KR20140021969A - Novel compounds, organic light emitting device display and organic solar battery using the same - Google Patents

Novel compounds, organic light emitting device display and organic solar battery using the same Download PDF

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KR20140021969A
KR20140021969A KR1020130092850A KR20130092850A KR20140021969A KR 20140021969 A KR20140021969 A KR 20140021969A KR 1020130092850 A KR1020130092850 A KR 1020130092850A KR 20130092850 A KR20130092850 A KR 20130092850A KR 20140021969 A KR20140021969 A KR 20140021969A
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이경은
최진석
안용훈
김우삼
이유석
이주동
김동준
노영석
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희성소재 (주)
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K50/14—Carrier transporting layers
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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Abstract

The present invention relates to a compound represented by a chemical formula 1, an organic electroluminescent device including the same, and an organic solar cell including the same. In the chemical formula 1, R1 to R6, are Ar1. And A, X and n are the same as defined in the specification.

Description

신규한 화합물, 이를 포함하는 유기전계발광소자 및 유기태양전지{NOVEL COMPOUNDS, ORGANIC LIGHT EMITTING DEVICE DISPLAY AND ORGANIC SOLAR BATTERY USING THE SAME}Novel compounds, organic electroluminescent devices and organic solar cells comprising the same {NOVEL COMPOUNDS, ORGANIC LIGHT EMITTING DEVICE DISPLAY AND ORGANIC SOLAR BATTERY USING THE SAME}

본 발명은 신규한 화합물, 이를 포함하는 유기전계발광소자 및 유기태양전지에 관한 것이다. The present invention relates to novel compounds, organic electroluminescent devices and organic solar cells comprising the same.

최근에 고효율, 장수명 유기전계발광소자의 개발이 시급한 과제로 대두되고 있다. 특히, 중대형 유기전계발광소자 패널에서 요구하고 있는 특성 수준을 고려해 볼 때, 종래의 발광 재료에 비해 매우 우수한 재료의 개발이 시급한 실정이다. 따라서, 고효율 장수명의 RGB 발광재료의 개발이 유기전계발광소자 전체의 특성을 향상시키는데 중요한 과제라고 할 수 있다.Recently, the development of high efficiency, long life organic light emitting diodes has emerged as an urgent task. In particular, considering the level of characteristics required of the medium-large organic light emitting diode panel, it is urgent to develop a material that is much superior to the conventional light emitting material. Therefore, the development of a high efficiency long life RGB light emitting material can be said to be an important problem in improving the characteristics of the whole organic light emitting device.

한편, 풀칼라 유기전계발광소자 특성이 가장 우수한 소자 구조로는 호스트에 도펀트를 도핑하여 발광층을 만드는 것으로 알려져 있다. 따라서, 호스트 재료의 개발이 해결해야 할 가장 중요한 요소 중의 하나이다. 왜냐하면, 호스트 재료는 고체 상태의 용매와 에너지 전달자의 역할을 하기 때문이다. 이러한 호스트 재료는 순도가 높고 진공증착이 가능하도록 적당한 분자량을 갖는 것이 바람직하다. 또한, 호스트 재료는 유리전이온도와 열분해온도가 높아 열적 안정성이 확보되어야 한다. 또한, 호스트 재료는 장수명화를 위해 높은 전기화학적 안정성이 요구된다. 또한, 호스트 재료는 무정형 박막을 형성하기 용이해야 하며, 인접한 다른 층의 재료들과는 접착력이 좋은 반면, 층간 이동은 하지 않아야 한다.On the other hand, it is known that the light emitting layer is formed by doping a dopant to a host as the device structure having the best characteristics of the full color organic light emitting device. Therefore, development of host material is one of the most important factors to be solved. This is because the host material acts as a solvent and energy carrier in the solid state. Such a host material is preferably high in purity and has a suitable molecular weight to enable vacuum deposition. In addition, the host material has a high glass transition temperature and pyrolysis temperature to ensure thermal stability. In addition, host materials require high electrochemical stability for long life. In addition, the host material should be easy to form an amorphous thin film and have good adhesion with materials of other adjacent layers, while not allowing interlayer movement.

최근에는 유기전계발광소자의 발광층으로 호스트 물질에 형광 또는 인광물질을 도펀트로서 도핑한 시스템이 활발히 연구되고 있다. 이와 같은 호스트-도펀트 시스템의 발광층은 하전입자(전자 및 정공)의 흐름을 용이하게 하여 발광소자의 구동전압을 낮출 수 있다는 장점이 있다.Recently, a system of doping a fluorescent material or a phosphor as a dopant in a host material as an emission layer of an organic light emitting device has been actively studied. The light emitting layer of the host-dopant system has an advantage that the driving voltage of the light emitting device can be lowered by facilitating the flow of charged particles (electrons and holes).

예를 들어, 종래의 청색 재료의 경우, 이데미쓰-고산의 디페닐비닐-비페닐(DPVBi, 하기 화학식 a로 표시되는 화합물) 이후로 많은 재료가 개발되어 상업화되어 있다. 예를 들면, 이데미쓰-고산의 청색 재료 시스템과 코닥의 디나프틸안트라센(dinaphthylanthracen; DNA, 하기 화학식 b로 표시되는 화합물)의 시스템 등이 알려져 있다. 그러나, 아직도 많은 연구 개발이 이루어져야 할 것으로 판단된다. 왜냐하면, 현재까지 가장 효율이 좋다고 알려진 이데미쓰-고산의 디스트릴(distryl) 화합물의 시스템은 전력 효율의 경우, 6㏐/W이고 소자 수명이 30,000시간 이상으로 좋긴 하지만, 구동 시간에 따른 색순도의 저하로 인하여 풀칼라 디스플레이에 적용했을 때, 수명이 불과 수천 시간에 불과하기 때문이다. 그리고, 청색 발광은 발광 파장이 장파장 쪽으로 조금만 이동해도 발광 효율 측면에서는 유리해지나, 순청색을 만족시키지 못해 고품위의 디스플레이에는 적용이 쉽지 않고, 색순도, 효율 및 열안정성에 문제가 있어 연구 개발이 시급하다.For example, in the case of the conventional blue material, many materials have been developed and commercialized since diphenylvinyl biphenyl (DPVBi, a compound represented by the following formula a) of Idemitsu-high acid. For example, the blue material system of Idemitsu-high acid, the system of Kodak dinaphthylanthracen (DNA, a compound represented by following formula (b)), etc. are known. However, much research and development still needs to be done. This is because the system of Idemitsu-high acid disryl compound, which is known to be the most efficient to date, has a power efficiency of 6 mW / W and a device life of more than 30,000 hours, but the color purity decreases with driving time. This is because, when applied to a full color display, its lifetime is only a few thousand hours. In addition, blue light emission is advantageous in terms of light emission efficiency even if the light emission wavelength is shifted to a longer wavelength, but it is not easy to apply to high-quality displays because it does not satisfy pure blue color, and there is a problem in color purity, efficiency, and thermal stability, and therefore research and development is urgent. .

Figure pat00001
Figure pat00001

또한, 경상대와 삼성 SDI에서 발표한 TBSA[Kwon, S. K. et. al. Advanced Materials, 2001, 13, 1690; JP2002-121547A]의 경우, 7.7V에서 3㏅/A 의 발광효율과 (0.15, 0.11)의 비교적 좋은 색좌표를 보였으나 단일층의 재료로 적용되었을 때, 상용화 수준에는 미흡한 것으로 알려져 있다. 또한, 국립대만대에서 발표한 TSF[Wu, C. -C., et. al. Advanced Materials, 2004, 16, 61; US2005-0074631A]의 경우 비교적 우수한 5.3%의 외부 양자효율을 보였으나, 역시 상용화 수준에는 역시 미흡하다. 또한, 대만의 칭화국립대에서 발표한 BTP의 경우[Cheng, C. -H, et. al. Advanced Materials, 2002, 14, 1409; US2004-0076852A] 2.76 ㏅/A의 발광효율과 (0.16, 0.14)의 비교적 좋은 색좌표를 보였으나 상용화 수준에는 미흡하다. In addition, the TBSA [Kwon, S. K. et. al. Advanced Materials, 2001, 13, 1690; JP2002-121547A] exhibited a luminous efficiency of 3 ㏅ / A and relatively good color coordinates of (0.15, 0.11) at 7.7V, but it is known to be insufficient in commercialization level when applied as a single layer material. In addition, TSF [Wu, C.-C., et. al. Advanced Materials, 2004, 16, 61; US2005-0074631A] had a relatively good external quantum efficiency of 5.3%, but it was also insufficient for commercialization. In addition, BTP presented by Tsinghua National University of Taiwan [Cheng, C. -H, et. al. Advanced Materials, 2002, 14, 1409; US2004-0076852A] The luminous efficiency of 2.76 ㏅ / A and the relatively good color coordinate of (0.16, 0.14) were shown, but the level of commercialization was insufficient.

이와 같이, 종래의 재료들은 호스트-도펀트 박막층을 구성하지 않고 단일층으로 구성되어 있으며, 색순도 및 효율 측면에서 상용화가 어려운 것으로 판단되며, 장수명에 대한 신뢰성 있는 데이터도 미비한 상황이다.As described above, the conventional materials are composed of a single layer without forming a host-dopant thin film layer, and it is determined that commercialization is difficult in terms of color purity and efficiency, and reliable data on long life is insufficient.

한편, 일본의 미쯔이 화학의 US2005-0074631A에 의하면 하기 화합물들이 4.6㏅/A의 발광효율을 보이는 것으로 확인되었다.On the other hand, according to US 2005-0074631A of Mitsui Chemicals, Japan, the following compounds were confirmed to exhibit luminous efficiency of 4.6 ㏅ / A.

Figure pat00002
Figure pat00002

그러나, 이 화합물들의 경우, 청록색(bluish green color)으로 명시하고 있다. 특히, 상기와 같은 대칭적 구조에서는 순청색의 구현이 불가능하며, 이러한 순청색의 발광을 갖지 못하는 재료로는 풀칼라용 디스플레이 적용을 위한 상용화에는 미흡하다고 판단된다.However, in the case of these compounds, they are specified in bluish green color. In particular, it is impossible to implement pure blue in the symmetrical structure as described above, and it is judged that the material having no pure blue light emission is insufficient in commercialization for full color display applications.

상기 선행기술에 개시된 유기 발광 화합물들은 열안정성이 낮이 이를 이용하여 제조된 발광소자의 수명이 길지 않다는 문제점이 계속되고 있다. 이에, 본 발명자들은 안트라센과 그에 치환된 측쇄기를 링으로 형성시켜 발광 화합물의 열안정성을 향상시키고 이를 유기발광소자에 적용하는 경우. 종래의 발광물질을 적용하는 경우에 비하여 현저하게 유기발광소자의 수명 및 효율, 색 순도가 높아 질 수 될 수 있음을 확인하고 본 발명을 완성하였다.The organic light emitting compounds disclosed in the prior art have a low thermal stability and continue to have a long lifespan of light emitting devices manufactured using the same. Thus, the present inventors form anthracene and substituted side chain groups thereof in a ring to improve the thermal stability of the light emitting compound and apply it to an organic light emitting device. Compared to the case of applying a conventional light emitting material, it was confirmed that the lifespan, efficiency, and color purity of the organic light emitting device can be significantly increased, and completed the present invention.

본 발명의 목적은 열안정성이 뛰어나고 색순도가 우수한 화합물을 제공하는 것이다. 보다 상세하게 설명하면, 본 발명의 목적은 안트라센과 그에 치환된 측쇄기를 고리로 형성시킴으로써, 안트라센 골격과 측쇄기의 구조가 평면을 유지시켜 분자간 결합을 매우 높여 열안정성이 뛰어나고 발광효율 및 수명이 우수한 유기화합물을 제공하는 것이다.An object of the present invention is to provide a compound having excellent thermal stability and excellent color purity. In more detail, an object of the present invention is to form an anthracene and a side chain group substituted therein as a ring, the structure of the anthracene skeleton and the side chain group to maintain a flat surface to increase the intermolecular bonds very excellent thermal stability and excellent luminous efficiency and lifetime It is to provide an organic compound.

또한, 본 발명의 목적은 발광효율 및 수명이 우수한 유기전계발광소자 및 유기태양전지를 제공하는 것이다.In addition, an object of the present invention is to provide an organic light emitting device and an organic solar cell excellent in luminous efficiency and lifetime.

본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다;The present invention provides a compound represented by the following formula (1);

Figure pat00003
Figure pat00003

상기 화학식 1에서,In Formula 1,

R1 내지 R6은 서로 같거나 다르고, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60 )알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이며, 상기 R1 내지 R6는 인접하는 기와 서로 결합하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하거나, 치환 또는 비치환된 (C2-C60)알킬렌 또는 (C2-C60)알케닐렌으로 서로 연결하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하고,R 1 to R 6 are the same as or different from each other, and each independently, hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 5 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; Or (C 6 -C 60 ) arylcarbonyl, wherein R 1 to R 6 are bonded to adjacent groups to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, or a substituted or unsubstituted (C 2 -C 60). Linking together with alkylene or (C 2 -C 60 ) alkenylene to form an aliphatic ring, an aromatic ring, a heteroaromatic ring,

Ar1은 1∼5개의 고리를 갖는 치환 또는 비치환된 (C6-C60)의 방향족 화합물 또는 융합고리형 방향족 화합물이고, Ar 1 is a substituted or unsubstituted (C 6 -C 60 ) aromatic compound or fused ring aromatic compound having 1 to 5 rings,

A는 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C2-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; (C6-C60)아릴카보닐; 또는

Figure pat00004
이되,A is adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 2 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; (C 6 -C 60 ) arylcarbonyl; or
Figure pat00004
However,

Ar3는 치환 또는 비치환된 (C1-C60)알킬렌옥시; 치환 또는 비치환된 (C1-C60)알킬렌티오; 치환 또는 비치환된 (C6-C60)아릴렌옥시; (C6-C60)아릴렌티오; 치환 또는 비치환된 (C6-C60)아릴렌; 또는 (C3-C60)헤테로아릴렌이고,Ar 3 is substituted or unsubstituted (C 1 -C 60 ) alkyleneoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylenethio; Substituted or unsubstituted (C 6 -C 60 ) aryleneoxy; (C 6 -C 60 ) arylenethio; Substituted or unsubstituted (C 6 -C 60 ) arylene; Or (C 3 -C 60 ) heteroarylene,

R7은 R1 내지 R6의 기재와 동일하고,R 7 is the same as described for R 1 to R 6 ,

n은 0 내지 3이고,n is from 0 to 3,

n이 0이 아닐 경우, X는 -O-, -Si(-R21)(-R22)-, -N(-R21)- 또는 -C(-R21)(-R22)-로서, If n is not 0, X is -O-, -Si (-R 21 ) (-R 22 )-, -N (-R 21 )-or -C (-R 21 ) (-R 22 )- ,

이때, R21 및 R22는 각각 독립적으로 수소; 직쇄상 또는 분지상의 (C1-C60)알킬; (C6-C60)아릴; (C6-C60)알콕시아릴; (C1-C60)알킬티오(C6-C60)아릴; 또는 아미노(C6-C60)아릴, (C1-C60)알킬실릴(C6-C60)아릴이고, In this case, R 21 and R 22 are each independently hydrogen; Linear or branched (C 1 -C 60 ) alkyl; (C 6 -C 60 ) aryl; (C 6 -C 60 ) alkoxyaryl; (C 1 -C 60 ) alkylthio (C 6 -C 60 ) aryl; Or amino (C 6 -C 60 ) aryl, (C 1 -C 60 ) alkylsilyl (C 6 -C 60 ) aryl,

상기 R1 내지 R6, Ar1, A 및 Ar3에서의 치환은 서로 같거나 다르고, 각각 독립적으로, 할로겐, (C1-C60)알킬, (C6-C60)아릴, (C2-C60)헤테로아릴, N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬, (C3-C60)시클로알킬, 트리(C1-C60)알킬실릴, 디(C1-C60)알킬(C6-C60)아릴실릴, 트리(C6-C60)아릴실릴, 아다만틸, (C7-C60)바이시클로알킬, (C2-C60)알케닐, (C2-C60)알키닐, (C1-C60)알콕시, 시아노, (C1-C60)알킬아미노, (C6-C60)아릴아미노, (C6-C60)아르(C1-C60)알킬, (C6-C60)아릴옥시, (C1-C60)알킬티오, (C6-C60)아릴티오, (C1-C60)알콕시카보닐, (C1-C60)알킬카보닐, (C6-C60)아릴카보닐, 카복실산, 나이트로 또는 하이드록시로 치환될 수 있다. Substituents in R 1 to R 6 , Ar 1 , A and Ar 3 are the same as or different from each other, and each independently, halogen, (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryl, (C 2 -C 60) heteroaryl, N, O, S, and 5-or 6-membered heterocycloalkyl containing one or two or more selected from Si, (C 3 -C 60) cycloalkyl, tri (C 1 - C 60 ) alkylsilyl, di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl, tri (C 6 -C 60 ) arylsilyl, adamantyl, (C 7 -C 60 ) bicycloalkyl , (C 2 -C 60 ) alkenyl, (C 2 -C 60 ) alkynyl, (C 1 -C 60 ) alkoxy, cyano, (C 1 -C 60 ) alkylamino, (C 6 -C 60 ) Arylamino, (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryloxy, (C 1 -C 60 ) alkylthio, (C 6 -C 60 ) arylthio, (C 1 -C 60 ) alkoxycarbonyl, (C 1 -C 60 ) alkylcarbonyl, (C 6 -C 60 ) arylcarbonyl, carboxylic acid, nitro or hydroxy.

본 발명은 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고, 상기 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 것을 특징으로 하는 유기전계발광소자를 제공한다.The present invention relates to a plasma display panel comprising a first electrode; A second electrode; And an organic film disposed between the first electrode and the second electrode and including an compound represented by Chemical Formula 1.

본 발명은 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고 상기 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 것을 특징으로 하는 유기태양전지를 제공한다.The present invention relates to a plasma display panel comprising a first electrode; A second electrode; And it provides between the first electrode and the second electrode provides an organic solar cell comprising an organic film comprising a compound represented by the formula (1).

