KR101571588B1 - 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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KR101571588B1
KR101571588B1 KR1020120100611A KR20120100611A KR101571588B1 KR 101571588 B1 KR101571588 B1 KR 101571588B1 KR 1020120100611 A KR1020120100611 A KR 1020120100611A KR 20120100611 A KR20120100611 A KR 20120100611A KR 101571588 B1 KR101571588 B1 KR 101571588B1
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bromophenyl
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김충한
연규만
김동연
최태진
송보경
김지이
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주식회사 두산
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Abstract

본 발명은 발광능, 정공 수송능, 전자 수송능 등이 우수한 신규의 유기발광 화합물 및 상기 화합물을 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 electroluminescent compound having excellent light emitting performance, hole transporting ability, and electron transporting ability, and an organic electroluminescent device having improved characteristics such as luminous efficiency, driving voltage and lifetime by incorporating the compound into one or more organic layers .

Description

유기발광 화합물 및 이를 이용한 유기 전계 발광 소자 {ORGANIC LIGHT-EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME} TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound, and an organic electroluminescent device using the same. BACKGROUND ART [0002]

본 발명은 신규의 유기발광 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 발광능, 정공 수송능, 전자 수송능 등이 우수한 신규의 유기발광 화합물 및 상기 화합물을 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. More particularly, the present invention relates to a novel organic light emitting compound having excellent light emitting performance, hole transporting ability, and electron transporting ability, Thereby improving the characteristics such as luminous efficiency, driving voltage, lifetime, and the like.

유기 전계 발광 소자(organic electroluminescent device) (이하, 유기 EL 소자라 함)는 통상 양극, 음극, 및 이들 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 EL 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층(HIL), 정공 수송층(HTL), 발광층(EML), 전자 수송층(ETL), 전자 주입층(EIL) 등을 포함할 수 있다. An organic electroluminescent device (hereinafter referred to as an organic EL element) usually has a structure including an anode, a cathode, and an organic layer therebetween. Here, in order to increase the efficiency and stability of the organic EL device, the organic material layer has a multi-layered structure composed of different materials. For example, the organic material layer includes a hole injection layer (HIL), a hole transport layer (HTL), a light emitting layer (EML) ), An electron injection layer (EIL), and the like.

이러한 유기 EL 소자의 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층으로 주입되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다.When a voltage is applied between the two electrodes of the organic EL device, holes are injected into the anode, electrons are injected into the organic layer, and excitons are formed when injected holes and electrons meet. When falling, the light comes out.

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 통해 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도펀트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도펀트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도펀트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 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. Further, in order to increase the luminous efficiency through an increase in color purity and energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with a light emitting layer in a small amount, the excitons generated in the host are transported as a dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, light of a desired wavelength can be obtained according to the kind of the dopant used.

일반적으로 인광 호스트 재료로는 CBP(4,4-dicarbazolybiphenyl) 등의 카바졸계 화합물 등이 사용되며, 인광 도판트 재료로는 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물이 널리 사용되고 있다. 그러나 현재 사용되는 인광 호스트 재료인 CBP의 경우 유리전이온도(Tg)가 110℃ 정도로 낮으며, 소자 내의 결정화가 쉽게 일어나 유기 EL 소자의 수명이 150 시간 정도로 매우 짧은 문제점이 있다.
In general, a phosphorescent host material is a carbazole-based compound such as 4,4-dicarbazolylbiphenyl (CBP), and a phosphorescent dopant is a metal complex compound containing heavy atoms such as Ir and Pt . However, CBP, which is a phosphorescent host material currently used, has a low glass transition temperature (T g ) of about 110 ° C. and easily crystallizes in the device, resulting in a very short lifetime of the organic EL device to about 150 hours.

본 발명은 상기한 문제점을 해결하기 위해 안출된 것으로서, 발광효율, 구동전압, 열적 안정성, 수명 등의 특성을 향상시킬 수 있는 유기발광 화합물 및 이를 이용한 유기 EL 소자를 제공하는 것을 목적으로 한다.
SUMMARY OF THE INVENTION The present invention has been devised to solve the problems described above, and it is an object of the present invention to provide an organic light emitting compound and an organic EL device using the same, which can improve characteristics such as luminous efficiency, driving voltage, thermal stability and 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 112012073412813-pat00001
Figure 112012073412813-pat00001

상기 식에서,In this formula,

X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이고;X and Y are the same or different and are each independently N or CH;

R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C6~C40의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬옥시기, -NR3R4, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 1 and R 2 are the same or different and each independently represents a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 ~ C 40 of the alkynyl group, a substituted or unsubstituted C 6 ~ C 40 aryl group, a substituted or unsubstituted nuclear atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted C 6 ~ aryloxy of C 40 A substituted or unsubstituted C 1 to C 40 alkyloxy group, -NR 3 R 4 , a substituted or unsubstituted C 3 to C 40 cycloalkyl group, and a substituted or unsubstituted heteroaryl group having 3 to 40 nucleus atoms A cycloalkyl group, or a group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with a group adjacent to the condensed aliphatic ring,

상기 R3 및 R4는 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 3 and R 4 are the same or different and each independently represents a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted nucleus A heteroaryl group having 5 to 40 atoms, a substituted or unsubstituted C 3 to C 40 cycloalkyl group, and a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nucleus atoms, or a group selected from the group consisting of A condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring,

여기서, 상기 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기는, 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.Here, the C 1 to C 40 alkyl group, C 2 to C 40 alkenyl group, C 2 to C 40 alkynyl group, C 6 to C 40 aryl group, heteroaryl group having 5 to 40 nuclear atoms, C C 6 -C 40 aryloxy groups, C 1 -C 40 alkyloxy groups, C 3 -C 40 cycloalkyl groups and heterocyclic cycloalkyl groups having 3 to 40 nuclear atoms are each independently substituted by deuterium, halogen, cyano, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C 6 ~ C of A C 1 to C 40 alkyloxy group, a C 6 to C 40 arylamine group, a C 6 to C 40 arylalkyl group, a C 3 to C 40 cycloalkyl group, a C 3 to C 40 A heterocycloalkyl group, a C 1 to C 40 alkylsilyl group, and a C 6 to C 40 arylsilyl group.

또한, 본 발명은 (i) 양극, (ⅱ) 음극, 및 (ⅲ) 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 EL 소자로서, 상기 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 EL 소자를 제공한다. The present invention also provides an organic EL device comprising (i) a positive electrode, (ii) a negative electrode, and (iii) at least one organic material layer sandwiched between the positive electrode and the negative electrode, 1 < / RTI >

이때, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 이루어진 군에서 선택될 수 있으며, 구체적으로 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트로 사용될 수 있다.
In this case, the organic compound layer including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer. Specifically, the compound represented by Formula 1 may be used as a phosphorescent host of a light emitting layer.

본 발명의 화학식 1로 표시되는 화합물은 우수한 발광능, 전자 수송능 및 정공 수송능을 가지고 있다. 따라서, 이를 포함하는 유기 EL 소자는 발광성능, 구동전압, 수명 등의 특성이 크게 향상될 수 있으므로, 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.
The compound represented by the general formula (1) of the present invention has excellent light emitting ability, electron transporting ability and hole transporting ability. Therefore, the organic EL device including the same can be effectively applied to a full color display panel and the like because the characteristics such as light emitting performance, driving voltage, and life can be greatly improved.

이하, 본 발명에 대하여 상세히 설명한다. Hereinafter, the present invention will be described in detail.

<신규 화합물><Novel compound>

본 발명에 따른 신규 유기발광 화합물은 퀴녹살린(Quinoxaline)계 모핵에 다양한 치환체, 특히 N-함유 헤테로환, 방향족 고리 등이 연결된 상기 화학식 1로 표시되는 구조를 가진다. 이러한 구조를 통해 충분히 높은 삼중항 에너지 레벨을 달성하여 인광특성을 개선함과 동시에 전자(electron) 및/또는 정공(hole) 수송 능력, 발광효율, 구동전압, 수명 특성 등에서 개선된 효능을 달성할 수 있다.The novel organic electroluminescent compound according to the present invention has a structure represented by the above formula (1) in which various substituents, particularly N-containing heterocyclic rings, aromatic rings, and the like are connected to quinoxaline-based mother nuclei. Through such a structure, it is possible to attain a sufficiently high triplet energy level to improve the phosphorescence characteristic and at the same time to achieve an improved effect in electron and / or hole transporting ability, luminous efficiency, driving voltage, have.

본 발명의 화학식 1로 표시되는 화합물에서, 상기 X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이다. 일례로, Y가 N이고 X가 CH이거나, 또는 Y가 CH이고 X가 N일 수 있다. 또한 X 및 Y 모두가 CH이거나, 또는 N일 수도 있다. In the compound represented by formula (1) of the present invention, X and Y are the same or different and each independently N or CH. In one example, Y is N and X is CH, or Y may be CH and X may be N. [ Also, both X and Y may be CH or N. [

상기 화학식 1에서, R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, -NR3R4, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나; 또는 이들이 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기일 수 있다. Wherein R 1 and R 2 are the same or different and each independently represents a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, a C 2 to C 40 alkynyl group, a C 6 to C 40 alkynyl group, for C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C 6 ~ C 40 of the aryloxy group, C 1 ~ C 40 alkyloxy group of, -NR 3 R 4, C of 3 ~ C 40 cycloalkyl An alkyl group and a heterocycloalkyl group having 3 to 40 nuclear atoms; Or a group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring by bonding with the adjacent groups.

