 180] [화학식 181] [화학식 182]
Figure pat00154

[화학식 183] [화학식 184] [화학식 185] [화학식 186]
Figure pat00155

[화학식 187] [화학식 188] [화학식 189] [화학식 190]
Figure pat00156

[화학식 191] [화학식 192] [화학식 193] [화학식 194]
Figure pat00157

[화학식 195] [화학식 196] [화학식 197] [화학식 198]
Figure pat00158

[화학식 199] [화학식 200] [화학식 201] [화학식 202]
Figure pat00159

[화학식 203] [화학식 204] [화학식 205] [화학식 206]
Figure pat00160

[화학식 207] [화학식 208] [화학식 209] [화학식 210]
Figure pat00161

[화학식 211] [화학식 212] [화학식 213] [화학식 214]
Figure pat00162

[화학식 215] [화학식 216] [화학식 217] [화학식 218]
Figure pat00163

[화학식 219] [화학식 220] [화학식 221] [화학식 222]
Figure pat00164

[화학식 223] [화학식 224] [화학식 225] [화학식 226]
Figure pat00165

[화학식 227] [화학식 228] [화학식 229] [화학식 230]
Figure pat00166

[화학식 231] [화학식 232] [화학식 233] [화학식 234]
Figure pat00167

[화학식 235] [화학식 236] [화학식 237] [화학식 238]
Figure pat00168

[화학식 239] [화학식 240] [화학식 241] [화학식 242]The method of claim 1,
A spiro compound, characterized in that any one selected from the compounds represented by the following [Formula 3] or [Formula 242]:
Figure pat00109

[Formula 3] [Formula 4] [Formula 5] [Formula 6]
Figure pat00110

[Formula 7] [Formula 8] [Formula 9] [Formula 10]
Figure pat00111

[Formula 11] [Formula 12] [Formula 13] [Formula 14]
Figure pat00112

[Formula 15] [Formula 16] [Formula 17] [Formula 18]
Figure pat00113

[Formula 19] [Formula 20] [Formula 21] [Formula 22]
Figure pat00114

[Formula 23] [Formula 24] [Formula 25] [Formula 26]
Figure pat00115

[Formula 27] [Formula 28] [Formula 29] [Formula 30]
Figure pat00116

[Formula 31] [Formula 32] [Formula 33] [Formula 34]
Figure pat00117

[Formula 35] [Formula 36] [Formula 37] [Formula 38]
Figure pat00118

[Formula 39] [Formula 40] [Formula 41] [Formula 42]
Figure pat00119

[Formula 43] [Formula 44] [Formula 45] [Formula 46]
Figure pat00120

[Formula 47] [Formula 48] [Formula 49] [Formula 50]
Figure pat00121

[Formula 51] [Formula 52] [Formula 53] [Formula 54]
Figure pat00122

[Formula 55] [Formula 56] [Formula 57] [Formula 58]
Figure pat00123

[Formula 59] [Formula 60] [Formula 61] [Formula 62]
Figure pat00124

[Formula 63] [Formula 64] [Formula 65] [Formula 66]
Figure pat00125

[Formula 67] [Formula 68] [Formula 69] [Formula 70]
Figure pat00126

[Formula 71] [Formula 72] [Formula 73] [Formula 74]
Figure pat00127

[Formula 75] [Formula 76] [Formula 77] [Formula 78]

