KR20110079401A - Organic light emitting device and organic light emitting compound for the same - Google Patents

Organic light emitting device and organic light emitting compound for the same Download PDF

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KR20110079401A
KR20110079401A KR1020100002430A KR20100002430A KR20110079401A KR 20110079401 A KR20110079401 A KR 20110079401A KR 1020100002430 A KR1020100002430 A KR 1020100002430A KR 20100002430 A KR20100002430 A KR 20100002430A KR 20110079401 A KR20110079401 A KR 20110079401A
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compound
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KR101247956B1 (en
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김복영
안중복
강지승
이재성
진성민
안도환
박노길
한근희
시상만
이대균
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(주)씨에스엘쏠라
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

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Abstract

PURPOSE: An organic light emitting device and an organic light emitting compound for the same are provided to ensure excellent luminous efficiency, luminous brightness, color purity and luminous lifetime. CONSTITUTION: An organic light emitting device comprises a first electrode, a second electrode and at least monolayered organic film between the first electrode and the second electrode. The organic film includes an organic light emitting compound of chemical formula (a). In chemical formula (a), A1, A2, A3, A4, A5 and A6 are independently hydrogen, substituted or unsubstituted C6-C50 aryl group, substituted or unsubstituted C2-C50 heteroaryl group, substituted or unsubstituted C2-C50 cycloalkyl group, or substituted or unsubstituted C2-C50 heterocycloalkyl group.

Description

유기 발광 소자 및 이를 위한 유기 발광 화합물{ORGANIC LIGHT EMITTING DEVICE AND ORGANIC LIGHT EMITTING COMPOUND FOR THE SAME}Organic light emitting device and organic light emitting compound therefor {ORGANIC LIGHT EMITTING DEVICE AND ORGANIC LIGHT EMITTING COMPOUND FOR THE SAME}

본 발명은 유기 발광 소자 및 이에 사용되는 유기 발광 화합물에 관한 것으로서, 보다 상세하게는 우수한 발광효율, 발광 휘도, 색순도 및 발광 수명을 구현할 수 있는 유기 발광 소자와 이에 사용되는 유기 발광 화합물에 관한 것이다.
The present invention relates to an organic light emitting device and an organic light emitting compound used therein. More particularly, the present invention relates to an organic light emitting device capable of realizing excellent luminous efficiency, light emitting brightness, color purity, and light emitting lifetime, and an organic light emitting compound used therein.

정보화시대로 급속히 진입하면서 전자 정보 기기와 인간의 인터페이스 역할을 하는 디스플레이(Display)의 중요성이 더욱 커지고 있다. 특히 언제 어디서나 편리하게 사용할 수 있고, 현장감 있게 생생한 화면을 보여 줄 수 있는 디스플레이를 개발하기 위한 노력이 절실히 필요하게 되었다. 더 나아가서 디스플레이를 유리 기판 대신에 플라스틱과 같은 유연한 기판 위에 제작하여 더 얇고, 더 가볍고, 깨지지 않는 플렉서블 디스플레이(flexible display)를 개발하는 연구가 활발하게 진행되고 있다. 유기발광다이오드(OLED) 디스플레이는 이와 같은 응용에 가장 적합한 차세대 평판디스플레이 기술로 큰 주목을 받고 있다.As the information age rapidly enters, the importance of a display, which serves as an interface between the electronic information device and the human being, is increasing. In particular, there is an urgent need to develop a display that can be conveniently used anytime and anywhere, and provides a vivid screen with a sense of reality. Further research is being conducted to develop thinner, lighter, unbreakable flexible displays by fabricating displays on flexible substrates such as plastic instead of glass substrates. Organic light emitting diode (OLED) displays are attracting great attention as next generation flat panel display technologies that are best suited for such applications.

유기반도체에서의 전기발광 현상은 1963년 Pope, Kallmann, Magnate에 의해 안트라센 결정에서 처음으로 발견되었고[M. Pope, H. P. Kallmamm and P. Magnae, J. Chem. Phys. 38, 2042 (1963)], 이어서 1965년에 W. Helfrich [W. Helfrich and W. G. Schneider, Phys. Rev. Lett. 14, 229(1965)] 등의 연구가 이어졌다. 그런데 고순도의 안트라센 결정은 전기전도도가 10-20 s/cm 이하의 절연체이므로 수백볼트 이상의 높은 전압을 가해야 전자와 정공이 주입되고 발광효율이 아주 낮았다. 그리고 반응성이 높은 알칼리 금속을 전극으로 사용한 실용적인 측면에서는 큰 문제가 있었다. 이후 1982년에 Vincett 등은 진공 증착 방법으로 비결정질의 안트라센 박막을 형성하고 유기 발광다이오드를 제작하는데 성공하였다. 이 소자의 발광효율은 약 0.05% 수준으로 아주 낮았으나, 이 방법은 현재까지 대표적인 OLED 제작 방법으로 사용되고 있다.
Electroluminescence in organic semiconductors was first discovered in anthracene crystals in 1963 by Pope, Kallmann and Magnate [M. Pope, HP Kallmamm and P. Magnae, J. Chem. Phys. 38 , 2042 (1963), followed by W. Helfrich [W. Helfrich and WG Schneider, Phys. Rev. Lett. 14 , 229 (1965)]. However, the high purity anthracene crystal is an insulator with an electric conductivity of 10 -20 s / cm or less. Therefore, electrons and holes are injected and light emission efficiency is very low when a high voltage of several hundred volts is applied. In addition, there was a big problem in terms of practical use of highly reactive alkali metals as electrodes. Since 1982, Vincett et al. Succeeded in forming an amorphous anthracene thin film and fabricating an organic light emitting diode by vacuum deposition. The luminous efficiency of this device was very low at about 0.05%, but this method has been used as a typical OLED manufacturing method to date.

1987년 Kodak사의 Tang등이 발광층과 전하 수송층으로 각각 Alq3 와 TPD라는 이중 층 저분자 유기물 박막을 형성하여 효율과 안정성이 개선된 녹색의 발광 현상을 발견한 이후로 저분자 OLED 디스플레이의 개발이 급속도로 빠르게 이루어졌다. 이러한 소자 구조에서는 정공 수송 물질과 전자 수송 물질의 전자 에너지 준위의 차이에 의해 전자와 정공이 diamine/Alq3 계면에 축척되어 전자-정공의 재결함 확률이 높아진다. 그 결과 이 소자는 10V 이하의 구동 전압에서 1000 cd/m2 이상의 휘도와 1.5 lm/W 수준의 높은 발광 효율을 나타냈다. 이 결과는 유기박막 발광다이오드를 이용하여 고휘도, 고효율 디스플레이를 개발할 수 있는 가능성을 제시하기 때문에 큰 주목을 끌어서 전 세계적으로 OLED 연구를 활성화하는데 큰 역할을 했다.
In 1987 the light-emitting layer and a charge transport layer, such as Kodak's Tang each Alq 3 The development of low molecular OLED displays has been rapid since the formation of green light emitting phenomena with improved efficiency and stability by forming a double-layer low molecular organic thin film called and TPD. In this device structure, electrons and holes accumulate at the diamine / Alq 3 interface due to the difference in the electron energy levels of the hole transporting material and the electron transporting material, thereby increasing the probability of electron-hole recombination. As a result, the device showed a luminance of 1000 cd / m 2 or higher and a high luminous efficiency of 1.5 lm / W at a driving voltage of 10V or lower. This result shows the possibility of developing a high-brightness, high-efficiency display using an organic thin-film light emitting diode, so it played a big role in activating OLED research worldwide.

1980년대 후반 저분자 OLED 소자의 구조는 양극(ITO), 정공수송층 (Hole Transfer Layer, HTL) 발광층 (Emission Layer, EML), 음극(Mg:Ag)의 간단한 구조에서 출발하였다. 이후 형광소자의 경우는 CuPc같은 정공주입층(Hole Injedtion Layer, HIL)이 도입되었고, Cathode와 전자주입층 재료로 Al:Li이 개발되고 LiF 같은 재료가 개발되면서 구조가 복잡해지게 되었다. 이에 따라서 전기광학적인 특성도 효율과 구동전압이 혁신적으로 개선이 이루어지게 되었다.
In the late 1980s, the structure of the low molecular OLED device started with a simple structure of an anode (ITO), a hole transfer layer (HTL) emission layer (EML), and a cathode (Mg: Ag). Later, in the case of a fluorescent device, a hole injection layer (HIL) such as CuPc was introduced, and the structure became complicated as Al: Li was developed as a cathode and an electron injection layer material, and a material such as LiF was developed. Accordingly, the efficiency and driving voltage of the electro-optical characteristics have been improved.

발광 소자(light emitting device)는 자발광형 소자로 시야각이 넓으며 콘트라스트가 우수할 뿐만 아니라 응답시간이 빠르다는 장점을 가진다. 상기 발광 소자는 발광층(emitting layer)에 무기 화합물을 사용하는 무기 발광 소자와 유기 화합물을 사용하는 유기 발광 소자(Organic Light Emitting Deveice : OLED)로 구분된다. 유기 발광 소자는 무기 발광 소자에 비하여 높은 휘도, 낮은 구동전압, 짧은 응답속도 등의 물성이 우수하고 다색화가 가능하다는 점에서 많은 연구의 대상이 된다.상기 유기 발광 소자는 일반적으로 애노드/유기 발광층/캐소드의 적층구조를 가지며, 애노드/정공주입층/정공수송층/발광층/전자수송층/전자주입층/캐소드 또는 애노드/정공주입층/정공수송층/발광층/정공저지층/전자수송층/전자주입층/캐소드 등과 같은 다양한 구조를 가질 수 있다.
The light emitting device is a self-luminous device, and has a wide viewing angle, excellent contrast, and fast response time. The light emitting device is classified into an inorganic light emitting device using an inorganic compound and an organic light emitting device (OLED) using an organic compound as an emitting layer. The organic light emitting device is a subject of many studies in that it has excellent physical properties such as high luminance, low driving voltage, short response speed, and the like, and can be multicolored, compared to the inorganic light emitting device. It has a stacked structure of cathode and has anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode or anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode It may have various structures such as.

한편, 발광 효율이 높고 작동 수명이 긴 유기 발광 소자가 구현되기 위해서 고성능의 유기 발광 화합물이 중요시된다.On the other hand, high-performance organic light emitting compounds are important to realize organic light emitting devices having high luminous efficiency and long operating life.

대형화되고 저소비전력이 요구되는 패널을 제조하기 위하여, 상기 유기 발광 화합물들은 발광 효율, 발광 휘도 등이 추가적으로 개선되어야 하며 특히 수명 특성이 개선되어야 한다.
In order to manufacture a panel having a large size and low power consumption, the organic light emitting compounds should further improve luminous efficiency, luminous brightness, and the like, and particularly, life characteristics.

본 발명이 이루고자 하는 첫 번째 기술적 과제는 발광 효율, 발광 휘도, 색순도 및 발광 수명이 향상된 유기 발광 소자를 제공하는 것이다.The first technical problem to be achieved by the present invention is to provide an organic light emitting device having improved luminous efficiency, luminous brightness, color purity and luminous lifetime.

본 발명이 이루고자 하는 두 번째 기술적 과제는 새로운 유기 발광 화합물을 제공하는 것이다.
The second technical problem to be achieved by the present invention is to provide a new organic light emitting compound.

본 발명의 제 1태양에 따른 유기 발광 소자는, 제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 적어도 한 층의 유기막을 포함하는 유기 발광 소자로서, 상기 유기막이 하기 화학식 a의 유기 발광 화합물을 포함한다:The organic light emitting device according to the first aspect of the present invention, the first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode, the organic film comprising an organic light emitting compound of formula a:

<화학식 a><Formula a>

Figure pat00001

Figure pat00001

상기 식에서 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 치환 또는 비치환된 C6-C50아릴기, 치환 또는 비치환된 C2-C50헤테로아릴기, 치환 또는 비치환된 C2-C50사이클로알킬기, 또는 치환 또는 비치환된 C2-C50헤테로사이클로알킬기이다.Wherein A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2- A C50 cycloalkyl group or a substituted or unsubstituted C2-C50 heterocycloalkyl group.

상기 본 발명의 또 다른 과제를 이루기 위하여, 상기 화학식 a로 표시되는 유기 발광 화합물을 제공한다.
In order to achieve another object of the present invention, an organic light emitting compound represented by Chemical Formula a is provided.

본 발명에 따른 유기 발광 소자는 높은 발광 효율, 높은 발광 휘도, 높은 색순도 및 현저히 향상된 발광 수명을 제공한다.
The organic light emitting device according to the present invention provides high luminous efficiency, high luminous brightness, high color purity and significantly improved luminous lifetime.

이하 첨부된 도면을 참고하여 본 발명을 상세히 설명하도록 한다.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings.

본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 구현예(態樣, aspect)(또는 실시예)들을 본문에 상세하게 설명하고자 한다. 그러나 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. The present invention may be modified in various ways and may have various forms, and thus embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

각 도면에서 동일한 참조부호, 특히 십의 자리 및 일의 자리 수, 또는 십의 자리, 일의 자리 및 알파벳이 동일한 참조부호는 동일 또는 유사한 기능을 갖는 부재를 나타내고, 특별한 언급이 없을 경우 도면의 각 참조부호가 지칭하는 부재는 이러한 기준에 준하는 부재로 파악하면 된다.In each of the drawings, the same reference numerals, in particular, the tens and ones digits, or the same digits, tens, ones, and alphabets refer to members having the same or similar functions, and unless otherwise specified, each member in the figures The member referred to by the reference numeral may be regarded as a member conforming to these criteria.

본 명세서에서 사용한 용어는 단지 특정한 구현예(태양, 態樣, aspect)(또는 실시예)를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, ~포함하다~ 또는 ~이루어진다~ 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments (suns, aspects, and embodiments) (or embodiments) only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms “comprises” or “consists” are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof described on the specification, but one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, parts, or combinations thereof.

다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

본 명세서에서 유기 발광 화합물은 유기 발광 소자에 사용되는 화합물이라는 의미로서 반드시 발광이 가능한 화합물로 그 범위가 한정되지 않으며, 그 적용 범위도 유기 발광층에 한정되지 않고, 전하 주입층 및 전하 수송층 등 유기 발광 소자를 구성하는 어느 층에나 모두 사용될 수 있다.In the present specification, the organic light emitting compound is a compound used in an organic light emitting device, and is not necessarily limited to a compound capable of emitting light. All layers may be used in any layer constituting the device.

본 발명의 제 1태양에 따르는 유기 발광 소자는, 제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 적어도 한 층의 유기막을 포함하는 유기 발광 소자로서, 상기 유기막이 하기 화학식 a의 유기 발광 화합물을 포함한다:An organic light emitting device according to the first aspect of the present invention, the first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode, the organic film comprising an organic light emitting compound of formula a:

<화학식 a><Formula a>

Figure pat00002

Figure pat00002

상기 anthra[2,3-b]benzo[d]thiophene계 유도체에 대한 화학식에서 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 치환 또는 비치환된 C6-C50아릴기, 치환 또는 비치환된 C2-C50헤테로아릴기, 치환 또는 비치환된 C2-C50사이클로알킬기, 또는 치환 또는 비치환된 C2-C50헤테로사이클로알킬기이다.
In the chemical formulas for the anthra [2,3-b] benzo [d] thiophene derivatives, A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, and a substituent. Or an unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2-C50 cycloalkyl group, or a substituted or unsubstituted C2-C50 heterocycloalkyl group.

본 발명의 발명자는 상기 화학식 a로 표시되는 화합물의 치환기에서 A1, A2, A3, A4, A5 및 A6를 선택 특정한, 다양한 anthra[2,3-b]benzo[d]thiophene계 유도체를 개발하여 전자수송층(ETL)이나 발광층(EML) 등, 제1전극과 상기 제2전극 사이의 각종 유기막으로 사용될 수 있는 유기 발광 화합물 및 이를 이용한 유기 발광 소자를 개발하고, 효율 증가와 구동 전압의 감소와 같은 성능의 개선 및 OLED 재료로서의 능력을 극대화시킬 수 있고, 특히 발광 수명이 현저히 향상됨을 발견하고 본 발명을 완성하였다.
The inventor of the present invention selects A1, A2, A3, A4, A5 and A6 from the substituents of the compound represented by the above formula (A), and develops various anthra [2,3-b] benzo [d] thiophene derivatives. Developing an organic light emitting compound that can be used as various organic films between the first electrode and the second electrode, such as a transport layer (ETL) or a light emitting layer (EML), and an organic light emitting device using the same, such as increasing the efficiency and reducing the driving voltage The present invention has been found to be able to maximize the performance and to maximize the ability as an OLED material, and in particular to significantly improve the light emission lifetime.

상기 화학식 a로 표시되는 화합물은 유기 발광 소자 중 제1전극과 제2전극 사이에 개재된 유기막을 이루는 물질로 적합하다. 상기 화학식 a로 표시되는 화합물은 유기 발광 소자의 유기막, 특히 발광층 또는 전자수송층에 사용되기 적합하며 호스트 재료뿐만 아니라 도판트 재료로서도 사용된다. 상기 화학식 a로 표시되는 화합물은 청색 내지 녹색인 색상을 제공하며 백색 발광 소자에 사용하기에 적합하다.The compound represented by Chemical Formula a is suitable as a material forming an organic film interposed between the first electrode and the second electrode of the organic light emitting device. The compound represented by Chemical Formula a is suitable for use in an organic film, particularly a light emitting layer or an electron transport layer of an organic light emitting device, and is used as a dopant material as well as a host material. The compound represented by Chemical Formula a provides a color of blue to green and is suitable for use in a white light emitting device.

상기 아릴기는 방향족 고리 시스템을 갖는 1가 그룹으로서, 2 이상의 고리 시스템을 포함할 수 있으며, 상기 2이상의 고리 시스템은 서로 결합 또는 융합된 형태로 존재할 수 있다. 상기 헤테로아릴기는 상기 아릴기 중 하나 이상의 탄소가 N, O, S 및 P로 이루어진 군으로부터 선택된 하나 이상으로 치환된 그룹을 가리킨다. The aryl group is a monovalent group having an aromatic ring system, and may include two or more ring systems, and the two or more ring systems may exist in a bonded or fused form with each other. The heteroaryl group refers to a group in which at least one carbon in the aryl group is substituted with at least one selected from the group consisting of N, O, S, and P.

한편, 사이클로알킬기는 고리 시스템을 갖는 알킬기를 가리키며, 상기 헤테로사이클로알킬기는 상기 사이클로알킬기 중 하나 이상의 탄소가 N, O, S 및 P로 이루어진 군으로부터 선택된 하나 이상으로 치환된 그룹을 가리킨다. Meanwhile, a cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon of the cycloalkyl group is substituted with at least one selected from the group consisting of N, O, S and P.

상기 아릴기 및 헤테로아릴기의 하나 이상의 수소가 치환될 경우, 이들의 치환기는 C1-C50알킬기; C1-C50알콕시기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C6-C50아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C2-C50헤테로아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C5-C50사이클로알킬기및 비치환 또는 C1-C20알킬기 또는 C1-C20알콕시기로 치환된 C5-C50헤테로사이클로알킬기로 표시되는 그룹으로 이루어진 군으로부터 선택된 하나 이상일 수 있다.
When one or more hydrogen of the aryl group and heteroaryl group is substituted, their substituents are C1-C50 alkyl group; C1-C50 alkoxy group; C 6 -C 50 aryl groups which are unsubstituted or substituted with C 1 -C 50 alkyl groups or C 1 -C 50 alkoxy groups; C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; From the group consisting of a C5-C50 cycloalkyl group substituted with an unsubstituted or C1-C50 alkyl group or a C1-C50 alkoxy group and a C5-C50 heterocycloalkyl group substituted with an unsubstituted or C1-C20 alkyl group or a C1-C20 alkoxy group It may be one or more selected.

보다 구체적으로, A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 페닐기, 톨일기, 비페닐기, 펜타레닐기, 인데닐기, 나프틸기, 비페닐레닐기, 안트라세닐기, 벤조안트라세닐기, 아즈레닐기, 헵타레닐기, 아세나프틸레닐기, 페나레닐기, 메틸안트릴기, 페난트레닐기, 트리페닐레닐기, 피레닐기, 크리세닐기, 피세닐기, 페릴레닐기, 클로로페릴레닐기, 펜타페닐기, 펜타세닐기, 테트라페닐레닐기, 헥사페닐기, 헥사세닐기, 루비세닐기, 코로네닐기, 트리나프틸레닐기, 헵타페닐기, 헵타세닐기, 플루오레닐기, 피란트레닐기, 오바레닐기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 티오페닐기, 인돌일기, 푸리닐기, 벤즈이미다졸일기, 퀴놀리닐기, 벤조티오페닐기, 파라티아지닐기, 피롤일기, 피라졸릴기, 이미다졸릴기, 이미다졸리닐기, 옥사졸릴기, 티아졸릴기, 트리아졸릴기, 테트라졸일기, 옥사디아졸릴기, 피리디닐기, 피리다지닐기, 피리미디닐기, 피라지닐기, 티안트레닐기(thianthrenyl), 사이클로펜틸기, 사이클로헥실기, 옥시라닐기, 피롤리디닐기, 피라졸리디닐기, 이미다졸리디닐기, 피페리디닐기, 피페라지닐기, 모르폴리닐기, 디(C6-C50아릴)아미노기 및 이들의 유도체로 이루어진 군으로부터 선택될 수 있다.
More specifically, A1, A2, A3, A4, A5 and A6 independently of each other, hydrogen, phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzo Anthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perrylenyl group, Chloroperrylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptathenyl group, fluorenyl group, pyrantrenil Neyl group, Ovarenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroyl group , Pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, Azolyl, triazolyl, tetrazolyl, oxadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxy Selected from the group consisting of a ranyl group, a pyrrolidinyl group, a pyrazolidinyl group, an imidazolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group and derivatives thereof Can be.

본 명세서에 있어서, 상기 "유도체"란 용어는 상기 나열한 그룹들 중 하나 이상의 수소가 전술한 바와 같은 치환기로 치환된 그룹을 가리키는 것이다.In the present specification, the term "derivative" refers to a group in which at least one hydrogen of the groups listed above is substituted with a substituent as described above.

바람직하게는, 상기 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 페닐기, 비페닐기, 톨일기, 나프틸기, 나프탈레닐페닐기, 디메틸벤질기, 피레닐기, 페난트레닐기, 벤조[de]안트라세닐기, 벤조[a]안트라세닐기, 벤조[b]안트라세닐기, 벤조[c]안트라세닐기, 11,11 -디메틸벤조[de]안트라세닐기, 11,11 -디에틸벤조[de]안트라세닐기, 11,11 -디메틸벤조[a]안트라세닐기, 11,11 -디메틸벤조[b]안트라세닐기, 11,11 -디메틸벤조[c]안트라세닐기, 바이플루오레닐기, 6,6 ,12,12 -테트라메틸-인데노[1,2-b]플루오레닐기, N-페닐카르바졸릴기, N-에틸카르바졸릴기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 이미다졸리닐기, 인돌일기, 퀴놀리닐기, 디페닐아미노기, 디비페닐아미노기, 디(tert-부틸벤질)아미노기, (톨일)(페닐)아미노기, (페닐)(비페닐)아미노기, (페닐)(나프틸)아미노기, 디(비페틸)아미노기, 디플루오레닐아미노기, 디-p-톨일아미노기 및 이들의 유도체로 이루어진 군으로부터 선택될 수 있다.Preferably, A1, A2, A3, A4, A5 and A6 are each independently hydrogen, phenyl group, biphenyl group, tolyl group, naphthyl group, naphthalenylphenyl group, dimethylbenzyl group, pyrenyl group, phenanthrenyl group, Benzo [de] anthracenyl group, benzo [a] anthracenyl group, benzo [b] anthracenyl group, benzo [c] anthracenyl group, 11, 11-dimethylbenzo [de] anthracenyl group, 11, 11-di Ethyl benzo [de] anthracenyl group, 11, 11- dimethyl benzo [a] anthracenyl group, 11, 11- dimethyl benzo [b] anthracenyl group, 11, 11- dimethyl benzo [c] anthracenyl group, biflu Orenyl group, 6,6,12,12-tetramethyl-indeno [1,2-b] fluorenyl group, N-phenylcarbazolyl group, N-ethylcarbazolyl group, carbazolyl group, dibenzo Furanyl group, dibenzothiophenyl group, imidazolinyl group, indolyl group, quinolinyl group, diphenylamino group, dibiphenylamino group, di (tert-butylbenzyl) amino group, (tolyl) (phenyl) amino group, (phenyl) (non Phenyl) amino group, (phenyl) (naphthyl) It may be selected from the unexposed group, a di (non petil) amino group, di-fluorenyl group, a di -p- tolyl group, and derivatives thereof.

보다 상세하게 본 발명의 일 구현예에 따르면, 본 발명의 유기 발광 소자에 사용되는 유기 발광 화합물은 하기의 화학식 1 내지 117의 구조(본 명세서에서 '화학식'은 생략하고 숫자만 기재함)를 가질 수 있으나 이에 한정되는 것은 아니다:
In more detail, according to an embodiment of the present invention, the organic light emitting compound used in the organic light emitting device of the present invention has a structure of the formula (1) to 117 (in the present specification, the chemical formula is omitted, only the numbers are described) This may be, but is not limited to:

Figure pat00003

Figure pat00003

Figure pat00004

Figure pat00004

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

상기 화학식 a로 표시되는 본 발명에 따른 유기 발광 화합물은 통상의 합성 방법을 이용하여 합성될 수 있으며, 상기 화합물의 보다 상세한 합성 경로는 하기 합성예의 반응식 1 내지 117을 참조한다. 상기 화학식 a의 화합물은 유기 발광 소자의 유기막, 특히 발광층 또는 전자수송층에 사용되기 적합하다. 본 발명을 따르는 유기 발광 소자의 구조는 매우 다양하다. 상기 제1전극과 제2전극 사이에 정공주입층, 정공수송층, 정공저지층, 전자저지층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택된 하나 이상의 층을 더 포함할 수 있다.The organic light emitting compound according to the present invention represented by Chemical Formula a may be synthesized using a conventional synthetic method, and for more detailed synthetic routes of the compound, see Schemes 1 to 117 of the following Synthesis Examples. The compound of formula (a) is suitable for use in an organic film, particularly a light emitting layer or an electron transport layer of an organic light emitting device. The structure of the organic light emitting device according to the present invention is very diverse. One or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, an electron transport layer and an electron injection layer may be further included between the first electrode and the second electrode.

보다 구체적으로, 본 발명을 따르는 유기 발광 소자의 구현예는 More specifically, embodiments of the organic light emitting device according to the present invention

먼저, 유기 발광 소자는 제1전극/정공주입층/발광층/전자수송층/전자주입층/제2전극으로 이루어진 구조를 가질 수 있고, First, the organic light emitting device may have a structure consisting of a first electrode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / second electrode,

또 유기 발광 소자는 제1전극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/제2전극으로 이루어진 구조를 가질 수 있으며,In addition, the organic light emitting device may have a structure consisting of a first electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode,

나아가 유기 발광 소자는 제1전극/정공주입층/정공수송층/발광층/정공저지층/전자수송층/전자주입층/제2전극의 구조를 가질 수 있다.Furthermore, the organic light emitting device may have a structure of a first electrode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / second electrode.

