KR20130076223A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Organic light-emitting compound and organic electroluminescent device using the same Download PDF

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KR20130076223A
KR20130076223A KR1020110144728A KR20110144728A KR20130076223A KR 20130076223 A KR20130076223 A KR 20130076223A KR 1020110144728 A KR1020110144728 A KR 1020110144728A KR 20110144728 A KR20110144728 A KR 20110144728A KR 20130076223 A KR20130076223 A KR 20130076223A
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김성무
백영미
손효석
신진용
박호철
김태형
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주식회사 두산
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Abstract

PURPOSE: An organic electroluminescent device is provided to put novel acridine compound, which has excellent hole injection, transmission ability and capability of radiation etc, into at least one organic layer, thereby improving luminous efficiency, driving voltage, durability etc. CONSTITUTION: The compound represented by chemical formula 1 is provided. An organic electroluminescent device comprises (i) positive electrode, (ii) negative electrode, (iii) one or more organic layer anode which is interposed between the positive electrode and the negative electrode. At least one among the one or more organic layer includes the compound of the chemical formula 1. The organic layer is selected from a group consisting of a hole injection layer, a hole-transport layer and a light-emitting layer. The compound represented by chemical formula 1 is used as phosphorescence host or fluorescence host of the light-emitting layer.

Description

유기 발광 화합물 및 이를 이용한 유기 전계 발광 소자 {ORGANIC LIGHT­EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME} Organic light emitting compound and organic electroluminescent device using same {ORGANIC LIGHT EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

본 발명은 신규한 유기 발광 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 정공 주입 및 수송능, 발광능 등이 우수한 신규한 아크리딘계 화합물 및 이를 하나 이상의 유기물층에 포함함으로써 발광효율, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same, and more particularly, a novel acridine-based compound having excellent hole injection and transporting ability, light emitting ability, etc. The present invention relates to an organic EL device having improved characteristics such as driving voltage and lifetime.

1950년대 Bernanose의 유기 박막 발광 관측을 시점으로 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광 (electroluminescent, EL) 소자(이하, 간단히 '유기 EL 소자'로 칭함)에 대한 연구는 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 EL 소자가 제시되었다. 이후 고효율, 고수명의 유기 EL 소자를 만들기 위하여, 소자 내 각각의 특징적인 유기물 층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다. A study on organic electroluminescent (EL) devices (hereinafter simply referred to as "organic EL devices") led to blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film luminosity of Bernanose in the 1950s, (Tang) and a functional layer of a light emitting layer. In order to produce high efficiency and high number of organic EL devices, the organic EL device has been developed to introduce each characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때 유기물층으로 사용되는 물질은 그 기능에 따라, 발광 물질, 정공 주입 물질, 정공 수송 물질, 전자 수송 물질, 전자 주입 물질 등으로 분류될 수 있다. In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.

유기 EL 소자의 발광층 형성재료는 발광색에 따라 청색, 녹색, 적색 발광 재료로 구분될 수 있다. 그밖에, 보다 나은 천연색을 구현하기 위한 발광재료로 노란색 및 주황색 발광재료도 사용된다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. 도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 이러한 인광 재료의 개발은 이론적으로 형광에 비해 4배까지의 발광 효율을 향상시킬 수 있어 인광 도판트 뿐만 아니라 인광 호스트 재료들에 대해 관심이 집중되고 있다. The light emitting layer forming material of the organic EL device can be classified into blue, green and red light emitting materials depending on the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. In addition, a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such phosphorescent materials can theoretically improve luminous efficiency up to 4 times compared to fluorescence, and thus, attention has been focused on phosphorescent dopants as well as phosphorescent host materials.

현재까지 정공 주입층, 정공 수송층. 정공 차단층, 전자 수송층으로는, 하기 화학식으로 표현된 NPB, BCP, Alq3 등이 널리 알려져 있고, 발광 재료는 안트라센 유도체들이 형광 도판트/호스트 재료로서 보고되고 있다. 특히 발광재료 중 효율 향상 측면에서 큰 장점을 가지고 있는 인광 재료로서는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색, 녹색, 적색 도판트 재료로 사용되고 있다. 현재까지는 CBP가 인광 호스트 재료로 우수한 특성을 나타내고 있다. Up to now, hole injecting layer, hole transporting layer. As the hole blocking layer and the electron transporting layer, NPB, BCP and Alq 3 represented by the following formulas are widely known, and an anthracene derivative as a luminescent material has been reported as a fluorescent dopant / host material. Particularly, phosphorescent materials having great advantages in terms of efficiency improvement among light emitting materials include metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2, such as blue, green, and red dopant materials. Is being used. So far, CBP has shown excellent properties as a phosphorescent host material.

Figure pat00001
Figure pat00001

Figure pat00002
Figure pat00002

그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮고 열적 안정성이 매우 좋지 않아 유기 EL 소자에서의 수명 측면에서 만족할만한 수준이 되지 못하고 있다.
However, existing materials have advantages in terms of light emitting properties, but their glass transition temperature is low and their thermal stability is not very good, which is not satisfactory in terms of lifetime in organic EL devices.

대한민국 공개특허 2011-0066763Republic of Korea Patent Publication 2011-0066763

본 발명은 유기 전계 발광 소자에 적용할 수 있으며, 정공 주입 및 수송능, 발광능 등이 모두 우수한 신규 유기 화합물을 제공하는 것을 목적으로 한다. The present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel organic compound having excellent hole injection, transporting ability, light emitting ability, and the like.

또한 본 발명은 상기 신규 유기 화합물을 포함하여 낮은 구동전압과 높은 발광효율을 나타내며 수명이 향상되는 유기 전계 발광 소자를 제공하는 것을 또 다른 목적으로 한다.
It is another object of the present invention to provide an organic electroluminescent device including the novel organic compound and exhibiting a low driving voltage and a high luminous efficiency and having an improved lifetime.

상기 목적을 달성하기 위하여 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.In order to achieve the above object, the present invention provides a compound represented by the following general formula (1).

Figure pat00003
Figure pat00003

상기 식에서,Where

R1과 R2 또는 R2와 R3는 하기 화학식 2로 표시되는 축합(fused) 고리를 형성하며;R 1 and R 2 or R 2 and R 3 form a fused ring represented by the following formula (2);

Figure pat00004
Figure pat00004

상기 식에서,Where

X는 CAr2Ar3, NAr4, O, S 및 SiAr5Ar6 로 구성된 군으로부터 선택되고;X is selected from the group consisting of CAr 2 Ar 3 , NAr 4 , O, S and SiAr 5 Ar 6 ;

R4 내지 R14는 서로 같거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 C3~C40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되고, 이때 이들은 인접한 기와 축합(fused) 고리를 형성하거나 또는 비형성하며;R 4 to R 14 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 2 to C 40 alkenyl groups, substituted or unsubstituted C 2 to C 40 alkynyl groups, substituted or unsubstituted C 3 to C 40 cycloalkyl groups, substituted or unsubstituted C 3 to C 40 heterocycloalkyl groups, substituted or Unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 Aryloxy group of -C 60 , substituted or unsubstituted C 1 -C 40 alkylsilyl group, substituted or unsubstituted C 6 -C 60 arylsilyl group, and substituted or unsubstituted C 6 -C 60 Arylamine groups, wherein they form a fused ring with an adjacent group or do not form a fused ring;

Ar1 내지 Ar6 은 서로 같거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 C3~C40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되고, 이때 이들은 인접한 기와 축합(fused) 고리를 형성하거나 또는 비형성한다. Ar 1 to Ar 6 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkene A substituted or unsubstituted C 2 -C 40 alkynyl group, a substituted or unsubstituted C 3 -C 40 cycloalkyl group, a substituted or unsubstituted C 3 -C 40 heterocycloalkyl group, a substituted or unsubstituted group C 6 ~ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ~ C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 An aryloxy group, a substituted or unsubstituted C 1 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C 60 arylsilyl group, and a substituted or unsubstituted C 6 to C 60 arylamine group Selected from the group consisting of, where they form or not form fused rings with adjacent groups.

여기서, 상기 R4 내지 R14, 및 Ar1 내지 Ar6 중에서, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기 또는 C6~C60의 아릴아민기는 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 하나 이상으로 치환되거나 또는 비치환된다. In the above R 4 to R 14 , and Ar 1 to Ar 6 , C 1 ~ C 40 Alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 3 ~ C 40 Cyclo alkyl group, C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy of C 60 of The C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group or C 6 to C 60 arylamine group are each independently deuterium, halogen, nitrile group, nitro group, cyano group, C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 1 ~ C 40 alkoxy group, C 1 ~ C 40 amino group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atom 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group and C 6 ~ C 60 arylamine group selected from the group consisting of Is unsubstituted or substituted with one or more.

또한, 본 발명은 (i) 양극, (ⅱ) 음극, 및 (ⅲ) 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자를 제공한다. The present invention also provides an organic electroluminescent device comprising at least one organic material layer interposed between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, wherein at least one of the one or more organic layers One is an organic electroluminescent device comprising a compound represented by the general formula (1).

이때, 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트 또는 형광 호스트로 사용될 수 있다.
In this case, the compound represented by Chemical Formula 1 may be used as a phosphorescent host or a fluorescent host of the emission layer.

본 발명의 화학식 1로 표시되는 신규 아크리딘계 화합물은 우수한 내열성, 정공 주입 및 수송능, 발광능 등을 나타낼 수 있다 The novel acridine-based compound represented by Formula 1 of the present invention may exhibit excellent heat resistance, hole injection and transport ability, light emitting ability, and the like.

따라서 상기 화학식 1로 표시되는 화합물을 정공 주입/수송층 또는 발광층의 인광/형광 호스트, 도판트 등으로 포함하는 유기 EL 소자는 발광성능, 구동전압, 수명, 효율 등의 측면에서 크게 향상될 수 있으므로, 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.
Therefore, an organic EL device including the compound represented by Formula 1 as a hole injection / transport layer or a phosphorescent / fluorescent host or dopant of a light emitting layer can be greatly improved in terms of light emitting performance, driving voltage, lifetime, efficiency, A full color display panel, and the like.

본 발명은 종래 유기 EL 소자용 재료 [예: 4,4-dicarbazolybiphenyl (이하 CBP로 표시함)] 보다 높은 분자량을 가지면서, 우수한 구동 전압 특성과 효율을 갖는 신규한 아크리딘계 화합물을 제공한다.The present invention provides a novel acridine-based compound having a higher molecular weight than a conventional organic EL device material (for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as CBP)) and having excellent driving voltage characteristics and efficiency.