본 발명의 화합물은 열안정성이 뛰어나므로 유기전계발광소자에 적용했을 때, 수명이 길고, 발광효율 및 색좌표가 우수하다. 본 발명의 화합물은 적색, 녹색, 청색의 형광 및 인광의 유기전계발광소자의 유기막층 재료에 적합하다. 특히, 본 발명의 화합물은 정공수송층의 청색 형광용 재료로 적합하다. 본 발명의 유기전계발광소자는 수명이 길고 발광효율이 우수하고, 색순도가 높다.Since the compound of the present invention has excellent thermal stability, when applied to an organic light emitting device, it has a long life, and is excellent in luminous efficiency and color coordinate. The compound of the present invention is suitable for the organic film layer material of organic electroluminescent devices of red, green and blue fluorescence and phosphorescence. In particular, the compound of the present invention is suitable as a blue fluorescent material for the hole transport layer. The organic electroluminescent device of the present invention has a long lifetime, excellent luminous efficiency, and high color purity.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 예를 들어 본 발명에 따른 화합물, 이의 제조방법 및 유기전계발광소자를 설명하나, 이는 단지 그 실시 양태를 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하는 것은 아니다.
Hereinafter, for the detailed understanding of the present invention, for example, a compound according to the present invention, a method for preparing the same, and an organic light emitting display device according to the present invention will be described. It does not limit the scope of the invention.

Ⅰ. 화합물Ⅰ. compound

본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).

Figure pat00005
Figure pat00005

상기 화학식 1에서,In Formula 1,

R1 내지 R6은 서로 같거나 다르고, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60 )알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이며, 상기 R1 내지 R6는 인접하는 기와 서로 결합하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하거나, 치환 또는 비치환된 (C2-C60)알킬렌 또는 (C2-C60)알케닐렌으로 서로 연결하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하고,R 1 to R 6 are the same as or different from each other, and each independently, hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 5 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; Or (C 6 -C 60 ) arylcarbonyl, wherein R 1 to R 6 are bonded to adjacent groups to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, or a substituted or unsubstituted (C 2 -C 60). Linking together with alkylene or (C 2 -C 60 ) alkenylene to form an aliphatic ring, an aromatic ring, a heteroaromatic ring,

Ar1은 1∼5개의 고리를 갖는 치환 또는 비치환된 (C6-C60)의 방향족 화합물 또는 융합고리형 방향족 화합물이고, Ar 1 is a substituted or unsubstituted (C 6 -C 60 ) aromatic compound or fused ring aromatic compound having 1 to 5 rings,

A는 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C2-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; (C6-C60)아릴카보닐; 또는

Figure pat00006
이되,A is adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 2 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; (C 6 -C 60 ) arylcarbonyl; or
Figure pat00006
However,

Ar3는 치환 또는 비치환된 (C1-C60)알킬렌옥시; 치환 또는 비치환된 (C1-C60)알킬렌티오; 치환 또는 비치환된 (C6-C60)아릴렌옥시; (C6-C60)아릴렌티오; 치환 또는 비치환된 (C6-C60)아릴렌; 또는 (C3-C60)헤테로아릴렌이고,Ar 3 is substituted or unsubstituted (C 1 -C 60 ) alkyleneoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylenethio; Substituted or unsubstituted (C 6 -C 60 ) aryleneoxy; (C 6 -C 60 ) arylenethio; Substituted or unsubstituted (C 6 -C 60 ) arylene; Or (C 3 -C 60 ) heteroarylene,

R7은 R1 내지 R6의 기재와 동일하고,R 7 is the same as described for R 1 to R 6 ,

n은 0 내지 3이고,n is from 0 to 3,

n이 0이 아닐 경우, X는 -O-, -Si(-R21)(-R22)-, -N(-R21)- 또는 -C(-R21)(-R22)-로서, If n is not 0, X is -O-, -Si (-R 21 ) (-R 22 )-, -N (-R 21 )-or -C (-R 21 ) (-R 22 )- ,

이때, R21 및 R22는 각각 독립적으로 수소; 직쇄상 또는 분지상의 (C1-C60)알킬; (C6-C60)아릴; (C6-C60)알콕시아릴; (C1-C60)알킬티오(C6-C60)아릴; 또는 아미노(C6-C60)아릴, (C1-C60)알킬실릴(C6-C60)아릴이고, In this case, R 21 and R 22 are each independently hydrogen; Linear or branched (C 1 -C 60 ) alkyl; (C 6 -C 60 ) aryl; (C 6 -C 60 ) alkoxyaryl; (C 1 -C 60 ) alkylthio (C 6 -C 60 ) aryl; Or amino (C 6 -C 60 ) aryl, (C 1 -C 60 ) alkylsilyl (C 6 -C 60 ) aryl,

상기 R1 내지 R6, Ar1, A 및 Ar3에서의 치환은 서로 같거나 다르고, 각각 독립적으로, 할로겐, (C1-C60)알킬, (C6-C60)아릴, (C2-C60)헤테로아릴, N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬, (C3-C60)시클로알킬, 트리(C1-C60)알킬실릴, 디(C1-C60)알킬(C6-C60)아릴실릴, 트리(C6-C60)아릴실릴, 아다만틸, (C7-C60)바이시클로알킬, (C2-C60)알케닐, (C2-C60)알키닐, (C1-C60)알콕시, 시아노, (C1-C60)알킬아미노, (C6-C60)아릴아미노, (C6-C60)아르(C1-C60)알킬, (C6-C60)아릴옥시, (C1-C60)알킬티오, (C6-C60)아릴티오, (C1-C60)알콕시카보닐, (C1-C60)알킬카보닐, (C6-C60)아릴카보닐, 카복실산, 나이트로 또는 하이드록시로 치환될 수 있다.
Substituents in R 1 to R 6 , Ar 1 , A and Ar 3 are the same as or different from each other, and each independently, halogen, (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryl, (C 2 -C 60) heteroaryl, N, O, S, and 5-or 6-membered heterocycloalkyl containing one or two or more selected from Si, (C 3 -C 60) cycloalkyl, tri (C 1 - C 60 ) alkylsilyl, di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl, tri (C 6 -C 60 ) arylsilyl, adamantyl, (C 7 -C 60 ) bicycloalkyl , (C 2 -C 60 ) alkenyl, (C 2 -C 60 ) alkynyl, (C 1 -C 60 ) alkoxy, cyano, (C 1 -C 60 ) alkylamino, (C 6 -C 60 ) Arylamino, (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryloxy, (C 1 -C 60 ) alkylthio, (C 6 -C 60 ) arylthio, (C 1 -C 60 ) alkoxycarbonyl, (C 1 -C 60 ) alkylcarbonyl, (C 6 -C 60 ) arylcarbonyl, carboxylic acid, nitro or hydroxy.

상기 화학식 1로 표시되는 화합물은 하기 화학식 1A로 표시되는 화합물인 것이 바람직하다.The compound represented by Chemical Formula 1 is preferably a compound represented by the following Chemical Formula 1A.

Figure pat00007
Figure pat00007

상기 화학식 1A에 있어서,In Chemical Formula 1A,

R1 내지 R6은 상기 화학식 1에서 정의한 바와 같고,R 1 to R 6 are the same as defined in Formula 1,

A는 치환 또는 비치환된 (C6-C60)아릴 또는 치환 또는 비치환된 (C2-C60)헤테로 아릴이고,A is substituted or unsubstituted (C 6 -C 60 ) aryl or substituted or unsubstituted (C 2 -C 60 ) hetero aryl,

n은 0 내지 1이고, n is 0 to 1,

n이 1일 경우, X는 -N(-R21)- 또는 -C(-R21)(-R22)-이고,when n is 1, X is -N (-R 21 )-or -C (-R 21 ) (-R 22 )-,

R21 및 R22는 상기 화학식 1에서 정의한 바와 같고,R 21 and R 22 are the same as defined in Formula 1,

R17 내지 R20은 인접하는 기끼리 서로 결합하여 1종 또는 2종 이상의 방향족 또는 지방족 환을 형성한다.R 17 to R 20 combine with each other to form one or two or more aromatic or aliphatic rings.

그리고, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 화학식 13으로부터 선택되는 것이 바람직하다.In addition, the compound represented by Chemical Formula 1 is preferably selected from Chemical Formulas 2 to 13.

<화학식 2> <화학식 3> <화학식 4><Formula 2> <Formula 3> <Formula 4>

Figure pat00008
Figure pat00009
Figure pat00010
Figure pat00008
Figure pat00009
Figure pat00010

<화학식 5> <화학식 6> <화학식 7>&Lt; Formula 5 > < EMI ID =

Figure pat00011
Figure pat00012
Figure pat00013
Figure pat00011
Figure pat00012
Figure pat00013

<화학식 8> <화학식 9> <화학식 10>&Lt; Formula 8 > < EMI ID =

Figure pat00014
Figure pat00015
Figure pat00016
Figure pat00014
Figure pat00015
Figure pat00016

<화학식 11> <화학식 12> <화학식 13><Formula 11> <Formula 12> <Formula 13>

Figure pat00017
Figure pat00018
Figure pat00019
Figure pat00017
Figure pat00018
Figure pat00019

상기 화학식 2 내지 화학식 13에서,In Chemical Formulas 2 to 13,

A, R1 내지 R6은 상기 화학식 1에서 정의한 바와 같고,A, R 1 to R 6 are the same as defined in Formula 1,

R9 내지 R16은 각각 독립적으로, R1 내지 R6의 기재와 동일하며,R 9 to R 16 are each independently R 1 To the same as the description of R 6 ,

R21 및 R22는 각각 독립적으로 수소; 직쇄상 또는 분지상의 (C1-C60)알킬; (C6-C60)아릴; (C6-C60)알콕시아릴; (C1-C60)알킬티오(C6-C60)아릴; 아미노(C6-C60)아릴; 또는 (C1-C60)알킬실릴(C6-C60)아릴이다.R 21 and R 22 are each independently hydrogen; Linear or branched (C 1 -C 60 ) alkyl; (C 6 -C 60 ) aryl; (C 6 -C 60 ) alkoxyaryl; (C 1 -C 60 ) alkylthio (C 6 -C 60 ) aryl; Amino (C 6 -C 60 ) aryl; Or (C 1 -C 60 ) alkylsilyl (C 6 -C 60 ) aryl.

한편, 상기 R1 내지 R6의 구체적인 예로는, 수소, 클로로, 플루오르, 아다만틸, 카복실산, 나이트로, 하이드록시, 시아노, 메틸, 에틸, n-프로필, n-부틸, t-부틸, n-펜틸, n-헥실, n-헵틸, n-옥틸, 2-에틸헥실, n-노닐, 데실, 도데실, 헥사데실, 벤질, 트리플루오르메틸, 퍼플루오르에틸, 트리플루오르에틸, 퍼플루오르프로필, 퍼플루오르부틸, 메톡시, 에톡시, n-프로폭시, i-프로폭시, n-부톡시, i-부톡시, t-부톡시, n-펜톡시, i-펜톡시, n-헥실옥시, n-헵톡시, 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 시클로헵틸, 시클로옥틸, 시클로노닐, 시클로데실, 모폴리노, 티오모폴리노, 페닐, 나프틸, 비페닐, 9,9-디메틸플루오레닐, 9,9-디페닐플루오레닐, 페난트릴, 안트릴, 플루오란텐일, 트리페닐렌일, 피렌일, 크라이세닐, 나프타세닐, 페릴렌일, 스피로바이플루오레닐, 피리딜, 피롤릴, 퓨란일, 티오펜일, 이미다졸릴, 벤조이미다졸릴, 피라진일, 피리미딘일, 피리다진일, 퀴놀릴, 트리아진일, 벤조퓨란일, 벤조티오펜일, 피라졸릴, 인돌릴, 카바졸릴, 티아졸릴, 옥사졸릴, 벤조티아졸릴, 벤조옥사졸릴, 페난트롤린일, 트리메틸실릴, 트리에틸실릴, 트리프로필실릴, 트리(t-부틸)실릴, t-부틸디메틸실릴, 디메틸페닐실릴, 트리페닐실릴, 바이시클로[2.2.1]헵틸, 바이시클로[2.2.2]옥틸, 바이시클로[3.2.1]옥틸, 바이시클로[5.2.0]노닐, 바이시클로[4.2.2]데실, 바이시클로[2.2.2]옥틸, 4-펜틸바이시클로[2.2.2]옥틸, 에테닐, 페닐에테닐, 에티닐, 페닐에티닐, 디메틸아미노, 디페닐아미노, 모노메틸아미노, 모노페닐아미노, 페닐옥시, 페닐티오, 메톡시카보닐, 에톡시카보닐, t-부톡시카보닐, 메틸카보닐, 에틸카보닐, 벤질카보닐 또는 페닐카보닐 등을 들 수 있다. 상기 R1 내지 R6은 서로 같거나 다를 수 있고, 각각 독립적이다.Meanwhile, specific examples of R 1 to R 6 include hydrogen, chloro, fluorine, adamantyl, carboxylic acid, nitro, hydroxy, cyano, methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, benzyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl , Perfluorobutyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i-pentoxy, n-hexyl jade C, n-heptoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, morpholino, thiomorpholino, phenyl, naphthyl, biphenyl, 9, 9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenanthryl, anthryl, fluoranthenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, peryleneyl, spirobifluor Renyl, pyridyl, pyrrolyl, furanyl, thiophenyl, imidazolyl, benzoimidazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, triazinyl, benzofuranyl, benzothiophenyl, Pyrazolyl, indolyl, carbazolyl, thiazolyl, oxazolyl, benzothiazolyl, benzooxazolyl, phenanthrolinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tri (t-butyl) silyl, t-butyldimethyl Silyl, dimethylphenylsilyl, triphenylsilyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, bicyclo [3.2.1] octyl, bicyclo [5.2.0] nonyl, bicyclo [4.2 .2] decyl, bicyclo [2.2.2] octyl, 4-pentylbicyclo [2.2.2] octyl, ethenyl, phenylethenyl, ethynyl, phenylethynyl, dimethylamino, diphenylamino, monomethylamino , Monophenylamino, phenyloxy, phenylthio, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, methylcarbonyl, ethylcarbonyl, benzylcarbonyl or phenyl And carbonyl may be mentioned. R 1 to R 6 may be the same as or different from each other, and each independently.

상기 Ar1에 대한 구체적인 예로서는, 치환 또는 비치환된 페닐, 치환 또는 비치환된 나프탈렌, 치환 또는 비치환된 페난트렌, 안트라센, 파이렌, 트리페닐렌, 테트라센, 크리센 등이 있다. 상기 Ar1은 그 임의의 탄소위치 2 이상에서 -(X)n-으로 포함하는 고리의 원소와 결합하여 융합고리를 형성할 수 있다.Specific examples of Ar 1 include substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthrene, anthracene, pyrene, triphenylene, tetracene, chrysene and the like. Ar 1 may form a fused ring by combining with an element of a ring including-(X) n -at an arbitrary carbon position of 2 or more.

한편, 치환체 A 는 수소와 할로겐 원자일 수 없다는 점을 제외하고는, R1 와 R6와 동일할 수 있다. 다만, 상기 치환체 A는 추가적으로

Figure pat00020
형태의 치환체일 수 있다. 이때, Ar3는 치환 또는 비치환된 (C1-C60)알킬렌옥시; 치환 또는 비치환된 (C1-C60)알킬렌티오; 치환 또는 비치환된 (C6-C60)아릴렌옥시; (C6-C60)아릴렌티오; 치환 또는 비치환된 (C6-C60)아릴렌; 또는 (C3-C60)헤테로아릴렌이고, R7은 R1 내지 R6은와 동일하다. On the other hand, substituent A may be the same as R 1 and R 6 , except that it may not be hydrogen and a halogen atom. However, the substituent A is additionally
Figure pat00020
It may be a substituent in the form. In this case, Ar 3 is a substituted or unsubstituted (C 1 -C 60 ) alkyleneoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylenethio; Substituted or unsubstituted (C 6 -C 60 ) aryleneoxy; (C 6 -C 60 ) arylenethio; Substituted or unsubstituted (C 6 -C 60 ) arylene; Or (C 3 -C 60 ) heteroarylene, R 7 is the same as R 1 to R 6 are.

상기 치환체 A의 구체적인 예는 하기와 같을 수 있으나, 이에 한정되는 것은 아니다.Specific examples of the substituent A may be as follows, but are not limited thereto.

Figure pat00021
Figure pat00021

Figure pat00022
Figure pat00022

한편, 상기 화학식 1로 표시되는 화합물과 관련된 치환기가 치환될 경우, 서로 같거나 다르고, 각각 독립적으로, 할로겐, (C1-C60)알킬, (C6-C60)아릴, (C2-C60)헤테로아릴, N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬, (C3-C60)시클로알킬, 트리(C1-C60)알킬실릴, 디(C1-C60)알킬(C6-C60)아릴실릴, 트리(C6-C60)아릴실릴, 아다만틸, (C7-C60)바이시클로알킬, (C2-C60)알케닐, (C2-C60)알키닐, (C1-C60)알콕시, 시아노, (C1-C60)알킬아미노, (C6-C60)아릴아미노, (C6-C60)아르(C1-C60)알킬, (C6-C60)아릴옥시, (C1-C60)알킬티오, (C6-C60)아릴티오, (C1-C60)알콕시카보닐, (C1-C60)알킬카보닐, (C6-C60)아릴카보닐, 카복실산, 나이트로 또는 하이드록시로 치환될 수 있다. 각각의 치환기는 서로 동일하거나 상이할 수 있다. Meanwhile, when the substituents associated with the compound represented by Formula 1 are substituted, they are the same as or different from each other, and each independently, halogen, (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryl, (C 2- C 60 ) 5 or 6 membered heterocycloalkyl containing one or two or more selected from heteroaryl, N, O, S and Si, (C 3 -C 60 ) cycloalkyl, tri (C 1 -C 60 ) alkylsilyl, di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl, tri (C 6 -C 60 ) arylsilyl, adamantyl, (C 7 -C 60 ) bicycloalkyl, (C 2 -C 60 ) alkenyl, (C 2 -C 60 ) alkynyl, (C 1 -C 60 ) alkoxy, cyano, (C 1 -C 60 ) alkylamino, (C 6 -C 60 ) aryl Amino, (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryloxy, (C 1 -C 60 ) alkylthio, (C 6 -C 60 ) arylthio, ( C 1 -C 60 ) alkoxycarbonyl, (C 1 -C 60 ) alkylcarbonyl, (C 6 -C 60 ) arylcarbonyl, carboxylic acid, nitro or hydroxy. Each substituent may be the same or different from one another.

