KR20120009984A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device using the same Download PDF

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KR20120009984A
KR20120009984A KR1020100071335A KR20100071335A KR20120009984A KR 20120009984 A KR20120009984 A KR 20120009984A KR 1020100071335 A KR1020100071335 A KR 1020100071335A KR 20100071335 A KR20100071335 A KR 20100071335A KR 20120009984 A KR20120009984 A KR 20120009984A
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김영길
김치식
조영준
권혁주
김봉옥
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롬엔드하스전자재료코리아유한회사
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

PURPOSE: An organic electroluminescent compound is provided to excellent luminous efficiency and life time properties, thereby using for manufacturing an organic electroluminescent device of which driving life time is very superior. CONSTITUTION: An organic electroluminescent compound is in chemical formula 1. An organic electroluminescent device comprises the organic electroluminescent compound, the organic electroluminescent compound is using as material for hole injection or hole transport. The organic electroluminescent compound comprises a first electrode, a second electrode, and one or more organic material layer between the first electrode and the second electrode. The organic layer comprises the organic electroluminescent compound in chemical formula 1. The organic layer comprises a light emitting layer and a charge generating layer at the same time.

Description

신규한 유기 발광 화합물 및 이를 포함하는 유기 전계 발광 소자{Novel organic electroluminescent compounds and organic electroluminescent device using the same}Novel organic electroluminescent compounds and organic electroluminescent device using the same

본 발명은 신규한 유기 발광 화합물 및 이를 포함하고 있는 유기 전계 발광 소자에 관한 것으로, 보다 구체적으로는 정공수송재료 또는 정공주입재료로서 사용되는 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic light emitting compound and an organic electroluminescent device comprising the same, and more particularly to a novel organic light emitting compound used as a hole transport material or a hole injection material and an organic electroluminescent device employing the same. It is about.

현재 가장 널리 사용되고 있는 액정표시장치(LCD)는 비발광형 표시소자로 소비전력이 적고 가볍긴 하지만, 소자 구동 시스템이 복잡하고 응답시간, 콘트라스트 등의 특성이 만족할만한 수준에 이르지 못하고 있다. 따라서, 최근에 차세대 평판 디스플레이(Flat panel display)로 주목받고 있는 유기전기발광소자에 대한 연구가 활발히 진행되고 있다.Liquid crystal display (LCD), which is the most widely used at present, is a non-light emitting display device, which consumes little power and is light. However, the device driving system is complicated and characteristics such as response time and contrast are not satisfactory. Therefore, research on organic electroluminescent devices, which are recently attracting attention as a next-generation flat panel display, is being actively conducted.

표시 소자 중, 전기 발광 소자(electroluminescence device: EL device)는 자체 발광형 표시 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐만 아니라 응답속도가 빠르다는 장점을 가지고 있으며, 1987년 이스트만 코닥(Eastman Kodak)사에서는 발광층 형성용 재료로서 저분자인 방향족 디아민과 알루미늄 착물을 이용하고 있는 유기 EL 소자를 처음으로 개발하였다[Appl. Phys. Lett. 51, 913, 1987].Among the display elements, an electroluminescence device (EL device) is a self-luminous display element that has a wide viewing angle, excellent contrast, and high response speed.Eastman Kodak Co., Ltd. in 1987 An organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer formation material was first developed [Appl. Phys. Lett. 51, 913, 1987].

유기 EL 소자의 발광 매커니즘은 전자 주입 전극(음극) 과 정공 주입 전극(양극) 사이에 형성된 유기막에 전하를 주입하면 전자와 정공이 쌍을 이룬 후 소멸하면서 빛을 방출한다. 플라스틱 같은 휠 수 있는(flexible) 투명 기판 위에도 소자를 형성할 수 있을 뿐 아니라, 플라즈마 디스플레이 패널(Plasma Display Panel)이나 무기 EL 디스플레이에 비해 낮은 전압에서 (10V이하) 구동이 가능하고, 전력 소모가 비교적 적으며, 색감이 뛰어나다는 장점이 있다. In the light emitting mechanism of the organic EL device, when charge is injected into the organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode), electrons and holes are paired and then disappear to emit light. The device can be formed on a flexible transparent substrate such as plastic, and can be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic EL display, and has a relatively low power consumption. It has a small and excellent color.

유기 EL 소자에서 유기재료는 크게 발광재료와 전하수송재료로 나눌수 있다. 발광재료는 발광색 및 발광효율에 직접적으로 관계가 있는데, 요구되는 몇 가지 특성으로는 고체상태에서 형광 양자 수율이 커야하고, 전자와 정공의 이동도가 높아야 하며, 진공 증착시 쉽게 분해되지 않아야 하고, 균일한 박막을 형성, 안정해야한다. Organic materials in organic EL devices can be roughly divided into light emitting materials and charge transport materials. The luminescent material is directly related to the emission color and the luminous efficiency. Some of the required properties are that the fluorescence quantum yield should be high in the solid state, the mobility of electrons and holes should be high, and not easily decomposed during vacuum deposition. It should be stable, forming a uniform thin film.

한편, 정공 주입 및 수송 재료로는 구리 프탈로시아닌(CuPc), NPB, TPD, MTDATA(4, 4', 4"-tris(3-methylphenylphenylamino)triphenylamine) 등이 있다. 이러한 물질을 정공 주입 및 수송층에 포함시킨 소자는 효율 및 수명이 저하되는 문제가 있었다. 그 이유는 유기 EL 소자를 높은 전류에서 구동하게 되면, 양극과 정공 주입층 사이에서 열 스트레스(Thermal stress)가 발생하고, 이러한 열 스트레스에 의해 소자의 수명이 급격히 저하되기 때문이다. 또한, 정공 주입층에 사용되는 유기물질은 정공의 운동성이 매우 크기 때문에, 정공과 전자의 전하 밸런스(hole-electron charge balance)가 깨지고 이로 인해 양자 효율(cd/A)이 낮아지게 된다. Hole injection and transport materials include copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4, 4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine), etc. These materials are included in the hole injection and transport layer. The device has a problem in that the efficiency and lifespan are lowered, because when the organic EL device is driven at a high current, thermal stress is generated between the anode and the hole injection layer. In addition, since the organic material used in the hole injection layer has a very high hole mobility, the hole-electron charge balance between the holes and the electrons is broken, and thus the quantum efficiency (cd / A) becomes low.

유기 EL소자의 내구성을 높이기 위해서는 박막 안정성이 양호한 화합물과 비결정성이 높은 화합물일수록 박막 안정성이 높다고 보고되어 있다. 이때 비결정성의 지표로서 유리전이점(Tg)이 사용된다. 기존의 MTDATA의 유리전이온도는 76℃로서 비결정성이 높다고는 할 수 없다. 이러한 재료들은 유기 EL 소자의 내구성면에서, 또한 정공주입, 수송의 특성에 기인하는 발광효율에서도 만족스러운 특성을 얻지 못하였다.In order to increase the durability of the organic EL device, it is reported that the compound having good thin film stability and the compound having high amorphousness have higher thin film stability. At this time, the glass transition point (Tg) is used as an index of amorphousness. MTDATA's glass transition temperature is 76 ℃, which means that its amorphousness is not high. These materials did not obtain satisfactory characteristics in terms of durability of the organic EL element and also in luminous efficiency due to the characteristics of hole injection and transport.

따라서 본 발명의 목적은 상기한 문제점들을 해결하기 위하여 기존의 정공주입 또는 정공전달 재료보다 발광 효율 및 소자 수명이 좋은 우수한 골격의 유기 발광 화합물을 제공하는 것이며, 신규한 유기 발광 화합물을 정공주입층 또는 정공전달층에 채용하는 유기 전계 발광 소자를 제공하는 것이다. Accordingly, an object of the present invention is to provide an organic light emitting compound having an excellent luminescence efficiency and device life better than the existing hole injection or hole transport material in order to solve the above problems, and to provide a novel organic light emitting compound in the hole injection layer or An organic electroluminescent element employed in a hole transport layer is provided.

본 발명은 하기 화학식 1로 표시되는 유기 발광 화합물, 이를 포함하고 있는 유기 전계 발광 소자에 관한 것으로, 본 발명에 따른 유기 발광 화합물은 유기 전계 발광 소자의 정공주입층 또는 정공전달층에 포함되어 소자의 구동전압을 낮추면서 발광효율을 개선시킬 수 있다.The present invention relates to an organic light emitting compound represented by Chemical Formula 1, and an organic electroluminescent device comprising the same, wherein the organic light emitting compound according to the present invention is included in the hole injection layer or the hole transport layer of the organic electroluminescent device The luminous efficiency can be improved while lowering the driving voltage.

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

[상기 화학식 1에서,[In Formula 1,

Y1는 -O-, -S-, -C(R11R12)- 또는 -Si(R13R14)-이며;Y 1 is —O—, —S—, —C (R 11 R 12 ) — or —Si (R 13 R 14 ) —;

Y2는 -O-, -S-, -C(R11R12)-, -Si(R13R14)- 또는 -N(R15)이고;Y 2 is —O—, —S—, —C (R 11 R 12 ) —, —Si (R 13 R 14 ) — or —N (R 15 );

A고리 및 C고리는 각각 독립적으로

Figure pat00002
이며;Ring A and Ring C are each independently
Figure pat00002
Is;

B고리는

Figure pat00003
이고;B ring
Figure pat00003
ego;

Y3 및 Y4는 각각 독립적으로 CH 또는 N이고;Y 3 and Y 4 are each independently CH or N;

Y5 및 Y6는 각각 독립적으로 화학결합, -O-, -S-, -C(R11R12)-, -Si(R13R14)- 또는 -N(R15)-이고, 단 Y5 및 Y6가 동시에 화학결합인 경우는 제외하며;Y 5 and Y 6 are each independently a chemical bond, —O—, —S—, —C (R 11 R 12 ) —, —Si (R 13 R 14 ) — or —N (R 15 ) — Unless Y 5 and Y 6 are chemical bonds at the same time;

R1 내지 R4는 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C1-C30)알킬실릴기, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아르(C1-C30)알킬, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 5원 내지 7원의 헤테로시클로알킬이거나 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 (C3-C30)시클로알킬, -N(R16R17), -Si(R18R19R20), -SR21, -OR22 , 시아노, 나이트로 또는 하이드록시이고, R1 내지 R4가 복수인 경우 서로 결합하여 환상 구조를 형성할 수도 있으며;R 1 to R 4 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkylsilyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted ( C6-C30) Ar (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, fused with one or more cycloalkyl, 5- to 7-membered hetero, fused with one or more substituted or unsubstituted aromatic rings (C3-C30) cycloalkyl which is cycloalkyl or has one or more substituted or unsubstituted aromatic rings, -N (R 16 R 17 ), -Si (R 18 R 19 R 20 ), -SR 21 , -OR 22 , Cyano, nitro or hydroxy, and when there are a plurality of R 1 to R 4 , may combine with each other to form a cyclic structure;

L1 및 L2는 각각 독립적으로 화학결합, 치환 또는 비치환된 (C6-C30)아릴렌, 치환 또는 비치환된 (C3-C30)헤테로아릴렌이거나 치환 또는 비치환된 (C3-C30)시클로알킬렌이고, 인접한 L1 및 L2는 서로 결합하여 환상 구조를 형성할 수 있으며, 단 L1 및 L2가 동시에 화학결합인 경우는 제외하며;L 1 and L 2 are each independently a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene or a substituted or unsubstituted (C3-C30) cyclo Alkylene, adjacent L 1 and L 2 may be bonded to each other to form a cyclic structure, except that L 1 and L 2 are at the same time a chemical bond;

Ar은 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴이고;Ar is substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted (C6-C30) aryl in which at least one cycloalkyl is fused;

R11 내지 R22는 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알킬이거나 인접한 치환체와 융합고리를 포함하거나 포함하지 않는 치환 또는 비치환된 (C3-C30)알킬렌 또는 치환 또는 비치환된 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있으며, 상기 형성된 지환족 고리 및 단일환 또는 다환의 방향족 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있고;R 11 to R 22 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;

l, m, n 및 p는 각각 독립적으로 0 내지 4의 정수이고, l, m, n 또는 p가 2 이상의 정수인 경우 각각의 R1, R2, R3 및 R4은 서로 동일하거나 상이할 수 있고, 인접한 치환기들이 서로 결합하여 고리를 형성할 수 있으며;l, m, n and p are each independently integers of 0 to 4, and when l, m, n or p is an integer of 2 or more, each of R 1 , R 2 , R 3 and R 4 may be the same or different from each other. Adjacent substituents may combine with each other to form a ring;

상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.]
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

본 발명에 기재된 ‘알킬’ 및 그 외 ‘알킬’ 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하고, ‘시클로알킬’은 단일 고리계 뿐만 아니라 치환 또는 비치환된 아다만틸 또는 치환 또는 비치환된 (C7-C30)바이시클로알킬과 같은 여러 고리계 탄화수소도 포함한다. 본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐(indenyl), 플루오레닐, 페난트릴, 트라이페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 플루오란텐일 등을 포함하지만, 이에 한정되지 않는다. 상기 나프틸은 1-나프틸 및 2-나프틸을 포함하며, 안트릴은 1-안트릴, 2-안트릴 및 9-안트릴을 포함하며, 플루오레닐은 1-플루오레닐, 2-플루오레닐, 3-플루오레닐, 4-플루오레닐 및 9-플루오레닐을 모두 포함한다. 본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P, P(=O), Si 및 Se로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 상기 헤테로아릴기는 고리내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다. 구체적인 예로 퓨릴, 티에닐, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아지닐, 테트라지닐, 트리아졸릴, 테트라졸릴, 퓨라자닐, 피리딜, 피라지닐, 피리미디닐, 피리다지닐 등의 단환 헤테로아릴, 벤조퓨릴, 벤조티에닐, 이소벤조퓨릴, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴놀리진일, 퀴녹살리닐, 카바졸릴, 페난트리디닐, 벤조디옥솔릴, 나프틸리딘닐, 다이벤조퓨릴, 다이벤조싸이오페닐 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 포함하지만, 이에 한정되지 않는다.Substituents comprising the 'alkyl' and other 'alkyl' moieties described herein include both straight and pulverized forms, and 'cycloalkyl' is substituted or unsubstituted adamantyl or substituted or unsubstituted as well as a single ring system It also includes several ring-based hydrocarbons such as cyclic (C7-C30) bicycloalkyl. "Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. It is not limited to this. Said naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. "Heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P, P (= O), Si and Se as aromatic ring skeleton atoms, and the remaining aromatic ring skeletons. Means an aryl group whose atoms are carbon, 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl Monocyclic heteroaryl such as furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoy Soxazolyl, Benzoxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinolizinyl, Quinoxalinyl, Carbazolyl, Phenantri Polycyclic heteroaryls such as diyl, benzodioxyl, naphthyridinyl, dibenzofuryl, dibenzothiophenyl and their corresponding N-oxides (e.g. pyridyl N-oxides, quinolyl N-oxides) , Quaternary salts thereof, and the like, No.