본 발명에 따라 상기 화학식 1로 표시되는 화합물은, 아크리딘계 기본 골격에 축합(fused) 탄소고리 또는 축합 헤테로환 모이어티, 바람직하게는 축합 헤테로환 모이어티가 연결되고, 여러 치환체에 의해 에너지 레벨이 조절됨으로써 넓은 밴드갭 (sky blue ~ red)을 갖는다. 이로 인해 소자의 인광특성을 개선함과 동시에 전자 및/또는 정공 수송 능력, 발광효율, 구동전압, 수명 특성 등이 개선될 수 있어, 발광층뿐만 아니라 여러 치환체의 도입으로 정공 수송층, 전자 수송층, 발광 호스트 등으로 응용될 수 있다. 특히, 아크리딘계 기본골격으로 인해 기존 CBP에 비해 발광 호스트 재료로서의 우수한 특성을 나타낼 수 있다. According to the present invention, the compound represented by Chemical Formula 1 has a condensed cyclic ring or a condensed heterocyclic moiety, preferably a condensed heterocyclic moiety, connected to an acridine-based skeleton, and has an energy level by various substituents. This control has a wide bandgap (sky blue to red). As a result, the phosphorescence property of the device may be improved, and the electron and / or hole transport ability, the luminous efficiency, the driving voltage, and the lifespan characteristics may be improved. And the like can be applied. In particular, the acridine-based skeleton can exhibit excellent properties as a light emitting host material compared to the existing CBP.

또한 아크리딘계 기본 골격에, 다양한 방향족 환(aromatic ring) 치환체가 도입되어 화합물의 분자량이 유의적으로 증대됨으로써, 유리전이온도가 향상되고, 이로 인해 종래 CBP 보다 높은 열적 안정성을 가질 수 있다. 따라서 본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자는 내구성 및 수명 특성을 크게 향상시킬 수 있다. In addition, a variety of aromatic ring substituents are introduced into the acridine-based skeleton to significantly increase the molecular weight of the compound, thereby improving the glass transition temperature, and thus having higher thermal stability than the conventional CBP. Accordingly, the organic electroluminescent device comprising the compound represented by Formula 1 of the present invention can greatly improve the durability and lifetime characteristics.

아울러, 본 발명의 화학식 1로 표시되는 화합물을 유기 전계 발광(EL) 소자의 정공 주입/수송층, 청색, 녹색 및/또는 적색의 인광 호스트 재료 또는 형광 호스트 재료로 채택할 경우, CBP 대비 효율 및 수명 면에서 월등히 우수한 효과를 발휘할 수 있다. 따라서 본 발명에 따른 화합물은 유기 EL 소자의 성능 개선 및 수명 향상에 크게 기여할 수 있다. In addition, when the compound represented by the formula (1) of the present invention is employed as a hole injection / transport layer of an organic electroluminescence (EL) device, a blue, green and / or red phosphorescent host material or a fluorescent host material, It is possible to exert a remarkably excellent effect on the surface. Therefore, the compounds according to the present invention can greatly contribute to improvement of the performance and lifetime of the organic EL device.

본 발명에 따른 화학식 1로 표기되는 화합물에서, 넓은 밴드갭과 열안정성을 고려했을 때, Ar1 내지 Ar6는 서로 같거나 상이하며, 각각 독립적으로 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기인 것이 바람직하다. 이때 상기 C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기는, 각각 독립적으로 중수소, 할로겐, C1~C40의 알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기 및 C6~C60의 아릴아민기로 구성된 군으로부터 선택된 하나 이상의 치환기로 치환될 수 있다.In the compound represented by Formula 1 according to the present invention, when considering a wide bandgap and thermal stability, Ar 1 to Ar 6 are the same as or different from each other, each independently substituted or unsubstituted C 6 ~ C 60 aryl Group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms. At this time, the C 6 ~ C 60 aryl group, the heteroaryl group of 5 to 60 nuclear atoms, each independently is deuterium, halogen, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 heterocycloalkyl groups, C 6 to C 60 aryl groups, 5 to 60 heteroaryl groups, C 1 to C 40 alkyloxy groups, C 6 to C 60 aryloxy groups, C 1 to C It may be substituted with one or more substituents selected from the group consisting of 40 alkylsilyl groups, C 6 ~ C 60 arylsilyl groups and C 6 ~ C 60 arylamine groups.

본 발명의 Ar1 내지 Ar4에서, 상기 아릴기 또는 핵원자수 5 내지 60의 헤테로아릴기는 페닐, 나프틸, 인덴, 안트라센, 페난트렌, 파이렌, 트리페닐렌, 피리딘, 피리미딘, 피라진, 트리아진, 퀴놀린, 이소퀴놀린, 퀴녹살린, 플루오렌, 카바졸, 디벤조싸이오펜, 디벤조퓨란, 아크리딘, 인돌, 벤조퓨란, 벤조싸이오펜, 벤즈이미다졸, 벤조싸이아졸, 퓨린, 페난트롤린인 경우가 바람직하다. In Ar 1 to Ar 4 of the present invention, the aryl group or the heteroaryl group having 5 to 60 nuclear atoms may be selected from phenyl, naphthyl, indene, anthracene, phenanthrene, pyrene, triphenylene, pyridine, pyrimidine, pyrazine, Triazine, quinoline, isoquinoline, quinoxaline, fluorene, carbazole, dibenzothiophene, dibenzofuran, acridine, indole, benzofuran, benzothiophene, benzimidazole, benzothiazole, purine, phenan Preferred is the trolline.

또한 본 발명에 따른 화학식 1로 표기되는 화합물에서, R4 내지 R14는 각각 독립적으로 수소, 할로겐, 시아노, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기인 것이 바람직하다. 이때, 상기 C1~C40의 알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, C1~C40의 알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기 및 C6~C60의 아릴아민기로 구성된 군으로부터 선택된 하나 이상의 치환기로 치환될 수 있다. In addition, in the compound represented by Formula 1 according to the present invention, R 4 to R 14 are each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1 ~ C 40 alkyl group, substituted or unsubstituted C 6 ~ is a heteroaryl group in the C 60 aryl group, a substituted or unsubstituted nuclear atoms of 5 to 60 is preferred. In this case, the C 1 ~ C 40 Alkyl group, C 6 ~ C 60 Aryl group, nuclear atoms 5 to 60 heteroaryl group are each independently deuterium, halogen, C 1 ~ C 40 Alkyl group, C 3 ~ C 40 Of a cycloalkyl group, a C 3 to C 40 heterocycloalkyl group, a C 6 to C 60 aryl group, a nuclear atom having 5 to 60 heteroaryl groups, a C 1 to C 40 alkyloxy group, a C 6 to C 60 group It may be substituted with one or more substituents selected from the group consisting of an aryloxy group, a C 1 to C 40 alkylsilyl group, a C 6 to C 60 arylsilyl group and a C 6 to C 60 arylamine group.

한편 R4 내지 R14 가 수소 이외의 치환기로 치환되는 경우, 전술한 할로겐, 시아노, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기는 상기 화학식 1의 R7, R8, R13에 각각 위치할 수 있다. 상기 화학식 1의 R4 내지 R14 중에서 R7, R8 , R13 위치는 상대적으로 치환체의 도입이 용이하므로, 수소 이외의 치환기가 도입되는 경우 화합물의 분자량이 유의적으로 증대됨으로써, 유리전이온도가 향상되고, 이로 인해 높은 열적 안정성을 가질 수 있다.Meanwhile, when R 4 to R 14 are substituted with a substituent other than hydrogen, the aforementioned halogen, cyano, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 6 to C 60 aryl group, The substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms may be positioned at R 7 , R 8, and R 13 of Chemical Formula 1, respectively. R 7 , R 8 and R 13 in R 4 to R 14 of Formula 1 are relatively easy to introduce a substituent, when the substituents other than hydrogen is introduced, the molecular weight of the compound is significantly increased, the glass transition temperature Can be improved, thereby having high thermal stability.

본 발명에 따른 화학식 1의 화합물에서, Ar1 내지 Ar6 또는 R7, R8, R13 는 각각 독립적으로 하기 치환체(작용기) 그룹으로부터 선택될 수 있다.In the compound of Formula 1 according to the present invention, Ar 1 to Ar 6 or R 7 , R 8, R 13 may be each independently selected from the following substituent (functional group) groups.

Figure pat00005
Figure pat00005

Figure pat00006
Figure pat00006

Figure pat00007
Figure pat00007

Figure pat00008

Figure pat00008

본 발명에 따라 화학식 1로 표시되는 아크리딘계 화합물은 하기 예시된 화학식 3 및/또는 화학식 4의 화합물로서 보다 구체화될 수 있다.The acridine-based compound represented by the formula (1) according to the present invention may be more specified as a compound of the formula (3) and / or formula (4) illustrated below.

Figure pat00009
Figure pat00009

Figure pat00010
Figure pat00010

상기 식에서, Where

X, R1 내지 R14 , Ar1 내지 Ar6 은 상기 화학식 1에서 정의된 바와 같다.X, R 1 to R 14 , Ar 1 To Ar 6 Is as defined in Formula 1 above.

전술한 바와 같이, 상기 R7, R8, R13은 각각 독립적으로 수소, 할로겐, 시아노, C1~C40의 알킬기, C6~C60의 아릴기, C3~C60의 헤테로아릴기인 것이 바람직하다. As described above, R 7 , R 8 , R 13 are each independently hydrogen, halogen, cyano, C 1 ~ C 40 alkyl group, C 6 ~ C 60 aryl group, C 3 ~ C 60 heteroaryl It is preferable that it is a group.

본 발명에서 사용되는 "비치환된 알킬"은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소를 지칭하는 것으로서, 이의 비제한적인 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있다. As used herein, "unsubstituted alkyl" refers to straight or branched chain saturated hydrocarbons having 1 to 40 carbon atoms, including but not limited to methyl, ethyl, propyl, isobutyl, sec- - Amyl, hexyl and the like.

또한 "비치환된 아릴"은 단독 고리 혹은 2 이상의 고리가 조합된, 탄소수 6 내지 60의 방향족 부위를 의미한다. 이때 2 이상의 고리는 서로 단순 부착(pendant)되거나 축합된(fused) 형태로 부착될 수 있다. "Unsubstituted aryl" means an aromatic moiety having from 6 to 60 carbon atoms, either alone or in combination with at least two rings. Where the two or more rings may be attached to each other in a pendant or fused form to each other.

또한 "비치환된 헤테로아릴"은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 부위를 의미하는 것으로서, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 이때 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된(fused) 형태로 부착될 수 있고, 나아가 아릴기와의 축합된 형태도 포함하는 것으로 해석된다. "Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 60 nuclear atoms in which at least one carbon, preferably one to three carbons, of the ring is replaced by N, O , S, or Se. Wherein two or more rings may be attached to each other in a pendant or fused form to each other and further include a condensed form with an aryl group.

나아가, "축합(fused) 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.Further, "fused ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

이상에서 설명한 본 발명에 따라 화학식 1로 표시되는 화합물은 하기 예시된 화학식들로 보다 구체화될 수 있다. 그러나 본 발명의 화학식 1로 표시되는 화합물이 하기 예시된 것들에 의해 한정되는 것은 아니다.According to the present invention described above, the compound represented by Formula 1 may be further embodied by the formulas illustrated below. However, the compounds represented by formula (1) of the present invention are not limited by the following examples.

