KR20140109058A - Compound for an organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Compound for an organic electronic element, organic electronic element using the same, and an electronic device thereof Download PDF

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KR20140109058A
KR20140109058A KR1020130023247A KR20130023247A KR20140109058A KR 20140109058 A KR20140109058 A KR 20140109058A KR 1020130023247 A KR1020130023247 A KR 1020130023247A KR 20130023247 A KR20130023247 A KR 20130023247A KR 20140109058 A KR20140109058 A KR 20140109058A
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KR102119673B1 (en
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박정철
이선희
박용욱
지희선
강문성
이범성
여승원
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덕산하이메탈(주)
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/32—Stacked devices having two or more layers, each emitting at different wavelengths
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
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    • Y02E10/549—Organic PV cells

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Abstract

The present invention provides a novel compound capable of improving light emitting efficiency, stability, and lifespan of an element, an organic electronic element using same, and an electronic device for the same. In one aspect, the present invention provides a compound represented by combination of chemical formula 1 and chemical formula 2. The compounds according to the present invention by utilizing a light emitting device of high efficiency, low driving voltage, high heat resistance can be achieved, and the color purity of the device can greatly improve the service life.

Description

유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치{COMPOUND FOR AN ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다. In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

유기 전기 발광소자에 있어 가장 문제시되는 것은 수명과 효율인데, 디스플레이가 대면적화되면서 이러한 효율이나 수명 문제는 반드시 해결해야 되는 상황이다.The most problematic aspects of organic electroluminescent devices are their lifetime and efficiency. As the display becomes larger, such efficiency and lifetime problems must be solved.

효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동시 발생되는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다. The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase.

하지만 상기 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and the T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time.

또한, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 반드시 정공수송층과 발광층 사이에 발광보조층이 존재하여야 하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광 보조층의 개발이 필요한 시점이다. In order to solve the problem of light emission in the hole transporting layer in recent organic electroluminescent devices, it is necessary to have a light emitting auxiliary layer between the hole transporting layer and the light emitting layer, It is time to develop the layer.

일반적으로 전자수송층에서 발광층으로 전자(electron)이 전달되고 정공(hole)이 정공수송층에서 발광층으로 전달되어 재조합(recombination)에 의해 엑시톤(exciton)이 생성된다. Generally, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

하지만 정공수송층에 사용되는 물질의 경우 낮은 HOMO 값을 가져야 하기 때문에 대부분 낮은 T1 값을 가지며, 이로 인해 발광층에서 생성된 엑시톤(exciton)이 정공수송층으로 넘어가게 되어 결과적으로 발광층 내 전하불균형(charge unbalance)을 초래하여 정공수송층 계면에서 발광하게 된다.However, the material used for the hole transport layer has a low HOMO value and therefore has a low T 1 value. As a result, the exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in a charge unbalance in the light emitting layer. And emits light at the interface of the hole transporting layer.

정공수송층 계면에서 발광될 경우, 유기전기소자의 색순도 및 효율이 저하되고 수명이 짧아지는 문제점이 발생하게 된다. 따라서 높은 T1 값을 가지며, 정공 수송층 HOMO 에너지 level과 발광층의 HOMO 에너지 level 사이의 HOMO level를 갖는 발광보조층이 개발이 절실히 요구된다.When light is emitted from the interface of the hole transporting layer, the color purity and efficiency of the organic electronic device are lowered and the lifetime is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T 1 value and a HOMO level between the HOMO energy level of the hole transporting layer and the HOMO energy level of the light emitting layer.

한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투확산되는 것을 지연시키면서, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 정공수송층 재료의 낮은 유리전이 온도는 소자 구동시, 박막 표면의 균일도를 저하시키는 특성이 있는바, 이는 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자는 주로 증착방법에 의해 형성되는데, 증착시 오랫동안 견딜 수 있는 재료, 즉 내열특성이 강한 재료 개발이 필요한 실정이다. On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.

즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질, 발광보조층 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정되고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서, 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광보조층과 정공수송층의 재료 조합에 대한 개발이 절실히 요구되고 있다. That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, However, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently developed yet. Therefore, the development of new materials is continuously required, and in particular, development of a combination of materials for the light emission-assisting layer and the hole transporting layer is urgently required.

본 발명은 소자의 높은 발광효율, 낮은 구동전압, 고내열성, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a compound capable of improving a high luminous efficiency, a low driving voltage, a high heat resistance, a color purity and a lifetime of the device, an organic electric device using the same, and an electronic device thereof.

일측면에서, 본 발명은 화학식 1과 화학식 2의 조합으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by a combination of Formula (1) and Formula (2).

<화학식 1> <화학식 2>&Lt; Formula 1 > < EMI ID =

Figure pat00001
,
Figure pat00002
Figure pat00001
,
Figure pat00002

다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.

본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다. By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

도 1은 본 발명에 따른 유기전기발광소자의 예시도이다. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

한편, 본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소, 염소, 브롬, 및 요오드를 포함한다. The term " halo "or" halogen "as used herein, on the other hand, includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkyl" or "alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

본 발명에 사용된 용어 "알케닐" 또는 "알키닐"은 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 여기에 제한되는 것은 아니다. The term "alkenyl" or "alkynyl ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms,

본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다. The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

본 발명에 사용된 용어 "알콕시기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkoxy group" as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, but is not limited thereto.

본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto.

본 발명에서 아릴기 또는 아릴렌기는 단일환 또는 복소환의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 링을 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다. In the present invention, an aryl group or an arylene group means an aromatic group having a single ring or a heterocyclic ring, and the neighboring substituent includes an aromatic ring formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 3 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다.The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 3 to 60 carbon atoms each containing at least one heteroatom, But includes a single ring as well as a heterocyclic ring and may be formed by bonding adjacent groups.

본 발명에 사용된 용어 "헤테로시클로알킬", "헤테로고리기"는 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다. 또한, "헤테로고리기"는 헤테로원자를 포함하는 지환족 및/또는 방향족을 의미할 수 있다.The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 및 Si를 나타낸다. As used herein, the term "heteroatom " refers to N, O, S, P and Si, unless otherwise indicated.

다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

다른 설명이 없는 한, 본 발명에 사용된 용어 "포화 또는 불포화 고리"는 포화 또는 불포화 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 헤테로고리를 의미한다.Unless otherwise indicated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or hetero ring having 6 to 60 carbon atoms.