이때, 상기 발광층 및 전자수송층 중 하나 이상은 본 발명을 따르는 화합물을 포함할 수 있다.In this case, at least one of the light emitting layer and the electron transport layer may include a compound according to the present invention.

본 발명을 따르는 유기 발광 소자의 발광층은 적색, 녹색, 청색 또는 백색을 포함하는 인광 또는 형광 도펀트를 포함할 수 있다. 이 중, 상기 인광 도펀트는 Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb 및 Tm으로 이루어진 군으로부터 선택된 하나 이상의 원소를 포함하는 유기금속화합물일 수 있다. 또한, 본 발명에 따르는 화합물은 발광층에서 형광 도펀트로도 사용될 수 있다.The light emitting layer of the organic light emitting device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. Among these, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, and Tm. The compounds according to the invention can also be used as fluorescent dopants in light emitting layers.

이하, 본 발명을 따르는 유기 발광 소자의 제조 방법을 살펴보기로 한다. 먼저 기판 상부에 높은 일함수를 갖는 제1전극용 물질을 증착법 또는 스퍼터링법 등에 의해 형성하여 제1전극을 형성한다. 상기 제1전극은 애노드(Anode)일 수 있다. 여기에서 기판으로는 통상적인 유기 발광 소자에서 사용되는 기판을 사용하는데 기계적 강도, 열적 안정성, 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판이 바람직하다. 제1전극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용한다.Hereinafter, a method of manufacturing an organic light emitting device according to the present invention will be described. First, a first electrode material having a high work function on the substrate is formed by a deposition method or a sputtering method to form a first electrode. The first electrode may be an anode. Herein, a substrate used in a conventional organic light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. Indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used as the material for the first electrode.

다음으로, 상기 제1전극 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 정공주입층(HIL)을 형성할 수 있다.Next, a hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

진공증착법에 의하여 정공주입층을 형성하는 경우, 그 증착 조건은 정공주입층의 재료로서 사용하는 화합물, 목적으로 하는 정공주입층의 구조 및 열적 특성 등에 따라 다르지만, 일반적으로 증착온도 100 내지 500℃, 진공도 10-5 내지 10-3 torr, 증착속도 0.01 내지 100Å/sec, 막 두께는 통상 100Å 내지 1㎛ 범위에서 적절히 선택하는 것이 바람직하다.In the case of forming the hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the hole injection layer, and the like. It is preferable that a vacuum degree of 10 -5 to 10 -3 torr, a deposition rate of 0.01 to 100 Pa / sec, and a film thickness are appropriately selected in the range of usually 100 Pa to 1 µm.

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

상기 정공주입층 물질은 전술한 바와 같은 화학식 a를 갖는 화합물일 수 있다. The hole injection layer material may be a compound having Formula a as described above.

또는, 예를 들어, 미국특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 Advanced Material, 6, p.677(1994)에 기재되어 있는 스타버스트형 아민 유도체류인 TCTA, m-MTDATA, m-MTDAPB, 2-TNATA(4,4 ,4 -tris(N-(2-naphtyl)-N-phenylamino)triphenylamine:4,4 ,4 -트리스(N-(나프틸)-N-페닐아미노)트리페닐아민), 용해성이 있는 전도성 고분자인 Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid:폴리아닐린/도데실벤젠술폰산) 또는 PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate):폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)), PANI/CSA (Polyaniline/Camphor sulfonicacid:폴리아닐린/캠퍼술폰산) 또는 PANI/PSSOr phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or the starburst type amine derivatives described in Advanced Material, 6, p.677 (1994), for example, TCTA, m-MTDATA, m-. MTDAPB, 2-TNATA (4,4,4-tris (N- (2-naphtyl) -N-phenylamino) triphenylamine: 4,4,4-tris (N- (naphthyl) -N-phenylamino) triphenyl Amines), Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3, 4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), PANI / CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) or PANI / PSS

(Polyaniline)/Poly(4-styrenesulfonate):폴리아닐린)/폴리(4-스티렌술포네이트)) 등과 같은 공지된 정공주입 물질을 사용할 수 있다.
Known hole injection materials such as (Polyaniline) / Poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) and the like can be used.

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

다르게는, 상기 정공주입층은 진공기상증착법에 의해 형성할 수 있다. 구체적인 증착조건은 사용하는 화합물에 따라 다르지만, 일반적인 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다. 예를 들어 DNTPD(N,N-bis-[4-(di-m-tolylamino)phenyl]-N,N -diphenylbiphenyl-4,4 -diamine) 등이 사용될 수 있다.Alternatively, the hole injection layer may be formed by vacuum vapor deposition. Although specific deposition conditions depend on the compound used, they are selected from the range of conditions substantially the same as the formation of a general hole injection layer. For example, DNTPD (N, N-bis- [4- (di-m-tolylamino) phenyl] -N, N-diphenylbiphenyl-4,4-diamine) may be used.

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

상기 정공수송층 물질은 전술한 바와 같은 화학식 a의 화합물을 포함할 수 있다. 또는, 예를 들어, N-페닐카르바졸, 폴리비닐카르바졸 등의 카르바졸 유도체, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N,N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상적인 아민 유도체 등과 같은 공지된 정공수송 물질을 사용할 수 있다.상기 정공수송층의 두께는 약 50Å 내지 1000Å, 바람직하게는 100Å 내지 600Å일 수 있다. 상기 정공수송층의 두께가 50Å 미만인 경우, 정공수송 특성이 저하될 수 있으며, 상기 정공수송층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The hole transport layer material may include a compound of Formula a as described above. Or, for example, carbazole derivatives, such as N-phenylcarbazole and polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [1,1-biphenyl] Conventional amine derivatives having aromatic condensed rings such as -4,4'-diamine (TPD), N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (? -NPD), and the like The same well-known hole transport material may be used. The hole transport layer may have a thickness of about 50 kPa to 1000 kPa, preferably 100 kPa to 600 kPa. This is because when the thickness of the hole transport layer is less than 50 kV, hole transport characteristics may be degraded, and when the thickness of the hole transport layer exceeds 1000 kW, the driving voltage may increase.

다음으로 상기 정공수송층 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법을 이용하여 발광층(EML)을 형성할 수 있다. 진공증착법 및 스핀코팅법에 의해 발광층을 형성하는 경우, 그 증착조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.Next, the light emitting layer EML may be formed on the hole transport layer by using a vacuum deposition method, a spin coating method, a cast method, an LB method, or the like. When the light emitting layer is formed by the vacuum deposition method or the spin coating method, the deposition conditions vary depending on the compound used, but are generally selected from the ranges of conditions substantially the same as those of forming the hole injection layer.

상기 발광층은 전술한 바와 같이 본 발명을 따르는 화학식 a의 화합물을 포함할 수 있다. 이 때, 화학식 a의 화합물은 적합한 공지의 호스트 재료와 함께 사용될 수 있거나, 공지의 도펀트 재료와 함께 사용될 수 있다.The light emitting layer may include a compound of Formula a according to the present invention as described above. At this time, the compound of formula a may be used with a suitable known host material or may be used with a known dopant material.

상기 화학식 a의 화합물을 단독으로 사용하는 것도 가능하다. 호스트 재료의 경우, 예를 들면, Alq3(tris(8-hydroxy-quinolatealuminium) 또는 CBP(4,4'-N,N'-디카바졸-비페닐), 또는 PVK(폴리(n-비닐카바졸)) 등을 사용할 수 있다.
It is also possible to use the compound of formula (A) alone. For host materials, for example, Alq3 (tris (8-hydroxy-quinolatealuminium) or CBP (4,4'-N, N'-dicarbazole-biphenyl), or PVK (poly (n-vinylcarbazole) ) Can be used.

도펀트 재료의 경우, 형광 도펀트로서는 이데미츠사(Idemitsu사)에서 구입 가능한 IDE102, IDE105 및 하야시바라사에서 구입 가능한 C545T 등을 사용할 수 있으며, 인광 도펀트로서는 적색 인광 도펀트 PtOEP, UDC사의 RD61, 녹색 인광 도판트 Ir(PPy)3(PPy=2-phenylpyridine), 청색 인광 도펀트인 F2Irpic, UDC사의 적색 인광 도펀트 RD 61 등을 사용할 수 있다. MQD(N-methylquinacridone), 쿠마린(Coumarine)유도체 등도 사용할 수 있다.In the case of the dopant material, IDE102, IDE105, and C545T, available from Hayashibara Corp., can be used as fluorescent dopants, and red phosphorescent dopants PtOEP, RD61 from UDC, green phosphorescent dopants Ir, etc. can be used. (PPy) 3 (PPy = 2-phenylpyridine), F2Irpic which is a blue phosphorescent dopant, red phosphorescent dopant RD 61 by UDC, etc. can be used. MQD (N-methylquinacridone), coumarin (Coumarine) derivative, etc. can also be used.

도핑 농도는 특별히 제한 되지 않으나 통상적으로 호스트100 중량부를 기준으로 하여 상기 도펀트의 함량은 0.01 ~ 15 중량부이다.상기 발광층의 두께는 약 100Å 내지 1000Å, 바람직하게는 200Å 내지 600Å일 수 있다.The doping concentration is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host. The thickness of the light emitting layer may be about 100 kPa to 1000 kPa, preferably 200 kPa to 600 kPa.

상기 발광층의 두께가 100Å 미만인 경우, 발광 특성이 저하될 수 있으며, 상기 발광층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.This is because, when the thickness of the light emitting layer is less than 100 kW, the light emission characteristics may be reduced, and when the thickness of the light emitting layer exceeds 1000 kW, the driving voltage may increase.

발광층에 발광 화합물이 인광 도펀트와 함께 사용할 경우에는 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지하기 위하여, 상기 발광층 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 방법을 이용하여 정공저지층(HBL)을 형성할 수 있다. 진공증착법 및 스핀코팅법에 의해 정공저지층을 형성하는 경우, 그 조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다. 사용가능한 공지의 정공저지재료, 예를 들면 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP 등을 들 수 있다.When a light emitting compound is used with a phosphorescent dopant in the light emitting layer, a method such as vacuum deposition, spin coating, cast method, LB method, etc. is used on the light emitting layer to prevent the triplet excitons or holes from diffusing into the electron transport layer. The hole blocking layer HBL can be formed. In the case of forming the hole blocking layer by vacuum deposition or spin coating, the conditions vary depending on the compound used, but are generally selected from the ranges of conditions almost the same as that of forming the hole injection layer. Known hole blocking materials that can be used include, for example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and BCP.

상기 정공저지층의 두께는 약 50Å 내지 1000Å, 바람직하게는 100Å 내지 300Å일 수 있다. 상기 정공저지층의 두께가 50Å 미만인 경우, 정공저지 특성이 저하될 수 있으며, 상기 정공저지층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.상기 정공저지층이 생략될 경우 도 1b에 도시된 구조를 가지는 유기발광 소자가 얻어진다.The hole blocking layer may have a thickness of about 50 kPa to 1000 kPa, preferably 100 kPa to 300 kPa. This is because when the thickness of the hole blocking layer is less than 50 kV, the hole blocking property may be deteriorated, and when the thickness of the hole blocking layer is more than 1000 kV, the driving voltage may increase. The hole blocking layer may be omitted. In this case, an organic light emitting device having the structure shown in FIG. 1B is obtained.

다음으로 전자수송층(ETL)을 진공증착법, 또는 스핀코팅법, 캐스트법 등의 다양한 방법을 이용하여 형성한다.Next, the electron transport layer (ETL) is formed using various methods such as vacuum deposition, spin coating, and casting.

진공증착법 및 스핀코팅법에 의해 전자수송층을 형성하는 경우, 그 조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다. 상기 전자수송층 재료는 전자주입전극(Cathode)로부터 주입된 전자를 안정하게 수송하는 기능을 하는 것으로서 퀴놀린 유도체, 특히 트리스(8-퀴놀리노레이트)알루미늄(Alq3), TAZ, Balq, PBD등과 같은 공지의 재료를 사용할 수도 있다.
When the electron transport layer is formed by the vacuum deposition method or the spin coating method, the conditions vary depending on the compound used, but are generally selected from the ranges of conditions almost the same as that of the formation of the hole injection layer. The electron transport layer material functions to stably transport electrons injected from an electron injection electrode (Cathode), and a quinoline derivative, particularly tris (8-quinolinorate) aluminum (Alq3), TAZ, Balq, PBD and the like are known. Materials may also be used.

상기 전자수송층의 두께는 약 100Å 내지 1000Å, 바람직하게는 200Å 내지 500Å일 수 있다. 상기 전자수송층의 두께가 100Å 미만인 경우, 전자수송 특성이 저하될 수 있으며, 상기 전자수송층의 두께가 1000Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The electron transport layer may have a thickness of about 100 kPa to 1000 kPa, preferably 200 kPa to 500 kPa. This is because when the thickness of the electron transport layer is less than 100 kV, the electron transport characteristic may be degraded, and when the thickness of the electron transport layer exceeds 1000 kW, the driving voltage may increase.

또한 전자수송층 상부에 음극으로부터 전자의 주입을 용이하게 하는 기능을 가지는 물질인 전자주입층(EIL)이 적층될 수 있으며 이는 특별히 재료를 제한하지 않는다.In addition, an electron injection layer (EIL), which is a material having a function of facilitating injection of electrons from the cathode, may be stacked on the electron transport layer, which does not particularly limit the material.

전자 주입층으로서는 LiF, NaCl, CsF, Li2O, BaO 등과 같은 전자주입층 형성 재료로서 공지된 임의의 물질을 이용할 수 있다. 상기 전자주입층의 증착조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li 2 O, BaO or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from the range of conditions almost the same as the formation of the hole injection layer.

상기 전자주입층의 두께는 약 1Å 내지 100Å, 바람직하게는 5Å 내지 50Å일 수 있다. 상기 전자주입층의 두께가 1Å 미만인 경우, 전자주입 특성이 저하될 수 있으며, 상기 전자주입층의 두께가 100Å를 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The electron injection layer may have a thickness of about 1 kPa to 100 kPa, preferably 5 kPa to 50 kPa. This is because, when the thickness of the electron injection layer is less than 1 kW, the electron injection characteristic may be deteriorated, and when the thickness of the electron injection layer exceeds 100 kW, the driving voltage may increase.

마지막으로 전자주입층 상부에 진공증착법이나 스퍼터링법 등의 방법을 이용하여 제2전극을 형성할 수 있다.Finally, the second electrode may be formed on the electron injection layer by using a vacuum deposition method or a sputtering method.

상기 제2전극은 캐소드(Cathode)로 사용될 수 있다. 상기 제2전극 형성용 금속으로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로서는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag)등을 들 수 있다. 또한 전면 발광소자를 얻기 위하여 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다.The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

본 발명의 다른 구현예에 따르는 유기 전계 발광 화합물은 상기 화학식 a로 표현될 수 있으며, 보다 구체적으로는 상기 화학식 1 내지 117로 표현될 수 있다. 상기 화합물들에 대한 구체적인 내용은 상술한 유기 발과 소자에 대하여 설명한 부분과 동일하다.
The organic electroluminescent compound according to another embodiment of the present invention may be represented by Chemical Formula a, and more specifically, may be represented by Chemical Formulas 1 to 117. Details of the compounds are the same as those described for the above-mentioned organic feet and devices.

이하에서, 본 발명의 합성예 및 실시예를 구체적으로 예시하지만, 본 발명이 하기의 합성예 및 실시예로 한정되는 것은 아니다. 이하의 합성예에서 중간체 화합물은 최종 생성물의 번호에 일련번호를 추가하는 방식으로 표기한다. 예를 들어, 화합물 1은 화합물 [1] 로 상기 화합물의 중간체 화합물은 [1-1] 등으로 표기한다. 본 명세서에서 화학물의 번호는 화학식의 번호로서 표기한다. 예를 들어, 화학식 1로 표시되는 화합물은 화합물 1로 표기한다.
Hereinafter, the synthesis examples and examples of the present invention will be specifically illustrated, but the present invention is not limited to the following synthesis examples and examples. In the following synthesis, the intermediate compound is indicated by adding the serial number to the number of the final product. For example, compound 1 is represented by compound [1], and the intermediate compound of the said compound is described by [1-1] etc. In the present specification, the chemical number is indicated as the chemical formula number. For example, the compound represented by the formula (1) is represented by compound 1.

[합성 예 1] 화합물 [1]의 합성Synthesis Example 1 Synthesis of Compound [1]

Figure pat00013
Figure pat00013

3L 라운드 플라스크에 무수프탈산 80.4g(0.543mol)과 알루미늄클로라이드 181g(1.36mol)을 디클로로메탄 1L로 교반한다. 디벤조티오펜 100g(0.543mol)을 디클로로메탄 500mL로 녹여 상기의 상온에서 반응액에 적가시킨다. 상온에서 6시간 동안 교반후 반응액을 정제수 2Ldp 붓는다. 유기층을 분리하고 포화 소금물 2L로 세척한다. 유기층을 분리하여 무수황산 마그네슘으로 건조 후 여과한다. 여과액을 감압 농축하고 디클로로메탄과 노말-헥산으로 재경정화하여 흰색 고체의 중간체 화합물 [1-1] 120g(66%)을 수득하였다.
In a 3 L round flask, 80.4 g (0.543 mol) of phthalic anhydride and 181 g (1.36 mol) of aluminum chloride are stirred with 1 L of dichloromethane. 100 g (0.543 mol) of dibenzothiophene is dissolved in 500 mL of dichloromethane and added dropwise to the reaction solution at room temperature. After stirring for 6 hours at room temperature, the reaction solution was poured into 2 Ldp of purified water. The organic layer is separated and washed with 2 L of saturated brine. The organic layer is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and re-cured with dichloromethane and normal-hexane to give 120 g (66%) of the intermediate compound [1-1] as a white solid.

플라스크에 중간체 화합물[1-1] 120g (0.361mol), 활성화된 아연 236g(3.61mol), 수산화 나트륨 144g(3.61mol)을 투입하고 디에틸렌글리콜 1.2L 가하여 150℃ 에서 12시간 동안 교반시킨다. 상온으로 냉각시키고 규조토를 사용하여 반응액을 여과한다. 여과액을 정제수 5L 에 붓고 진한 염산으로 산성화시킨다. 생성된 흰색 고체를 여과하여 중간체 화합물 [1-2] 95g (82%)을 수득하였다.
120 g (0.361 mol) of intermediate compound [1-1] , 236 g (3.61 mol) of activated zinc, and 144 g (3.61 mol) of sodium hydroxide were added to the flask, and 1.2 L of diethylene glycol was added thereto, followed by stirring at 150 ° C. for 12 hours. Cool to room temperature and filter the reaction solution using diatomaceous earth. The filtrate is poured into 5 L of purified water and acidified with concentrated hydrochloric acid. The resulting white solid was filtered to give 95 g (82%) of intermediate compound [1-2] .

플라스크에 중간체 화합물 [1-2] 95g(0.298mol)을 투입하고 메탄술폰산 300mL로 상온에서 5시간 동안 교반한다. 반응액을 정제수 3Ldp 부어 고체화 시킨다. 주황색 고체를 메탄올로 세척하여 중간체 화합물 [1-3] 80g (89%)을 수득하였다.
95 g (0.298 mol) of the intermediate compound [1-2] were added to the flask, and stirred with 300 mL of methanesulfonic acid at room temperature for 5 hours. The reaction solution is poured into 3 Ldp of purified water and solidified. The orange solid was washed with methanol to yield 80 g (89%) of intermediate compound [1-3] .

플라스크에 중간체 화합물 [1-3] 80g(0.266mol)을 투입하고 무수 테트라히드로퓨란 1L로 0℃에서 교반한다. 페닐마그네슘브로마이드(1몰 테트라히드로퓨란 용액)799mL (0.799mol)를 적가하고 12시간 동안 환류교반시킨다. 반응액을 상온으로 냉각하고 1몰 염산 수용액에 반응액을 붓는다. 유기층을 분리하고 포화 소금물로 세척한다. 유기층 분리하여 무수황산 마그네슘으로 건조하여 여과한다. 여과액을 감압 농축하여 얻은 노란색 고체를 디클로로메탄과 메탄올로 재결정화 하여 노란색 고체의 중간체 화합물 [1-4] 75g (78%)을 수득하였다.
80 g (0.266 mol) of an intermediate compound [1-3] were added to the flask, followed by stirring with 1 L of anhydrous tetrahydrofuran at 0 ° C. 799 mL (0.799 mol) of phenylmagnesium bromide (1 mol tetrahydrofuran solution) was added dropwise and stirred under reflux for 12 hours. Cool the reaction solution to room temperature and pour the reaction solution into 1 mol aqueous hydrochloric acid. The organic layer is separated and washed with saturated brine. The organic layer is separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the yellow solid obtained was recrystallized from dichloromethane and methanol to give 75 g (78%) of the intermediate compound [1-4] as a yellow solid.

플라스크에 중간체 화합물 [1-4] 75g(0.208mol)을 N,N-디메틸포름아미드 1L 로 교반한다. 상온에서 N-브로모숙시니미드 (0.229mol)을 첨가하여 8시간 교반한다. 반응액에 메탄올을 가하여 생성된 노란색 고체를 여과한다. 고체를 진공 건조하여 중간체 화합물 [1-5] 80g (87%)을 수득하였다.
75 g (0.208 mol) of the intermediate compound [1-4] are stirred in a flask with 1 L of N, N-dimethylformamide. N-bromosuccinimide (0.229 mol) is added at room temperature and stirred for 8 hours. Methanol is added to the reaction solution, and the resulting yellow solid is filtered. The solid was dried in vacuo to yield 80 g (87%) of the intermediate compound [1-5] .

250mL 둥근바닥플라스크에 중간체 화합물 5.0g(11.38mmol), 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-일)피리딘 2.57g (12.52mmol), 테트라키스(트리페닐포스핀)팔라듐 263mg(0.228mmol), 2몰-탄산나트륨수용액 10mL, 1,4-디옥산 100mL를 가한 후 질소 분위기에서 10시간 동안 환류교반한다. 상온에서 메탄올을 가하여 결정화 시킨다. 고체를 여과하고 디클로로메탄과 메탄올로 재결정화하여 미색고체의 목적화합물 [1] 3.7g(74%)을 수득하였다.5.0 g (11.38 mmol) of intermediate compound, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine 2.57 g (12.52 mmol) in 250 mL round bottom flask ), 263 mg (0.228 mmol) of tetrakis (triphenylphosphine) palladium, 10 mL of 2 mol-sodium carbonate aqueous solution and 100 mL of 1,4-dioxane are added, followed by stirring under reflux for 10 hours in a nitrogen atmosphere. Methanol is added at room temperature to crystallize. The solid was filtered and recrystallized with dichloromethane and methanol to obtain 3.7 g (74%) of the target compound [1] as an off-white solid.

1H NMR (300 MHz, CDCl3) : δ 7.05~7.20(m, 2H), 7.25~7.55(m, 10H), 7.89~7.99(m, 5H), 8.35(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.05 ~ 7.20 (m, 2H), 7.25 ~ 7.55 (m, 10H), 7.89 ~ 7.99 (m, 5H), 8.35 (m, 2H)

MS/FAB : 437(M+)
MS / FAB: 437 (M + )

[[ 합성예Synthetic example 2] 화합물 [2]의 합성 2] Synthesis of Compound [2]

Figure pat00014
Figure pat00014

합성예 1과 동일한 방법으로 중간체 화합물 5.0g(11.38mmol), 피리딘-3-일보론산 1.54g (12.52mmol)을 사용하여 미색고체의 목적화합물 [2] 3.3g(66%)을 수득하였다. In the same manner as in Synthesis example 1 , 3.3 g (66%) of the target compound [2] was obtained by using 5.0 g (11.38 mmol) of the intermediate compound and 1.54 g (12.52 mmol) of pyridin-3-ylboronic acid.

1H NMR (300 MHz, CDCl3) : δ 7.40~7.60(m, 10H), 7.86~8.01(m, 5H), 8.40~8.70(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.40 ~ 7.60 (m, 10H), 7.86 ~ 8.01 (m, 5H), 8.40 ~ 8.70 (m, 4H)

MS/FAB : 437(M+)
MS / FAB: 437 (M + )

[[ 합성예Synthetic example 3] 화합물 [3]의 합성 3] Synthesis of Compound [3]

Figure pat00015
Figure pat00015

합성예 1과동일한방법으로중간체화합물5.0g(11.38mmol), 피리딘-4-일보론산 1.54g (12.52mmol)을 사용하여 미색고체의 목적화합물 [3] 3.5g(70%)을 수득하였다. Synthesis Example In the same manner as 1 , 3.5 g (70%) of the target compound [3] was obtained using an intermediate compound of 5.0 g (11.38 mmol) and pyridin-4-ylboronic acid 1.54 g (12.52 mmol).

1H NMR (300 MHz, CDCl3):δ 7.41~7.59(m, 9H), 7.89~8.00(m, 7H), 8.45~8.55(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.41-7.59 (m, 9H), 7.89-8.00 (m, 7H), 8.45-8.55 (m, 3H)

MS/FAB : 437(M+)MS / FAB: 437 (M + )

[[ 합성예Synthetic example 4] 화합물 [4]의 합성 4] Synthesis of Compound [4]

Figure pat00016
Figure pat00016

플라스크에 중간체 화합물 [1-5] 40g (91.03mmol)을 무수 테트라히드로퓨란 1L 로 교반하고 -78℃에서 2.5몰-부틸리튬 43.7mL (0.109mol)을 천천히 적가 시킨다. 동온도에서 2-이소프로폭시-4,4,5,5-테트라메틸-1,3,2-디옥사보로레인 22.24mL(0.109mol)를 천천히 적가시킨다. 상온까지 10시간 동안 서서히 올리고 반응액을 포화 암모늄 수용액 1L 에 부어 층 분리시킨다. 유기층을 분리하고 포화 소금물 1L로 세척한다. 유기층 분리 후 무수황산 마그네슘으로 건조하여 여과한다. 여액을 감압 농축하여 디클로로메탄과 노말-헥산으로 재결정화하여 노란색 고체의 중간체 화합물 [4-1] 36g (81%)을 수득하였다. 40 g (91.03 mmol) of the intermediate compound [1-5] were stirred with 1 L of anhydrous tetrahydrofuran, and 43.7 mL (0.109 mol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. At the same temperature, 22.24 mL (0.109 mol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane is slowly added dropwise. The mixture was gradually raised to room temperature for 10 hours, and the reaction solution was poured into 1 L of saturated aqueous ammonium solution to separate the layers. The organic layer is separated and washed with 1 L of saturated brine. The organic layer was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized with dichloromethane and normal-hexane to give 36g (81%) of the intermediate compound [4-1] as a yellow solid.

합성예 1과동일한방법으로2-브로모피리미딘 3.0g(18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [4] 5.5g(66%)을 수득하였다. Synthesis Example 1 In the same manner, to obtain 5.5 g (66%) of the target compound [4] as a pale solid using 3.0 g (18.87 mmol) of 2-bromopyrimidine and 10.1 g (20.76 mmol) of the intermediate compound [4-1]. It was.