또한, 본 발명에 기재되어 있는 '(C1-C30)알킬 또는 (C6-C30)아르(C1-C30)알킬'기의 알킬은 (C1-C20)알킬 또는 (C1-C10)알킬을 포함하고, '(C6-C30)아릴 및 (C6-C30)아르(C1-C30)알킬'기의 아릴은 (C6-C20)아릴 또는 (C6-C12)아릴을 포함한다. '(C3-C30)헤테로아릴'기는 (C3-C20)헤테로아릴 또는 (C3-C12)헤테로아릴을 포함하고, '(C3-C30)시클로알킬'기는 (C3-C20)시클로알킬 또는 (C3-C7)시클로알킬을 포함한다. '(C3-C30)알킬렌 또는 알케닐렌'기는 (C3-C20)알킬렌 또는 알케닐렌, (C3-C10)알킬렌 또는 알케닐렌을 포함한다.In addition, the alkyl of the '(C1-C30) alkyl or (C6-C30) ar (C1-C30) alkyl' group described in the present invention includes (C1-C20) alkyl or (C1-C10) alkyl, Aryl of the '(C6-C30) aryl and (C6-C30) ar (C1-C30) alkyl' groups includes (C6-C20) aryl or (C6-C12) aryl. '(C3-C30) heteroaryl' group includes (C3-C20) heteroaryl or (C3-C12) heteroaryl, and the '(C3-C30) cycloalkyl' group is (C3-C20) cycloalkyl or (C3- C7) cycloalkyl. '(C3-C30) alkylene or alkenylene' groups include (C3-C20) alkylene or alkenylene, (C3-C10) alkylene or alkenylene.

또한 본 발명에 기재되어 있는 “치환 또는 비치환”이라는 기재에서 ‘치환’은 비치환된 치환기에 더 치환되는 경우를 뜻하며, 상기 R1 내지 R4, R11 내지 R22, L1, L2 및 Ar에 더 치환되는 치환기는 서로 독립적으로 중수소, 할로겐, 할로겐이 치환 또는 비치환된 (C1-C30)알킬, (C6-C30)아릴, (C6-C30)아릴이 치환 또는 비치환된 (C3-C30)헤테로아릴, 5원 내지 7원의 헤테로시클로알킬, 방향족고리가 하나이상 융합된 5원 내지 7원의 헤테로시클로알킬, (C3-C30)시클로알킬, 방향족고리가 하나이상 융합된 (C6-C30)시클로알킬, R31R32R33Si-, (C2-C30)알케닐, (C2-C30)알키닐, 시아노, 카바졸릴, -NR34R35, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, R36S-, R37O-, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상이고, R31 내지 R37은 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴, (C3-C30)헤테로아릴, 또는 (C3-C30)시클로알킬인 것을 의미한다.
In addition, in the description of "substituted or unsubstituted" described in the present invention, "substituted" means a case where is further substituted with an unsubstituted substituent, the R 1 To R 4 , R 11 to R 22 , L 1 , L 2, and Ar are further substituted with each other independently of deuterium, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl (C3-C30) heteroaryl substituted or unsubstituted (C6-C30) aryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3 -C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, R 31 R 32 R 33 Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carba Zolyl, -NR 34 R 35 , (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R 36 S-, R 37 O-, nitro or hydroxy At least one selected from the group consisting of R 31 to R 37 independently of one another is (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, or (C 3 -C 30) cycloalkyl it means.

또한 상기 화학식 1의

Figure pat00004
은 하기 구조에서 선택되나, 이에 한정되지는 않는다.Also of Formula 1
Figure pat00004
Is selected from the following structures, but is not limited thereto.

Figure pat00005
Figure pat00005

Figure pat00006
Figure pat00006

Figure pat00007
Figure pat00007

Figure pat00008
Figure pat00008

Figure pat00009
Figure pat00009

Figure pat00010
Figure pat00010

Figure pat00011
Figure pat00011

Figure pat00012
Figure pat00012

Figure pat00013
Figure pat00013

Figure pat00014
Figure pat00014

Figure pat00015
Figure pat00015

Figure pat00016
Figure pat00016

[R3, R4, R11 내지 R15, l 및 p은 상기 화학식 1에서의 정의와 동일하다.]
[R 3 , R 4 , R 11 to R 15 , l and p are the same as defined in Formula 1 above.]

본 발명에 따른 유기 발광 화합물은 보다 구체적으로 하기의 화합물로서 예시될 수 있으나, 하기 화합물이 본 발명을 한정하는 것은 아니다.The organic light emitting compound according to the present invention may be more specifically exemplified as the following compound, but the following compound does not limit the present invention.

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

본 발명에 따른 유기 발광 화합물은 예를 들어 하기 반응식 1에 나타난 바와 같이 제조될 수 있으나, 하기 반응식으로만 한정되는 것은 아니다.The organic light emitting compound according to the present invention may be prepared, for example, as shown in Scheme 1 below, but is not limited thereto.

[반응식 1]Scheme 1

Figure pat00031
Figure pat00031

[상기 반응식 1에서 A, B, C, R1 내지 R3, Y1, Y2, L1, L2, Ar, l, m, n 및 p는 상기 화학식 1에서의 정의와 동일하다.][Scheme 1, A, B, C, R 1 to R 3 , Y 1 , Y 2 , L 1 , L 2 , Ar, l, m, n and p are the same as defined in Formula 1 above.]

또한 본 발명은 유기 전계 발광 소자를 제공하며, 본 발명에 따른 유기 발광 화합물은 정공주입재료 또는 정공수송재료로 사용되는 것을 특징으로 한다.In another aspect, the present invention provides an organic electroluminescent device, characterized in that the organic light emitting compound according to the invention is used as a hole injection material or a hole transport material.

본 발명에 따른 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극 및 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어진 유기 전계 발광 소자에 있어서, 상기 유기물층은 상기 화학식 1의 유기 발광 화합물을 하나 이상 포함하는 것을 특징으로 한다.The organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one organic light emitting compound of Formula 1.

본 발명의 유기 전계 발광 소자에 있어서, 화학식 1의 유기 발광 화합물을 포함하고, 동시에 아릴아민계 화합물 또는 스티릴아릴아민계 화합물로 이루어진 군으로부터 선택된 하나 이상의 화합물을 포함할 수 있으며, 아릴아민계 화합물 또는 스티릴아릴아민계 화합물의 구체적인 예는 특허출원 제10-2008-0060393호의 식별번호<212> 내지 <224>에 예시되어 있으며, 이에 한정되는 것은 아니다.In the organic electroluminescent device of the present invention, it may include one or more compounds selected from the group consisting of an organic light emitting compound of formula (1), and at the same time an arylamine compound or a styrylarylamine compound, an arylamine compound Or specific examples of the styrylarylamine-based compound are exemplified in the identification number <212> to <224> of Patent Application No. 10-2008-0060393, but is not limited thereto.

또한, 본 발명의 유기 전계 발광 소자에 있어서, 유기물층에 상기 화학식 1의 유기 발광 화합물 이외에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체화합물을 더 포함할 수도 있고, 상기 유기물층은 발광층 및 전하생성층을 포함할 수 있다.In addition, in the organic electroluminescent device of the present invention, in the organic material layer, in addition to the organic light emitting compound of Chemical Formula 1, a group consisting of Group 1, Group 2, 4 cycle, 5 cycle transition metal, lanthanide series metal and organic metal of d-transition element It may further comprise one or more metals or complex compounds selected from, the organic material layer may include a light emitting layer and a charge generating layer.

본 발명의 화학식 1의 유기 발광 화합물을 포함하는 유기 전계 발광 소자를 서브픽셀로 하고, Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au 및 Ag로 이루어진 군에서 선택되는 하나 이상의 금속화합물을 포함하는 서브픽셀 하나 이상을 동시에 병렬로 패터닝한 독립발광방식의 픽셀구조를 가진 유기 전계 발광 소자를 구현할 수도 있다.An organic electroluminescent device comprising an organic light emitting compound of Formula 1 of the present invention is a subpixel, and includes Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and An organic electroluminescent device having an independent light emitting pixel structure in which at least one subpixel including at least one metal compound selected from the group consisting of Ag is simultaneously patterned in parallel may be implemented.

또한, 상기 유기물층에 상기 유기 전계 발광 화합물 이외에 적색, 녹색 또는 청색 발광 화합물을 포함하는 유기발광층 하나 이상을 동시에 포함하여 백색 발광을 하는 유기 발광 소자를 형성할 수 있다. 상기 청색, 녹색 또는 적색 발광을 하는 화합물은 출원번호 제10-2008-0123276호, 제10-2008-0107606호 또는 제10-2008-0118428호에 예시되어 있으나, 이에 한정되지는 않는다. In addition, an organic light emitting device that emits white light may be formed by simultaneously including one or more organic light emitting layers including red, green, or blue light emitting compounds in addition to the organic electroluminescent compound. The compound emitting blue, green, or red light is exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but is not limited thereto.

본 발명의 유기 전계 발광 소자에 있어서, 한 쌍의 전극의 적어도 한쪽의 내측표면에, 칼코제나이드(chalcogenide)층, 할로겐화 금속층 및 금속 산화물층으로부터 선택되는 일층(이하, 이들을 "표면층"이라고 지칭함) 이상을 배치하는 것이 바람직하다. 구체적으로는, 발광 매체층 측의 양극 표면에 규소 및 알루미늄의 금속의 칼코제나이드(산화물을 포함한다)층을, 또한 발광매체층 측의 음극 표면에 할로겐화 금속층 또는 금속 산화물층을 배치하는 것이 바람직하다. 이것에 의해, 구동의 안정화를 얻을 수 있다. 상기 칼코제나이드로서는 예컨대 SiOx(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON 등을 바람직하게 들 수 있으며, 할로겐화 금속으로서는 예컨대 LiF, MgF2, CaF2, 불화 희토류 금속 등을 바람직하게 들 수 있으며, 금속 산화물로서는 예컨대 Cs2O, Li2O, MgO, SrO, BaO, CaO 등을 바람직하게 들 수 있다.In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer &quot;) is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Examples of the chalcogenide include SiO x (1 ≦ X ≦ 2 ), AlO X (1 ≦ X ≦ 1.5), SiON, SiAlON, and the like, and examples of the metal halide include LiF, MgF 2 , CaF 2 , and fluoride. Rare earth metals and the like are preferable. Examples of the metal oxides include Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO and the like.

또한, 본 발명의 유기 전계 발광 소자에 있어서, 이렇게 제작된 한 쌍의 전극의 적어도 한쪽의 표면에 전자 전달 화합물과 환원성 도판트의 혼합 영역 또는 정공 전달 화합물과 산화성 도판트의 혼합 영역을 배치하는 것도 바람직하다. 이러한 방식으로, 전자 전달 화합물이 음이온으로 환원되므로 혼합 영역으로부터 발광 매체에 전자를 주입 및 전달하기 용이해진다. 또한, 정공 전달 화합물은 산화되어 양이온으로 되므로 혼합 영역으로부터 발광 매체에 정공을 주입 및 전달하기 용이해진다. 바람직한 산화성 도판트로서는 각종 루이스산 및 억셉터(acceptor) 화합물을 들 수 있다. 바람직한 환원성 도판트로서는 알칼리 금속, 알칼리 금속 화합물, 알칼리 토류 금속, 희토류 금속 및 이들의 혼합물을 들 수 있다. 또한 환원성 도판트층을 전하생성층으로 사용하여 두 개 이상의 발광층을 가진 백색 유기 전계 발광 소자를 제작할 수 있다.Further, in the organic electroluminescent device of the present invention, disposing a mixed region of an electron transfer compound and a reducing dopant or a mixed region of a hole transfer compound and an oxidative dopant on at least one surface of the pair of electrodes thus produced desirable. In this way, the electron transfer compound is reduced to an anion, thereby facilitating injection and transfer of electrons from the mixed region into the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. In addition, a white organic electroluminescent device having two or more light emitting layers may be manufactured using a reducing dopant layer as a charge generation layer.

본 발명에 따른 유기 발광화합물을 정공수송재료 또는 정공주입재료로서 이용한 유기 전계 발광 소자는 발광효율이 좋고 재료의 수명특성이 뛰어나 소자의 구동수명이 매우 우수한 OLED 소자를 제조할 수 있는 장점이 있다.The organic electroluminescent device using the organic light emitting compound according to the present invention as a hole transporting material or a hole injection material has an advantage of producing an OLED device having excellent luminous efficiency and excellent material life characteristics and excellent driving life of the device.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 들어 본 발명에 따른 유기 발광 화합물, 이의 제조방법 및 소자의 발광특성을 설명하나, 이는 단지 그 실시 양태를 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the organic light emitting compound according to the present invention, a method for preparing the same and a light emitting property of the device are described for the detailed understanding of the present invention, but the present invention is only intended to illustrate the embodiments of the present invention. It does not limit the scope of the invention.

[제조예 1]화합물 2의 제조Preparation Example 1 Preparation of Compound 2

Figure pat00032
Figure pat00032

Figure pat00033
Figure pat00033

화합물 compound 1-11-1 의 제조Manufacture

1L의 2구-RBF에 사이클로헥산-1,2-다이원 25g(0.22mol)을 넣고 페닐하이드라진 70.9g(0.49mol), H2SO4 1.18mL(0.02mol), MeOH 720mL(0.3M)를 첨가한 후 100℃로 가열시켜 4시간동안 교반한다. 반응이 완결되면 실온으로 냉각하고, 생성된 고체를 필터하여 메탄올로 씻어준다. 씻어준 고체를 1L의 2구-RBF 넣고, TFA 60g, AcOH 600mL를 넣고 100℃로 가열시켜 12시간동안 교반한다. 반응이 종결되면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후, 컬럼크로마토그래피로 정제하여 화합물 1-1 17g (29%)를 얻었다.25 g (0.22 mol) of cyclohexane-1,2-dione was added to 1 L of 2-neck-RBF, and 70.9 g (0.49 mol) of phenylhydrazine, 1.18 mL (0.02 mol) of H 2 SO 4, and 720 mL (0.3 M) of MeOH were added. After addition, it is heated to 100 ° C. and stirred for 4 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and the resulting solid is filtered and washed with methanol. The washed solid was put into 1L two-ball-RBF, TFA 60g, AcOH 600mL was added and heated to 100 ℃ and stirred for 12 hours. After completion of the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator, and purified by column chromatography to obtain compound 1-1 17g (29%).

화합물 compound 1-21-2 의 제조Manufacture

1L의 2구-RBF에 화합물 1-1 15g(0.058mol)을 넣고 아이오도벤젠 47g(0.23mol), CuI 33g(0.17mol), Cs2CO3 76g(0.23mol), 퀴놀린 650mL를 첨가한 후 190℃로 가열시켜 12시간동안 교반한다. 반응이 끝나면 증류장치를 이용하여 용매를 제거한 후, 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후, 컬럼크로마토그래피로 정제하여 화합물 1-2 15g (65%)를 얻었다.15 g (0.058 mol) of compound 1-1 was added to 1 L of two-ball-RBF, 47 g (0.23 mol) of iodobenzene, 33 g (0.17 mol) of CuI, 76 g (0.23 mol) of Cs 2 CO 3 , and 650 mL of quinoline were added. Heat to 190 ° C. and stir for 12 hours. After the reaction, the solvent was removed using a distillation apparatus, washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4, and then removed with a rotary evaporator, and then purified by column chromatography to obtain a compound 1-2 15g (65 %) Was obtained.

화합물 compound 1-31-3 의 제조Manufacture

1L의 2구-RBF에 화합물 1-2 6.6g(0.016mol)을 넣고 NBS 3.3g(0.018mol), THF 300mL 를 첨가한 후 실온에서 12시간 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 헥산으로 씻어서 화합물 1-3 7.2g (92%)를 얻었다.6.6 g (0.016 mol) of Compound 1-2 was added to 1 L of two-ball-RBF, NBS 3.3 g (0.018 mol) and THF 300 mL were added, followed by stirring at room temperature for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4 , solvent was removed by rotary evaporation, and washed with hexane to obtain compound 1-3 7.2g (92%).