전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, 및 C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다. One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C for use in the present invention alkoxy group, C 1 ~ C 20 alkyl amine group of 20, C 1 ~ C 20 alkyl thiophene group, C 6 ~ C 20 aryl thiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 8 ~ C 20 arylalkenyl group, a silane group, a boron of Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, a germanium group, and a C 5 to C 20 heterocyclic group, and is not limited to these substituents.

도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an illustration of an organic electroluminescent device according to an embodiment of the present invention.

도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 본 발명에 따른 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다. The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다. Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 캐핑층의 재료로 사용될 수 있을 것이다. 바람직하게는, 본 발명의 화합물은 정공수송층(140) 및/또는 발광보조층(151)으로 사용될 수 있을 것이다.The compound according to the present invention applied to the organic material layer may be used as a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, . Preferably, the compound of the present invention may be used as the hole transporting layer 140 and / or the light emitting auxiliary layer 151.

한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when energy level and T1 value between each organic material layer, and the intrinsic characteristics (mobility, interfacial characteristics, etc.) of the material are optimized, long life and high efficiency can be achieved at the same time.

이미 설명한 것과 같이, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 정공수송층과 발광층 사이에 발광보조층이 형성하는 것이 바람직하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광보조층의 개발이 필요한 시점이다. 한편, 발광보조층의 경우 정공수송층 및 발광층(호스트)과의 상호관계를 파악해야하므로 유사한 코어를 사용하더라도 사용되는 유기물층이 달라지면 그 특징을 유추하기는 매우 어려울 것이다. As described above, in order to solve the emission problem in the hole transporting layer in recent organic electroluminescent devices, it is preferable that a light emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer, and the light emitting layer (R, G, B) It is necessary to develop different luminescent auxiliary layers. On the other hand, in the case of the light-emission-assisting layer, it is difficult to deduce the characteristics of the organic layer to be used even if a similar core is used because the relationship between the hole-transport layer and the light-emitting layer (host)

따라서, 본 발명에서는 화학식 1 및 화학식 2의 조합으로 표시되는 화합물을 사용하여 정공수송층 또는 발광보조층을 형성함으로써 각 유기물층 간의 에너지 레벨(level) 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다. Accordingly, in the present invention, by forming a hole transporting layer or a light-emitting auxiliary layer by using a compound represented by the combination of the general formulas (1) and (2), energy levels and T1 values between the organic layers, mobility, ) Can be optimized to improve the lifetime and efficiency of the organic electronic device at the same time.

본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer can be formed using a variety of polymer materials by a solution process other than a vapor deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be made of a number of layers. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

또한, 본 발명에 따른 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.The organic electroluminescent device according to the present invention may be one of an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, the compound according to one aspect of the present invention will be described.

일측면에서, 본 발명은 하기 화학식 1과 화학식 2의 조합으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by a combination of the following formulas (1) and (2).

<화학식 1> <화학식 2>&Lt; Formula 1 > < EMI ID =

Figure pat00003
,
Figure pat00004
Figure pat00003
,
Figure pat00004

이때, Y를 포함하는 오각형의 환이 형성되도록 화학식 2가 화학식 1의 이웃한 두 탄소에 결합된다. 즉, 화학식 2는 화학식 1의 바로 이웃한 두 *에 결합한다. 화학식 2에서 결합부위는

Figure pat00005
로 표시되어 있다.At this time, the formula (2) is bonded to two neighboring carbons of formula (1) such that a pentagonal ring containing Y is formed. That is, Formula (2) bonds to immediately adjacent two * of Formula (1). In the formula (2)
Figure pat00005
Respectively.

따라서, 화학식 2가 화학식 1에 결합되면 다음과 같은 화학식으로 표시될 수 있을 것이다.Therefore, when the formula (2) is bonded to the formula (1), it can be represented by the following formula.

<화학식 3> <화학식 4> <화학식 5> &Lt; Formula 3 > < EMI ID =

Figure pat00006
Figure pat00007
Figure pat00006
Figure pat00007

상기 화학식 1 내지 5에서, R1~R5 및 R11은 서로 독립적으로, 수소; C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; C1~C50의 알킬기; 플루오렌일기; 및 -L-N(Ar1)(Ar2)로 이루어진 군에서 선택되고, n은 1 또는 2의 정수이다. 단, 상기 R1~R4 중 적어도 하나 또는 R11이 -L-N(Ar1)(Ar2)이거나, R1~R4 중 적어도 하나와 R11이 모두 -L-N(Ar1)(Ar2)이다.In the above Chemical Formulas 1 to 5, R 1 to R 5 and R 11 independently represent hydrogen; A C 6 to C 60 aryl group; O, N, S, Si and P, A C 3 to C 60 heterocyclic group; A C 1 to C 50 alkyl group; A fluorenyl group; And -LN (Ar 1 ) (Ar 2 ), and n is an integer of 1 or 2. And at least one of R 1 to R 4 or R 11 is -LN (Ar 1 ) (Ar 2 ), or at least one of R 1 to R 4 and R 11 are both -LN (Ar 1 ) (Ar 2 ) to be.

상기 화학식에서, Y는 S, O 또는 CR'R"이며, 여기서 R' 및 R"은 ⅰ) 서로 독립적으로, 수소; C1~C50의 알킬기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; 및 -L-N(Ar1)(Ar2)로 이루어진 군에서 선택되거나, 또는 ⅱ) 서로 결합하여 스피로 화합물을 형성하며,Wherein Y is S, O or CR'R &quot;, wherein R 'and R "are independently selected from the group consisting of: i) independently of one another hydrogen; A C 1 to C 50 alkyl group; A C 6 to C 60 aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si, and C 3 ~ containing at least one hetero atom in the P C 60; And -LN (Ar 1 ) (Ar 2 ), or ii) bonded to each other to form a spiro compound,

상기 L은 C6~C60의 직접결합; 아릴렌기; O, N, S, Si, P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로아릴렌기; 및 플루오레닐렌기;로 이루어진 군에서 선택되고 (단, 이들 각각은 니트로기, 시아노기, 할로겐기, C1~C20의 알킬기, C6~C20의 아릴기, C2~C20의 헤테로고리기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환될 수 있음),L is a direct bond of C 6 to C 60 ; An arylene group; Containing at least one heteroatom selected from O, N, S, Si, P A C 3 to C 60 heteroarylene group; And a fluorenylene group, provided that each of these is selected from the group consisting of a nitro group, a cyano group, a halogen group, a C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, a C 2 to C 20 A heterocyclic group, a C 1 to C 20 alkoxy group, and an amino group,

상기 Ar1, Ar2는 C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; C1~C50의 알킬기; 및 플루오렌일기;로 이루어진 군에서 선택된다.Ar 1 and Ar 2 are C 6 to C 60 aryl groups; O, N, S, Si and P, A C 3 to C 60 heterocyclic group; A C 1 to C 50 alkyl group; And a fluorenyl group.