1H NMR (300 MHz, CDCl3):δ 7.35~7.55(m, 10H), 7.88~7.99(m, 5H), 8.40(d, 1H), 8.78(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.55 (m, 10H), 7.88-7.99 (m, 5H), 8.40 (d, 1H), 8.78 (m, 2H)

MS/FAB : 438(M+)MS / FAB: 438 (M + )

[[ 합성예Synthetic example 5] 화합물 [5]의 합성 5] Synthesis of Compound [5]

Figure pat00017
Figure pat00017

합성예4와동일한방법으로2-브로모-4,6-디페닐피리미딘 5.87g(18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [5] 7.5g(67%)을 수득하였다. Synthesis Example 4 as a vortex same method of 2-bromo-4,6-diphenyl-pyrimidine 5.87g (18.87mmol), intermediate compound [4-1] The desired compound of the off-white solid using 10.1g (20.76mmol) [5 ] to give the 7.5g (67%).

1H NMR (300 MHz, CDCl3):δ 7.34~7.60(m, 15H), 7.70~8.00(m, 9H), 8.30~8.45(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.34-7.60 (m, 15H), 7.70-8.00 (m, 9H), 8.30-8.45 (m, 2H)

MS/FAB : 590(M+)MS / FAB: 590 (M + )

[[ 합성예Synthetic example 6] 화합물 [6]의 합성 6] Synthesis of Compound [6]

Figure pat00018
Figure pat00018

합성예4와동일한방법으로2-브로모-1,3,5-트리아진 3.01g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [6] 5.1g(61%)을 수득하였다. Synthesis Example 4 as a vortex same method of 2-bromo-1,3,5-triazine 3.01g (18.87mmol), intermediate compound [4-1] The desired compound of the off-white solid using 10.1g (20.76mmol) [6 ] to give the 5.1g (61%).

1H NMR (300 MHz, CDCl3):δ 7.36~7.55(m, 9H), 7.90~8.03(m, 5H), 8.40~8.50(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.55 (m, 9H), 7.90-8.03 (m, 5H), 8.40-8.50 (m, 3H)

MS/FAB : 439(M+)MS / FAB: 439 (M + )

[[ 합성예Synthetic example 7] 화합물 [7]의 합성 7] Synthesis of Compound [7]

Figure pat00019
Figure pat00019

합성예4와동일한방법으로2-브로모-4,6-디페닐-1,3,5-트리아진 5.89g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [7] 6.5g(58%)을 수득하였다. In the same manner as in Synthesis Example 4 , using 5.89 g (18.87 mmol) of 2-bromo-4,6-diphenyl-1,3,5-triazine and 10.1 g (20.76 mmol) of the intermediate compound [4-1] 6.5g (58%) of the title compound [7] was obtained as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.35~7.60(m, 15H), 7.88~7.99(m, 5H), 8.25~8.40(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.60 (m, 15H), 7.88-7.99 (m, 5H), 8.25-8.40 (m, 5H)

MS/FAB : 591(M+)MS / FAB: 591 (M + )

[[ 합성예Synthetic example 8] 화합물 [8]의 합성 8] Synthesis of Compound [8]

Figure pat00020
Figure pat00020

합성예4와동일한방법으로1-브로모이소퀴놀린 3.93g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [8] 4.5g(48%)을 수득하였다. In the same manner as in Synthesis Example 4 , 3.93 g (18.87 mmol) of 1-bromoisoquinoline and 10.1 g (20.76 mmol) of an intermediate compound [4-1] were used as a target compound of an off-white solid. [8] 4.5 g (48%) Obtained.

1H NMR (300 MHz, CDCl3):δ 7.10~7.70(m, 13H), 7.85~7.95(m, 6H), 8.40(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.10-7.70 (m, 13H), 7.85-7.95 (m, 6H), 8.40 (m, 2H)

MS/FAB : 487(M+)MS / FAB: 487 (M + )

[[ 합성예Synthetic example 9] 화합물 [9]의 합성 9] Synthesis of Compound [9]

Figure pat00021
Figure pat00021

합성예4와동일한방법으로 2-브로모퀴놀린 3.93g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 미색고체의 목적화합물 [9] 5.5g(60%)을 수득하였다. In the same manner as in Synthesis Example 4 , 5.5g (60%) of the target compound [9] was obtained using 3.93 g (18.87 mmol) of 2-bromoquinoline and 10.1 g (20.76 mmol) of the intermediate compound [4-1] . Obtained.

1H NMR (300 MHz, CDCl3):δ 7.30~7.55(m, 11H), 7.75~8.13(m, 9H), 8.45(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.30-7.55 (m, 11H), 7.75-8.13 (m, 9H), 8.45 (d, 1H)

MS/FAB : 487(M+)MS / FAB: 487 (M + )

[[ 합성예Synthetic example 10] 화합물 [10]의 합성 10] Synthesis of Compound [10]

Figure pat00022
Figure pat00022

합성예4와동일한방법으로2-브로모퀴나졸린3.94g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 노란색고체의 목적화합물 [10] 5.1g(55%)을 수득하였다. In the same manner as in Synthesis Example 4 , 2.94 g (18.87 mmol) of 2-bromoquinazolin and 10.1 g (20.76 mmol) of the intermediate compound [4-1] were used to obtain the target compound as a yellow solid [10] 5.1 g (55%) Obtained.

1H NMR (300 MHz, CDCl3):δ 7.35~7.56(m, 10H), 7.77~7.99(m, 7H), 8.40~8.50(m, 2H), 9.4(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.56 (m, 10H), 7.77-7.99 (m, 7H), 8.40-8.50 (m, 2H), 9.4 (s, 1H)

MS/FAB : 488(M+)MS / FAB: 488 (M + )

[[ 합성예Synthetic example 11] 화합물 [11]의 합성 11] Synthesis of Compound [11]

Figure pat00023
Figure pat00023

합성예4와동일한방법으로2-브로모퀴나졸린3.94g (18.87mmol), 중간체 화합물 [4-1] 10.1g (20.76mmol)을 사용하여 노란색고체의 목적화합물 [11] 6.1g(66%)을 수득하였다. In the same manner as in Synthesis Example 4 , 2.94 g (18.87 mmol) of 2-bromoquinazolin and 10.1 g (20.76 mmol) of the intermediate compound [4-1] were used as target compounds of yellow solid [11] 6.1 g (66%) Obtained.

1H NMR (300 MHz, CDCl3):δ 7.38~7.53(m, 9H), 7.63~8.01(m, 9H), 8.43(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.53 (m, 9H), 7.63-8.01 (m, 9H), 8.43 (m, 2H)

MS/FAB : 488(M+)MS / FAB: 488 (M + )

[[ 합성예Synthetic example 12] 화합물 [12]의 합성 12] Synthesis of Compound [12]

Figure pat00024
Figure pat00024

플라스크에 1-페닐-1H-이미다졸 3.0g (20.81mmol)을 무수 테트라히드로퓨란 100mL 로 교반하고 -78℃에서 2.5몰-부틸리튬 8.32mL (20.81mol)을 천천히 적가 시킨다. 동온도에서 트리메틸틴 클로라이드4.15g(20.81mmol)을 첨가시킨다. 상온까지 10시간 동안 서서히 올리고 반응액을 감압 농축한다. 농축액을 N,N-디메틸포름아미드 100mL로 녹이고 중간체 화합물 [1-5] 8.2g(18.73mmol)과 테트라키스(트리페닐포스핀)팔라듐 433mg(0.375mmol)을 첨가하여 160℃에서 12시간 동안 환류 교반한다. 반응액을 상온으로 냉각하고 메탄올 100mL를 가하여 노란색 고체의 목적 화합물 [12] 5.6g (59%)을 수득하였다. To the flask was stirred 3.0 g (20.81 mmol) of 1-phenyl-1H-imidazole with 100 mL of anhydrous tetrahydrofuran, and 8.32 mL (20.81 mol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. At the same temperature, 4.15 g (20.81 mmol) of trimethyltin chloride are added. Raise slowly for 10 hours to room temperature and concentrate the reaction solution under reduced pressure. The concentrate was dissolved in 100 mL of N, N-dimethylformamide, and 8.2 g (18.73 mmol) of the intermediate compound [1-5] and 433 mg (0.375 mmol) of tetrakis (triphenylphosphine) palladium were added and refluxed at 160 ° C. for 12 hours. Stir. The reaction solution was cooled to room temperature, and 100 mL of methanol was added to yield 5.6 g (59%) of the title compound [12] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.17~7.55(m, 16H), 7.90~8.00(m, 5H), 8.40(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.17 to 7.55 (m, 16H), 7.90 to 8.00 (m, 5H), 8.40 (d, 1H)

MS/FAB : 502(M+)MS / FAB: 502 (M + )

[[ 합성예Synthetic example 13] 화합물 [13]의 합성 13] Synthesis of Compound [13]

Figure pat00025
Figure pat00025

합성예 12와동일한방법으로티아졸1.77g (20.81mmol) 과 중간체 화합물 [1-5] 8.2g(18.73mmol)을 사용하여 미색 고체의 목적 화합물 [13] 4.6g (55%)을 수득하였다. Synthesis Example In the same manner as in 12, 4.6 g (55%) of the target compound [13] as a pale solid was obtained using 1.77 g (20.81 mmol) of thiazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] .

1H NMR (300 MHz, CDCl3):δ 7.38~7.54(m, 10H), 7.75~8.00(m, 6H), 8.41(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.54 (m, 10H), 7.75-8.00 (m, 6H), 8.41 (d, 1H)

MS/FAB : 443(M+)MS / FAB: 443 (M + )

[[ 합성예Synthetic example 14] 화합물 [14]의 합성 14] Synthesis of Compound [14]

Figure pat00026
Figure pat00026

플라스크에 중간체 화합물 [1-5] 8.2g(18.73mmol), 4H-1,2,4-트리아졸 1.29g(18.73mmol), 톨루엔 100mL 를 투입한다. 질소분위기에서 팔라듐아세테이트(II) 84mg (0.375mmol), 소디움터트부톡시드 2.7g(28.1mmol), 더트부틸포스핀(50% 톨루엔 용액) 1.8mL (0.75mmol)을 첨가하여 10시간동안 120℃에서 환류교반 시킨다. 반응액을 상온으로 냉각시켜 메탄올을 적가한다. 생성된 고체를 여과한다. 상온에서 진공건조하여 미색고체의 목적화합물 [14] 4.9g(61%)을 수득하였다. 8.2 g (18.73 mmol) of the intermediate compound [1-5] , 1.29 g (18.73 mmol) of 4H-1,2,4-triazole, and 100 mL of toluene were added to the flask. In a nitrogen atmosphere, 84 mg (0.375 mmol) of palladium acetate (II), 2.7 g (28.1 mmol) of sodium tertbutoxide, and 1.8 mL (0.75 mmol) of dibutyl butyl phosphine (50% toluene solution) were added for 10 hours at 120 DEG C. Stir at reflux. The reaction solution is cooled to room temperature and methanol is added dropwise. The resulting solid is filtered. Drying in vacuo at room temperature afforded 4.9 g (61%) of the target compound [14] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.35~7.54(m, 9H), 7.90~7.99(m, 5H), 8.45(d, 1H), 8.90(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.54 (m, 9H), 7.90-7.99 (m, 5H), 8.45 (d, 1H), 8.90 (s, 2H)

MS/FAB : 427(M+)MS / FAB: 427 (M + )

[[ 합성예Synthetic example 15] 화합물 [15]의 합성 15] Synthesis of Compound [15]

Figure pat00027
Figure pat00027

합성예 12와동일한방법으로1-페닐-1H-벤조[d]이미다졸 4.04g (20.81mmol) 과 중간체 화합물 [1-5] 8.2g(18.73mmol)을 사용하여 미색 고체의 목적 화합물 [15] 6.4g (65%)을 수득하였다. Synthesis Example 12. Vortex same manner as 1-phenyl -1H- benzo [d] imidazole 4.04g (20.81mmol) and the intermediate compound [1-5] 8.2g (18.73mmol) off-white solid target compound [15] 6.4g of Use (65%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.20~7.63(m, 17H), 7.90~8.00(m, 5H), 8.40~8.50(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.20-7.63 (m, 17H), 7.90-8.00 (m, 5H), 8.40-8.50 (m, 2H)

MS/FAB : 522(M+)MS / FAB: 522 (M + )

[[ 합성예Synthetic example 16] 화합물 [16]의 합성 16] Synthesis of Compound [16]

Figure pat00028
Figure pat00028

합성예 12와동일한방법으로벤조[d]옥사졸2.48g (20.81mmol) 과 중간체 화합물 [1-5] 8.2g(18.73mmol)을 사용하여 미색 고체의 목적 화합물 [16] 5.8g (65%)을 수득하였다. Synthesis Example 12. In the same manner, 2.5.8 g (20.81 mmol) of benzo [d] oxazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] were obtained to obtain 5.8 g (65%) of the target compound [16] as an off-white solid. It was.

1H NMR (300 MHz, CDCl3):δ 7.38~7.54(m, 11H), 7.74~8.01(m, 7H), 8.43(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.54 (m, 11H), 7.74-8.01 (m, 7H), 8.43 (d, 1H)

MS/FAB : 477(M+)MS / FAB: 477 (M + )

[[ 합성예Synthetic example 17] 화합물 [17]의 합성 17] Synthesis of Compound [17]

Figure pat00029
Figure pat00029

합성예 12와동일한방법으로벤조[d]티아졸 2.81g (20.81mmol) 과 중간체 화합물 [1-5] 8.2g (18.73mmol)을 사용하여 미색 고체의 목적 화합물 [17] 6.3g (68%)을 수득하였다. Synthesis Example 12. In the same manner, 2.81 g (20.81 mmol) of benzo [d] thiazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] were obtained to obtain 6.3 g (68%) of the target compound [17] as an off-white solid. It was.

1H NMR (300 MHz, CDCl3):δ 7.35~7.50(m, 11H), 7.89~8.05(m, 6H), 8.15(d, 1H), 8.45(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35 ~ 7.50 (m, 11H), 7.89 ~ 8.05 (m, 6H), 8.15 (d, 1H), 8.45 (d, 1H)

MS/FAB : 493(M+)MS / FAB: 493 (M + )

[[ 합성예Synthetic example 18] 화합물 [18]의 합성 18] Synthesis of Compound [18]

Figure pat00030
Figure pat00030

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 3-(1-페닐-1H-벤조[d]이미다졸-2-일)페닐 보론산4.29g(13.65mmol)을 사용하여 미색 고체의 목적 화합물 [18] 4.8g (67%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.29 g (13.65 mmol) of 3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl boronic acid in the same manner as in Synthesis example 1 To give 4.8 g (67%) of the title compound [18] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.20~7.26(m, 2H), 7.35~7.73(m, 18H), 7.90~8.00(m, 5H), 8.20~8.53(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.20-7.26 (m, 2H), 7.35-7.73 (m, 18H), 7.90-8.00 (m, 5H), 8.20-8.53 (m, 3H)

MS/FAB : 628(M+)MS / FAB: 628 (M + )

[[ 합성예Synthetic example 19] 화합물 [19]의 합성 19] Synthesis of Compound [19]

Figure pat00031
Figure pat00031

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 3-(벤조[d]티아졸-2-일)페닐 보론산3.48g(13.65mmol)을 사용하여 노란색 고체의 목적 화합물 [19] 4.1g (63%)을 수득하였다. In the same manner as in Synthesis example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.48 g (13.65 mmol) of 3- (benzo [d] thiazol-2-yl) phenylboronic acid were used to obtain a yellow solid. 4.1 g (63%) of the desired compound [19] were obtained.

1H NMR (300 MHz, CDCl3):δ 7.39~7.57(m, 13H), 7.88~8.01(m, 7H), 8.15(d, 1H), 8.40(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.57 (m, 13H), 7.88 to 8.01 (m, 7H), 8.15 (d, 1H), 8.40 (d, 1H)

MS/FAB : 569(M+)MS / FAB: 569 (M + )

[[ 합성예Synthetic example 20] 화합물 [20]의 합성 20] Synthesis of Compound [20]

Figure pat00032
Figure pat00032

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(4,5-디페닐-4H-1,2,4-트리아졸-3-일)페닐보론산4.66g (13.65mmol)을 사용하여 노란색 고체의 목적 화합물 [20] 4.9g (66%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid4.66 in the same manner as in Synthesis example 1 g (13.65 mmol) was used to obtain 4.9 g (66%) of the title compound [20] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.24(m, 2H), 7.35~7.54(m, 17H), 7.80~7.99(m, 7H), 8.25~8.40(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 (m, 2H), 7.35-7.54 (m, 17H), 7.80-7.99 (m, 7H), 8.25-8.40 (m, 3H)

MS/FAB : 655(M+)MS / FAB: 655 (M + )

[[ 합성예Synthetic example 21] 화합물 [21]의 합성 21] Synthesis of Compound [21]

Figure pat00033
Figure pat00033

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(3,5-디페닐-4H-1,2,4-트리아졸-4-일)페닐 보론산4.66g (13.65mmol)을 사용하여 노란색 고체의 목적 화합물 [21] 4.3g (58%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (3,5-diphenyl-4H-1,2,4-triazol-4-yl) phenyl boronic acid4.66 in the same manner as in Synthesis example 1 g (13.65 mmol) was used to give 4.3 g (58%) of the title compound [21] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.39~7.53(m, 15H), 7.60~7.80(m, 4H), 7.89~8.00(m, 5H), 8.25~8.39(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.53 (m, 15H), 7.60 to 7.80 (m, 4H), 7.89 to 8.00 (m, 5H), 8.25 to 8.39 (m, 5H)

MS/FAB : 655(M+)MS / FAB: 655 (M + )

[[ 합성예Synthetic example 22] 화합물 [22]의 합성 22] Synthesis of Compound [22]

Figure pat00034
Figure pat00034

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(2-페닐-1H-벤조[d]이미다졸-1-일)페닐 보론산4.29g (13.65mmol)을 사용하여 미색 고체의 목적 화합물 [22] 4.0g (56%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl boronic acid in the same manner as in Synthesis example 1 4.29 g (13.65 mmol) To give 4.0 g (56%) of the title compound [22] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.23(m, 2H), 7.37~7.50(m,13H), 7.65~7.75(m, 4H), 7.88~7.98(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.23 (m, 2H), 7.37 to 7.50 (m, 13H), 7.65 to 7.75 (m, 4H), 7.88 to 7.98 (m, 5H)

MS/FAB : 628(M+)MS / FAB: 628 (M + )

[[ 합성예Synthetic example 23] 화합물 [23]의 합성 23] Synthesis of Compound [23]

Figure pat00035
Figure pat00035

합성예 12와동일한방법으로6-브로모-2,2'-비피리딘 2.94g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [23] 3.3g (56%)을 수득하였다. Synthesis Example 12. Vortex same manner as 6-bromo-2,2'-bipyridine 2.94g (12.52mmol) and the intermediate compound [1-5] 5.0g (11.38mmol) off-white solid target compound [23] 3.3g of Use (56%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.01~7.10(m, 2H), 7.38~7.53(m, 9H), 7.65(m, 2H), 7.91~7.99(m, 5H), 8.40~8.55(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.10 (m, 2H), 7.38-7.53 (m, 9H), 7.65 (m, 2H), 7.91-7.99 (m, 5H), 8.40-8.55 ( m, 4H)

MS/FAB : 514(M+)MS / FAB: 514 (M + )

[[ 합성예Synthetic example 24] 화합물 [24]의 합성 24] Synthesis of Compound [24]

Figure pat00036
Figure pat00036

합성예 12와동일한방법으로티에노[3,2-b]티오펜 1.76g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [24] 3.0g (53%)을 수득하였다. Synthesis Example 12. In the same manner, 3.0 g of the target compound [24] as an off-white solid using 1.76 g (12.52 mmol) of thieno [3,2-b] thiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] 53%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.01~7.09(m, 3H), 7.38~7.55(m, 9H), 7.88~7.96(m, 5H), 8.41(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.09 (m, 3H), 7.38-7.55 (m, 9H), 7.88-7.96 (m, 5H), 8.41 (d, 1H)

MS/FAB : 498(M+)MS / FAB: 498 (M + )

[[ 합성예Synthetic example 25] 화합물 [25]의 합성 25] Synthesis of Compound [25]

Figure pat00037
Figure pat00037

합성예 12와동일한방법으로디티에노[3,2-b;2’,3’-d]티오펜 2.46g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [25] 3.3g (52%)을 수득하였다. Synthesis Example In the same manner as in 12 , off-white solid using 2.46 g (12.52 mmol) of dithieno [3,2-b; 2 ', 3'-d] thiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] 3.3 g (52%) of the desired compound [25] were obtained.

1H NMR (300 MHz, CDCl3):δ 7.10~7.20(m, 3H), 7.37~7.51(m, 9H), 7.89~7.98(m, 5H), 8.39(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.10-7.20 (m, 3H), 7.37-7.51 (m, 9H), 7.89-7.98 (m, 5H), 8.39 (d, 1H)

MS/FAB : 554(M+)MS / FAB: 554 (M + )

[[ 합성예Synthetic example 26] 화합물 [26]의 합성 26] Synthesis of Compound [26]

Figure pat00038
Figure pat00038

합성예 12와동일한방법으로티아졸로[5,4-d]티아졸 1.78g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [26] 2.8g (49%)을 수득하였다. Synthesis Example 12. In the same manner, 2.8 g of a target compound as an off-white solid using 1.78 g (12.52 mmol) of thiazolo [5,4-d] thiazole and 5.0 g (11.38 mmol) of the intermediate compound [1-5] ( 26) 49%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.35~7.55(m, 9H), 7.90~7.99(m, 5H), 8.41(d, 1H), 8.95(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.55 (m, 9H), 7.90-7.99 (m, 5H), 8.41 (d, 1H), 8.95 (s, 1H)

MS/FAB : 500(M+)MS / FAB: 500 (M + )

[[ 합성예Synthetic example 27] 화합물 [27]의 합성 27] Synthesis of Compound [27]

Figure pat00039
Figure pat00039

합성예 12와동일한방법으로벤조디티오펜 2.38g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [27] 3.0g (48%)을 수득하였다. Synthesis Example In the same manner as in 12, 2.38 g (12.52 mmol) of benzodithiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.0 g (48%) of the target compound [27] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.25~7.55(m, 10H), 7.60(d, 1H), 7.75~8.00(8H), 8.43(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.25 to 7.55 (m, 10H), 7.60 (d, 1H), 7.75 to 8.00 (8H), 8.43 (d, 1H)

MS/FAB : 548(M+)MS / FAB: 548 (M + )

[[ 합성예Synthetic example 28] 화합물 [28]의 합성 28] Synthesis of Compound [28]

Figure pat00040
Figure pat00040

합성예 12와동일한방법으로벤조디티아졸 2.40g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [28] 3.1g (49%)을 수득하였다. Synthesis Example In the same manner as in 12, 2.40 g (12.52 mmol) of benzodithiazole and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.1 g (49%) of the target compound [28] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.35~7.54(m, 10H), 7.65(s, 1H), 7.90~8.00(m, 5H), 8.40(d, 1H), 8.90(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.54 (m, 10H), 7.65 (s, 1H), 7.90-8.00 (m, 5H), 8.40 (d, 1H), 8.90 (s, 1H)

MS/FAB : 550(M+)MS / FAB: 550 (M + )

[[ 합성예Synthetic example 29] 화합물 [29]의 합성 29] Synthesis of Compound [29]

Figure pat00041
Figure pat00041

합성예 12와동일한방법으로나프토디티오펜 2.68g (12.52mmol) 과 중간체 화합물 [1-5] 5.0g (11.38mmol)을 사용하여 미색 고체의 목적 화합물 [29] 3.3g (51%)을 수득하였다. Synthesis Example In the same manner as in 12, 2.68 g (12.52 mmol) of naphthodithiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.3 g (51%) of the target compound [29] as an off-white solid.

1H NMR (300 MHz, CDCl3):δ 7.36~7.60(m, 11H), 7.79~8.01(m, 7H), 8.30~8.39(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.60 (m, 11H), 7.79-8.01 (m, 7H), 8.30-8.39 (m, 2H)

MS/FAB : 572(M+)MS / FAB: 572 (M + )

[[ 합성예Synthetic example 30] 화합물 [30]의 합성 30] Synthesis of Compound [30]

Figure pat00042
Figure pat00042

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(티에노[3,2-b]티오펜-2-일)페닐 보론산3.55g (13.65mmol)을 사용하여 연노란색 고체의 목적 화합물 [30] 4.1g (63%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.55 g (13.65 mmol) of 4- (thieno [3,2-b] thiophen-2-yl) phenyl boronic acid were prepared in the same manner as in Synthesis example 1 . To give 4.1 g (63%) of the desired compound [30] as a light yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.15~7.25(m, 5H), 7.36~7.53(m, 9H), 7.81~8.00(m, 7H), 8.39(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.15-7.25 (m, 5H), 7.36-7.53 (m, 9H), 7.81-8.00 (m, 7H), 8.39 (d, 1H)

MS/FAB : 574(M+)MS / FAB: 574 (M + )

[[ 합성예Synthetic example 31] 화합물 [31]의 합성 31] Synthesis of Compound [31]

Figure pat00043
Figure pat00043

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(티아졸로[5,4-d]티아졸-2-일) 페닐 보론산3.58g (13.65mmol)을 사용하여 연노란색 고체의 목적 화합물 [31] 3.8g (58%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.58 g (13.65 mmol) of 4- (thiazolo [5,4-d] thiazol-2-yl) phenylboronic acid were prepared in the same manner as in Synthesis example 1 . To give 3.8 g (58%) of the title compound [31] as a pale yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.25~7.55(m, 11H), 7.83~7.99(m, 7H), 8.41(d, 1H), 8.96(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.25 to 7.55 (m, 11H), 7.83 to 7.99 (m, 7H), 8.41 (d, 1H), 8.96 (s, 1H)

MS/FAB : 576(M+)MS / FAB: 576 (M + )

[[ 합성예Synthetic example 32] 화합물 [32]의 합성 32] Synthesis of Compound [32]

Figure pat00044
Figure pat00044

합성예1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(4,6-디페닐-1,3,5-트리아진-2-일) 페닐 보론산4.82g (13.65mmol)을 사용하여 연노란색 고체의 목적 화합물 [32] 4.8g (63%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.82 g of 4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl boronic acid in the same manner as in Synthesis example 1 13.65 mmol) was used to obtain 4.8 g (63%) of the title compound [32] as a light yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.23~7.53(m, 17H), 7.83~8.00(m, 7H), 8.27~8.38(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.23-7.53 (m, 17H), 7.83-8.00 (m, 7H), 8.27-8.38 (m, 5H)

MS/FAB : 667(M+)MS / FAB: 667 (M + )

[[ 합성예Synthetic example 33] 화합물 [33]의 합성 33] Synthesis of Compound [33]

Figure pat00045
Figure pat00045

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 디벤조[b,d]티오펜-4-일보론산3.11g (13.65mmol)을 사용하여 목적 화합물 [33] 3.6g (58%)을 수득하였다. In the same manner as in Synthesis Example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.11 g (13.65 mmol) of dibenzo [b, d] thiophen-4-ylboronic acid were used to obtain the target compound [33] 3.6 g (58%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.37~7.54(m, 12H), 7.90~8.00(m, 6H), 8.20~8.40(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.37-7.54 (m, 12H), 7.90-8.00 (m, 6H), 8.20-8.40 (m, 4H)

MS/FAB : 542(M+)MS / FAB: 542 (M + )

[[ 합성예Synthetic example 34] 화합물 [34]의 합성 34] Synthesis of Compound [34]

Figure pat00046
Figure pat00046

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 3-(디벤조[b,d]티오펜-3-일)페닐 보론산 4.15g (13.65mmol)을 사용하여 목적 화합물 [34] 4.6g (65%)을 수득하였다. 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.15 g (13.65 mmol) of 3- (dibenzo [b, d] thiophen-3-yl) phenyl boronic acid were used in the same manner as in Synthesis example 1. 4.6 g (65%) of the title compound [34] were obtained.