Figure pat00011
Figure pat00011

Figure pat00012
Figure pat00012

Figure pat00013
Figure pat00013

Figure pat00014

Figure pat00014

Figure pat00015
Figure pat00015

Figure pat00016
Figure pat00016

Figure pat00017
Figure pat00017

Figure pat00018
Figure pat00018

Figure pat00019
Figure pat00019

Figure pat00020
Figure pat00020

Figure pat00021
Figure pat00021

Figure pat00022
Figure pat00022

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 pat00036
Figure pat00036

Figure pat00037
Figure pat00037

Figure pat00038

Figure pat00038

Figure pat00039
Figure pat00039

Figure pat00040

Figure pat00040

Figure pat00041

Figure pat00041

본 발명의 화학식 1의 화합물은 일반적인 합성방법에 따라 합성될 수 있다. 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다.The compound of formula 1 of the present invention may be synthesized according to a general synthetic method. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자에 관한 것이다. According to another aspect of the present invention, there is provided an organic electroluminescent device comprising the compound represented by Formula 1 according to the present invention.

구체적으로, 본 발명에 따른 유기 전계 발광 소자는 (i) 양극, (ⅱ) 음극, 및 (ⅲ) 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 1종 이상 포함하는 것을 특징으로 하는 한다.Specifically, the organic electroluminescent device according to the present invention comprises at least one organic layer sandwiched between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, wherein at least one Is one or more compounds represented by the formula (1).

여기서, 본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있다. 바람직하게는, 상기 화학식 1로 표시되는 화합물은 발광층 물질로서 유기 전계 발광 소자에 포함될 수 있다. 이 경우 유기 전계 발광 소자는 발광효율, 휘도, 전력효율 열적 안정성 및 소자 수명이 향상될 수 있다. Herein, the organic material layer including the compound represented by Chemical Formula 1 may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the compound represented by Formula 1 may be included in the organic electroluminescent device as a light emitting layer material. In this case, the organic EL device may improve luminous efficiency, brightness, power efficiency, thermal stability, and device life.

특히 본 발명에 따라 화학식 1로 표시되는 화합물은 발광층의 인광 호스트 또는 형광 호스트나 이의 도펀트 재료로 이용될 수 있다. 바람직하게는, 상기 화학식 1로 표시되는 화합물은 청색, 녹색 및/또는 적색의 인광 호스트, 형광 호스트, 또는 도펀트 재료로서 유기 발광 소자에 포함될 수 있다. In particular, the compound represented by the formula (1) according to the present invention can be used as a phosphorescent host or a fluorescent host or a dopant material of the light emitting layer. Preferably, the compound represented by Formula 1 may be included in the organic light emitting device as a blue, green, and / or red phosphorescent host, a fluorescent host, or a dopant material.

또한 본 발명에 따른 유기 전계 발광 소자에서, 상기 화학식 1의 화합물을 포함하는 유기물층 이외의 다른 유기물층은 정공주입층, 정공수송층, 발광층 및/또는 전자수송층일 수 있다. In addition, in the organic electroluminescent device according to the present invention, the organic compound layer other than the organic compound layer including the compound of Formula 1 may be a hole injecting layer, a hole transporting layer, a light emitting layer, and / or an electron transporting layer.

본 발명에 따른 유기 전계 발광 소자 구조의 비제한적인 예를 들면, 기판, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 것일 수 있다. 이때 정공 주입층, 정공 수송층 및 발광층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 1종 이상 포함할 수 있다. 또한, 본 발명의 화합물은 발광층의 인광 호스트 또는 형광 호스트로 이용될 수 있다. 상기 전자 수송층 위에는 전자 주입층이 위치할 수도 있다.As a non-limiting example of the organic electroluminescent device structure according to the present invention, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode may be sequentially stacked. At this time, at least one of the hole injecting layer, the hole transporting layer and the light emitting layer may contain at least one compound represented by the above formula (1). In addition, the compound of the present invention can be used as a phosphorescent host or a fluorescent host of the luminescent layer. An electron injection layer may be disposed on the electron transport layer.

또한, 본 발명에 따른 유기 EL 소자는 전술한 바와 같이 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입될 수 있다. In addition, the organic EL device according to the present invention may have an insulating layer or an adhesive layer inserted into the interface between the electrode and the organic layer as well as the structure in which the anode, one or more organic layers and the cathode are sequentially stacked, as described above.

본 발명에 따른 유기 전계 발광 소자에 있어서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 진공증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에만 한정되지 않는다. In the organic electroluminescent device according to the present invention, the organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

본 발명에 따른 유기 전계 발광 소자는, 유기물층 중 1층 이상을 본 발명의 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 유기물층 및 전극을 형성함으로써 제조될 수 있다. The organic electroluminescent device according to the present invention may be formed using an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Chemical Formula 1 of the present invention. By forming.

예컨대, 기판으로는 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다. For example, a silicon wafer, quartz or glass plate, a metal plate, a plastic film or a sheet can be used as the substrate.

양극 물질로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자; 또는 카본블랙 등이 있으나, 이들에만 한정되는 것은 아니다. Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but are not limited thereto.

음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.

또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당업계에 알려진 통상의 물질이 사용될 수 있다. The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and conventional materials known in the art can be used.

이하, 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[[ 제조예Manufacturing example 1] 7,9- 1] 7,9- dihydrobenzodihydrobenzo [[ klkl ]] indoloindolo [3,2-b][3,2-b] acridineacridine 및 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine의 합성 And synthesis of 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine

<단계 1> 3-(4,4,5,5-<Step 1> 3- (4,4,5,5- tetramethyltetramethyl -1,3,2--1,3,2- dioxaborolandioxaborolan -2--2- ylyl )-9H-) -9H- carbazolecarbazole 의 합성Synthesis of

Figure pat00042
Figure pat00042

질소 기류 하에서 3-bromo-9H-carbazole 31.50 g (0.128 mol)과 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 48.58 g (0.191 mol), Pd(dppf)Cl2 5.20 g (5 mol %), KOAc 37.55 g (0.383 mol), DMF 900 ml를 넣고 130℃에서 12 시간 교반한 후 반응을 종결시키고, 에틸아세테이트로 추출하여 MgSO4로 수분을 제거하였다. 용매를 제거한 반응물은 컬럼크로마토그래피를 이용하여 목적 화합물인 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 15.01 g (yield : 40 %)을 획득하였다. 31.50 g (0.128 mol) of 3-bromo-9H-carbazole and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3, 2-dioxaborolane) 48.58 g (0.191 mol), Pd (dppf) Cl 2 5.20 g (5 mol%), KOAc 37.55 g (0.383 mol) and 900 ml of DMF were added and stirred at 130 ° C. for 12 hours to terminate the reaction. , Extracted with ethyl acetate to remove water with MgSO 4 . The solvent was removed using a column chromatography 15.01 g (yield: 40% of the target compound 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole using column chromatography ) Was obtained.

1H-NMR : δ 1.24 (s, 12H), 7.30 (t, 1H), 7.55 (m, 4H), 7.98 (m, 2H), 10.42 (s, 1H)
 1 H-NMR: δ 1.24 (s, 12H), 7.30 (t, 1H), 7.55 (m, 4H), 7.98 (m, 2H), 10.42 (s, 1H)

<단계 2> 3-(8-nitronaphthalen-1-yl)-9H-carbazole의 합성<Step 2> Synthesis of 3- (8-nitronaphthalen-1-yl) -9H-carbazole

Figure pat00043
Figure pat00043

질소 기류 하에서 8.22 g (39.6 mmol)의 1-chloro-8-nitronaphthalene, 11.61 g (39.6 mmol)의 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole, 4.75 g (118.8 mmol)의 NaOH과 200 ml/100 ml의 THF/H2O를 넣고 교반하였다. 40℃에서 1.15g (5 mol%)의 Pd(PPh3)4를 넣고 80℃에서 12시간 동안 교반하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터링하였다. 필터링된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 3-(8-nitronaphthalen-1-yl)-9H-carbazole 9.25 g (yield: 69%)을 획득하였다. 8.22 g (39.6 mmol) of 1-chloro-8-nitronaphthalene, 11.61 g (39.6 mmol) of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) under nitrogen stream -9H-carbazole, 4.75 g (118.8 mmol) of NaOH and 200 ml / 100 ml of THF / H 2 O were added and stirred. 1.15 g (5 mol%) of Pd (PPh 3 ) 4 was added at 40 ° C, and the mixture was stirred at 80 ° C for 12 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, and the mixture was filtered with MgSO 4 . 9.25 g (yield: 69%) of 3- (8-nitronaphthalen-1-yl) -9H-carbazole as a target compound was obtained by removing the solvent of the filtered organic layer using column chromatography.

1H-NMR : δ 7.31 (t, 1H), 7.60 (m, 4H), 7.81 (m, 3H), 8.31 (m, 5H), 10.39 (s, 1H)
 1 H-NMR: δ 7.31 (t, 1H), 7.60 (m, 4H), 7.81 (m, 3H), 8.31 (m, 5H), 10.39 (s, 1H)

<단계 3> 7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 및 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine의 합성Step 3 Synthesis of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine and 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine

Figure pat00044
Figure pat00044

질소 기류 하에서 3-(8-nitronaphthalen-1-yl)-9H-carbazole 6.46 g (19.10 mmol)과 triphenylphosphine 12.52 g (47.72 mmol), 1,2-dichlorobenzene 50 ml를 넣은 후 12시간 교반하였다. 반응 종료 후 1,2-dichlorobenzene를 제거하고 디클로로메탄으로 추출하였다. 추출된 유기층은 MgSO4로 물을 제거하고, 컬럼크로마토그래피를 이용하여 목적 화합물인 7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 1.93 g (yield : 33 %)과 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine 2.69 g (yield : 46 %)을 획득하였다. Under nitrogen stream, 6.46 g (19.10 mmol) of 3- (8-nitronaphthalen-1-yl) -9H-carbazole, 12.52 g (47.72 mmol) of triphenylphosphine, and 50 ml of 1,2-dichlorobenzene were added thereto, followed by stirring for 12 hours. After completion of the reaction, 1,2-dichlorobenzene was removed and extracted with dichloromethane. The extracted organic layer was removed with water using MgSO 4 , and the target compound 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine 1.93 g (yield: 33%) and 9,14 were purified by column chromatography. 2.69 g (yield: 46%) of -dihydrobenzo [kl] indolo [2,3-c] acridine were obtained.

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine에 대한 1H-NMR: δ 6.67 (s, 1H) 6.80 (s, 1H), 7.01 (d, 1H), 7.29 (m, 2H), 7.59 (m, 5H), 7.99 (m, 1H), 8.21 (m, 2H), 10.64 (s, 1H) 1 H-NMR for 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine: δ 6.67 (s, 1H) 6.80 (s, 1H), 7.01 (d, 1H), 7.29 (m, 2H ), 7.59 (m, 5H), 7.99 (m, 1H), 8.21 (m, 2H), 10.64 (s, 1H)

9,14-dihydrobenzo[kl]indolo[2,3-c]acridine에 대한 1H-NMR: δ 6.65 (s, 1H) 6.91 (d, 1H), 7.01 (d, 1H), 7.32 (m, 2H), 7.63 (m, 5H), 8.01 (m, 2H), 8.41 (m, 1H), 10.63 (s, 1H)
 1 H-NMR for 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine: δ 6.65 (s, 1H) 6.91 (d, 1H), 7.01 (d, 1H), 7.32 (m, 2H ), 7.63 (m, 5H), 8.01 (m, 2H), 8.41 (m, 1H), 10.63 (s, 1H)

[제조예 2] 9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine의 합성 Preparation Example 2 Synthesis of 9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine

<단계 1> 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole의 합성Step 1 Synthesis of 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole

Figure pat00045
Figure pat00045

3-bromo-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 1>과 동일한 과정을 수행하여 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 을 얻었다.Except for using 3-bromo-9-phenyl-9H-carbazole instead of 3-bromo-9H-carbazole, 9-phenyl-3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole was obtained.