한편, 상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 아릴기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,On the other hand, the R 1 ~ R 5, R 11 , R ' and R ", Ar 1, and if Ar 2 is an aryl group, which is heavy hydrogen, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C 1 - of C 20 come alkylthio, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 of alkenyl groups (alkenyl), an alkynyl of C 2 - C 20 group (alkynyl), the A C 6 to C 20 aryl group, a C 6 to C 20 aryl group substituted with deuterium, a C 2 to C 20 heterocyclic group, a C 3 to C 20 cycloalkyl group, a C 7 to C 20 An arylalkyl group, and an arylalkenyl group having 8 to 20 carbon atoms,

상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 헤테로고리기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, 니트로기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 a heterocyclic group, which is heavy hydrogen, an alkoxyl group, a halogen, a silane group, a cyano group, a nitro group, C 1 ~ C 20, C 1 ~ C 20 alkyl group, C 2 ~ C 20 of alkenyl groups (alkenyl), C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 2 ~ heterocycle of the C 20 Group, a C 3 to C 20 cycloalkyl group, a C 7 to C 20 An arylalkyl group, and an arylalkenyl group having 8 to 20 carbon atoms,

상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 플루오렌일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 fluorene group in which heavy hydrogen, a halogen, a silane group, a cyano group, C alkyl group of 1 ~ C 20, C 2 ~ An alkenyl group of C 20 , a C 6 to C 20 aryl group, a C 6 to C 20 aryl group substituted by deuterium, a C 2 to C 20 heterocyclic group, and a C 3 to C 20 cycloalkyl group Lt; / RTI &gt; may be substituted with one or more substituents selected from the group consisting &lt; RTI ID =

상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 알킬기인 경우, 이는 할로겐, 실란기, 붕소기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 is an alkyl group, which is a halogen, a silane group, a boron group, cyano group, C 1 ~ C 20 alkoxy group, C 1 ~ of alkyl group of C 20, C 2 ~ C 20 of alkenyl groups (alkenyl), C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, C 2 ~ C 20 heterocyclic group, C of 7 to C 20 An arylalkyl group and an arylalkenyl group having from 8 to 20 carbon atoms.

또한, 화학식 1과 화학식 2의 조합은 하기 화학식 중 하나로 표시될 수 있을 것이다.The combination of formula (1) and formula (2) may be represented by one of the following formulas.

<화학식 6> <화학식 7> <화학식 8> &Lt; Formula 6 > < EMI ID =

Figure pat00008
Figure pat00008

<화학식 9> <화학식 10> <화학식 11>&Lt; Formula 9 > < EMI ID =

Figure pat00009
Figure pat00009

(상기 화학식 6 내지 11에서, R1~R4, R11, Y, L, Ar1, Ar2 및 n은 화학식 1 및 화학식 2의 정의에서 정의된 것과 같다)(Wherein R 1 to R 4 , R 11 , Y, L, Ar 1 , Ar 2 and n are the same as defined in the definitions of formulas (1) and (2)

구체적으로, 화학식 1과 화학식 2의 조합으로 표시되는 화합물은 하기 화합물 중 하나일 수 있다.Specifically, the compound represented by the combination of the formulas (1) and (2) may be one of the following compounds.

Figure pat00010
Figure pat00010

Figure pat00011
Figure pat00011

Figure pat00012
Figure pat00012

Figure pat00013
Figure pat00013

Figure pat00014
Figure pat00014

Figure pat00015
Figure pat00015

Figure pat00016
Figure pat00016

Figure pat00017
Figure pat00017

Figure pat00018
Figure pat00018

Figure pat00019
Figure pat00019

Figure pat00020
Figure pat00020

Figure pat00021
Figure pat00021

Figure pat00022
Figure pat00022

이하, 본 발명에 따른 화합물 제조예를 설명한다. 하기 합성예는 본 발명에 따른 화합물을 설명하기 위한 일실시예에 지나지 아니하므로 이에 의해 본 발명의 권리범위가 제한되지는 않는다.Hereinafter, a preparation example of the compound according to the present invention will be described. The following Synthesis Examples are only illustrative examples for explaining the compounds according to the present invention, and thus the scope of the present invention is not limited thereto.

<< 합성예Synthetic example >>

본 발명에 따른 화합물(final products)은 하기 반응식 1과 반응식 2와 같은 반응경로에 의해 합성될 수 있을 것이다.The compounds according to the invention (final products) may be synthesized by the reaction pathways as shown in the following Reaction Schemes 1 and 2.

<반응식 1><Reaction Scheme 1>

Figure pat00023
Figure pat00023

<반응식 2><Reaction Scheme 2>

Figure pat00024
Figure pat00024

SubSub 1-A,  1-A, SubSub 1-B,  1-B, Sub 1-C의Sub 1-C 합성 예시 Synthetic example

반응식 1의 sub 1-A, sub 1-B, sub 1-C는 하기 반응식 3과 같은 반응경로에 의해 합성될 수 있다.Sub1-A, sub1-B, and sub1-C in Scheme 1 can be synthesized by the reaction pathway as shown in the following reaction formula (3).

<반응식 3><Reaction Scheme 3>

Figure pat00025
Figure pat00025

Figure pat00026
Figure pat00026

SubSub 1-2-A(B,C) 합성 1-2-A (B, C) Synthesis

Sub 1-1-A(B,C) (1당량)을 둥근바닥플라스크에 DMF로 녹인 후에, Bis(pinacolato)diboron (1.1당량), Pd(dppf)Cl2 (0.03당량), KOAc (3당량)를 첨가하고 90°C에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1-2-A(B,C)를 얻었다.Sub 1-1 -A (B, C) (1 eq.) Was dissolved in DMF in a round bottom flask followed by Bis (pinacolato) diboron (1.1 eq.), Pd (dppf) Cl 2 (3 eq) and stir at 90 [deg.] C. When the reaction was complete, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1-2-A (B, C).

SubSub 1-4-A(B,C) 합성 1-4-A (B, C) Synthesis

Sub 1-2-A(B,C) (1당량)와 Sub 1-3 (1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피로 분리하여 원하는 Sub 1-4-A(B,C)를 얻었다.Sub 1-2-A (B, C) (1 equivalent), Sub 1-3 (1 equivalent), Pd (PPh 3 ) 4 (0.03 equivalent) and K 2 CO 3 Dissolved in water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 1-4-A (B, C).