화합물 compound 1-41-4 의 제조Manufacture

1000mL 2구-RBF에 화합물 1-3 10g(0.020mol)을 넣고 나프탈렌-1-아민 2.4g(0.026mol), Pd2(dba)3 375mg(0.4mmol), P(cy)3 229mg(0.8mmol), Naot-Bu 5.9g(0.06mol)넣고 진공 건조 시킨 뒤 아르곤 가스를 채운다. 톨루엔 300mL를 첨가한 후 120℃로 가열시켜 12시간 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로 정제하여 화합물 1-4 7.8g(76%) 를 얻었다. Add 10 g (0.020 mol) of compound 1-3 to 1000 mL 2-neck-RBF, add 2.4 g (0.026 mol) of naphthalene-1-amine, 375 mg (0.4 mmol) of Pd 2 (dba) 3 , 229 mg (0.8 mmol) of P (cy) 3 ), Naot-Bu 5.9g (0.06mol) and dried under vacuum and filled with argon gas. After adding 300 mL of toluene, it heated at 120 degreeC and stirred for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4 , solvent was removed by rotary evaporation, and purified by column chromatography to obtain compound 1-4 7.8g (76%).

화합물 compound 1-51-5 의 제조Manufacture

1L 2구-RBF에 화합물 1-4 7.8g (0.015mol)을 넣고 1-브로모-4-아이오도벤젠 6.6g(0.023mol), Pd(oAc)2 175mg(0.7mmol), P(t-Bu)3 508mg(1.56mmol), Naot-Bu 4.5g(0.046mol)넣고 진공 건조시킨 뒤 질소가스를 채운다. 톨루엔 200mL를 첨가한 후 120℃로 가열시켜 12시간동안 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼 정제하여 화합물 1-5 6.8g (66%)를 얻었다.7.8 g (0.015 mol) of Compound 1-4 in 1 L 2-neck-RBF, 6.6 g (0.023 mol) of 1-bromo-4-iodobenzene, 175 mg (0.7 mmol) of Pd (oAc) 2 , P (t- Bu) 3 508mg (1.56mmol), Naot-Bu 4.5g (0.046mol) and vacuum dried and filled with nitrogen gas. 200 mL of toluene is added and then heated to 120 ° C. and stirred for 12 hours. After the reaction was washed with distilled water and extracted with EA, the organic layer was dried with MgSO 4 and the solvent was removed by rotary evaporator to obtain a compound 1-5 6.8g (66%).

화합물 compound 1-61-6 의 제조Manufacture

500 mL RBF에 화합물 1-5 6.8g(0.010mol)을 넣고 진공 건조시킨 뒤 질소가스를 채운다. THF 100mL를 첨가한 후 -78℃로 냉각시킨다. n-BuLi(2.5M) 6.2mL(0.015mol)을 천천히 첨가한 뒤 1시간 동안 저온을 유지하며 교반한다. -78℃에서 B(OMe)3 1.7mL (0.015mmol)을 첨가한 뒤 12시간 교반한다. 반응이 종결되면 1M HCl을 첨가하고 10분 뒤 증류수로 씻어주어 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼 정제하여 화합물 1-6 5.2g (81%)를 얻었다. 6.8g (0.010mol) of Compound 1-5 was added to 500 mL RBF, and the mixture was dried in vacuo and filled with nitrogen gas. 100 mL of THF is added and then cooled to -78 ° C. 6.2 mL (0.015 mol) of n-BuLi (2.5M) was added slowly, followed by stirring while maintaining a low temperature for 1 hour. 1.7 mL (0.015 mmol) of B (OMe) 3 was added at -78 ° C, followed by stirring for 12 hours. After the reaction was completed, 1M HCl was added, washed with distilled water after 10 minutes, extracted with EA, and the organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator to purify the column to obtain Compound 1-6 5.2g (81%). .

화합물compound 2 2 의 제조Manufacture

100mL 2구-RBF에 화합물 1-6 1.8g(7.0mmol)을 넣고 4-브로모다이벤조[b,d]싸이오펜 5.2g(8.0mmol), Pd(PPh3)4 395mg(0.3mmol), K2CO3(2M) 10mL, EtOH 10mL,넣고, 톨루엔 20mL를 첨가한 후 120℃로 가열시켜 4시간 동안 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로 정제하여 화합물 2 4.5g (88%)를 얻었다.1.8 g (7.0 mmol) of Compound 1-6 were added to 100 mL 2-neck-RBF, and 5.2 g (8.0 mmol) of 4- bromodibenzo [b, d] thiophene, Pd (PPh 3 ) 4 395 mg (0.3 mmol), K 10 mL of 2 CO 3 (2M), 10 mL of EtOH, and 20 mL of toluene were added, followed by heating to 120 ° C. and stirring for 4 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4 , solvent was removed on a rotary evaporator, and purified by column chromatography to obtain Compound 2 4.5g (88%).

1H NMR(CDCl3, 200 MHz)δ = 0.23(1H, m), 5.93(1H, m), 6.69(2H, m), 6.98(1H, m), 7.25(1H, m), 7.33~7.38(2H, m), 7.45~7.53(20H, m), 7.69(1H, m), 7.94~8.12(5H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.55(1H, m) ; MS/FAB found 822, calculated 821.021 H NMR (CDCl 3, 200 MHz) δ = 0.23 (1H, m), 5.93 (1H, m), 6.69 (2H, m), 6.98 (1H, m), 7.25 (1H, m), 7.33-7.38 (2H , m), 7.45-7.53 (20H, m), 7.69 (1H, m), 7.94-8.12 (5H, m), 8.2 (1H, m), 8.41-8.45 (2H, m), 8.55 (1H, m) ); MS / FAB found 822, calculated 821.02

[제조예 2]화합물 4의 제조Preparation Example 2 Preparation of Compound 4

Figure pat00034
Figure pat00034

Figure pat00035
Figure pat00035

화합물 compound 2-12-1 의 제조Manufacture

4-바이페닐보로닉산 10g(43.84mmol), 브로모니트로벤젠 8.85g(43.84mmol), 2M Na2CO3 수용액 70mL, 톨루엔 200mL, 에탄올 70mL를 섞고 환류 교반하였다. 5시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 유기층을 MgSO4으로 건조하고 감압 증류한 후, 컬럼크로마토그래피로 분리하여 화합물 2-1 10g(32.74 mmol, 74.68%)을 얻었다.10 g (43.84 mmol) of 4-biphenylboronic acid, 8.85 g (43.84 mmol) of bromonitrobenzene, 70 mL of 2M Na 2 CO 3 aqueous solution, 200 mL of toluene and 70 mL of ethanol were mixed and stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. The organic layer was dried over MgSO 4 , distilled under reduced pressure, and separated by column chromatography to obtain 10 g (32.74 mmol, 74.68%) of Compound 2-1 .

화합물 compound 2-22-2 의 제조Manufacture

화합물 2-1 10g(32.74mmol)을 트리에틸포스파이트 100mL에 섞고 150℃로 7시간동안 교반하였다. 상온으로 냉각하고 감압 증류하였다. EA로 재결정 하여 화합물 2-2 7g(25.60mmol, 78.19%) 을 얻었다. 10 g (32.74 mmol) of Compound 2-1 were mixed with 100 mL of triethyl phosphite and stirred at 150 ° C. for 7 hours. Cooled to room temperature and distilled under reduced pressure. Recrystallization from EA yielded Compound 2-2 7g (25.60 mmol, 78.19%).

화합물 compound 2-32-3 의 제조Manufacture

화합물 2-2 7g(25.60mmol), 아이오도벤젠 10.44g(51.21mmol), CuI 2.5g(12.80mmol), K3PO4 16.30g(76.82mmol), 톨루엔 200mL 을 넣고 50℃ 가열 후 에틸렌다이아민 1.72mL(25.60mmol)을 넣고, 12시간 동안 환류 교반하였다. 상온으로 냉각하고 EA로 추출하고 NaHCO3수용액으로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 2-3 8g(22.89mmol, 89.41%) 을 얻었다. Compound 2-2 7g (25.60mmol), iodobenzene 10.44g (51.21mmol), CuI 2.5g (12.80mmol), K 3 PO 4 16.30g (76.82mmol), toluene 200mL was added and heated to 50 ℃ and ethylenediamine 1.72 mL (25.60 mmol) was added and stirred under reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO 3 aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Separated by column chromatography to give compound 2-3 to give a 8g (22.89mmol, 89.41%).

화합물 compound 2-42-4 의 제조Manufacture

화합물 2-3 8g(22.89mmol), NBS 4.07g(22.89mmol), 클로로포름 200mL에 녹이고 상온에서 12시간 교반하였다. 증류수를 넣고 다이클로로메탄으로 추출하였다. 감압 증류하고 EA로 재결정하여 화합물 2-4 8g(18.67mmol, 81.56%)을 얻었다. Compound 2-3 was dissolved in 8 g (22.89 mmol), NBS 4.07 g (22.89 mmol), and 200 mL of chloroform, followed by stirring at room temperature for 12 hours. Distilled water was added and extracted with dichloromethane. Distillation under reduced pressure and recrystallization with EA yielded 8 g (18.67 mmol, 81.56%) of compound 2-4 .

화합물 compound 2-52-5 의 제조Manufacture

화합물 2-4 8g(18.67mmol), 4-아미노바이페닐 4.7g(28.01mmol), Pd(OAc)2 0.209g(0.933mmol), P(t-bu)3 0.92mL(1.867mmol, 50% in xylene), Cs2CO3 15.21g(46.69mmol), 톨루엔 300mL을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 2-5 6g(11.61mmol, 62.18%)을 얻었다.Compound 2-4 8 g (18.67 mmol), 4-aminobiphenyl 4.7 g (28.01 mmol), Pd (OAc) 2 0.209 g (0.933 mmol), P (t-bu) 3 0.92 mL (1.867 mmol, 50% in xylene), 15.21 g (46.69 mmol) of Cs 2 CO 3 , and 300 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 6 g (11.61 mmol, 62.18%) of compound 2-5 .

화합물 compound 2-62-6 의 제조Manufacture

4-다이벤조싸이오펜보로닉산 10g(43.84mmol), 1-브로모-4-아이오도벤젠 24.8g(87.69mmol), PdCl2(PPh3)4 0.61g(0.87mmol), 2M Na2CO3 43mL, 톨루엔 300ml 을 섞고 90℃로 5시간동안 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 컬럼크로마토그래피로 분리하여 화합물 2-6 5.2g(15.53mmol, 35.42%) 을 얻었다. 10 g (43.84 mmol) of 4-dibenzothiophenboronic acid, 24.8 g (87.69 mmol) of 1-bromo-4-iodobenzene, PdCl 2 (PPh 3 ) 4 0.61 g (0.87 mmol), 2M Na 2 CO 3 43 mL and 300 ml of toluene were mixed and stirred at 90 ° C. for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. Drying with magnesium sulfate and separation by column chromatography yielded 5.2 g (15.53 mmol, 35.42%) of compound 2-6 .

화합물 compound 44 의 제조Manufacture

화합물 2-5 6g(11.61mmol), 화합물 2-6 3.9g(11.61mmol), Pd(OAc)2 0.13g(0.58mmol), P(t-bu)3 0.52ml(1.16mmol, 50% in xylene), NaOt-bu 2.79g(29.03mmol), 톨루엔 100mL을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 4 4.2g(5.42mmol, 46.68%)을 얻었다.Compound 2-5 6 g (11.61 mmol), Compound 2-6 3.9 g (11.61 mmol), Pd (OAc) 2 0.13 g (0.58 mmol), P (t-bu) 3 0.52 ml (1.16 mmol, 50% in xylene ), NaOt-bu 2.79 g (29.03 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 4.2 g (5.42 mmol, 46.68%) of compound 4 .

1H NMR(CDCl3, 200 MHz)δ = 5.93(1H, m), 6.69(4H, m), 7.33(1H, m), 7.41~7.51(20H, m), 7.69(1H, m), 7.98(2H, m), 8.05(1H, m), 8.2(1H, m), 8.41~8.45(3H, m) ; MS/FAB found 775, calculated 774.991 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (4H, m), 7.33 (1H, m), 7.41-7.51 (20H, m), 7.69 (1H, m), 7.98 (2H , m), 8.05 (1H, m), 8.2 (1H, m), 8.41-8.45 (3H, m); MS / FAB found 775, calculated 774.99

[제조예 3]화합물 13의 제조Preparation Example 3 Preparation of Compound 13

Figure pat00036
Figure pat00036

Figure pat00037
Figure pat00037

화합물 compound 3-13-1 의 제조Manufacture

1L 2구-RBF에 1-브로모-2-니트로벤젠 15g(0.074mol)을 넣고 9,9-다이메틸-9H-플루오렌-2-일보로닉산 23g(0.096mol), Pd(PPh3)4 4.2g(0.003mol), Na2CO3(2M) 111mL, EtOH 111mL, 톨루엔 200mL를 첨가한 후 120℃로 가열시켜 3시간동안 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼로 정제하여 화합물 3-1 22g (95%)를 얻었다.15 g (0.074 mol) of 1-bromo-2-nitrobenzene was added to 1 L 2-neck-RBF, and 23 g (0.096 mol) of 9,9-dimethyl-9H-fluoren-2-ylboronic acid and Pd (PPh 3 ) 4 4.2 g (0.003 mol), 111 mL of Na 2 CO 3 (2M), 111 mL of EtOH, and 200 mL of toluene were added, followed by heating to 120 ° C. and stirring for 3 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4 , solvent was removed on a rotary evaporator, and purified by column to obtain compound 3-1 22g (95%).

화합물 compound 3-23-2 의 제조Manufacture

1L 2구-RBF에 화합물 3-1 24g(0.076mol)을 넣고, 트리에틸포스파이트 200mL, 1,2-다이클로로벤젠 200mL를 첨가한 후 140℃로 가열시킨다. 12시간 교반한다. 반응이 끝나면 용매를 증류하고, 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로 정제하여 화합물 3-2 7g (33%)를 얻었다.24 g (0.076 mol) of Compound 3-1 was added to 1 L two-ball-RBF, 200 mL of triethylphosphite and 200 mL of 1,2-dichlorobenzene were added, followed by heating to 140 ° C. Stir for 12 hours. After the reaction, the solvent was distilled off, washed with distilled water, extracted with EA, the organic layer was dried over MgSO 4 , the solvent was removed with a rotary evaporator, and purified by column chromatography to obtain a compound 3-2 7g (33%).

화합물 compound 3-33-3 의 제조Manufacture

1L 2구-RBF에 화합물 3-2 8.1g(0.028mol)를 넣고, DMF 300mL 를 넣고 0℃에서 10분간 교반한다. NBS 5.08g(0.028mol)를 DMF 300mL에 넣고 녹인 후 반응물에 천천히 첨가한다. 0℃에서 6시간동안 교반한다. 반응이 종결되면, 증류수로 중화하고, 에틸아세테이트로 추출한다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 에틸아세테이트를 전개 용매로 하여 컬럼크로마토그래피로 정제하여 화합물 3-3 9g(87%)를 얻었다. 8.1 g (0.028 mol) of Compound 3-2 was added to 1 L two-ball-RBF, 300 mL of DMF was added thereto, and the mixture was stirred at 0 ° C. for 10 minutes. 5.08 g (0.028 mol) of NBS was added to 300 mL of DMF, and then slowly added to the reaction. Stir at 0 ° C. for 6 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Then, ethyl acetate was used as a developing solvent and purified by column chromatography to obtain compound 3-3 9g (87%).