여기서, R3 및 R4는 서로 같거나 또는 상이하며, 각각 독립적으로 C1~C40의 알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나; 또는 이들이 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기일 수 있다.Wherein R 3 and R 4 are the same or different and each independently represents a C 1 to C 40 alkyl group, a C 6 to C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C 3 to C selected from the group consisting of cycloalkyl group and 40 nuclear atoms, 3 to 40 or a heterocycloalkyl group of; Or a group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring by bonding with the adjacent groups.

한편 본원 화학식 1에서, '치환 또는 비치환된'이라는 용어가 기재된 치환기인 R1~R4, 보다 구체적으로 상기 R1~R4 에서, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기는, 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.R 1 to R 4 , which are substituents described in the present invention as the 'substituted or unsubstituted group', more specifically, in R 1 to R 4 , a C 1 to C 40 alkyl group, a C 2 to C 40 alkenyl group, C 2 ~ C 40 of the alkynyl group, C 6 ~ C 40 aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, a C 6 ~ C 40 aryloxy group, C 1 ~ C 40 of alkyloxy group, C 3 ~ C 40 is a cycloalkyl group and nuclear atoms, 3 to heterocycloalkyl group 40, each independently selected from deuterium, halogen, cyano group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, an aryloxy group of nuclear atoms aryl of from 5 to 40 heteroaryl group, C 6 ~ C 40, alkyloxy group of C 1 ~ C 40 of, C group 6 ~ C 40 aryl amine, C 6 ~ C 40 aryl alkyl group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 heterocycloalkyl group, C 1 ~ C 40 alkyl silyl group, and C 6 of the is selected from the group consisting of aryl silyl ~ C 40 With one or more substituents may be substituted.

본 발명에 따른 화학식 1로 표기되는 화합물에서, 삼중항 에너지 레벨을 고려했을 때, 상기 R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, -NR3R4 이거나, 또는 이들 작용기가 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 것이 바람직하다. 이때 R1 및 R2가 각각 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4인 경우가 더욱 바람직하며, NR3R4인 경우가 가장 바람직하다.In the compound represented by the formula (1) according to the present invention, when considering the triplet energy level, R 1 and R 2 are the same or different and each independently represents a C 6 to C 40 aryl group, A heteroaryl group having 5 to 40 carbon atoms, -NR 3 R 4 , or these functional groups are bonded to each other to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring. Wherein R 1 and R 2 is more preferably in each case a C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group or NR 3 R 4 in, and is most preferably in the case of NR 3 R 4.

여기서, 상기 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, R3, R4는 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다. Here, the C 6 ~ C 40 aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, R 3, R 4 are each independently a heavy hydrogen, a halogen, cyano group, C 1 ~ C 40 alkyl group, C 2 ~ of aryloxy C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C 6 ~ C 40 of, C 1 ~ C 40 A C 6 to C 40 arylamine group, a C 6 to C 40 arylalkyl group, a C 3 to C 40 cycloalkyl group, a C 3 to C 40 heterocycloalkyl group, a C 1 to C 40 alkyl A silyl group, and an arylsilyl group of C 6 to C 40 may be substituted with at least one substituent selected from the group consisting of

일례로, 상기 C6~C40의 아릴기 또는 핵원자수 5 내지 40의 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, 페난트롤린일 수 있다. For example, the C 6 -C 40 aryl group or the heteroaryl group having 5 to 40 nuclear atoms may be substituted with at least one group selected from phenyl, naphthyl, indene, anthracene, phenanthrene, pyrene, triphenylene, pyridine, pyrimidine, pyrazine, And examples thereof include azine, quinoline, isoquinoline, quinoxaline, fluorene, carbazole, dibenzothiophene, dibenzofuran, acridine, indole, benzofuran, benzothiophene, benzimidazole, benzothiazole, It can be Lin.

본 발명에 따른 상기 화학식 1의 화합물은 하기 화학식 2 내지 화학식 4로 표시되는 화합물 중 어느 하나로 보다 구체화될 수 있다.The compound of formula (1) according to the present invention may be further compounded by any one of the compounds represented by the following formulas (2) to (4).

Figure 112012073412813-pat00002
Figure 112012073412813-pat00002

Figure 112012073412813-pat00003
Figure 112012073412813-pat00003

Figure 112012073412813-pat00004
Figure 112012073412813-pat00004

상기 식에서, In this formula,

R1는 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4이고; R 1 is a C 6 to C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms or NR 3 R 4 ;

R2, R3 및 R4는 앞서 정의한 바와 같다.R 2 , R 3 and R 4 are as defined above.

이때 R2는 C6~C40의 아릴기 또는 핵원자수 5 내지 40의 헤테로아릴기인 것이 바람직하다. R 2 is preferably a C 6 to C 40 aryl group or a heteroaryl group having 5 to 40 nuclear atoms.

본 발명에서 사용된 "비치환된 알킬"은 탄소수 1 내지 40(10)의 직쇄 또는 측쇄의 포화 탄화수소이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 포함한다.As used herein, "unsubstituted alkyl" is a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms, examples of which include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, Hexyl, and the like.

"비치환된 아릴"은 단독 고리 혹은 2 이상의 고리가 조합된, 탄소수 6 내지 40(8)의 방향족 부위를 의미한다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태로 부착될 수 있다."Unsubstituted aryl" means an aromatic moiety having from 6 to 40 (8) carbon atoms, either alone or in combination with at least two rings. Two or more rings may be attached to each other in a pendant or condensed form.

"비치환된 헤테로아릴"은 핵원자수 5 내지 40(8)의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 부위를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S와 같은 헤테로원자로 치환된다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태로 부착될 수 있고, 나아가 지방족 고리 또는 방향족 고리와의 축합된 형태도 포함하는 것으로 해석한다."Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety of 5 to 40 nuclear atoms, wherein at least one carbon, preferably one to three carbons, of the ring is replaced by N, O, S, &lt; / RTI &gt; Two or more rings may be attached in a pendant or condensed form to each other and further include a condensed form with an aliphatic ring or an aromatic ring.

"축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다."Condensation 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 발명의 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. The compound represented by the formula (1) of the present invention described above can be further specified by the formulas shown below. However, the compounds represented by formula (1) of the present invention are not limited by the following examples.

일례로, 본원 화학식 2로 표시되는 화합물은 하기 예시된 화합물 1-1 내지 1-22 로 보다 구체화될 수 있으며, 상기 화학식 3으로 표시되는 화합물은 하기 예시된 화합물 2-1 내지 2-22로 보다 구체화될 수 있다. 또한 상기 화학식 4로 표시되는 화합물은 하기 예시된 화합물 3-1 내지 3-22로 보다 구체화될 수 있다. For example, the compound represented by the general formula (2) may be more specifically exemplified by the following compounds 1-1 to 1-22, and the compound represented by the general formula (3) may be exemplified by the following compounds 2-1 to 2-22 Can be embodied. Further, the compound represented by the above formula (4) can be further compounded by the following exemplified compounds 3-1 to 3-22.

Figure 112012073412813-pat00005
Figure 112012073412813-pat00005

Figure 112012073412813-pat00006

Figure 112012073412813-pat00006

Figure 112012073412813-pat00007

Figure 112012073412813-pat00007

Figure 112012073412813-pat00008
Figure 112012073412813-pat00008

Figure 112012073412813-pat00009
Figure 112012073412813-pat00009

Figure 112012073412813-pat00010

Figure 112012073412813-pat00010

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 (I) of the present invention can be synthesized according to a general synthesis method. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later.

<유기 전계 발광 소자>&Lt; Organic electroluminescent device &

한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(유기 EL 소자)에 관한 것이다. Another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the general formula (1) according to the present invention described above.

보다 구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode); 음극(cathode); 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다. 이때, 상기 화학식 1로 표시되는 화합물은 1종 또는 2종 이상이 포함될 수 있다.More specifically, the organic electroluminescent device according to the present invention includes an anode; A cathode; And at least one organic material layer interposed between the anode and the cathode, wherein at least one of the organic material layers includes at least one compound represented by the formula (1). At this time, the compound represented by the formula (1) may include one kind or two or more kinds.