SubSub 1-5-A(B,C) 합성 1-5-A (B, C) Synthesis

Sub 1-4-A(B,C)를 아세트산(acetic acid)에 녹이고 과산화수소(hydrogen peroxide)를 아세트산에 용해시킨 것을 한방울씩 떨어뜨려 상온에서 6시간 교반한다. 반응이 종결되면 감압장치를 이용하여 아세트산을 제거하고 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 1-5-A(B,C)를 얻었다.Sub 1-4-A (B, C) is dissolved in acetic acid and hydrogen peroxide is dissolved in acetic acid. Dropwise dropwise and stir at room temperature for 6 hours. After the reaction was completed, acetic acid was removed using a pressure-reducing device and column chromatography was carried out to obtain the desired Sub 1-5-A (B, C).

SubSub 1-6-A(B,C) 합성 1-6-A (B, C) Synthesis

Sub 1-5-A(B,C)와 트리풀루오로메탄술폰산(trifluoromethanesulfonic acid)를 넣고 상온에서 24시간 교반한 다음 물과 피리딘(8:1)을 천천히 넣고 30분 환류한다. 온도를 내리고 CH2Cl2로 추출하고 물로 닦아준다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과한 후, 유기 용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 1-6-A(B,C)를 얻었다.Add Sub 1-5-A (B, C) and trifluoromethanesulfonic acid, stir at room temperature for 24 hours, add water and pyridine (8: 1) slowly and reflux for 30 minutes. The temperature is lowered, extracted with CH 2 Cl 2 and wiped with water. A small amount of water was removed with anhydrous MgSO 4 and filtered under reduced pressure. The organic solvent was concentrated, and the resulting product was subjected to column chromatography to obtain the desired Sub 1-6-A (B, C).

SubSub 1-7-A(B,C) 합성 1-7-A (B, C) Synthesis

Sub 1-6-A(B,C) (1당량)을 둥근바닥플라스크에 DMF로 녹인 후에, Bis(pinacolato)diboron (1.1당량), Pd(dppf)Cl2 (0.03당량), KOAc (3당량)를 첨가하고 90°C에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 1-7-A(B,C)를 얻었다.Sub-1-6-A (B, C) (1 eq.) Was dissolved in DMF in a round bottom flask followed by Bis (pinacolato) diboron (1.1 eq.), Pd (dppf) Cl 2 (3 eq) and stir at 90 [deg.] C. When the reaction was complete, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1-7-A (B, C).

SubSub 1-A(B,C) 합성 1-A (B, C) Synthesis

Sub 1-7-A(B,C) (1당량)와 I-L-Br 화합물(1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피로 분리하여 원하는 Sub 1-A(B,C)를 얻었다.Pd (PPh 3 ) 4 (0.03 eq.) And K 2 CO 3 (3 eq.) Were mixed with anhydrous THF and a small amount of (1 eq.) Sub 1-7-A (B, Dissolved in water, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 1-A (B, C).

Sub 1-A, Sub1-B, Sub1-C의 예시는 다음과 같으나, 이에 한정되는 것은 아니다. Examples of Sub1-A, Sub1-B, and Sub1-C are as follows, but are not limited thereto.

Figure pat00027
Figure pat00027

Figure pat00028
Figure pat00028

상기 화합물에 대한 FD-MS 값은 하기 표 1과 같다.The FD-MS values for the above compounds are shown in Table 1 below.

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 1(1)Sub 1 (1) m/z=326.97(C16H10BrNS=328.23)m / z = 326.97 (C 16 H 10 BrNS = 328.23) Sub 1(2)Sub 1 (2) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(3)Sub 1 (3) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(4)Sub 1 (4) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(5)Sub 1 (5) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(6)Sub 1 (6) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(7)Sub 1 (7) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(8)Sub 1 (8) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(9)Sub 1 (9) m/z=327.97(C15H9BrN2S=329.97) m / z = 327.97 (C 15 H 9 BrN 2 S = 329.97) Sub 1(10)Sub 1 (10) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(11)Sub 1 (11) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(12)Sub 1 (12) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(13)Sub 1 (13) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(14)Sub 1 (14) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(15)Sub 1 (15) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(16)Sub 1 (16) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(17)Sub 1 (17) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(18)Sub 1 (18) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 1(19)Sub 1 (19) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(20)Sub 1 (20) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(21)Sub 1 (21) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(22)Sub 1 (22) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(23)Sub 1 (23) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(24)Sub 1 (24) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(25)Sub 1 (25) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(26)Sub 1 (26) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(27)Sub 1 (27) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 1(28)Sub 1 (28) m/z=403.00(C22H14BrNS=404.32)m / z = 403.00 (C 22 H 14 BrNS 404.32 =) Sub 1(29)Sub 1 (29) m/z=453.02(C26H16BrNS=454.38)m / z = 453.02 (C 26 H 16 BrNS = 454.38) Sub 1(30)Sub 1 (30) m/z=453.02(C26H16BrNS=454.38)m / z = 453.02 (C 26 H 16 BrNS = 454.38) Sub 1(31)Sub 1 (31) m/z=479.03(C28H18BrNS=480.42)m / z = 479.03 (C 28 H 18 BrNS 480.42 =) Sub 1(32)Sub 1 (32) m/z=508.99(C28H16BrNS2=510.47) m / z = 508.99 (C 28 H 16 BrNS 2 = 510.47) Sub 1(33)Sub 1 (33) m/z=493.01(C28H16BrNOS=494.4) m / z = 493.01 (C 28 H 16 BrNOS = 494.4) Sub 1(34)Sub 1 (34) m/z=519.07(C31H22BrNS=520.48)m / z = 519.07 (C 31 H 22 BrNS = 520.48) Sub 1(35)Sub 1 (35) m/z=643.10(C41H26BrNS=644.62)m / z = 643.10 (C 41 H 26 BrNS = 644.62) Sub 1(36)Sub 1 (36) m/z=387.03(C22H14BrNO=388.26) m / z = 387.03 (C 22 H 14 BrNO = 388.26) Sub 1(37)Sub 1 (37) m/z=437.04(C26H16BrNO=438.32)m / z = 437.04 (C 26 H 16 BrNO = 438.32) Sub 1(38)Sub 1 (38) m/z=463.09(C29H22BrN=464.40)m / z = 463.09 (C 29 H 22 BrN = 464.40) Sub 1(39)Sub 1 (39) m/z=489.11(C31H24BrN=490.43)m / z = 489.11 (C 31 H 24 BrN = 490.43) Sub 1(40)Sub 1 (40) m/z=493.01(C28H16BrNOS=494.40) m / z = 493.01 (C 28 H 16 BrNOS = 494.40) Sub 1(41)Sub 1 (41) m/z=503.09(C31H22BrNO=504.42)m / z = 503.09 (C 31 H 22 BrNO = 504.42) Sub 1(42)Sub 1 (42) m/z=503.09(C31H22BrNO=504.42)m / z = 503.09 (C 31 H 22 BrNO = 504.42) Sub 1(43)Sub 1 (43) m/z=653.17(C44H32BrN=654.64)m / z = 653.17 (C 44 H 32 BrN = 654.64)