상기 화학식 1로 표시되는 화합물의 보다 구체적인 예는 하기와 같을 수 있으나, 이에 한정되는 것은 아니다.More specific examples of the compound represented by Formula 1 may be as follows, but are not limited thereto.

Figure pat00023
Figure pat00023

Figure pat00024
Figure pat00024

Figure pat00025
Figure pat00025

Figure pat00026
Figure pat00026

Figure pat00027
Figure pat00027

Figure pat00028
Figure pat00028

Figure pat00029
Figure pat00029

Figure pat00030
Figure pat00030

Figure pat00031
Figure pat00031

Figure pat00032
Figure pat00032

Figure pat00033
Figure pat00033

Figure pat00034
Figure pat00034

Figure pat00035
Figure pat00035

Figure pat00036
Figure pat00036

Figure pat00037
Figure pat00037

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

Figure pat00040
Figure pat00040

Figure pat00041
Figure pat00041

한편, 본 발명에 있어서, 알킬, 알콕시 및 그 밖의 알킬관련 치환체는 직쇄 또는 분지쇄 형태를 의미한다.On the other hand, in the present invention, alkyl, alkoxy and other alkyl-related substituents mean a straight or branched chain form.

본 발명에서, 아릴은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7, 바람직하게는 5 또는 6의 고리원자를 포함하는 단일 또는 융합고리계를 포함한다. 구체적인 예로는 페닐, 나프틸, 비페닐, 아트릴, 테트라히드로나프틸, 인다닐(indanyl), 플루오레닐, 페난트릴, 트라이페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등을 포함할 수 있다. 하지만, 이에 한정되지는 않는다.In the present invention, aryl is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and includes a single or fused ring system each ring containing 4 to 7, preferably 5 or 6 ring atoms, suitably. do. Specific examples include phenyl, naphthyl, biphenyl, atryl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthenyl, fluorane Tenyl and the like. However, the present invention is not limited thereto.

본 발명에서, 헤테로아릴은 방향족 고리 골격 원자로서 N, O, S 및 Si로부터 선택되는 1종 또는 2종 이상의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴그룹을 의미하는 것으로서, 5 또는 6원의 단환 헤테로아릴, 및 하나 이상의 벤젠환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 상기 헤테로아릴기는 고리내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적인 예로 퓨릴, 티오펜일, 피롤릴, 피란일, 이미다졸릴, 피라졸리, 티아졸리, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아지일, 테트라진일, 트리아졸릴, 테테르졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴놀리진일, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드 이들의 4차 염 등을 포함하지만, 이에 한정되지는 않는다.In the present invention, heteroaryl means an aryl group containing one or two or more heteroatoms selected from N, O, S, and Si as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon, 5 or 6-membered monocyclic heteroaryl and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazoli, thiazoli, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tri Monocyclic heteroaryl such as aziyl, tetrazinyl, triazolyl, terterzolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, isobenzofuranyl, benzoimidazolyl, benzo Thiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazole, quinolyl, isoquinolyl, cinolinyl, quinazolinyl, quinolizinyl, Polycyclic heteroaryls such as quinoxalinyl, carbazolyl, phenantridinyl, benzodioxolyl, and their corresponding N-oxides quaternary salts thereof, and the like.

상기 기술된 본 발명의 화합물은 열안정성이 뛰어나므로 수명이 길고, 발광효율 및 색좌표가 우수하다는 특성을 갖는다. 특히, 본 발명의 화합물은 청색, 녹색 형광용 재료로 적합하다.
The compound of the present invention described above has a property of long life, excellent luminous efficiency and color coordinate because of excellent thermal stability. In particular, the compound of the present invention is suitable as a blue, green fluorescent material.

Ⅱ. Ⅱ. 유기전계발광소자Organic electroluminescent device

본 발명은 또한 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고 상기 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 유기전계발광소자를 제공한다.The invention also provides a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1.

상기 유기막은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택되는 1종 또는 2종 이상이고, 정공주입층, 정공수송층 및 발광층으로 이루어진 군에서 선택되는 1종 또는 2종 이상인 것이 바람직하다. 왜냐하면, 상기 화학식 1의 화합물이 정공주입 및 정공전달 특성이 우수하여 정공주입층 또는 정공수송층 재료로 유용하기 때문이다. 그중에서도 정공전달 특성이 우수하여, 정공수송층 재료로 보다 유용하다. 또한, 상기 화학식 1의 화합물은 발광층에서 도펀트로 에너지를 전달하는 특성이 우수하여 청색, 녹색, 적색 형광 및 인광 소자의 호스트 재료로 유용하다. 상기 화학식 1의 화합물은 인광 소자 보다는 형광 소자의 호스트 재료로 보다 유용하다.The organic layer is one or two or more selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, one or two selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer. It is preferable that it is a species or more. This is because the compound of Formula 1 is useful as a hole injection layer or a hole transport layer material due to its excellent hole injection and hole transport characteristics. Among them, it is excellent in hole transport characteristics, which is more useful as a hole transport layer material. In addition, the compound of Formula 1 is excellent as a property of transferring energy to the dopant in the light emitting layer is useful as a host material of blue, green, red fluorescent and phosphorescent devices. The compound of Formula 1 is more useful as a host material of a fluorescent device than a phosphorescent device.

한편, 상기 유기막은 화학식 1의 화합물 이외에, 하기 화학식 14로 표시되는 화합물, 하기 화학식 15로 표시되는 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 1종을 추가로 포함할 수 있다.Meanwhile, the organic film may further include one selected from the group consisting of a compound represented by the following Formula 14, a compound represented by the following Formula 15, and a mixture thereof in addition to the compound of Formula 1.

<화학식 14> <화학식 15><Formula 14> <Formula 15>

Figure pat00042
Figure pat00043
Figure pat00042
Figure pat00043

상기 화학식 14 및 화학식 15에서, In Formula 14 and Formula 15,

Ar5는 (C6-C60)아릴 또는 (C4-C60)헤테로아릴이며,Ar 5 is (C 6 -C 60 ) aryl or (C 4 -C 60 ) heteroaryl,

Ar6 및 Ar7는 서로 같거나 다를 수 있고, 각각 독립적으로, 치환 또는 비치환된 (C6-C60)아릴, 치환 또는 비치환된 (C4-C60)헤테로아릴, (C6-C60)아릴아미노, N, O 및 S로부터 선택된 하나 이상을 포함하는 5원 내지 6원의 헤테로시클로알킬 또는 치환 또는 비치환된 (C3-C60)시클로알킬이며, 상기 Ar6 및 Ar7는 융합고리를 포함하거나 포함하지 않는 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있으며, Ar 6 and Ar 7 may be the same as or different from each other, and each independently, substituted or unsubstituted (C 6 -C 60 ) aryl, substituted or unsubstituted (C 4 -C 60 ) heteroaryl, (C 6- C 60 ) arylamino, N, O and S 5 to 6 membered heterocycloalkyl or substituted or unsubstituted (C 3 -C 60 ) cycloalkyl containing at least one selected from Ar 6 and Ar 7 May form an alicyclic ring, a monocyclic or polycyclic aromatic ring with or without a fused ring,

Ar8는 서로 독립적으로, (C6-C60)아릴렌 또는 (C4-C60)헤테로아릴렌이고, 상기 Ar8은 융합고리를 포함하거나 포함하지 않는 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있으며,Ar 8 is independently of each other, (C 6 -C 60 ) arylene or (C 4 -C 60 ) heteroarylene, wherein Ar 8 is an alicyclic, monocyclic or polycyclic ring containing or without a fused ring Can form an aromatic ring,

a는 1 내지 4이고, b는 1 내지 4이고, c는 0 내지 1이다.
a is 1-4, b is 1-4, c is 0-1.

상기 화학식 14 및 15의 예로는 하기와 같은 화합물을 들 수 있으나, 이에 한정되는 것은 아니다.Examples of Chemical Formulas 14 and 15 include the following compounds, but are not limited thereto.

Figure pat00044
Figure pat00044

상기 유기막은 또한 상기 화합물들 이외에 아릴아민계 화합물, 스티릴아릴아민계 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 1종을 추가로 포함할 수 있다.The organic layer may further include one selected from the group consisting of arylamine compounds, styrylarylamine compounds, and mixtures thereof in addition to the compounds.

또한 상기 유기막은 상기 화합물들 이외에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 추가로 포함할 수 있다.
In addition, the organic layer may further include one or two or more selected from the group consisting of Group 1, Group 2, 4 cycle, 5 cycle transition metals, lanthanide series metals and organic metals of d-transition elements in addition to the compounds. Can be.

본 발명의 유기전계발광소자를 보다 상세하게 살펴보면, 상기 화학식 1의 화합물을 함유하는 유기막은 정공주입층, 정공수송층 또는 발광층일 수 있고, 정공주입 및 정공수송 기능을 동시에 갖는 단일막일 수 있다. 또는 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함한 유기막은 발광층일 수도 있다. 이때, 상기 화학식 1로 표시되는 화합물은 청색, 녹색 또는 적색의 형광 또는 인광 재료의 호스트 재료로서 사용될 수 있다. 더욱 바람직하게는, 청색의 형광 호스트 재료로 사용되는 것이다.Looking at the organic electroluminescent device of the present invention in more detail, the organic film containing the compound of Formula 1 may be a hole injection layer, a hole transport layer or a light emitting layer, it may be a single film having a hole injection and hole transport function at the same time. Alternatively, the organic layer including the heterocyclic compound represented by Formula 1 may be a light emitting layer. In this case, the compound represented by Chemical Formula 1 may be used as a host material of blue, green, or red fluorescent or phosphorescent materials. More preferably, it is used as a blue fluorescent host material.

바람직하게는 상기 화학식 1로 표시되는 화합물을 포함한 유기막은 정공주입층 또는 정공수송층이다. 전술한 바와 같은 유기전계발광소자는 필요에 따라, 정공주입층, 정공수송층, 전자저지층, 발광층, 정공저지층, 전자수송층 및 전자주입층 중 하나 이상의 층을 더 구비할 수 있고, 필요에 따라 상기 유기층들을 2층의 유기층으로 형성하는 것도 가능하다.Preferably, the organic film including the compound represented by Chemical Formula 1 is a hole injection layer or a hole transport layer. As described above, the organic light emitting device may further include one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, as necessary. It is also possible to form the organic layers as two organic layers.

예를 들어, 본 발명을 따르는 유기전계발광소자는 제 1 전극/정공주입층/발광층/제 2 전극, 제 1 전극/정공주입층/정공수송층/발광층/전자수송층/제 2 전극 또는 제 1 전극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/제 2 전극 구조를 가질 수 있다. 또는 상기 유기전계발광소자는 제 1 전극/정공주입 기능 및 정공수송 기능을 동시에 갖는 단일막/발광층/전자수송층/제 2 전극 또는 제 1 전극/정공주입 기능 및 정공 수송 기능을 동시에 갖는 단일막/발광층/전자수송층/전자주입층/제 2 전극 구조를 가질 수 있다.For example, the organic light emitting display device according to the present invention may include a first electrode / hole injection layer / light emitting layer / second electrode, first electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / second electrode or first electrode. It may have a hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode structure. Alternatively, the organic light emitting display device may have a single film / light emitting layer / electron transport layer / second electrode or a first electrode / hole injection function and a hole transport function and a single film / having a hole transport function. It may have a light emitting layer / electron transport layer / electron injection layer / second electrode structure.

본 발명에 따르는 유기전계발광소자는 전면 발광형, 배면 발광형 등 다양한 구조로 적용 가능하다.The organic light emitting display device according to the present invention can be applied in various structures such as a top emission type and a bottom emission type.

본 발명에 따르는 유기전계발광소자의 제조방법은 하기와 같다.The manufacturing method of the organic light emitting device according to the present invention is as follows.

먼저 기판 상부에 높은 일함수를 갖는 제 1 전극용 물질을 증착법 또는 스퍼터링법 등에 의해 형성하여 제 1 전극을 형성한다. 상기 제 1 전극은 애노드(Anode) 또는 캐소드(cathode)일 수 있다. 여기에서 기판으로는 통상적인 유기전계발광소자에서 사용되는 기판을 사용하는데 기계적 강도, 열적 안정성, 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판이 바람직하다. 제 1 전극용 물질로는 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO), Al, Ag, Mg 등을 이용할 수 있으며, 투명 전극 또는 반사 전극으로 형성될 수 있다.First, the first electrode material having a high work function on the substrate is formed by vapor deposition, sputtering, or the like to form the first electrode. The first electrode may be an anode or a cathode. Herein, a substrate used in a conventional organic electroluminescent device is used, but a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the first electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), Al, Ag, Mg and the like having excellent conductivity may be used. Or a reflective electrode.

다음으로, 상기 제 1 전극 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 정공주입층(HIL)을 형성할 수 있다.Next, a hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

진공증착법에 의하여 정공주입층을 형성하는 경우, 그 증착 조건은 정공주입층의 재료로서 사용하는 화합물, 목적으로 하는 정공주입층의 구조 및 열적 특성 등에 따라 다르지만, 일반적으로 증착온도 100 내지 500℃, 진공도 10-8 내지 10-3torr, 증착속도 0.01 내지 100Å/sec, 막 두께는 통상 10Å 내지 5㎛ 범위에서 적절히 선택하는 것이 바람직하다.In the case of forming the hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the hole injection layer, and the like. It is preferable that a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 mW / sec, and a film thickness are usually appropriately selected in the range of 10 mV to 5 m.

스핀코팅법에 의하여 정공주입층을 형성하는 경우, 그 코팅 조건은 정공주입층의 재료로서 사용하는 화합물, 목적하는 하는 정공주입층의 구조 및 열적 특성에 따라 상이하지만, 약 2000rpm 내지 5000rpm의 코팅 속도, 코팅 후 용매 제거를 위한 열처리 온도는 약 80℃ 내지 200℃의 온도 범위에서 적절히 선택하는 것이 바람직하다.When the hole injection layer is formed by the spin coating method, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal properties of the desired hole injection layer, but the coating speed is preferably from about 2000 rpm to 5000 rpm , And the heat treatment temperature for removing the solvent after coating is suitably selected within a temperature range of about 80 캜 to 200 캜.

상기 정공주입층 물질로는 전술한 바와 같은 화학식 1로 표시되는 화합물을 이용하거나, 공지된 정공주입층 물질을 사용할 수도 있는데, 예를 들면, 미국특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 Advanced Material, 6, p.677(1994)에 기재되어 있는 스타버스트형 아민 유도체류인 TCTA, m-MTDATA, m-MTDAPB, 용해성이 있는 전도성 고분자인 Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: 폴리아닐린/도데실벤젠술폰산) 또는 PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate):폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)), Pani/CSA (Polyaniline/Camphor sulfonic acid:폴리아닐린/캠퍼술폰산) 또는 PANI/PSS (Polyaniline)/Poly (4-styrene-sulfonate):폴리아닐린)/폴리(4-스티렌술포네이트)) 등을 사용할 수 있다.As the hole injection layer material, a compound represented by Chemical Formula 1 as described above may be used, or a known hole injection layer material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or TCTA, m-MTDATA, m-MTDAPB, starburst amine derivatives described in Advanced Material, 6, p.677 (1994), and Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodec) Silbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline) / Poly (4-styrene-sulfonate): polyaniline) / poly (4-styrenesulfonate)).

상기 정공주입층의 두께는 약 100Å 내지 10000Å 바람직하게는 100Å 내지 1000Å일 수 있다. 상기 정공주입층의 두께가 100Å 미만인 경우, 정공주입 특성이 저하될 수 있으며, 상기 정공주입층의 두께가 10000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The hole injection layer may have a thickness of about 100 kPa to 10000 kPa, preferably 100 kPa to 1000 kPa. If the thickness of the hole injection layer is less than 100 angstroms, the hole injection characteristics may be degraded. If the thickness of the hole injection layer exceeds 10000 angstroms, the driving voltage may increase.

다음으로 상기 정공주입층 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 정공수송층(HTL)을 형성할 수 있다. 진공증착법 및 스핀팅법에 의하여 정공수송층을 형성하는 경우, 그 증착조건 및 코팅조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.Next, a hole transport layer (HTL) may be formed on the hole injection layer by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

상기 정공수송층 물질은 전술한 바와 같은 화학식 1로 표시되는 화합물이거나 공지된 정공수송층 물질을 이용할 수도 있는데, 예를 들면, N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, 4,4'-비스[N-(1-나프틸)-N-페닐아미노]비페닐(NPB), N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N,N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상적인 아민 유도체 등이 사용된 주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.The hole transport layer material may be a compound represented by Formula 1 as described above or a known hole transport layer material. For example, carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, 4,4 ' -Bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl ] 4,4'-diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD), and other conventional amine derivatives having aromatic condensed rings And the like are selected from a range of conditions almost identical to the formation of the injection layer used.

상기 전자주입층의 두께는 약 1Å 내지 100Å 바람직하게는 5Å 내지 90Å일 수 있다. 상기 전자주입층의 두께가 1Å 미만인 경우, 전자주입 특성이 저하될 수 있으며, 상기 전자주입층의 두께가 100Å 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The electron injection layer may have a thickness of about 1 kPa to 100 kPa, preferably 5 kPa to 90 kPa. This is because, when the thickness of the electron injection layer is less than 1 kW, the electron injection characteristic may be degraded. When the thickness of the electron injection layer is more than 100 kW, the driving voltage may increase.

마지막으로 전자주입층 상부에 진공증착법이나 스퍼터링법 등의 방법을 이용하여 제 2 전극을 형성할 수 있다. 상기 제 2 전극은 캐소드 또는 애노드로 사용될 수 있다. 상기 제 2 전극 형성용 물질로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로서는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag)등을 들 수 있다. 또한, 전면 발광 장치를 얻기 위하여 ITO, IZO를 사용한 투명 캐소드를 사용할 수도 있다.Finally, the second electrode may be formed on the electron injection layer by using a method such as vacuum deposition or sputtering. The second electrode may be used as a cathode or an anode. As the material for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . In addition, a transparent cathode using ITO and IZO may be used to obtain a top light emitting device.