1H NMR (300 MHz, CDCl3):δ 7.35~7.70(m, 15H), 7.91~8.10(m, 9H), 8.40(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.70 (m, 15H), 7.91-8.10 (m, 9H), 8.40 (m, 2H)

MS/FAB : 618(M+)MS / FAB: 618 (M + )

[[ 합성예Synthetic example 35] 화합물 [35]의 합성 35] Synthesis of Compound [35]

Figure pat00047
Figure pat00047

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(디벤조[b,d]티오펜-4-일) 페닐 보론산 4.15g (13.65mmol)을 사용하여 목적 화합물 [35] 4.1g (58%)을 수득하였다. In the same manner as in Synthesis Example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.15 g (13.65 mmol) of 4- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid were used. 4.1 g (58%) of the title compound [35] were obtained.

1H NMR (300 MHz, CDCl3):δ 7.25~7.55(m, 16H), 7.91~7.99(m, 6H), 8.21~8.39(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.25 to 7.55 (m, 16H), 7.91 to 7.99 (m, 6H), 8.21 to 8.39 (m, 4H)

MS/FAB : 618(M+)MS / FAB: 618 (M + )

[[ 합성예Synthetic example 36] 화합물 [36]의 합성 36] Synthesis of Compound [36]

Figure pat00048
Figure pat00048

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 4-(9H-카바졸-9-일) 페닐 보론산 3.92g (13.65mmol)을 사용하여 목적 화합물 [36] 3.8g (55%)을 수득하였다. Using the intermediate compound [1-5] 5.0g (11.38mmol) and 4- (9H- carbazol-9-yl) phenylboronic acid 3.92g (13.65mmol) in the same manner as in Synthesis Example 1, the desired compound [36] 3.8 g (55%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.20~7.50(m, 13H), 7.69(m, 3H), 7.80(m, 2H), 7.90~8.10(m, 7H), 8.40~8.50(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.20 to 7.50 (m, 13H), 7.69 (m, 3H), 7.80 (m, 2H), 7.90 to 8.10 (m, 7H), 8.40 to 8.50 (m, 2H)

MS/FAB : 601(M+)MS / FAB: 601 (M + )

[[ 합성예Synthetic example 37] 화합물 [37]의 합성 37] Synthesis of Compound [37]

Figure pat00049
Figure pat00049

합성예 1과 동일한 방법으로 중간체 화합물 [1-5] 5.0g (11.38mmol) 과 9-페닐-9H-카바졸-3-일보론산 3.92g (13.65mmol)을 사용하여 목적 화합물 [37] 4.0g (58%)을 수득하였다. 4.0 g of the target compound [37] using 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.92 g (13.65 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid in the same manner as in Synthesis example 1. (58%) was obtained.

1H NMR (300 MHz, CDCl3):δ 7.30~7.60(m, 17H), 7.75(s, 1H), 7.90~8.00(m, 6H), 8.10(m, 2H), 8.40(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.30-7.70 (m, 17H), 7.75 (s, 1H), 7.90-8.00 (m, 6H), 8.10 (m, 2H), 8.40 (d, 1H)

MS/FAB : 601(M+)MS / FAB: 601 (M + )

[합성 예 38] 화합물 [38]의 합성 Synthesis Example 38 Synthesis of Compound [38]

Figure pat00050
Figure pat00050

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [1-5]의 합성과 동일한 방법으로 4-페닐디벤조[b,d]티오펜을 사용하여 합성한 중간체화합물[38-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)피리딘 2.40g(11.68mmol), 테트라키스포스5 g of intermediate compound [38-1] synthesized using 4-phenyldibenzo [b, d] thiophene in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]. (9.73 mmol) and 2.40 g (11.68 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine, tetrakisphos

피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [38] 3.4g(68%)를 얻었다.The off-white target compound [38] 3.4g (68%) was obtained using pinopalladium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(t, 1H), 7.38~7.54(m, 15H), 7.90~7.92(m, 4H), 8.21~8.22(d, 1H), 8.41~8.42(d, 1H), 8.50~8.51(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 ~ 7.02 (t, 1H), 7.38 ~ 7.54 (m, 15H), 7.90 ~ 7.92 (m, 4H), 8.21 ~ 8.22 (d, 1H), 8.41 ~ 8.42 (d, 1H), 8.50 ~ 8.51 (d, 1H)

MS/FAB : 513(M+)MS / FAB: 513 (M + )

[합성 예 39] 화합물 [39]의 합성Synthesis Example 39 Synthesis of Compound [39]

Figure pat00051
Figure pat00051

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)피리미딘 2.41g(11.68mmol), 테트라키스포스피노팔 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-yl) pyrimidine 2.41 g (11.68 mmol), tetrakisphosphinopal

라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [39] 3.1g(62%)를 얻었다.Radium and potassium carbonate were used to obtain 3.1 g (62%) of an off-white target compound .

1H NMR (300 MHz, CDCl3):δ 7.33~7.55(m, 14H), 7.90~7.92(m, 4H), 8.21~8.22(d, 1H), 8.41~8.42(d, 1H), 8.86~8.87(d, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.33 ~ 7.55 (m, 14H), 7.90 ~ 7.92 (m, 4H), 8.21 ~ 8.22 (d, 1H), 8.41 ~ 8.42 (d, 1H), 8.86 ~ 8.87 (d, 2 H)

MS/FAB : 514(M+)MS / FAB: 514 (M + )

[합성 예 40] 화합물 [40]의 합성Synthesis Example 40 Synthesis of Compound [40]

Figure pat00052
Figure pat00052

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)트리아진 2.42g(11.68mmol), 테트라키스포스피노팔 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) triazine 2.42 g (11.68 mmol), tetrakisphosphinopal

라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [40] 3.2g(63%)를 얻었다.3.2 g (63%) of off-white target compound were obtained using radium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.38~7.55(m, 13H), 7.90~7.92(m, 4H), 8.22~8.23(d, 1H), 8.42~8.43(d, 1H), 8.70(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.55 (m, 13H), 7.90-7.72 (m, 4H), 8.22-8.23 (d, 1H), 8.42-8.43 (d, 1H), 8.70 ( s, 2H)

MS/FAB : 515(M+)MS / FAB: 515 (M + )

[합성 예 41] 화합물 [41]의 합성Synthesis Example 41 Synthesis of Compound [41]

Figure pat00053
Figure pat00053

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 1-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)아이소퀴놀린 3.00g(11.68mmol), 테트라키스포스피 In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [38-1] and 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) isoquinoline 3.00 g (11.68 mmol), tetrakisphospho

노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [41] 4.1g(72%)를 얻었다.Nopalladium and potassium carbonate were used to obtain 4.1 g (72%) of an off-white target compound .

1H NMR (300 MHz, CDCl3):δ 7.10~7.11(d, 1H), 7.42~7.64(m, 16H), 7.90~7.92(m, 5H), 8.21~8.22(d, 1H), 8.41~8.42(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.10 to 7.71 (d, 1H), 7.42 to 7.74 (m, 16H), 7.90 to 7.72 (m, 5H), 8.21 to 8.22 (d, 1H), 8.41 to 8.42 (m, 2 H)

MS/FAB : 564(M+)MS / FAB: 564 (M + )

[합성 예 42] 화합물 [42]의 합성Synthesis Example 42 Synthesis of Compound [42]

Figure pat00054
Figure pat00054

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)퀴나졸린 3.00g(11.68mmol), 테트라키스포스피노팔 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) quinazoline 3.00 g (11.68 mmol), tetrakisphosphinopal

라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [42] 3.7g(68%)를 얻었다.3.7 g (68%) of off-white target compound were obtained using radium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.38~7.59(m, 14H), 7.85~7.91(m, 6H), 8.17~8.20(m, 2H), 8.40~8.41(d, 1H), 9.18(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.59 (m, 14H), 7.85-7.91 (m, 6H), 8.17-8.20 (m, 2H), 8.40-8.41 (d, 1H), 9.18 ( s, 1 H)

MS/FAB : 564(M+)MS / FAB: 564 (M + )

[합성 예 43] 화합물 [43]의 합성Synthesis Example 43 Synthesis of Compound [43]

Figure pat00055
Figure pat00055

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 1-페닐-2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)-1H-벤조[d]이미다졸3.74g(11.68mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [43] 3.6g(59%)를 얻었다. In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of intermediate compound [38-1] and 1-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-di 3.6 g (59%) of off-white target compound [43] was obtained by using oxaborolan-2-yl) -1H-benzo [d] imidazole (3.74 g, 11.68 mmol), tetrakisphosphinopalladium and potassium carbonate. Got it.

1H NMR (300 MHz, CDCl3):δ 7.21~7.22(m, 2H), 7.39~7.61(m, 19H), 7.89~7.90(m, 4H), 8.19~8.20(d, 1H), 8.41~8.42(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21 ~ 7.22 (m, 2H), 7.39 ~ 7.61 (m, 19H), 7.89 ~ 7.90 (m, 4H), 8.19 ~ 8.20 (d, 1H), 8.41 ~ 8.42 (m, 2 H)

MS/FAB : 628 (M+)MS / FAB: 628 (M + )

[합성 예 44] 화합물 [44]의 합성Synthesis Example 44 Synthesis of Compound [44]

Figure pat00056
Figure pat00056

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)-1H-벤조[d]티아졸3.10g(11.68mmol), 테트라키스 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl) -1H-benzo [d] thiazole3.10 g (11.68 mmol), tetrakis

포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [44] 3.3g(60%)를 얻었다.3.3 g (60%) of off-white target compound was obtained using phosphinopalladium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.39~7.54(m, 15H), 7.90~7.91(m, 4H), 8.00~8.01(d, 1H), 8.19~8.20(m, 2H), 8.41~8.42(m, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.54 (m, 15H), 7.90 to 7.91 (m, 4H), 8.00 to 8.01 (d, 1H), 8.19 to 8.20 (m, 2H), 8.41 to 8.42 (m, 1 H)

MS/FAB : 569 (M+)MS / FAB: 569 (M + )

[합성 예 45] 화합물 [45]의 합성Synthesis Example 45 Synthesis of Compound [45]

Figure pat00057
Figure pat00057

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 1-페닐-2-(3-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)페닐)-1H-벤조[d]이미다졸 4.63g(11.68 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 1-phenyl-2- (3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborane-2-yl) phenyl) -1H-benzo [d] imidazole 4.63 g (11.68)

mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [45] 4.8g(70%mmol), tetrakisphosphinopalladium, potassium carbonate, off-white compound [45] 4.8 g (70%)

)를 얻었다.)

1H NMR (300 MHz, CDCl3):δ 7.21~7.22(m, 2H), 7.38~7.59(m, 21H), 7.69(s, 1H), 7.90~7.91(m, 4H), 8.19~8.22(m, 2H), 8.41~8.42(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.22 (m, 2H), 7.38-7.59 (m, 21H), 7.69 (s, 1H), 7.90-7.91 (m, 4H), 8.19-8.22 ( m, 2H), 8.41-8.42 (m, 2H)

MS/FAB : 704 (M+)MS / FAB: 704 (M + )

[합성 예 46] 화합물 [46]의 합성Synthesis Example 46 Synthesis of Compound [46]

Figure pat00058
Figure pat00058

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 3,4-디페닐- In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 3,4-diphenyl-

5-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)페닐)-4H-1,2,4-트리아졸 4.94g(11.684.94 g (11.68) of 5- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -4H-1,2,4-triazole

mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [46]5.1g(71%mmol), tetrakisphosphinopalladium and potassium carbonate to give off-white compound [46] 5.1 g (71%)

)를 얻었다.)

1H NMR (300 MHz, CDCl3):δ 7.24~7.25(d, 2H), 7.38~7.60(m, 21H), 7.86~7.91(m, 6H), 8.20~8.21(d, 1H), 8.29~8.30(d, 2H), 8.41~8.42(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 to 7.25 (d, 2H), 7.38 to 7.60 (m, 21H), 7.86 to 7.91 (m, 6H), 8.20 to 8.21 (d, 1H), 8.29 to 8.30 (d, 2H), 8.41-8.42 (d, 1H)

MS/FAB : 731 (M+)MS / FAB: 731 (M + )

[합성 예 47] 화합물 [47]의 합성Synthesis Example 47 Synthesis of Compound [47]

Figure pat00059
Figure pat00059

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [38-1] 5g(9.73mmol)과 6'-(4,4,5,5- In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [38-1] and 6 '-(4,4,5,5-

테트라메틸-1,3,2-디옥사보란-2-닐)-2,3'-비피리딘 3.30g(11.68mmol), 테트라키스포스Tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30 g (11.68 mmol), tetrakisphos

피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [46] 3.6g(62%)를 얻었다.3.6 g (62%) of off-white target compound was obtained using pinopalladium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.35~7.51(m, 15H), 7.86~7.91(m, 5H), 8.05~8.06(d, 1H), 8.21~8.22(m, 4H), 8.41~8.42(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35 to 7.51 (m, 15H), 7.86 to 7.91 (m, 5H), 8.05 to 8.06 (d, 1H), 8.21 to 8.22 (m, 4H), 8.41 to 8.42 (d, 1 H)

MS/FAB : 590 (M+)MS / FAB: 590 (M + )

[합성 예 48] 화합물 [48]의 합성Synthesis Example 48 Synthesis of Compound [48]

Figure pat00060
Figure pat00060

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [1-5]의 합성과 동일한 방법으로 2-페닐디벤조[b,d]티오펜을 사용하여 합성한 중간체화합물[48-1] 5g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로란-2-닐)피리딘 2.40g(11.68mmol), 테트라키스포스5 g of intermediate compound [48-1] synthesized using 2-phenyldibenzo [b, d] thiophene in the same manner as in the synthesis of Synthesis Example [1] in the same manner as in the synthesis of intermediate compound [1-5]. (9.73 mmol) and 2.40 g (11.68 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine, tetrakisphos

피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [48] 3.2g(65%)를 얻었다.Pinopalladium and potassium carbonate were used to obtain 3.2 g (65%) of off-white target compound [48] .

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(t, 1H), 7.25~7.26(d, 1H), 7.39~7.52(m, 13H), 7.86~7.91(m, 5H), 7.99~8.00(m, 2H), 8.19~8.20(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 ~ 7.02 (t, 1H), 7.25 ~ 7.26 (d, 1H), 7.39 ~ 7.52 (m, 13H), 7.86 ~ 7.91 (m, 5H), 7.99 ~ 8.00 (m, 2H), 8.19-8.20 (d, 1H)

MS/FAB : 513(M+)MS / FAB: 513 (M + )

[합성 예 49] 화합물 [49]의 합성Synthesis Example 49 Synthesis of Compound [49]

Figure pat00061
Figure pat00061

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [48-1] 5g(9.73mmol)과 2-(3-(4,4,5, In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 2- (3- (4,4,5,

5-테트라메틸-1,3,2-디옥사보란-2-닐)페닐)벤조[d]티아졸 3.94g(11.68mmol), 테트라키스5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) benzo [d] thiazole 3.94 g (11.68 mmol), tetrakis

포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [49] 4.3g(68%)를 얻었다.4.3 g (68%) of off-white target compound was obtained using phosphinopalladium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.38~7.54(m, 16H), 7.71(s, 1H), 7.85~7.91(m, 5H), 7.99~8.02(m, 4H), 8.18~8.19(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.54 (m, 16H), 7.71 (s, 1H), 7.85-7.91 (m, 5H), 7.99-8.02 (m, 4H), 8.18-8.19 ( d, 1H)

MS/FAB : 645 (M+)MS / FAB: 645 (M + )

[합성 예 50] 화합물 [50]의 합성Synthesis Example 50 Synthesis of Compound [50]

Figure pat00062
Figure pat00062

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [48-1] 5g(9.73mmol)과 3,5-페닐-4- In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 3,5-phenyl-4-

(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)페닐)-4H-1,2,4-트리아졸 4.94g(11.68m4.94 g (11.68 m) (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -4H-1,2,4-triazole

mol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [50] 4.6g(64%mol), using off tetrakisphosphinopalladium and potassium carbonate, off-white compound [50] 4.6 g (64%)

)를 얻었다.)

1H NMR (300 MHz, CDCl3):δ 7.39~7.52(m, 18H), 7.68~7.69(d, 2H), 7.79~7.91(m, 7H), 7.99~8.01(m, 2H), 8.27~8.28(d, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.52 (m, 18H), 7.68 to 7.69 (d, 2H), 7.79 to 7.91 (m, 7H), 7.99 to 8.01 (m, 2H), 8.27 to 8.28 (d, 4H)

MS/FAB : 731 (M+)
MS / FAB: 731 (M + )

[합성 예 51] 화합물 [51]의 합성Synthesis Example 51 Synthesis of Compound [51]

Figure pat00063
Figure pat00063

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [48-1] 5g(9.73mmol)과 2-(4,4,5,5- In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [48-1] and 2- (4,4,5,5-

테트라메틸-1,3,2-디옥사보란-2-닐)페닐)-벤조[1,2-b:4,5-b']디티아졸 3.71g(11.68mmol), Tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -benzo [1,2-b: 4,5-b '] dithiazole 3.71 g (11.68 mmol),

테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [51] 3.8g(62%)를 얻Tetrakisphosphinopalladium and potassium carbonate were used to obtain 3.8 g (62%) of off-white target compound [51].

었다.It was.

1H NMR (300 MHz, CDCl3):δ 7.38~7.55(m, 13H), 7.66(s, 1H), 7.86~7.91(m, 5H), 7.99~8.01(m, 2H), 9.10(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.55 (m, 13H), 7.66 (s, 1H), 7.86-7.91 (m, 5H), 7.99-8.01 (m, 2H), 9.10 (s, 1H)

MS/FAB : 626 (M+)MS / FAB: 626 (M + )

[합성 예 52] 화합물 [52]의 합성Synthesis Example 52 Synthesis of Compound [52]

Figure pat00064
Figure pat00064

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [48-1] 5g(9.73mmol)과 4,4,5,5-테트 In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 4,4,5,5-tet

라메틸-2-(4-(티에노[3,2-b]티오펜-2-닐)페닐)-1,3,2-디옥산보란 4.00g(11.68mmol), 테Lamethyl-2- (4- (thieno [3,2-b] thiophen-2-yl) phenyl) -1,3,2-dioxaneborane 4.00 g (11.68 mmol), te

트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [52] 4.3g(68%)를 얻었Using trikisphosphinopalladium and potassium carbonate, 4.3g (68%) of off-white title compound [52] was obtained.

다.All.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(m, 2H), 7.22~7.25(m, 3H), 7.38~7.52(m, 12H), 7.86~7.91(m, 7H), 7.99~8.01(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 ~ 7.02 (m, 2H), 7.22 ~ 7.25 (m, 3H), 7.38 ~ 7.52 (m, 12H), 7.86 ~ 7.91 (m, 7H), 7.99 ~ 8.01 (m, 2H)

MS/FAB : 650 (M+)MS / FAB: 650 (M + )

[합성 예 53] 화합물 [53]의 합성Synthesis Example 53 Synthesis of Compound [53]

Figure pat00065
Figure pat00065

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [1-5]의 합성과 동일한 방법으로 2,42,4 in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]

-디페닐디벤조[b,d]티오펜을 사용하여 합성한 중간체화합물[53-1] 5.76g(9.73mmol)과 6'5.76 g (9.73 mmol) of intermediate compound [53-1] synthesized using diphenyldibenzo [b, d] thiophene and 6 '

-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)-2,3'-비피리딘 3.30g(11.68mmol), 테트-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30 g (11.68 mmol), tet

라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [53] 4.3g(66%)를 얻었다.Using rakisphosphinopalladium and potassium carbonate, 4.3g (66%) of off-white target compound [53] was obtained.

1H NMR (300 MHz, CDCl3):δ 7.36~7.52(m, 19H), 7.78(s, 1H), 7.90~7.96(m, 6H), 8.05~8.06(d, 1H), 8.19~8.20(d, 2H), 8.41~8.42(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.52 (m, 19H), 7.78 (s, 1H), 7.90-7.96 (m, 6H), 8.05-8.06 (d, 1H), 8.19-8.20 ( d, 2H), 8.41-8.42 (d, 1H)

MS/FAB : 666(M+)MS / FAB: 666 (M + )

[합성 예 54] 화합물 [54]의 합성Synthesis Example 54 Synthesis of Compound [54]

Figure pat00066
Figure pat00066

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [1-5]의 합성과 동일한 방법으로 In the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]

5-브로모무수프탈산을 사용하여 합성한 중간체화합물[54-1]에페닐을치환시킨후합성한 Intermediate compound [54-1] synthesized using 5-bromophthalic anhydride was substituted with phenyl and then synthesized.

중간체화합물 [54-3] 5.01g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보로레인-2-닐)-디티에노[3,2-b:2',3'-d]티오펜 3.76g(11.68mmol), 테트라키스포스피노팔라듐, Intermediate Compound [54-3] 5.01 g (9.73 mmol) and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl) -dithieno [3, 2-b: 2 ', 3'-d] thiophene 3.76 g (11.68 mmol), tetrakisphosphinopalladium,

탄산칼륨을 사용하여 미색의 목적화합물 [54] 4.0g(65%)를 얻었다.Potassium carbonate was used to obtain 4.0 g (65%) of an off-white compound .

1H NMR (300 MHz, CDCl3):δ 7.01~7.03(m, 2H), 7.18~7.19(d, 1H), 7.41~7.62(m, 13H), 7.91~7.98(m, 4H), 8.12(s, 1H), 8.19~8.20(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.03 (m, 2H), 7.18-7.19 (d, 1H), 7.41-7.82 (m, 13H), 7.91-7.98 (m, 4H), 8.12 ( s, 1H), 8.19-8.20 (d, 1H)

MS/FAB : 630(M+)MS / FAB: 630 (M + )

[합성 예 55] 화합물 [55]의 합성Synthesis Example 55 Synthesis of Compound [55]

Figure pat00067
Figure pat00067

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [54-3] 5.01g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)티아졸로[5,4-d]티아졸 3.13g(11.68mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [55] 3.4g(61%)를 얻었다. In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 3.13 g (11.68 mmol) of 2-yl) thiazolo [5,4-d] thiazole, tetrakisphosphinopalladium and potassium carbonate were used to obtain 3.4 g (61%) of an off-white target compound .

1H NMR (300 MHz, CDCl3):δ 7.41~7.60(m, 13H), 7.91~7.97(m, 4H), 8.12(s, 1H), 8.19~8.20(d, 1H), 9.10(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.41-7.60 (m, 13H), 7.91-7.97 (m, 4H), 8.12 (s, 1H), 8.19-8.20 (d, 1H), 9.10 (s, 1H)

MS/FAB : 576(M+)MS / FAB: 576 (M + )

[합성 예 56] 화합물 [56]의 합성Synthesis Example 56 Synthesis of Compound [56]

Figure pat00068
Figure pat00068

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [54-3] 5.01g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)- 벤조[1,2-b:4,5-b']디티오펜 3.69g(11.68 In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 2-neyl)- 3.69 g (11.68) benzo [1,2-b: 4,5-b '] dithiophene

mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [56] 3.6g(59%)를 얻었다.mmol), tetrakisphosphinopalladium, and potassium carbonate were used to obtain 3.6 g (59%) of an off-white target compound .

1H NMR (300 MHz, CDCl3):δ 7.38~7.62(m, 15H), 7.79~7.98(m, 7H), 8.13(s, 1H), 8.19~8.20(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.38-7.82 (m, 15H), 7.79-7.98 (m, 7H), 8.13 (s, 1H), 8.19-8.20 (d, 1H)

MS/FAB : 624(M+)MS / FAB: 624 (M + )

[합성 예 57] 화합물 [57]의 합성Synthesis Example 57 Synthesis of Compound [57]

Figure pat00069
Figure pat00069

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [54-3] 5.01g(9.73mmol)과 2-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)- 디벤조디티오펜 3.97g(11.68mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [57] 4.0g(64%)를 얻었다. In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 2-neyl)- 4.0 g (64%) of off-white target compound were obtained using 3.97 g (11.68 mmol) of dibenzodithiophene, tetrakisphosphinopalladium and potassium carbonate.

1H NMR (300 MHz, CDCl3):δ 7.40~7.58(m, 15H), 7.80~7.98(m, 6H), 8.13(s, 1H), 8.19~8.20(d, 1H), 8.24(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.40 to 7.58 (m, 15H), 7.80 to 7.98 (m, 6H), 8.13 (s, 1H), 8.19 to 8.20 (d, 1H), 8.24 (s, 1H)

MS/FAB : 648(M+)MS / FAB: 648 (M + )

[합성 예 58] 화합물 [58]의 합성Synthesis Example 58 Synthesis of Compound [58]

Figure pat00070
Figure pat00070

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [54-3] 5.01g(9.73mmol)과 4,4,5,5- In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 4,4,5,5-

테트라메틸-2-(4-(티아졸로[3,2-b]티아졸-2-닐)페닐)-1,3,2-디옥산보란 4.02g(11.68mmTetramethyl-2- (4- (thiazolo [3,2-b] thiazol-2-yl) phenyl) -1,3,2-dioxaneborane 4.02 g (11.68 mm)

ol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [58] 4.3g(68%)를 ol), tetrakisphosphinopalladium and potassium carbonate, to give 4.3 g (68%) of off-white target compound .

얻었다.Got it.

1H NMR (300 MHz, CDCl3):δ 7.24~7.25(d, 2H), 7.40~7.61(m, 13H), 7.85~7.98(m, 6H), 8.12(s, 1H), 8.19~8.20(d, 1H), 9.10(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 to 7.25 (d, 2H), 7.40 to 7.61 (m, 13H), 7.85 to 7.98 (m, 6H), 8.12 (s, 1H), 8.19 to 8.20 ( d, 1H), 9.10 (s, 1H)

MS/FAB : 652(M+)MS / FAB: 652 (M + )

[합성 예 59] 화합물 [59]의 합성Synthesis Example 59 Synthesis of Compound [59]

Figure pat00071
Figure pat00071

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [54-3] 5.01g(9.73mmol)과 2,4-디페 In the same manner as in Synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of intermediate compound [54-3] and 2,4-dipe

닐-6-(4-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)페닐)-1,3,5-트리아진 5.08g(11.68Neil-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -1,3,5-triazine 5.08 g (11.68

mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [59] 4.8g(66mmol), tetrakisphosphinopalladium, potassium carbonate, off-white compound [59] 4.8 g (66)

%)를 얻었다.%) Was obtained.