SubSub 2의 합성 예시 2 Synthetic Example

반응식 1의 sub 2는 하기 반응식 4의 반응경로에 의해 합성될 수 있다.Sub 2 of Scheme 1 can be synthesized by the reaction path of Scheme 4 below.

<반응식 4><Reaction Scheme 4>

Figure pat00029
Figure pat00029

Br이 치환된 Ar2 (1.1당량)를 둥근바닥플라스크에 toluene으로 녹인 후에, NH2가 치환되어 있는 Ar3 (1당량), Pd2(dba)3 (0.3당량), 50% P(t-Bu)3 (9당량), NaOt-Bu (3당량)을 첨가하고 40°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 2를 얻었다.After the Ar 2 (1.1 eq.) Of Br-substituted dissolved in toluene in a round bottom flask, Ar 3 (1 eq.) With NH 2 is substituted, Pd 2 (dba) 3 ( 0.3 equiv), 50% P (t - Bu) 3 (9 eq), NaO t- Bu (3 eq) and stir at 40 ° C. After completion of the reaction, the reaction mixture was extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain Sub 2.

Sub 2의 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 2 include, but are not limited to, the following.

Figure pat00030
Figure pat00030

Figure pat00031
Figure pat00031

상기 화합물에 대한 FD-MS 값은 하기 표 2와 같다.The FD-MS values for the above compounds are shown in Table 2 below.

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 2-1Sub 2-1 m/z=169.09(C12H11N=169.22)m / z = 169.09 (C 12 H 11 N = 169.22) Sub 2-2Sub 2-2 m/z=219.10(C16H13N=219.28)m / z = 219.10 (C 16 H 13 N = 219.28) Sub 2-3Sub 2-3 m/z=219.10(C16H13N=219.28)m / z = 219.10 (C 16 H 13 N = 219.28) Sub 2-4Sub 2-4 m/z=245.12(C18H15N=245.32) m / z = 245.12 (C 18 H 15 N = 245.32) Sub 2-5Sub 2-5 m/z=170.08(C11H10N2=170.21)m / z = 170.08 (C 11 H 10 N 2 = 170.21) Sub 2-6Sub 2-6 m/z=199.10(C10H13NO=199.25) m / z = 199.10 (C 10 H 13 NO = 199.25) Sub 2-7Sub 2-7 m/z=225.15(C16H19N=225.33)m / z = 225.15 (C 16 H 19 N = 225.33) Sub 2-8Sub 2-8 m/z=285.15(C21H19N=285.38) m / z = 285.15 (C 21 H 19 N = 285.38) Sub 2-9Sub 2-9 m/z=409.18(C31H23N=409.52)m / z = 409.18 (C 31 H 23 N = 409.52) Sub 2-10Sub 2-10 m/z=407.17(C31H21N=407.51)m / z = 407.17 (C 31 H 21 N = 407.51) Sub 2-11Sub 2-11 m/z=269.12(C20H15N=269.34) m / z = 269.12 (C 20 H 15 N = 269.34) Sub 2-12Sub 2-12 m/z=269.12(C20H15N=269.34) m / z = 269.12 (C 20 H 15 N = 269.34) Sub 2-13Sub 2-13 m/z=295.14(C22H17N=295.38) m / z = 295.14 (C 22 H 17 N = 295.38) Sub 2-14Sub 2-14 m/z=220.10(C15H12N2=220.27) m / z = 220.10 (C 15 H 12 N 2 = 220.27) Sub 2-15Sub 2-15 m/z=249.12(C17H12NO=249.31) m / z = 249.12 (C 17 H 12 NO = 249.31) Sub 2-16Sub 2-16 m/z=275.17(C20H21N=275.39)m / z = 275.17 (C 20 H 21 N = 275.39) Sub 2-17Sub 2-17 m/z=335.17(C25H21N=335.44) m / z = 335.17 (C 25 H 21 N = 335.44) Sub 2-18Sub 2-18 m/z=459.20(C35H25N=459.58) m / z = 459.20 (C 35 H 25 N = 459.58) Sub 2-19Sub 2-19 m/z=457.18(C35H23N=457.56) m / z = 457.18 (C 35 H 23 N = 457.56) Sub 2-20Sub 2-20 m/z=269.12(C20H15N=269.34) m / z = 269.12 (C 20 H 15 N = 269.34) Sub 2-21Sub 2-21 m/z=295.14(C22H17N=295.38) m / z = 295.14 (C 22 H 17 N = 295.38) Sub 2-22Sub 2-22 m/z=220.10(C15H2N2=220.27) m / z = 220.10 (C 15 H 2 N 2 = 220.27) Sub 2-23Sub 2-23 m/z=249.12(C17H15NO=249.31) m / z = 249.12 (C 17 H 15 NO = 249.31) Sub 2-24Sub 2-24 m/z=275.17(C20H21N=275.39)m / z = 275.17 (C 20 H 21 N = 275.39) Sub 2-25Sub 2-25 m/z=335.17(C25H21N=335.44) m / z = 335.17 (C 25 H 21 N = 335.44) Sub 2-26Sub 2-26 m/z=459.20(C35H25N=459.58) m / z = 459.20 (C 35 H 25 N = 459.58) Sub 2-27Sub 2-27 m/z=457.18(C35H23N=457.56) m / z = 457.18 (C 35 H 23 N = 457.56) Sub 2-28Sub 2-28 m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) Sub 2-29Sub 2-29 m/z=246.12(C17H14N2=246.31) m / z = 246.12 (C 17 H 14 N 2 = 246.31) Sub 2-30Sub 2-30 m/z=275.13(C19H17NO=275.34) m / z = 275.13 (C 19 H 17 NO = 275.34) Sub 2-31Sub 2-31 m/z=301.18(C22H23N=301.42) m / z = 301.18 (C 22 H 23 N = 301.42) Sub 2-32Sub 2-32 m/z=361.18(C27H23N=361.48)m / z = 361.18 (C 27 H 23 N = 361.48) Sub 2-33Sub 2-33 m/z=485.21(C37H27N=485.62) m / z = 485.21 (C 37 H 27 N = 485.62) Sub 2-34Sub 2-34 m/z=483.20(C37H25N=483.60) m / z = 483.20 (C 37 H 25 N = 483.60) Sub 2-35Sub 2-35 m/z=171.08(C10H09N3=171.20) m / z = 171.08 (C 10 H 09 N 3 = 171.20) Sub 2-36Sub 2-36 m/z=200.09(C12H12N2O=200.24)m / z = 200.09 (C 12 H 12 N 2 O = 200.24) Sub 2-37Sub 2-37 m/z=226.15(C15H18N2=226.32) m / z = 226.15 (C 15 H 18 N 2 = 226.32) Sub 2-38Sub 2-38 m/z=286.15(C20H18N2=286.37) m / z = 286.15 (C 20 H 18 N 2 = 286.37) Sub 2-39Sub 2-39 m/z=410.18(C30H22N2=410.51) m / z = 410.18 (C 30 H 22 N 2 = 410.51) Sub 2-40Sub 2-40 m/z=408.16(C30H20N2=408.49) m / z = 408.16 (C 30 H 20 N 2 = 408.49) Sub 2-41Sub 2-41 m/z=229.11(C14H15NO2=229.27) m / z = 229.11 (C 14 H 15 NO 2 = 229.27) Sub 2-42Sub 2-42 m/z=255.16(C17H21NO=255.35) m / z = 255.16 (C 17 H 21 NO = 255.35) Sub 2-43Sub 2-43 m/z=315.16(C22H21NO=315.41) m / z = 315.16 (C 22 H 21 NO = 315.41) Sub 2-44Sub 2-44 m/z=439.19(C32H25NO=439.55)m / z = 439.19 (C 32 H 25 NO = 439.55) Sub 2-45Sub 2-45 m/z=437.18(C32H23NO=437.53)m / z = 437.18 (C 32 H 23 NO = 437.53) Sub 2-46Sub 2-46 m/z=281.21(C20H27N=281.44)m / z = 281.21 (C 20 H 27 N = 281.44) Sub 2-47Sub 2-47 m/z=341.21(C25H27N=341.49) m / z = 341.21 (C 25 H 27 N = 341.49) Sub 2-48Sub 2-48 m/z=465.25(C35H31N=465.63) m / z = 465.25 (C 35 H 31 N = 465.63) Sub 2-49Sub 2-49 m/z=463.23(C35H29N=463.61) m / z = 463.23 (C 35 H 29 N = 463.61) Sub 2-50Sub 2-50 m/z=401.21(C30H27N=401.54) m / z = 401.21 (C 30 H 27 N = 401.54) Sub 2-51Sub 2-51 m/z=525.25(C40H31N=525.68)m / z = 525.25 (C 40 H 31 N = 525.68) Sub 2-52Sub 2-52 m/z=523.23(C40H29N=523.66)m / z = 523.23 (C 40 H 29 N = 523.66)