화합물 compound 3-43-4 의 제조Manufacture

3L 2구-RBF에 화합물 3-3 9g(0.024mol)를 넣고, 아이오도벤젠 6g(0.029mol), Pd(OAc)2 123mg(0.0005mol), P(t-Bu)3 50% 0.5mL(0.002mmol), NaOt-Bu 4.7g(0.049mol)를 넣고 진공 상태로 만든 후 질소 분위기로 만든다. 톨루엔 200mL을 넣고 120℃에서 12시간 동안 교반한다. 반응이 종결되면, 증류수로 중화하고, 에틸아세테이트로 추출한다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 에틸아세테이트를 전개 용매로 하여 컬럼크로마토그래피로 정제하여 화합물 3-4 8g(74%)를 얻었다.9 g (0.024 mol) of compound 3-3 was added to 3 L 2-gut-RBF, 6 g (0.029 mol) of iodobenzene, 123 mg (0.0005 mol) of Pd (OAc) 2 , P (t-Bu) 3 50% 0.5 mL ( 0.002 mmol) and 4.7 g (0.049 mol) of NaOt-Bu are added to a vacuum and then placed in a nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 12 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and ethyl acetate was used as a developing solvent to purify the mixture by column chromatography, obtaining 8 g (74%) of the compound 3-4 .

화합물 compound 3-53-5 의 제조Manufacture

500mL 2구-RBF에 화합물 2-6 9g(0.026mol)를 넣고 아닐린 2.9g(0.032 mol), Pd(OAc)2 179mg(0.0008mol), P(t-Bu)3 50% 1.7mL(0.002mmol), Cs2CO3 17.3g(0.053mol)를 넣고 진공 상태로 만든 후 질소 분위기로 만든다. 톨루엔 200mL을 넣고 120℃에서 4시간 동안 교반한다. 반응이 종결되면, 증류수로 중화하고, 에틸아세테이트로 추출한다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 에틸아세테이트를 전개 용매로 하여 컬럼크로마토그래피로 정제하여 화합물 3-5 7g(75%)를 얻었다. Add 9 g (0.026 mol) of compound 2-6 to 500 mL 2-neck-RBF, add 2.9 g (0.032 mol) of aniline, 179 mg (0.0008 mol) of Pd (OAc) 2 , P (t-Bu) 3 50% 1.7 mL (0.002 mmol) ), Cs 2 CO 3 17.3g (0.053mol) and put in a vacuum to make a nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 4 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Then, ethyl acetate was used as a developing solvent and purified by column chromatography to obtain compound 3-5 (7 g, 75%).

화합물 compound 1313 의 제조Manufacture

500mL 2구-RBF에 화합물 3-4 5g(0.011mol)를 넣고, 화합물 3-5 4.8g(0.013 mol), Pd(OAc)2 127mg(0.0005mol), P(t-Bu)3 50% 0.76mL(0.001mmol), Naot-Bu 3.2g(0.034mol)를 넣고 진공 상태로 만든 후 질소 분위기로 만든다. 톨루엔 200mL을 넣고 120℃에서 4시간 동안 교반한다. 반응이 종결되면, 증류수로 중화하고, 에틸아세테이트로 추출한다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 에틸아세테이트를 전개 용매로 하여 컬럼크로마토그래피로 정제하여 화합물 13 5g(62%)를 얻었다. 5 g (0.011 mol) of Compound 3-4 was added to 500 mL 2-neck-RBF, 4.8 g (0.013 mol) of Compound 3-5 , 127 mg (0.0005 mol) Pd (OAc) 2 , P (t-Bu) 3 50% 0.76 Put mL (0.001mmol) and 3.2g (0.034mol) of Naot-Bu, make it in vacuum and make it into nitrogen atmosphere. Add 200 mL of toluene and stir at 120 ° C. for 4 hours. Upon completion of the reaction, neutralize with distilled water and extract with ethyl acetate. The organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and purified by column chromatography using ethyl acetate as a developing solvent to obtain compound 13 (5 g, 62%).

1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 6.58(1H, m), 6.69~6.75(3H, m), 7.04(1H, m), 7.28(1H, m), 7.38~7.41(2H, m), 7.5~7.53(11H, m), 7.78~7.79(3H, m), 7.87(1H, m), 7.98(1H, m), 8.07(1H, m), 8.2(1H, m), 8.41~8.49(3H, m) ; MS/FAB found 709, calculated 708.911 H NMR (CDCl 3, 200 MHz) δ = 1.72 (6H, s), 6.58 (1H, m), 6.69-6.75 (3H, m), 7.04 (1H, m), 7.28 (1H, m), 7.38-7.41 (2H, m), 7.5-7.53 (11H, m), 7.78-7.79 (3H, m), 7.87 (1H, m), 7.98 (1H, m), 8.07 (1H, m), 8.2 (1H, m) ), 8.41-8.49 (3H, m); MS / FAB found 709, calculated 708.91

[제조예 4]화합물 17의 제조Preparation Example 4 Preparation of Compound 17

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

화합물 compound 4-14-1 의 제조Manufacture

다이벤조싸이오펜 50g(271.3mmol)을 CHCl3 1000mL에 녹이고 0℃에서 Br2 30mL(596.9mmol)을 천천히 넣었다. 상온에서 12시간 교반 후 소듐싸이오설페이트 수용액을 넣어 주었다. 반응 용액 색깔이 노란색으로 변하면 다이클로로메탄으로 추출하고 이 유기층을 KOH 수용액으로 중성화 했다. 유기층을 황산마그네슘으로 건조하고 감압 증류하였다. EA와 메탄올로 재결정하여 화합물 4-1 74g(216.3mmol, 79.70%)을 얻었다. 50 g (271.3 mmol) of dibenzothiophene was dissolved in 1000 mL of CHCl 3 , and 30 mL (596.9 mmol) of Br 2 was slowly added at 0 ° C. After stirring at room temperature for 12 hours, an aqueous sodium thiosulfate solution was added thereto. When the reaction solution turned yellow, the mixture was extracted with dichloromethane and the organic layer was neutralized with an aqueous KOH solution. The organic layer was dried over magnesium sulfate and distilled under reduced pressure. 74 g (216.3 mmol, 79.70%) of Compound 4-1 was obtained by recrystallization with EA and methanol.

화합물 compound 4-24-2 의 제조Manufacture

화합물 4-1 74g(216.3mmol) 을 THF에 녹이고 -78℃에서 n-buLi 86.5mL(216.3mmol, 2.5M in hexane)을 천천히 넣었다. 한 시간 후 트리메틸보레이트 28.9mL(259.6mmol)을 넣었다. 12시간 상온에서 교반하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 EA와 헥산으로 재결정하여 화합물 4-2 40g(136.8mmol, 62.96%)을 얻었다.74 g (216.3 mmol) of Compound 4-1 were dissolved in THF, and 86.5 mL (216.3 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After one hour 28.9 mL (259.6 mmol) of trimethylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization with EA and hexane gave 40 g (136.8 mmol, 62.96%) of compound 4-2 .

화합물 compound 4-34-3 의 제조Manufacture

화합물 4-2 40g(136.8mmol), 아이오도니트로벤젠 37.4g(150.5mmol), Pd(PPh3)4 6.32g(5.47mmol), 2M Na2CO3 170mL, 톨루엔을 넣고 100℃ 4시간 교반하였다. 상온으로 냉각하고 증류수를 넣고 EA로 추출하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 4-3 28g(72.86mmol, 52.94%)을 얻었다.Compound 4-2 40g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh 3 ) 4 6.32g (5.47mmol), 2M Na 2 CO 3 170mL, toluene was added and stirred for 4 hours at 100 ℃. . After cooling to room temperature, distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 4-3 28g (72.86mmol, 52.94%) was obtained by column chromatography.

화합물 compound 4-44-4 의 제조Manufacture

화합물 4-3 28g(72.86mmol)을 트리에틸포스파이트 300mL에 섞고 150℃로 12시간 교반하였다. 상온으로 냉각하고 감압 증류하였다. EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 4-4 11g(31.22mmol, 43.05%)을 얻었다. 28 g (72.86 mmol) of Compound 4-3 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. for 12 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound chromatography ( 4-4) 11g (31.22mmol, 43.05%) was obtained by column chromatography.

화합물 compound 4-54-5 의 제조Manufacture

화합물 4-4 11g(31.22mmol), 아이오도벤젠 12.7g(62.45mmol), CuI 2.9g(15.61mmol), K3PO4 19.8g(93.68mmol), 톨루엔 300mL 을 넣고 50℃로 가열 후 에틸렌다이아민 2.1mL(31.22mmol)을 넣었다. 12시간 환류 교반하였다. 상온으로 냉각하고 EA로 추출하고 NaHCO3수용액으로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 4-5 12g(28.01mmol, 90.32%) 을 얻었다. Compound 4-4 11g (31.22mmol), iodobenzene 12.7g (62.45mmol), CuI 2.9g (15.61mmol), K 3 PO 4 19.8g (93.68mmol), toluene 300mL was added and heated to 50 ℃ and ethylene diamond 2.1 mL (31.22 mmol) was added. Stirring at reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO 3 aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography gave 12 g (28.01 mmol, 90.32%) of compound 4-5 .

화합물 compound 4-64-6 의 제조Manufacture

화합물 4-5 12g(28.01mmol), 9-아미노안트라센(9-aminoanthracene) 8.1g(42.02mmol), Pd(OAc)2 0.25g(1.12mmol), P(t-bu)3 1.38mL(2.80mmol, 50% in xylene), Cs2CO3 22.8g(70.03mmol), 톨루엔 500mL 을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하여 화합물 4-6 9g(16.64mmol, 59.42%)을 얻었다.Compound 4-5 12 g (28.01 mmol), 9-aminoanthracene 8.1 g (42.02 mmol), Pd (OAc) 2 0.25 g (1.12 mmol), P (t-bu) 3 1.38 mL (2.80 mmol , 50% in xylene), 22.8 g (70.03 mmol) of Cs 2 CO 3 , and 500 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. Drying over magnesium sulfate and distillation under reduced pressure yielded 9 g (16.64 mmol, 59.42%) of compound 4-6 .

화합물 compound 1717 의 제조Manufacture

화합물 4-6 7g(12.94mmol), 화합물 2-6 5.2g(15.53mmol), Pd(OAc)2 0.11g(0.51mmol), P(t-bu)3 0.63mL(1.29mmol, 50% in xylene), NaOt-bu 3.1g(32.36mmol), 톨루엔 100mL을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 17 4g(5.00mmol, 38.68%)을 얻었다.Compound 4-6 7 g (12.94 mmol), Compound 2-6 5.2 g (15.53 mmol), Pd (OAc) 2 0.11 g (0.51 mmol), P (t-bu) 3 0.63 mL (1.29 mmol, 50% in xylene ), NaOt-bu 3.1 g (32.36 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded Compound 17 (4 g, 5.00 mmol, 38.68%).

1H NMR(CDCl3, 200 MHz) δ = 6.69(2H, m), 6.86~6.91(2H, m), 7.29(1H, m), 7.4~7.63(13H, m), 7.73(1H, m), 7.78(1H, s), 7.82(2H, m), 7.86(1H, s), 7.88(2H, m), 7.98(1H, m), 8.12(3H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.93(2H, m) ; MS/FAB found 800, calculated 799.011 H NMR (CDCl 3, 200 MHz) δ = 6.69 (2H, m), 6.86-6.61 (2H, m), 7.29 (1H, m), 7.4-7.63 (13H, m), 7.73 (1H, m), 7.78 (1H, s), 7.82 (2H, m), 7.86 (1H, s), 7.88 (2H, m), 7.98 (1H, m), 8.12 (3H, m), 8.2 (1H, m), 8.41- 8.45 (2H, m), 8.93 (2H, m); MS / FAB found 800, calculated 799.01

[제조예 5]화합물 19의 제조Preparation Example 5 Preparation of Compound 19

Figure pat00040
Figure pat00040

Figure pat00041
Figure pat00041

화합물 compound 5-15-1 의 제조Manufacture

다이벤조퓨란 50g(271.3mmol)을 CHCl3 1000mL 에 녹이고 0℃에서 Br2 30mL(596.9mmol)을 천천히 넣었다. 상온에서 12시간 교반 후 싸이오황산나트륨 수용액을 넣어 주었다. 반응 용액 색깔이 노란색으로 변하면 다이클로로메탄으로 추출하고 이 유기층을 KOH 수용액으로 중성화 했다. 유기층을 황산마그네슘으로 건조하고 감압 증류하였다. EA와 메탄올로 재결정하여 화합물 5-1 74g(216.3mmol, 79.70%)을 얻었다. 50 g (271.3 mmol) of dibenzofuran was dissolved in 1000 mL of CHCl 3 , and 30 mL (596.9 mmol) of Br 2 was slowly added at 0 ° C. After stirring for 12 hours at room temperature was added sodium thiosulfate aqueous solution. When the reaction solution turned yellow, the mixture was extracted with dichloromethane and the organic layer was neutralized with an aqueous KOH solution. The organic layer was dried over magnesium sulfate and distilled under reduced pressure. 74 g (216.3 mmol, 79.70%) of Compound 5-1 was obtained by recrystallization with EA and methanol.

화합물 compound 5-25-2 의 제조Manufacture

화합물 5-1 74g(216.3mmol) 을 THF에 녹이고 -78℃에서 n-buLi 86.5mL(216.3mmol, 2.5M in hexane)을 천천히 넣었다. 한시간 후 트리메틸보레이트 28.9mL(259.6mmol)을 넣었다. 12시간 상온에서 교반하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 EA와 헥산으로 재결정하여 화합물 5-2 40g(136.8mmol, 62.96%)을 얻었다.74 g (216.3 mmol) of Compound 5-1 were dissolved in THF, and 86.5 mL (216.3 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After an hour, 28.9 mL (259.6 mmol) of trimethylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization with EA and hexane gave Compound 5-2 40 g (136.8 mmol, 62.96%).

화합물 compound 5-35-3 의 제조Manufacture

화합물 5-2 40g(136.8mmol), 아이오도니트로벤젠 37.4g(150.5mmol), Pd(PPh3)4 6.32g(5.47mmol), 2M Na2CO3 170mL, 톨루엔 을 넣고 100℃ 4시간 교반하였다. 상온으로 냉각하고 증류수를 넣고 EA로 추출하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 5-3 28g(72.86mmol, 52.94%)을 얻었다.Compound 5-2 40g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh 3 ) 4 6.32g (5.47mmol), 2M Na 2 CO 3 170mL, toluene was added and stirred for 4 hours at 100 ℃. . After cooling to room temperature, distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 5-3 28g (72.86mmol, 52.94%) was obtained by column chromatography.

화합물 compound 5-45-4 의 제조Manufacture

화합물 5-3 28g(72.86mmol)을 트리에틸포스파이트 300mL 에 섞고 150℃로 12시간 교반하였다. 상온으로 냉각하고 감압 증류하였다. EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 5-4 11g(31.22mmol, 43.05%)을 얻었다. 28 g (72.86 mmol) of Compound 5-3 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. for 12 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-4 11g (31.22mmol, 43.05%).

화합물 compound 5-55-5 의 제조Manufacture

화합물 5-4 11g(31.22mmol), 아이오도벤젠 12.7g(62.45mmol), CuI 2.9g(15.61mmol), K3PO4 19.8g(93.68mmol), 톨루엔 300mL 을 넣고 50℃ 가열 후 에틸렌다이아민 2.1mL(31.22mmol)을 넣었다. 12시간 환류 교반하였다. 상온으로 냉각하고 EA로 추출하고 NaHCO3수용액으로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 5-5 12g(28.01mmol, 90.32%) 을 얻었다. Compound 5-4 11g (31.22mmol), iodobenzene 12.7g (62.45mmol), CuI 2.9g (15.61mmol), K 3 PO 4 19.8g (93.68mmol), toluene 300mL was added and heated to 50 ℃ and ethylenediamine 2.1 mL (31.22 mmol) was added. Stirring at reflux for 12 hours. Cooled to room temperature, extracted with EA and washed with NaHCO 3 aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-5 12g (28.01mmol, 90.32%).