본 발명을 따르는 유기전계발광소자는 다양한 형태의 평판 표시 장치, 예를 들면 수동 매트릭스 유기 발광 표시 장치 및 능동 매트릭스 유기 발광 표시 장치에 구비될 수 있다. 특히, 능동 매트릭스 유기 발광 표시 장치에 구비되는 경우, 기판 측에 구비된 제 1 전극은 화소 전극으로서 박막 트랜지스터의 소스 전극 또는 드레인 전극과 전기적으로 연결될 수 있다. 또한, 상기 유기전계발광소자는 양면으로 화면을 표시할 수 있는 평판 표시 장치에 구비될 수 있다.The organic light emitting display device according to the present invention may be provided in various types of flat panel display devices, for example, passive matrix organic light emitting display devices and active matrix organic light emitting display devices. In particular, when provided in the active matrix organic light emitting display device, the first electrode provided on the substrate side may be electrically connected to the source electrode or the drain electrode of the thin film transistor as the pixel electrode. In addition, the organic light emitting display device may be provided in a flat panel display that can display a screen on both sides.

본 발명의 유기전계발광소자는 수명이 길고 발광효율이 우수하고, 색순도가 높다.The organic electroluminescent device of the present invention has a long lifetime, excellent luminous efficiency, and high color purity.

Ⅲ. 태양전지Ⅲ. Solar cell

본 발명은 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고 상기 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 태양전지를 제공한다.The present invention relates to a plasma display panel comprising a first electrode; A second electrode; And an organic film disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1.

상기 화학식 1의 화합물은 정공주입 특성 및 정공전달 특성이 우수한 정공수송층 재료로서 유용하다. 화학식 1의 화합물을 함유하는 유기막은 본 발명의 태양전지에서 정공주입층, 정공수송층일 수 있고, 정공주입 및 정공수송 기능을 동시에 갖는 단일막일 수 있다. 바람직하게는 상기 화학식 1로 표시되는 화합물을 포함한 유기막은 정공주입층 또는 정공수송층이다.The compound of Formula 1 is useful as a hole transport layer material having excellent hole injection characteristics and hole transfer characteristics. The organic film containing the compound of Formula 1 may be a hole injection layer, a hole transport layer in the solar cell of the present invention, and may be a single film having both hole injection and hole transport functions. Preferably, the organic film including the compound represented by Chemical Formula 1 is a hole injection layer or a hole transport layer.

본 발명의 태양전지는 필요에 따라, 정공주입층, 정공수송층, 전자저지층, 버퍼층, 정공저지층, 전자수송층 및 전자주입층 중 하나 이상의 층을 더 구비할 수 있고, 필요에 따라 상기 유기층들을 2층의 유기층으로 형성하는 것도 가능하다.
The solar cell of the present invention may further include one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, a hole blocking layer, an electron transport layer and an electron injection layer, if necessary, the organic layers It is also possible to form with two organic layers.

이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. Hereinafter, the present invention will be described in more detail with reference to Examples.

본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다. This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

<실시예><Examples>

합성예Synthetic example 1: 화합물 1의 제조 1: Preparation of compound 1

하기 반응식 1의 반응 경로를 거쳐 화합물 1을 합성하였다.Compound 1 was synthesized through the reaction route of Scheme 1 below.

<반응식 1><Reaction Scheme 1>

Figure pat00045
Figure pat00045

(1) 화합물 1-1의 제조 (1) Preparation of Compound 1-1

9-브로모안트라센 10g(39㏖), 2-포밀페닐보론산 7g(47m㏖), Pd(PPh3)4 4.5g(3.9m㏖) 및 K2CO3 10.5g(76m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 1-1 8g(73%)을 수득하였다.9-bromoanthracene 10 g (39 mol), 2-formylphenylboronic acid 7 g (47 mmol), Pd (PPh 3 ) 4 4.5 g (3.9 mmol) and K 2 CO 3 10.5 g (76 mmol) was dissolved in toluene / ethanol / distilled water 200ml / 50ml / 40ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 8 g (73%) of the title compound 1-1.

(2) 화합물 1-2의 제조(2) Preparation of Compound 1-2

IPy2BF4 21g(56m㏖)을 디클로로메탄에 녹인 후 -78℃로 냉각하였다. HBF4 18.2g(112m㏖)을 가한 뒤 10분 동안 -78℃에서 교반하였다. 고체를 여과 후 여액을 -60?로 냉각한 뒤, 화합물 1-1 8g(28m㏖)을 천천히 첨가하였다. 반응이 완결되면 얼음물로 반응종결 후 유기물을 추출하였다. 유기물을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 1-2 4.7g(60%)을 수득하였다.IPy 2 BF 4 21 g (56 mmol) was dissolved in dichloromethane and cooled to -78 ° C. 18.2 g (112 mmol) of HBF 4 was added and stirred at −78 ° C. for 10 minutes. After the solid was filtered, the filtrate was cooled to -60 ° C, and 8 g (28 mmol) of Compound 1-1 was slowly added. When the reaction was completed, the reaction was completed with ice water and the organics were extracted. The organics were dried over MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.7 g (60%) of the title compound 1-2.

(3) 화합물 1-3의 제조(3) Preparation of Compound 1-3

화합물 1-2 4.7g(17m㏖)을 다이에틸에테르 100㎖에 녹이고, AlCl3 2.7g(20.4m㏖)을 천천히 첨가하였다. 이를 15분 동안 교반한 후, 0℃로 냉각하고 리튬알루미늄하이드라이드(LAH) 1g(26m㏖)를 천천히 첨가하였다. 이를 1시간 동안 환류 교반한 후 반응이 완결되면 상온으로 천천히 냉각하고, 여기에 EA를 거품이 일어나지 않을 때까지 천천히 넣어주었다. 그 후, 6N HCl 20㎖을 넣어주고, 증류수와 에틸아세테이트로 추출하였다. 유기물을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디틀로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 화합물 1-3.4g(90%)을 수득하였다.4.7 g (17 mmol) of Compound 1-2 were dissolved in 100 mL of diethyl ether, and 2.7 g (20.4 mmol) of AlCl 3 was slowly added. After stirring for 15 minutes, it was cooled to 0 ° C and slowly added 1 g (26 mmol) of lithium aluminum hydride (LAH). After stirring for 1 hour under reflux, the reaction was slowly cooled to room temperature when the reaction was completed, and EA was slowly added thereto until no foaming occurred. Then, 20 ml of 6N HCl was added thereto, and extracted with distilled water and ethyl acetate. The organics were dried over MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain compound 1-3.4 g (90%).

(4) 화합물 1-4의 제조(4) Preparation of Compound 1-4

화합물 1-3 4g(15m㏖)을 DMSO 40㎖에 녹인 다음, 상온에서 소듐 tert-부톡사이드 10.7g(112m㏖)를 넣어주고 70℃에서 15분 동안 교반하였다. 이에 요오드화 메틸 19g(132m㏖)을 천천히 첨가하고 1시간 동안 더 교반하였다. 반응이 완결되면 상온에서 냉각하고 증류수를 넣어 20분간 교반하였다. 이때 고체가 생성되는데 이를 여과하고, 얻어진 고체를 에탄올과 아세톤으로 재결정하여 목적 화합물 1-4 2.6g(60%)을 수득하였다.4 g (15 mmol) of Compound 1-3 was dissolved in 40 mL of DMSO, and then added 10.7 g (112 mmol) of sodium tert-butoxide at room temperature, followed by stirring at 70 ° C. for 15 minutes. To this was slowly added 19 g (132 mmol) of methyl iodide and further stirred for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added and stirred for 20 minutes. At this time, a solid was formed, which was filtered and the obtained solid was recrystallized from ethanol and acetone to obtain 2.6 g (60%) of the title compound 1-4.

(5) 화합물 1-5의 제조(5) Preparation of Compound 1-5

화합물 1-4 2.6g(8.8m㏖)을 DMF 30㎖에 녹이고, N-브로모숙신이미드 1.6g(8.8m㏖)을 천천히 첨가하였다. 이를 상온에서 하루 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기물을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼 크로마토그래피로 정제하여 목적 화합물 1-5 2.6g(80%)을 수득하였다.2.6 g (8.8 mmol) of Compound 1-4 were dissolved in 30 mL of DMF, and 1.6 g (8.8 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organics were dried over MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 2.6 g (80%) of the title compound 1-5.

(6) 화합물 1의 제조(6) Preparation of Compound 1

화합물 1-5 10g(26.8m㏖), 페닐보론산 3.9g(32m㏖), Pd(PPh3)4 4.5g(3.1m㏖) 및 K2CO3 7.4g(53.6m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 최종 화합물인 화합물 1, 8.4g(85%)을 수득하였다.10 g (26.8 mmol) of Compound 1-5, 3.9 g (32 mmol) of phenylboronic acid, 4.5 g (3.1 mmol) of Pd (PPh 3 ) 4 and 7.4 g (53.6 mmol) of K 2 CO 3 were dissolved in toluene / ethanol. It was dissolved in distilled water 200ml / 50ml / 40ml and stirred at 100 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 8.4 g (85%) of the final compound 1.

합성예Synthetic example 2: 화합물 42의 제조 2: Preparation of Compound 42

하기 반응식 2의 반응 경로를 거쳐 화합물 42를 합성하였다.Compound 42 was synthesized through the reaction route of Scheme 2 below.

<반응식 2><Reaction Scheme 2>

Figure pat00046
Figure pat00046

(1) 화합물 2-1의 제조(1) Preparation of Compound 2-1

화합물 1-5 10g(26.8m㏖), 4-브로모페닐보론산 6.4g(32m㏖), Pd(PPh3)4 4.5g(2.7m㏖) 및 K2CO3 7.4g(53.6m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 2-1 10.7g(80%)을 수득하였다.10 g (26.8 mmol) of Compound 1-5, 6.4 g (32 mmol) of 4-bromophenylboronic acid, 4.5 g (2.7 mmol) of Pd (PPh 3 ) 4 and 7.4 g (53.6 mmol) of K 2 CO 3 Was dissolved in toluene / ethanol / distilled water 200ml / 50ml / 40ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 10.7 g (80%) of the title compound 2-1.

(2) 화합물 42의 제조(2) Preparation of Compound 42

화합물 2-1 5g(11.1m㏖), 9,9-디메틸플루오렌-2-보론산보론산 3.2g (13.3m㏖), Pd(PPh3)4 1.3g(1.1m㏖) 및 K2CO3 3.1g(22.2m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 최종 화합물인 화합물 42, 5g(80%)을 수득하였다.Compound 2-1 5 g (11.1 mmol), 9,9-dimethylfluorene-2-boronic acid boronic acid 3.2 g (13.3 mmol), Pd (PPh3) 4 1.3 g (1.1 mmol) and K 2 CO 3 3.1 g (22.2 mmol) was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain the final compound, Compound 42, 5g (80%).

합성예Synthetic example 3: 화합물 77의 제조 3: Preparation of Compound 77

하기 반응식 3의 반응 경로를 거쳐 화합물 77를 합성하였다.Compound 77 was synthesized through the reaction route of Scheme 3 below.

<반응식 3><Reaction Scheme 3>

Figure pat00047
Figure pat00047

(1) 화합물 3-1의 제조(1) Preparation of Compound 3-1

9-브로모안트라센 20g(78m㏖), 2-메톡시페닐보론산 14.2g(93m㏖), Pd(PPh3)4 7.8g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 3-1 20g(90%)을 수득하였다.20 g (78 mmol) of 9-bromoanthracene, 14.2 g (93 mmol) of 2-methoxyphenylboronic acid, 7.8 g (7.8 mmol) of Pd (PPh3) 4 and 21.5 g (156 mmol) of K 2 CO 3 toluene It was dissolved in 390 mL / 97 mL / 78 mL of ethanol / distilled water and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 20 g (90%) of the title compound 3-1.

(2) 화합물 3-2의 제조(2) Preparation of Compound 3-2

화합물 3-1 13g(45.7m㏖)을 디클로로메탄 130㎖에 녹인 후 0℃로 냉각하였다. 여기에 보론트리브로마이드 92㎖(92m㏖)를 천천히 첨가하였다. 온도를 상온으로 가온한 뒤 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 톨루엔 용매 하에서 교반한 뒤 여과하여 목적 화합물 3-2 11g(89%)을 수득하였다.13 g (45.7 mmol) of Compound 3-1 was dissolved in 130 ml of dichloromethane, and then cooled to 0 ° C. 92 ml (92 mmol) of boron tribromide was added slowly here. The temperature was warmed to room temperature and then stirred. After the reaction was completed, the mixture was extracted with distilled water and dichloromethane. The organics were dried over anhydrous MgSO 4, the solvent was removed with a rotary evaporator, and then stirred under toluene solvent and filtered to obtain 11 g (89%) of the title compound 3-2.

(3) 화합물 3-3의 제조(3) Preparation of Compound 3-3

화합물 3-2 11g(40m㏖)을 디클로로메탄에 녹인 후 2,6-루티딘(2,6-lutidine) 7.1㎖(61m㏖)을 넣고 온도를 -30℃로 냉각한 뒤 교반하였다. 여기에 트리플루오로메탄설포닉 언하이드라이드 8.2㎖(49m㏖)을 천천히 첨가하였다. 온도를 0?로 가온한 뒤 1시간 동안 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 3-3 15g(93%)을 수득하였다.11 g (40 mmol) of Compound 3-2 was dissolved in dichloromethane, and 7.1 ml (61 mmol) of 2,6-lutidine was added thereto, and the temperature was cooled to −30 ° C., followed by stirring. To this was slowly added 8.2 mL (49 mmol) of trifluoromethanesulphonic anhydride. The temperature was warmed to 0? And stirred for 1 hour. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 15 g (93%) of the title compound 3-3.

(4) 화합물 3-4의 제조(4) Preparation of Compound 3-4

화합물 3-3 15g(37.3m㏖), Pd(PPh3)2Cl2 2.6g(3.7m㏖), 리튬클로라이드 4.7g(112m㏖) 및 DBU 6.7㎖(44.7m㏖)을 디메틸포름이미드 190㎖에 녹인 후 140℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적 화합물 3-4 7.5g(80%)을 수득하였다.Compound 3-3 15 g (37.3 mmol), Pd (PPh 3 ) 2 Cl 2 2.6 g (3.7 mmol), lithium chloride 4.7 g (112 mmol) and DBU 6.7 mL (44.7 mmol) were diluted with dimethylformimide 190 It was dissolved in ㎖ and stirred at 140 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 7.5 g (80%) of the title compound 3-4.

(5) 화합물 3-5의 제조(5) Preparation of Compound 3-5

화합물 3-4 7.5g(30m㏖)을 DMF 100㎖에 녹이고, N-브로모숙신이미드 5.5g(30m㏖)을 천천히 첨가하였다. 이를 상온에서 하루 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼 크로마토그래피로 정제하여 목적 화합물 3-5 7.4g(75%)을 수득하였다.7.5 g (30 mmol) of Compound 3-4 were dissolved in 100 mL of DMF, and 5.5 g (30 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organics were dried over anhydrous MgSO 4, the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 7.4 g (75%) of the title compound 3-5.

(6) 화합물 77의 제조(6) Preparation of Compound 77

화합물 3-5 5g(15m㏖), 디베조티오펜-2-닐 보론산 4.1g(18m㏖), Pd(PPh3)4 1.7g(1.5m㏖) 및 K2CO3 4.1g(30m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100?에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 최종 화합물인 화합물 77, 5.5g(85%)을 수득하였다.Compound 3-5 5 g (15 mmol), dibezothiophen-2-yl boronic acid 4.1 g (18 mmol), Pd (PPh 3 ) 4 1.7 g (1.5 mmol) and K 2 CO 3 4.1 g (30 mmol) Was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 5.5 g (85%) of the title compound 77.

합성예Synthetic example 4: 화합물 169의 제조 4: Preparation of Compound 169

하기 화학 반응식 4의 반응 경로를 거쳐 화합물 169를 합성하였다.Compound 169 was synthesized through the reaction route of Chemical Scheme 4 below.

<반응식 4><Reaction Scheme 4>

Figure pat00048
Figure pat00048

(1) 화합물 4-1의 제조(1) Preparation of Compound 4-1

9-브로모안트라센 20g(78m㏖), 2-니트로페닐보론산 15.5g(93m㏖), Pd(PPh3)4 9g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100?에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 4-1 20g(85%)을 수득하였다.20 g (78 mmol) of 9-bromoanthracene, 15.5 g (93 mmol) of 2-nitrophenylboronic acid, 9 g (7.8 mmol) of Pd (PPh 3 ) 4 and 21.5 g (156 mmol) of K 2 CO 3 are toluene / It was dissolved in 390 ml / 97 ml / 78 ml of ethanol / distilled water and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 20 g (85%) of the title compound 4-1.

(2) 화합물 4-2의 제조(2) Preparation of Compound 4-2

화합물 4-1 20g(67m㏖)을 트리에틸포스파이트 100㎖에 섞고 180℃로 4시간 교반하였다. 상온으로 냉각한 후 용매를 감압 증류하였다. 메탄올로 결정화하여 목적 화합물 4-2 12.5g(75%)을 수득하였다.20 g (67 mmol) of Compound 4-1 were mixed with 100 ml of triethyl phosphite and stirred at 180 ° C. for 4 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Crystallization with methanol gave 12.5 g (75%) of the title compound 4-2.

(3) 화합물 4-3의 제조(3) Preparation of Compound 4-3

화합물 4-2 4.7g(17.6m㏖), 구리 0.6g(8.8m㏖), 18-크라운-6 0.2g(0.9m㏖), K2CO3 4.8g(35.1m㏖) 및 1,2-디클로로벤젠 100㎖을 섞고 180℃에서 12시간 환류 교반시켰다. 상온으로 냉각시키고 감압 증류한 후 MC로 추출하고 증류수로 세척하였다. 무수 MgSO4로 건조하고 감압 증류하여 얻어진 잔사를 컬럼 분리하여 화합물 4-3 3.6(60%)을 수득하였다. 4.7 g (17.6 mmol) of compound 4-2, 0.6 g (8.8 mmol) of copper, 0.2 g (0.9 mmol) of 18-crown-6, 4.8 g (35.1 mmol) of K 2 CO 3 and 1,2- 100 ml of dichlorobenzene was mixed and stirred under reflux at 180 ° C for 12 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO 4 and distillation under reduced pressure was separated by column to obtain compound 4-3 3.6 (60%).

(4) 화합물 4-4의 제조(4) Preparation of Compound 4-4

화합물 4-3 3g(7.1m㏖)을 DMF 40㎖에 녹이고, N-브로모숙신이미드 1.3g(7.1m㏖)을 천천히 첨가하였다. 이를 상온에서 하루 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 4-4 2.7g(90%)을 수득하였다.3 g (7.1 mmol) of Compound 4-3 were dissolved in 40 mL of DMF, and 1.3 g (7.1 mmol) of N-bromosuccinimide was added slowly. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent, to obtain 2.7 g (90%) of the title compound 4-4.