여기서, 본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기물층은 발광층, 정공주입층, 정공수송층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있으며, 바람직하게는 발광층, 정공수송층 및/또는 전자수송층일 수 있다.Here, the organic material layer containing the compound represented by the formula (1) of the present invention may be any one or more of a light emitting layer, a hole injecting layer, a hole transporting layer, an electron transporting layer and an electron injecting layer, Lt; / RTI &gt;

본 발명에 따른 유기 전계 발광 소자의 발광층은 호스트 재료를 함유할 수 있는데, 이때 호스트 재료로 상기 화학식 1로 표시되는 화합물 중 어느 하나를 사용할 수 있다. 이와 같이 발광층이 상기 화학식 1로 표시되는 화합물 중 어느 하나를 함유할 경우, 발광층에서 정공과 전자의 결합력이 높아지기 때문에 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등이 우수한 유기 전계 발광 소자를 제공할 수 있다. 상기 화학식 1로 표시되는 화합물은 청색, 녹색 및/또는 적색의 인광 호스트, 형광 호스트, 또는 도펀트 재료로서 유기 발광 소자에 포함될 수 있다. 또한 도펀트 재료로 이용될 수 있다. The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material, and any one of the compounds represented by the above formula (1) may be used as a host material. When the light emitting layer contains any one of the compounds represented by the above formula (1), the bonding strength between the hole and the electron in the light emitting layer is increased, and thus the organic light emitting layer having excellent efficiency (light emitting efficiency and power efficiency), lifetime, Device can be provided. The compound represented by Formula 1 may be included in an organic light emitting device as a blue, green, and / or red phosphorescent host, a fluorescent host, or a dopant material. It can also be used as a dopant material.

본 발명의 유기 EL 소자 구조는 특별히 한정되지 않으나, 전극간에 유기물층을 1층 또는 2층 이상 적층한 구조일 수 있다. 이의 비제한적인 예를 들면 (i) 양극, 발광층, 음극; (ⅱ) 양극, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 음극; 또는 (ⅲ) 양극, 정공주입층, 정공수송층, 발광층, 음극 등의 구조를 들 수 있다.The structure of the organic EL device of the present invention is not particularly limited, but may be a structure in which one or more organic layers are laminated between electrodes. Non-limiting examples thereof include (i) an anode, a light emitting layer, a cathode; (Ii) an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, a cathode; Or (iii) a structure such as an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, and a cathode.

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 EL 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 EL device according to the present invention, the organic material layer containing 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 EL 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 EL device according to the present invention can be formed by forming an organic layer and an electrode using materials and methods known in the art, except that one or more of the organic layers are formed so as to include the compound represented by the formula 1 of the present invention .

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 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질이 사용될 수 있다. The hole injecting layer, the hole transporting layer and the electron transporting layer are not particularly limited, and ordinary 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 examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[합성예 1] 화합물 1,4-bis(4-(9H-carbazol-9-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline)의 합성 Synthesis Example 1 Synthesis of Compound 1,4-bis (4- (9H-carbazol-9-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline)

Figure 112012073412813-pat00011
Figure 112012073412813-pat00011

<단계 1> 1,2,3,4-<Step 1> 1,2,3,4- tetrahydroquinoxalinetetrahydroquinoxaline 합성 synthesis

Quinoxaline (10g, 74.52mmol)을 테트라하이드로퓨란 100 ㎖에 녹인 다음 NaBH4 (10g, 26.4mmol)을 넣고 교반하였다. 이후, 반응온도를 0℃로 낮추고 트리플루오로아세트산 (10ml, 5.89mmol)을 천천히 30분 동안 적가하였다. 적가가 완료되면 온도를 상온으로 천천히 올린 후 2시간 동안 교반하였다. Quinoxaline (10 g, 74.52 mmol) was dissolved in 100 ml of tetrahydrofuran, followed by addition of NaBH 4 (10 g, 26.4 mmol) and stirring. The reaction temperature was then lowered to 0 ° C and trifluoroacetic acid (10ml, 5.89mmol) was slowly added dropwise over 30 minutes. When the addition was completed, the temperature was slowly raised to room temperature and stirred for 2 hours.

TLC를 이용하여 반응이 종결된 것을 확인한 후 증류수를 투입하고 에틸아세테이트로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(7g, 수율68%)을 얻었다. HRMS [M]+: 134.08
After confirming that the reaction was completed using TLC, distilled water was added thereto and extracted with ethyl acetate. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and then purified by column chromatography to obtain the title compound (7 g, yield 68%). HRMS [M] &lt; + & gt ; : 134.08

<단계 2> 1,4-&Lt; Step 2 > bisbis (4-(9H-(4- (9H- carbazolcarbazole -9--9- ylyl )) phenylphenyl )-1,2,3,4-tetrahydroquinoxaline 합성) -1,2,3,4-tetrahydroquinoxaline &lt; / RTI &gt;

상기 <단계 1>에서 얻은 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol)을 9-(4-bromophenyl)-9H-carbazole(21.1g, 104.33mmol), Pd(OAc)2(1.28g, 5.73mmol), Cs2CO3 (37.38g, 114.7mmol)과 함께 톨루엔 140ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.31g, 1.56mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. The <step 1> 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) of 9- (4-bromophenyl) -9H- carbazole (21.1g, 104.33mmol) obtained from, Pd (OAc) 2 (1.28g , 5.73 mmol) and Cs2CO3 (37.38 g, 114.7 mmol) were stirred in toluene (140 ml) at room temperature for 15 minutes. Thereafter, tri- (tert-butyl) phosphine (0.31 g, 1.56 mmol) was slowly added dropwise and the reaction mixture was refluxed for 24 hours.

반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물 1-1 (22g, 수율68.5%)을 얻었다. HRMS [M]+: 616.26
After the reaction was completed, distilled water was added and the mixture was extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure, and then purified by column chromatography to obtain the title compound 1-1 (22 g, yield 68.5%). HRMS [M] &lt; + & gt ; : 616.26

[합성예 2] 화합물 1,4-bis(9-phenyl-9H-carbazol-3-yl)-1,2,3,4-tetrahydroquinoxaline 의 합성Synthesis Example 2 Synthesis of Compound 1,4-bis (9-phenyl-9H-carbazol-3-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-2(수율 81%)을 얻었다. HRMS [M]+: 603.73
(Yield: 81%) was obtained by following the same procedure as in Synthesis Example 1, except that 3-bromo-9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 603.73

[합성예 3] 화합물 1,4-bis(4,6-diphenylpyridin-2-yl)-1,2,3,4-tetrahydroquinoxaline 의 합성Synthesis Example 3 Synthesis of Compound 1,4-bis (4,6-diphenylpyridin-2-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-3(수율 67%)을 얻었다. HRMS [M]+: 592.73
(Yield 67%) was obtained by following the same procedure as in Synthesis Example 1, except that 2-bromo-4,6-diphenylpyridine was used in place of 9- (4-bromophenyl) -9H- . HRMS [M] &lt; + & gt ; : 592.73

[합성예 4] 화합물 3,3'-((5,6-divinyl-2,3-dihydropyrazine-1,4-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole) 의 합성Synthesis Example 4 Synthesis of 3,3 '- ((5,6-divinyl-2,3-dihydropyrazine-1,4-diyl) bis (4,1- Synthesis of

9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-4(수율 71%)을 얻었다. HRMS [M]+: 768.94
The same procedures as in Synthesis Example 1 were carried out except that 3- (4-bromophenyl) -9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 71%). HRMS [M] &lt; + & gt ; : 768.94

[합성예 5] 화합물 1,4-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 5 Synthesis of Compound 1,4-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-5(수율 67%)을 얻었다. HRMS [M]+: 650.85
Dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole was used in place of 4- (4-bromophenyl) Yield: 67%). HRMS [M] &lt; + & gt ; : 650.85

[합성예 6] 화합물 1,4-di(fluoranthen-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성[Synthesis Example 6] Synthesis of compound 1,4-di (fluoranthen-3-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-6(수율 64%)을 얻었다. HRMS [M]+: 534.65
The title compound 1-6 (yield 64%) was obtained by following the same procedure as in Synthesis Example 1, except that 3-bromofluoranthene was used instead of 9- (4-bromophenyl) -9H-carbazole. HRMS [M] &lt; + & gt ; : 534.65

[합성예 7] 화합물 1,4-bis(9,9,10-triphenyl-9,10-dihydroacridin-2-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 7 Synthesis of Compound 1,4-bis (9,9,10-triphenyl-9,10-dihydroacridin-2-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-7(수율 66%)을 얻었다. HRMS [M]+: 949.19
The procedure of Synthesis Example 1 was repeated except that 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine was used in place of 9- (4-bromophenyl) -9H- -7 (yield 66%). HRMS [M] &lt; + & gt ; : 949.19

[합성예 8] 화합물 1-(9,9'-spirobi[fluoren]-2-yl)-4-(9,9'-spirobi[fluoren]-7-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 8 Synthesis of Compound 1- (9,9'-spirobi [fluoren] -2-yl) -4- (9,9'-spirobi [fluoren] -7- Synthesis of tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-8(수율 90%)을 얻었다. HRMS [M]+: 762.94
The procedure of Synthesis Example 1 was repeated except that 2-bromo-9,9'-spirobi [fluorene] was used in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 1-8 90%). HRMS [M] &lt; + & gt ; : 762.94

[합성예 9] 화합물N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)-9H-fluoren-2-amine)의 합성Synthesis Example 9 Synthesis of Compound N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9- -3,4-dihydroquinoxalin-1 (2H) -yl) phenyl) -9H-fluoren-2-amine

Figure 112012073412813-pat00012
Figure 112012073412813-pat00012

<단계 1> 1,2,3,4-tetrahydroquinoxaline 합성<Step 1> Synthesis of 1,2,3,4-tetrahydroquinoxaline

Quinoxaline (10g, 74.5mmol)을 테트라하이드로퓨란 100 ㎖에 녹인 다음 NaBH4 (10g, 26.4mmol)을 넣고 교반하였다. 이후, 반응온도를 0℃로 낮추고 트리플루오로아세트산 (10ml, 5.89mmol)을 천천히 30분 동안 적가하였다. 적가가 완료되면 온도를 상온으로 천천히 올린 후 2시간 동안 교반하였다. Quinoxaline (10 g, 74.5 mmol) was dissolved in 100 mL of tetrahydrofuran, followed by addition of NaBH 4 (10 g, 26.4 mmol) and stirring. The reaction temperature was then lowered to 0 ° C and trifluoroacetic acid (10ml, 5.89mmol) was slowly added dropwise over 30 minutes. When the addition was completed, the temperature was slowly raised to room temperature and stirred for 2 hours.