화합물 compound 5-65-6 의 제조Manufacture

화합물 5-5 10g(24.25mmol), 4-아미노니트로페닐아민 9.47g(36.36mmol), Pd(OAc)2 0.21g(0.97mmol), P(t-bu)3 1.1mL(2.42mmol, 50% in xylene), Cs2CO3 19.75g(60.63mmol), 톨루엔 500mL 을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 5-6 8g(13.52mmol, 55.75%)을 얻었다.10 g (24.25 mmol) of Compound 5-5 , 9.47 g (36.36 mmol) of 4-aminonitrophenylamine, 0.21 g (0.97 mmol) of Pd (OAc) 2 , 1.1 mL (2.42 mmol, 50%) of P (t-bu) 3 in xylene), 19.75 g (60.63 mmol) of Cs 2 CO 3 , and 500 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 5-6 8g (13.52mmol, 55.75%).

화합물 compound 1919 의 제조Manufacture

화합물 5-6 7.6g(12.94mmol), 화합물 2-6 5.2g(15.53mmol), Pd(OAc)2 0.11g(0.51mmol), P(t-bu)3 0.63mL(1.29mmol, 50% in xylene), NaOt-bu 3.1g(32.36mmol), 톨루엔 100mL 을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 19 5g(5.88mmol, 45.45%)을 얻었다.Compound 5-6 7.6 g (12.94 mmol), Compound 2-6 5.2 g (15.53 mmol), Pd (OAc) 2 0.11 g (0.51 mmol), P (t-bu) 3 0.63 mL (1.29 mmol, 50% in xylene), NaOt-bu 3.1 g (32.36 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded Compound 19 (5 g, 5.88 mmol, 45.45%).

1H NMR(CDCl3, 200 MHz)δ = 6.38~6.39(5H, m), 6.63(4H, m), 6.69(2H, m), 6.81(2H, m), 7.2(4H, m), 7.29(1H, m), 7.41(1H, m), 7.42(1H, s), 7.45(1H, m), 7.49(1H, s), 7.5~7.65(12H, m), 7.98(1H, m), 8.12(1H, m), 8.2(1H, m), 8.41~8.45(2H, m) ; MS/FAB found 851, calculated 850.041 H NMR (CDCl 3, 200 MHz) δ = 6.38 to 6.39 (5H, m), 6.63 (4H, m), 6.69 (2H, m), 6.81 (2H, m), 7.2 (4H, m), 7.29 (1H) , m), 7.41 (1H, m), 7.42 (1H, s), 7.45 (1H, m), 7.49 (1H, s), 7.5-7.75 (12H, m), 7.98 (1H, m), 8.12 ( 1H, m), 8.2 (1H, m), 8.41-8.45 (2H, m); MS / FAB found 851, calculated 850.04

[제조예 6]화합물 25의 제조Preparation Example 6 Preparation of Compound 25

Figure pat00042
Figure pat00042

Figure pat00043
Figure pat00043

화합물 compound 6-16-1 의 제조Manufacture

2-아이오도니트로벤젠 30g(120.4mmol), 4-브로모페닐보로닉산 26g(132.5mmol), Pd(PPh3)4 6.9g(6.02mmol), 2M Na2CO3 150mL, 톨루엔을 섞고 100℃로 가열하였다. 4시간 후 상온으로 냉각하고 EA로 추출하였다. 증류수로 씻어 주고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 6-1 28g(100.68mmol, 83,33%)을 얻었다. Mix 30 g (120.4 mmol) of 2-iodonitrobenzene, 26 g (132.5 mmol) of 4-bromophenylboronic acid, 6.9 g (6.02 mmol) of Pd (PPh 3 ) 4 , 150 mL of 2M Na 2 CO 3 , and mix with toluene. Heated to ° C. After 4 hours, the mixture was cooled to room temperature and extracted with EA. Washed with distilled water and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 28 g (100.68 mmol, 83,33%) of compound 6-1 .

화합물 compound 6-26-2 의 제조Manufacture

화합물 6-1 28g(100.68mmol) 을 트리에틸포스파이트 300mL 에 섞고 150℃ 교반하였다. 6시간 후 상온으로 냉각하고 감압 증류하였다. EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 6-2 11g(44.69mmol, 44.38%)을 얻었다.28 g (100.68 mmol) of Compound 6-1 were mixed with 300 mL of triethyl phosphite and stirred at 150 ° C. After 6 hours, the mixture was cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 11 g (44.69 mmol, 44.38%) of Compound 6-2 .

화합물 compound 6-36-3 의 제조Manufacture

화합물 6-2 11g(44.69mmol), 아이오도벤젠 18.23g(89.39mmol), CuI 4.25g(22.34mmol), K3PO4 28.4g(134.09mmol), 톨루엔 200mL을 섞고 50℃ 가열하였다. 에틸렌다이아민 3.01mL(44.69mmol)을 넣고 환류 교반하였다. 14시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 6-3 12g(37.24mmol, 83.32%) 을 얻었다. 11 g (44.69 mmol) of compound 6-2 , 18.23 g (89.39 mmol) of iodobenzene, 4.25 g (22.34 mmol) of CuI, 28.4 g (134.09 mmol) of K 3 PO 4 , and 200 mL of toluene were mixed and heated to 50 ° C. 3.01 mL (44.69 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 12 g (37.24 mmol, 83.32%) of compound 6-3 .

화합물 compound 6-46-4 의 제조Manufacture

화합물 6-3 20g(62.07mmol)을 THF에 녹이고 -78℃에서 n-buLi 29.79mL(74.48mmol, 2.5M in Hexne)을 천천히 넣었다. 한시간 후 트리메틸보레이트 10.38mL(93.10mmol)을 넣었다. 12시간 상온에서 교반 후 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 EA와 헥산으로 재결정하였다. 화합물 6-4 12g(41.79mmol, 67.32%) 을 얻었다. 20 g (62.07 mmol) of Compound 6-3 was dissolved in THF, and 29.79 mL (74.48 mmol, 2.5 M in Hexne) of n-buLi was slowly added at -78 ° C. After one hour, 10.38 mL (93.10 mmol) of trimethylborate was added. After stirring at room temperature for 12 hours, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization from EA and hexane. 12 g (41.79 mmol, 67.32%) of Compound 6-4 were obtained.

화합물 compound 6-56-5 의 제조Manufacture

화합물 6-4 12g(41.79mmol), 메틸-2,5-다이브로모벤조에이트 13.51g(45.97mmol), Pd(PPh3)4 1.9g(1.67mmol), 2M Na2CO3 60mL, 톨루엔 200mL 를 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 6-5 8g(17.53mmol, 41.95%)을 얻었다. Compound 6-4 12 g (41.79 mmol), methyl-2,5-dibromobenzoate 13.51 g (45.97 mmol), Pd (PPh 3 ) 4 1.9 g (1.67 mmol), 2 M Na 2 CO 3 60 mL, toluene 200 mL Mix and stir at reflux. After 12 hours, the mixture was cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8 g (17.53 mmol, 41.95%) of compound 6-5 .

화합물 compound 6-66-6 의 제조Manufacture

화합물 6-5 8g(17.53mmol)을 THF에 녹이고 메틸마그네슘브로마이드 14.60mL(43.82mmol, 3.0M in diethyl ether) 을 넣었다. 60℃로 가열하고 6시간 후 상온으로 냉각하였다. 증류수를 넣고 EA로 추출하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 6-6 6g(13.14mmol, 74.95%)을 얻었다. 8 g (17.53 mmol) of Compound 6-5 was dissolved in THF, and 14.60 mL (43.82 mmol, 3.0 M in diethyl ether) of methylmagnesium bromide was added thereto. Heated to 60 ℃ and cooled to room temperature after 6 hours. Distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 6-6 (g. 13.14 mmol, 74.95%) was obtained by column chromatography.

화합물 compound 6-76-7 의 제조Manufacture

화합물 6-6 6g(13.14mmol), 아세트산 50mL, 인산 50mL 를 섞고 50℃로 5시간 교반하였다. 상온으로 냉각하고 NaOH수용액으로 중성을 만들었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류 후 컬럼크로마토그래피로 분리하여 화합물 6-7 4.6g(10.49mmol, 79.83%)을 얻었다. 6 g (13.14 mmol) of compound 6-6 , acetic acid 50mL and phosphoric acid 50mL were mixed and stirred at 50 ° C for 5 hours. Cooled to room temperature and neutralized with aqueous NaOH solution. Extracted with EA and dried over magnesium sulfate. After distillation under reduced pressure, the residue was separated by column chromatography to obtain 4.6 g (10.49 mmol, 79.83%) of Compound 6-7 .

화합물 compound 6-86-8 의 제조Manufacture

화합물 6-7 4.6g(10.49mmol), 4-아미노트리페닐아민 4.09g(15.74mmol), Pd(OAc)2 0.11g(0.52mmol), P(t-bu)3 0.51mL(1.04mmol, 50% in xylene), Cs2CO3 8.54g(26.23mmol), 톨루엔 100mL 을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 6-8 4g(6.47mmol, 61.67%)을 얻었다.Compound 6-7 4.6 g (10.49 mmol), 4.09 g (15.74 mmol) 4-aminotriphenylamine, 0.11 g (0.52 mmol) Pd (OAc) 2 , 0.51 mL (1.04 mmol, 50) P (t-bu) 3 % in xylene), 8.54 g (26.23 mmol) Cs 2 CO 3 , and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography afforded 4 g (6.47 mmol, 61.67%) of Compound 6-8 .

화합물 compound 2525 의 제조Manufacture

화합물 6-8 4g(6.47mmol), 화합물 2-6 2.63g(7.76mmol), Pd(OAc)2 0.058g(0.25mmol), P(t-bu)3 0.31mL(0.64mmol, 50% in xylene), NaOt-bu 1.55g(16.18mmol), 톨루엔 70mL 을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 25 3.0g(3.42mmol, 52.92%)을 얻었다.Compound 6-8 4 g (6.47 mmol), Compound 2-6 2.63 g (7.76 mmol), Pd (OAc) 2 0.058 g (0.25 mmol), P (t-bu) 3 0.31 mL (0.64 mmol, 50% in xylene ), NaOt-bu 1.55 g (16.18 mmol) and toluene 70 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 3.0 g (3.42 mmol, 52.92%) of compound 25 .

1H NMR(CDCl3, 200 MHz)δ = 1.72(6H, s), 6.38(4H, m), 6.63~6.69(7H, m), 6.81(3H, m), 7.2~7.25(5H, m), 7.33(1H, m), 7.45~7.58(10H, m), 7.71(1H, m), 7.84(1H, m), 7.94~8(3H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.55(1H, m) ; MS/FAB found 877, calculated 876.121 H NMR (CDCl 3, 200 MHz) δ = 1.72 (6H, s), 6.38 (4H, m), 6.63-6.69 (7H, m), 6.81 (3H, m), 7.2-7.25 (5H, m), 7.33 (1H, m), 7.45-7.58 (10H, m), 7.71 (1H, m), 7.84 (1H, m), 7.94-8 (3H, m), 8.2 (1H, m), 8.41-8.45 (2H m), 8.55 (1 H, m); MS / FAB found 877, calculated 876.12

[제조예 7]화합물 28의 제조Preparation Example 7 Preparation of Compound 28

Figure pat00044
Figure pat00044

Figure pat00045
Figure pat00045

Figure pat00046
Figure pat00046

화합물 compound 7-17-1 의 제조Manufacture

화합물 2,5-다이브로모니트로벤젠 50g(177.99mol), 1-나프탈렌보로닉산(1-naphthaleneboronic acid) 36.7g(213.59mmol), Pd(PPh3)4 10.28g(8.89mmol), 2M Na2CO3 533.97mmol) 톨루엔 700mL, 에탄올 200mL을 섞고 100℃로 5시간 교반하였다. 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 7-1 50g(152.36mmol, 85.60%)을 얻었다. Compound 2,5-Dibromonitrobenzene 50g (177.99mol), 1-naphthaleneboronic acid 36.7g (213.59mmol), Pd (PPh 3 ) 4 10.28g (8.89mmol), 2M Na 2 CO 3 533.97 mmol) 700 mL of toluene and 200 mL of ethanol were mixed and stirred at 100 ° C. for 5 hours. Cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 50 g (152.36 mmol, 85.60%) of Compound 7-1 .

화합물 compound 7-27-2 의 제조Manufacture

화합물 7-1 50g(152.36mmol), 트리에틸포스파이트 500mL 를 섞고 150℃ 7시간 교반하였다. 상온으로 냉각하고 감압 증류하였다. EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하엿다. 컬럼크로마토그래피로 분리하여 화합물 7-2 30g(101.29mmol, 66.64%)을 얻었다. 50 g (152.36 mmol) of Compound 7-1 and 500 mL of triethyl phosphite were mixed and stirred at 150 ° C. for 7 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 7-2 30g (101.29mmol, 66.64%) was obtained by column chromatography.

화합물 compound 7-37-3 의 제조Manufacture

화합물 7-2 30g(101.29mmol), 아이오도벤젠 41.3g(202.59mmol), CuI 9.6g(50.64mmol), Cs2CO3 82.5g(253.2mmol), 톨루엔 600mL 을 섞고 50℃ 가열하였다. 에틸렌다이아민 6.8mL(101.29mmol)을 넣고 환류 교반하였다. 14시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 7-3 32g(85.96mmol, 84.86%) 을 얻었다. 30 g (101.29 mmol) of Compound 7-2 , 41.3 g (202.59 mmol) of iodobenzene, 9.6 g (50.64 mmol) of CuI, 82.5 g (253.2 mmol) of Cs 2 CO 3 , and 600 mL of toluene were mixed and heated to 50 ° C. 6.8 mL (101.29 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography gave 32 g (85.96 mmol, 84.86%) of compound 7-3 .

화합물 compound 7-47-4 의 제조Manufacture

화합물 7-3 32g(85.96mmol) 을 THF 300mL 에 녹이고 -78℃에서 n-buLi 37.8mL(94.55mmol, 2.5M in hexane)을 천천히 넣었다. 한시간 후 트리메틸보레이트 12.4mL(111.7mmol)을 넣었다. 상온에서 12시간 교반 후 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 7-4 20g(59.31mmol, 69.00%) 을 얻었다. 32 g (85.96 mmol) of Compound 7-3 was dissolved in 300 mL of THF, and 37.8 mL (94.55 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After 1 hour trimethyl borate 12.4 mL (111.7 mmol) was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 20 g (59.31 mmol, 69.00%) of compound 7-4 .

화합물 compound 7-57-5 의 제조Manufacture

화합물 7-4 20g(59.31mmol), 브로모니트로벤젠 14.3g(71.17mmol), Pd(PPh3)4 2.7g(2.37mmol), 2M Na2CO3 75mL, 톨루엔 300mL, 에탄올 70mL 를 섞고 환류 교반하였다. 5시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 7-5 20g(48.25mmol, 81.36%)을 얻었다. Compound 7-4 20g (59.31mmol), bromonitrobenzene 14.3g (71.17mmol), Pd (PPh 3 ) 4 2.7g (2.37mmol), 2M Na 2 CO 3 75mL, toluene 300mL, ethanol 70mL and stirred under reflux It was. After 5 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 20 g (48.25 mmol, 81.36%) of compound 7-5 .

화합물 compound 7-67-6 의 제조Manufacture

화합물 7-5 20g(48.25mmol)을 트리에틸포스파이트 200mL와 섞고 150℃로 6시간 교반하였다. 상온으로 냉각하고 감압 증류하였다. EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 7-6 7g(18.30mmol, 37.93%)을 얻었다. 20 g (48.25 mmol) of Compound 7-5 were mixed with 200 mL of triethylphosphite and stirred at 150 ° C. for 6 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Compound 7-6 (7.30 mmol, 37.93%) was obtained by column chromatography.