1H-NMR : δ 1.24 (s, 12H), 7.30 (m, 1H), 7.54 (m, 8H) , 7.99 (m, 3H)
 1 H-NMR: δ 1.24 (s, 12H), 7.30 (m, 1H), 7.54 (m, 8H), 7.99 (m, 3H)

<단계 2> 3-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole의 합성<Step 2> Synthesis of 3- (8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole

Figure pat00046
Figure pat00046

3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 대신 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 2>와 동일한 과정을 수행하여 3-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 얻었다.9-phenyl-3- (4,4,5,5-tetramethyl-1,3 instead of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole Except for using 2-dioxaborolan-2-yl) -9H-carbazole, the process was carried out in the same manner as in <Step 2> of Preparation Example 1 to 3- (8-nitronaphthalen-1-yl) -9- Phenyl-9H-carbazole was obtained.

1H-NMR : δ 7.30 (m, 1H), 7.59 (m, 8H), 7.89 (m, 2H) , 8.22 (m, 7H)
 1 H-NMR: δ 7.30 (m, 1H), 7.59 (m, 8H), 7.89 (m, 2H), 8.22 (m, 7H)

<단계 3> 9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine의 합성Step 3 Synthesis of 9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine

Figure pat00047
Figure pat00047

3-(8-nitronaphthalen-1-yl)-9H-carbazole 대신 3-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 3>와 동일한 과정을 수행하여 9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine를 얻었다.<Step of Preparation Example 1, except that 3- (8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole was used instead of 3- (8-nitronaphthalen-1-yl) -9H-carbazole. 3> was carried out the same process to obtain 9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine.

1H-NMR: δ 6.65 (s, 1H), 6.92 (m, 2H), 7.53 (m, 12H), 8.11 (m, 3H)
 1 H-NMR: δ 6.65 (s, 1H), 6.92 (m, 2H), 7.53 (m, 12H), 8.11 (m, 3H)

[제조예 3] 12-bromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine의 합성 Preparation Example 3 Synthesis of 12-bromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine

<단계 1> 3-bromo-9-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 의 합성<Step 1> Synthesis of 3-bromo-9-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole

Figure pat00048
Figure pat00048

3-bromo-9H-carbazole 대신 3,6-dibromo-9-phenyl-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 1>와 동일한 과정을 수행하여 3-bromo-9-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole을 얻었다. Except for using 3,6-dibromo-9-phenyl-9H-carbazole instead of 3-bromo-9H-carbazole, the same process as in <Step 1> of Preparation Example 1 was carried out to 3-bromo-9- Phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole was obtained.

1H-NMR : δ 1.23 (s, 12H), 7.31 (m, 1H), 7.52 (m, 7H) , 7.99 (m, 3H)
 1 H-NMR: δ 1.23 (s, 12H), 7.31 (m, 1H), 7.52 (m, 7H), 7.99 (m, 3H)

<단계 2> 3-bromo-6-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole의 합성<Step 2> Synthesis of 3-bromo-6- (8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole

Figure pat00049
Figure pat00049

3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 대신 3-bromo-9-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 2>와 동일한 과정을 수행하여 3-bromo-6-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 얻었다.3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole instead of 3-bromo-9-phenyl-6- (4,4,5,5-tetramethyl Except for using -1,3,2-dioxaborolan-2-yl) -9H-carbazole, 3-bromo-6- (8-nitronaphthalen) was carried out in the same manner as in <Step 2> of Preparation Example 1 above. -1-yl) -9-phenyl-9H-carbazole was obtained.

1H-NMR : δ 7.28 (m, 1H), 7.63 (m, 7H), 7.90 (m, 2H) , 8.20 (m, 7H)
 1 H-NMR: δ 7.28 (m, 1H), 7.63 (m, 7H), 7.90 (m, 2H), 8.20 (m, 7H)

<단계 3> 12-bromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine의 합성Step 3 Synthesis of 12-bromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine

Figure pat00050
Figure pat00050

3-(8-nitronaphthalen-1-yl)-9H-carbazole 대신 3-bromo-6-(8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 3>와 동일한 과정을 수행하여 12-bromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine를 얻었다.The preparation example above, except that 3-bromo-6- (8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole was used instead of 3- (8-nitronaphthalen-1-yl) -9H-carbazole. 12-bromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine was obtained in the same manner as in <Step 3> of 1.

1H-NMR: δ 6.60 (s, 1H), 6.92 (m, 2H), 7.51 (m, 11H), 8.08 (m, 3H)
 1 H-NMR: δ 6.60 (s, 1H), 6.92 (m, 2H), 7.51 (m, 11H), 8.08 (m, 3H)

[제조예 4] 3,12-dibromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 의 합성 Preparation Example 4 Synthesis of 3,12-dibromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine

<단계 1> 3-bromo-6-(4-bromo-8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole의 합성<Step 1> Synthesis of 3-bromo-6- (4-bromo-8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole

Figure pat00051
Figure pat00051

1-chloro-8-nitronaphthalene 대신 1,4-dibromo-5-nitronaphthalene을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 2>와 동일한 과정을 수행하여 3-bromo-6-(4-bromo-8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 얻었다.Except for using 1,4-dibromo-5-nitronaphthalene instead of 1-chloro-8-nitronaphthalene, the same procedure as in <Step 2> of Preparation Example 1 was carried out to 3-bromo-6- (4-bromo -8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole was obtained.

1H-NMR : δ 7.30 (m, 1H), 7.60 (m, 6H), 7.98 (m, 2H) , 8.23 (m, 7H)
 1 H-NMR: δ 7.30 (m, 1H), 7.60 (m, 6H), 7.98 (m, 2H), 8.23 (m, 7H)

<단계 2> 3,12-<Step 2> 3,12- dibromodibromo -9--9- phenylphenyl -7,9--7,9- dihydrobenzodihydrobenzo [[ klkl ]] indoloindolo [3,2-b]acridine 의 합성Synthesis of [3,2-b] acridine

Figure pat00052
Figure pat00052

3-(8-nitronaphthalen-1-yl)-9H-carbazole 대신 3-bromo-6-(4-bromo-8-nitronaphthalen-1-yl)-9-phenyl-9H-carbazole을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 3>와 동일한 과정을 수행하여 3,12-dibromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine을 얻었다.Except for using 3-bromo-6- (4-bromo-8-nitronaphthalen-1-yl) -9-phenyl-9H-carbazole instead of 3- (8-nitronaphthalen-1-yl) -9H-carbazole , 3,12-dibromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine was obtained in the same manner as in <Step 3> of Preparation Example 1.

1H-NMR: δ 6.62 (s, 1H), 6.97 (m, 2H), 7.58 (m, 10H), 8.11 (m, 3H)
 1 H-NMR: δ 6.62 (s, 1H), 6.97 (m, 2H), 7.58 (m, 10H), 8.11 (m, 3H)

[제조예 5] 9,9-dimethyl-7,9-dihydrobenzo[kl]indeno[1,2-b]acridine의 합성 Preparation Example 5 Synthesis of 9,9-dimethyl-7,9-dihydrobenzo [kl] indeno [1,2-b] acridine

<단계 1> 2-(9,9-dimethyl-9H-fluoren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane의 합성<Step 1> Synthesis of 2- (9,9-dimethyl-9H-fluoren-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Figure pat00053
Figure pat00053

3-bromo-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene을 사용하는 것을 제외하고는, 제조예 1의 <단계 1>과 동일한 과정을 수행하여 2-(9,9-dimethyl-9H-fluoren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane을 얻었다.Except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 3-bromo-9H-carbazole, the same procedure as in <Step 1> of Preparation Example 1 was carried out to provide 2- (9,9- Dimethyl-9H-fluoren-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.

1H-NMR : δ 1.23 (s, 12H), 1.73 (s, 6H), 7.00 (m, 2H), 7.21 (m, 1H), 7.32 (m, 2H) , 7.79 (m, 2H)
 1 H-NMR: δ 1.23 (s, 12H), 1.73 (s, 6H), 7.00 (m, 2H), 7.21 (m, 1H), 7.32 (m, 2H), 7.79 (m, 2H)

<단계 2> 9,9-dimethyl-3-(8-nitronaphthalen-1-yl)-9H-fluorene의 합성Step 2 Synthesis of 9,9-dimethyl-3- (8-nitronaphthalen-1-yl) -9H-fluorene

Figure pat00054
Figure pat00054

3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 대신 2-(9,9-dimethyl-9H-fluoren-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 2>와 동일한 과정을 수행하여 9,9-dimethyl-3-(8-nitronaphthalen-1-yl)-9H-fluorene을 얻었다.2- (9,9-dimethyl-9H-fluoren-3-yl) -4, instead of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole, Except for using 4,5,5-tetramethyl-1,3,2-dioxaborolane, 9,9-dimethyl-3- (8-nitronaphthalen) was subjected to the same procedure as in <Step 2> of Preparation Example 1 above. -1-yl) -9H-fluorene was obtained.

1H-NMR : δ 1.72 (s, 6H), 7.30 (m, 2H), 7.59 (m, 4H), 7.90 (m, 3H) , 8.23 (m, 4H)
 1 H-NMR: δ 1.72 (s, 6H), 7.30 (m, 2H), 7.59 (m, 4H), 7.90 (m, 3H), 8.23 (m, 4H)

<단계 3> 9,9-dimethyl-7,9-dihydrobenzo[kl]indeno[1,2-b]acridine의 합성Step 3 Synthesis of 9,9-dimethyl-7,9-dihydrobenzo [kl] indeno [1,2-b] acridine

Figure pat00055
Figure pat00055

3-(8-nitronaphthalen-1-yl)-9H-carbazole 대신 9,9-dimethyl-3-(8-nitronaphthalen-1-yl)-9H-fluorene을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 3>과 동일한 과정을 수행하여 9,9-dimethyl-7,9-dihydrobenzo[kl]indeno[1,2-b]acridine를 얻었다.Except for using 9,9-dimethyl-3- (8-nitronaphthalen-1-yl) -9H-fluorene instead of 3- (8-nitronaphthalen-1-yl) -9H-carbazole, 9,9-dimethyl-7,9-dihydrobenzo [kl] indeno [1,2-b] acridine was obtained in the same manner as in <Step 3>.