TLC를 이용하여 반응이 종결된 것을 확인한 후 증류수를 투입하고 에틸아세테이트로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에서 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(7g, 수율68%)을 얻었다. HRMS [M]+: 134.08
After confirming that the reaction was completed using TLC, distilled water was added thereto and extracted with ethyl acetate. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and then purified by column chromatography to obtain the title compound (7 g, yield 68%). HRMS [M] &lt; + & gt ; : 134.08

<단계 2> 3-(3,4-dihydroquinoxalin-1(2H)-yl)-9-phenyl-9H-carbazole의 합성<Step 2> Synthesis of 3- (3,4-dihydroquinoxalin-1 (2H) -yl) -9-phenyl-9H-carbazole

상기 <단계 1>에서 얻은 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol)을 3-bromo-9-phenyl-9H-carbazole(10.55g, 52.16mmol), Pd(OAc)2(0.64g, 2.86mmol), Cs2CO3 (20.39g, 62.59mmol)과 함께 톨루엔 100ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.15g, 0.78mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. A 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) obtained in the above <Step 1> 3-bromo-9- phenyl-9H-carbazole (10.55g, 52.16mmol), Pd (OAc) 2 (0.64g , 2.86 mmol) and Cs 2 CO 3 (20.39 g, 62.59 mmol) in 100 ml of toluene, and the mixture was stirred at room temperature for 15 minutes. Thereafter, tri- (tert-butyl) phosphine (0.15 g, 0.78 mmol) was slowly added dropwise and the reaction mixture was refluxed for 24 hours.

반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(6.26g, 수율32%)을 얻었다. HRMS [M]+: 375.17
After the reaction was completed, distilled water was added and the mixture was extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure, and then purified by column chromatography to give the title compound (6.26 g, yield 32%). HRMS [M] &lt; + & gt ; : 375.17

<단계 3> N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)-9H-fluoren-2-amine)의 합성Step 3: Synthesis of N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- , 4-dihydroquinoxalin-1 (2H) -yl) phenyl) -9H-fluoren-2-amine

상기 <단계 2>에서 얻은 3-(3,4-dihydroquinoxalin-1(2H)-yl)-9-phenyl-9H-carbazole (6.26g, 16.68mmol)을 N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine(8.59g, 16.68mmol), Pd(OAc)2(0.20g, 0.91mmol), Cs2CO3 (6.52g, 20mmol)과 함께 톨루엔 100ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.05g, 0.25mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. 9- phenyl-9H-carbazole (6.26 g, 16.68 mmol) obtained in the above Step 2 was dissolved in N - ([1,1'-biphenyl] 4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine (8.59 g, 16.68 mmol), Pd (OAc) 2 (0.20 g, 0.91 mmol), Cs2CO3 6.52 g, 20 mmol) in 100 ml of toluene was stirred at room temperature for 15 minutes. Thereafter, tri- (tert-butyl) phosphine (0.05 g, 0.25 mmol) was slowly added dropwise and the reaction mixture was refluxed for 24 hours.

반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물 1-19 (9.19g, 수율68%)을 얻었다. HRMS [M]+: 810.37
After the reaction was completed, distilled water was added and the mixture was extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure, and then purified by column chromatography to obtain the title compound 1-19 (9.19 g, yield 68%). HRMS [M] &lt; + & gt ; : 810.37

[합성예 10] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)naphthalen-1-amine의 합성Synthesis Example 10 Synthesis of Compound N-phenyl-N- (4- (9- phenyl-9H-carbazol-3-yl) -3,4-dihydroquinoxalin- Synthesis of -amine

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 표제 화합물 1-9(수율 57%)을 얻었다. HRMS [M]+: 668.83
The same procedures as in Synthesis Example 9 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-2-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 57%). HRMS [M] &lt; + & gt ; : 668.83

[합성예 11] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 11 Synthesis of Compound N, N '- ((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 표제 화합물 1-10(수율 75%)을 얻었다. HRMS [M]+: 668.83
The same procedures as in Synthesis Example 9 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-1-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 75%). HRMS [M] &lt; + & gt ; : 668.83

[합성예 12] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 12 Synthesis of Compound N, N '- ((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-11(수율 88%)을 얻었다. HRMS [M]+: 720.9
The same procedures as in Synthesis Example 1 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-2-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 88%). HRMS [M] &lt; + & gt ; : 720.9

[합성예 13] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 13 Synthesis of Compound N, N '- ((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-12(수율 78%)을 얻었다. HRMS [M]+: 720.9
The same procedures as in Synthesis Example 1 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-1-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 78%). HRMS [M] &lt; + & gt ; : 720.9

[합성예 14] 화합물 1,4-bis(6-(9H-carbazol-9-yl)pyridin-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 14 Synthesis of Compound 1,4-bis (6- (9H-carbazol-9-yl) pyridin-3-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-13(수율 59%)을 얻었다. HRMS [M]+: 681.73
The same procedure as in Synthesis Example 1 was carried out except that 9- (5-bromopyridin-2-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 59%). HRMS [M] &lt; + & gt ; : 681.73

[합성예 15] 화합물 1,4-bis(9,9-dimethyl-9H-fluoren-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 15 Synthesis of Compound 1,4-bis (9,9-dimethyl-9H-fluoren-3-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물1-14(수율 60%)을 얻었다. HRMS [M]+: 518.69
The procedure of Synthesis Example 1 was repeated except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 9- (4-bromophenyl) -9H- 60%). HRMS [M] &lt; + & gt ; : 518.69

[합성예 16] 화합물 1,4-bis(5-(9H-carbazol-9-yl)pyridin-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 16 Synthesis of Compound 1,4-bis (5- (9H-carbazol-9-yl) pyridin-3-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-15(수율 48%)을 얻었다. HRMS [M]+: 618.73
The same procedures as in Synthesis Example 1 were carried out except that 9- (5-bromopyridin-3-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 48%). HRMS [M] &lt; + & gt ; : 618.73

[[ 합성예Synthetic example 17] 화합물 1,4- 17] The compound 1,4- bisbis (3-(9H-(3- (9H- carbazolcarbazole -9--9- ylyl )) phenylphenyl )-1,2,3,4-tetrahydroquinoxaline의 합성) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-16(수율 50%)을 얻었다. HRMS [M]+: 616.75
(Yield: 50%) was obtained by following the same procedure as in Synthesis Example 1, except that 9- (3-bromophenyl) -9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 616.75

[합성예 18] 화합물 1,4-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 18 Synthesis of Compound 1,4-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-17(수율 77%)을 얻었다. HRMS [M]+: 518.61
The same procedure as in Synthesis Example 1 was carried out except that 2- (3-bromophenyl) imidazo [1,2-a] pyridine was used in place of 9- (4-bromophenyl) -9H- 17 (yield: 77%). HRMS [M] &lt; + & gt ; : 518.61

[합성예 19] 화합물 1,4-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 19 Synthesis of Compound 1,4-bis (3- (1-phenyl- 1H-benzo [d] imidazol-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-18(수율 65%)을 얻었다. HRMS [M]+: 670.8
The same procedure as in Synthesis Example 1 was carried out except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used in place of 9- (4-bromophenyl) Compound 1-18 (yield 65%) was obtained. HRMS [M] &lt; + & gt ; : 670.8

[합성예 20] 화합물 1,4-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 20 Synthesis of Compound 1,4-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-20(수율 50%)을 얻었다. HRMS [M]+: 744.92
The procedure of Synthesis Example 1 was repeated except for using 2- (4-bromophenyl) -4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 1-20 50%). HRMS [M] &lt; + & gt ; : 744.92

[합성예 21] 화합물 1,4-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 21 Synthesis of Compound 1,4-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-21(수율 70%)을 얻었다. HRMS [M]+: 650.85
Dibenzo [b, d] thiophene instead of 4- (3-bromophenyl) -9H-carbazole was used in place of 4- (3-bromophenyl) dibenzo [ Yield: 70%). HRMS [M] &lt; + & gt ; : 650.85

[합성예 22] 화합물 1,4-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 22 Synthesis of Compound 1,4-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -1,2,3,4-tetrahydroquinoxaline

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-22(수율 72%)을 얻었다. HRMS [M]+: 596.68
The same procedures as in Synthesis Example 1 were carried out except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used in place of 9- (4-bromophenyl) -9H- -22 (yield: 72%). HRMS [M] &lt; + & gt ; : 596.68

[합성예 23] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9H-carbazole)의 합성Synthesis Example 23 Synthesis of 9,9 '- ((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9H-carbazole)

Figure 112012073412813-pat00013
Figure 112012073412813-pat00013

Quinoxaline 대신 pteridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 2-1 (수율 50%)을 합성하였다. Compound 2-1 (yield 50%) was synthesized in the same manner as in Synthesis Example 1, except that pteridine was used in place of quinoxaline.