FinalFinal ProductProduct 1의 합성 Synthesis of 1

둥근바닥플라스크에 Sub 1 화합물 (1.1당량), Sub 2 화합물 (1당량), Pd2(dba)3 (0.05당량), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Product를 얻었다.(1.1 eq.), Sub 2 compound (1 eq.), Pd 2 (dba) 3 (0.05 eq.), P (t-Bu) 3 (0.1 eq.), NaO t -Bu ) and toluene (10.5 mL / 1 mmol), and the reaction is carried out at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain a product.

화합물 1-5의 합성 예시Examples of synthesis of compound 1-5

Figure pat00032
Figure pat00032

둥근바닥플라스크에 5-bromo-1,2,3-triphenyl-1H-benzo[4,5]thieno[2,3-b]pyrrole (11.5g, 24mmol), N-phenylphenanthren-9-amine (5.4g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 7.9g (수율: 59%) 얻었다.A round bottom flask was charged with 5-bromo-1,2,3-triphenyl-1H-benzo [4,5] thieno [2,3-b] pyrrole (11.5 g, 24 mmol) and N-phenylphenanthren- after loading a, 20mmol), Pd 2 (dba ) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 eq.), toluene (10.5 mL / 1 mmol) 100 Lt; 0 &gt; C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.9 g (yield: 59%) of the product.

화합물 1-42의 합성 예시Synthesis Example of Compound 1-42

Figure pat00033
Figure pat00033

둥근바닥플라스크에 7-bromo-2-phenyl-2H-benzofuro[2,3-c]pyrrole (7.5g, 24mmol), N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-9H-fluoren-2-amine (9.7g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 8.0g (수율: 56%) 얻었다.To a round bottom flask was added 7-bromo-2-phenyl-2H-benzofuro [2,3-c] pyrrole (7.5 g, 24 mmol), N - ([1,1'-biphenyl] -diphenyl-9H-fluoren-2- amine (9.7g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 equivalents) , toluene (10.5 mL / 1 mmol), and the reaction proceeds at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 8.0 g (yield: 56%) of the product.

화합물 1-87의 합성예시Synthesis Example of Compound 1-87

Figure pat00034
Figure pat00034

둥근바닥플라스크에 1-([1,1'-biphenyl]-4-yl)-5-(4-bromophenyl)-1H-benzo[4,5]thieno[2,3-b]pyrrole (11.5g, 24mmol), di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 9.6g (수율: 67%) 얻었다.1H-benzo [4,5] thieno [2,3-b] pyrrole (11.5 g, 0.15 mmol) was added to a round bottom flask, 24mmol), di ([1,1'- biphenyl] -4-yl) amine (6.4g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 eq.) , NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol) were added to the reaction mixture, followed by reaction at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.6 g (yield: 67%) of the product.

화합물 1-96의 합성예시Synthesis Example of Compound 1-96

Figure pat00035
Figure pat00035

둥근바닥플라스크에 6'-(4-bromophenyl)-1'-(pyridin-2-yl)-1'H-spiro[fluorene-9,4'-indeno[1,2-b]pyrrole] (12.9g, 24mmol), N-([1,1'-biphenyl]-4-yl)phenanthren-9-amine (6.9g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 9.0g (수율: 56%) 얻었다.To a round bottom flask was added 6 '- (4-bromophenyl) -1' - (pyridin-2-yl) -1'H- spiro [fluorene- 9,4'-indeno [ , 24mmol), N - ([ 1,1'-biphenyl] -4-yl) phenanthren-9-amine (6.9g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu ) 3 (0.1 eq.), NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.0 g (yield: 56%) of the product.