1H-NMR : δ 1.72 (s, 6H), 6.62 (s, 1H), 7.29 (m, 2H), 7.58 (m, 3H), 7.92 (m, 3H) , 8.21 (m, 4H)
 1 H-NMR: δ 1.72 (s, 6H), 6.62 (s, 1H), 7.29 (m, 2H), 7.58 (m, 3H), 7.92 (m, 3H), 8.21 (m, 4H)

[제조예 6] 7H-benzo[kl]benzothieno[3,2-b]acridine의 합성 Preparation Example 6 Synthesis of 7H-benzo [kl] benzothieno [3,2-b] acridine

<단계 1> 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane의 합성<Step 1> Synthesis of 2- (dibenzo [b, d] thiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Figure pat00056
Figure pat00056

3-bromo-9H-carbazole 대신 2-bromodibenzo[b,d]thiophene을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 1>과 동일한 과정을 수행하여 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane을 얻었다.Except for using 2-bromodibenzo [b, d] thiophene instead of 3-bromo-9H-carbazole, 2- (dibenzo [b, d] thiophen was prepared by the same procedure as in <Step 1> of Preparation Example 1. -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.

1H-NMR : δ 1.23 (s, 12H), 7.51 (m, 3H), 7.82 (m, 3H) , 8.31 (m, 1H)
 1 H-NMR: δ 1.23 (s, 12H), 7.51 (m, 3H), 7.82 (m, 3H), 8.31 (m, 1H)

<단계 2> 2-(8-nitronaphthalen-1-yl)dibenzo[b,d]thiophene의 합성<Step 2> Synthesis of 2- (8-nitronaphthalen-1-yl) dibenzo [b, d] thiophene

Figure pat00057
Figure pat00057

3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole 대신 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 2>와 동일한 과정을 수행하여 2-(8-nitronaphthalen-1-yl)dibenzo[b,d]thiophene을 얻었다.2- (dibenzo [b, d] thiophen-2-yl) -4,4, instead of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole Except for using 5,5-tetramethyl-1,3,2-dioxaborolane, the same procedure as in <Step 2> of Preparation Example 1 was carried out to give 2- (8-nitronaphthalen-1-yl) dibenzo [b , d] thiophene was obtained.

1H-NMR : δ 7.50 (m, 3H), 7.89 (m, 5H), 8.43 (m, 5H)
 1 H-NMR: δ 7.50 (m, 3H), 7.89 (m, 5H), 8.43 (m, 5H)

<단계 3> 7H-benzo[kl]benzothieno[3,2-b]acridine의 합성Step 3 Synthesis of 7H-benzo [kl] benzothieno [3,2-b] acridine

Figure pat00058
Figure pat00058

3-(8-nitronaphthalen-1-yl)-9H-carbazole 대신 2-(8-nitronaphthalen-1-yl)dibenzo[b,d]thiophene을 사용하는 것을 제외하고는, 상기 제조예 1의 <단계 3>와 동일한 과정을 수행하여 7H-benzo[kl]benzothieno[3,2-b]acridine를 얻었다.<Step 3 of Preparation Example 1, except that 2- (8-nitronaphthalen-1-yl) dibenzo [b, d] thiophene was used instead of 3- (8-nitronaphthalen-1-yl) -9H-carbazole. > The same process as in to obtain 7H-benzo [kl] benzothieno [3,2-b] acridine.

1H-NMR : δ 6.60 (s, 1H), 7.19 (m, 2H), 7.61 (m, 6H), 7.98 (m, 2H) , 8.34 (m, 2H)
 1 H-NMR: δ 6.60 (s, 1H), 7.19 (m, 2H), 7.61 (m, 6H), 7.98 (m, 2H), 8.34 (m, 2H)

[합성예 1] BIA-1의 합성Synthesis Example 1 Synthesis of BIA-1

Figure pat00059
Figure pat00059

질소 기류 하에서 제조예 1에서 제조된 화합물인 7,9-dihydrobenzo[kl]indolo[3,2-b]acridine (2.71 g, 8.86 mmol), 1-bromobenzene (4.17 g, 26.56 mmol), Cu powder(0.11 g, 1.77 mmol), K2CO3(2.44 g, 17.71 mmol), Na2SO4(2.52 g, 17.71 mmol) 및 nitrobenzene(100 ml)를 혼합하고 190℃에서 12시간 동안 교반하였다. 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine (2.71 g, 8.86 mmol), 1-bromobenzene (4.17 g, 26.56 mmol), Cu powder ( 0.11 g, 1.77 mmol), K 2 CO 3 (2.44 g, 17.71 mmol), Na 2 SO 4 (2.52 g, 17.71 mmol) and nitrobenzene (100 ml) were mixed and stirred at 190 ° C. for 12 hours.

반응이 종결된 후 nitrobenzene을 제거하고 메틸렌클로라이드로 유기층을 분리한 다음 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 BIA-1 (2.52 g, 수율 62%)을 얻었다. After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer was purified by column chromatography to give the title compound BIA-1 (2.52 g, 62% yield).

GC-Mass (이론치: 458.55 g/mol, 측정치: 458 g/mol)
GC-Mass (458.55 g / mol, measured: 458 g / mol)

[합성예 2] BIA-2의 합성Synthesis Example 2 Synthesis of BIA-2

Figure pat00060
Figure pat00060

1-bromobenzene 대신 3-bromopyridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-2 (2.54 g, 수율 65%)을 얻었다.Except for using 3-bromopyridine instead of 1-bromobenzene, the same process as in Synthesis Example 1 was carried out to obtain the target compound BIA-2 (2.54 g, yield 65%).

GC-Mass (이론치: 460.53 g/mol, 측정치: 460 g/mol)
GC-Mass (Theoretical value: 460.53 g / mol, Measured value: 460 g / mol)

[합성예 3] BIA-3의 합성Synthesis Example 3 Synthesis of BIA-3

Figure pat00061

Figure pat00061

1-bromobenzene 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-3 (4.08 g, 수율 60%)을 얻었다.Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound BIA-3 (4.08 g, yield 60%).

GC-Mass (이론치: 768.86 g/mol, 측정치: 768 g/mol)
GC-Mass (Theoretical value: 768.86 g / mol, Measured value: 768 g / mol)

[합성예 4] BIA-4의 합성Synthesis Example 4 Synthesis of BIA-4

Figure pat00062
Figure pat00062

1-bromobenzene 대신 2-bromo-4,6-diphenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-4 (4.34 g, 수율 65%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was performed to obtain BIA-4 (4.34 g, yield 65%) as a target compound.

GC-Mass (이론치: 764.91 g/mol, 측정치: 764 g/mol)
GC-Mass (Theoretical value: 764.91 g / mol, Measured value: 764 g / mol)

[합성예 5] BIA-5의 합성Synthesis Example 5 Synthesis of BIA-5

Figure pat00063
Figure pat00063

1-bromobenzene 대신 1-bromo-3,5-diphenylbenzene을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-5 (4.37 g, 수율 65%)을 얻었다.Except for using 1-bromo-3,5-diphenylbenzene instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was performed to obtain BIA-5 (4.37 g, yield 65%) as a target compound.

GC-Mass (이론치: 762.94 g/mol, 측정치: 762 g/mol)
GC-Mass (Theoretical value: 762.94 g / mol, Measured value: 762 g / mol)

[합성예 6] BIA-6의 합성Synthesis Example 6 Synthesis of BIA-6

Figure pat00064
Figure pat00064

1-bromobenzene 대신 3-bromobiphenyl을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-6 (2.49 g, 수율 60%)을 얻었다.Except for using 3-bromobiphenyl instead of 1-bromobenzene, the same process as in Synthesis Example 1 was carried out to obtain the target compound BIA-6 (2.49 g, yield 60%).

GC-Mass (이론치: 610.74 g/mol, 측정치: 610 g/mol)
GC-Mass (Theoretical value: 610.74 g / mol, Measured value: 610 g / mol)

[합성예 7] BIA-7의 합성Synthesis Example 7 Synthesis of BIA-7

Figure pat00065
Figure pat00065

1-bromobenzene 대신 6-bromo-2,3'-bipyridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-7 (2.10 g, 수율 57%)을 얻었다.Except for using 6-bromo-2,3'-bipyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound BIA-7 (2.10 g, yield 57%).

GC-Mass (이론치: 614.70 g/mol, 측정치: 614 g/mol)
GC-Mass (Theoretical value: 614.70 g / mol, Measured value: 614 g / mol)

[합성예 8] BIA-8의 합성Synthesis Example 8 Synthesis of BIA-8

Figure pat00066

Figure pat00066

1-bromobenzene 대신 2-bromo-6-phenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-8 (2.27 g, 수율 58%)을 얻었다.Except for using 2-bromo-6-phenylpyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was performed to obtain BIA-8 (2.27 g, yield 58%) as a target compound.

GC-Mass (이론치: 612.72 g/mol, 측정치: 612 g/mol)
GC-Mass (Theoretical value: 612.72 g / mol, Measured value: 612 g / mol)

[합성예 9] BIA-9의 합성Synthesis Example 9 Synthesis of BIA-9

Figure pat00067
Figure pat00067

1-bromobenzene 대신 9-(3-bromophenyl)-9H-carbazole을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-9 (4.20 g, 수율 60%)을 얻었다.Except for using 9- (3-bromophenyl) -9H-carbazole instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was performed to obtain BIA-9 (4.20 g, yield 60%) as a target compound.

GC-Mass (이론치: 788.93 g/mol, 측정치: 788 g/mol)
GC-Mass (Theoretical value: 788.93 g / mol, Measured value: 788 g / mol)

[합성예 10] BIA-10의 합성Synthesis Example 10 Synthesis of BIA-10

Figure pat00068
Figure pat00068

1-bromobenzene 대신 3-(3-bromophenyl)-9,9-dimethyl-9H-fluorene을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-10 (4.01 g, 수율 59%)을 얻었다.Except for using 3- (3-bromophenyl) -9,9-dimethyl-9H-fluorene instead of 1-bromobenzene, the same procedure as in Synthesis Example 1 was carried out to obtain the target compound BIA-10 (4.01 g, yield 59%).

GC-Mass (이론치: 843.06 g/mol, 측정치: 842 g/mol)
GC-Mass (Theoretical value: 843.06 g / mol, Measured value: 842 g / mol)

[합성예 11] BIA-11의 합성Synthesis Example 11 Synthesis of BIA-11

Figure pat00069
Figure pat00069

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-11 (2.48 g, 수율 61%)을 얻었다.The same procedure as in Synthesis Example 1 except for using 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine. Was carried out to obtain the title compound BIA-11 (2.48 g, 61% yield).

GC-Mass (이론치: 458.55 g/mol, 측정치: 458 g/mol)
GC-Mass (458.55 g / mol, measured: 458 g / mol)

[합성예 12] BIA-12의 합성Synthesis Example 12 Synthesis of BIA-12

Figure pat00070
Figure pat00070

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine을 사용하는 것을 제외하고는, 상기 합성예 2와 동일한 과정을 수행하여 목적 화합물인 BIA-12 (2.69 g, 수율 66%)을 얻었다.The same procedure as in Synthesis Example 2 except for using 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine Was carried out to obtain the title compound BIA-12 (2.69 g, yield 66%).