HRMS [M]+: 618.25
HRMS [M] &lt; + & gt ; : 618.25

[합성예 24] 화합물 3,3'-(6,7-dihydropteridine-5,8-diyl)bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 24 Synthesis of Compound 3,3 '- (6,7-dihydropteridine-5,8-diyl) bis (9-phenyl-9H-carbazole)

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-2(수율 78%)을 얻었다. HRMS [M]+: 618.73
(Yield 78%) was obtained by following the same procedure as in Synthesis Example 23, except that 3-bromo-9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 618.73

[합성예 25] 화합물 5,8-bis(4,6-diphenylpyridin-2-yl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 25 Synthesis of Compound 5,8-bis (4,6-diphenylpyridin-2-yl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예23과 동일한 과정을 수행하여 표제 화합물 2-3(수율 80%)을 얻었다. HRMS [M]+: 594.71
(Yield: 80%) was obtained by following the same procedure as in Synthesis Example 23, except that 2-bromo-4,6-diphenylpyridine was used in place of 9- (4-bromophenyl) -9H- . HRMS [M] &lt; + & gt ; : 594.71

[합성예 26] 화합물 3,3'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 26 Synthesis of 3,3 '- ((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9-phenyl-9H-

9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-4(수율 76%)을 얻었다. HRMS [M]+: 770.92
The same procedures as in Synthesis Example 23 were carried out except that 3- (4-bromophenyl) -9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 76%). HRMS [M] &lt; + & gt ; : 770.92

[합성예 27] 화합물 5,8-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 27 Synthesis of Compound 5,8-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-5(수율 77%)을 얻었다. Dibenzo [b, d] thiophene was used in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 2-5 Yield: 77%).

HRMS [M]+: 652.83
HRMS [M] &lt; + & gt ; : 652.83

[[ 합성예Synthetic example 28] 화합물 5,8- 28] Compound 5,8- didi (( fluoranthenfluoranthen -3--3- ylyl )-5,6,7,8-) -5,6,7,8- tetrahydropteridinetetrahydropteridine 의 합성Synthesis of

9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-6(수율 83%)을 얻었다. HRMS [M]+: 536.62
The title compound 2-6 (yield 83%) was obtained by following the procedure of Preparative Example 23 while using 3-bromofluoranthene instead of 9- (4-bromophenyl) -9H-carbazole. HRMS [M] &lt; + & gt ; : 536.62

[합성예 29] 화합물 2,2'-(6,7-dihydropteridine-5,8-diyl)bis(9,9,10-triphenyl-9,10-dihydroacridine)의 합성Synthesis Example 29 Synthesis of Compound 2,2 '- (6,7-dihydropteridine-5,8-diyl) bis (9,9,10-triphenyl-9,10-dihydroacridine)

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-7(수율 76%)을 얻었다. HRMS [M]+: 951.16
The same procedures as in Synthesis Example 23 were carried out except that 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine was used instead of 9- (4-bromophenyl) -9H- -7 (yield: 76%). HRMS [M] &lt; + & gt ; : 951.16

[합성예 30] 화합물 5-(9,9'-spirobi[fluoren]-2-yl)-8-(9,9'-spirobi[fluoren]-7-yl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 30 Synthesis of Compound 5- (9,9'-spirobi [fluoren] -2-yl) -8- (9,9'-spirobi [fluoren] -7- Synthesis of tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-8(수율 86%)을 얻었다. HRMS [M]+: 764.91
The same procedures as in Synthesis Example 23 were carried out except that 2-bromo-9,9'-spirobi [fluorene] was used in place of 9- (4-bromophenyl) -9H- 86%). HRMS [M] &lt; + & gt ; : 764.91

[[ 합성예Synthetic example 31]  31] 화합물compound N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(8-(9-N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (8- (9- phenylphenyl -9H--9H- carbazolcarbazole -3--3- ylyl )-7,8-) -7,8- dihydropteridindihydropteridine -5(6H)--5 (6H) - ylyl )) phenylphenyl )-9H-) -9H- fluorenfluoren -2-amine의 합성-2-amine

Figure 112012073412813-pat00014
Figure 112012073412813-pat00014

Quinoxaline 대신 pteridine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 화합물 2-19 (수율 21%)를 합성하였다. Compound 2-19 (yield: 21%) was synthesized in the same manner as in Synthesis Example 9, except that pteridine was used in place of quinoxaline.

HRMS [M]+: 812.36
HRMS [M] &lt; + & gt ; : 812.36

[합성예 32] 화합물 N-phenyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)naphthalen-2-amine의 합성Synthesis Example 32 Synthesis of Compound N-phenyl-N- (4- (8- (9-phenyl-9H-carbazol-3-yl) -7,8-dihydropteridin- Synthesis of -amine

N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 2-9(수율 79%)을 얻었다. HRMS [M]+: 671.8
(4-bromophenyl) -N-phenylnaphthalen-2-amine instead of N - ([1,1'-biphenyl] -4-yl) -N- -2-amine, the title compound 2-9 (yield 79%) was obtained by carrying out the same procedure as in Synthesis Example 31. HRMS [M] &lt; + & gt ; : 671.8

[합성예 33] 화합물 N-phenyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)naphthalen-1-amine 의 합성Synthesis Example 33 Synthesis of Compound N-phenyl-N- (4- (8- (9- phenyl-9H-carbazol-3-yl) -7,8-dihydropteridin- Synthesis of -amine

N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 2-10(수율 58%)을 얻었다. HRMS [M]+: 670.8
(4-bromophenyl) -N-phenylnaphthalen-2-amine instead of N - ([1,1'-biphenyl] -4-yl) -N- -1-amine, the title compound 2-10 (yield: 58%) was obtained by carrying out the same procedure as in Synthesis Example 31. HRMS [M] &lt; + & gt ; : 670.8

[합성예 34] 화합물 N,N'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine) 의 합성Synthesis Example 34 Synthesis of Compound N, N '- ((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-11(수율 62%)을 었다. HRMS [M]+:722.8
The same procedures as in Synthesis Example 23 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-2-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 62%). HRMS [M] &lt; + & gt ; : 722.8

[합성예 35] 화합물 N,N'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 35 Synthesis of Compound N, N '- ((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-12(수율 49%)을 얻었다. HRMS [M]+: 722.8
The procedure of Synthesis Example 23 was repeated except for using N- (4-bromophenyl) -N-phenylnaphthalen-1-amine instead of 9- (4-bromophenyl) -9H- 49%). HRMS [M] &lt; + & gt ; : 722.8

[합성예 36] 화합물 9,9'-(5,5'-(6,7-dihydropteridine-5,8-diyl)bis(pyridine-5,2-diyl))bis(9H-carbazole) 의 합성Synthesis Example 36 Synthesis of 9,9 '- (5,5' - (6,7-dihydropteridine-5,8-diyl) bis (pyridine-5,2-diyl) bis (9H-

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-13(수율 79%)을 얻었다. HRMS [M]+: 620.7
The same procedures as in Synthesis Example 23 were carried out except that 9- (5-bromopyridin-2-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 79%). HRMS [M] &lt; + & gt ; : 620.7

[합성예 37] 화합물 5,8-bis(9,9-dimethyl-9H-fluoren-3-yl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 37 Synthesis of Compound 5,8-bis (9,9-dimethyl-9H-fluoren-3-yl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물2-14(수율 56%)을 얻었다. HRMS [M]+: 520.67
The same procedures as in Synthesis Example 23 were carried out except that 3-bromo-9,9-dimethyl-9H-fluorene was used in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 2-14 56%). HRMS [M] &lt; + & gt ; : 520.67

[합성예 38] 화합물 9,9'-(5,5'-(6,7-dihydropteridine-5,8-diyl)bis(pyridine-5,3-diyl))bis(9H-carbazole) 의 합성Synthesis Example 38 Synthesis of 9,9 '- (5,5' - (6,7-dihydropteridine-5,8-diyl) bis (pyridine-5,3-diyl) bis (9H-

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-15(수율 65%)을 얻었다. HRMS [M]+: 620.7
The same procedures as in Synthesis Example 23 were carried out except that 9- (5-bromopyridin-3-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 65%). HRMS [M] &lt; + & gt ; : 620.7