SubSub 3,  3, SubSub 4,  4, SubSub 5의 합성 예시 Synthetic example of 5

반응식 2의 sub 3, sub 4, sub 5는 하기 반응식 5, 반응식 6의 반응경로에 의해 합성될 수 있다. 하기 반응식에서는 R5가 수소인 경우를 예로 들어 설명하지만, 수소 이외의 치환기가 결합되더라도 하기 반응이 의외의 반응으로 진행하지는 않을 것이다.Sub 3, sub 4, and sub 5 of Scheme 2 can be synthesized by the reaction path of Scheme 5 and Scheme 6. The following scheme describes, for the case of R 5 is hydrogen an example, this combination, even if a substituent other than hydrogen reaction will not proceed to an unexpected reaction.

<반응식 5><Reaction Scheme 5>

Figure pat00036
Figure pat00036

<반응식 6><Reaction Scheme 6>

Figure pat00037
Figure pat00037

SubSub 3-2, 4-2, 5-2 합성 3-2, 4-2, 5-2 Synthesis

Sub 3-1 or Sub 4-1 or Sub 5-1 (1당량)을 둥근바닥플라스크에 DMF로 녹인 후에, Bis(pinacolato)diboron (1.1당량), Pd(dppf)Cl2 (0.03당량), KOAc (3당량)를 첨가하고 90°C에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Sub 3-2 or Sub 4-2 or Sub 5-2를 얻었다.(1.1 eq.), Pd (dppf) Cl 2 (0.03 eq.), KOAc (0.1 eq.), (3 eq) and stir at 90 [deg.] C. When the reaction was complete, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 3-2 or Sub 4-2 or Sub 5-2.

SubSub 3-3, 4-3, 5-3 합성 3-3, 4-3, 5-3 Synthesis

Sub 3-2 or Sub 4-2 or Sub 5-2 (1당량)와 R1 ~4로 치환된 (2-bromophenyl)(methyl)sulfane (1당량), Pd(PPh3)4 (0.03당량), K2CO3(3당량)를 무수 THF와 소량의 물에 녹이고 난 후, 24시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, CH2Cl2로 추출하고 물로 닦아주었다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과 후, 유기용매를 농축하여 생성된 생성물을 컬럼크로마토그래피로 분리하여 원하는 Sub 3-3 or Sub 4-3 or Sub 5-3을 얻었다.3-2 or 4-2 or Sub Sub Sub 5-2 (1 eq.) And R a (2-bromophenyl) (methyl) sulfane (1 eq.) Substituted with 1 ~ 4, Pd (PPh 3 ) 4 (0.03 eq.) , K 2 CO 3 (3 eq.) Were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH 2 Cl 2 and wiped with water. A small amount of water was removed with anhydrous MgSO 4. After filtration under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 3-3 or Sub 4-3 or Sub 5-3.

SubSub 3-4, 4-4, 5-4 합성 3-4, 4-4, 5-4 Synthesis

Sub 3-3 or Sub 4-3 or Sub 5-3를 아세트산(acetic acid)에 녹이고 과산화수소(hydrogen peroxide)를 아세트산에 용해시킨 것을 한방울씩 떨어뜨려 상온에서 6시간 교반한다. 반응이 종결되면 감압장치를 이용하여 아세트산을 제거하고 컬럼크로마토그래피를 이용하여 분리하여 원하는 Sub 3-4 or Sub 4-4 or Sub 5-4를 얻었다. Sub 3-3 or Sub 4-3 or Sub 5-3 is dissolved in acetic acid and hydrogen peroxide is dissolved in acetic acid. Dropwise dropwise and stir at room temperature for 6 hours. When the reaction was completed, acetic acid was removed using a pressure-reducing apparatus and the resultant was separated by column chromatography to obtain a desired Sub 3-4 or Sub 4-4 or Sub 5-4.

SubSub 3-5, 4-5, 5-5 합성 3-5, 4-5, 5-5 Synthesis

Sub 3-4 or Sub 4-4 or Sub 5-4와 트리풀루오로메탄술폰산(trifluoromethanesulfonic acid)를 넣고 상온에서 24시간 교반한 다음 물과 피리딘(8:1)을 천천히 넣고 30분 환류한다. 온도를 내리고 CH2Cl2로 추출하고 물로 닦아준다. 소량의 물을 무수 MgSO4로 제거하고 감압 여과한 후, 유기 용매를 농축하여 생성된 생성물을 컬럼크로마토그래피를 이용하여 원하는 Sub 3-5 or Sub 4-5 or Sub 5-5를 얻었다. Sub 3-4 or Sub 4-4 or Sub 5-4 with trifluoromethanesulfonic acid, stir at room temperature for 24 hours, add water and pyridine (8: 1) slowly and reflux for 30 minutes. The temperature is lowered, extracted with CH 2 Cl 2 and wiped with water. A small amount of water was removed with anhydrous MgSO 4 , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was subjected to column chromatography to obtain a desired Sub 3-5 or Sub 4-5 or Sub 5-5.

SubSub 3(A),  3 (A), SubSub 4(A),  4 (A), SubSub 5(A) 합성 5 (A) Synthesis

둥근바닥플라스크에 Sub 3-5 or Sub 4-5 or Sub 5-5 화합물 (1.1당량), I-L-Br화합물 (1당량), Pd2(dba)3 (0.05당량), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Product를 얻었다.To a round bottom flask was added Sub 3-5 or Sub 4-5 or Sub 5-5 compound (1.1 eq), IL-Br compound (1 eq), Pd 2 (dba) 3 (0.05 eq) 3 (0.1 eq.), NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain a product.