(5) 화합물 169의 제조(5) Preparation of Compound 169

화합물 4-4 6.3g(15m㏖), 페닐보론산 2.2g(18m㏖), Pd(PPh3)4 1.7g (1.5m㏖) 및 K2CO3 4.1g (30m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100?에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 169, 5.5g(88%)을 수득하였다.Compound 4-4 6.3 g (15 mmol), phenylboronic acid 2.2 g (18 mmol), Pd (PPh 3 ) 4 1.7 g (1.5 mmol) and K 2 CO 3 4.1 g (30 mmol) were added to toluene / ethanol / It was dissolved in distilled water 100ml / 25ml / 20ml and stirred at 100 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 5.5 g (88%) of the title compound 169.

합성예Synthetic example 5: 화합물 225의 제조 5: Preparation of Compound 225

하기 반응식 5의 반응 경로를 거쳐 화합물 225을 합성하였다.Compound 225 was synthesized through the reaction route of Scheme 5 below.

<반응식 5><Reaction Scheme 5>

Figure pat00049
Figure pat00049

(1) 화합물 5-1의 제조(1) Preparation of Compound 5-1

9-브로모안트라센 20g(78m㏖), 2-메톡시나프탈렌보론산 18.8g(93m㏖), Pd(PPh3)4 7.8g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 5-1 23g(89%)을 수득하였다.20 g (78 mmol) of 9-bromoanthracene, 18.8 g (93 mmol) of 2-methoxynaphthalene boronic acid, 7.8 g (7.8 mmol) of Pd (PPh 3 ) 4 and 21.5 g (156 mmol) of K 2 CO 3 It was dissolved in toluene / ethanol / distilled water 390ml / 97ml / 78ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 23 g (89%) of the title compound 5-1.

(2) 화합물 5-2의 제조(2) Preparation of Compound 5-2

화합물 5-1 23g(68.8m㏖)을 디클로로메탄 230㎖에 녹인 후 0?로 냉각하였다. 여기에 보론트리브로마이드 138㎖(138m㏖)를 천천히 첨가하였다. 온도를 상온으로 가온한 뒤 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 톨루엔 용매 하에서 교반한 뒤 여과하여 목적 화합물 5-2 38g(86%)을 수득하였다.23 g (68.8 mmol) of Compound 5-1 was dissolved in 230 ml of dichloromethane, and cooled to 0 °. 138 ml (138 mmol) of boron tribromide was slowly added thereto. The temperature was warmed to room temperature and then stirred. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organics were dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and then stirred under toluene solvent and filtered to obtain 38 g (86%) of the title compound 5-2.

(3) 화합물 5-3의 제조(3) Preparation of Compound 5-3

화합물 5-2 10g(22m㏖)을 디클로로메탄에 녹인 후 2,6-lutidine 3.9㎖(33m㏖)을 넣고 온도를 -30℃로 냉각한 뒤 교반하였다. 여기에 트리플루오로메탄설포닉 안하이드라이드 4.5㎖(27m㏖)을 천천히 첨가하였다. 온도를 0℃로 가온한 뒤 한 시간 동안 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 5-3 9.4g(95%)을 수득하였다.After dissolving 10 g (22 mmol) of compound 5-2 in dichloromethane, 3.9 mL (33 mmol) of 2,6-lutidine was added thereto, the temperature was cooled to −30 ° C., and stirred. To this was slowly added 4.5 ml (27 mmol) of trifluoromethanesulphonic anhydride. The temperature was warmed to 0 ° C. and stirred for one hour. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 9.4 g (95%) of the title compound 5-3.

(4) 화합물 5-4의 제조(4) Preparation of Compound 5-4

화합물 5-3 9.4g(21m㏖), Pd(PPh3)2Cl2 2.9g(4.2m㏖), 리튬클로라이드 2.7g(63m㏖) 및 DBU 9.4㎖(63m㏖)을 디메틸포름이미드 150㎖에 녹인 후 140℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 3-4 4.7g(75%)을 수득하였다.Compound 5-3 9.4 g (21 mmol), Pd (PPh 3 ) 2 Cl 2 2.9 g (4.2 mmol), lithium chloride 2.7 g (63 mmol) and DBU 9.4 mL (63 mmol) 150 mL of dimethylformimide It was dissolved in and stirred at 140 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.7 g (75%) of the title compound 3-4.

(5) 화합물 5-5의 제조(5) Preparation of Compound 5-5

화합물 5-4 4g(13.2m㏖)을 DMF 80㎖에 녹이고, N-브로모숙신이미드 2.4g(13.2m㏖)을 천천히 첨가하였다. 이를 상온에서 하루 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 5-5 4.5g(90%)을 수득하였다.4 g (13.2 mmol) of Compound 5-4 was dissolved in 80 mL of DMF, and 2.4 g (13.2 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.5 g (90%) of the title compound 5-5.

(6) 화합물 225의 제조(6) Preparation of Compound 225

화합물 5-5 4.5g(11.8m㏖), 2-나프틸보론산 2.5g(14.2m㏖), Pd(PPh3)4 1.4g(1.2m㏖) 및 K2CO3 4.9g(35.4m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100?에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 최종 화합물인 화합물 225 4.3g(85%)을 수득하였다.4.5 g (11.8 mmol) of compound 5-5, 2.5 g (14.2 mmol) of 2-naphthylboronic acid, 1.4 g (1.2 mmol) of Pd (PPh 3 ) 4 and 4.9 g (35.4 mmol) of K 2 CO 3 ) Was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 °. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.3 g (85%) of the compound 225 as a final compound.

합성예Synthetic example 6: 화합물 287의 제조 6: Preparation of Compound 287

하기 반응식 6의 반응 경로를 거쳐 화합물 287을 합성하였다.Compound 287 was synthesized through the reaction route of Scheme 6 below.

<반응식 6><Reaction Scheme 6>

Figure pat00050
Figure pat00050

(1) 화합물 6-1의 제조(1) Preparation of Compound 6-1

화합물 9-브로모안트라센 20g(78m㏖), 1-메톡시-2-나프탈렌보론산 18.8g(93m㏖), Pd(PPh3)4 7.8g(7.8m㏖) 및 K2CO3, 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 6-1 23g(89%)을 수득하였다.20 g (78 mmol) of compound 9-bromoanthracene, 18.8 g (93 mmol) of 1-methoxy-2-naphthaleneboronic acid, 7.8 g (7.8 mmol) of Pd (PPh 3 ) 4 and 21.5 g of K 2 CO 3 (156 mmol) was dissolved in toluene / ethanol / distilled water 390ml / 97ml / 78ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent, to obtain 23 g (89%) of the title compound 6-1.

(2) 화합물 6-2의 제조(2) Preparation of Compound 6-2

화합물 6-1 23g(68.8m㏖)을 디클로로메탄 230㎖에 녹인 후 0℃로 냉각하였다. 여기에 보론트리브로마이드 138㎖(138m㏖)를 천천히 첨가하였다. 온도를 상온으로 가온한 뒤 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 톨루엔 용매하에서 교반한 뒤 여과하여 목적 화합물 6-2 38g(86%)을 수득하였다.23 g (68.8 mmol) of the compound 6-1 was dissolved in 230 ml of dichloromethane, and then cooled to 0 ° C. 138 ml (138 mmol) of boron tribromide was slowly added thereto. The temperature was warmed to room temperature and then stirred. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and then stirred in a toluene solvent and filtered to obtain 38 g (86%) of the title compound 6-2.

(3) 화합물 6-3의 제조(3) Preparation of Compound 6-3

화합물 6-2 10g(22m㏖)을 디클로로메탄에 녹인 후 2,6-루티딘(2,6-lutidine) 3.9㎖(33m㏖)을 넣고 온도를 -30℃로 냉각한 뒤 교반하였다. 여기에 트리플루오로메탄설포닉 안하이드라이드 4.5㎖(27m㏖)을 천천히 첨가하였다. 온도를 0℃로 가온한 뒤 한 시간 동안 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 6-3 9.4g(95%)을 수득하였다.After dissolving 10 g (22 mmol) of Compound 6-2 in dichloromethane, 3.9 ml (33 mmol) of 2,6-lutidine was added thereto, the temperature was cooled to -30 ° C, and the mixture was stirred. To this was slowly added 4.5 ml (27 mmol) of trifluoromethanesulphonic anhydride. The temperature was warmed to 0 ° C. and stirred for one hour. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 9.4 g (95%) of the title compound 6-3.

(4) 화합물 6-4의 제조(4) Preparation of Compound 6-4

화합물 6-3 9.4g(21m㏖), Pd(PPh3)2Cl2 2.9g(4.2m㏖), 리튬클로라이드 2.7g(63m㏖), 및 DBU 9.4㎖(63m㏖)을 디메틸포름이미드 150㎖에 녹인 후 140℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 6-4 4.7g(75%)을 수득하였다.9.4 g (21 mmol) of compound 6-3, 2.9 g (4.2 mmol) of Pd (PPh 3 ) 2 Cl 2 , 2.7 g (63 mmol) of lithium chloride, and 9.4 mL (63 mmol) of DBU were added to dimethylformimide 150. It was dissolved in ㎖ and stirred at 140 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.7 g (75%) of the title compound 6-4.

(5) 화합물 6-5의 제조(5) Preparation of Compound 6-5

화합물 6-4 4g(13.2m㏖)을 DMF 80㎖에 녹이고, N-브로모숙신이미드 2.4g(13.2m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 6-5 4.5g(90%)을 수득하였다.4 g (13.2 mmol) of Compound 6-4 was dissolved in 80 mL of DMF, and 2.4 g (13.2 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent, to obtain 4.5 g (90%) of the title compound 6-5.

(6) 화합물 287의 제조(6) Preparation of Compound 287

화합물 6-5 4.5g(11.8m㏖), 2-나프틸보론산 2.5g(14.2m㏖), Pd(PPh3)4 1.4g(1.2m㏖), 및 K2CO3, 4.9g(35.4m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 287 4.3g(85%)을 수득하였다.4.5 g (11.8 mmol) of compound 6-5, 2.5 g (14.2 mmol) of 2-naphthylboronic acid, 1.4 g (1.2 mmol) of Pd (PPh 3 ) 4 , and 4.9 g (35.4) of K 2 CO 3 mmol) was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.3 g (85%) of the title compound 287.

합성예Synthetic example 7: 화합물 337의 제조 7: Preparation of Compound 337

하기 반응식 7의 반응 경로를 거쳐 화합물 337을 합성하였다.Compound 337 was synthesized through the reaction route of Scheme 7 below.

<반응식 7><Reaction Scheme 7>

Figure pat00051
Figure pat00051

(1) 화합물 7-1의 제조(1) Preparation of Compound 7-1

화합물 9-브로모-10메톡시-페난트렌(9-bromo-10-methoxy-Phenanthrene) 22.4g(78m㏖), 9-안트라센보론산 20.7g(93m㏖), Pd(PPh3)4 7.8g(7.8m㏖) 및 K2CO3, 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 7-1 6.9g(23%)을 수득하였다.Compound 9-bromo-10-methoxy-phenanthrene 22.4 g (78 mmol), 9-anthracene boronic acid 20.7 g (93 mmol), Pd (PPh 3 ) 4 7.8 g (7.8 mmol) and K 2 CO 3 , 21.5 g (156 mmol) were dissolved in toluene / ethanol / distilled water 390 mL / 97 mL / 78 mL and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 6.9 g (23%) of the title compound 7-1.

(2) 화합물 7-2의 제조(2) Preparation of Compound 7-2

화합물 7-1 26.5g(68.8m㏖)을 디클로로메탄 270㎖에 녹인 후 0℃로 냉각하였다. 여기에 보론트리브로마이드 138㎖(138m㏖)를 천천히 첨가하였다. 온도를 상온으로 가온한 뒤 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 톨루엔 용매하에서 교반한 뒤 여과하여 목적 화합물 7-2 19.1g(75%)을 수득하였다.26.5 g (68.8 mmol) of Compound 7-1 was dissolved in 270 ml of dichloromethane, and cooled to 0 ° C. 138 ml (138 mmol) of boron tribromide was slowly added thereto. The temperature was warmed to room temperature and then stirred. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, stirred in toluene solvent and filtered to obtain 19.1 g (75%) of the title compound 7-2.

(3) 화합물 7-3의 제조(3) Preparation of Compound 7-3

화합물 7-2 8.1g(22m㏖)을 디클로로메탄에 녹인 후 2,6-루티딘(2,6-lutidine) 3.9㎖(33m㏖)을 넣고 온도를 -30℃로 냉각한 뒤 교반하였다. 여기에 트리플루오로메탄설포닉 안하이드라이드 4.5㎖(27m㏖)을 천천히 첨가하였다. 온도를 0℃로 가온한 뒤 한 시간 동안 교반하였다. 반응이 완결되면 증류수와 디클로로메탄으로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거 한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 7-3 9.1g(85%)을 수득하였다.After dissolving 8.1 g (22 mmol) of compound 7-2 in dichloromethane, 3.9 ml (33 mmol) of 2,6-lutidine was added thereto, the temperature was cooled to −30 ° C., and the mixture was stirred. To this was slowly added 4.5 ml (27 mmol) of trifluoromethanesulphonic anhydride. The temperature was warmed to 0 ° C. and stirred for one hour. When the reaction was complete, it was extracted with distilled water and dichloromethane. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 9.1 g (85%) of the title compound 7-3.

(4) 화합물 7-4의 제조(4) Preparation of Compound 7-4

화합물 7-3 10.6g(21m㏖), Pd(PPh3)2Cl2 2.9g(4.2m㏖), 리튬클로라이드 2.7g(63m㏖), 및 DBU 9.4㎖(63m㏖)을 디메틸포름이미드 200㎖에 녹인 후 140℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 7-4 2.6g(35%)을 수득하였다.Compound 7-3 10.6 g (21 mmol), Pd (PPh 3 ) 2 Cl 2 2.9 g (4.2 mmol), lithium chloride 2.7 g (63 mmol), and DBU 9.4 mL (63 mmol) were diluted with dimethylformimide 200 It was dissolved in ㎖ and stirred at 140 ℃. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 2.6 g (35%) of the title compound 7-4.

(5) 화합물 7-5의 제조(5) Preparation of Compound 7-5

화합물 7-4 4.6g(13.2m㏖)을 DMF 100㎖에 녹이고, N-브로모숙신이미드 2.4g(13.2m㏖)을 천천히 첨가하였다. 이를 상온에서 17시간 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 7-5 5.1g(90%)을 수득하였다.4.6 g (13.2 mmol) of Compound 7-4 were dissolved in 100 mL of DMF, and 2.4 g (13.2 mmol) of N-bromosuccinimide was slowly added. After stirring for 17 hours at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 5.1 g (90%) of the title compound 7-5.

(6) 화합물 337의 제조(6) Preparation of Compound 337

화합물 7-5 5.1g(11.8m㏖), 2-나프틸보론산 2.5g(14.2m㏖), Pd(PPh3)4 1.4g(1.2m㏖), 및 K2CO3, 4.9g(35.4m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 337 4.2g(75%)을 수득하였다.Compound 7-5 5.1 g (11.8 mmol), 2-naphthylboronic acid 2.5 g (14.2 mmol), Pd (PPh 3 ) 4 1.4 g (1.2 mmol), and K 2 CO 3 , 4.9 g (35.4) mmol) was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.2 g (75%) of the title compound 337.

합성예Synthetic example 8: 화합물 352의 제조 8: Preparation of Compound 352

하기 반응식 8의 반응 경로를 거쳐 화합물 352를 합성하였다.Compound 352 was synthesized through the reaction route of Scheme 8 below.

<반응식 8><Reaction Scheme 8>

Figure pat00052
Figure pat00052

(1) 화합물 8-1의 제조(1) Preparation of Compound 8-1

화합물 1-3 10g(37.5m㏖), 아이오도벤젠 19.2g(94m㏖)을 톨루엔 100㎖에 녹였다. 여기에 트라이사이클로헥실포스핀 1.2g(0.4m㏖), Pd(OAc)2 0.9g(4m㏖), 포타시움 t-부톡사이드 리튬클로라이드 2.7g(63m㏖)을 12시간 이상 환류시켰다. 상온으로 냉각한 뒤 물을 붓고 유기물을 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 8-1 12.5g(80%)을 수득하였다.10 g (37.5 mmol) of Compound 1-3 and 19.2 g (94 mmol) of iodobenzene were dissolved in 100 ml of toluene. 1.2 g (0.4 mmol) of tricyclohexylphosphine, 0.9 g (4 mmol) of Pd (OAc) 2 , and 2.7 g (63 mmol) of potassium t-butoxide lithium chloride were refluxed for 12 hours or more. After cooling to room temperature, water was poured and the organics were extracted. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 12.5 g (80%) of the title compound 8-1.

(2) 화합물 8-2의 제조(2) Preparation of Compound 8-2

화합물 8-1 10g(20m㏖)을 DMF 150㎖에 녹이고, N-브로모숙신이미드 3.6g(20m㏖)을 천천히 첨가하였다. 이를 상온에서 하루 동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거하였다. 그 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 8-2 8.9g(90%)을 수득하였다.10 g (20 mmol) of Compound 8-1 was dissolved in 150 mL of DMF, and 3.6 g (20 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organics were dried over anhydrous MgSO 4 and the solvent was removed by rotary evaporator. Thereafter, dichloromethane and hexane were purified by column chromatography using a developing solvent, to obtain 8.9 g (90%) of the title compound 8-2.

(3) 화합물 352의 제조(3) Preparation of Compound 352

화합물 8-2 8g(16.1m㏖), 2-나프틸-4-페닐보론산 4.8g(19.3m㏖), Pd(PPh3)4 1.8g(1.6m㏖) 및 K2CO3 4.5g(32.2m㏖)을 톨루엔/에탄올/증류수 160㎖/32㎖/32㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기물을 무수 MgSO4로 건조시킨 후 회전증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 최종 화합물인 화합물 352 8.5g(85%)을 수득하였다.8 g (16.1 mmol) of Compound 8-2, 4.8 g (19.3 mmol) of 2-naphthyl-4-phenylboronic acid, 1.8 g (1.6 mmol) of Pd (PPh 3 ) 4 and 4.5 g of K 2 CO 3 ( 32.2 mmol) was dissolved in toluene / ethanol / distilled water 160ml / 32ml / 32ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organics were dried over anhydrous MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent, to obtain 8.5 g (85%) of the final compound 352.