[합성예 39] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(3,1-phenylene))bis(9H-carbazole) 의 합성Synthesis Example 39 Synthesis of 9,9 '- ((6,7-dihydropteridine-5,8-diyl) bis (3,1-phenylene)) bis (9H-

9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-16(수율 70%)을 얻었다. HRMS [M]+: 520.67
The title compound 2-16 (Yield: 70%) was obtained by following the same procedure as in Synthesis Example 23, except that 9- (3-bromophenyl) -9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 520.67

[합성예 40] 화합물 5,8-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 40 Synthesis of Compound 5,8-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-17(수율 46%)을 얻었다. HRMS [M]+: 607.69
The procedure of Synthesis Example 23 was repeated except for using 2- (3-bromophenyl) imidazo [1,2-a] pyridine instead of 9- (4-bromophenyl) -9H- 17 (yield: 46%). HRMS [M] &lt; + & gt ; : 607.69

[합성예 41] 화합물 5,8-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 41 Synthesis of Compound 5,8-bis (3- (1-phenyl- 1H-benzo [d] imidazol-2-yl) phenyl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-18(수율 55%)을 얻었다. HRMS [M]+: 672.78
The procedure of Synthesis Example 23 was repeated except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used in place of 9- (4-bromophenyl) -9H- Compound 2-18 (yield: 55%) was obtained. HRMS [M] &lt; + & gt ; : 672.78

[합성예 42] 화합물 5,8-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 42 Synthesis of Compound 5,8-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-20(수율 60%)을 얻었다. HRMS [M]+: 746.9
The procedure of Synthetic Example 23 was repeated except for using 2- (4-bromophenyl) -4,6-diphenylpyridine in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 2-20 60%). HRMS [M] &lt; + & gt ; : 746.9

[합성예 43] 화합물 5,8-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 43 Synthesis of Compound 5,8-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-21(수율 54%)을 얻었다. HRMS [M]+: 652.83
Dibenzo [b, d] thiophene was used in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 2-21 ( Yield: 54%). HRMS [M] &lt; + & gt ; : 652.83

[합성예 44] 화합물 5,8-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 44 Synthesis of Compound 5,8-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -5,6,7,8-tetrahydropteridine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-22(수율 35%)을 얻었다. HRMS [M]+: 598.66
The same procedures as in Synthesis Example 23 were carried out except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used in place of 9- (4-bromophenyl) -9H- -22 (yield: 35%). HRMS [M] &lt; + & gt ; : 598.66

[합성예 45] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9H-carbazole)의 합성Synthesis Example 45 Synthesis of 9,9 '- ((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9H-carbazole)

Figure 112012073412813-pat00015
Figure 112012073412813-pat00015

Quinoxaline 대신 pyrido[2,3-b]pyrazine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 3-1 (수율 63%)을 합성하였다. Compound 3-1 (yield: 63%) was synthesized in the same manner as in Synthesis Example 1, except that pyrido [2,3-b] pyrazine was used instead of quinoxaline.

HRMS [M]+: 617.74
HRMS [M] &lt; + & gt ; : 617.74

[합성예 46] 3,3'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 46 Synthesis of 3,3 '- (2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (9-phenyl-9H-

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-2(수율 59%)을 얻었다. HRMS [M]+: 617.74
The title compound 3-2 (yield 59%) was prepared using the same procedure as in Synthesis Example 23, except that 3-bromo-9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 617.74

[합성예 47] 화합물 1,4-bis(4,6-diphenylpyridin-2-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 47 Synthesis of Compound 1,4-bis (4,6-diphenylpyridin-2-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예23과 동일한 과정을 수행하여 표제 화합물3-3(수율 650%)을 얻었다. HRMS [M]+: 593.72
The title compound 3-3 (yield: 650%) was prepared following the same procedure as in Synthesis Example 23, except that 2-bromo-4,6-diphenylpyridine was used in place of 9- (4-bromophenyl) . HRMS [M] &lt; + & gt ; : 593.72

[합성예 48] 화합물 3,3'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 48 Synthesis of 3,3 '- ((2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (4,1- carbazole)

9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물3-4(수율 70%)을 얻었다. HRMS [M]+: 769.93
The same procedure as in Synthesis Example 23 was carried out except that 3- (4-bromophenyl) -9-phenyl-9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 70%). HRMS [M] &lt; + & gt ; : 769.93

[합성예 49] 화합물 1,4-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 49 Synthesis of Compound 1,4-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-5(수율 63%)을 얻었다. HRMS [M]+: 651.84
Dibenzo [b, d] thiophene was used in place of 9- (4-bromophenyl) -9H-carbazole, the title compound 3-5 Yield: 63%). HRMS [M] &lt; + & gt ; : 651.84

[합성예 50] 화합물 1,4-di(fluoranthen-3-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 50 Synthesis of Compound 1,4-di (fluoranthen-3-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-6(수율 70%)을 얻었다. HRMS [M]+: 535.64
The title compound 3-6 (yield 70%) was obtained by following the same procedure as in Synthesis Example 23, except that 3-bromofluoranthene was used instead of 9- (4-bromophenyl) -9H-carbazole. HRMS [M] &lt; + & gt ; : 535.64

[합성예 51] 화합물 2,2'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(9,9,10-triphenyl-9,10-dihydroacridine)의 합성Synthesis Example 51 Synthesis of 2,2 '- (2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (9,9,10-triphenyl-9,10-dihydroacridine)

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-7(수율 70%)을 얻었다. HRMS [M]+: 950.18
The same procedures as in Synthesis Example 23 were carried out except that 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine was used in place of 9- (4-bromophenyl) -9H- -7 (yield 70%). HRMS [M] &lt; + & gt ; : 950.18

[합성예 52] 화합물 1-(9,9'-spirobi[fluoren]-2-yl)-4-(9,9'-spirobi[fluoren]-7-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 52 Synthesis of Compound 1- (9,9'-spirobi [fluoren] -2-yl) -4- (9,9'-spirobi [fluoren] -7- Synthesis of tetrahydropyrido [2,3-b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-8(수율 77%)을 얻었다. HRMS [M]+: 763.92
The procedure of Synthetic Example 23 was repeated except that 2-bromo-9,9'-spirobi [fluorene] was used in place of 9- (4-bromophenyl) -9H- 77%). HRMS [M] &lt; + & gt ; : 763.92

[합성예 53] 화합물N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)-9H-fluoren-2-amine의 합성Synthesis Example 53 Synthesis of Compound N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (8- (9- -7,8-dihydropteridin-5 (6H) -yl) phenyl) -9H-fluoren-2-amine

Figure 112012073412813-pat00016
Figure 112012073412813-pat00016

Quinoxaline 대신 pyrido[2,3-b]pyrazine를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 화합물 3-19 (수율 40%)를 합성하였다. Compound 3-19 (yield 40%) was synthesized in the same manner as in Synthesis Example 31, except that pyrido [2,3-b] pyrazine was used instead of quinoxaline.

HRMS [M]+: 812.01
HRMS [M] &lt; + & gt ; : 812.01

[합성예 54] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydropyrido[2,3-b]pyrazin-1(2H)-yl)phenyl)naphthalen-2-amine의 합성Synthesis Example 54 Synthesis of Compound N-phenyl-N- (4- (9- phenyl-9H-carbazol-3-yl) -3,4-dihydropyrido [2,3- b] pyrazin- -yl) phenyl) naphthalen-2-amine

N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 3-9(수율 67%)을 얻었다. HRMS [M]+: 681.844
(4-bromophenyl) -N-phenylnaphthalen-2-amine instead of N - ([1,1'-biphenyl] -4-yl) -N- -2-amine, the title compound 3-9 (yield 67%) was obtained by carrying out the same procedure as in Synthesis Example 31. HRMS [M] &lt; + & gt ; : 681.844

[합성예 55] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydropyrido[2,3-b]pyrazin-1(2H)-yl)phenyl)naphthalen-1-amine의 합성Synthesis Example 55 Synthesis of Compound N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) -3,4- dihydropyrido [2,3- b] pyrazin- -yl) phenyl) naphthalen-1-amine Synthesis of

N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 3-10(수율 61%)을 얻었다. HRMS [M]+: 669.81
(4-bromophenyl) -N-phenylnaphthalen-2-amine instead of N - ([1,1'-biphenyl] -4-yl) -N- -1-amine, the title compound 3-10 (yield: 61%) was obtained by carrying out the same procedure as in Synthesis Example 31. HRMS [M] &lt; + & gt ; : 669.81

[합성예 56] 화합물 N,N'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 56 Synthesis of Compound N, N '- ((2,3-dihydropyrido [2,3-b pyrazine-1,4-diyl) bis (4,1- amine)

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-11(수율 78%)을 얻었다. HRMS [M]+: 669.81
The same procedures as in Synthesis Example 23 were carried out except that N- (4-bromophenyl) -N-phenylnaphthalen-2-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 78%). HRMS [M] &lt; + & gt ; : 669.81