GC-Mass (이론치: 460.53 g/mol, 측정치: 460 g/mol)
GC-Mass (Theoretical value: 460.53 g / mol, Measured value: 460 g / mol)

[합성예 13] BIA-13의 합성Synthesis Example 13 Synthesis of BIA-13

Figure pat00071
Figure pat00071

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine을 사용하는 것을 제외하고는, 상기 합성예 3과 동일한 과정을 수행하여 목적 화합물인 BIA-13 (4.09 g, 수율 60%)을 얻었다.The same procedure as in Synthesis Example 3, except 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine is used instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine. Was carried out to obtain the title compound BIA-13 (4.09 g, yield 60%).

GC-Mass (이론치: 768.86 g/mol, 측정치: 768 g/mol)
GC-Mass (Theoretical value: 768.86 g / mol, Measured value: 768 g / mol)

[합성예 14] BIA-14의 합성Synthesis Example 14 Synthesis of BIA-14

Figure pat00072
Figure pat00072

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9,14-dihydrobenzo[kl]indolo[2,3-c]acridine을 사용하는 것을 제외하고는, 상기 합성예 4와 동일한 과정을 수행하여 목적 화합물인 BIA-14 (4.54 g, 수율 67%)을 얻었다.The same procedure as in Synthesis Example 4 except for using 9,14-dihydrobenzo [kl] indolo [2,3-c] acridine instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine Was carried out to obtain the title compound BIA-14 (4.54 g, yield 67%).

GC-Mass (이론치: 764.91 g/mol, 측정치: 764 g/mol)
GC-Mass (Theoretical value: 764.91 g / mol, Measured value: 764 g / mol)

[합성예 15] BIA-15의 합성Synthesis Example 15 Synthesis of BIA-15

Figure pat00073
Figure pat00073

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine을 사용하고, 1-bromobenzene 대신 2-bromopyridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 목적 화합물인 BIA-15 (2.81 g, 수율 69%)을 얻었다.9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine and 2-bromopyridine instead of 1-bromobenzene Except for using, the same procedure as in Synthesis Example 1 was performed to obtain BIA-15 (2.81 g, yield 69%) as a target compound.

GC-Mass (이론치: 459.54 g/mol, 측정치: 459 g/mol)
GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

[합성예 16] BIA-16의 합성Synthesis Example 16 Synthesis of BIA-16

Figure pat00074
Figure pat00074

2-bromopyridine 대신 3-bromopyridine 을 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 목적 화합물인 BIA-16 (2.32 g, 수율 57%)을 얻었다.Except for using 3-bromopyridine instead of 2-bromopyridine, the same procedure as in Synthesis Example 15 was carried out to obtain the target compound BIA-16 (2.32 g, yield 57%).

GC-Mass (이론치: 459.54 g/mol, 측정치: 459 g/mol)
GC-Mass (Theoretical value: 459.54 g / mol, Measured value: 459 g / mol)

[합성예 17] BIA-17의 합성Synthesis Example 17 Synthesis of BIA-17

Figure pat00075
Figure pat00075

2-bromopyridine 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 목적 화합물인 BIA-17 (3.32 g, 수율 61%)을 얻었다.Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 2-bromopyridine, the same procedure as in Synthesis Example 15 was carried out to obtain the target compound BIA-17 (3.32 g, yield 61%).

GC-Mass (이론치: 613.71 g/mol, 측정치: 613 g/mol)
GC-Mass (Theoretical value: 613.71 g / mol, Measured value: 613 g / mol)

[합성예 18] BIA-18의 합성Synthesis Example 18 Synthesis of BIA-18

Figure pat00076
Figure pat00076

2-bromopyridine 대신 2-bromo-4,6-diphenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 15와 동일한 과정을 수행하여 목적 화합물인 BIA-18 (3.30 g, 수율 61%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyridine instead of 2-bromopyridine, the same procedure as in Synthesis Example 15 was carried out to obtain the target compound BIA-18 (3.30 g, 61% yield).

GC-Mass (이론치: 611.73 g/mol, 측정치: 611 g/mol)
GC-Mass (Theoretical value: 611.73 g / mol, Measured value: 611 g / mol)

[합성예 19] BIA-19의 합성Synthesis Example 19 Synthesis of BIA-19

Figure pat00077
Figure pat00077

질소 기류 하에서, 12-bromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine (3.64 g, 7.88 mmol), phenylboronic acid (1.15 g, 9.47 mmol), NaOH(0.95 g, 23.67 mmol) 및 THF/H2O(100 ml/50 ml)를 혼합하여 교반한 다음, 40℃에서 0.46 g (5 mol%)의 Pd(PPh3)4를 넣고 80℃에서 12시간 동안 교반하였다. 반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층의 용매를 제거한 후 컬럼 크로마토그래피로 정제하여 중간 화합물인 BIA-19-1 (3.00 g, 수율 83%)을 얻었다.Under a stream of nitrogen, 12-bromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine (3.64 g, 7.88 mmol), phenylboronic acid (1.15 g, 9.47 mmol), NaOH (0.95) g, 23.67 mmol) and THF / H 2 O (100 ml / 50 ml) were mixed and stirred, followed by adding 0.46 g (5 mol%) of Pd (PPh 3 ) 4 at 40 ° C. for 12 hours at 80 ° C. Stirred. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO 4 and filtered. The solvent of the obtained organic layer was removed, and then purified by column chromatography to obtain BIA-19-1 (3.00 g, yield 83%) as an intermediate compound.

질소 기류 하에서 상기 중간 화합물인 BIA-19-1 (3.00 g, 6.54 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.10 g, 7.85 mmol), Cu powder(0.09 g, 1.38 mmol), K2CO3(1.91 g, 13.84 mmol), Na2SO4(1.97 g, 13.84 mmol) 및 nitrobenzene(80 ml)을 혼합하고 190℃에서 12시간 동안 교반하였다. 반응이 종결된 후 nitrobenzene을 제거하고 메틸렌클로라이드로 유기층을 분리한 다음 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼 크로마토그래피로 정제하여 목적 화합물인 BIA-19 (2.48 g, 수율 55%)를 얻었다.The intermediate compound BIA-19-1 (3.00 g, 6.54 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.10 g, 7.85 mmol), Cu powder (0.09 g) under nitrogen stream , 1.38 mmol), K 2 CO 3 (1.91 g, 13.84 mmol), Na 2 SO 4 (1.97 g, 13.84 mmol) and nitrobenzene (80 ml) were mixed and stirred at 190 ° C. for 12 hours. After the reaction was completed, the nitrobenzene was removed, the organic layer was separated with methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer was purified by column chromatography to give the title compound BIA-19 (2.48 g, 55% yield).

GC-Mass (이론치: 689.80 g/mol, 측정치: 689 g/mol)
GC-Mass (Theoretical value: 689.80 g / mol, Measured value: 689 g / mol)

[합성예 20] BIA-20의 합성Synthesis Example 20 Synthesis of BIA-20

Figure pat00078
Figure pat00078

phenylboronic acid 대신 pyridin-3-ylboronic acid를 사용하는 것을 제외하고는, 상기 합성예 19와 동일한 과정을 수행하여 목적 화합물인 BIA-20 (2.51 g, 수율 56%)을 얻었다.Except for using pyridin-3-ylboronic acid instead of phenylboronic acid, the same procedure as in Synthesis Example 19 was carried out to obtain a target compound BIA-20 (2.51 g, yield 56%).

GC-Mass (이론치: 690.70 g/mol, 측정치: 690 g/mol)
GC-Mass (Theoretical value: 690.70 g / mol, Measured value: 690 g / mol)

[합성예 21] BIA-21의 합성Synthesis Example 21 Synthesis of BIA-21

Figure pat00079
Figure pat00079

2-chloro-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 19와 동일한 방법을 수행하여 목적 화합물인 BIA-21 (2.46 g, 수율 54%)을 얻었다.Except for using 2-chloro-4,6-diphenylpyridine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, the same method as in Synthesis Example 19 was carried out to give the target compound BIA- 21 (2.46 g, yield 54%) was obtained.

GC-Mass (이론치: 687.84 g/mol, 측정치: 687 g/mol)
GC-Mass (Theoretical value: 687.84 g / mol, Measured value: 687 g / mol)

[합성예 22] BIA-22의 합성Synthesis Example 22 Synthesis of BIA-22

Figure pat00080
Figure pat00080

12-bromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 3,12-dibromo-9-phenyl-7,9-dihydrobenzo[kl]indolo[3,2-b]acridine을 사용하는 것을 제외하고는, 상기 합성예 19와 동일한 방법을 수행하여 목적 화합물인 BIA-22 (2.28 g, 수율 50%)을 얻었다.3,12-dibromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2- instead of 12-bromo-9-phenyl-7,9-dihydrobenzo [kl] indolo [3,2-b] acridine Except for using b] acridine, the same method as in Synthesis Example 19 was carried out to obtain BIA-22 (2.28 g, yield 50%) as a target compound.

GC-Mass (이론치: 765.90 g/mol, 측정치: 765 g/mol)
GC-Mass (Theoretical value: 765.90 g / mol, Measured value: 765 g / mol)

[합성예 23] BIA-23의 합성Synthesis Example 23 Synthesis of BIA-23

Figure pat00081
Figure pat00081

phenylboronic acid 대신 pyridin-3-ylboronic acid를 사용하는 것을 제외하고는, 상기 합성예 22와 동일한 방법을 수행하여 목적 화합물인 BIA-23 (2.46 g, 수율 54%)을 얻었다.Except for using pyridin-3-ylboronic acid instead of phenylboronic acid, the same method as in Synthesis Example 22 was carried out to obtain BIA-23 (2.46 g, yield 54%) as a target compound.

GC-Mass (이론치: 767.88 g/mol, 측정치: 767 g/mol)
GC-Mass (Theoretical value: 767.88 g / mol, Measured value: 767 g / mol)

[합성예 24] BIA-24의 합성Synthesis Example 24 Synthesis of BIA-24

Figure pat00082
Figure pat00082

2-chloro-4,6-diphenyl-1,3,5-triazine 대신 2-chloro-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 22와 동일한 방법을 수행하여 목적 화합물인 BIA-24 (2.69 g, 수율 59%)을 얻었다.Except for using 2-chloro-4,6-diphenylpyridine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, the same method as in Synthesis Example 22 was carried out to obtain the target compound BIA- 24 (2.69 g, yield 59%) was obtained.

GC-Mass (이론치: 763.92 g/mol, 측정치: 763 g/mol)
GC-Mass (Theoretical value: 763.92 g / mol, Measured value: 763 g / mol)

[합성예 25] BIA-25의 합성Synthesis Example 25 Synthesis of BIA-25

Figure pat00083
Figure pat00083

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 9,9-dimethyl-7,9-dihydrobenzo[kl]indeno[1,2-b]acridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 방법을 수행하여 목적 화합물인 BIA-25 (2.57 g, 수율 71%)을 얻었다.Except for using 9,9-dimethyl-7,9-dihydrobenzo [kl] indeno [1,2-b] acridine instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine The same method as in Synthesis Example 1 was performed to obtain BIA-25 (2.57 g, 71% yield) as a target compound.