합성예Synthetic example 9: 화합물 393의 제조 9: Preparation of Compound 393

하기 반응식 9의 반응 경로를 거쳐 화합물 393을 합성하였다.Compound 393 was synthesized through the reaction route of Scheme 9 below.

<반응식 9><Reaction Scheme 9>

Figure pat00053
Figure pat00053

(1) 화합물 9-1의 제조 (1) Preparation of Compound 9-1

화합물 9-브로모안트라센 10g(39mol), (2-포밀나프탈렌-1-일)보론산((2-formylnaphthalen-1-yl)boronic acid) 9.4g(47m㏖), Pd(PPh3)4 4.5g(3.9m㏖) 및 K2CO3 10.5g(76m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 9-1 5.8g(45%)을 수득하였다.Compound 9-bromoanthracene 10 g (39 mol), (2-formylnaphthalen-1-yl) boronic acid ((2-formylnaphthalen-1-yl) boronic acid) 9.4 g (47 mmol), Pd (PPh 3 ) 4 4.5 g (3.9 mmol) and 10.5 g (76 mmol) of K 2 CO 3 were dissolved in 200 mL / 50 mL / 40 mL of toluene / ethanol / distilled water, followed by stirring at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 5.8 g (45%) of the title compound 9-1.

(2) 화합물 9-2의 제조(2) Preparation of Compound 9-2

IPy2BF4 21g(56m㏖)을 디클로로메탄에 녹인 후 -78℃로 냉각하였다. HBF4 18.2g(112m㏖)을 가한 뒤 10분 동안 -78℃에서 교반하였다. 고체를 여과 후 여액을 -60℃로 냉각한 뒤 9-1 5.8g(17.5m㏖)을 천천히 첨가하였다. 반응이 완결되면 얼음물로 반응 종결 후 유기층을 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 9-2 3.0g(52%)을 수득하였다.21 g (56 mmol) of IPy 2 BF 4 was dissolved in dichloromethane and cooled to −78 ° C. 18.2 g (112 mmol) of HBF 4 was added and stirred at −78 ° C. for 10 minutes. After filtration of the solid, the filtrate was cooled to -60 ° C and 5.8 g (17.5 mmol) of 9-1 was slowly added. When the reaction was completed, the reaction was completed with ice water and the organic layer was extracted. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.0 g (52%) of the title compound 9-2.

(3) 화합물 9-3의 제조(3) Preparation of Compound 9-3

화합물 9-2 5.6g(17m㏖)을 다이에틸이써 100㎖에 녹이고, AlCl3 2.7g(20.4m㏖)을 천천히 첨가하였다. 이를 15분 동안 교반 한 후, 0℃로 냉각하고 리튬알루미늄하이드라이드(LAH) 1g(26m㏖)를 천천히 첨가하였다. 이를 1시간 동안 환류 교반한 후 반응이 완결되면 상온으로 천천히 냉각하고, 여기에 EA를 거품이 일어나지 않을 때까지 천천히 넣어주었다. 그 후, 6N HCl 20㎖을 넣어주고, 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디틀로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 화합물 9-3 4.3g(80%)을 수득하였다. 5.6 g (17 mmol) of Compound 9-2 was dissolved in 100 ml of diethyl ether, and 2.7 g (20.4 mmol) of AlCl 3 was slowly added. After stirring for 15 minutes, it was cooled to 0 ℃ and slowly added 1 g (26 mmol) of lithium aluminum hydride (LAH). After stirring for 1 hour under reflux, the reaction was slowly cooled to room temperature when the reaction was completed, and EA was slowly added thereto until no foaming occurred. Then, 20 ml of 6N HCl was added thereto, and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.3 g (80%) of the compound 9-3.

(4) 화합물 9-4의 제조(4) Preparation of Compound 9-4

화합물 9-3 4.7g(15m㏖)을 DMSO 40㎖에 녹인 다음, 상온에서 소듐 tert-부톡사이드 10.7g(112m㏖)를 넣어주고 70℃에서 15분간 교반하였다. 여기에 요오드화벤젠 26.9g(132m㏖)을 천천히 첨가하고 1시간 더 교반하였다. 반응이 완결되면 상온에서 냉각하고 증류수를 넣어 20분간 교반하였다. 이때, 고체가 생성되는데 이를 여과하고, 얻어진 고체를 에탄올과 아세톤으로 재결정하여 화합물 9-4 4.2g(60%)을 수득하였다.4.7 g (15 mmol) of Compound 9-3 was dissolved in 40 mL of DMSO, and then 10.7 g (112 mmol) of sodium tert-butoxide was added at room temperature, followed by stirring at 70 ° C. for 15 minutes. 26.9 g (132 mmol) of benzene iodide was slowly added thereto, and the mixture was further stirred for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added and stirred for 20 minutes. At this time, a solid was produced, which was filtered and the obtained solid was recrystallized from ethanol and acetone to obtain 4.2 g (60%) of compound 9-4.

(5) 화합물 9-5의 제조(5) Preparation of Compound 9-5

화합물 9-4 4.1g(8.8m㏖)을 DMF 30㎖에 녹이고, N-브로모숙신이미드 1.6g(8.8m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 9-5 4.3g(90%)을 수득하였다.4.1 g (8.8 mmol) of Compound 9-4 was dissolved in 30 mL of DMF, and 1.6 g (8.8 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.3 g (90%) of the title compound 9-5.

(6) 화합물 393의 제조(6) Preparation of Compound 393

화합물 9-5 14.7g(26.8m㏖), (9-phenyl-9H-carbazol-3-yl)boronic acid 9.2g(32m㏖), Pd(PPh3)4 4.5g(3.1m㏖) 및 K2CO3 7.4g(53.6m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 393 13.3g(70%)을 수득하였다.Compound 9-5 14.7 g (26.8 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid 9.2 g ( 32 mmol), Pd (PPh 3 ) 4 4.5 g (3.1 mmol) and K 2 7.4 g (53.6 mmol) of CO 3 was dissolved in toluene / ethanol / distilled water 200 ml / 50 ml / 40 ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 13.3 g (70%) of the title compound 393.

합성예Synthetic example 10: 화합물 414의 제조 10: Preparation of Compound 414

하기 반응식 10의 반응 경로를 거쳐 화합물 414을 합성하였다.Compound 414 was synthesized through the reaction route of Scheme 10 below.

<반응식 10><Reaction formula 10>

Figure pat00054
Figure pat00054

(1) 화합물 10-1의 제조 (1) Preparation of Compound 10-1

화합물 9-브로모안트라센 10g(39mol), (1-formylnaphthalen-2-yl)boronic acid 9.4g(47m㏖), Pd(PPh3)4 4.5g(3.9m㏖) 및 K2CO3 10.5g(76m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 10-1 1.9g(15%)을 수득하였다.10 g (39 mol) of compound 9-bromoanthracene, 9.4 g (47 mmol) of (1-formylnaphthalen-2-yl) boronic acid, 4.5 g (3.9 mmol) of Pd (PPh 3 ) 4 and 10.5 g of K 2 CO 3 ( 76 mmol) was dissolved in toluene / ethanol / distilled water 200ml / 50ml / 40ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 1.9 g (15%) of the title compound 10-1.

(2) 화합물 10-2의 제조(2) Preparation of Compound 10-2

IPy2BF4 21g(56m㏖)을 디클로로메탄에 녹인 후 -78℃로 냉각하였다. HBF4 18.2g(112m㏖)을 가한 뒤 10분 동안 -78℃에서 교반하였다. 고체를 여과 후 여액을 -60℃로 냉각 한 뒤 10-1 5.8g(17.5m㏖)을 천천히 첨가하였다. 21 g (56 mmol) of IPy 2 BF 4 was dissolved in dichloromethane and cooled to −78 ° C. 18.2 g (112 mmol) of HBF 4 was added and stirred at −78 ° C. for 10 minutes. After filtering the solid, the filtrate was cooled to -60 ℃ and 10-1 5.8g (17.5 mmol) was added slowly.

반응이 완결되면 얼음물로 반응 종결 후 유기층을 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 10-2 3.0g(52%)을 수득하였다.When the reaction was completed, the reaction was completed with ice water and the organic layer was extracted. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.0 g (52%) of the title compound 10-2.

(3) 화합물 10-3의 제조(3) Preparation of Compound 10-3

화합물 10-2 5.6g(17m㏖)을 다이에틸이써 100㎖에 녹이고, AlCl3 2.7g(20.4m㏖)을 천천히 첨가하였다. 이를 15분 동안 교반 한 후, 0℃로 냉각하고 리튬알루미늄하이드라이드(LAH) 1g(26m㏖)를 천천히 첨가하였다. 이를 1시간 동안 환류 교반한 후 반응이 완결되면 상온으로 천천히 냉각하고, 여기에 EA를 거품이 일어나지 않을 때까지 천천히 넣어주었다. 그 후, 6N HCl 20㎖을 넣어주고, 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디틀로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 화합물 10-3 3.8g(70%)을 수득하였다. 5.6 g (17 mmol) of Compound 10-2 was dissolved in 100 ml of diethyl ether, and 2.7 g (20.4 mmol) of AlCl 3 was slowly added. After stirring for 15 minutes, it was cooled to 0 ℃ and slowly added 1 g (26 mmol) of lithium aluminum hydride (LAH). After stirring for 1 hour under reflux, the reaction was slowly cooled to room temperature when the reaction was completed, and EA was slowly added thereto until no foaming occurred. Then, 20 ml of 6N HCl was added thereto, and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.8 g (70%) of compound 10-3.

(4) 화합물 10-4의 제조(4) Preparation of Compound 10-4

화합물 10-3 4.7g(15m㏖)을 DMSO 40㎖에 녹인 다음, 상온에서 소듐 tert-부톡사이드 10.7g(112m㏖)를 넣어주고 70℃에서 15분간 교반하였다. 여기에 요오드화벤젠 26.9g(132m㏖)을 천천히 첨가하고 1시간 더 교반하였다. 반응이 완결되면 상온에서 냉각하고 증류수를 넣어 20분간 교반하였다. 이때, 고체가 생성되는데 이를 여과하고, 얻어진 고체를 에탄올과 아세톤으로 재결정하여 화합물 10-4 4.2g(60%)을 수득하였다.4.7 g (15 mmol) of Compound 10-3 was dissolved in 40 mL of DMSO, and then 10.7 g (112 mmol) of sodium tert-butoxide was added at room temperature, followed by stirring at 70 ° C. for 15 minutes. 26.9 g (132 mmol) of benzene iodide was slowly added thereto, and the mixture was further stirred for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added and stirred for 20 minutes. At this time, a solid was produced, which was filtered and the obtained solid was recrystallized from ethanol and acetone to obtain 4.2 g (60%) of compound 10-4.

(5) 화합물 10-5의 제조(5) Preparation of Compound 10-5

화합물 10-4 4.1g(8.8m㏖)을 DMF 30㎖에 녹이고, N-브로모숙신이미드 1.6g(8.8m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 10-5 4.3g(90%)을 수득하였다.4.1 g (8.8 mmol) of Compound 10-4 was dissolved in 30 mL of DMF, and 1.6 g (8.8 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent, to obtain 4.3 g (90%) of the title compound 10-5.

(6) 화합물 414의 제조(6) Preparation of Compound 414

화합물 10-5 14.7g(26.8m㏖), 디베조티오펜-2-닐 보론산 7.3g(32m㏖), Pd(PPh3)4 4.5g(3.1m㏖) 및 K2CO3 7.4g(53.6m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 414 13.3g(70%)을 수득하였다.Compound 10-5 14.7 g (26.8 mmol), dibezothiophen-2-yl boronic acid 7.3 g (32 mmol), Pd (PPh 3 ) 4 4.5 g (3.1 mmol) and 7.4 g (53.6) K 2 CO 3 mmol) was dissolved in toluene / ethanol / distilled water 200ml / 50ml / 40ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 13.3 g (70%) of the title compound 414.

합성예Synthetic example 11: 화합물 472의 제조 11: Preparation of Compound 472

하기 반응식 11의 반응 경로를 거쳐 화합물 472을 합성하였다.Compound 472 was synthesized through the reaction path of Scheme 11 below.

<반응식 11><Reaction Scheme 11>

Figure pat00055
Figure pat00055

(1) 화합물 11-1의 제조 (1) Preparation of Compound 11-1

화합물 10-브로모-9-페난트렌카르복알데하이드(10-Bromo-9-phenanthrenecarboxaldehyde) 11.1g(39mol), 9-안트라센보론산9.4g(47m㏖), Pd(PPh3)4 4.5g(3.9m㏖) 및 K2CO3 10.5g(76m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 11-1 3.7g(25%)을 수득하였다.10-Bromo-9-phenanthrenecarboxaldehyde 11.1 g (39 mol), 9-anthracene boronic acid 9.4 g (47 mmol), Pd (PPh 3 ) 4 4.5 g (3.9) mmol) and K 2 CO 3 10.5 g (76 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 50ml / 40ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.7 g (25%) of the title compound 11-1.

(2) 화합물 11-2의 제조(2) Preparation of Compound 11-2

IPy2BF4 21g(56m㏖)을 디클로로메탄에 녹인 후 -78℃로 냉각하였다. HBF4 18.2g(112m㏖)을 가한 뒤 10분 동안 -78℃에서 교반하였다. 고체를 여과 후 여액을 -60℃로 냉각 한 뒤 11-1 6.7g(17.5m㏖)을 천천히 첨가하였다. 반응이 완결되면 얼음물로 반응 종결 후 유기층을 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 11-2 3.5g(52%)을 수득하였다.21 g (56 mmol) of IPy 2 BF 4 was dissolved in dichloromethane and cooled to −78 ° C. 18.2 g (112 mmol) of HBF 4 was added and stirred at −78 ° C. for 10 minutes. After filtration of the solid, the filtrate was cooled to -60 ° C and 6.7 g (17.5 mmol) of 11-1 was slowly added. When the reaction was completed, the reaction was completed with ice water and the organic layer was extracted. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.5 g (52%) of the title compound 11-2.

(3) 화합물 11-3의 제조(3) Preparation of Compound 11-3

화합물 11-2 6.5g(17m㏖)을 다이에틸이써 100㎖에 녹이고, AlCl3 2.7g(20.4m㏖)을 천천히 첨가하였다. 이를 15분 동안 교반 한 후, 0℃로 냉각하고 리튬알루미늄하이드라이드(LAH) 1g(26m㏖)를 천천히 첨가하였다. 이를 1시간 동안 환류 교반한 후 반응이 완결되면 상온으로 천천히 냉각하고, 여기에 EA를 거품이 일어나지 않을 때까지 천천히 넣어주었다. 그 후, 6N HCl 20㎖을 넣어주고, 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디틀로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 화합물 11-3 4.4g(70%)을 수득하였다. 6.5 g (17 mmol) of Compound 11-2 was dissolved in 100 ml of diethyl ether, and 2.7 g (20.4 mmol) of AlCl 3 was slowly added. After stirring for 15 minutes, it was cooled to 0 ℃ and slowly added 1 g (26 mmol) of lithium aluminum hydride (LAH). After stirring for 1 hour under reflux, the reaction was slowly cooled to room temperature when the reaction was completed, and EA was slowly added thereto until no foaming occurred. Then, 20 ml of 6N HCl was added thereto, and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.4 g (70%) of compound 11-3.

(4) 화합물 11-4의 제조(4) Preparation of Compound 11-4

화합물 11-3 5.5g(15m㏖)을 DMSO 40㎖에 녹인 다음, 상온에서 소듐 tert-부톡사이드 10.7g(112m㏖)를 넣어주고 70℃에서 15분간 교반하였다. 여기에 요오드화벤젠 26.9g(132m㏖)을 천천히 첨가하고 1시간 더 교반하였다. 반응이 완결되면 상온에서 냉각하고 증류수를 넣어 20분간 교반하였다. 이때, 고체가 생성되는데 이를 여과하고, 얻어진 고체를 에탄올과 아세톤으로 재결정하여 화합물 11-4 4.7g(60%)을 수득하였다.5.5 g (15 mmol) of Compound 11-3 was dissolved in 40 mL of DMSO, and then added 10.7 g (112 mmol) of sodium tert-butoxide at room temperature, followed by stirring at 70 ° C. for 15 minutes. 26.9 g (132 mmol) of benzene iodide was slowly added thereto, and the mixture was further stirred for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added and stirred for 20 minutes. At this time, a solid was produced, which was filtered and the obtained solid was recrystallized from ethanol and acetone to obtain 4.7 g (60%) of compound 11-4.

(5) 화합물 11-5의 제조(5) Preparation of Compound 11-5

화합물 11-4 4.6g(8.8m㏖)을 DMF 30㎖에 녹이고, N-브로모숙신이미드 1.6g(8.8m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 11-5 4.7g(90%)을 수득하였다.4.6 g (8.8 mmol) of Compound 11-4 were dissolved in 30 mL of DMF, and 1.6 g (8.8 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.7 g (90%) of the title compound 11-5.

(6) 화합물 472의 제조(6) Preparation of Compound 472

화합물 11-5 16g(26.8m㏖), 9-페닐-9H-카바졸-3-일)보론산((9-phenyl-9H-carbazol-3-yl)boronic acid) 9.2g(32m㏖), Pd(PPh3)4 4.5g(3.1m㏖) 및 K2CO3 7.4g(53.6m㏖)을 톨루엔/에탄올/증류수 200㎖/50㎖/40㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 472 11.4g(60%)을 수득하였다.Compound 11-5 16 g (26.8 mmol), 9-phenyl-9H-carbazol-3-yl) boronic acid ((9-phenyl-9H-carbazol-3-yl) boronic acid) 9.2 g (32 mmol), 4.5 g (3.1 mmol) of Pd (PPh 3 ) 4 and 7.4 g (53.6 mmol) of K 2 CO 3 were dissolved in 200 mL / 50 mL / 40 mL of toluene / ethanol / distilled water, followed by stirring at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 11.4 g (60%) of the title compound 472.

합성예Synthetic example 12: 화합물 509의 제조 12: Preparation of Compound 509

하기 반응식 12의 반응 경로를 거쳐 화합물 509을 합성하였다.Compound 509 was synthesized through the reaction route of Scheme 12 below.