[합성예 57] 화합물 N,N'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 57 Synthesis of Compound N, N '- ((2,3-dihydropyrido [2,3-b pyrazine-1,4-diyl) bis (4,1- amine)

9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-12(수율 91%)을 얻었다. HRMS [M]+: 721.89
Following the same procedure as in Synthesis Example 23, except that N- (4-bromophenyl) -N-phenylnaphthalen-1-amine was used in place of 9- (4-bromophenyl) -9H- (Yield: 91%). HRMS [M] &lt; + & gt ; : 721.89

[합성예 58] 화합물 9,9'-(5,5'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(pyridine-5,2-diyl))bis(9H-carbazole)의 합성Synthesis Example 58 Synthesis of Compound 9,9 '- (5,5' - (2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (pyridine-5,2- (9H-carbazole)

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-13(수율 80%)을 얻었다. HRMS [M]+: 721.89
The same procedures as in Synthesis Example 23 were carried out except that 9- (5-bromopyridin-2-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 80%). HRMS [M] &lt; + & gt ; : 721.89

[합성예 59] 화합물 1,4-bis(9,9-dimethyl-9H-fluoren-3-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 59 Synthesis of Compound 1,4-bis (9,9-dimethyl-9H-fluoren-3-yl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물3-14(수율 87%)을 얻었다. HRMS [M]+: 619.72
The procedure of Synthesis Example 23 was repeated except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 9- (4-bromophenyl) -9H- 87%). HRMS [M] &lt; + & gt ; : 619.72

[합성예 60] 화합물 9,9'-(5,5'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(pyridine-5,3-diyl))bis(9H-carbazole)의 합성Synthesis Example 60 Synthesis of Compound 9,9 '- (5,5' - (2,3-dihydropyrido [2,3-b pyrazine-1,4-diyl) bis (pyridine-5,3- (9H-carbazole)

9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-15(수율 54%)을 얻었다. HRMS [M]+: 617.74
The same procedures as in Synthesis Example 23 were carried out except that 9- (5-bromopyridin-3-yl) -9H-carbazole was used in place of 9- (4-bromophenyl) -9H- (Yield: 54%). HRMS [M] &lt; + & gt ; : 617.74

[합성예 61] 화합물 9,9'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(3,1-phenylene))bis(9H-carbazole) 의 합성Synthesis Example 61 Synthesis of 9,9 '- ((2,3-dihydropyrido [2,3-b pyrazine-1,4-diyl) bis (3,1-phenylene)) bis (9H-

9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-16(수율 77%)을 얻었다. HRMS [M]+: 519.6
The title compound 3-16 (Yield 77%) was obtained by following the same procedure as in Synthesis Example 23, except that 9- (3-bromophenyl) -9H-carbazole was used in place of 9- (4-bromophenyl) ). HRMS [M] &lt; + & gt ; : 519.6

[합성예 62] 화합물 1,4-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 62 Synthesis of Compound 1,4-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine synthesis

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-17(수율 69%)을 얻었다. HRMS [M]+: 671.79
Following the same procedure as in Synthesis Example 23, except for using 2- (3-bromophenyl) imidazo [1,2-a] pyridine instead of 9- (4-bromophenyl) -9H- 17 (yield 69%). HRMS [M] &lt; + & gt ; : 671.79

[합성예 63] 화합물 1,4-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 63 Synthesis of Compound 1,4-bis (3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [ Synthesis of pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-18(수율 86%)을 얻었다. HRMS [M]+: 519.6
The procedure of Synthesis Example 23 was repeated except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used in place of 9- (4-bromophenyl) -9H- Compound 3-18 (yield: 86%) was obtained. HRMS [M] &lt; + & gt ; : 519.6

[합성예 64] 화합물 1,4-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 64 Synthesis of Compound 1,4-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-20(수율 69%)을 얻었다. HRMS [M]+: 745.91
The same procedure as in Synthesis Example 23 was conducted, except that 2- (4-bromophenyl) -4,6-diphenylpyridine was used in place of 9- (4-bromophenyl) -9H-carbazole to obtain the title compound 3-20 69%). HRMS [M] &lt; + & gt ; : 745.91

[합성예 65] 화합물 1,4-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 65 Synthesis of Compound 1,4-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-21(수율 71%)을 얻었다. HRMS [M]+: 651.84
Dibenzo [b, d] thiophene was used in place of 9- (4-bromophenyl) -9H-carbazole, the title compound 3-21 Yield: 71%). HRMS [M] &lt; + & gt ; : 651.84

[합성예 66] 화합물 1,4-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 66 Synthesis of Compound 1,4-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -1,2,3,4-tetrahydropyrido [2,3- b] pyrazine

9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-22(수율 57%)을 얻었다. HRMS [M]+: 597.67
Following the same procedure as in Synthesis Example 23, except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used in place of 9- (4-bromophenyl) -9H- -22 (yield: 57%). HRMS [M] &lt; + & gt ; : 597.67

[실시예 1 ~ 32] 녹색 유기 EL 소자의 제작[Examples 1 to 32] Fabrication of green organic EL device

앞서 합성예에서 합성된 각 화합물 (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19)을 통상적으로 알려진 방법으로 고순도 승화정제를 수행한 후 아래의 과정에 따라 녹색 유기 EL 소자를 제작하였다.The compounds (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1 -20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1 , 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19) were subjected to high purity sublimation purification A green organic EL device was fabricated 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)/ 화합물 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (각각) + 10 % Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 녹색 유기 EL 소자를 제작하였다. M-MTDATA (60 nm) / TCTA (80 nm) / Compound 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, -14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14 , 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 ) + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) were stacked in this order to fabricate a green organic EL device.

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 112012073412813-pat00017
Figure 112012073412813-pat00017

Figure 112012073412813-pat00018

Figure 112012073412813-pat00018

[[ 비교예Comparative Example 1] 녹색 유기  1] Green organic ELEL 소자의 제작 Device fabrication

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

[평가예 1][Evaluation Example 1]

실시예 1-32 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.The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic EL devices manufactured in Example 1-32 and Comparative Example 1, and the results are shown in Table 1 below.

샘플Sample 호스트Host 구동 전압
(V)Driving voltage
(V) EL 피크
(nm)EL peak
(nm) 전류효율
(cd/A)Current efficiency
(cd / A) 실시예 1Example 1 1-11-1 6.786.78 517517 42.442.4 실시예 2Example 2 1-21-2 6.826.82 515515 41.141.1 실시예 3Example 3 1-51-5 6.796.79 517517 40.840.8 실시예 4Example 4 1-71-7 6.796.79 518518 41.041.0 실시예 5Example 5 1-91-9 6.856.85 516516 38.038.0 실시예 6Example 6 1-101-10 6.796.79 517517 40.840.8 실시예 7Example 7 1-121-12 6.936.93 518518 41.041.0 실시예 8Example 8 1-141-14 6.786.78 517517 38.038.0 실시예 9Example 9 1-171-17 6.786.78 518518 42.442.4 실시예 10 Example 10 1-191-19 6.826.82 516516 41.141.1 실시예 11Example 11 1-201-20 6.796.79 517517 40.840.8 실시예 12Example 12 1-221-22 6.856.85 518518 41.041.0 실시예 13 Example 13 2-12-1 6.796.79 517517 38.038.0 실시예 14Example 14 2-22-2 6.936.93 518518 42.442.4 실시예 15Example 15 2-52-5 6.786.78 517517 41.141.1 실시예 16Example 16 2-72-7 6.796.79 518518 40.840.8 실시예 17Example 17 2-92-9 6.856.85 516516 41.041.0 실시예 18Example 18 2-102-10 6.796.79 517517 41.041.0 실시예 19Example 19 2-122-12 6.936.93 518518 38.038.0 실시예 20Example 20 2-142-14 6.786.78 517517 42.442.4 실시예 21Example 21 2-172-17 6.826.82 518518 41.141.1 실시예 22Example 22 2-192-19 6.796.79 516516 40.840.8 실시예 23 Example 23 3-13-1 6.796.79 517517 41.041.0 실시예 24Example 24 3-23-2 6.796.79 517517 38.038.0 실시예 25Example 25 3-53-5 6.856.85 518518 42.442.4 실시예 26Example 26 3-73-7 6.796.79 516516 41.041.0 실시예 27Example 27 3-93-9 6.936.93 517517 41.041.0 실시예 28Example 28 3-103-10 6.786.78 518518 38.038.0 실시예 29Example 29 3-123-12 6.826.82 516516 42.442.4 실시예 30Example 30 3-143-14 6.826.82 517517 41.141.1 실시예 31Example 31 3-173-17 6.796.79 518518 40.840.8 실시예 32Example 32 3-193-19 6.856.85 517517 41.041.0 비교예 1Comparative Example 1 CBPCBP 6.936.93 516516 38.238.2

상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 녹색 유기 EL 소자의 발광층으로 사용하는 실시예 1~32의 유기 EL 소자는 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 devices of Examples 1 to 32, in which the compound according to the present invention is used as a light emitting layer of a green organic EL device, are superior to the green organic EL device of Comparative Example 1 using CBP It can be seen that it exhibits better performance in terms of efficiency and driving voltage.