화합물 compound 7-77-7 의 제조Manufacture

화합물 7-6 7g(18.30mmol), 아이오도벤젠 7.46g(36.60mmol), CuI 1.7g(9.15mmol), K3PO4 11.6g(54.90mmol), 톨루엔 100mL 을 섞고 50℃로 가열하였다. 에틸렌다이아민 1.2mL(18.30mmol)을 넣고 환류 교반하였다. 14시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 7-7 8g(17.44mmol, 95.33%) 을 얻었다. Compound 7-6 7 g (18.30 mmol), 7.46 g (36.60 mmol) iodobenzene, 1.7 g (9.15 mmol) CuI, 11.6 g (54.90 mmol) K 3 PO 4 , and 100 mL of toluene were mixed and heated to 50 ° C. 1.2 mL (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8 g (17.44 mmol, 95.33%) of compound 7-7 .

화합물 compound 7-87-8 의 제조Manufacture

화합물 7-7 8g(17.44mmol), NBS 3.1g(17.44mmol)을 CHCl3 200mL 에 녹이고 상온에서 10시간 교반하였다. 증류수를 넣고 다이클로로메탄으로 추출하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 7-8 8g(14.88mmol, 85.35%)을 얻었다. 8 g (17.44 mmol) of Compound 7-7 and 3.1 g (17.44 mmol) of NBS were dissolved in 200 mL of CHCl 3 , and the mixture was stirred at room temperature for 10 hours. Distilled water was added and extracted with dichloromethane. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was performed to give compound 7-8 8g (14.88mmol, 85.35%).

화합물 compound 7-97-9 의 제조Manufacture

화합물 7-8 8g(14.88mmol), 1-아미노나프탈렌 3.19g(22.32mmol), Pd(OAc)2 0.16g(0.74mmol), P(t-bu)3 0.73mL(1.48mmol, 50% in xylene), Cs2CO3 14.54g(44.65mmol), 톨루엔 100mL을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 7-9 7g(11.67mmol, 78.44%)을 얻었다.Compound 7-8 8 g (14.88 mmol), 1-aminonaphthalene 3.19 g (22.32 mmol), Pd (OAc) 2 0.16 g (0.74 mmol), P (t-bu) 3 0.73 mL (1.48 mmol, 50% in xylene ), Cs 2 CO 3 14.54 g (44.65 mmol) and toluene 100 mL were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 7 g (11.67 mmol, 78.44%) of compound 7-9 .

화합물 compound 2828 의 제조Manufacture

화합물 7-9 7g(11.67mmol), 화합물 2-6 4.75g(14.00mmol), Pd(OAc)2 0.13g(0.25mmol), P(t-bu)3 0.57mL(1.16mmol, 50% in xylene), NaOt-bu 2.8g(29.18mmol), 톨루엔 100mL 을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 28 4.0g(4.66mmol, 39.94%)을 얻었다.Compound 7-9 7 g (11.67 mmol), Compound 2-6 4.75 g (14.00 mmol), Pd (OAc) 2 0.13 g (0.25 mmol), P (t-bu) 3 0.57 mL (1.16 mmol, 50% in xylene ), NaOt-bu 2.8 g (29.18 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography and recrystallization with EA yielded 4.0 g (4.66 mmol, 39.94%) of compound 28 .

1H NMR(CDCl3, 200 MHz)δ = 5.93(1H, m), 6.69(2H, m), 6.98(1H, m), 7.38(1H, m), 7.45(2H, m), 7.5(5H, m), 7.52~7.57(16H, m), 7.94~8.02(8H, m), 8.41~8.45(2H, m), 8.54(1H, m) ; MS/FAB found 859, calculated 858.061 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (2H, m), 6.98 (1H, m), 7.38 (1H, m), 7.45 (2H, m), 7.5 (5H, m ), 7.52-7.57 (16H, m), 7.94-8.02 (8H, m), 8.41-8.45 (2H, m), 8.54 (1H, m); MS / FAB found 859, calculated 858.06

[제조예 8]화합물 32의 제조Preparation Example 8 Preparation of Compound 32

Figure pat00047
Figure pat00047

Figure pat00048
Figure pat00048

Figure pat00049
Figure pat00049

화합물 compound 8-18-1 의 제조Manufacture

1-나프탈렌보론산 10.2 g(59.4 mmol), 1-브로모-2-나이트로벤젠 10.0 g(49.5 mmol), Pd(PPh3)4 1.7 g(1.4 mmol), 2M K2CO3 수용액 70 mL, 톨루엔 200 mL 및 에탄올 100 mL를 넣고 12시간 환류 교반시켰다. 증류수로 씻어 주고 EA로 추출하고, 무수 MgSO4으로 건조하고 감압 증류시켜 얻어진 잔사를 컬럼크로마토그래피로 분리하여 화합물 8-1 9.0 g(73.7 %)을 얻었다. 10.2 g (59.4 mmol) of 1-naphthaleneboronic acid, 10.0 g (49.5 mmol) of 1-bromo-2-nitrobenzene, 1.7 g (1.4 mmol) of Pd (PPh 3 ) 4 , 2M K 2 CO 3 70 mL of aqueous solution, 200 mL of toluene and 100 mL of ethanol were added thereto, and the mixture was stirred under reflux for 12 hours. The residue was washed with distilled water, extracted with EA, dried over anhydrous MgSO 4 , and distilled under reduced pressure. The residue was separated by column chromatography to obtain 9.0 (73.7%) of Compound 8-1 .

화합물 compound 8-28-2 의 제조Manufacture

화합물 8-1 9.0 g(36.1 mmol)과 N-브로모쑥시니이미드 7.6 g(43.3 mmol)을 디클로로메탄 300 mL에 녹이고 12시간 상온에서 교반시켰다. 감압 증류하고 얻어진 고체를 증류수, 메탄올 및 헥산으로 차례로 세척한 후 화합물 8-2 9.6 g(81.3 %)을 얻었다. 9.0 g (36.1 mmol) of Compound 8-1 and 7.6 g (43.3 mmol) of N-bromosuccinimide were dissolved in 300 mL of dichloromethane and stirred at room temperature for 12 hours. After distillation under reduced pressure, the obtained solid was washed sequentially with distilled water, methanol and hexane to obtain 9.6 g (81.3%) of Compound 8-2 .

화합물 compound 8-38-3 의 제조Manufacture

화합물 8-2 9.6 g(29.3 mmol), FeC2O42H2O (iron oxalate dihydrate) 72.2 g(175.5 mmol) 을 섞고 205℃로 30분 가열시킨 후 상온으로 냉각시키고 EA로 추출하고 증류수로 세척하였다. 톨루엔으로 재결정하여 화합물 8-3 5.2 g(60.5 %) 을 얻었다. 9.6 g (29.3 mmol) of Compound 8-2 and 72.2 g (175.5 mmol) of iron oxalate dihydrate (FeC 2 O 4 2H 2 O) were mixed, heated to 205 ° C. for 30 minutes, cooled to room temperature, extracted with EA, and washed with distilled water. It was. Recrystallization from toluene gave 5.2 g (60.5%) of compound 8-3 .

화합물compound 8-4 8-4 의 제조Manufacture

화합물 8-3 5.2 g(17.6 mmol), 구리 0.6 g(8.8 mmol), 18-크라운-6 0.2 g(0.9 mmol), K2CO3 4.8 g(35.1 mmol) 및 1,2-디클로로벤젠 100 mL을 섞고 180℃에서 12시간동안 환류교반시켰다. 상온으로 냉각시키고 감압 증류한 후 MC로 추출하고 증류수로 세척하였다. 무수 MgSO4으로 건조하고 감압 증류하여 얻어진 잔사를 컬럼크로마토그래피로 분리하여 화합물 8-4 5.0 g(76.5 %)을 얻었다.Compound 8-3 5.2 g (17.6 mmol), 0.6 g (8.8 mmol) copper, 0.2 g (0.9 mmol) 18-crown-6, 4.8 g (35.1 mmol) K 2 CO 3 and 100 mL 1,2-dichlorobenzene The mixture was stirred and refluxed at 180 ° C. for 12 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with MC and washed with distilled water. The residue obtained by drying over anhydrous MgSO 4 and distillation under reduced pressure was separated by column chromatography to obtain 5.0 g (76.5%) of Compound 8-4 .

화합물 compound 8-58-5 의 제조Manufacture

화합물 8-4 23.1g(62.07mmol)을 THF에 녹이고 -78℃에서 n-buLi 29.79mL(74.48mmol, 2.5M in Hexne)을 천천히 넣었다. 한시간 후 트리메틸보레이트 10.38mL(93.10mmol)을 넣었다. 12시간 상온에서 교반 후 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고 EA와 hexane으로 재결정하였다. 화합물 8-5 14g(67%) 을 얻었다. 23.1 g (62.07 mmol) of Compound 8-4 was dissolved in THF, and 29.79 mL (74.48 mmol, 2.5 M in Hexne) of n-buLi was slowly added at -78 ° C. After one hour, 10.38 mL (93.10 mmol) of trimethylborate was added. After stirring at room temperature for 12 hours, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization from EA and hexane. 14g (67%) of compound 8-5 was obtained.

화합물 compound 8-68-6 의 제조Manufacture

화합물 8-5 14g(41.79mmol), 메틸-2,5-다이브로모벤조에이트 13.51g(45.97mmol), Pd(PPh3)4 1.9g(1.67mmol), 2M Na2CO3 60mL, 톨루엔 200mL 를 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 증류수를 넣었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류하고컬럼크로마토그래피로 분리하여 화합물 8-6 8.8g(42%)을 얻었다. 14 g (41.79 mmol) of compound 8-5 , 13.51 g (45.97 mmol) of methyl-2,5-dibromobenzoate, 1.9 g (1.67 mmol) of Pd (PPh 3 ) 4 , 60 mL of 2M Na 2 CO 3 , and 200 mL of toluene Mix and stir at reflux. After 12 hours, the mixture was cooled to room temperature and distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and separation by column chromatography yielded 8.8 g (42%) of the compound 8-6 .

화합물 compound 8-78-7 의 제조Manufacture

화합물 8-6 8.8g(17.53mmol)을 THF에 녹이고 메틸마그네슘브로마이드 14.60mL(43.82mmol, 3.0M in diethyl ether) 을 넣었다. 60℃로 가열하고 6시간 후 상온으로 냉각하였다. 증류수를 넣고 EA로 추출하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 8-7 6.6g(74%)을 얻었다. 8.8 g (17.53 mmol) of Compound 8-6 was dissolved in THF, and 14.60 mL (43.82 mmol, 3.0 M in diethyl ether) of methylmagnesium bromide was added thereto. Heated to 60 ℃ and cooled to room temperature after 6 hours. Distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography yielded 6.6 g (74%) of Compound 8-7 .

화합물 compound 8-88-8 의 제조Manufacture

화합물 8-7 6.6g(13.14mmol), 아세트산 50mL, 인산 50mL 를 섞고 50℃로 5시간 교반하였다. 상온으로 냉각하고 NaOH수용액으로 중성을 만들었다. EA로 추출하고 황산마그네슘으로 건조하였다. 감압 증류 후 컬럼크로마토그래피로 분리하여 화합물 8-8 5.1g(80%)을 얻었다. 6.6 g (13.14 mmol) of the compound 8-7 , 50 mL of acetic acid and 50 mL of phosphoric acid were mixed and stirred at 50 ° C for 5 hours. Cooled to room temperature and neutralized with aqueous NaOH solution. Extracted with EA and dried over magnesium sulfate. After distillation under reduced pressure, the residue was separated by column chromatography to obtain 5.1 g (80%) of the compound 8-8 .

화합물 compound 8-98-9 의 제조Manufacture

화합물 8-8 5.1g(10.49mmol), 아닐린 1.5g(15.74mmol), Pd(OAc)2 0.11g(0.52mmol), P(t-bu)3 0.51mL(1.04mmol, 50% in xylene), Cs2CO3 8.54g(26.23mmol), 톨루엔 100mL 을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 8-9 3.2g(62%)을 얻었다.Compound 8-8 5.1 g (10.49 mmol), aniline 1.5 g (15.74 mmol), Pd (OAc) 2 0.11 g (0.52 mmol), P (t-bu) 3 0.51 mL (1.04 mmol, 50% in xylene), Cs 2 CO 3 8.54 g (26.23 mmol) and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. 3.2 g (62%) of Compound 8-9 was obtained by column chromatography.

화합물 compound 3232 의 제조Manufacture

화합물 8-9 3.2g(6.47mmol), 화합물 2-6 2.63g(7.76mmol), Pd(OAc)2 0.058g(0.25mmol), P(t-bu)3 0.31mL(0.64mmol, 50% in xylene), NaOt-bu 1.55g(16.18mmol), 톨루엔 70mL 을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 32 2.6g(53%)을 얻었다.Compound 8-9 3.2 g (6.47 mmol), Compound 2-6 2.63 g (7.76 mmol), Pd (OAc) 2 0.058 g (0.25 mmol), P (t-bu) 3 0.31 mL (0.64 mmol, 50% in xylene), NaOt-bu 1.55 g (16.18 mmol) and toluene 70 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Column chromatography was isolated and recrystallized with EA to give compound 32 2.6g (53%).

1H NMR(CDCl3, 200 MHz)δ = 1.78(6H, s), 6.63~6.69(5H, m), 6.81(2H, m), 7.2~7.25(3H, m), 7.33(1H, m), 7.45~7.58(12H, m), 7.84(1H, m), 7.94~7.98(2H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.55(3H, m) ; MS/FAB found 759, calculated 758.971 H NMR (CDCl 3, 200 MHz) δ = 1.78 (6H, s), 6.63-6.69 (5H, m), 6.81 (2H, m), 7.2-7.25 (3H, m), 7.33 (1H, m), 7.45 ~ 7.58 (12H, m), 7.84 (1H, m), 7.94-7.98 (2H, m), 8.2 (1H, m), 8.41-8.45 (2H, m), 8.55 (3H, m); MS / FAB found 759, calculated 758.97

[제조예 9]화합물 36의 제조Preparation Example 9 Preparation of Compound 36

Figure pat00050
Figure pat00050

Figure pat00051
Figure pat00051

Figure pat00052
Figure pat00052

화합물 compound 9-19-1 의 제조Manufacture

화합물 6-3 12g(37.42mmol), 2-(메틸싸이오)페닐보로닉산 ( 2-(methylthio)phenylboronic acid) 7.5g(44.69mmol), Pd(PPh3)4 2.15g(1.6mmol), 2M Na2CO3 수용액 45mL , THF 200mL를 섞고 환류 교반하였다. 5시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 9-1 10g(27.36mmol, 73.47%) 을 얻었다. Compound 6-3 12 g (37.42 mmol), 2- (methylthio) phenylboronic acid 7.5 g (44.69 mmol), Pd (PPh 3 ) 4 2.15 g (1.6 mmol), 45 mL of 2M Na 2 CO 3 aqueous solution and 200 mL of THF were mixed and stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography gave 10 g (27.36 mmol, 73.47%) of compound 9-1 .

화합물 compound 9-29-2 의 제조Manufacture

화합물 9-1 10g(27.36mmol)을 아세트산 100mL 에 넣고 H2O2 2.65mL(30.09mmol, 35%) 을 천천히 넣었다. 상온에서 12시간 교반하고 아세트산을 감압 증류하였다. 다이클로로메탄으로 추출하고 NaHCO3 수용액으로 중성화하였다. 황산마그네슘으로 건조하고 감압 증류하였다. 화합물 9-2 10g(26.21mmol, 95.79%) 을 얻었다. 10 g (27.36 mmol) of Compound 9-1 was placed in 100 mL of acetic acid, and 2.65 mL (30.09 mmol, 35%) of H 2 O 2 was slowly added thereto. After stirring for 12 hours at room temperature, acetic acid was distilled under reduced pressure. Extracted with dichloromethane and neutralized with NaHCO 3 aqueous solution. It was dried over magnesium sulfate and distilled under reduced pressure. 10g (26.21 mmol, 95.79%) of Compound 9-2 was obtained.