<반응식 12><Reaction Scheme 12>

Figure pat00056
Figure pat00056

(1) 화합물 12-1의 제조(1) Preparation of Compound 12-1

화합물 9-브로모안트라센 20g(78m㏖), (2-나이트로나프탈렌-1-일)보론산 ((2-nitronaphthalen-1-yl)boronic acid) 20g(93m㏖), Pd(PPh3)4 9g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 12-1 13.6g(50%)을 수득하였다.Compound 9-bromoanthracene 20 g (78 mmol), (2-nitronaphthalen-1-yl) boronic acid ((2-nitronaphthalen-1-yl) boronic acid) 20 g (93 mmol), Pd (PPh 3 ) 4 9 g (7.8 mmol) and 21.5 g (156 mmol) of K 2 CO 3 were dissolved in toluene / ethanol / distilled water 390 ml / 97 ml / 78 ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 13.6 g (50%) of the title compound 12-1.

(2) 화합물 12-2의 제조(2) Preparation of Compound 12-2

화합물 12-1 23.4g(67m㏖)을 트리에틸포스파이트 100㎖에 섞고 180℃로 17시간 교반하였다. 상온으로 냉각한 후 용매를 감압 증류하였다. 메탄올로 결정화하여 목적 화합물 12-2 8.5g(40%)을 수득하였다.23.4 g (67 mmol) of the compound 12-1 were mixed with 100 ml of triethyl phosphite and stirred at 180 ° C. for 17 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Crystallization with methanol gave 8.5 g (40%) of the title compound 12-2.

(3) 화합물 12-3의 제조(3) Preparation of Compound 12-3

화합물 12-2 5.6g(17.6m㏖), 구리 0.6g(8.8m㏖), 18-크라운-6 0.2g(0.9m㏖), K2CO3 4.8g(35.1m㏖) 및 1,2-디클로로벤젠 100㎖을 섞고 180℃에서 17시간 환류 교반시켰다. 상온으로 냉각시키고 감압 증류한 후 MC로 추출하고 증류수로 세척하였다. 무수 MgSO4로 건조하고 감압 증류하여 얻어진 잔사를 컬럼 분리하여 화합물 12-3 4.2g(60%)을 수득하였다.Compound 12-2 5.6 g (17.6 mmol), copper 0.6 g (8.8 mmol), 18-crown-6 0.2 g (0.9 mmol), K 2 CO 3 4.8 g (35.1 mmol) and 1,2- 100 mL of dichlorobenzene was mixed and stirred under reflux at 180 ° C. for 17 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO 4 and distillation under reduced pressure was column separated to obtain 4.2 g (60%) of compound 12-3.

(4) 화합물 12-4의 제조(4) Preparation of Compound 12-4

화합물 12-3 2.8g(7.1m㏖)을 DMF 40㎖에 녹이고, N-브로모숙신이미드 1.3g(7.1m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 12-4 3.0g(90%)을 수득하였다.2.8 g (7.1 mmol) of Compound 12-3 were dissolved in 40 mL of DMF, and 1.3 g (7.1 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.0 g (90%) of the title compound 12-4.

(5) 화합물 509의 제조(5) Preparation of Compound 509

화합물 12-4 7.1g(15m㏖), 2-나프탈렌보론산 3.1g(18m㏖), Pd(PPh3)4 1.7g(1.5m㏖), 및 K2CO3, 4.1g(30m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 509 5g(65%)을 수득하였다.Compound 12-4 7.1 g (15 mmol), 2-naphthalene boronic acid 3.1 g (18 mmol), Pd (PPh 3 ) 4 1.7 g (1.5 mmol), and K 2 CO 3 , 4.1 g (30 mmol) It was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 5 g (65%) of the title compound 509.

합성예Synthetic example 13: 화합물 510의 제조 13: Preparation of Compound 510

하기 반응식 13의 반응 경로를 거쳐 화합물 510을 합성하였다.Compound 510 was synthesized through the reaction route of Scheme 13 below.

<반응식 13><Reaction Scheme 13>

Figure pat00057
Figure pat00057

(1) 화합물 13-1의 제조(1) Preparation of Compound 13-1

화합물 9-bromo-10-nitrophenanthrene 23.6g(78m㏖), (2-phenylanthracen-9-yl)boronic acid 27.7g(93m㏖), Pd(PPh3)4 9g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 13-1 3.7g(10%)을 수득하였다.Compound 9-bromo-10-nitrophenanthrene 23.6 g (78 mmol), (2-phenylanthracen-9-yl) boronic acid 27.7 g (93 mmol), Pd (PPh 3 ) 4 9 g (7.8 mmol) and K 2 CO 3 21.5 g (156 mmol) was dissolved in toluene / ethanol / distilled water 390 ml / 97 ml / 78 ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.7 g (10%) of the title compound 13-1.

(2) 화합물 13-2의 제조(2) Preparation of Compound 13-2

화합물 13-1 31.7g(67m㏖)을 트리에틸포스파이트 320㎖에 섞고 180℃로 17시간 교반하였다. 상온으로 냉각한 후 용매를 감압 증류하였다. 에탄올로 결정화하여 목적 화합물 13-2 17.8g(60%)을 수득하였다.31.7 g (67 mmol) of Compound 13-1 were mixed with 320 ml of triethyl phosphite and stirred at 180 ° C. for 17 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Crystallization with ethanol gave 17.8 g (60%) of the title compound 13-2.

(3) 화합물 13-3의 제조(3) Preparation of Compound 13-3

화합물 13-2 7.8g(17.6m㏖), 구리 0.6g(8.8m㏖), 18-크라운-6 0.2g(0.9m㏖), K2CO3 4.8g(35.1m㏖) 및 1,2-디클로로벤젠 100㎖을 섞고 180℃에서 17시간 환류 교반시켰다. 상온으로 냉각시키고 감압 증류 한 후 MC로 추출하고 증류수로 세척하였다. 무수 MgSO4로 건조하고 감압 증류하여 얻어진 잔사를 컬럼 분리하여 화합물 13-3 4.6g(50%)을 수득하였다.7.8 g (17.6 mmol) of compound 13-2, 0.6 g (8.8 mmol) of copper, 0.2 g (0.9 mmol) of 18-crown-6, 4.8 g (35.1 mmol) of K 2 CO 3 and 1,2- 100 mL of dichlorobenzene was mixed and stirred under reflux at 180 ° C. for 17 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO 4 and distillation under reduced pressure was column separated to obtain 4.6 g (50%) of compound 13-3.

(4) 화합물 13-4의 제조(4) Preparation of Compound 13-4

화합물 13-3 3.7g(7.1m㏖)을 DMF 40㎖에 녹이고, N-브로모숙신이미드 1.3g(7.1m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 13-4 3.6g(85%)을 수득하였다.3.7 g (7.1 mmol) of Compound 13-3 were dissolved in 40 mL of DMF, and 1.3 g (7.1 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.6 g (85%) of the title compound 13-4.

(5) 화합물 510의 제조(5) Preparation of Compound 510

화합물 13-4 9g(15m㏖), [1,1'-biphenyl]-3-ylboronic acid 3.6g(18m㏖), Pd(PPh3)4 1.7g(1.5m㏖), 및 K2CO3 4.1g(30m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 510 4.8g(50%)을 수득하였다.Compound 13-4 9 g (15 mmol), 3.6 g (18 mmol) of [1,1'-biphenyl] -3-ylboronic acid, 1.7 g (1.5 mmol) of Pd (PPh 3 ) 4 , and K 2 CO 3 4.1 g (30 mmol) was dissolved in toluene / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 4.8 g (50%) of the title compound 510.

합성예Synthetic example 14: 화합물 531의 제조 14: Preparation of Compound 531

하기 반응식 14의 반응 경로를 거쳐 화합물 531을 합성하였다.Compound 531 was synthesized through the reaction path of Scheme 14 below.

<반응식 14><Reaction Scheme 14>

Figure pat00058
Figure pat00058

(1) 화합물 14-1의 제조(1) Preparation of Compound 14-1

화합물 9-브로모안트라센 20g(78m㏖), (1-나이트로나프탈렌-2-일)보론산 ((1-nitronaphthalen-2-yl)boronic acid) 20g(93m㏖), Pd(PPh3)4 9g(7.8m㏖) 및 K2CO3 21.5g(156m㏖)을 톨루엔/에탄올/증류수 390㎖/97㎖/78㎖에 녹인 후 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 14-1 8.2g(30%)을 수득하였다.Compound 9-Bromoanthracene 20 g (78 mmol), (1-nitronaphthalen-2-yl) boronic acid ((1-nitronaphthalen-2-yl) boronic acid) 20 g (93 mmol), Pd (PPh 3 ) 4 9 g (7.8 mmol) and 21.5 g (156 mmol) of K 2 CO 3 were dissolved in toluene / ethanol / distilled water 390 ml / 97 ml / 78 ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 8.2 g (30%) of the title compound 14-1.

(2) 화합물 14-2의 제조(2) Preparation of Compound 14-2

화합물 14-1 23.4g(67m㏖)을 트리에틸포스파이트 100㎖에 섞고 180℃로 17시간 교반하였다. 상온으로 냉각한 후 용매를 감압 증류하였다. 에탄올로 결정화하여 목적 화합물 14-2 12.8g(60%)을 수득하였다.23.4 g (67 mmol) of Compound 14-1 were mixed with 100 ml of triethyl phosphite and stirred at 180 ° C. for 17 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. Crystallization with ethanol gave 12.8 g (60%) of the target compound 14-2.

(3) 화합물 14-3의 제조(3) Preparation of Compound 14-3

화합물 14-2 5.6g(17.6m㏖), 구리 0.6g(8.8m㏖), 18-크라운-6 0.2g(0.9m㏖), K2CO3 4.8g(35.1m㏖) 및 1,2-디클로로벤젠 100㎖을 섞고 180℃에서 17시간 환류 교반시켰다. 상온으로 냉각시키고 감압 증류한 후 MC로 추출하고 증류수로 세척하였다. 무수 MgSO4로 건조하고 감압 증류하여 얻어진 잔사를 컬럼 분리하여 화합물 14-3 4.2g(60%)을 수득하였다.Compound 14-2 5.6 g (17.6 mmol), copper 0.6 g (8.8 mmol), 18-crown-6 0.2 g (0.9 mmol), K 2 CO 3 4.8 g (35.1 mmol) and 1,2- 100 mL of dichlorobenzene was mixed and stirred under reflux at 180 ° C. for 17 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO 4 and distillation under reduced pressure was column separated to obtain 4.2 g (60%) of compound 14-3.

(4) 화합물 14-4의 제조(4) Preparation of Compound 14-4

화합물 14-3 2.8g(7.1m㏖)을 DMF 40㎖에 녹이고, N-브로모숙신이미드 1.3g(7.1m㏖)을 천천히 첨가하였다. 이를 상온에서 하루동안 교반한 후 반응이 완결되면 증류수와 에틸아세테이트로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼 크로마토그래피로 정제하여 목적 화합물 14-4 3.0g(90%)을 수득하였다.2.8 g (7.1 mmol) of Compound 14-3 were dissolved in 40 mL of DMF, and 1.3 g (7.1 mmol) of N-bromosuccinimide was slowly added. After stirring for one day at room temperature, the reaction was extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.0 g (90%) of the title compound 14-4.

(5) 화합물 531의 제조(5) Preparation of Compound 531

화합물 14-4 7.1g(15m㏖), 2-나프탈렌보론산 3.1g(18m㏖), Pd(PPh3)4 1.7g(1.5m㏖), 및 K2CO3 4.1g(30m㏖)을 톨루엔/에탄올/증류수 100㎖/25㎖/20㎖에 녹인 다음 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 추출하였다. 유기층을 무수 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 디클로로메탄과 헥산을 전개용매로 이용하여 컬럼크로마토그래피로 정제하여 목적 화합물 531 3.8g(50%)을 수득하였다.
Compound 14-4 7.1 g (15 mmol), 2-naphthalene boronic acid 3.1 g (18 mmol), Pd (PPh 3 ) 4 1.7 g (1.5 mmol), and K 2 CO 3 4.1 g (30 mmol) toluene It was dissolved in / ethanol / distilled water 100ml / 25ml / 20ml and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with distilled water and EA. The organic layer was dried over anhydrous MgSO 4 , and the solvent was removed using a rotary evaporator, and then purified by column chromatography using dichloromethane and hexane as a developing solvent to obtain 3.8 g (50%) of the title compound 531.

한편, 본 발명에 따른 화합물의 NMR값과 매스-스펙트럼(mass-spectrum data)를 하기 표 1에 기재하였다. 화합물 번호는 상기에 기재된 화합물의 번호와 동일하다.On the other hand, the NMR value and mass-spectrum data of the compound according to the present invention are described in Table 1 below. The compound number is the same as the number of the compound described above.

Figure pat00059
Figure pat00060
Figure pat00059
Figure pat00060

Figure pat00061
Figure pat00061

Figure pat00062
Figure pat00062

Figure pat00063
Figure pat00063

Figure pat00064
Figure pat00064

Figure pat00065
Figure pat00065

Figure pat00066
Figure pat00066

Figure pat00067
Figure pat00067

Figure pat00068
Figure pat00068

Figure pat00069
Figure pat00069

Figure pat00070
Figure pat00070

Figure pat00071
Figure pat00071

Figure pat00072
Figure pat00072

Figure pat00073
Figure pat00073

<< 실시예Example 1> 본 발명의 화합물을 이용한  1> using the compound of the present invention OLEDOLED 의 제작Production

우선, OLED용 글래스(삼성-코닝사 제조)(1)로부터 얻어진 투명전극 ITO 박막(2)을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다.First, the transparent electrode ITO thin film 2 obtained from the glass for OLED (manufactured by Samsung Corning Co., Ltd.) (1) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then placed in isopropanol. It was used after.

다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 구조의 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 넣고, 챔버 내의 진공도가 10-6torr에 도달할 때까지 배기시켰다. 그 후, 셀에 전류를 인가하여 NPB를 증발시켜 ITO 기판 상에 200Å 두께의 정공 주입층(3)을 증착하였다.Next, an ITO substrate is placed in the substrate folder of the vacuum deposition equipment, and N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4 'having the following structure in a cell in the vacuum deposition equipment. -Diamine (N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine: NPB) was added and evacuated until the vacuum in the chamber reached 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the NPB to deposit a hole injection layer 3 having a thickness of 200 m 3 on the ITO substrate.

Figure pat00074
Figure pat00074

이어서, 진공 증착 장비 내의 다른 셀에 하기 구조의 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민(4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2T-NATA)을 넣고, 셀에 전류를 인가하여 2-TNATA를 증발시켜 정공주입층 위에 600Å두께의 정공수송층(4)을 증착하였다.The 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine (4,4', 4" -tris () of the structure N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2T-NATA) was added thereto, and a current was applied to the cell to evaporate 2-TNATA to deposit a 600 kV hole transport layer 4 on the hole injection layer.

Figure pat00075
Figure pat00075

정공주입층, 정공수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 발광 재료로 본 발명에 따른 화합물(예: 화합물 235)을 넣었다. 또 다른 셀에는 하기 구조를 가진 도펀트 1을 넣은 후, 두 셀을 같이 가열, 도펀트 1의 증착속도 비율을 5중량%로 증착함으로써 상기 정공수송층 상에 400Å(호스트: 도펀트= 95:5중량비) 두께의 발광층(5)을 증착하였다.After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. In one cell in a vacuum deposition apparatus, a compound according to the present invention (eg Compound 235) was placed as a luminescent material. In another cell, dopant 1 having the following structure was added, and both cells were heated together, and the deposition rate ratio of dopant 1 was deposited at 5% by weight. The thickness of 400 kW (host: dopant = 95: 5 weight ratio) was increased on the hole transport layer. The light emitting layer 5 was deposited.

<화합물 235> <Compound 235>

Figure pat00076
Figure pat00076

<도펀트 1><Dopant 1>

Figure pat00077
Figure pat00077

이어서, 전자수송층(6)으로서 하기 구조의 트리스(8-하이드록시퀴놀린)알루미늄(Ⅲ)(tris(8-hydroxyquinoline)aluminum(Ⅲ): Alq3)를 200Å 두께로 증착하였다. 그 후 전자주입층(7)으로 하기 구조의 화합물 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착한 후, Al 음극(8)을 1,000Å의 두께로 증착하여 OLED를 제작하였다.Subsequently, tris (8-hydroxyquinoline) aluminum (III): Alq3 having the following structure was deposited as an electron transport layer 6 to a thickness of 200 Å. Thereafter, a compound lithium fluoride (LiF) having a structure of 10 으로 was deposited to the electron injection layer 7, and then an Al cathode 8 was deposited to a thickness of 1,000 Å to manufacture an OLED.

Figure pat00078
Figure pat00078

OLED 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6∼10-8torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다.All organic compounds required for OLED fabrication were vacuum sublimated and purified under 10-6 to 10-8 torr, respectively, for each material, and used for OLED fabrication.

<< 실시예Example 2> 본 발명의 화합물을 이용한  2> using the compound of the present invention OLEDOLED 소자의 제작 Device fabrication

실시예 1과 동일한 방법으로 정공주입층, 정공수송층을 형성시킨 후, 상기 진공 증착 장비 내의 한쪽 셀에 발광 재료로 본 발명에 따른 화합물 235을 넣고, 또 다른 셀에는 하기 구조를 가진 도펀트 2를 넣은 후, 두 물질을 다른 속도로 증발시켜 호스트를 기준으로 5 중량%로 도핑함으로써, 상기 정공수송층 위에 400Å 두께의 발광층을 증착하였다.After the hole injection layer and the hole transport layer were formed in the same manner as in Example 1, Compound 235 according to the present invention was added to one cell in the vacuum deposition equipment as a light emitting material, and another dopant 2 having the structure Thereafter, the two materials were evaporated at different rates and doped at 5 wt% based on the host, thereby depositing a 400 Å thick emitting layer on the hole transport layer.

<도펀트 2><Dopant 2>

Figure pat00079
Figure pat00079

<실시예 3∼290> 본 발명의 화합물을 이용한 OLED 소자의 제작Examples 3 to 290 Fabrication of OLED Devices Using Compounds of the Invention

하기 표 2에 기재한 호스트와 도펀트를 이용한 것을 제외하고는, 실시예 1과 동일한 방법으로 OLED를 제조하였다.An OLED was manufactured in the same manner as in Example 1, except that a host and a dopant described in Table 2 were used.