GC-Mass (이론치: 409.52 g/mol, 측정치: 409 g/mol)
GC-Mass (Theoretical value: 409.52 g / mol, Measured value: 409 g / mol)

[합성예 26] BIA-26의 합성Synthesis Example 26 Synthesis of BIA-26

Figure pat00084
Figure pat00084

1-bromobenzene 대신 3-bromopyridine을 사용하는 것을 제외하고는, 상기 합성예 25와 동일한 과정을 수행하여 목적 화합물인 BIA-26 (2.54 g, 수율 70%)을 얻었다.Except for using 3-bromopyridine instead of 1-bromobenzene, the same process as in Synthesis Example 25 was carried out to obtain the target compound BIA-26 (2.54 g, yield 70%).

GC-Mass (이론치: 410.51 g/mol, 측정치: 410 g/mol)
GC-Mass (Theoretical value: 410.51 g / mol, Measured value: 410 g / mol)

[합성예 27] BIA-27의 합성Synthesis Example 27 Synthesis of BIA-27

Figure pat00085
Figure pat00085

1-bromobenzene 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용하는 것을 제외하고는, 상기 합성예 25와 동일한 과정을 수행하여 목적 화합물인 BIA-27 (3.00 g, 수율 60%)을 얻었다.Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 25 was carried out to obtain the target compound BIA-27 (3.00 g, yield 60%).

GC-Mass (이론치: 564.68 g/mol, 측정치: 564 g/mol)
GC-Mass (Theoretical value: 564.68 g / mol, Measured value: 564 g / mol)

[합성예 28] BIA-28의 합성Synthesis Example 28 Synthesis of BIA-28

Figure pat00086
Figure pat00086

1-bromobenzene 대신 2-bromo-4,6-diphenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 25와 동일한 과정을 수행하여 목적 화합물인 BIA-28 (3.15 g, 수율 63%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 25 was carried out to obtain BIA-28 (3.15 g, yield 63%) as a target compound.

GC-Mass (이론치: 562.70 g/mol, 측정치: 562 g/mol)
GC-Mass (Theoretical value: 562.70 g / mol, Measured value: 562 g / mol)

[합성예 29] BIA-29의 합성Synthesis Example 29 Synthesis of BIA-29

Figure pat00087
Figure pat00087

1-bromobenzene 대신 2-bromo-4,6-diphenylpyrimidine을 사용하는 것을 제외하고는, 상기 합성예 25와 동일한 과정을 수행하여 목적 화합물인 BIA-29 (3.30 g, 수율 66%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyrimidine instead of 1-bromobenzene, the same procedure as in Synthesis Example 25 was performed to obtain BIA-29 (3.30 g, yield 66%) as a target compound.

GC-Mass (이론치: 563.69 g/mol, 측정치: 563 g/mol)
GC-Mass (Theoretical value: 563.69 g / mol, Measured value: 563 g / mol)

[합성예 30] BIA-30의 합성Synthesis Example 30 Synthesis of BIA-30

Figure pat00088
Figure pat00088

1-bromobenzene 대신 6-bromo-2,3'-bipyridine을 사용하는 것을 제외하고는, 상기 합성예 25와 동일한 과정을 수행하여 목적 화합물인 BIA-30 (3.11 g, 수율 65%)을 얻었다.Except for using 6-bromo-2,3'-bipyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 25 was carried out to obtain the target compound BIA-30 (3.11 g, yield 65%).

GC-Mass (이론치: 487.59 g/mol, 측정치: 487 g/mol)
GC-Mass (Theoretical value: 487.59 g / mol, Measured value: 487 g / mol)

[합성예 31] BIA-31의 합성Synthesis Example 31 Synthesis of BIA-31

Figure pat00089
Figure pat00089

7,9-dihydrobenzo[kl]indolo[3,2-b]acridine 대신 7H-benzo[kl]benzothieno[3,2-b]acridine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 방법을 수행하여 목적 화합물인 BIA-31 (2.44 g, 수율 69%)을 얻었다.The same method as in Synthesis Example 1 was performed except that 7H-benzo [kl] benzothieno [3,2-b] acridine was used instead of 7,9-dihydrobenzo [kl] indolo [3,2-b] acridine. To give BIA-31 (2.44 g, yield 69%) as a target compound.

GC-Mass (이론치: 399.51 g/mol, 측정치: 399 g/mol)
GC-Mass (Theoretical value: 399.51 g / mol, Measured value: 399 g / mol)

[합성예 32] BIA-32의 합성Synthesis Example 32 Synthesis of BIA-32

Figure pat00090
Figure pat00090

1-bromobenzene 대신 3-bromopyridine을 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 목적 화합물인 BIA-31 (2.48 g, 수율 70%)을 얻었다.Except for using 3-bromopyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 31 was carried out to obtain the target compound BIA-31 (2.48 g, yield 70%).

GC-Mass (이론치: 400.49 g/mol, 측정치: 400 g/mol)
GC-Mass (theory: 400.49 g / mol, measurement: 400 g / mol)

[합성예 33] BIA-33의 합성Synthesis Example 33 Synthesis of BIA-33

Figure pat00091
Figure pat00091

1-bromobenzene 대신 2-chloro-4,6-diphenyl-1,3,5-triazine을 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 목적 화합물인 BIA-33 (2.95 g, 수율 60%)을 얻었다.Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine instead of 1-bromobenzene, the same procedure as in Synthesis Example 31 was carried out to obtain the target compound BIA-33 (2.95 g, yield 60%).

GC-Mass (이론치: 554.66 g/mol, 측정치: 554 g/mol)
GC-Mass (Theoretical value: 554.66 g / mol, Measured value: 554 g / mol)

[합성예 34] BIA-34의 합성Synthesis Example 34 Synthesis of BIA-34

Figure pat00092
Figure pat00092

1-bromobenzene 대신 2-bromo-4,6-diphenylpyridine을 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 목적 화합물인 BIA-34 (3.18 g, 수율 65%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyridine instead of 1-bromobenzene, the same procedure as in Synthesis Example 31 was carried out to obtain BIA-34 (3.18 g, yield 65%) as a target compound.

GC-Mass (이론치: 552.69 g/mol, 측정치: 552 g/mol)
GC-Mass (Theoretical value: 552.69 g / mol, Measured value: 552 g / mol)

[합성예 35] BIA-35의 합성Synthesis Example 35 Synthesis of BIA-35

Figure pat00093
Figure pat00093

1-bromobenzene 대신 2-bromo-4,6-diphenylpyrimidine을 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 목적 화합물인 BIA-35 (3.22 g, 수율 66%)을 얻었다.Except for using 2-bromo-4,6-diphenylpyrimidine instead of 1-bromobenzene, the same procedure as in Synthesis Example 31 was carried out to obtain BIA-35 (3.22 g, yield 66%) as a target compound.

GC-Mass (이론치: 553.68 g/mol, 측정치: 553 g/mol)
GC-Mass (Theoretical value: 553.68 g / mol, Measured value: 553 g / mol)

[실시예 1 ~ 35] 녹색 유기 EL 소자의 제작Examples 1 to 35 Fabrication of Green Organic EL Device

합성예 1-35에서 합성된 BIA-1 ~ BIA-35 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 하기 과정에 따라 녹색 유기 EL 소자를 제작하였다.The BIA-1 to BIA-35 compounds synthesized in Synthesis Example 1-35 were subjected to high purity sublimation purification by a conventionally known method, and then a green organic EL device was manufactured according to the following procedure.

먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ BIA-1 ~ BIA-35의 각각의 화합물 + 10 % Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 EL 소자를 제작하였다. M-MTDATA (60 nm) / TCTA (80 nm) / BIA-1 to BIA-35 each compound + 10% Ir (ppy) 3 (300nm) / BCP (10 nm) / Alq on the thus prepared ITO transparent electrode An organic EL device was fabricated by stacking 3 (30 nm) / LiF (1 nm) / Al (200 nm) in this order.

m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP and BCP are as follows.

Figure pat00094
Figure pat00094

Figure pat00095
Figure pat00095

[비교예 1] 녹색 유기 EL 소자의 제작[Comparative Example 1] Production of green organic EL device

발광층 형성시 발광 호스트 물질로서 화합물 BIA-1 대신 CBP를 사용하는 것을 제외하고는 실시예 1과 동일한 과정으로 녹색 유기 EL 소자를 제작하였다.
A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound BIA-1 as a light emitting host material when forming the emission layer.

[평가예][Evaluation example]

실시예 1-35 및 비교예 1에서 제작한 각각의 녹색 유기 EL 소자에 대하여 전류밀도 (10) mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.For each of the green organic EL devices produced in Examples 1-35 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at current density (10) mA / cm 2 were measured, and the results are shown in Table 1 below. It was.

샘플Sample 호스트Host 구동 전압
(V)Driving voltage
(V) EL 피크
(nm)EL peak
(nm) 전류효율
(cd/A)Current efficiency
(cd / A) 실시예 1Example 1 BIA-1BIA-1 6.786.78 515515 42.042.0 실시예 2Example 2 BIA-2BIA-2 6.816.81 518518 41.841.8 실시예 3Example 3 BIA-3BIA-3 6.636.63 517517 40.840.8 실시예 4Example 4 BIA-4BIA-4 6.816.81 515515 41.741.7 실시예 5Example 5 BIA-5BIA-5 6.866.86 518518 41.541.5 실시예 6Example 6 BIA-6BIA-6 6.816.81 515515 39.439.4 실시예 7Example 7 BIA-7BIA-7 6.816.81 518518 41.041.0 실시예 8Example 8 BIA-8BIA-8 6.766.76 517517 41.041.0 실시예 9Example 9 BIA-9BIA-9 6.486.48 515515 40.640.6 실시예 10Example 10 BIA-10BIA-10 6.866.86 518518 41.041.0 실시예 11Example 11 BIA-11BIA-11 6.816.81 516516 42.042.0 실시예 12Example 12 BIA-12BIA-12 6.816.81 518518 41.341.3 실시예 13Example 13 BIA-13BIA-13 6.776.77 515515 41.141.1 실시예 14Example 14 BIA-14BIA-14 6.466.46 518518 40.440.4 실시예 15Example 15 BIA-15BIA-15 6.816.81 517517 41.041.0 실시예 16Example 16 BIA-16BIA-16 6.796.79 515515 41.341.3 실시예 17Example 17 BIA-17BIA-17 6.576.57 518518 39.439.4 실시예 18Example 18 BIA-18BIA-18 6.866.86 516516 41.541.5 실시예 19Example 19 BIA-19BIA-19 6.896.89 518518 40.740.7 실시예 20Example 20 BIA-20BIA-20 6.456.45 517517 41.341.3 실시예 21Example 21 BIA-21BIA-21 6.836.83 515515 39.039.0 실시예 22Example 22 BIA-22BIA-22 6.816.81 518518 41.141.1 실시예 23Example 23 BIA-23BIA-23 6.836.83 516516 38.238.2 실시예 24Example 24 BIA-24BIA-24 6.816.81 518518 39.139.1 실시예 25Example 25 BIA-25BIA-25 6.796.79 515515 36.236.2 실시예 26Example 26 BIA-26BIA-26 6.876.87 515515 39.339.3 실시예 27Example 27 BIA-27BIA-27 6.896.89 518518 38.938.9 실시예 28Example 28 BIA-28BIA-28 6.796.79 517517 39.639.6 실시예 29Example 29 BIA-29BIA-29 6.876.87 515515 38.938.9 실시예 30Example 30 BIA-30BIA-30 6.896.89 518518 39.639.6 실시예 31Example 31 BIA-31BIA-31 6.656.65 517517 41.341.3 실시예 32Example 32 BIA-32BIA-32 6.696.69 515515 39.039.0 실시예 33Example 33 BIA-33BIA-33 6.696.69 517517 41.041.0 실시예 34Example 34 BIA-34BIA-34 6.676.67 515515 38.238.2 실시예 35Example 35 BIA-35BIA-35 6.716.71 518518 39.039.0 비교예 1Comparative Example 1 CBPCBP 6.936.93 516516 38.238.2

상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물(BIA-1 ~ BIA-35)을 녹색 유기 EL 소자의 발광층으로 사용하는 실시예 1 내지 실시예 35의 유기 EL소자는, 종래 CBP를 사용하는 비교예 1의 녹색 유기 EL 소자와 비교해 볼 때, 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 1, the organic EL device of Examples 1 to 35, which uses the compounds (BIA-1 to BIA-35) according to the present invention as the light emitting layer of the green organic EL device, uses a conventional CBP. When compared with the green organic electroluminescent element of the comparative example 1, it turns out that it shows more excellent performance in efficiency and a drive voltage.