[실시예 33~64] 청색 유기 EL 소자의 제조[Examples 33 to 64] Preparation of blue organic EL device

앞서 합성예에서 합성된 각 화합물 (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19)을 통상적으로 알려진 방법으로 고순도 승화정제를 수행한 후 아래의 과정에 따라 청색 유기 EL 소자를 제작하였다.The compounds (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1 -20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1 , 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19) were subjected to high purity sublimation purification A blue organic EL device was fabricated 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 CuPc (10 nm)/ TPAC (30 nm)/ 화합물 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (각각) + 7 % Flrpic (30nm)/ Alq3 (30 nm)/ LiF (0.2 nm)/Al (150 nm) 순으로 적층하여 청색 유기 EL 소자를 제작하였다. On this ITO transparent electrode, CuPc (10 nm) / TPAC (30 nm) / Compounds 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14 , 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2 -17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (respectively) + (30 nm) / Alq 3 (30 nm) / LiF (0.2 nm) / Al (150 nm) were stacked in this order to obtain a blue organic EL device.

CuPc, TPAC, Flrpic의 구조는 하기와 같다.The structures of CuPc, TPAC and Flrpic are as follows.

Figure 112012073412813-pat00019

Figure 112012073412813-pat00019

[비교예 2] 유기 EL 소자의 제작[Comparative Example 2] Fabrication of organic EL device

발광층 형성시 발광 호스트 물질로서 화합물 1-1 대신 CBP를 사용하는 것을 제외하고는 실시예 33과 동일한 과정으로 청색 유기 EL 소자를 제작하였다.
A blue organic EL device was fabricated in the same manner as in Example 33, except that CBP was used instead of Compound 1-1 as a luminescent host material in forming the light emitting layer.

[평가예 2][Evaluation Example 2]

실시예 33~64 및 비교예 2에서 제작한 각각의 청색 유기 EL 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 2에 나타내었다.The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the blue organic EL devices manufactured in Examples 33 to 64 and Comparative Example 2, and the results are shown in Table 2 below.

샘플Sample 호스트Host 구동 전압
(V)Driving voltage
(V) EL 피크
(nm)EL peak
(nm) 전류효율
(cd/A)Current efficiency
(cd / A) 실시예 33Example 33 1-11-1 7.337.33 473473 5.995.99 실시예 34Example 34 1-21-2 7.137.13 474474 6.346.34 실시예 35Example 35 1-51-5 7.127.12 475475 6.346.34 실시예 36Example 36 1-71-7 7.557.55 475475 5.995.99 실시예 37Example 37 1-91-9 7.557.55 472472 5.855.85 실시예 38Example 38 1-101-10 7.257.25 472472 5.895.89 실시예 39Example 39 1-121-12 7.767.76 473473 5.855.85 실시예 40Example 40 1-141-14 7.337.33 474474 6.906.90 실시예 41Example 41 1-171-17 7.527.52 475475 6.346.34 실시예 42Example 42 1-191-19 7.017.01 475475 6.656.65 실시예 43Example 43 1-201-20 7.347.34 473473 5.995.99 실시예 44Example 44 1-221-22 7.377.37 474474 5.855.85 실시예 45Example 45 2-12-1 7.227.22 473473 6.346.34 실시예 46Example 46 2-22-2 7.217.21 474474 6.146.14 실시예 47Example 47 2-52-5 7.197.19 475475 5.875.87 실시예 48Example 48 2-72-7 7.117.11 472472 5.855.85 실시예 49Example 49 2-92-9 7.127.12 472472 5.755.75 실시예 50Example 50 2-102-10 7.127.12 473473 5.855.85 실시예 51Example 51 2-122-12 7.547.54 473473 6.346.34 실시예 52Example 52 2-142-14 7.527.52 474474 6.216.21 실시예 53Example 53 2-172-17 7.117.11 475475 5.595.59 실시예 54Example 54 2-192-19 7.137.13 472472 5.995.99 실시예 55Example 55 3-13-1 7.127.12 472472 5.855.85 실시예 56Example 56 3-23-2 7.447.44 473473 6.906.90 실시예 57Example 57 3-53-5 7.347.34 474474 6.346.34 실시예 58Example 58 3-73-7 7.187.18 475475 5.995.99 실시예 59Example 59 3-93-9 7.137.13 472472 5.855.85 실시예 60Example 60 3-103-10 7.127.12 472472 6.346.34 실시예 61Example 61 3-123-12 7.217.21 473473 5.785.78 실시예 62Example 62 3-143-14 7.557.55 474474 5.855.85 실시예 63Example 63 3-173-17 7.417.41 475475 6.906.90 실시예 64Example 64 3-193-19 7.137.13 474474 6.346.34 비교예 2Comparative Example 2 CBPCBP 7.807.80 474474 5.805.80

상기 표 2에 나타낸 바와 같이, 본 발명에 따른 화합물을 청색 유기 EL 소자의 발광층으로 사용하는 실시예 33~64의 유기 EL 소자는 종래 CBP를 사용하는 비교예 2의 청색 유기 EL 소자와 비교해 볼 때 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 2, the organic EL devices of Examples 33 to 64, in which the compound according to the present invention is used as a light emitting layer of a blue organic EL device, are different from the conventional blue organic EL devices of Comparative Example 2 using CBP It can be seen that it exhibits better performance in terms of efficiency and driving voltage.

Claims (8)

하기 화학식 1로 표시되는 유기 발광 화합물:
[화학식 1]
Figure 112015039059219-pat00020

상기 식에서,
X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이고;
R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C6~C40의 아릴기, 및 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기로 이루어진 군에서 선택되며,
상기 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기가 치환될 경우는, 각각 독립적으로 C1~C40의 알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, 및 C6~C40의 아릴아민기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환됨을 의미함.An organic light-emitting compound represented by the following formula (1):
[Chemical Formula 1]
Figure 112015039059219-pat00020

In this formula,
X and Y are the same or different and are each independently N or CH;
R 1 and R 2 are the same or different and each independently selected from the group consisting of a substituted or unsubstituted C 6 -C 40 aryl group and a substituted or unsubstituted heteroaryl group having 5 to 40 nucleus atoms And,
When the C 6 to C 40 aryl group and the heteroaryl group having 5 to 40 nuclear atoms are substituted, it is preferable that each of C 1 to C 40 alkyl groups, C 6 to C 40 aryl groups, A heteroaryl group having 6 to 40 carbon atoms, and an arylamine group having 6 to 40 carbon atoms. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 화학식 4로 표시되는 화합물 중에서 선택되는 어느 하나의 화합물인 것을 특징으로 하는 유기 발광 화합물:
[화학식 2]
Figure 112015039059219-pat00021

[화학식 3]
Figure 112015039059219-pat00022

[화학식 4]
Figure 112015039059219-pat00023

상기 식에서,
R1 및 R2는 서로 같거나 또는 상이하며, 각각 독립적으로 C6~C40의 아릴기, 또는 핵원자수 5 내지 40의 헤테로아릴기이다. The organic electroluminescent compound according to claim 1, wherein the compound represented by the formula (1) is any one selected from compounds represented by the following formulas (2) to (4)
(2)
Figure 112015039059219-pat00021

(3)
Figure 112015039059219-pat00022

[Chemical Formula 4]
Figure 112015039059219-pat00023

In this formula,
R 1 and R 2 are the same or different and each independently is a C 6 to C 40 aryl group or a heteroaryl group having 5 to 40 nuclear atoms. 삭제delete 제2항에 있어서, 상기 화학식 2로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 유기 발광 화합물:
Figure 112014076486415-pat00024

Figure 112014076486415-pat00025
The organic electroluminescent compound according to claim 2, wherein the compound represented by the formula (2) is selected from the group of compounds represented by the following formula:
Figure 112014076486415-pat00024

Figure 112014076486415-pat00025
 제2항에 있어서, 상기 화학식 3으로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 유기 발광 화합물:
Figure 112014076486415-pat00026

Figure 112014076486415-pat00027
The organic electroluminescent compound according to claim 2, wherein the compound represented by the formula (3) is selected from the group of compounds represented by the following formula:
Figure 112014076486415-pat00026

Figure 112014076486415-pat00027
 제2항에 있어서, 상기 화학식 4로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 유기 발광 화합물:
Figure 112014076486415-pat00028

Figure 112014076486415-pat00029
The organic electroluminescent compound according to claim 2, wherein the compound represented by the formula (4) is selected from the group of compounds represented by the following formula:
Figure 112014076486415-pat00028

Figure 112014076486415-pat00029
 (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, 제2항, 제4항 내지 제6항 중 어느 한 항에 따른 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 according to any one of claims 1, 2, and 4 to 6. 제 7 항에 있어서, 상기 화합물은 발광층, 전자 수송층 및 정공 수송층으로 구성된 군으로부터 선택된 적어도 하나의 층에 포함되는 것을 특징으로 하는 유기 전계 발광 소자. The organic electroluminescent device according to claim 7, wherein the compound is contained in at least one layer selected from the group consisting of a light emitting layer, an electron transporting layer and a hole transporting layer.
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