화합물 compound 9-39-3 의 제조Manufacture

화합물 9-2 10g(26.21mmol)을 트리플루오로메탄설포닉산 70mL 와 섞고 100℃로 교반하였다. 5시간 후 상온으로 냉각하고 이것을 피리딘 : 증류수 = 1:5 100mL 에 넣었다. 한 시간 환류 교반하였다. 상온으로 냉각하고 생성된 고체를 감압 여과하였다. 컬럼크로마토그래피로 분리하여 화합물 9-3 6g(17.16mmol, 65.47%) 을 얻었다. 10 g (26.21 mmol) of Compound 9-2 were mixed with 70 mL of trifluoromethanesulphonic acid and stirred at 100 ° C. After 5 hours, the mixture was cooled to room temperature, which was added to pyridine: distilled water = 1: 5 100 mL. It was stirred at reflux for 1 hour. Cooled to room temperature and the resulting solid was filtered under reduced pressure. Separation by column chromatography yielded 6 g (17.16 mmol, 65.47%) of compound 9-3 .

화합물 compound 9-49-4 의 제조Manufacture

화합물 9-3 6g(17.16mmol), NBS 3.36g(18.88mmol) 을 CHCl3 200mL에 녹이고 상온에서 12시간 교반하였다. 감압 증류하고 컬럼크로마토그래피로 분리하여 화합물 9-4 7g(16.34mmol, 95.22%)을 얻었다. 6 g (17.16 mmol) of Compound 9-3 and 3.36 g (18.88 mmol) of NBS were dissolved in 200 mL of CHCl 3 , and the mixture was stirred at room temperature for 12 hours. Distillation under reduced pressure and separation by column chromatography yielded 7 g (16.34 mmol, 95.22%) of compound 9-4 .

화합물 compound 9-59-5 의 제조Manufacture

화합물 9-4 7g(16.34mmol), 아닐린 2.28g(24.51mmol), Pd(OAc)2 0.14g(0.65mmol), P(t-bu)3 0.80mL(1.63mmol, 50% in xylene), Cs2CO3 13.31g(40.85mmol), 톨루엔 100mL 을 섞고 환류 교반하였다. 12시간 후 상온으로 냉각하고 EA로 추출하고 증류수로 씻어 주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하여 화합물 9-5 5g(11.34mmol, 69.40%)을 얻었다.Compound 9-4 7 g (16.34 mmol), aniline 2.28 g (24.51 mmol), Pd (OAc) 2 0.14 g (0.65 mmol), P (t-bu) 3 0.80 mL (1.63 mmol, 50% in xylene), Cs 13.31 g (40.85 mmol) of 2 CO 3 and 100 mL of toluene were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature, extracted with EA, and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Separation by column chromatography afforded 5 g of compound 9-5 (11.34 mmol, 69.40%).

화합물 compound 9-69-6 의 제조Manufacture

4-다이벤조싸이오펜보로닉산 10g(43.84mmol), 4,4'-다이브로모페닐 27.3g(87.69mmol), PdCl2(PPh3)4 0.61g(0.87mmol), 2M Na2CO3 43mL ,톨루엔 300mL 을 섞고 90℃로 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 컬럼크로마토그래피로 분리하여 화합물 9-6 5.6g(13.61mmol, 31.04%) 을 얻었다. 10 g (43.84 mmol) of 4-dibenzothiophenboronic acid, 27.3 g (87.69 mmol) of 4,4'-dibromophenyl, PdCl 2 (PPh 3 ) 4 0.61 g (0.87 mmol), 2M Na 2 CO 3 43 mL Toluene 300mL was mixed and stirred at 90 degreeC for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. Drying with magnesium sulfate and separation by column chromatography yielded 5.6 g (13.61 mmol, 31.04%) of compound 9-6 .

화합물 compound 3636 의 제조Manufacture

화합물 9-5 5g(11.34mmol), 화합물 9-6 5.6g(13.61mmol), Pd(OAc)2 0.10g(0.45mmol), P(t-bu)3 0.56mL(1.13mmol, 50% in xylene), NaOt-bu 2.7g(28.37mmol), 톨루엔 100mL 을 섞고 5시간 교반하였다. 상온으로 냉각하고 EA로 추출하고 증류수로 씻어주었다. 황산마그네슘으로 건조하고 감압 증류하였다. 컬럼크로마토그래피로 분리하고 EA로 재결정하여 화합물 36 3.6g(4.64mmol, 40.96%)을 얻었다. 5 g (11.34 mmol) of compound 9-5, 5.6 g (13.61 mmol) of compound 9-6 , 0.10 g (0.45 mmol) of Pd (OAc) 2 , 0.56 mL (1.13 mmol, 50% in xylene) P (t-bu) 3 ), NaOt-bu 2.7 g (28.37 mmol) and toluene 100 mL were mixed and stirred for 5 hours. Cooled to room temperature, extracted with EA and washed with distilled water. It was dried over magnesium sulfate and distilled under reduced pressure. Isolation by column chromatography and recrystallization with EA yielded 3.6 g (4.64 mmol, 40.96%) of compound 36 .

1H NMR(CDCl3, 200 MHz)δ = 5.93(1H, m), 6.63(2H, m), 6.69(2H, m), 6.81(1H, m), 7.2~7.25(6H, m), 7.45~7.63(14H, m), 7.69(1H, m), 7.98(2H, m), 8.05(1H, m), 8.2(1H, m), 8.41~8.45(3H, m) ; MS/FAB found 775, calculated 774.991 H NMR (CDCl3, 200 MHz) δ = 5.93 (1H, m), 6.63 (2H, m), 6.69 (2H, m), 6.81 (1H, m), 7.2-7.45 (6H, m), 7.45-7.63 (14H, m), 7.69 (1H, m), 7.98 (2H, m), 8.05 (1H, m), 8.2 (1H, m), 8.41-8.45 (3H, m); MS / FAB found 775, calculated 774.99

[제조예 10]화합물 48의 제조Preparation Example 10 Preparation of Compound 48

Figure pat00053
Figure pat00053

화합물 compound 10-110-1 의 제조Manufacture

1L 2구-RBF 에 화합물 2-5 7.7g (0.015mol)을 넣고 1-브로모-4-아이오도벤젠 6.6g(0.023mol), Pd(oAc)2 175mg(0.7mmol), P(t-Bu)3 508mg(1.56mmol), Naot-Bu 4.5g(0.046mol)넣고 진공 건조 시킨 뒤 질소가스를 채운다. 톨루엔 200mL를 첨가한 후 120℃로 가열시킨다. 12시간 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로 정제하여 화합물 10-1 6.2g (62%)를 얻었다.7.7g (0.015mol) of compound 2-5 was added to 1L 2-neck-RBF, and 6.6g (0.023mol) of 1-bromo-4-iodobenzene, 175mg (0.7mmol) of Pd (oAc) 2, P (t- Bu) 3 508mg (1.56mmol) and Naot-Bu 4.5g (0.046mol) are put in vacuum and filled with nitrogen gas. 200 mL of toluene is added and then heated to 120 ° C. Stir for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, dried over MgSO 4 , dried over MgSO 4 , solvent was removed by rotary evaporation, and purified by column chromatography to obtain 6.2 g (62%) of Compound 10-1 .

화합물 compound 10-210-2 의 제조Manufacture

500 mL RBF에 화합물 10-1 6.8g (0.010mol)을 넣고 진공 건조 시킨 뒤 질소가스를 채운다. THF 100mL를 첨가한 후 -78℃로 냉각시킨다. n-BuLi(2,5M) 6.2mL (0.015mol)을 천천히 첨가한 뒤 1시간 동안 저온을 유지하며 교반한다. -78℃에서 B(OMe)3 1.7mL (0.015mmol)을 첨가한 뒤 12시간 교반한다. 반응이 종결되면1M HCl을 첨가한 뒤10분 뒤 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로 정제하여 화합물 10-2 4.3g (67%)를 얻었다. 6.8 g (0.010 mol) of Compound 10-1 was added to 500 mL RBF, followed by vacuum drying. 100 mL of THF is added and then cooled to -78 ° C. 6.2 mL (0.015 mol) of n-BuLi (2,5M) is slowly added, followed by stirring at low temperature for 1 hour. 1.7 mL (0.015 mmol) of B (OMe) 3 was added at -78 ° C, followed by stirring for 12 hours. After the reaction was completed 10 minutes later, washed with 1M HCl was added to distilled water after purifying the organic layer was back extracted with EA by column chromatography after removal of solvent on a rotary evaporator then dried with MgSO 4 and compound 10-2 4.3g (67 %) Was obtained.

화합물compound 48 48 의 제조Manufacture

100mL 2구-RBF 에 화합물 10-2 4.4g(7.0mmol)을 넣고 4-브로모다이벤조[b,d]싸이오펜 5.2g(8.0mmol), Pd(PPh3)4 395mg(0.3mmol), K2CO3(2M) 10mL, EtOH 10mL,넣고, 톨루엔 20mL를 첨가한 후 120℃로 가열시킨다. 4시간 교반한다. 반응이 끝나면 증류수로 씻어주고 EA로 추출한 뒤 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거한 후 컬럼크로마토그래피로로 정제하여 화합물 48 2.9g (54%)를 얻었다.4.4 g (7.0 mmol) of Compound 10-2 was added to 100 mL 2-neck-RBF, and 5.2 g (8.0 mmol) of 4- bromodibenzo [b, d] thiophene, Pd (PPh 3 ) 4 395 mg (0.3 mmol), K 10 mL of 2 CO 3 (2M) and 10 mL of EtOH are added thereto, and 20 mL of toluene is added thereto, followed by heating to 120 ° C. Stir for 4 hours. After the reaction was washed with distilled water, extracted with EA, the organic layer was dried with MgSO 4 and the solvent was removed by rotary evaporation to purified by column chromatography to give the compound 48 2.9g (54%).

1H NMR(CDCl3, 200 MHz)δ = 5.93(1H, m), 6.69(4H, m), 7.33(1H, m), 7.41(1H, m), 7.45~7.52(19H, m), 7.69(1H, m), 7.82(1H, m), 7.94~7.98(3H, m), 8.05(1H, m), 8.45(2H, m) ; MS/FAB found 775, calculated 774.99
1 H NMR (CDCl 3, 200 MHz) δ = 5.93 (1H, m), 6.69 (4H, m), 7.33 (1H, m), 7.41 (1H, m), 7.45-7.52 (19H, m), 7.69 (1H , m), 7.82 (1H, m), 7.94-7.98 (3H, m), 8.05 (1H, m), 8.45 (2H, m); MS / FAB found 775, calculated 774.99

[실시예 1] 본 발명에 따른 유기 발광 화합물을 이용한 OLED 소자 제작Example 1 Fabrication of an OLED Device Using an Organic Light Emitting Compound According to the Present Invention

본 발명의 발광 재료를 이용한 구조의 OLED 소자를 제작하였다. 우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막(15 Ω/□)을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. 다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 2-TNATA[4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine]을 넣고, 챔버 내의 진공도가 10-6 torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 60 nm 두께의 정공주입층을 증착하였다. 이어서, 진공 증착 장비 내의 다른 셀에 본 발명에 따른 화합물 4을 넣고, 셀에 전류를 인가하여 화합물 1을 증발시켜 정공주입층 위에 20 nm 두께의 정공전달층을 증착하였다. 정공주입층, 정공전달층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 호스트로서 CBP[4,4'-N,N'-dicarbazole-biphenyl]을 넣고, 또 다른 셀에는 도판트로서 (piq)2Ir(acac)[bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]를 각각 넣은 후, 두 물질을 다른 속도로 증발시켜 4 내지 10%중량으로 도핑 함으로서 상기 정공 전달층 위에 30 nm 두께의 발광층을 증착하였다. 이어서 상기 발광층 위에 정공차단층으로 비스(2-메틸-8-퀴놀리네이토)(p-페닐페놀레이토)알루미늄(III) (BAlq)을 10nm의 두께로 증착시키고, 이어서 전자전달층으로써 Alq[tris(8-hydroxyquinoline)-An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15? It was used after. Next, the ITO substrate is installed in the substrate folder of the vacuum deposition equipment, and 2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine] is installed in the cell in the vacuum deposition equipment. And evacuated until the vacuum in the chamber reached 10 −6 torr, followed by applying a current to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate. Compounds according to the invention in other cells in deposition equipment 4 was added, a current was applied to the cell, and compound 1 was evaporated to deposit a 20 nm thick hole transport layer on the hole injection layer. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. CBP [4,4'-N, N'-dicarbazole-biphenyl] is added as a host to one cell in the vacuum deposition equipment and (piq) 2 Ir (acac) [bis- (1-phenylisoquinolyl) as a dopant in another cell. ) iridium (III) acetylacetonate] was added, and the light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by evaporating the two materials at different rates and doping at 4 to 10% by weight. Subsequently, bis (2-methyl-8-quinolinate) ( p -phenylphenolrato) aluminum (III) (BAlq) was deposited to a thickness of 10 nm on the light emitting layer with a hole blocking layer, followed by Alq [ tris (8-hydroxyquinoline)-

aluminum(III)]를 20 nm 두께로 증착하였다. 다음으로 전자전달층으로써 Alq[tris(8-hydroxyquinoline)-aluminum(III)] 를 20 nm 두께로 증착한 다음, 전자주입층으로 Liq[lithium quinolate]를 1 내지 2 nm 두께로 증착한 후, 다른 진공 증착 장비를 이용하여 Al 음극을 150 nm의 두께로 증착하여 OLED소자를 제작하였다. aluminum (III)] was deposited to a thickness of 20 nm. Next, Alq [tris (8-hydroxyquinoline) -aluminum (III)] was deposited to a thickness of 20 nm as an electron transport layer, and then Liq [lithium quinolate] was deposited to a thickness of 1 to 2 nm using an electron injection layer. An OLED was fabricated by depositing an Al cathode to a thickness of 150 nm using a vacuum deposition equipment.

재료 별로 각 화합물은 10-6 torr 하에서 진공 승화 정제하여 OLED 발광재료로 사용하였다.Each compound was vacuum sublimated and purified under 10 -6 torr to be used as an OLED light emitting material.

그 결과, 7.0 V의 전압에서 16.1 mA/cm2의 전류가 흘렀으며, 1200 cd/m2의 적색발광이 확인되었다.As a result, a current of 16.1 mA / cm 2 flowed at a voltage of 7.0 V, and red light emission of 1200 cd / m 2 was confirmed.

[실시예 2] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 2 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

정공수송 재료로서 본 발명의 화합물 13을 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 1, except that Compound 13 of the present invention was used as a hole transport material.

그 결과, 7.3 V의 전압에서 17.1 mA/cm2의 전류가 흘렀으며, 1260 cd/m2의 적색발광이 확인되었다.As a result, a current of 17.1 mA / cm 2 flowed at a voltage of 7.3 V, and red light emission of 1260 cd / m 2 was confirmed.

[실시예 3] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 3 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

정공수송 재료로서 본 발명의 화합물 30을 이용하고, 발광층에서 발광 도판트로서 유기 이리듐 착물 Ir(ppy)3[tris(2-phenylpyridine)iridium]을 이용한 것 외에는, 실시예 1과 동일한 방법으로 OLED소자를 제작하였다.OLED device in the same manner as in Example 1, except that Compound 30 of the present invention was used as a hole transport material, and an organic iridium complex Ir (ppy) 3 [tris (2-phenylpyridine) iridium] was used as a light emitting dopant in the light emitting layer. Was produced.