Claims (9)

하기 화학식 1로 표시되는 화합물:
[화학식 1]
Figure pat00096

상기 식에서,
R1과 R2 또는 R2와 R3는 하기 화학식 2로 표현된 축합(fused) 고리를 형성하며;
[화학식 2]
Figure pat00097

상기 식에서,
X는 CAr2Ar3, NAr4, O, S 및 SiAr5Ar6 로 구성된 군으로부터 선택되고;
R4 내지 R14는 서로 같거나 또는 상이하며, 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 C3~C40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되고, 이때 이들은 인접한 기와 축합(fused) 고리를 형성하거나 또는 비형성하며;
Ar1 내지 Ar6 은 서로 같거나 또는 상이하며, 수소, 중수소, 할로겐, 시아노기, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C3~C40의 시클로알킬기, 치환 또는 비치환된 C3~C40의 헤테로시클로알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기, 치환 또는 비치환된 C1~C40의 알킬옥시기, 치환 또는 비치환된 C6~C60의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬실릴기, 치환 또는 비치환된 C6~C60의 아릴실릴기, 및 치환 또는 비치환된 C6~C60의 아릴아민기로 구성된 군으로부터 선택되고, 이때 이들은 인접한 기와 축합(fused) 고리를 형성하거나 또는 비형성한다. A compound represented by the following formula (1):
[Formula 1]
Figure pat00096

In this formula,
R 1 and R 2 or R 2 and R 3 form a fused ring represented by the following formula (2);
(2)
Figure pat00097

In this formula,
X is selected from the group consisting of CAr 2 Ar 3 , NAr 4 , O, S and SiAr 5 Ar 6 ;
R 4 to R 14 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 2 to C 40 alkenyl groups, substituted or unsubstituted C 2 to C 40 alkynyl groups, substituted or unsubstituted C 3 to C 40 cycloalkyl groups, substituted or unsubstituted C 3 to C 40 heterocycloalkyl groups, substituted or Unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 to C 40 alkyloxy group, substituted or unsubstituted C 6 Aryloxy group of -C 60 , substituted or unsubstituted C 1 -C 40 alkylsilyl group, substituted or unsubstituted C 6 -C 60 arylsilyl group, and substituted or unsubstituted C 6 -C 60 Arylamine groups, wherein they form a fused ring with an adjacent group or do not form a fused ring;
Ar 1 to Ar 6 are the same as or different from each other, hydrogen, deuterium, halogen, cyano group, each independently substituted or unsubstituted C 1 ~ C 40 alkyl group, substituted or unsubstituted C 2 ~ C 40 alkenes A substituted or unsubstituted C 2 -C 40 alkynyl group, a substituted or unsubstituted C 3 -C 40 cycloalkyl group, a substituted or unsubstituted C 3 -C 40 heterocycloalkyl group, a substituted or unsubstituted group C 6 ~ C 60 aryl group, substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, substituted or unsubstituted C 1 ~ C 40 alkyloxy group, substituted or unsubstituted C 6 ~ C 60 An aryloxy group, a substituted or unsubstituted C 1 to C 40 alkylsilyl group, a substituted or unsubstituted C 6 to C 60 arylsilyl group, and a substituted or unsubstituted C 6 to C 60 arylamine group Selected from the group consisting of, where they form or not form fused rings with adjacent groups. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 3 또는 화학식 4로 표시되는 것을 특징으로 하는 화합물:
[화학식 3]
Figure pat00098

[화학식 4]
Figure pat00099

상기 식에서,
X, R1 내지 R14, Ar1 내지 Ar6 은 제1항에서 정의된 바와 같다.The compound of claim 1, wherein the compound represented by Chemical Formula 1 is represented by the following Chemical Formula 3 or Chemical Formula 4:
(3)
Figure pat00098

[Chemical Formula 4]
Figure pat00099

In this formula,
X, R 1 to R 14, Ar 1 to Ar 6 are as defined in claim 1 . 제2항에 있어서, 상기 X 는 CAr2Ar3, NAr4 및 S로 구성된 군으로부터 선택되는 것을 특징으로 하는 화합물.The compound of claim 2, wherein X is selected from the group consisting of CAr 2 Ar 3 , NAr 4, and S. 4 . 제 3항에 있어서, 상기 Ar1 내지 Ar4는 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C6~C60의 아릴기, 또는 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기이고,
상기 C6~C60의 아릴기 또는 핵원자수 5 내지 60의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, C1~C40의 알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, 및 C6~C60의 아릴아민기로 구성된 군으로부터 선택된 하나 이상의 치환기로 치환되거나 또는 비치환되는 것을 특징으로 하는 화합물. According to claim 3, Ar 1 to Ar 4 are the same as or different from each other, each independently represent a substituted or unsubstituted C 6 ~ C 60 aryl group, or a substituted or unsubstituted 5 to 60 nuclear atoms Heteroaryl group,
The C 6 ~ C 60 aryl group or the heteroaryl group of 5 to 60 nuclear atoms are each independently deuterium, halogen, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 Heterocycloalkyl group, C 6 ~ C 60 aryl group, C 5 ~ C 60 heteroaryl group, C 1 ~ C 40 Alkyloxy group, C 6 ~ C 60 Aryloxy group, C 1 ~ C 40 A compound, which is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkylsilyl group, a C 6 -C 60 arylsilyl group, and a C 6 -C 60 arylamine group. 제2항에 있어서, 상기 R4 내지 R14는 서로 같거나 또는 상이하며, 각각 독립적으로 수소, 할로겐, 시아노, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 및 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기 로 구성된 군으로부터 선택되며,
상기 C1~C40의 알킬기, C6~C60의 아릴기 또는 핵원자수 5 내지 60의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, C1~C40의 알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, 및 C6~C60의 아릴아민기로 구성된 군으로부터 선택된 하나 이상의 치환기로 치환되거나 또는 비치환되는 것을 특징으로 하는 화합물.According to claim 2, wherein R 4 To R 14 They are the same as or different from each other, and each independently hydrogen, halogen, cyano, substituted or unsubstituted C 1 ~ C 40 Alkyl group, substituted or unsubstituted C 6 An aryl group of ~ C 60 , and a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms,
The C 1 to C 40 alkyl group, C 6 to C 60 aryl group or nuclear atom 5 to 60 heteroaryl group are each independently deuterium, halogen, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cyclo alkyl group, C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy of C 60 of Or substituted or unsubstituted with one or more substituents selected from the group consisting of C 1 to C 40 alkylsilyl groups, C 6 to C 60 arylsilyl groups, and C 6 to C 60 arylamine groups compound. 제5항에 있어서, 상기 R7, R8, 및 R13는 서로 같거나 또는 상이하며, 각각 독립적으로 할로겐, 시아노, 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C60의 아릴기, 및 치환 또는 비치환된 핵원자수 5 내지 60의 헤테로아릴기로 구성된 군으로부터 선택되며,
상기 C1~C40의 알킬기, C6~C60의 아릴기 또는 핵원자수 5 내지 60의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, C1~C40의 알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, 및 C6~C60의 아릴아민기로 구성된 군으로부터 선택된 하나 이상의 치환기로 치환되거나 또는 비치환되는 것을 특징으로 하는 화합물.The method according to claim 5, wherein R 7 , R 8 , and R 13 are the same as or different from each other, and each independently a halogen, cyano, substituted or unsubstituted C 1 to C 40 alkyl group, substituted or unsubstituted C 6 ~ C 60 aryl group, and substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms,
The C 1 to C 40 alkyl group, C 6 to C 60 aryl group or nuclear atom 5 to 60 heteroaryl group are each independently deuterium, halogen, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cyclo alkyl group, C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy of C 60 of Or substituted or unsubstituted with one or more substituents selected from the group consisting of C 1 to C 40 alkylsilyl groups, C 6 to C 60 arylsilyl groups, and C 6 to C 60 arylamine groups compound. (i) 양극, (ⅱ) 음극, 및 (ⅲ) 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서,
상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제6항 중 어느 한 항에 기재된 화학식 1의 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자. An organic electroluminescent device comprising: (i) a cathode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
Wherein at least one of the one or more organic layers includes a compound of the formula (1) according to any one of claims 1 to 6. 제7 항에 있어서, 상기 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 구성된 군으로부터 선택되는 것을 특징으로 하는 유기 전계 발광 소자. The organic electroluminescent device according to claim 7, wherein the organic material layer is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer. 제7 항에 있어서, 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트 또는 형광 호스트로 사용되는 것을 특징으로 하는 유기 전계 발광 소자.The organic electroluminescent device according to claim 7, wherein the compound represented by Chemical Formula 1 is used as a phosphorescent host or a fluorescent host of the emission layer.
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015167223A1 (en) * 2014-04-29 2015-11-05 주식회사 동진쎄미켐 Novel compound, and organic light emitting device containing same
KR20150124911A (en) * 2014-04-29 2015-11-06 주식회사 동진쎄미켐 Novel compound and organic electroluminescent device comprising same
KR20170057544A (en) * 2015-11-17 2017-05-25 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
KR20170096942A (en) * 2016-02-16 2017-08-25 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
KR20170120233A (en) * 2016-04-20 2017-10-31 덕산네오룩스 주식회사 Compound for organic electric element, organic electric element comprising the same and electronic device thereof
WO2019203613A1 (en) * 2018-04-19 2019-10-24 주식회사 엘지화학 Compound and organic light emitting diode comprising same
CN111868048A (en) * 2018-04-19 2020-10-30 株式会社Lg化学 Compound and organic light emitting device including the same
CN111868048B (en) * 2018-04-19 2023-05-19 株式会社Lg化学 Compound and organic light emitting device comprising the same
US11812658B2 (en) 2018-04-19 2023-11-07 Lg Chem, Ltd. Compound and organic light emitting diode comprising same

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