<< 비교예Comparative Example 1∼4> 종래의 유기 발광 화합물을 이용한  1 to 4> using a conventional organic light emitting compound OLEDOLED 의 제작Production

상기 실시예 1과 동일한 방법으로 정공주입층(3), 정공수송층(4)을 형성시켰다. 그 후, 상기 진공 증착 장비 내의 다른 셀에 발광 호스트 재료인 ADN(dinaphthylanthracene)의 이성질체 2가지(비교화합물 1, 2)를 사용하였으며, 또 다른 셀에는 실시예 1 과 같은 도펀트 1을 각각 넣은 후, 상기 정공수송층 위에 30㎚ 두께의 발광층(5)을 증착하였다.In the same manner as in Example 1, the hole injection layer 3 and the hole transport layer 4 were formed. Thereafter, two isomers (Comparative Compounds 1 and 2) of ADN (dinaphthylanthracene), which are light emitting host materials, were used in another cell in the vacuum deposition apparatus. A 30 nm thick light emitting layer 5 was deposited on the hole transport layer.

<비교화합물 1> <비교화합물 2> <Comparative Compound 1> <Comparative Compound 2>

Figure pat00080
Figure pat00081
Figure pat00080
Figure pat00081

이어서, 실시예 1과 동일한 방법으로 전자수송층(6)과 전자주입층(7)을 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극(8)을 150㎚의 두께로 증착하여 OLED를 제작하였다.Subsequently, the electron transport layer 6 and the electron injection layer 7 were deposited in the same manner as in Example 1, and then an Al cathode 8 was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED. .

<< 실험예Experimental Example > > OLEDOLED 의 특성 평가Characterization of

OLED의 효율 및 특성을 평가하여 하기 표 2에 기재하였다. 효율은 cd/A에서 그리고, 수명은 효율이 50%까지 떨어질 때까지의 시간을 하기 표 2에 기재하였다.The efficiency and characteristics of the OLEDs were evaluated and listed in Table 2 below. The efficiency is at cd / A, and the lifetime is shown in Table 2 below until the efficiency drops to 50%.

Figure pat00082
Figure pat00083
Figure pat00084
Figure pat00085
Figure pat00086
Figure pat00087
Figure pat00088
Figure pat00082
Figure pat00083
Figure pat00084
Figure pat00085
Figure pat00086
Figure pat00087
Figure pat00088

Figure pat00089
Figure pat00090
Figure pat00089
Figure pat00090

Figure pat00091
Figure pat00091

Figure pat00092
Figure pat00092

Figure pat00093

Figure pat00093

상기 표 2을 참조하면, 본 발명의 화합물을 이용하여 제조된 소자가 비교예에 비해 효율, 수명 및 열적 안정성이 우수함을 알 수 있다.Referring to Table 2, it can be seen that the device manufactured using the compound of the present invention is superior in efficiency, life and thermal stability compared to the comparative example.

Claims (11)

하기 화학식 1로 표시되는 화합물:
Figure pat00094

상기 화학식 1에서,
R1 내지 R6은 서로 같거나 다르고, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60 )알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이며, 상기 R1 내지 R6는 인접하는 기와 서로 결합하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하거나, 치환 또는 비치환된 (C2-C60)알킬렌 또는 (C2-C60)알케닐렌으로 서로 연결하여 지방족 고리, 방향족 고리, 헤테로 방향족 고리를 형성하고,
Ar1은 1∼5개의 고리를 갖는 치환 또는 비치환된 (C6-C60)의 방향족 화합물 또는 융합고리형 방향족 화합물이고,
A는 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C2-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; (C6-C60)아릴카보닐; 또는
Figure pat00095
이되,
Ar3는 치환 또는 비치환된 (C1-C60)알킬렌옥시; 치환 또는 비치환된 (C1-C60)알킬렌티오; 치환 또는 비치환된 (C6-C60)아릴렌옥시; (C6-C60)아릴렌티오; 치환 또는 비치환된 (C6-C60)아릴렌; 또는 (C3-C60)헤테로아릴렌이고,
R7은 R1 내지 R6의 기재와 동일하고,
n은 0 내지 3이고,
n이 0이 아닐 경우, X는 -O-, -Si(-R21)(-R22)-, -N(-R21)- 또는 -C(-R21)(-R22)-로서,
이때, R21 및 R22는 각각 독립적으로 수소; 직쇄상 또는 분지상의 (C1-C60)알킬; (C6-C60)아릴; (C6-C60)알콕시아릴; (C1-C60)알킬티오(C6-C60)아릴; 또는 아미노(C6-C60)아릴, (C1-C60)알킬실릴(C6-C60)아릴이고,
상기 R1 내지 R6, Ar1, A 및 Ar3에서의 치환은 서로 같거나 다르고, 각각 독립적으로, 할로겐, (C1-C60)알킬, (C6-C60)아릴, (C2-C60)헤테로아릴, N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬, (C3-C60)시클로알킬, 트리(C1-C60)알킬실릴, 디(C1-C60)알킬(C6-C60)아릴실릴, 트리(C6-C60)아릴실릴, 아다만틸, (C7-C60)바이시클로알킬, (C2-C60)알케닐, (C2-C60)알키닐, (C1-C60)알콕시, 시아노, (C1-C60)알킬아미노, (C6-C60)아릴아미노, (C6-C60)아르(C1-C60)알킬, (C6-C60)아릴옥시, (C1-C60)알킬티오, (C6-C60)아릴티오, (C1-C60)알콕시카보닐, (C1-C60)알킬카보닐, (C6-C60)아릴카보닐, 카복실산, 나이트로 또는 하이드록시로 치환될 수 있다. A compound represented by the following formula (1):
Figure pat00094

In Formula 1,
R 1 to R 6 are the same as or different from each other, and each independently, hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 5 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; Or (C 6 -C 60 ) arylcarbonyl, wherein R 1 to R 6 are bonded to adjacent groups to form an aliphatic ring, an aromatic ring, a heteroaromatic ring, or a substituted or unsubstituted (C 2 -C 60). Linking together with alkylene or (C 2 -C 60 ) alkenylene to form an aliphatic ring, an aromatic ring, a heteroaromatic ring,
Ar 1 is a substituted or unsubstituted (C 6 -C 60 ) aromatic compound or fused ring aromatic compound having 1 to 5 rings,
A is adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryl; Substituted or unsubstituted (C 2 -C 60 ) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C 3 -C 60 ) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60 ) alkylsilyl; Substituted or unsubstituted di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted tri (C 6 -C 60 ) arylsilyl; Substituted or unsubstituted (C 7 -C 60 ) bicycloalkyl; Substituted or unsubstituted (C 2 -C 60 ) alkenyl; Substituted or unsubstituted (C 2 -C 60 ) alkynyl; Substituted or unsubstituted (C 1 -C 60 ) alkoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylamino; Substituted or unsubstituted (C 6 -C 60 ) arylamino; Substituted or unsubstituted (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl; Substituted or unsubstituted (C 6 -C 60 ) aryloxy; Substituted or unsubstituted (C 6 -C 60 ) arylthio; Substituted or unsubstituted (C 1 -C 60 ) alkylthio; Substituted or unsubstituted (C 1 -C 60 ) alkoxycarbonyl; Substituted or unsubstituted (C 1 -C 60 ) alkylcarbonyl; (C 6 -C 60 ) arylcarbonyl; or
Figure pat00095
However,
Ar 3 is substituted or unsubstituted (C 1 -C 60 ) alkyleneoxy; Substituted or unsubstituted (C 1 -C 60 ) alkylenethio; Substituted or unsubstituted (C 6 -C 60 ) aryleneoxy; (C 6 -C 60 ) arylenethio; Substituted or unsubstituted (C 6 -C 60 ) arylene; Or (C 3 -C 60 ) heteroarylene,
R 7 is the same as described for R 1 to R 6 ,
n is from 0 to 3,
If n is not 0, X is -O-, -Si (-R 21 ) (-R 22 )-, -N (-R 21 )-or -C (-R 21 ) (-R 22 )- ,
In this case, R 21 and R 22 are each independently hydrogen; Linear or branched (C 1 -C 60 ) alkyl; (C 6 -C 60 ) aryl; (C 6 -C 60 ) alkoxyaryl; (C 1 -C 60 ) alkylthio (C 6 -C 60 ) aryl; Or amino (C 6 -C 60 ) aryl, (C 1 -C 60 ) alkylsilyl (C 6 -C 60 ) aryl,
Substituents in R 1 to R 6 , Ar 1 , A and Ar 3 are the same as or different from each other, and each independently, halogen, (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryl, (C 2 -C 60) heteroaryl, N, O, S, and 5-or 6-membered heterocycloalkyl containing one or two or more selected from Si, (C 3 -C 60) cycloalkyl, tri (C 1 - C 60 ) alkylsilyl, di (C 1 -C 60 ) alkyl (C 6 -C 60 ) arylsilyl, tri (C 6 -C 60 ) arylsilyl, adamantyl, (C 7 -C 60 ) bicycloalkyl , (C 2 -C 60 ) alkenyl, (C 2 -C 60 ) alkynyl, (C 1 -C 60 ) alkoxy, cyano, (C 1 -C 60 ) alkylamino, (C 6 -C 60 ) Arylamino, (C 6 -C 60 ) ar (C 1 -C 60 ) alkyl, (C 6 -C 60 ) aryloxy, (C 1 -C 60 ) alkylthio, (C 6 -C 60 ) arylthio, (C 1 -C 60 ) alkoxycarbonyl, (C 1 -C 60 ) alkylcarbonyl, (C 6 -C 60 ) arylcarbonyl, carboxylic acid, nitro or hydroxy. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물이 하기 화학식 1A로 표시되는 화합물인 것을 특징으로 하는 상기 화합물:
Figure pat00096

상기 화학식 1A에 있어서,
R1 내지 R6은 제1항의 화학식 1에서 정의한 바와 같고,
A는 치환 또는 비치환된 (C6-C60)아릴 또는 치환 또는 비치환된 (C2-C60)헤테로 아릴이고,
n은 0 내지 1이고,
n이 1일 경우, X는 -N(-R21)- 또는 -C(-R21)(-R22)-이고,
R21 및 R22는 상기 화학식 1에서 정의한 바와 같고,
R17 내지 R20은 인접하는 기끼리 서로 결합하여 1종 또는 2종 이상의 방향족 또는 지방족 환을 형성한다.The compound of claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 1A:
Figure pat00096

In Chemical Formula 1A,
R 1 to R 6 are the same as defined in Formula 1 of claim 1,
A is substituted or unsubstituted (C 6 -C 60 ) aryl or substituted or unsubstituted (C 2 -C 60 ) hetero aryl,
n is 0 to 1,
when n is 1, X is -N (-R 21 )-or -C (-R 21 ) (-R 22 )-,
R 21 and R 22 are the same as defined in Formula 1,
R 17 to R 20 combine with each other to form one or two or more aromatic or aliphatic rings. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물이 하기 화학식 2 내지 화학식 13으로 표시되는 화합물 군에서 선택되는 어느 하나인 것을 특징으로 하는 상기 화합물:
<화학식 2> <화학식 3> <화학식 4>
Figure pat00097
Figure pat00098
Figure pat00099

<화학식 5> <화학식 6> <화학식 7>
Figure pat00100
Figure pat00101
Figure pat00102

<화학식 8> <화학식 9> <화학식 10>
Figure pat00103
Figure pat00104
Figure pat00105

<화학식 11> <화학식 12> <화학식 13>
Figure pat00106
Figure pat00107
Figure pat00108

상기 화학식 2 내지 화학식 13에서,
A, R1 내지 R6은 제 1항의 화학식 1에서 정의한 바와 같고,
R9 내지 R16은 각각 독립적으로, R1 내지 R6의 기재와 동일하며,
R21 및 R22는 각각 독립적으로 수소; 직쇄상 또는 분지상의 (C1~C60)알킬; (C6-C60)아릴; (C6-C60)알콕시아릴; (C1~C60)알킬티오(C6-C60)아릴; 아미노(C6-C60)아릴 또는 (C1~C60)알킬실릴(C6-C60)아릴이다.The compound of claim 1, wherein the compound represented by Chemical Formula 1 is any one selected from the group of compounds represented by Chemical Formulas 2 to 13.
&Lt; Formula 2 >< EMI ID =
Figure pat00097
Figure pat00098
Figure pat00099

<Formula 5><Formula6><Formula7>
Figure pat00100
Figure pat00101
Figure pat00102

<Formula 8><Formula9><Formula10>
Figure pat00103
Figure pat00104
Figure pat00105

<Formula 11><Formula12><Formula13>
Figure pat00106
Figure pat00107
Figure pat00108

In Chemical Formulas 2 to 13,
A, R 1 to R 6 are the same as defined in Formula 1 of claim 1,
R 9 to R 16 are each independently the same as described for R 1 to R 6 ,
R 21 and R 22 are each independently hydrogen; Linear or branched (C 1 -C 60 ) alkyl; (C 6 -C 60 ) aryl; (C 6 -C 60 ) alkoxyaryl; (C 1 ~ C 60) alkylthio (C 6 -C 60) aryl; An amino (C 6 -C 60) aryl or (C 1 ~ C 60) alkylsilyl (C 6 -C 60) aryl. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물이 하기의 구조식으로 표시되는 화합물 중 어느 하나인 것을 특징으로 하는 상기 화합물:
Figure pat00109

Figure pat00110

Figure pat00111

Figure pat00112

Figure pat00113

Figure pat00114

Figure pat00115

Figure pat00116

Figure pat00117

Figure pat00118

Figure pat00119

Figure pat00120

Figure pat00121

Figure pat00122

Figure pat00123

Figure pat00124

Figure pat00125

Figure pat00126

Figure pat00127
The compound of claim 1, wherein the compound represented by Chemical Formula 1 is any one of compounds represented by the following structural formulas:
Figure pat00109

Figure pat00110

Figure pat00111

Figure pat00112

Figure pat00113

Figure pat00114

Figure pat00115

Figure pat00116

Figure pat00117

Figure pat00118

Figure pat00119

Figure pat00120

Figure pat00121

Figure pat00122

Figure pat00123

Figure pat00124

Figure pat00125

Figure pat00126

Figure pat00127
 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고, 제1항의 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 유기전계발광소자.A first electrode; A second electrode; And an organic film disposed between the first electrode and the second electrode, the organic film including the compound represented by Chemical Formula 1 of claim 1. 제5항에 있어서, 상기 유기막이 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 상기 유기전계발광소자.The organic electroluminescent device according to claim 5, wherein the organic film is one or two or more selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. 제5항에 있어서, 상기 유기막이 정공주입층, 정공수송층 및 발광층으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상인 것을 특징으로 하는 상기 유기전계발광소자.The organic electroluminescent device according to claim 5, wherein the organic film is one or two or more selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer. 제5항에 있어서, 상기 유기막이 제1항의 화학식 1로 표시되는 화합물에, 하기 화학식 14로 표시되는 화합물 또는 하기 화학식 15로 표시되는 화합물에서 선택되는 단독 또는 그 혼합형태가 더 포함된 것을 특징으로 하는 유기전계발광소자:
<화학식 14> <화학식 15>
Figure pat00128
Figure pat00129

상기 화학식 14 및 화학식 15에서,
Ar5는 (C6-C60)아릴 또는 (C4-C60)헤테로아릴이며,
Ar6 및 Ar7는 서로 같거나 다를 수 있고, 각각 독립적으로, 치환 또는 비치환된 (C6-C60)아릴, 치환 또는 비치환된 (C4-C60)헤테로아릴, (C6-C60)아릴아미노, N, O 및 S로부터 선택된 하나 이상을 포함하는 5원 내지 6원의 헤테로시클로알킬 또는 치환 또는 비치환된 (C3-C60)시클로알킬이며, 상기 Ar6 및 Ar7는 융합고리를 포함하거나 포함하지 않는 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있으며,
Ar8는 서로 독립적으로, (C6-C60)아릴렌 또는 (C4-C60)헤테로아릴렌이고, 상기 Ar8은 융합고리를 포함하거나 포함하지 않는 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있으며,
a는 1 내지 4이고, b는 1 내지 4이고, c는 0 내지 1이다.The method according to claim 5, wherein the organic film further comprises a compound represented by Formula 1 of claim 1 or a mixture thereof selected from the compound represented by the following Formula 14 or the compound represented by the following Formula 15: Organic electroluminescent device:
&Lt; Formula 14 >< EMI ID =
Figure pat00128
Figure pat00129

In Formula 14 and Formula 15,
Ar 5 is (C 6 -C 60 ) aryl or (C 4 -C 60 ) heteroaryl,
Ar 6 and Ar 7 may be the same as or different from each other, and each independently, substituted or unsubstituted (C 6 -C 60 ) aryl, substituted or unsubstituted (C 4 -C 60 ) heteroaryl, (C 6- C 60 ) arylamino, N, O and S 5 to 6 membered heterocycloalkyl or substituted or unsubstituted (C 3 -C 60 ) cycloalkyl containing at least one selected from Ar 6 and Ar 7 May form an alicyclic ring, a monocyclic or polycyclic aromatic ring with or without a fused ring,
Ar 8 is independently of each other, (C 6 -C 60 ) arylene or (C 4 -C 60 ) heteroarylene, wherein Ar 8 is an alicyclic, monocyclic or polycyclic ring containing or without a fused ring Can form an aromatic ring,
a is 1-4, b is 1-4, c is 0-1. 제5항에 있어서, 상기 유기막이 아릴아민계 화합물, 스티릴아릴아민계 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 1종을 더 포함하는 것을 특징으로 하는 상기 유기전계발광소자.The organic electroluminescent device according to claim 5, wherein the organic film further comprises one selected from the group consisting of arylamine compounds, styrylarylamine compounds, and mixtures thereof. 제5항 내지 제9항 중 어느 한 항에 있어서, 상기 유기막이 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 더 포함하는 것을 특징으로 하는 상기 유기전계발광소자.The organic film according to any one of claims 5 to 9, wherein the organic film is selected from the group consisting of Group 1, Group 2, 4 and 5 cycle transition metals, lanthanide series metals and organic metals of d-transition elements. Or the organic electroluminescent device further comprising two or more kinds. 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고 제1항의 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함하는 유기태양전지.A first electrode; A second electrode; And an organic film disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1 of claim 1.
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