1H NMR (300 MHz, CDCl3):δ 7.24~7.25(d, 2H), 7.41~7.60(m, 19H), 7.86~7.97(m, 6H), 8.12(s, 1H), 8.21~8.22(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 to 7.25 (d, 2H), 7.41 to 7.60 (m, 19H), 7.86 to 7.97 (m, 6H), 8.12 (s, 1H), 8.21 to 8.22 ( m, 5H)

MS/FAB : 743(M+)MS / FAB: 743 (M + )

[합성 예 60] 화합물 [60]의 합성Synthesis Example 60 Synthesis of Compound [60]

Figure pat00072
Figure pat00072

합성예 [1]의 합성과 동일한 방법으로, 중간체화합물 [1-5]의 합성과 동일한 방법으로 2,4-2,4- in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5].

디페닐디벤조[b,d]티오펜과 5-브로모무수프탈산 사용하여 합성한 중간체화합물[60-1] 6. Intermediate compounds synthesized using diphenyldibenzo [b, d] thiophene and 5-bromophthalic anhydride [60-1] 6.

50g(9.73mmol)과 6'-(4,4,5,5-테트라메틸-1,3,2-디옥사보란-2-닐)-2,3'-비피리딘 3.3050 g (9.73 mmol) and 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30

g(11.68mmol), 테트라키스포스피노팔라듐, 탄산칼륨을 사용하여 미색의 목적화합물 [60] Off-white compound using g (11.68 mmol), tetrakisphosphinopalladium, potassium carbonate [60]

4.7g(65%)를 얻었다.4.7 g (65%) were obtained.

1H NMR (300 MHz, CDCl3):δ 7.32~7.60(m, 23H), 7.76(s, 1H), 7.85~8.12(m, 8H), 8.21~8.22(d, 1H), 8.41~8.42(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.32-7.60 (m, 23H), 7.76 (s, 1H), 7.85-8.12 (m, 8H), 8.21-8.22 (d, 1H), 8.41-8.42 ( d, 1H)

MS/FAB : 742(M+)MS / FAB: 742 (M + )

[합성 예 61] 화합물 [61]의 합성Synthesis Example 61 Synthesis of Compound [61]

Figure pat00073
Figure pat00073

플라스크에 2-브로모피리딘 20g(66.58mmol), 마그네슘(Mg) 1.78g(73.24mmol), 무수 테트라하이드로퓨란 0.5L를 넣고 환류교반한다. Mg가 완전히 녹으면 상온에서 [1-3] 20g(66.58mmol)을 넣고 환류교반한다. 반응종료 후 상온에서 층분리하여 얻은 유기층을 무수황산마그네슘으로 건조 후 여과한다. 여과액을 감압증류하여 얻은 고체를 디클로로메탄과 메탄올로 재결정하여 노란색의 중간체 화합물 [61-1] 10.1g(42%)을 수득하였다 20 g (66.58 mmol) of 2-bromopyridine, 1.78 g (73.24 mmol) of magnesium (Mg), and 0.5 L of anhydrous tetrahydrofuran are added and stirred under reflux. When Mg is completely dissolved, add 20 g (66.58 mmol) of [1-3] at room temperature and reflux the mixture. After completion of the reaction, the organic layer obtained by layer separation at room temperature is dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure and the solid obtained was recrystallized from dichloromethane and methanol to obtain 10.1 g (42%) of a yellow intermediate compound [61-1].

합성예 1 과 동일한 방법으로 중간체 화합물 [61-1], N-브로모숙신이미드, 디메틸포름 아미드를 사용하여 중간체 화합물 [61-2]를얻었다. The intermediate compound [61-2] was obtained using the intermediate compound [ 61-1], N-bromosuccinimide and dimethylform amide in the same manner as in Synthesis example 1 .

합성예 1과 동일한 방법으로 중간체 화합물 [61-2] 5g(11.35mmol), 페닐보론산, 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적 화합물 [61] 3.6g(73%)을 수득하였다. In the same manner as in Synthesis Example 1 , 3.6 g (73%) of off-white target compound [61] was obtained by using 5 g (11.35 mmol) of intermediate compound [61-2], phenylboronic acid, and tetrakis (triphenylphosphine) palladium. Obtained.

1H NMR (300 MHz, CDCl3):δ 7.01~7.03(t, 1H), 7.26~7.27(d, 1H), 7.40~7.53(m, 10H), 7.92~8.01(m, 5H), 8.45~8.50(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 ~ 7.03 (t, 1H), 7.26 ~ 7.27 (d, 1H), 7.40 ~ 7.53 (m, 10H), 7.92 ~ 8.01 (m, 5H), 8.45 ~ 8.50 (m, 2 H)

MS/FAB : 437 (M+)MS / FAB: 437 (M + )

[합성 예 62] 화합물 [62]의 합성 Synthesis Example 62 Synthesis of Compound [62]

Figure pat00074
Figure pat00074

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 2-클로로피리미딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [62] 3.4g(70%)을 수득하였다Intermediate compound [1-3], 2-chloropyrimidine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [62] 3.4g (70%) to give

1H NMR (300 MHz, CDCl3):δ 7.36~7.41(m, 4H), 7.47~7.54(m, 6H), 7.90~7.98(m, 5H), 8.45~8.46(d, 1H), 8.85~8.87(d, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.41 (m, 4H), 7.47-7.54 (m, 6H), 7.90-7.98 (m, 5H), 8.45-8.46 (d, 1H), 8.85- 8.87 (d, 2 H)

MS/FAB : 438 (M+)MS / FAB: 438 (M + )

[합성 예 63] 화합물 [63]의 합성Synthesis Example 63 Synthesis of Compound [63]

Figure pat00075
Figure pat00075

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 2-클로로-4,6-디페닐-1,3,5-트리아진, 마그네슘, N-브로모썩신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [63] 3.2g(65%)을 수득하였다Intermediate compound [1-3], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 3.2 g (65%) of off-white target compound [63].

1H NMR (300 MHz, CDCl3):δ 7.33~7.40(m, 5H), 7.42~7.53(m, 10H), 7.91~7.97(m, 5H), 8.26~8.30(m, 4H), 8.45~8.46(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.33-7.40 (m, 5H), 7.42-7.53 (m, 10H), 7.91-7.97 (m, 5H), 8.26-8.30 (m, 4H), 8.45- 8.46 (d, 1 H)

MS/FAB : 591 (M+)MS / FAB: 591 (M + )

[합성 예 64] 화합물 [64]의 합성Synthesis Example 64 Synthesis of Compound [64]

Figure pat00076
Figure pat00076

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 2-클로로퀴놀린, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [64] 3.7g(76%)을 수득하였다Intermediate compound [1-3], 2-chloroquinoline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 3.7 g (76%) of an off-white target compound [64].

1H NMR (300 MHz, CDCl3):δ 7.44~7.52(m, 5H), 7.55~7.62(m, 6H), 7.78~7.83(m, 2H), 7.90~7.97(m, 5H), 8.07~8.11(m, 2H), 8.45~8.46(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.44 to 7.52 (m, 5H), 7.55 to 7.72 (m, 6H), 7.78 to 7.83 (m, 2H), 7.90 to 7.97 (m, 5H), 8.07 to 8.11 (m, 2H), 8.45-8.46 (d, 1H)

MS/FAB : 487 (M+)MS / FAB: 487 (M + )

[합성 예 65] 화합물 [65]의 합성Synthesis Example 65 Synthesis of Compound [65]

Figure pat00077
Figure pat00077

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 2-클로로퀴노잘린, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [65] 3.5g(71%)을 수득하였다Intermediate compound [1-3], 2-chloroquinozaline, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [65] 3.5g (71%) to give

1H NMR (300 MHz, CDCl3):δ 7.39~7.51(m, 9H), 7.67~7.69(m, 2H), 7.80~7.83(m, 2H), 7.93~7.99(m, 5H), 8.44~8.45(d, 1H), 8.72(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.51 (m, 9H), 7.67 to 7.69 (m, 2H), 7.80 to 7.83 (m, 2H), 7.93 to 7.99 (m, 5H), 8.44 to 8.45 (d, 1 H), 8.72 (s, 1 H)

MS/FAB : 488 (M+)MS / FAB: 488 (M + )

[합성 예 66] 화합물 [66]의 합성Synthesis Example 66 Synthesis of Compound [66]

Figure pat00078
Figure pat00078

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 2-(3-브로모페닐)-1-패닐-1H-벤조[d]이미다졸, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [66] 2.5g(52%)을 수득하였다Intermediate compound [1-3], 2- (3-bromophenyl) -1-panyl-1H-benzo [d] imidazole, magnesium, N-bromosuccinimide, phenyl boron in the same manner as in Synthesis example 61 mountain. Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [66] 2.5g (52%) to give

1H NMR (300 MHz, CDCl3):δ 7.23~7.25(m, 2H), 7.36~7.49(m, 6H), 7.53~7.74(m, 12H), 7.93~8.01(m, 5H), 8.25~8.26(d, 1H), 8.52~8.57(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.23 ~ 7.25 (m, 2H), 7.36 ~ 7.49 (m, 6H), 7.53 ~ 7.74 (m, 12H), 7.93 ~ 8.01 (m, 5H), 8.25 ~ 8.26 (d, 1 H), 8.52-8.57 (m, 2 H)

MS/FAB : 628 (M+)MS / FAB: 628 (M + )

[합성 예 67] 화합물 [67]의 합성Synthesis Example 67 Synthesis of Compound [67]

Figure pat00079
Figure pat00079

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 3,4,5-트리페닐-4H-1,2,4-트리아졸, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [67] 2.3g(46%)을 수득하였다Intermediate compound [1-3], 3,4,5-triphenyl-4H-1,2,4-triazole, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [67] 2.3g (46%) to give

1H NMR (300 MHz, CDCl3):δ 7.24~7.27(m, 2H), 7.36~7.54(m, 17H), 7.86~7.99(m, 7H), 8.37~8.42(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 to 7.27 (m, 2H), 7.36 to 7.74 (m, 17H), 7.86 to 7.99 (m, 7H), 8.37 to 8.42 (m, 3H)

MS/FAB : 655 (M+)MS / FAB: 655 (M + )

[합성 예 68] 화합물 [68]의 합성Synthesis Example 68 Synthesis of Compound [68]

Figure pat00080
Figure pat00080

합성예 61과 동일한 방법으로 중간체 화합물 [1-3], 6-브로모-2,3-바이피리딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [68] 2.8g(58%)을 수득하였다Intermediate compound [1-3], 6-bromo-2,3-bipyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [68] 2.8g (58%) to give

1H NMR (300 MHz, CDCl3):δ 7.30~7.39(m, 5H), 7.42~7.53(m, 6H), 7.89~8.00(m, 6H), 8.09~8.13(m, 2H), 8.48~8.52(m, 2H), 9.27(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.30-7.39 (m, 5H), 7.42-7.53 (m, 6H), 7.89-8.00 (m, 6H), 8.09-8.13 (m, 2H), 8.48- 8.52 (m, 2H), 9.27 (s, 1H)

MS/FAB : 514 (M+)MS / FAB: 514 (M + )

[합성 예 69] 화합물 [69]의 합성Synthesis Example 69 Synthesis of Compound [69]

Figure pat00081
Figure pat00081

합성예 61과 동일한 방법으로 합성예 [38]의중간체화합물, 2-브로모피리딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [69] 2.3g(46%)을 수득하였다Intermediate compound of Synthesis Example [38] , 2-bromopyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [69] 2.3g (46%) to give

1H NMR (300 MHz, CDCl3):δ 7.16~7.19(m, 2H), 7.38~7.44(m, 4H), 7.46~7.55(m, 10H), 7.88~7.93(m, 4H), 8.21(d, 1H), 8.42~8.48(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.16 to 7.19 (m, 2H), 7.38 to 7.44 (m, 4H), 7.46 to 7.55 (m, 10H), 7.88 to 7.73 (m, 4H), 8.21 ( d, 1H), 8.42-8.48 (m, 2H)

MS/FAB : 513 (M+)MS / FAB: 513 (M + )

[합성 예 70] 화합물 [70]의 합성Synthesis Example 70 Synthesis of Compound [70]

Figure pat00082
Figure pat00082

합성예 61과 동일한 방법으로 합성예 [38]의중간체화합물, 2-브로모피리미딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [70] 2.0g(41%)을 수득하였다The intermediate compound of Synthesis Example [38] , 2-bromopyrimidine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 2.0 g (41%) of off-white target compound [70].

1H NMR (300 MHz, CDCl3):δ 7.36~7.50(m, 14H), 7.87~7.92(m, 4H), 8.30~8.33(m, 2H), 8.85~8.88(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36 to 7.50 (m, 14H), 7.87 to 7.72 (m, 4H), 8.30 to 8.33 (m, 2H), 8.85 to 8.88 (m, 2H)

MS/FAB : 514 (M+)MS / FAB: 514 (M + )

[합성 예 71] 화합물 [71]의 합성Synthesis Example 71 Synthesis of Compound [71]

Figure pat00083
Figure pat00083

합성예 61과 동일한 방법으로 합성예 [38]의중간체화합물, 2-클로로-4,6-디페닐-1,3,5-트리아진, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)The intermediate compound of Synthesis Example [38], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine)

팔라듐을 사용하여 미색의 목적화합물 [71] 1.6g(32%)을 수득하였다Palladium was used to obtain 1.6 g (32%) of off-white compound [71].

1H NMR (300 MHz, CDCl3):δ 7.36~7.42(m, 6H), 7.47~7.53(m, 13H), 7.89~7.93(m, 4H), 8.21~8.26(m, 5H), 8.40~8.41(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.42 (m, 6H), 7.47-7.53 (m, 13H), 7.89-7.83 (m, 4H), 8.21-8.26 (m, 5H), 8.40- 8.41 (d, 1 H)

MS/FAB : 667 (M+)MS / FAB: 667 (M + )

[합성 예 72] 화합물 [72]의 합성Synthesis Example 72 Synthesis of Compound [72]

Figure pat00084
Figure pat00084

합성예 61과 동일한 방법으로 합성예 [48]의중간체화합물, 2-클로로퀴놀린, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [72] 2.2g(44%)을 수득하였다The intermediate compound of Synthesis Example [48] , 2-chloroquinoline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [72] 2.2g (44%) to give

1H NMR (300 MHz, CDCl3):δ 7.35~7.42(m, 5H), 7.51~7.58(m, 9H), 7.91~7.99(m, 6H), 8.02~8.12(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.42 (m, 5H), 7.51-7.58 (m, 9H), 7.91-7.99 (m, 6H), 8.02-8.12 (m, 5H)

MS/FAB : 563 (M+)MS / FAB: 563 (M + )

[합성 예 73] 화합물 [73]의 합성Synthesis Example 73 Synthesis of Compound [73]

Figure pat00085
Figure pat00085

합성예 61과 동일한 방법으로 합성예 [48]의중간체화합물, 2-클로로퀴노잘린, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [73] 1.7g(35%)을 수득하였다The intermediate compound of Synthesis Example [48] , 2-chloroquinozaline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [73] 1.7g (35%) to give

1H NMR (300 MHz, CDCl3):δ 7.39~7.42(m, 4H), 7.47~7.54(m, 8H), 7.61~7.65(m, 2H), 7.88~7.96(m, 7H), 7.99~8.01(m, 2H), 8.72(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.42 (m, 4H), 7.47 to 7.74 (m, 8H), 7.61 to 7.75 (m, 2H), 7.88 to 7.96 (m, 7H), 7.99 to 8.01 (m, 2H), 8.72 (s, 1H)

MS/FAB : 564 (M+)MS / FAB: 564 (M + )

[합성 예 74] 화합물 [74]의 합성Synthesis Example 74 Synthesis of Compound [74]

Figure pat00086
Figure pat00086

합성예 61과 동일한 방법으로 합성예 [48]의중간체화합물, 2-(3-브로모페닐)-1-패닐-1H-벤조[d]이미다졸, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [74] 1.6g(33%)을 수득하였다Intermediate compound of Synthesis Example [48] , 2- (3-bromophenyl) -1-panyl-1H-benzo [d] imidazole, magnesium, N-bromosuccinimide, phenyl in the same manner as in Synthesis Example 61 Boronic acid. Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [74] 1.6g (33%) to give

1H NMR (300 MHz, CDCl3):δ 7.21~7.23(m, 2H), 7.35~7.48(m, 11H), 7.55~7.69(m, 10H), 7.87~7.94(m, 5H), 8.00~8.03(m, 2H), 8.41~8.44(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21 ~ 7.23 (m, 2H), 7.35 ~ 7.48 (m, 11H), 7.55 ~ 7.69 (m, 10H), 7.87 ~ 7.94 (m, 5H), 8.00 ~ 8.03 (m, 2H), 8.41-8.44 (m, 2H)

MS/FAB : 704 (M+)MS / FAB: 704 (M + )

[합성 예 75] 화합물 [75]의 합성Synthesis Example 75 Synthesis of Compound [75]

Figure pat00087
Figure pat00087

합성예 61과 동일한 방법으로 합성예 [54]의중간체화합물, 3,4,5-트리페닐-4H-1,2,4-트리아졸, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [75] 1.3g(26%)을 수득하였다The intermediate compound of Synthesis Example [54], 3,4,5-triphenyl-4H-1,2,4-triazole, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 1.3 g (26%) of off-white target compound [75].

1H NMR (300 MHz, CDCl3):δ 7.24~7.26(m, 2H), 7.38~7.53(m, 21H), 7.86~7.91(m, 4H), 7.98~8.02(m, 3H), 8.36~8.41(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.24 to 7.26 (m, 2H), 7.38 to 7.53 (m, 21H), 7.86 to 7.91 (m, 4H), 7.98 to 8.02 (m, 3H), 8.36 to 8.41 (m, 3 H)

MS/FAB : 731 (M+)MS / FAB: 731 (M + )

[합성 예 76] 화합물 [76]의 합성Synthesis Example 76 Synthesis of Compound [76]

Figure pat00088
Figure pat00088

합성예 61과 동일한 방법으로 합성예 [54]의중간체화합물, 6-브로모-2,3-바이피리딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [76] 2.1g(43%)을 수득하였다The intermediate compound of Synthesis Example [54], 6-bromo-2,3-bipyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [76] 2.1g (43%) to give

1H NMR (300 MHz, CDCl3):δ 7.45~7.52(m, 9H), 7.54~7.62(m, 6H), 7.86~7.99(m, 5H), 8.14~8.19(m, 3H), 8.48~8.51(m, 2H), 9.28(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.45 to 7.52 (m, 9H), 7.54 to 7.72 (m, 6H), 7.86 to 7.99 (m, 5H), 8.14 to 8.19 (m, 3H), 8.48 to 8.51 (m, 2H), 9.28 (s, 1H)

MS/FAB : 590 (M+)MS / FAB: 590 (M + )

[합성 예 77] 화합물 [77]의 합성Synthesis Example 77 Synthesis of Compound [77]

Figure pat00089
Figure pat00089

합성예 61과 동일한 방법으로 합성예 [60]의중간체화합물, 2-브로모피리딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [77] 1.9g(38%)을 수득하였다The intermediate compound of Synthesis Example [60], 2-bromopyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [77] 1.9g (38%) to give

1H NMR (300 MHz, CDCl3):δ 7.08~7.11(m, 2H), 7.44~7.56(m, 21H), 7.69~7.71(m, 2H), 7.97~8.07(m, 5H), 8.49(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.08 to 7.71 (m, 2H), 7.44 to 7.72 (m, 21H), 7.69 to 7.71 (m, 2H), 7.97 to 8.07 (m, 5H), 8.49 ( s, 1 H)

MS/FAB : 665 (M+)MS / FAB: 665 (M + )

[합성 예 78] 화합물 [78]의 합성Synthesis Example 78 Synthesis of Compound [78]

Figure pat00090
Figure pat00090

합성예 61과 동일한 방법으로 합성예 [60]의중간체화합물, 2-브로모피리미딘, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)팔라듐을 사용하여 미색의 목적화합물 [78] 1.6g(33%)을 수득하였다The intermediate compound of Synthesis Example [60], 2-bromopyrimidine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 1.6 g (33%) of off-white target compound [78].

1H NMR (300 MHz, CDCl3):δ 7.36~7.44(m, 11H), 7.47~7.52(m, 10H), 7.69~7.72(m, 2H), 7.98~8.05(m, 5H), 8.83~8.85(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.36-7.44 (m, 11H), 7.47-7.52 (m, 10H), 7.69-7.72 (m, 2H), 7.98-8.05 (m, 5H), 8.83- 8.85 (m, 2 H)

MS/FAB : 666 (M+)MS / FAB: 666 (M + )

[합성 예 79] 화합물 [79]의 합성Synthesis Example 79 Synthesis of Compound [79]

Figure pat00091
Figure pat00091

합성예 61과 동일한 방법으로 합성예 [60]의중간체화합물, 2-클로로-4,6-디페닐-1,3,5-트리아진, 마그네슘, N-브로모숙신이미드, 페닐보론산. 테트라키스(트리페닐포스핀)Intermediate compound of Synthesis Example [60], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine)

팔라듐을 사용하여 미색의 목적화합물 [79] 0.9g(18%)을 수득하였다Palladium was used to obtain 0.9 g (18%) of an off-white compound.

1H NMR (300 MHz, CDCl3):δ 7.37~7.42(m, 6H), 7.47~7.56(m, 20H), 7.68~7.71(m, 2H), 7.96~8.04(m, 5H), 8.27~8.30(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.37 to 7.42 (m, 6H), 7.47 to 7.72 (m, 20H), 7.68 to 7.71 (m, 2H), 7.96 to 8.04 (m, 5H), 8.27 to 8.30 (m, 4H)

MS/FAB : 820 (M+)MS / FAB: 820 (M + )

[합성 예 80] 화합물 [80]의 합성Synthesis Example 80 Synthesis of Compound [80]

Figure pat00092
Figure pat00092

합성예 1과 동일한 방법으로 2-브로모피리딘 10g(63.29mmol), 디벤조d[b,d]싸이오펜-4-일보론산 17.3g(75.94mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.26mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[80-1] 12.4g(75%)을 수득하였다.2-bromopyridine 10g (63.29mmol), dibenzod [b, d] thiophen-4-ylboronic acid 17.3g (75.94mmol), tetrakis (triphenylphosphine) palladium 1.4 in the same manner as in Synthesis example 1 g (1.26 mmol), 2M aqueous sodium carbonate solution was used to obtain 12.4 g (75%) of an intermediate compound [ 80-1] as a yellow solid.

합성예 1과 동일한 방법으로 화합물[80-1] 12g(45.91mmol), 이소벤조퓨란-1,3-디온 6.1g(41.32mmol), 알루미늄 클로라이드 15.3g(114.79mmol)을 사용하여 연노란 고체의 중간체 화합물[80-2] 14.4g(85%)을 수득하였다.12 g (45.91 mmol) of Compound [80-1] , 6.1 g (41.32 mmol) of isobenzofuran-1,3-dione, and 15.3 g (114.79 mmol) of aluminum chloride were used in the same manner as in Synthesis example 1. 14.4 g (85%) of compound [80-2] was obtained.

250ml 둥근바닥 플라스크에 화합물[80-1] 14g(45.91mmol), 펜타클로로인산 10g(mmol), 알루미늄 클로라이드 15.3g(114.79mmol), 1,2-디클로로벤젠 150ml을 사용하여 140℃에서 12시간 환류교반한다. 반응액을 실온까지 냉각 실리카겔여과 후 여액을 메탄올로 재결정화 하여 노란색 고체의 중간체 화합물[80-3] 14.0g(70%)을 수득하였다.Refrigerated at 140 ° C for 12 hours using 14 g (45.91 mmol) of Compound [80-1] , 10 g (mmol) of pentachlorophosphate, 15.3 g (114.79 mmol) of aluminum chloride, and 150 ml of 1,2-dichlorobenzene in a 250 ml round bottom flask. Stir. The reaction solution was cooled to room temperature and then filtered through silica gel, and the filtrate was recrystallized from methanol to obtain 14.0 g (70%) of an intermediate compound [80-3] as a yellow solid.

500ml 둥근바닥 플라스크에 화합물 화합물[80-1] 14g(35.76mmol), 테트라히드로퓨란 300ml을 가하여 녹인 후 질소분위기에서 0℃까지 냉각한 다음 수소화 알류미늄 리튬 5.4g(143.06mmol)을 천천히 가한 후 2시간 교반한다. 동온도에서 수소화 알류미늄 리튬 2.7g(71.53mmol)을 천천히 가한 후 실온에서 2시간 교반한다. 반응종료 후 반응액을 냉각한 다음 염산수용액(6M)을 천천히 가하여 결정화 한다. 고체 여과 후 물,에탄올과 헥산으로 세척한 다음 테트라히드로퓨란과 메탄올로 재결정화하여 노란색 고체의 중간체 화합물[80-4] 7.7g(60%)을 수득하였다. After dissolving 14 g (35.76 mmol) of compound [80-1] and 300 ml of tetrahydrofuran in a 500 ml round bottom flask, the mixture was cooled to 0 ° C. in a nitrogen atmosphere, and then slowly added 5.4 g (143.06 mmol) of lithium aluminum hydride slowly. Stir. 2.7 g (71.53 mmol) of lithium aluminum hydride are slowly added at the same temperature, followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was cooled and crystallized by slowly adding an aqueous hydrochloric acid solution (6M). After solid filtration, the mixture was washed with water, ethanol and hexane, and then recrystallized with tetrahydrofuran and methanol to obtain 7.7 g (60%) of the intermediate compound [80-4] as a yellow solid.

합성예 1과 동일한 방법으로 화합물[80-4] 7g(20.50mmol), N-브로모석신이미드 8.0g (45.10mmol)을 사용하여 노란색 고체의 중간체 화합물[80-5] 8.5g(80%)을 수득하였다. 8.5 g (80%) of an intermediate compound [80-5] as a yellow solid using 7 g (20.50 mmol) of compound [80-4] and 8.0 g (45.10 mmol) of N-bromosuccinimide in the same manner as in Synthesis example 1. ) Was obtained.