그 결과, 7.1 V의 전압에서 3.2 mA/cm2의 전류가 흘렀으며, 1015 cd/m2의 녹색발광이 확인되었다.As a result, a current of 3.2 mA / cm 2 flowed at a voltage of 7.1 V, and green light emission of 1015 cd / m 2 was confirmed.

[실시예 4] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 4 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

정공수송 재료로서 본 발명의 화합물 37을 이용한 것 외에는, 실시예 3과 동일한 방법으로 OLED소자를 제작하였다.An OLED device was manufactured in the same manner as in Example 3, except that Compound 37 of the present invention was used as the hole transport material.

그 결과, 7.0 V의 전압에서 3.9 mA/cm2의 전류가 흘렀으며, 1115 cd/m2의 녹색발광이 확인되었다.As a result, a current of 3.9 mA / cm 2 flowed at a voltage of 7.0 V, and green light emission of 1115 cd / m 2 was confirmed.

[실시예 5] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 5 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

정공주입 재료로서 2-TNATA[4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) as hole injection material

triphenylamine] 대신 본 발명의 화합물 25을 이용한 것 외에는 실시예 1과 동일한 방법으로 OLED소자를 제작하였다. triphenylamine] was manufactured in the same manner as in Example 1 except that Compound 25 of the present invention was used.

그 결과, 7.2 V의 전압에서 15.9 mA/cm2의 전류가 흘렀으며, 1095 cd/m2의 적색발광이 확인되었다.As a result, a current of 15.9 mA / cm 2 flowed at a voltage of 7.2 V, and red light emission of 1095 cd / m 2 was confirmed.

[실시예 6] 본 발명에 따른 유기발광화합물을 이용한 OLED 소자 제작Example 6 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

정공주입 재료로서 2-TNATA[4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) as hole injection material

triphenylamine] 대신 본 발명의 화합물 42을 이용한 것 외에는 실시예 3과 동일한 방법으로 OLED소자를 제작하였다. triphenylamine] was manufactured in the same manner as in Example 3, except that Compound 42 of the present invention was used.

그 결과, 6.6 V의 전압에서 3.0 mA/cm2의 전류가 흘렀으며, 990 cd/m2의 녹색발광이 확인되었다.As a result, a current of 3.0 mA / cm 2 flowed at a voltage of 6.6 V, and green light emission of 990 cd / m 2 was confirmed.

[비교예 1] 종래의 발광 재료를 이용한 OLED 소자의 발광 특성[Comparative Example 1] Light emission characteristics of OLED device using conventional light emitting material

진공 증착 장비 내의 한쪽 셀에 정공수송재료로서 본 발명의 화합물 대신 NPB[N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine]을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 OLED소자를 제작하였다.Except for using NPB [N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine] as a hole transporting material in one cell in the vacuum deposition equipment An OLED device was manufactured in the same manner as in Example 1 .

그 결과, 7.5 V의 전압에서 15.3 mA/cm2의 전류가 흘렀으며, 1000 cd/m2의 적색발광이 확인되었다.As a result, a current of 15.3 mA / cm 2 flowed at a voltage of 7.5 V, and red light emission of 1000 cd / m 2 was confirmed.

[비교예 2] 종래의 발광 재료를 이용한 OLED 소자의 발광 특성Comparative Example 2 Light Emitting Characteristics of OLED Devices Using Conventional Light-Emitting Materials

진공 증착 장비 내의 한쪽 셀에 정공수송재료로서 본 발명의 화합물 대신 NPB[N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine]을 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 OLED소자를 제작하였다. , Except that the - [ 'N, N -bis ( α-naphthyl)'-diphenyl-4,4'-diamine N, N] to the one cell of the vacuum vapor-deposit device as a hole-transporting material NPB instead of the compound of the invention An OLED device was manufactured in the same manner as in Example 3 .

그 결과, 7.5 V의 전압에서 3.8 mA/cm2의 전류가 흘렀으며, 1000 cd/m2의 녹색발광이 확인되었다.
As a result, a current of 3.8 mA / cm 2 flowed at a voltage of 7.5 V, and green light emission of 1000 cd / m 2 was confirmed.

본 발명에서 개발한 유기 발광 화합물들은 발광 특성이 종래의 재료 대비 우수한 특성을 보이는 것을 확인할 수 있었다. 또한 본 발명에 따른 유기 발광 화합물을 정공수송재료 또는 정공주입재료로 사용한 유기발광소자는 가장 낮은 비점유된 분자궤도함수(LUMO ; Lowest Unoccupied Molecular Orbital)를 올리고, 삼중항(triplet)을 크게 하여 발광층에 존재하는 삼중항 여기자들을 발광층에 잘 머물도록 효과적으로 블로킹(blocking)를 크게 함으로써 특히 인광에서의 발광효율이 좋고, 재료의 수명특성이 뛰어나 소자의 구명수명이 매우 우수한 OLED 소자를 제조할수 있는 장점이 있다.The organic light emitting compounds developed in the present invention was confirmed that the light emitting properties are superior to the conventional material. In addition, the organic light emitting device using the organic light emitting compound according to the present invention as a hole transporting material or a hole injection material has the lowest unoccupied molecular orbital function (LUMO; Lowest Unoccupied Molecular Orbital), the triplet (triplet) to increase the light emitting layer By effectively blocking the triplet excitons present in the light emitting layer to effectively block the light emitting layer, the light emitting efficiency is excellent in phosphorescence, and the lifespan characteristics of the material are excellent. have.

Claims (10)

하기 화학식 1로 표시되는 유기 발광 화합물.
[화학식 1]
Figure pat00054

[상기 화학식 1에서,
Y1는 -O-, -S-, -C(R11R12)- 또는 -Si(R13R14)-이며;
Y2는 -O-, -S-, -C(R11R12)-, -Si(R13R14)- 또는 -N(R15)이고;
A고리 및 C고리는 각각 독립적으로
Figure pat00055
이며;
B고리는
Figure pat00056
이고;
Y3 및 Y4는 각각 독립적으로 CH 또는 N이고;
Y5 및 Y6는 각각 독립적으로 화학결합, -O-, -S-, -C(R11R12)-, -Si(R13R14)- 또는 -N(R15)-이고, 단 Y5 및 Y6가 동시에 화학결합인 경우는 제외하며;
R1 내지 R4는 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 (C3-C30)시클로알킬, 치환 또는 비치환된 (C1-C30)알킬실릴기, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C6-C30)아르(C1-C30)알킬, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 5원 내지 7원의 헤테로시클로알킬이거나 치환 또는 비치환된 방향족 고리가 하나 이상 융합된 (C3-C30)시클로알킬, -N(R16R17), -Si(R18R19R20), -SR21, -OR22 , 시아노, 나이트로 또는 하이드록시이고, R1 내지 R4가 복수인 경우 서로 결합하여 환상 구조를 형성할 수도 있으며;
L1 및 L2는 각각 독립적으로 화학결합, 치환 또는 비치환된 (C6-C30)아릴렌, 치환 또는 비치환된 (C3-C30)헤테로아릴렌이거나 치환 또는 비치환된 (C3-C30)시클로알킬렌이고, 인접한 L1 및 L2는 서로 결합하여 환상 구조를 형성할 수 있으며, 단 L1 및 L2가 동시에 화학결합인 경우는 제외하며;
Ar은 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 시클로알킬이 하나 이상 융합된 치환 또는 비치환된 (C6-C30)아릴이고;
R11 내지 R22는 각각 독립적으로 수소, 중수소, 할로겐, 치환 또는 비치환된 (C1-C30)알킬, 치환 또는 비치환된 (C6-C30)아릴, 치환 또는 비치환된 (C3-C30)헤테로아릴, 치환 또는 비치환된 5원 내지 7원의 헤테로시클로알킬, 치환 또는 비치환된 (C3-C30)시클로알킬이거나 인접한 치환체와 융합고리를 포함하거나 포함하지 않는 치환 또는 비치환된 (C3-C30)알킬렌 또는 치환 또는 비치환된 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있으며, 상기 형성된 지환족 고리 및 단일환 또는 다환의 방향족 고리의 탄소 원자는 질소, 산소 및 황으로부터 선택되는 하나 이상의 헤테로원자로 치환될 수 있고;
l, m, n 및 p는 각각 독립적으로 0 내지 4의 정수이고, l, m, n 또는 p가 2 이상의 정수인 경우 각각의 R1, R2, R3 및 R4은 서로 동일하거나 상이할 수 있고, 인접한 치환기들이 서로 결합하여 고리를 형성할 수 있으며;
상기 헤테로시클로알킬 및 헤테로아릴은 B, N, O, S, P(=O), Si 및 P로부터 선택된 하나 이상의 헤테로원자를 포함한다.]An organic light emitting compound represented by Formula 1 below.
[Formula 1]
Figure pat00054

[In the above formula (1)
Y 1 is —O—, —S—, —C (R 11 R 12 ) — or —Si (R 13 R 14 ) —;
Y 2 is —O—, —S—, —C (R 11 R 12 ) —, —Si (R 13 R 14 ) — or —N (R 15 );
Ring A and Ring C are each independently
Figure pat00055
Is;
B ring
Figure pat00056
ego;
Y 3 and Y 4 are each independently CH or N;
Y 5 and Y 6 are each independently a chemical bond, —O—, —S—, —C (R 11 R 12 ) —, —Si (R 13 R 14 ) — or —N (R 15 ) — Unless Y 5 and Y 6 are chemical bonds at the same time;
R 1 to R 4 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C1-C30) alkylsilyl group, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted ( C6-C30) Ar (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, fused with one or more cycloalkyl, 5- to 7-membered hetero, fused with one or more substituted or unsubstituted aromatic rings (C3-C30) cycloalkyl which is cycloalkyl or has one or more substituted or unsubstituted aromatic rings, -N (R 16 R 17 ), -Si (R 18 R 19 R 20 ), -SR 21 , -OR 22 , Cyano, nitro or hydroxy, and when there are a plurality of R 1 to R 4 , may combine with each other to form a cyclic structure;
L 1 and L 2 are each independently a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene or a substituted or unsubstituted (C3-C30) cyclo Alkylene, adjacent L 1 and L 2 may be bonded to each other to form a cyclic structure, except that L 1 and L 2 are at the same time a chemical bond;
Ar is substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted (C6-C30) aryl in which at least one cycloalkyl is fused;
R 11 to R 22 are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;
l, m, n and p are each independently integers of 0 to 4, and when l, m, n or p is an integer of 2 or more, each of R 1 , R 2 , R 3 and R 4 may be the same or different from each other. Adjacent substituents may combine with each other to form a ring;
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.] 제 1항에 있어서,
상기 R1 내지 R4, R11 내지 R22, L1, L2 및 Ar에 더 치환되는 치환기는 서로 독립적으로 중수소, 할로겐, 할로겐이 치환 또는 비치환된 (C1-C30)알킬, (C6-C30)아릴, (C6-C30)아릴이 치환 또는 비치환된 (C3-C30)헤테로아릴, 5원 내지 7원의 헤테로시클로알킬, 방향족고리가 하나이상 융합된 5원 내지 7원의 헤테로시클로알킬, (C3-C30)시클로알킬, 방향족고리가 하나이상 융합된 (C6-C30)시클로알킬, R31R32R33Si-, (C2-C30)알케닐, (C2-C30)알키닐, 시아노, 카바졸릴, -NR34R35, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, R36S-, R37O-, 나이트로 또는 하이드록시로 이루어진 군으로부터 선택되는 하나 이상이고, R31 내지 R37은 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴, (C3-C30)헤테로아릴, 또는 (C3-C30)시클로알킬인 것을 특징으로 하는 유기 발광 화합물.The method of claim 1,
Substituents further substituted with R 1 to R 4 , R 11 to R 22 , L 1 , L 2, and Ar independently of each other, deuterium, halogen, (C1-C30) alkyl substituted or unsubstituted, (C6- C30) aryl, (C6-C30) aryl substituted or unsubstituted (C3-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings , (C3-C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, R 31 R 32 R 33 Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cya No, carbazolyl, -NR 34 R 35 , (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R 36 S-, R 37 O-, nitro or At least one selected from the group consisting of hydroxy, and R 31 to R 37 independently of one another are (C 1 -C 30) alkyl, (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, or (C 3 -C 30) cyclo An organic light emitting compound, characterized in that alkyl. 제 1항에 있어서,
상기 화학식 1의
Figure pat00057
은 하기 구조에서 선택되는 것을 특징으로 하는 유기 발광 화합물.
Figure pat00058

Figure pat00059

Figure pat00060

Figure pat00061

Figure pat00062

Figure pat00063

Figure pat00064

Figure pat00065

Figure pat00066

Figure pat00067

Figure pat00068

Figure pat00069

[R3, R4, R11 내지 R15, l 및 p은 상기 화학식 1에서의 정의와 동일하다.]The method of claim 1,
Of Formula 1
Figure pat00057
Is an organic light emitting compound, characterized in that selected from the following structure.
Figure pat00058

Figure pat00059

Figure pat00060

Figure pat00061

Figure pat00062

Figure pat00063

Figure pat00064

Figure pat00065

Figure pat00066

Figure pat00067

Figure pat00068

Figure pat00069

[R 3 , R 4 , R 11 to R 15 , l and p are the same as defined in Formula 1 above.] 제 1항에 있어서,
하기 화합물로부터 선택되는 것을 특징으로 하는 유기 발광 화합물.
Figure pat00070

Figure pat00071

Figure pat00072

Figure pat00073

Figure pat00074

Figure pat00075

Figure pat00076

Figure pat00077

Figure pat00078

Figure pat00079

Figure pat00080

Figure pat00081

Figure pat00082

Figure pat00083
The method of claim 1,
An organic light emitting compound, which is selected from the following compounds.
Figure pat00070

Figure pat00071

Figure pat00072

Figure pat00073

Figure pat00074

Figure pat00075

Figure pat00076

Figure pat00077

Figure pat00078

Figure pat00079

Figure pat00080

Figure pat00081

Figure pat00082

Figure pat00083
 제 1항 내지 제 4항에서 선택되는 어느 한 항에 따른 유기 발광 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자. An organic electroluminescent device comprising the organic light emitting compound according to any one of claims 1 to 4. 제 5항에 있어서,
상기 유기 발광 화합물은 정공주입 또는 정공수송재료로 사용되는 것을 특징으로 하는 유기 전계 발광 소자.6. The method of claim 5,
The organic light emitting device is an organic electroluminescent device, characterized in that used as a hole injection or hole transport material. 제 6항에 있어서,
상기 유기 전계 발광 소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층으로 이루어져 있으며, 상기 유기물층은 상기 화학식 1의 유기 발광 화합물을 하나 이상 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 6,
The organic electroluminescent device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer comprises at least one organic light emitting compound of Chemical Formula 1. 제 7항에 있어서,
상기 유기물층에 1족, 2족, 4주기, 5주기 전이금속, 란탄계열금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 하나 이상의 금속 또는 착체화합물을 더 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 7, wherein
An organic electric field further comprising at least one metal or a complex compound selected from the group consisting of Group 1, Group 2, 4, 5 cycle transition metals, lanthanum series metals and organic metals of d-transition elements in the organic layer. Light emitting element. 제 7항에 있어서,
상기 유기물층은 발광층 및 전하생성층을 동시에 포함하는 것을 특징으로 하는 유기 전계 발광 소자.The method of claim 7, wherein
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer at the same time. 제 7항에 있어서,
상기 유기물층에 적색, 녹색 또는 청색 발광을 하는 유기발광층 하나 이상을 더 포함하여 백색 발광을 하는 유기 전계 발광 소자.The method of claim 7, wherein
An organic electroluminescent device for emitting white light, further comprising at least one organic light emitting layer emitting red, green, or blue light to the organic material layer.
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