Figure pat00128

[Formula 79] [Formula 80] [Formula 81] [Formula 82]
Figure pat00129

[Formula 83] [Formula 84] [Formula 85] [Formula 86]
Figure pat00130

[Formula 87] [Formula 88] [Formula 89] [Formula 90]
Figure pat00131

[Formula 91] [Formula 92] [Formula 93] [Formula 94]
Figure pat00132

[Formula 95] [Formula 96] [Formula 97] [Formula 98]
Figure pat00133

[Formula 99] [Formula 100] [Formula 101] [Formula 102]
Figure pat00134

[Formula 103] [Formula 104] [Formula 105] [Formula 106]
Figure pat00135

[Formula 107] [Formula 108] [Formula 109] [Formula 110]
Figure pat00136

[Formula 111] [Formula 112] [Formula 113] [Formula 114]
Figure pat00137

[Formula 115] [Formula 116] [Formula 117] [Formula 118]
Figure pat00138

[Formula 119] [Formula 120] [Formula 121] [Formula 122]
Figure pat00139

[Formula 123] [Formula 124] [Formula 125] [Formula 126]
Figure pat00140

[Formula 127] [Formula 128] [Formula 129] [Formula 130]
Figure pat00141

[Formula 131] [Formula 132] [Formula 133] [Formula 134]
Figure pat00142

[Formula 135] [Formula 136] [Formula 137] [Formula 138]
Figure pat00143

[Formula 139] [Formula 140] [Formula 141] [Formula 142]
Figure pat00144

[Formula 143] [Formula 144] [Formula 145] [Formula 146]
Figure pat00145

[Formula 147] [Formula 148] [Formula 149] [Formula 150]
Figure pat00146

[Formula 151] [Formula 152] [Formula 153] [Formula 154]
Figure pat00147

[Formula 155] [Formula 156] [Formula 157] [Formula 158]
Figure pat00148

[Formula 159] [Formula 160] [Formula 161] [Formula 162]
Figure pat00149

[Formula 163] [Formula 164] [Formula 165] [Formula 166]
Figure pat00150

[Formula 167] [Formula 168] [Formula 169] [Formula 170]
Figure pat00151

[Formula 171] [Formula 172] [Formula 173] [Formula 174]
Figure pat00152

[Formula 175] [Formula 176] [Formula 177] [Formula 178]
Figure pat00153

[Formula 179] [Formula 180] [Formula 181] [Formula 182]
Figure pat00154

[Formula 183] [Formula 184] [Formula 185] [Formula 186]
Figure pat00155

[Formula 187] [Formula 188] [Formula 189] [Formula 190]
Figure pat00156

[Formula 191] [Formula 192] [Formula 193] [Formula 194]
Figure pat00157

[Formula 195] [Formula 196] [Formula 197] [Formula 198]
Figure pat00158

[Formula 199] [Formula 200] [Formula 201] [Formula 202]
Figure pat00159

[Formula 203] [Formula 204] [Formula 205] [Formula 206]
Figure pat00160

[Formula 207] [Formula 208] [Formula 209] [Formula 210]
Figure pat00161

[Formula 211] [Formula 212] [Formula 213] [Formula 214]
Figure pat00162

[Formula 215] [Formula 216] [Formula 217] [Formula 218]
Figure pat00163

[Formula 219] [Formula 220] [Formula 221] [Formula 222]
Figure pat00164

[Formula 223] [Formula 224] [Formula 225] [Formula 226]
Figure pat00165

[Formula 227] [Formula 228] [Formula 229] [Formula 230]
Figure pat00166

[Formula 231] [Formula 232] [Formula 233] [Formula 234]
Figure pat00167

[Formula 235] [Formula 236] [Formula 237] [Formula 238]
Figure pat00168

[Formula 239] [Formula 240] [Formula 241] [Formula 242] 애노드; 캐소드; 및 상기 애노드와 캐소드 사이에 제1항 내지 제3항 중 어느 한 항에 따른 스피로 화합물을 포함하는 층을 구비한 유기전계발광소자.Anode; Cathode; And a layer comprising a spiro compound according to any one of claims 1 to 3 between the anode and the cathode. 제4항에 있어서,
상기 애노드와 캐소드 사이에 정공주입층, 정공수송층, 발광층, 전자저지층, 정공저지층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택된 하나 이상의 층을 포함하는 것을 특징으로 하는 유기전계발광소자.The method of claim 4, wherein
An organic light emitting device comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer between the anode and the cathode. 제5항에 있어서,
상기 스피로 화합물은 상기 애노드 및 캐소드 사이의 발광층에 포함되는 것을 특징으로 하는 유기전계발광소자.
The method of claim 5,
The spiro compound is an organic light emitting device, characterized in that included in the light emitting layer between the anode and the cathode.
KR1020100134674A 2010-12-24 2010-12-24 Spiro compound and organic electroluminescent devices comprising the same KR20120072785A (en)

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