합성예 1과 동일한 방법으로 화합물[80-5] 5g(9.62mmol), 페닐보론산 2.8g(23.11mmol), 테트라키스(트리페닐포스핀)팔라듐 445mg(0.38mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[80] 3.7g(75%)을 수득하였다. In the same manner as in Synthesis Example 1 , 5 g (9.62 mmol) of compound [80-5] , 2.8 g (23.11 mmol) of phenylboronic acid, 445 mg (0.38 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 3.7 g (75%) of the desired compound [ 80] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01(t, 1H), 7.26(d, 1H), 7.39~7.61(m, 14H), 7.81~7.85(m, 4H), 8.11(d, 1H), 8.27~8.30(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 (t, 1H), 7.26 (d, 1H), 7.39 ~ 7.61 (m, 14H), 7.81 ~ 7.85 (m, 4H), 8.11 (d, 1H) , 8.27-8.30 (m, 2H)

MS/FAB : 513 (M+)MS / FAB: 513 (M + )

[합성 예 81] 화합물 [81]의 합성Synthesis Example 81 Synthesis of Compound [81]

Figure pat00093
Figure pat00093

합성예 1과 동일한 방법으로 5-브로모-2,2'-바이피리딘 15g(63.80mmol), 디벤조d[b,d]싸이오펜-4-일보론산 17.4g(76.56mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.27mm ol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[81-1] 15.7g(73%)을 수득하였다. In the same manner as in Synthesis example 1 , 15 g (63.80 mmol) of 5-bromo-2,2'-bipyridine, 17.4 g (76.56 mmol) of dibenzod [b, d] thiophen-4-ylboronic acid, tetrakis ( 15.7 g (73%) of a yellow solid intermediate compound [ 81-1] was obtained using 1.4 g (1.27 mm ol) of triphenylphosphine) palladium and 2 M aqueous sodium carbonate solution.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[81-2] 9.5g을 수득하였다.9.5 g of an intermediate compound [ 81-2] was obtained as a yellow solid by the same method as in Synthesis example 80 .

합성예 1과 동일한 방법으로 화합물[81-2] 6g(10.06mmol), 나프탈렌-2-일보론산 4.1g(24.14mmol), 테트라키스(트리페닐포스핀)팔라듐 465mg(0.40mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[81] 4.8g(70%)을 수득하였다.6 g (10.06 mmol) of compound [81-2] , 4.1 g (24.14 mmol) of naphthalen-2-ylboronic acid, 465 mg (0.40 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution in the same manner as in Synthesis example 1 4.8 g (70%) of the desired compound [ 81] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.14(t, 1H), 7.39~7.40(m, 2H), 7.58~7.73(m, 10H), 7.88~8.00(m, 12H), 8.21(d, 1H), 8.33(d, 1H), 8.61(s, 1H), 8.79(d, 1H), 9.10(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.14 (t, 1H), 7.39-7.40 (m, 2H), 7.58-7.73 (m, 10H), 7.88-8.00 (m, 12H), 8.21 (d, 1H), 8.33 (d, 1H), 8.61 (s, 1H), 8.79 (d, 1H), 9.10 (d, 1H)

MS/FAB : 690 (M+)MS / FAB: 690 (M + )

[합성 예 82] 화합물 [82]의 합성Synthesis Example 82 Synthesis of Compound

Figure pat00094
Figure pat00094

합성예 1과 동일한 방법으로 2-브로모-4,6-디페닐-1,3,5-트리아진 10g(32.03mmol), 디벤조d[b,d]싸이오펜-4-일보론산 8.7g(38.44mmol), 테트라키스(트리페닐포스핀)팔라듐 7 44mg(0.64mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[82-1] 9.7g(73%)을 수득하였다.2-bromo-4,6-diphenyl-1,3,5-triazine 10 g (32.03 mmol) and 8.7 g of dibenzod [b, d] thiophen-4-ylboronic acid in the same manner as in Synthesis example 1 (38.44 mmol), tetrakis (triphenylphosphine) palladium 7 44 mg (0.64 mmol), 2M aqueous sodium carbonate solution was used to obtain 9.7 g (73%) of an intermediate compound [ 82-1] .

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[82-2] 5.8g을 수득하였다.5.8 g of an intermediate compound [ 82-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

합성예 1과 동일한 방법으로 화합물[82-2] 5g(7.42mmol), 나프탈렌-2일보론산 3.0g (17.81mmol), 테트라키스(트리페닐포스핀)팔라듐 343mg(0.29mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[82] 3.9g(70%)을 수득하였다. In the same manner as in Synthesis Example 1 , 5 g (7.42 mmol) of compound [82-2] , naphthalene-2 ylboronic acid 3.0 g (17.81 mmol), tetrakis (triphenylphosphine) palladium 343 mg (0.29 mmol), and a 2M aqueous solution of sodium carbonate were prepared. To give 3.9 g (70%) of the title compound [ 82] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.39~7.59(m, 15H), 7.73~7.80(m, 3H), 7.91~8.00(m, 10H), 8.18~8.21(m, 4H), 8.31(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 to 7.59 (m, 15H), 7.73 to 7.80 (m, 3H), 7.91 to 8.00 (m, 10H), 8.18 to 8.21 (m, 4H), 8.31 ( d, 1H)

MS/FAB : 767 (M+)MS / FAB: 767 (M + )

[합성 예 83] 화합물 [83]의 합성Synthesis Example 83 Synthesis of Compound [83]

Figure pat00095
Figure pat00095

합성예 1과 동일한 방법으로 2-(3-브로모페닐)-1-페닐-1H-벤조[d]이미다졸 10g(2 8.63mmol), 디벤조d[b,d]싸이오펜-4-일보론산 7.8g(34.36mmol), 테트라키스(트리페닐포스핀)팔라듐 661mg(0.52mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[83-1] 8.9g(75%)을 수득하였다.2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole 10 g (2 8.63 mmol) and dibenzod [b, d] thiophen-4-ylbo in the same manner as in Synthesis example 1 8.9 g (75%) of a yellow solid intermediate compound [ 83-1] was obtained using 7.8 g (34.36 mmol) of lonic acid, 661 mg (0.52 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[83-2] 5.3g을 수득하였다.5.3 g of an intermediate compound [ 83-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

합성예 1과 동일한 방법으로 화합물[83-2] 5g(7.03mmol), 페닐보론산 2.0g(16.88mmol), 테트라키스(트리페닐포스핀)팔라듐 325mg(0.28mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[83] 3.4g(69%)을 수득하였다. In the same manner as in Synthesis Example 1 , using 5 g (7.03 mmol) of compound [83-2] , 2.0 g (16.88 mmol) of phenylboronic acid, 325 mg (0.28 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 3.4 g (69%) of the desired compound [ 83] as a yellow solid was obtained.

1H NMR (300 MHz, CDCl3):δ 7.21~7.22(m, 2H), 7.39~7.58(m, 21H), 7.70(s, 1H), 7.90~7.92(m, 4H), 8.00~8.04(m, 2H), 8.21(d, 1H), 8.36(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.22 (m, 2H), 7.39-7.58 (m, 21H), 7.70 (s, 1H), 7.90-7.92 (m, 4H), 8.00-8.04 ( m, 2H), 8.21 (d, 1H), 8.36 (d, 1H)

MS/FAB : 704 (M+)MS / FAB: 704 (M + )

[합성 예 84] 화합물 [84]의 합성Synthesis Example 84 Synthesis of Compound

Figure pat00096
Figure pat00096

합성예 1과 동일한 방법으로 2-브로모퀴놀린 10g(48.06mmol), 디벤조d[b,d]싸이오펜-4-일보론산 13.1g(57.67mmol), 테트라키스(트리페닐포스핀)팔라듐 1.1g(0.96mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[84-1] 11.2g(75%)을 수득하였다.10 g (48.06 mmol) of 2-bromoquinoline, 13.1 g (57.67 mmol) of dibenzod [b, d] thiophen-4-ylboronic acid, and tetrakis (triphenylphosphine) palladium 1.1 in the same manner as in Synthesis example 1 g (0.96 mmol), 2M aqueous sodium carbonate solution, afforded 11.2 g (75%) of an intermediate compound [ 84-1] as a yellow solid.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[84-2] 6.7g을 수득하였다.6.7 g of a yellow solid intermediate compound [ 84-2] was obtained in the same manner as in Synthesis example 80 .

합성예 1과 동일한 방법으로 화합물[84-2] 6g(10.53mmol), 페닐보론산 3.0g(25.29 mmol), 테트라키스(트리페닐포스핀)팔라듐 487mg(0.42mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[84] 4.1g(70%)을 수득하였다. In the same manner as in Synthesis Example 1 , 6 g (10.53 mmol) of compound [ 84-2], 3.0 g (25.29 mmol) of phenylboronic acid, 487 mg (0.42 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 4.1 g (70%) of the desired compound [ 84] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.35~7.61(m, 15H), 7.78(t, 1H), 7.91~8.10(m, 7H), 8.21(d, 1H), 8.37(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.35-7.61 (m, 15H), 7.78 (t, 1H), 7.91-8.10 (m, 7H), 8.21 (d, 1H), 8.37 (d, 1H)

MS/FAB : 563 (M+)MS / FAB: 563 (M + )

[합성 예 85] 화합물 [85]의 합성Synthesis Example 85 Synthesis of Compound

Figure pat00097
Figure pat00097

합성예 1과 동일한 방법으로 2-브로모피리딘 10g(63.29mmol), 디벤조d[b,d]싸이오펜-2-일보론산 17.3g(75.94mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.26mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[85-1] 12.4g(75%)을 수득하였다.2-bromopyridine 10g (63.29mmol), dibenzod [b, d] thiophen-2-ylboronic acid 17.3g (75.94mmol), tetrakis (triphenylphosphine) palladium 1.4 in the same manner as in Synthesis example 1 g (1.26 mmol), 2M aqueous sodium carbonate solution was used to obtain 12.4 g (75%) of an intermediate compound [ 85-1] as a yellow solid.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[85-2] 8.4g을 수득하였다.8.4 g of an intermediate compound [ 85-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

합성예 1과 동일한 방법으로 화합물[85-2] 8g(15.40mmol), 페닐보론산 4.5g(36.97 mmol), 테트라키스(트리페닐포스핀)팔라듐 712mg(0.61mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[85] 5.6g(72%)을 수득하였다. In the same manner as in Synthesis Example 1 , using 8 g (15.40 mmol) of compound [85-2] , 4.5 g (36.97 mmol) of phenylboronic acid, 712 mg (0.61 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 5.6 g (72%) of the title compound [ 85] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01(t, 1H), 7.25(d, 1H), 7.39~7.52(m, 13H), 7.89~7.91(m, 5H), 8.11(d, 1H), 8.30~8.31(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01 (t, 1H), 7.25 (d, 1H), 7.39 ~ 7.52 (m, 13H), 7.89 ~ 7.91 (m, 5H), 8.11 (d, 1H) , 8.30-8.31 (m, 2H)

MS/FAB : 513 (M+)MS / FAB: 513 (M + )

[합성 예 86] 화합물 [86]의 합성Synthesis Example 86 Synthesis of Compound

Figure pat00098
Figure pat00098

합성예 1과 동일한 방법으로 4-브로모피리미딘 10g(62.90mmol), 디벤조d[b,d]싸이오펜-2-일보론산 17.2g(75.48mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.25mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[86-1] 11.8g(72%)을 수득하였다. In the same manner as in Synthesis example 1 , 10 g (62.90 mmol) of 4-bromopyrimidine, 17.2 g (75.48 mmol) of dibenzod [b, d] thiophen-2-ylboronic acid, tetrakis (triphenylphosphine) palladium 1.4 g (1.25 mmol), 2M aqueous sodium carbonate solution was used to obtain 11.8 g (72%) of an intermediate compound [ 86-1] as a yellow solid.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[86-2] 7.6g을 수득하였다.7.6 g of an intermediate compound [ 86-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

합성예 1과 동일한 방법으로 화합물[86-2] 7g(13.45mmol), 페닐보론산 3.9g(32.29 mmol), 테트라키스(트리페닐포스핀)팔라듐 621mg(0.58mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[86] 4.9g(72%)을 수득하였다. In the same manner as in Synthesis Example 1 , using Compound [86-2] 7 g (13.45 mmol), phenyl boronic acid 3.9 g (32.29 mmol), tetrakis (triphenylphosphine) palladium 621 mg (0.58 mmol), and a 2M aqueous sodium carbonate solution 4.9 g (72%) of the title compound [ 86] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.39~7.52(m, 12H), 7.80~7.91(m, 6H), 8.00(s, 1H), 8.11(d, 1H), 8.66(d, 1H), 9.07(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39-7.52 (m, 12H), 7.80-7.91 (m, 6H), 8.00 (s, 1H), 8.11 (d, 1H), 8.66 (d, 1H) , 9.07 (s, 1H)

MS/FAB : 514 (M+)MS / FAB: 514 (M + )

[합성 예 87] 화합물 [87]의 합성Synthesis Example 87 Synthesis of Compound [87]

Figure pat00099
Figure pat00099

합성예 1과 동일한 방법으로 2-브로모-1,3,5-트리아진 10g(62.51mmol), 디벤조d[b,d]싸이오펜-2-일보론산 17.1g(75.01mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.25mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[87-1] 11.5g(70%)을 수득하였다. In the same manner as in Synthesis example 1 , 10 g (62.51 mmol) of 2-bromo-1,3,5-triazine, 17.1 g (75.01 mmol) of dibenzod [b, d] thiophen-2-ylboronic acid, tetrakis 11.5 g (70%) of a yellow solid intermediate compound [ 87-1] was obtained using 1.4 g (1.25 mmol) of (triphenylphosphine) palladium and 2 M aqueous sodium carbonate.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[87-2] 7.1g을 수득하였다.7.1 g of an intermediate compound [ 87-2] was obtained as a yellow solid by the same method as in Synthesis example 80 .

합성예 1과 동일한 방법으로 화합물[87-2] 7g(13.42mmol), 나프탈렌-1-일보론산 5.5g(32.23mmol), 테트라키스(트리페닐포스핀)팔라듐 620mg(0.53mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[87] 5.3g(65%)을 수득하였다. In the same manner as in Synthesis example 1 , Compound [ 87-2 ] 7g (13.42mmol), naphthalen-1-ylboronic acid 5.5g (32.23mmol), tetrakis (triphenylphosphine) palladium 620mg (0.53mmol), 2M sodium carbonate solution To give 5.3 g (65%) of the title compound [ 87] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.39~7.40(m, 2H), 7.55~7.61(m, 6H), 7.80~7.91(m, 6H), 8.00~8.08(m, 5H), 8.21~8.22(m, 2H), 8.35~8.36(m, 2H), 8.51(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39-7.40 (m, 2H), 7.55-7.61 (m, 6H), 7.80-7.91 (m, 6H), 8.00-8.08 (m, 5H), 8.21- 8.22 (m, 2H), 8.35 ~ 8.36 (m, 2H), 8.51 (s, 2H)

MS/FAB : 615 (M+)MS / FAB: 615 (M + )

[합성 예 88] 화합물 [88]의 합성Synthesis Example 88 Synthesis of Compound [88]

Figure pat00100
Figure pat00100

합성예 1과 동일한 방법으로 디벤조[b,d]싸이오펜 10g(54.27mmol), 5-브로모이소벤조 퓨란-1,3-디온 14g(48.84mmol), 알루미늄 클로라이드 18.0g(135.67mmol)을 사용하여 노르스름한 고체의 중간체 화합물[88-1] 15.8g(79%)을 수득하였다. In the same manner as in Synthesis Example 1 , 10 g (54.27 mmol) of dibenzo [b, d] thiophene, 14 g (48.84 mmol) of 5-bromoisobenzofuran-1,3-dione, and 18.0 g (135.67 mmol) of aluminum chloride were added. 15.8 g (79%) of an intermediate compound [88-1] as a yellowish solid was obtained.

합성예 80과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[88-2] 7.2g을 수득하였다.7.2 g of an intermediate compound [ 88-2] was obtained in the same manner as in Synthesis example 80 .

합성예 1과 동일한 방법으로 화합물[88-2] 7g(19.26mmol), 3-(1-페닐-1H-벤조[d]이미다졸-2-일)페닐보론산 7.26g(23.12mmol), 테트라키스(트리페닐포스핀)팔라듐 445mg(0.38 mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[88-3] 7.4g(70%)을 수득하였다. By the same method as in Example 1, the compound [88-2] 7g (19.26mmol), 3- (1- phenyl -1H- benzo [d] imidazol-2-yl) phenylboronic acid 7.26g (23.12mmol), tetra 7.4 g (70%) of a yellow solid intermediate compound [ 88-3] was obtained by using 445 mg (0.38 mmol) of kiss (triphenylphosphine) palladium and 2M aqueous sodium carbonate solution.

합성예 1과 동일한 방법으로 화합물[88-3] 7g(12.66mmol), N-브로모석신이미드 4.9g (27.86mmol)을 사용하여 노란색 고체의 중간체 화합물[88-4] 7.0g(78%)을 수득하였다. 7.0 g (78%) of a yellow solid intermediate compound [88-4] using 7 g (12.66 mmol) of compound [88-3] and 4.9 g (27.86 mmol) of N-bromosuccinimide in the same manner as in Synthesis example 1. ) Was obtained.

합성예 1과 동일한 방법으로 화합물[88-4] 7g(9.85mmol), 나프탈렌-2-일보론산 4.0g(23.64mmol), 테트라키스(트리페닐포스핀)팔라듐 455mg(0.39mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[88] 5.1g(65%)을 수득하였다. In the same manner as in Synthesis Example 1 , Compound [88-4] 7g ( 9.85 mmol ), naphthalen-2-ylboronic acid 4.0 g (23.64 mmol), tetrakis (triphenylphosphine) palladium 455 mg (0.39 mmol), 2M aqueous sodium carbonate solution To give 5.1 g (65%) of the title compound [ 88] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.21~7.22(m, 2H), 7.48~7.59(m, 17H), 7.70~7.73(m, 3H), 7.91~8.00(m, 10H), 8.13(s, 1H), 8.24(d, 1H), 8.35(d, 1H), 8.46(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.22 (m, 2H), 7.48-7.59 (m, 17H), 7.70-7.73 (m, 3H), 7.91-8.00 (m, 10H), 8.13 ( s, 1H), 8.24 (d, 1H), 8.35 (d, 1H), 8.46 (d, 1H)

MS/FAB : 805 (M+)
MS / FAB: 805 (M + )

[합성 예 89] 화합물 [88]의 합성Synthesis Example 89 Synthesis of Compound [88]

Figure pat00101
Figure pat00101

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[89-1] 6.6g을 수득하였다.6.6 g of an intermediate compound [ 89-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

합성예 1과 동일한 방법으로 화합물[89-4] 6.5g(10.90mmol), 나프탈렌-2-일보론산 3.1g(26.16mmol), 테트라키스(트리페닐포스핀)팔라듐 503mg(0.43mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[89] 4.5g(70%)을 수득하였다.6.5 g (10.90 mmol) of compounds [ 89-4], 3.1 g (26.16 mmol) of naphthalen-2-ylboronic acid, 503 mg (0.43 mmol) of tetrakis (triphenylphosphine) palladium, 2M sodium carbonate in the same manner as in Synthesis example 1 The aqueous solution was used to obtain 4.5 g (70%) of an intermediate compound [ 89] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.12~7.14(m, 2H), 7.41~7.52(m, 12H), 7.63~7.70(m, 2H), 7.91(s, 2H), 7.98~8.00(m, 2H), 8.07(s, 1H), 8.25(d, 1H), 8.33(d, 1H), 8.44(s, 1H), 8.70(d, 1H), 9.10(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.12-7.14 (m, 2H), 7.41-7.72 (m, 12H), 7.63-7.70 (m, 2H), 7.91 (s, 2H), 7.98-8.00 ( m, 2H), 8.07 (s, 1H), 8.25 (d, 1H), 8.33 (d, 1H), 8.44 (s, 1H), 8.70 (d, 1H), 9.10 (d, 1H)

MS/FAB : 590 (M+)MS / FAB: 590 (M + )

[합성 예 90] 화합물 [90]의 합성Synthesis Example 90 Synthesis of Compound

Figure pat00102
Figure pat00102

합성예 1과 동일한 방법으로 2-브로모피리딘 10g(63.29mmol), 디벤조[b,d]싸이오펜-2,4-디일보론산10.3g(37.97mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.26mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[90-1] 14.5g(68%)을 수득하였다.2-bromopyridine 10g (63.29mmol), dibenzo [b, d] thiophene-2,4-diylboronic acid 10.3g (37.97mmol), tetrakis (triphenylphosphine) by the same method as the synthesis example 1 1.4 g (1.26 mmol) of palladium, 2M aqueous sodium carbonate solution was used to obtain 14.5 g (68%) of an intermediate compound [ 90-1] as a yellow solid.

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[90-2] 6.8g을 수득하였다.6.8 g of an intermediate compound [ 90-2] as a yellow solid was obtained in the same manner as in Synthesis example 88 .

합성예 1과 동일한 방법으로 화합물[90-2] 6.5g(10.90mmol), 나프탈렌-1-일보론산 4.4g(26.16mmol), 테트라키스(트리페닐포스핀)팔라듐 503mg(0.43mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[90] 5.1g(69%)을 수득하였다.6.5 g (10.90 mmol) of compounds [90-2] , 4.4 g (26.16 mmol) of naphthalen-1-ylboronic acid, 503 mg (0.43 mmol) of tetrakis (triphenylphosphine) palladium, 2M sodium carbonate in the same manner as in Synthesis example 1 The aqueous solution was used to obtain 5.1 g (69%) of the title compound ( 90 ) as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(m, 2H), 7.25~7.26(m, 2H), 7.38~7.39(m, 2H), 7.51~7.61(m, 8H), 7.91~7.93(m, 3H), 8.04~8.08(m, 4H), 8.22~8.35(m, 7H), 8.57(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.38-7.39 (m, 2H), 7.51-7.61 (m, 8H), 7.91- 7.93 (m, 3H), 8.04-8.08 (m, 4H), 8.22-8.35 (m, 7H), 8.57 (s, 1H)

MS/FAB : 690 (M+)MS / FAB: 690 (M + )

[합성 예 91] 화합물 [91]의 합성Synthesis Example 91 Synthesis of Compound [91]

Figure pat00103
Figure pat00103

합성예 1과 동일한 방법으로 4-브로모피리미딘 10g(62.90mmol), 디벤조[b,d]싸이오펜-2,4-디일보론산10.2g(37.74mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.25mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[91-1] 14.5g(68%)을 수득하였다.10 g (62.90 mmol) of 4-bromopyrimidine, 10.2 g (37.74 mmol) of dibenzo [b, d] thiophene-2,4-diylboronic acid, and tetrakis (triphenylphosphine) in the same manner as in Synthesis example 1 14.5 g (68%) of a yellow solid intermediate compound [ 91-1] was obtained using 1.4 g (1.25 mmol) of palladium and a 2M aqueous solution of sodium carbonate.

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[91-2] 6.3g을 수득하였다.6.3 g of an intermediate compound [ 91-2] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

합성예 1과 동일한 방법으로 화합물[91-2] 6g(10.02mmol), 바이페닐-3-일보론산 4.7g(26.06mmol), 테트라키스(트리페닐포스핀)팔라듐 463mg(0.40mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[91] 4.9g(66%)을 수득하였다.6 g (10.02 mmol) of Compound [91-2] , 4.7 g (26.06 mmol) of biphenyl-3-ylboronic acid, 463 mg (0.40 mmol) of tetrakis (triphenylphosphine) palladium, and 2M sodium carbonate in the same manner as in Synthesis Example 1 An aqueous solution was used to obtain 4.9 g (66%) of the title compound [ 91] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.39~7.57(m, 18H), 7.70~7.75(m, 3H), 7.91~7.96(m, 5H), 8.10~8.11(m, 2H), 8.65~8.66(m, 2H), 9.07(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.39 ~ 7.57 (m, 18H), 7.70 ~ 7.75 (m, 3H), 7.91 ~ 7.96 (m, 5H), 8.10 ~ 8.11 (m, 2H), 8.65 ~ 8.66 (m, 2 H), 9.07 (s, 2 H)

MS/FAB : 744 (M+)MS / FAB: 744 (M + )

[합성 예 92] 화합물 [92]의 합성Synthesis Example 92 Synthesis of Compound

Figure pat00104
Figure pat00104

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[92-1] 6.5g을 수득하였다.6.5 g of an intermediate compound [ 92-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

합성예 1과 동일한 방법으로 화합물[92-1] 6.5g(10.90mmol), 페닐보론산 3.1g(26.16 mmol), 테트라키스(트리페닐포스핀)팔라듐 436mg(0.43mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[92] 4.3g(68%)을 수득하였다. In the same manner as in Synthesis Example 1 , Compound [92-1] 6.5g (10.90mmol), phenylboronic acid 3.1g (26.16mmol), tetrakis (triphenylphosphine) palladium 436mg (0.43mmol), and 2M aqueous sodium carbonate solution were used. This gave 4.3 g (68%) of the title compound [ 92] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(m, 2H), 7.25~7.26(m, 2H), 7.41~7.61(m, 13H), 7.91(s, 2H), 8.00(d, 1H), 8.21(d, 1H), 8.37~8.40(m, 3H), 8.54(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.41-7.61 (m, 13H), 7.91 (s, 2H), 8.00 (d, 1H), 8.21 (d, 1H), 8.37-8.40 (m, 3H), 8.54 (s, 1H)

MS/FAB : 590 (M+)MS / FAB: 590 (M + )

[합성 예 93] 화합물 [93]의 합성Synthesis Example 93 Synthesis of Compound [93]

Figure pat00105
Figure pat00105

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[93-1] 6.6g을 수득하였다.6.6 g of an intermediate compound [ 93-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

합성예 1과 동일한 방법으로 화합물[93-1] 6.5g(10.90mmol), 페닐보론산 3.1g(26.16 mmol), 테트라키스(트리페닐포스핀)팔라듐 436mg(0.43mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[93] 4.2g(66%)을 수득하였다. In the same manner as in Synthesis Example 1 , Compound [93-1] 6.5g (10.90mmol), phenylboronic acid 3.1g (26.16mmol), tetrakis (triphenylphosphine) palladium 436mg (0.43mmol), and 2M aqueous sodium carbonate solution were used. This gave 4.2 g (66%) of the desired compound [ 93] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(m, 2H), 7.25~7.26(m, 2H), 7.41~7.52(m, 12H), 7.89~7.91(m, 3H), 8.00(d, 1H), 8.12(d, 1H), 8.21(d, 1H), 8.40~8.41(m, 3H), 8.54(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.41-7.52 (m, 12H), 7.89-7.91 (m, 3H), 8.00 ( d, 1H), 8.12 (d, 1H), 8.21 (d, 1H), 8.40-8.41 (m, 3H), 8.54 (s, 1H)

MS/FAB : 590 (M+)MS / FAB: 590 (M + )

[합성 예 94] 화합물 [94]의 합성Synthesis Example 94 Synthesis of Compound [94]

Figure pat00106
Figure pat00106

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[94-1] 6.3g을 수득하였다.6.3 g of an intermediate compound [ 94-1] as a yellow solid was obtained in the same manner as in Synthesis example 88 .

합성예 1과 동일한 방법으로 화합물[94-1] 6g(8.90mmol), 페닐보론산 2.6g(21.38mmol), 테트라키스(트리페닐포스핀)팔라듐 411mg(0.35mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[94] 3.9g(67%)을 수득하였다. In the same manner as in Synthesis Example 1 , using 6 g (8.90 mmol) of compound [94-1] , 2.6 g (21.38 mmol) of phenylboronic acid, 411 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 3.9 g (67%) of the title compound [ 94] were obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.01~7.02(m, 3H), 7.25~7.26(m, 3H), 7.41~7.52(m, 13H), 7.91(s, 2H), 8.00(d, 1H), 8.12(d, 1H), 8.40~8.43(m, 4H), 8.54(s, 1H), 8.67(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.01-7.02 (m, 3H), 7.25-7.26 (m, 3H), 7.41-7.52 (m, 13H), 7.91 (s, 2H), 8.00 (d, 1H), 8.12 (d, 1H), 8.40-8.43 (m, 4H), 8.54 (s, 1H), 8.67 (s, 1H)

MS/FAB : 667 (M+)MS / FAB: 667 (M + )

[합성 예 95] 화합물 [95]의 합성Synthesis Example 95 Synthesis of Compound

Figure pat00107
Figure pat00107

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[95-1] 6.4g을 수득하였다.6.4 g of a yellow solid intermediate compound [ 95-1] was obtained in the same manner as in Synthesis example 88 .

합성예 1과 동일한 방법으로 화합물[95-1] 6g(8.80mmol), 페닐보론산 2.5g(21.28mmol), 테트라키스(트리페닐포스핀)팔라듐 411mg(0.35mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[95] 3.9g(67%)을 수득하였다. In the same manner as in Synthesis Example 1 , 6 g (8.80 mmol) of compound [95-1] , 2.5 g (21.28 mmol) of phenylboronic acid, 411 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 3.9 g (67%) of the title compound [ 95] was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.31~7.61(m, 12H), 7.75(s, 1H), 7.91~7.97(m, 4H), 8.11~8.13(m, 3H), 8.65~8.67(m, 4H), 9.07(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.31-7.81 (m, 12H), 7.75 (s, 1H), 7.91-7.97 (m, 4H), 8.11-8.13 (m, 3H), 8.65-8.67 ( m, 4H), 9.07 (s, 2H)

MS/FAB : 670 (M+)MS / FAB: 670 (M + )

[합성 예 96] 화합물 [96]의 합성Synthesis Example 96 Synthesis of Compound

Figure pat00108
Figure pat00108

합성예 1과 동일한 방법으로 2-브로모-1,3,5-트리아진 10g(62.51mmol), 디벤조[b,d] 싸이오펜-2,4-디일보론산10.1g(37.50mmol), 테트라키스(트리페닐포스핀)팔라듐 1.4g(1.25 mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 중간체 화합물[96-1] 14.5g (68%)을 수득하였다. In the same manner as in Synthesis example 1 , 10 g (62.51 mmol) of 2-bromo-1,3,5-triazine, 10.1 g (37.50 mmol) of dibenzo [b, d] thiophene-2,4-diylboronic acid, Tetrakis (triphenylphosphine) palladium 1.4 g (1.25 mmol) and 2M aqueous sodium carbonate solution were used to obtain 14.5 g (68%) of an intermediate compound [ 96-1] as a yellow solid.

합성예 88과 동일한 방법을 통하여 노란색 고체의 중간체 화합물[96-2] 6.2g을 수득하였다.6.2 g of an intermediate compound [ 96-2] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

합성예 1과 동일한 방법으로 화합물[96-2] 6g(8.83mmol), 3,4-디메틸페닐보론산 3.1g(21.96mmol), 테트라키스(트리페닐포스핀)팔라듐 408mg(0.35mmol), 2M 탄산나트륨수용액을 사용하여 노란색 고체의 목적 화합물[96] 3.6g(57%)을 수득하였다.6 g (8.83 mmol) of compound [96-2] , 3.1 g (21.96 mmol) of 3,4-dimethylphenylboronic acid, 408 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, 2M in the same manner as in Synthesis example 1 An aqueous sodium carbonate solution was used to yield 3.6 g (57%) of the title compound [ 96] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 2.35(s, 12H), 7.14~7.17(m, 4H), 7.62~7.67(m, 3H), 7.75(s, 1H), 7.91(s, 2H), 7.96~7.97(m, 2H), 8.13(s, 1H), 8.61(s, 6H) 1 H NMR (300 MHz, CDCl 3 ): δ 2.35 (s, 12H), 7.14 ~ 7.17 (m, 4H), 7.62 ~ 7.67 (m, 3H), 7.75 (s, 1H), 7.91 (s, 2H) , 7.96-7.97 (m, 2H), 8.13 (s, 1H), 8.61 (s, 6H)

MS/FAB : 729 (M+)MS / FAB: 729 (M + )

[합성 예 97] 화합물 [97]의 합성Synthesis Example 97 Synthesis of Compound [97]

Figure pat00109
Figure pat00109

합성예 80과 동일한 방법으로 디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [97-1] 5.0g(11.31 mmol)과 페닐 보론산 3.0g (24.88mmol)을 사용하여 합성예1과동일한방법으로노란색고체의 목적화합물 [97] 3.3g(67%)을 수득하였다. Dibenzo in the same manner as in Synthesis Example 80 [b, d] Intermediate compound obtained using thiophene [97-1] 5.0g (11.31 mmol) and phenylboronic acid as in Synthesis Example 1 by using 3.0g (24.88mmol) the desired compound in a yellow solid in the same manner [97] to give the 3.3g (67%).

1H NMR (300 MHz, CDCl3):δ 7.19~7.31(m, 14H), 7.71~7.78(m, 5H), 8.15(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.31 (m, 14H), 7.71-7.78 (m, 5H), 8.15 (d, 1H)

MS/FAB : 437(M+)MS / FAB: 437 (M + )

[[ 합성예Synthetic example 98] 화합물 [98]의 합성 98] Synthesis of Compound [98]

Figure pat00110
Figure pat00110

합성예 1과동일한방법으로중간체화합물[97-1] 5.0g(11.31mmol), 나프탈렌-2-일보론산 4.3g (24.88mmol)을 사용하여 노란색고체의 목적화합물 [98] 4.3g(70%)을 수득하였다. Synthesis Example 1 In the same manner, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.3 g (24.88 mmol) of naphthalene-2-ylboronic acid were used to obtain 4.3 g (70%) of the target compound [98] as a yellow solid. It was.

1H NMR (300 MHz, CDCl3):δ 7.19(d, 2H), 7.30~7.39(m, 8H), 7.53(d, 2H), 7.71~7.80(m, 11H), 8.15(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19 (d, 2H), 7.30-7.39 (m, 8H), 7.53 (d, 2H), 7.71-7.80 (m, 11H), 8.15 (d, 1H)

MS/FAB : 537(M+)MS / FAB: 537 (M + )

[[ 합성예Synthetic example 99] 화합물 [99]의 합성 99] Synthesis of Compound [99]

Figure pat00111
Figure pat00111

합성예 1과동일한방법으로중간체화합물[97-1] 5.0g(11.31mmol), 나프탈렌-1-일보론산 4.3g (24.88mmol)을 사용하여 노란색고체의 목적화합물 [99] 3.1g(51%)을 수득하였다. Synthesis Example 1 In the same manner, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.3 g (24.88 mmol) of naphthalene-1-ylboronic acid were used to obtain 3.1 g (51%) of the target compound [99]. It was.

1H NMR (300 MHz, CDCl3):δ 7.19(d, 2H), 7.30~7.41(m, 8H), 7.71~7.88(m, 9H), 8.15~8.25(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19 (d, 2H), 7.30-7.41 (m, 8H), 7.71-7.88 (m, 9H), 8.15-8.25 (m, 5H)

MS/FAB : 537(M+)MS / FAB: 537 (M + )

[[ 합성예Synthetic example 100] 화합물 [100]의 합성 100] Synthesis of Compound [100]

Figure pat00112
Figure pat00112

합성예 1과동일한방법으로중간체화합물[97-1] 5.0g(11.31mmol), 바이페닐-4-일보론산 4.9g (24.88mmol)을 사용하여 노란색고체의 목적화합물 [100] 4.8g(72%)을 수득하였다. Synthesis Example 1 In the same way, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.9 g (24.88 mmol) of the biphenyl-4-ylboronic acid were used to obtain 4.8 g (72%) of the target compound [100] as a yellow solid. Obtained.

1H NMR (300 MHz, CDCl3):δ 7.05(s, 8H), 7.19~7.32(m, 14H), 7.71~7.78(m, 5H), 8.15(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.05 (s, 8H), 7.19 ~ 7.32 (m, 14H), 7.71 ~ 7.78 (m, 5H), 8.15 (d, 1H)

MS/FAB : 589(M+)MS / FAB: 589 (M + )

[[ 합성예Synthetic example 101] 화합물 [101]의 합성 101] Synthesis of Compound [101]

Figure pat00113
Figure pat00113

합성예 1과동일한방법으로중간체화합물[97-1] 5.0g(11.31mmol), 9,9-디메틸-9H-플로렌-3-일보론산 5.9g (24.88mmol)을 사용하여 노란색고체의 목적화합물 [101] 4.9g(65%)을 수득하였다. Synthesis Example 1 Intermediate compound [97-1] 5.0 g (11.31 mmol) and 9,9-dimethyl-9H-floren-3-ylboronic acid 5.9 g (24.88 mmol) in the same manner as the target compound of yellow solid [101] ] to give the 4.9g (65%).

1H NMR (300 MHz, CDCl3):δ 1.62(s, 12H), 7.08(d, 2H), 7.18~7.19(m, 4H), 7.32~7.35(m, 4H), 7.43(d, 2H), 7.57(s, 2H), 7.67~7.78(m, 9H), 8.15(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 1.62 (s, 12H), 7.08 (d, 2H), 7.18 ~ 7.19 (m, 4H), 7.32 ~ 7.35 (m, 4H), 7.43 (d, 2H) , 7.57 (s, 2H), 7.67 ~ 7.78 (m, 9H), 8.15 (d, 1H)

MS/FAB : 669(M+)MS / FAB: 669 (M + )

[[ 합성예Synthetic example 102] 화합물 [102]의 합성 102] Synthesis of Compound [102]

Figure pat00114
Figure pat00114

합성예 1과 동일한 방법으로 중간체 화합물 [1-3]을 사용하여 얻은 중간체 화합물 [102-1] 5.0g(10.22 mmol)과 3-(나프탈렌-2-일)페닐보론산 2.8g (11.24mmol)을 사용하여 노란색고체의 목적화합물 [102] 4.5g(72%)을 수득하였다. 5.0 g (10.22 mmol) of intermediate compound [102-1] and 2.8 g (11.24 mmol) of 3- (naphthalen-2-yl) phenylboronic acid obtained using intermediate compound [1-3] in the same manner as in Synthesis example 1 . of the target compound [102] 4.5g (72%) of a yellow solid was obtained using.

1H NMR (300 MHz, CDCl3):δ 7.28~7.41(m, 13H), 7.50~7.53(m, 2H), 7.71~7.88(m, 10H), 8.15~8.25(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.28-7.41 (m, 13H), 7.50-7.53 (m, 2H), 7.71-7.88 (m, 10H), 8.15-8.25 (m, 3H)

MS/FAB : 613(M+)MS / FAB: 613 (M + )

[[ 합성예Synthetic example 103] 화합물 [103]의 합성 103] Synthesis of Compound [103]

Figure pat00115
Figure pat00115

합성예 1과 동일한 방법으로 중간체 화합물 [1-3]을 사용하여 얻은 중간체 화합물 [103-1] 5.0g(10.22 mmol)과 4-(나프탈렌-1-일)페닐보론산 2.8g (11.24mmol)을 사용하여 노란색고체의 목적화합물 [103] 4.4g(71%)을 수득하였다. 5.0 g (10.22 mmol) of intermediate compound [103-1] and 2.8 g (11.24 mmol) of 4- (naphthalen-1-yl) phenylboronic acid obtained using intermediate compound [1-3] in the same manner as in Synthesis example 1 . 4.4 g (71%) of the title compound (103 ) was obtained as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.05(s, 4H), 7.19~7.41(m, 10H), 7.53(d, 1H), 7.71~7.88(m, 10H), 8.15~8.25(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.05 (s, 4H), 7.19-7.41 (m, 10H), 7.53 (d, 1H), 7.71-7.88 (m, 10H), 8.15-8.25 (m, 3H)

MS/FAB : 613(M+)MS / FAB: 613 (M + )

[[ 합성예Synthetic example 104] 화합물 [104]의 합성 104] Synthesis of Compound [104]

Figure pat00116
Figure pat00116

합성예 80과 동일한 방법으로 4-페닐디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [104-1] 5.0g(9.65 mmol)과 페닐보론산 2.6g (21.22mmol)을 사용하여 합성예1과동일한방법으로노란색고체의 목적화합물 [104] 3.6g(73%)을 수득하였다. Intermediate compound obtained using 4-dibenzo [b, d] thiophene in the same manner as in Synthesis Example 80 [104-1] 5.0g (9.65 mmol ) and synthesized by using a phenylboronic acid 2.6g (21.22mmol) of example 1, to give the desired compound [104] 3.6g (73%) of a yellow solid in the same manner.

1H NMR (300 MHz, CDCl3):δ 7.19~7.38(m, 18H), 7.71(m, 4H), 8.10~8.21(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.38 (m, 18H), 7.71 (m, 4H), 8.10-8.21 (m, 2H)

MS/FAB : 513(M+)MS / FAB: 513 (M + )

[[ 합성예Synthetic example 105] 화합물 [105]의 합성 105] Synthesis of Compound [105]

Figure pat00117
Figure pat00117

합성예 1과동일한방법으로중간체화합물[104-1] 5.0g(9.65mmol), 나프탈렌-2-일보론산 5.9g (21.22mmol)을 사용하여 노란색고체의 목적화합물 [105] 3.8g(64%)을 수득하였다. Synthesis Example In the same manner, 3.8 g (64%) of the title compound (105 ) was obtained using 5.0 g (9.65 mmol) of the intermediate compound [104-1] and 5.9 g (21.22 mmol) of naphthalene-2-ylboronic acid. It was.

1H NMR (300 MHz, CDCl3):δ 7.19~7.39(m, 14H), 7.53(d, 2H), 7.71~7.80(m, 10H), 8.15~8.20(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.39 (m, 14H), 7.53 (d, 2H), 7.71-7.80 (m, 10H), 8.15-8.20 (m, 2H)

MS/FAB : 613(M+)MS / FAB: 613 (M + )

[[ 합성예Synthetic example 106] 화합물 [106]의 합성 106] Synthesis of Compound [106]

Figure pat00118
Figure pat00118

합성예 80과 동일한 방법으로 4-(나프탈렌-2-일)디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [106-1] 5.0g(8.80 mmol)과 나프탈렌-2-일보론산 3.3g (19.36mmol)을 사용하여 합성예1과동일한방법으로노란색고체의 목적화합물 [106] 4.0g(69%)을 수득하였다. 5.0 g (8.80 mmol) of the intermediate compound [106-1] obtained by using 4- (naphthalen-2-yl) dibenzo [b, d] thiophene in the same manner as in Synthesis Example 80 and 3.3 of naphthalen-2-ylboronic acid the g (19.36mmol) in synthesis example 1 and the target compound [106] of the yellow solid in the same manner using 4.0g (69%) of the title compound.

1H NMR (300 MHz, CDCl3):δ 7.19(d, 2H), 7.38~7.39(m, 10H), 7.53~7.54(m, 3H), 7.71~7.80(m, 13H), 8.15~8.20(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19 (d, 2H), 7.38-7.39 (m, 10H), 7.53-7.54 (m, 3H), 7.71-7.80 (m, 13H), 8.15-8.20 ( m, 2H)

MS/FAB : 663(M+)MS / FAB: 663 (M + )

[[ 합성예Synthetic example 107] 화합물 [107]의 합성 107] Synthesis of Compound [107]

Figure pat00119
Figure pat00119

합성예 1과 동일한 방법으로 4-페닐디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [107-1] 5.0g(8.84 mmol)과 3-(나프탈렌-1-yl)페닐보론산 2.4g (9.73mmol)을 사용하여 노란색고체의 목적화합물 [107] 3.8g(65%)을 수득하였다. 5.0 g (8.84 mmol) of the intermediate compound [107-1] and 4- (naphthalene-1-yl) phenylboronic acid obtained using 4-phenyldibenzo [b, d] thiophene in the same manner as in Synthesis Example 1 g (9.73 mmol) was used to obtain 3.8 g (65%) of the title compound (107 ) as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.19~7.38(m, 17H), 7.50~7.53(m, 2H), 7.71~7.88(m, 9H), 8.15~8.25(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.38 (m, 17H), 7.50-7.73 (m, 2H), 7.71-7.88 (m, 9H), 8.15-8.25 (m, 4H)

MS/FAB : 689(M+)MS / FAB: 689 (M + )

[[ 합성예Synthetic example 108] 화합물 [108]의 합성 108] Synthesis of Compound [108]

Figure pat00120
Figure pat00120

합성예 1과 동일한 방법으로 4-페닐디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [108-1] 5.0g(8.85 mmol)과 3-(나프탈렌-1-yl)페닐보론산 1.6g (9.30mmol)을 사용하여 노란색고체의 목적화합물 [108] 3.2g(59%)을 수득하였다. 5.0 g (8.85 mmol) of the intermediate compound [108-1], obtained by using 4-phenyldibenzo [b, d] thiophene in the same manner as in Synthesis Example 1 , and 3- (naphthalene-1-yl) phenylboronic acid 1.6 use g (9.30mmol) to give the target compound as a yellow solid [108] 3.2g (59%) .

1H NMR (300 MHz, CDCl3):δ 7.05(s, 4H), 7.19~7.41(m, 16H), 7.71(m, 4H), 7.84~7.88 (m, 3H), 8.15~8.25(m, 3H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.05 (s, 4H), 7.19-7.41 (m, 16H), 7.71 (m, 4H), 7.84-7.88 (m, 3H), 8.15-8.25 (m, 3H)

MS/FAB : 639(M+)MS / FAB: 639 (M + )

[[ 합성예Synthetic example 109] 화합물 [109]의 합성 109] Synthesis of Compound [109]

Figure pat00121
Figure pat00121

합성예 80과 동일한 방법으로 2,4-다이페닐디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [109-1] 5.0g(8.41 mmol)과 페닐보론산 2.3g (18.51mmol)을 사용하여 합성예1과동일한방법으로노란색고체의 목적화합물 [109] 3.5g(71%)을 수득하였다. 5.0 g (8.41 mmol) of the intermediate compound [109-1] and 2.3 g (18.51 mmol) of phenylboronic acid obtained using 2,4-diphenyldibenzo [b, d] thiophene were prepared in the same manner as in Synthesis example 80 . of the title compound a yellow solid in the same manner as in synthesis example 1 by using [109] 3.5g (71%) of the title compound.

1H NMR (300 MHz, CDCl3):δ 7.19~7.32(m, 22H), 7.55(s, 1H), 7.71~7.76(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.32 (m, 22H), 7.55 (s, 1H), 7.71-7.72 (m, 5H)

MS/FAB : 589(M+)MS / FAB: 589 (M + )

[[ 합성예Synthetic example 110] 화합물 [110]의 합성 110] Synthesis of Compound [110]

Figure pat00122
Figure pat00122

합성예 1과 동일한 방법으로 중간체 화합물 [109-1] 5.0g(8.41 mmol)과 나프탈렌-2-일보론산 3.2g (18.51mmol)을 사용하여 노란색고체의 목적화합물 [110] 3.6g(62%)을 수득하였다. 3.6 g (62%) of the title compound [110] as a yellow solid using 5.0 g (8.41 mmol) of the intermediate compound [109-1] and 3.2 g (18.51 mmol) of naphthalen-2-ylboronic acid in the same manner as in Synthesis example 1 . Obtained.

1H NMR (300 MHz, CDCl3):δ 7.19~7.41(m, 18H), 7.55(s, 1H), 7.71~7.76(m, 5H), 7.84~7.88(m, 4H), 8.15~8.25(m, 4H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.41 (m, 18H), 7.55 (s, 1H), 7.71-7.72 (m, 5H), 7.84-7.88 (m, 4H), 8.15-8.25 ( m, 4H)

MS/FAB : 689(M+)MS / FAB: 689 (M + )

[[ 합성예Synthetic example 111] 화합물 [111]의 합성 111] Synthesis of Compound [111]

Figure pat00123
Figure pat00123

합성예 1과 동일한 방법으로 중간체 화합물 [109-1] 5.0g(8.41 mmol)과 바이페닐-3-일보론산 3.7g (18.51mmol)을 사용하여 노란색고체의 목적화합물 [111] 4.1g(66%)을 수득하였다. 4.1 g (66%) of the target compound [111] as a yellow solid using 5.0 g (8.41 mmol) of the intermediate compound [109-1] and 3.7 g (18.51 mmol) of biphenyl-3-ylboronic acid in the same manner as in Synthesis example 1. ) Was obtained.

1H NMR (300 MHz, CDCl3):δ 7.19~7.37(m, 28H), 7.50~7.55(m, 3H), 7.71~7.76(m, 5H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.37 (m, 28H), 7.50-7.55 (m, 3H), 7.71-7.72 (m, 5H)

MS/FAB : 741(M+)MS / FAB: 741 (M + )

[[ 합성예Synthetic example 112] 화합물 [112]의 합성 112] Synthesis of Compound [112]

Figure pat00124
Figure pat00124

합성예 1과 동일한 방법으로 2,4-디페닐벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [112-1] 5.0g(7.79mmol)과 4-(나프탈렌-2-일)페닐보론산 2.1g (8.57mmol)을 사용하여 노란색고체의 목적화합물 [112] 3.9g(65%)을 수득하였다. 5.0 g (7.79 mmol) and 4- (naphthalen-2-yl) phenyl boron of the intermediate compound [112-1] obtained using 2,4-diphenylbenzo [b, d] thiophene in the same manner as in Synthesis example 1. 2.1 g (8.57 mmol) of acid were used to obtain 3.9 g (65%) of the title compound (112 ) as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.05(s, 4H), 7.19~7.41(m, 18H), 7.53~7.55(m, 2H), 7.71~7.88(m, 10H), 8.15~8.25(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.05 (s, 4H), 7.19-7.41 (m, 18H), 7.53-7.55 (m, 2H), 7.71-7.88 (m, 10H), 8.15-8.25 ( m, 2H)

MS/FAB : 765(M+)MS / FAB: 765 (M + )

[[ 합성예Synthetic example 113] 화합물 [113]의 합성 113] Synthesis of Compound [113]

Figure pat00125
Figure pat00125

합성예 1과 동일한 방법으로 2,4-디페닐벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [113-1] 5.0g(7.79mmol)과 나프탈렌-1-일페닐보론산 1.5g (8.57mmol)을 사용하여 노란색고체의 목적화합물 [113] 3.1g(58%)을 수득하였다. 5.0 g (7.79 mmol) of an intermediate compound [113-1] and 1.5 g of naphthalen-1-ylphenylboronic acid obtained using 2,4-diphenylbenzo [b, d] thiophene in the same manner as in Synthesis Example 1 8.57 mmol) was obtained to give 3.1 g (58%) of the title compound [113] as a yellow solid.

1H NMR (300 MHz, CDCl3):δ 7.19~7.41(m, 18H), 7.53~7.55(m, 2H), 7.71~7.88(m, 10H), 8.11~8.15(m, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.19-7.41 (m, 18H), 7.53-7.55 (m, 2H), 7.71-7.88 (m, 10H), 8.11-8.15 (m, 2H)

MS/FAB : 689(M+)MS / FAB: 689 (M + )

[[ 합성예Synthetic example 114] 화합물 [114]의 합성 114] Synthesis of Compound [114]

Figure pat00126
Figure pat00126

합성예 88과 동일한 방법으로 2,4-다이페닐디벤조[b,d]티오펜을 사용하여 얻은 중간체 화합물 [114-1] 5.0g(7.46 mmol)과 페닐보론산 2.0g (16.41mmol)을 사용하여 합성예1과동일한방법으로노란색고체의 목적화합물 [114] 3.6g(73%)을 수득하였다. 5.0 g (7.46 mmol) of the intermediate compound [114-1] obtained by using 2,4-diphenyldibenzo [b, d] thiophene and 2.0 g (16.41 mmol) of phenylboronic acid were obtained in the same manner as in Synthesis example 88 . of the title compound a yellow solid in the same manner as in synthesis example 1 by using [114] 3.6g (73%) of the title compound.

1H NMR (300 MHz, CDCl3):δ 7.21~7.41(m, 26H), 7.55(s, 1H), 7.71~7.77(m, 4H), 7.93(s, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.41 (m, 26H), 7.55 (s, 1H), 7.71-7.77 (m, 4H), 7.93 (s, 1H)

MS/FAB : 665(M+)MS / FAB: 665 (M + )

[[ 합성예Synthetic example 115] 화합물 [115]의 합성 115] Synthesis of Compound [115]

Figure pat00127
Figure pat00127

합성예 1과 동일한 방법으로 중간체 화합물 [114-1] 5.0g(7.46 mmol)과 3,4-디메틸페닐보론산 2.5g (16.41mmol)을 사용하여 노란색고체의 목적화합물 [115] 3.8g(70%)을 수득하였다. Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and 3,4-dimethylphenyl boronic acid 2.5g (16.41mmol) of the target compound as a yellow solid [115] 3.8g (70 using %) Was obtained.

1H NMR (300 MHz, CDCl3):δ 2.04~2.06(m, 12H), 7.04~7.07(m, 4H), 7.21~7.41(m, 16H), 7.47(s, 2H), 7.55(s, 1H), 7.71~7.77(m, 4H), 7.93(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 2.04-2.06 (m, 12H), 7.04-7.07 (m, 4H), 7.21-7.41 (m, 16H), 7.47 (s, 2H), 7.55 (s, 1H), 7.71-7.77 (m, 4H), 7.93 (d, 1H)

MS/FAB : 721(M+)MS / FAB: 721 (M + )

[[ 합성예Synthetic example 116] 화합물 [116]의 합성 116] Synthesis of Compound [116]

Figure pat00128
Figure pat00128

합성예 1과 동일한 방법으로 중간체 화합물 [114-1] 5.0g(7.46 mmol)과 나프탈렌-2-일보론산 2.8g (16.41mmol)을 사용하여 노란색고체의 목적화합물 [116] 4.1g(71%)을 수득하였다. Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and naphthalene-2 target compound as a yellow solid by Daily acid using 2.8g (16.41mmol) [116] 4.1g (71%) Obtained.

1H NMR (300 MHz, CDCl3):δ 7.21~7.41(m, 22H), 7.53(d, 3H), 7.71~7.80(m, 10H), 7.93(d, 1H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.41 (m, 22H), 7.53 (d, 3H), 7.71-7.80 (m, 10H), 7.93 (d, 1H)

MS/FAB : 765(M+)MS / FAB: 765 (M + )

[[ 합성예Synthetic example 117] 화합물 [117]의 합성 117] Synthesis of Compound [117]

Figure pat00129
Figure pat00129

합성예 1과 동일한 방법으로 중간체 화합물 [114-1] 5.0g(7.46 mmol)과 바이페닐-2-일보론산 3.3g (16.41mmol)을 사용하여 노란색고체의 목적화합물 [117] 3.2g(52%)을 수득하였다. Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and biphenyl-2-Daily acid 3.3g (16.41mmol) of the target compound as a yellow solid [117] using 3.2g (52% ) Was obtained.

1H NMR (300 MHz, CDCl3):δ 7.21~7.41(m, 26H), 7.55~7.71(m, 11H), 7.76(s, 1H), 7.93(s, 2H) 1 H NMR (300 MHz, CDCl 3 ): δ 7.21-7.41 (m, 26H), 7.55-7.71 (m, 11H), 7.76 (s, 1H), 7.93 (s, 2H)

MS/FAB : 817(M+)
MS / FAB: 817 (M + )

비교예Comparative example 1 One

하기 화학식 α로 표시되는 화합물 a를 발광층 물질로 사용하고, 화학식 b로 표시되는 2-TNATA(4,4',4"-tris(N-naphthalen-2-yl)-N-phenylamino)-triphenylamine)을 정공주입층 물질로 사용하고, 화학식 c로 표시되는 α-NPD(N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine)을 정공수송층 물질로 사용하여, 다음과 같은 구조를 갖는 유기발광소자를 제작하였다: ITO/2-TNATA(80nm)/α-NPD(30nm)/화합물a(30nm)/Alq3(30nm)/LiF(0.5nm) /Al(60nm). 2-TNATA (4,4 ', 4 "-tris (N-naphthalen-2-yl) -N-phenylamino) -triphenylamine) represented by Chemical Formula b using compound a represented by Chemical Formula α as a light emitting layer material Is used as the hole injection layer material, and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) represented by Chemical Formula c is used as the hole transport layer material. An organic light emitting device having a structure was prepared: ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / Compound a (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

애노드는 코닝(Corning)사의 15Ω/cm2 (1000Å) ITO 유리 기판을 50mm x 50mm x 0.7mm크기로 잘라서 아세톤 이소프로필 알콜과 순수물 속에서 각 15분 동안 초음파 세정한 후, 30분 동안 UV 오존 세정하여 사용하였다. 상기 기판 상부에 2-TANATA를 진공 증착하여 80nm 두께의 정공주입층을 형성하였다. 상기 정공주입층 상부에, α-NPD를 진공 증착하여 30nm 두께의 정공수송층을 형성하였다. 상기 정공수송층 상부에 화학식 α로 표시되는 화합물 a를 진공 증착하여 25nm두께의 발광층을 형성하였다. 이후, 상기 발광층 상부에 Alq3 화합물을 30nm의 두께로 진공증착하여 전자수송층을 형성하였다. 상기 전자수송층 상부에 LiF 0.5nm(전자주입층)과 Al 600nm(캐소드)를 순차적으로 진공증착하여, 도 1b에 도시된 바와 같은 유기발광소자를 제조하였다. 이를 비교샘플 1이라고 한다. Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound a represented by Chemical Formula α was vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 25 nm. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is called Comparative Sample 1.

본 실시예 및 이하의 실시예들에서는 디오브이사에서 제작한 EL 증착기를 사용하여 소자를 제작하였다. In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

<화학식 α> <화학식 b> <Formula α> <Formula b>

Figure pat00130
Figure pat00131
Figure pat00130
Figure pat00131

<화학식 c> <화학식 d> <Formula c> <Formula d>

Figure pat00132
Figure pat00133
Figure pat00132
Figure pat00133

<화학식 e><Formula e>

Figure pat00134
Figure pat00134

실시예Example 1~117 1-117

상기 비교예 1 중, 발광층 화합물로서 화합물 α 대신 상기 합성예에 개시된 화합물 1~117을 EML층 화합물로 각각 이용한 것을 제외하고는 상기 비교예 1과 동일한 방법으로 ITO/2-TNATA(80nm)/α-NPD(30nm)/[EML 화합물 1~117](30nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)의 구조를 갖는 유기발광소자를 제조하였다. 이를 각각 샘플 1 내지 117라고 한다. In Comparative Example 1, except that Compounds 1 to 117 disclosed in Synthesis Example were used as EML layer compounds instead of Compound α, ITO / 2-TNATA (80nm) / α in the same manner as in Comparative Example 1 An organic light emitting diode having a structure of -NPD (30nm) / [EML Compound 1 ~ 117] (30nm) / Alq3 (30nm) / LiF (0.5nm) / Al (60nm) was prepared. These are called Samples 1 to 117, respectively.

평가예Evaluation example 1 : 비교샘플 1 및 샘플 1~117의 발광 특성 평가 1: Evaluation of light emission characteristics of Comparative Sample 1 and Samples 1 to 117

비교샘플 1 및 샘플 1~117에 대하여, Keithley SMU 235, PR650를 이용하여 구동전압, 발광 휘도, 발광 효율, 발광피크를 각각 평가하여, 그 결과를 하기 [표 1]에 나타내었다. 상기 샘플들은 476~488nm 범위에서 청색 발광피크값을 보여주었다.
For Comparative Sample 1 and Samples 1 to 117, driving voltage, emission luminance, emission efficiency, and emission peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 1]. The samples showed blue emission peaks in the range of 476-488 nm.

[표 1]TABLE 1

Figure pat00135
Figure pat00135

Figure pat00136
Figure pat00136

Figure pat00137
Figure pat00137

상기 표 1에 보여지는 바와 같이 샘플 1 내지 117은 비교샘플 1에 비하여 향상된 발광 특성을 나타내었다.  As shown in Table 1, Samples 1 to 117 showed improved luminescence properties compared to Comparative Sample 1.

실시예Example 118~215 118-215

상기 비교예 1 중, 전자수송층 화합물로서 Alq3 대신 상기 합성예에 개시된 화합물 1~96을 전자수송층 화합물로 각각 이용한 것을 제외하고는 상기 비교예 1과 동일한 방법으로 ITO/2-TNATA(80nm)/α-NPD(30nm)/ 화학식 α(30nm)/ 화학식 1~96(30nm)/LiF(0.5nm)/Al(60nm)의 구조를 갖는 유기발광소자를 제조하였다. 이를 각각 샘플 118 내지 127라고 한다 ITO / 2-TNATA (80nm) / α in the same manner as in Comparative Example 1, except that Compounds 1 to 96 disclosed in Synthesis Example were used as the electron transporting layer compound instead of Alq3 as the electron transporting layer compound, respectively. An organic light emitting diode having a structure of -NPD (30 nm) / Chemical Formula α (30 nm) / Chemical Formulas 1 to 96 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. These are called samples 118-127, respectively.

평가예Evaluation example 2 : 비교샘플 1 및 샘플 118 ~ 215의 발광 특성 평가 2: Evaluation of Luminescence Characteristics of Comparative Sample 1 and Samples 118 to 215

비교샘플 1 및 샘플 118~215에 대하여, Keithley SMU 235, PR650를 이용하여 구동전압, 발광 휘도, 발광 효율, 발광피크를 각각 평가하여, 그 결과를 하기 [표 2]에 나타내었다. 상기 샘플들은 456~478nm 범위에서 청색 발광피크값을 보여주었다. For Comparative Sample 1 and Samples 118 to 215, Keithley SMU 235 and PR650 were used to evaluate driving voltage, emission luminance, emission efficiency, and emission peak, respectively, and the results are shown in the following [Table 2]. The samples showed blue emission peak values in the range of 456-478 nm.

[표 2]TABLE 2

Figure pat00138

Figure pat00138

Figure pat00139

Figure pat00139

상기 표 2에 보여지는 바와 같이 샘플 118 내지 215은 비교샘플 1에 비하여 향상된 발광 특성을 나타내었다  As shown in Table 2, Samples 118 to 215 showed improved luminescence properties compared to Comparative Sample 1.

비교예Comparative example 2 2

하기 화학식 α로 표시되는 화합물 α를 발광층 호스트 물질로 사용하고, 화학식 d로 표시되는 자사의 발광층 도판트 물질을 도핑하였으며 b로 표시되는 2-TNATA(4,4',4"-tris(N-naphthalen-2-yl)-N-phenylamino)-triphenylamine)을 정공주입층 물질로 사용하고, 화학식 c로 표시되는 α-NPD(N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine)을 정공수송층 물질로 사용하여, 다음과 같은 구조를 갖는 유기발광소자를 제작하였다: ITO/2-TNATA(80nm)/α-NPD(30nm)/ 화합물a+화합물d(30nm)/Alq3(30nm)/LiF(0.5nm) /Al(60nm). The compound α represented by the following formula α is used as a light emitting layer host material, and its light emitting layer dopant material represented by the formula d is doped, and 2-TNATA (4,4 ', 4 "-tris (N- α-NPD (N, N'-di (naphthalene-1-yl) -N, N ', represented by Chemical Formula c, using naphthalen-2-yl) -N-phenylamino) -triphenylamine) as the hole injection layer material -diphenylbenzidine) was used as a hole transporting material, and an organic light emitting device having the following structure was fabricated: ITO / 2-TNATA (80nm) / α-NPD (30nm) / Compound a + Compound d (30nm) / Alq3 ( 30 nm) / LiF (0.5 nm) / Al (60 nm).

애노드는 코닝(Corning)사의 15Ω/cm2 (1000Å) ITO 유리 기판을 50mm x 50mm x 0.7mm크기로 잘라서 아세톤 이소프로필 알콜과 순수물 속에서 각 15분 동안 초음파 세정한 후, 30분 동안 UV 오존 세정하여 사용하였다. 상기 기판 상부에 2-TANATA를 진공 증착하여 80nm 두께의 정공주입층을 형성하였다. 상기 정공주입층 상부에, α-NPD를 진공 증착하여 30nm 두께의 정공수송층을 형성하였다. 상기 정공수송층 상부에 화학식 α로 표시되는 호스트 화합물 α에 화학식 d로 표시되는 화합물 d를 5.0% 도핑하여 30nm두께의 발광층을 형성하였다. 이후, 상기 발광층 상부에 Alq3 화합물을 30nm의 두께로 진공증착하여 전자수송층을 형성하였다. 상기 전자수송층 상부에 LiF 0.5nm(전자주입층)과 Al 600nm(캐소드)를 순차적으로 진공증착하여, 도 1b에 도시된 바와 같은 유기발광소자를 제조하였다. 이를 비교샘플 2이라고 한다. Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The light emitting layer having a thickness of 30 nm was formed by doping 5.0% of the compound d represented by the formula d to the host compound α represented by the formula α on the hole transport layer. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is called comparison sample 2.

본 실시예 및 이하의 실시예 들에서는 디오브이사에서 제작한 EL 증착기를 사용하여 소자를 제작하였다. In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

실시예Example 216~236 216-236

상기 비교예 2 중, 발광층 화합물로서 화합물 α 대신 상기 합성예에 개시된 화합물 97~117을 호스트 화합물로 각각 이용한 것을 제외하고는 상기 비교예 2과 동일한 방법으로 ITO/2-TNATA(80nm)/α-NPD(30nm)/[호스트 화합물 96~117및 도판트 화합물 d(5.0%)](30nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)의 구조를 갖는 유기발광소자를 제조하였다. 이를 각각 샘플 216 내지 236라고 한다.In Comparative Example 2, ITO / 2-TNATA (80nm) / α- in the same manner as in Comparative Example 2, except that Compound 97-117 disclosed in Synthesis Example was used as a host compound instead of Compound α as a light emitting layer compound. An organic light emitting diode having a structure of NPD (30 nm) / [Host Compound 96-117 and Dopant Compound d (5.0%)] (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. . These are called samples 216 to 236, respectively.

평가예Evaluation example 3 : 비교샘플 2 및 샘플 216 ~ 236의 발광 특성 평가 3: Evaluation of Luminescence Characteristics of Comparative Sample 2 and Samples 216 to 236

비교샘플 2및 샘플 216~236에 대하여, Keithley SMU 235, PR650를 이용하여 구동전압, 발광 휘도, 발광 효율, 발광피크를 각각 평가하여, 그 결과를 하기 [표 3]에 나타내었다. 상기 샘플들은 456~478nm 범위에서 청색 발광피크값을 보여주었다. For Comparative Sample 2 and Samples 216 to 236, driving voltage, emission luminance, emission efficiency, and emission peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 3]. The samples showed blue emission peak values in the range of 456-478 nm.

[표 3][Table 3]

Figure pat00140
Figure pat00140

상기 표 3에 보여지는 바와 같이 샘플 216 내지 236은 비교샘플 2에 비하여 향상된 발광 특성을 나타내었다. As shown in Table 3, Samples 216 to 236 showed improved luminescence properties compared to Comparative Sample 2.

비교예Comparative example 3 3

하기 화학식 α로 표시되는 화합물 α를 발광층 호스트 물질로 사용하고, 화학식 e로 표시되는 발광층 도판트 물질을 도핑하였으며 b로 표시되는 2-TNATA(4,4',4"-tris(N-naphthalen-2-yl)-N-phenylamino)-triphenylamine)을 정공주입층 물질로 사용하고, 화학식 c로 표시되는 α-NPD(N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine)을 정공수송층 물질로 사용하여, 다음과 같은 구조를 갖는 유기발광소자를 제작하였다: ITO/2-TNATA(80nm)/α-NPD(30nm)/ 화합물a+화합물e(30nm)/Alq3(30nm)/LiF(0.5nm) /Al(60nm). Using a compound α represented by the following formula α as a light emitting layer host material, doped the light emitting layer dopant material represented by the formula e and 2-TNATA (4,4 ', 4 "-tris (N-naphthalen- Α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine represented by Chemical Formula c) using 2-yl) -N-phenylamino) -triphenylamine) as a hole injection layer material ) Was used as a hole transport layer material to fabricate an organic light emitting device having the following structure: ITO / 2-TNATA (80nm) / α-NPD (30nm) / Compound a + Compound e (30nm) / Alq3 (30nm) / LiF (0.5 nm) / Al (60 nm).

애노드는 코닝(Corning)사의 15Ω/cm2 (1000Å) ITO 유리 기판을 50mm x 50mm x 0.7mm크기로 잘라서 아세톤 이소프로필 알콜과 순수물 속에서 각 15분 동안 초음파 세정한 후, 30분 동안 UV 오존 세정하여 사용하였다. 상기 기판 상부에 2-TANATA를 진공 증착하여 80nm 두께의 정공주입층을 형성하였다. 상기 정공주입층 상부에, α-NPD를 진공 증착하여 30nm 두께의 정공수송층을 형성하였다. 상기 정공수송층 상부에 화학식 α로 표시되는 호스트 화합물 α에 화학식 d로 표시되는 화합물 e를 3.0% 도핑하여 30nm두께의 발광층을 형성하였다. 이후, 상기 발광층 상부에 Alq3 화합물을 30nm의 두께로 진공증착하여 전자수송층을 형성하였다. 상기 전자수송층 상부에 LiF 0.5nm(전자주입층)과 Al 600nm(캐소드)를 순차적으로 진공증착하여, 도 1b에 도시된 바와 같은 유기발광소자를 제조하였다. 이를 비교샘플 3이라고 한다. Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The light emitting layer having a thickness of 30 nm was formed by doping 3.0% of the compound e represented by the formula d to the host compound α represented by the formula α on the hole transport layer. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is called Comparative Sample 3.

본 실시예 및 이하의 실시예 들에서는 디오브이사에서 제작한 EL 증착기를 사용하여 소자를 제작하였다. In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

실시예Example 237~243 237-243

상기 비교예 3 중, 발광층 화합물로서 화합물 α 대신 상기 합성예에 개시된 화합물 97~103을 호스트 화합물로 각각 이용한 것을 제외하고는 상기 비교예 3과 동일한 방법으로 ITO/2-TNATA(80nm)/α-NPD(30nm)/[호스트 화합물 96~103및 도판트 화합물 e(3.0%)](30nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)의 구조를 갖는 유기발광소자를 제조하였다. 이를 각각 샘플 237 내지 243라고 한다.In Comparative Example 3, ITO / 2-TNATA (80nm) / α- in the same manner as in Comparative Example 3, except that Compound 97-103 disclosed in Synthesis Example was used as a host compound instead of Compound α as a light emitting layer compound, respectively. An organic light emitting diode having a structure of NPD (30 nm) / [Host Compound 96-103 and Dopant Compound e (3.0%)] (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. . These are referred to as samples 237 to 243, respectively.

평가예Evaluation example 3 : 비교샘플 3 및 샘플 237 ~ 243의 발광 특성 평가 3: Evaluation of Luminescence Characteristics of Comparative Sample 3 and Samples 237 to 243

비교샘플 3 및 샘플 237~243에 대하여, Keithley SMU 235, PR650를 이용하여 구동전압, 발광 휘도, 발광 효율, 발광피크를 각각 평가하여, 그 결과를 하기 [표 4]에 나타내었다. 상기 샘플들은 516~520nm 범위에서 녹색 발광 피크 값을 보여주었다. For Comparative Sample 3 and Samples 237 to 243, Keithley SMU 235 and PR650 were used to evaluate driving voltage, emission luminance, emission efficiency, and emission peak, and the results are shown in the following [Table 4]. The samples showed green emission peak values in the range of 516-520 nm.

[표 4][Table 4]

Figure pat00141
Figure pat00141

상기 표 4에 확인할 수 있는 바와 같이 샘플 237 내지 243은 비교샘플 3에 비하여 향상된 발광 특성을 나타내었다.
As can be seen in Table 4, Samples 237 to 243 showed improved luminescence properties compared to Comparative Sample 3.

Claims (10)

제1전극; 제2전극; 및 상기 제1전극과 상기 제2전극 사이에 적어도 한 층의 유기막을 포함하는 유기 발광 소자로서, 상기 유기막이 하기 화학식 a의 유기 발광 화합물을 포함하는 것을 특징으로 하는 유기 발광 소자:
<화학식 a>
Figure pat00142


상기 식에서 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 치환 또는 비치환된 C6-C50아릴기, 치환 또는 비치환된 C2-C50헤테로아릴기, 치환 또는 비치환된 C2-C50사이클로알킬기, 또는 치환 또는 비치환된 C2-C50헤테로사이클로알킬기이다.A first electrode; A second electrode; And an organic light emitting device comprising at least one organic film between the first electrode and the second electrode, wherein the organic film comprises an organic light emitting compound represented by Chemical Formula a:
<Formula a>
Figure pat00142


Wherein A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2- A C50 cycloalkyl group or a substituted or unsubstituted C2-C50 heterocycloalkyl group. 제 1 항에 있어서,
상기 아릴기, 헤테로아릴기, 사이클로알킬기 및 헤테로사이클로알킬기의 치환기가,
C1-C50알킬기; C1-C50알콕시기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C6-C50아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C2-C50헤테로아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C5-C50사이클로알킬기; 및 비치환 또는 C1-C20알킬기 또는 C1-C20알콕시기로 치환된 C5-C50헤테로사이클로알킬기로 이루어진 군으로부터 선택된 하나 이상의 치환기인 것을 특징으로 하는 유기 발광 소자.The method of claim 1,
Substituents of the aryl group, heteroaryl group, cycloalkyl group and heterocycloalkyl group,
C1-C50 alkyl group; C1-C50 alkoxy group; C 6 -C 50 aryl groups which are unsubstituted or substituted with C 1 -C 50 alkyl groups or C 1 -C 50 alkoxy groups; C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; A C5-C50 cycloalkyl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; And one or more substituents selected from the group consisting of an unsubstituted or a C5-C50 heterocycloalkyl group substituted with a C1-C20 alkyl group or a C1-C20 alkoxy group. 제 1 항에 있어서,
상기 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로,
수소, 페닐기, 톨일기, 비페닐기, 펜타레닐기, 인데닐기, 나프틸기, 비페닐레닐기, 안트라세닐기, 벤조안트라세닐기, 아즈레닐기, 헵타레닐기, 아세나프틸레닐기, 페나레닐기, 메틸안트릴기, 페난트레닐기, 트리페닐레닐기, 피레닐기, 크리세닐기, 피세닐기, 페릴레닐기, 클로로페릴레닐기, 펜타페닐기, 펜타세닐기, 테트라페닐레닐기, 헥사페닐기, 헥사세닐기, 루비세닐기, 코로네닐기, 트리나프틸레닐기, 헵타페닐기, 헵타세닐기, 플루오레닐기, 피란트레닐기, 오바레닐기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 티오페닐기, 인돌일기, 푸리닐기, 벤즈이미다졸일기, 퀴놀리닐기, 벤조티오페닐기, 파라티아지닐기, 피롤일기, 피라졸릴기, 이미다졸릴기, 이미다졸리닐기, 옥사졸릴기, 티아졸릴기, 트리아졸릴기, 테트라졸일기, 옥사디아졸릴기, 피리디닐기, 피리다지닐기, 피리미디닐기, 피라지닐기, 티안트레닐기(thianthrenyl), 사이클로펜틸기, 사이클로헥실기, 옥시라닐기, 피롤리디닐기, 피라졸리디닐기, 이미다졸리디닐기, 피페리디닐기, 피페라지닐기, 모르폴리닐기, 디(C6-C50아릴)아미노기 및 이들의 유도체로 이루어진 군으로부터 선택된 것을 특징으로 하는 유기 발광 소자.The method of claim 1,
A1, A2, A3, A4, A5 and A6 are independently of each other,
Hydrogen, phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group , Methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, Hexenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group , Thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, thia Zolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group , Pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxiranyl, pyrrolidinyl, pyrazolidinyl, imidazoli An organic light emitting device, characterized in that selected from the group consisting of a diyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group, and derivatives thereof. 제 1 항에 있어서,
상기 화합물이 하기 화학식 1 내지 117로 표시되는 것을 특징으로 하는 유기 발광 소자:

Figure pat00143


Figure pat00144


Figure pat00145


Figure pat00146


Figure pat00147


Figure pat00148


Figure pat00149


Figure pat00150


Figure pat00151


Figure pat00152

The method of claim 1,
An organic light emitting diode, characterized in that the compound is represented by the formula 1 to 117:

Figure pat00143


Figure pat00144


Figure pat00145


Figure pat00146


Figure pat00147


Figure pat00148


Figure pat00149


Figure pat00150


Figure pat00151


Figure pat00152

 제 1 항에 있어서,
상기 유기막은 전자수송층 또는 발광층인 것을 특징으로 하는 유기 발광 소자.The method of claim 1,
The organic film is an organic light emitting device, characterized in that the electron transport layer or light emitting layer. 하기 화학식 a로 표시되는 유기 발광 화합물:
<화학식 a>
Figure pat00153


상기 식에서 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 치환 또는 비치환된 C6-C50아릴기, 치환 또는 비치환된 C2-C50헤테로아릴기, 치환 또는 비치환된 C2-C50사이클로알킬기, 또는 치환 또는 비치환된 C2-C50헤테로사이클로알킬기이다.An organic light emitting compound represented by formula (a):
<Formula a>
Figure pat00153


Wherein A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C2- A C50 cycloalkyl group or a substituted or unsubstituted C2-C50 heterocycloalkyl group. 제 6 항에 있어서,
상기 A1, A2, A3, A4, A5 및 A6 중 하나 이상이 페닐기인 것을 특징으로 하는 유기 발광 화합물.The method according to claim 6,
At least one of A1, A2, A3, A4, A5 and A6 is a phenyl group. 제 6 항에 있어서,
상기 아릴기, 헤테로아릴기, 사이클로알킬기 및 헤테로사이클로알킬기의 치환기가,
C1-C50알킬기; C1-C50알콕시기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C6-C50아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C2-C50헤테로아릴기; 비치환 또는 C1-C50알킬기 또는 C1-C50알콕시기로 치환된 C5-C50사이클로알킬기; 및 비치환 또는 C1-C20알킬기 또는 C1-C20알콕시기로 치환된 C5-C50헤테로사이클로알킬기로 이루어진 군으로부터 선택된 하나 이상의 치환기인 것을 특징으로 하는 유기 발광 화합물.The method according to claim 6,
Substituents of the aryl group, heteroaryl group, cycloalkyl group and heterocycloalkyl group,
C1-C50 alkyl group; C1-C50 alkoxy group; C 6 -C 50 aryl groups which are unsubstituted or substituted with C 1 -C 50 alkyl groups or C 1 -C 50 alkoxy groups; C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; A C5-C50 cycloalkyl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; And at least one substituent selected from the group consisting of an unsubstituted or a C5-C50 heterocycloalkyl group substituted with a C1-C20 alkyl group or a C1-C20 alkoxy group. 제 6 항에 있어서,
상기 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로,
수소, 페닐기, 톨일기, 비페닐기, 펜타레닐기, 인데닐기, 나프틸기, 비페닐레닐기, 안트라세닐기, 벤조안트라세닐기, 아즈레닐기, 헵타레닐기, 아세나프틸레닐기, 페나레닐기, 메틸안트릴기, 페난트레닐기, 트리페닐레닐기, 피레닐기, 크리세닐기, 피세닐기, 페릴레닐기, 클로로페릴레닐기, 펜타페닐기, 펜타세닐기, 테트라페닐레닐기, 헥사페닐기, 헥사세닐기, 루비세닐기, 코로네닐기, 트리나프틸레닐기, 헵타페닐기, 헵타세닐기, 플루오레닐기, 피란트레닐기, 오바레닐기, 카르바졸릴기, 디벤조퓨라닐기, 디벤조티오페닐기, 티오페닐기, 인돌일기, 푸리닐기, 벤즈이미다졸일기, 퀴놀리닐기, 벤조티오페닐기, 파라티아지닐기, 피롤일기, 피라졸릴기, 이미다졸릴기, 이미다졸리닐기, 옥사졸릴기, 티아졸릴기, 트리아졸릴기, 테트라졸일기, 옥사디아졸릴기, 피리디닐기, 피리다지닐기, 피리미디닐기, 피라지닐기, 티안트레닐기(thianthrenyl), 사이클로펜틸기, 사이클로헥실기, 옥시라닐기, 피롤리디닐기, 피라졸리디닐기, 이미다졸리디닐기, 피페리디닐기, 피페라지닐기, 모르폴리닐기, 디(C6-C50아릴)아미노기 및 이들의 유도체로 이루어진 군으로부터 선택된 것을 특징으로 하는 유기 발광 화합물.The method according to claim 6,
A1, A2, A3, A4, A5 and A6 are independently of each other,
Hydrogen, phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzoanthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group , Methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perylenyl group, chloroperylenyl group, pentaphenyl group, pentaxenyl group, tetraphenylenyl group, hexaphenyl group, Hexenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptasenyl group, fluorenyl group, pyrantrenyl group, obarenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group , Thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, thia Zolyl group, triazolyl group, tetrazolyl group, oxadiazolyl group , Pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxiranyl, pyrrolidinyl, pyrazolidinyl, imidazoli An organic light emitting compound, characterized in that selected from the group consisting of a diyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group, and derivatives thereof. 제 6 항에 있어서,
상기 화합물이 하기 화학식 1 내지 117로 표시되는 것을 특징으로 하는 유기 발광 화합물:

Figure pat00154


Figure pat00155


Figure pat00156


Figure pat00157


Figure pat00158


Figure pat00159


Figure pat00160


Figure pat00161


Figure pat00162


Figure pat00163

The method according to claim 6,
An organic light emitting compound characterized in that the compound is represented by the formula 1 to 117:

Figure pat00154


Figure pat00155


Figure pat00156


Figure pat00157


Figure pat00158


Figure pat00159


Figure pat00160


Figure pat00161


Figure pat00162


Figure pat00163
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