SubSub 3-7, 4-7, 5-7 합성 3-7, 4-7, 5-7 Synthesis

Sub 3-6 or Sub 4-6 or Sub 5-6 (1당량)을 디옥산에 녹인 후 R1 ~4로 치환된 1-피롤리디노-1-시클로헥센 (1.1당량)을 첨가하여 18시간 동안 환류시켰다. 물을 첨가하고 2시간 동안 가열시킨 후 에테르와 5% HCl, 5% NaHCO3 용액으로 Work-up 한 후 생성된 유기물을 silicagel column 및 재결정하여 Sub 3-7 or Sub 4-7 or Sub 5-7을 얻었다.Sub Sub 3-6 or 4-6 or 5-6 and then the Sub (1 eq) dissolved in dioxane was added to a 1-pyrrolidino-1-cyclohexene (1.1 equiv.) Is substituted by R 1 ~ 4 18 sigan Lt; / RTI &gt; After addition of water and heating for 2 hours, ether and 5% HCl, 5% NaHCO 3 The solution was worked up and the resulting organic material was purified by silicagel column and recrystallized to obtain Sub 3-7 or Sub 4-7 or Sub 5-7.

SubSub 3-8, 4-8, 5-8 합성 3-8, 4-8, 5-8 Synthesis

Sub 3-7 or Sub 4-7 or Sub 5-7을 CHCl3와 10% 메탄설폰산 혼합용액 70ml에 녹인 후 상온에서 2시간동안 교반시켰다. 바이카보네이트 용액으로 반응을 종결시킨 후 메틸렌클로라이드, NaHCO3과 물로 Work-up하였다. 용매를 휘발시키고 컬럼크로마토그래피로 분리한 후 트리글라임에 10% Pd/C와 함께 녹여 16시간 동안 환류시켰다. 그 후 헥산으로 컬럼크로마토그래피하여 Sub 3-8 or Sub 4-8 or Sub 5-8을 얻었다.Sub 3-7 or Sub 4-7 or Sub 5-7 was dissolved in 70 ml of a mixed solution of CHCl 3 and 10% methanesulfonic acid, followed by stirring at room temperature for 2 hours. The reaction was terminated with bicarbonate solution and worked up with methylene chloride, NaHCO 3 and water. The solvent was evaporated, separated by column chromatography, dissolved in triglyme with 10% Pd / C and refluxed for 16 hours. Subsequently, column chromatography with hexane gave Sub 3-8 or Sub 4-8 or Sub 5-8.

SubSub 3-9, 4-9, 5-9 합성 3-9, 4-9, 5-9 Synthesis

Sub 3-8 or Sub 4-8 or Sub 5-8 (1당량)을 테트라히드로퓨란에 녹이고 -78°C로 온도를 낮춘 다음 n-BULi 1.1당량(1.6M in hexane)을 천천히 적가해주었다. 1시간 반응 후 요오도메탄 (1.3당량)을 가한 다음 온도를 서서히 올려 실온에서 1시간동안 교반하고 다시 온도를 -78°C로 낮추고 n-BULi 1.1당량(1.6M in hexane)을 천천히 적가해주었다. 1시간 반응 후 요오드 메탄 1.3당량을 가한 다음 온도를 서서히 올려 실온에서 15시간동안 교반한 다음 NH2Cl수용액과 증류수를 가해 반응을 종료하고, 유기층을 감압제거시킨 후 헥산으로 재결정하여 Sub 3-9 or Sub 4-9 or Sub 5-9를 얻었다.Sub 3-8 or Sub 4-8 or Sub 5-8 (1 equivalent) was dissolved in tetrahydrofuran, the temperature was lowered to -78 ° C, and 1.1 eq. (1.6 M in hexane) of n-BULi was slowly added thereto. After 1 hour of reaction, iodomethane (1.3 equivalents) was added, the temperature was slowly raised, and the mixture was stirred at room temperature for 1 hour. Then, the temperature was lowered to -78 ° C and 1.1 molar equivalents of n-BULi (1.6 M in hexane) . After 1 hour of reaction, 1.3 equivalents of iodomethane was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 15 hours. NH 4 Cl aqueous solution and distilled water were added to terminate the reaction. The organic layer was removed under reduced pressure, or Sub 4-9 or Sub 5-9.

SubSub 3(B),  3 (B), SubSub 4(B),  4 (B), SubSub 5(B) 합성 5 (B) Synthesis

둥근바닥플라스크에 Sub 3-9 or Sub 4-9 or Sub 5-9 화합물(1.1당량)과, I-L-Br화합물 (1당량), Pd2(dba)3 (0.05당량), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Product를 얻었다.To a round bottom flask was added Sub 3-9 or Sub 4-9 or Sub 5-9 compound (1.1 eq), IL-Br compound (1 eq), Pd 2 (dba) 3 (0.05 eq) ) 3 (0.1 eq.), NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain a product.

Sub 3, 4, 5 예시는 다음과 같으나, 이에 한정되는 것은 아니다.Examples of Sub 3, 4, and 5 are as follows, but are not limited thereto.

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

상기 화합물에 대한 FD-MS는 하기 표 3과 같다.The FD-MS of the compound is shown in Table 3 below.

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 3(1)Sub 3 (1) m/z=326.97(C16H10BrNS=328.23)m / z = 326.97 (C 16 H 10 BrNS = 328.23) Sub 3(2)Sub 3 (2) m/z=403.00(C22H14BrNS=404.32)m / z = 403.00 (C 22 H 14 BrNS 404.32 =) Sub 3(3)Sub 3 (3) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 3(4)Sub 3 (4) m/z=432.96(C22H12BrNS2=434.37) m / z = 432.96 (C 22 H 12 BrNS 2 = 434.37) Sub 3(5)Sub 3 (5) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 3(6)Sub 3 (6) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 3(7)Sub 3 (7) m/z=387.03(C22H14BrNO=388.26) m / z = 387.03 (C 22 H 14 BrNO = 388.26) Sub 3(8)Sub 3 (8) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32) Sub 3(9)Sub 3 (9) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 3(10)Sub 3 (10) m/z=401.01(C22H12BrNO2=402.24) m / z = 401.01 (C 22 H 12 BrNO 2 = 402.24) Sub 3(11)Sub 3 (11) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 3(12)Sub 3 (12) m/z=413.08(C25H20BrN=414.34) m / z = 413.08 (C 25 H 20 BrN = 414.34) Sub 3(13)Sub 3 (13) m/z=453.11(C28H24BrN=454.40) m / z = 453.11 (C 28 H 24 BrN = 454.40) Sub 3(14)Sub 3 (14) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 3(15)Sub 3 (15) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32) Sub 4(1)Sub 4 (1) m/z=326.97(C16H10BrNS=328.23)m / z = 326.97 (C 16 H 10 BrNS = 328.23) Sub 4(2)Sub 4 (2) m/z=403.00(C22H14BrNS=404.32)m / z = 403.00 (C 22 H 14 BrNS 404.32 =) Sub 4(3)Sub 4 (3) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 4(4)Sub 4 (4) m/z=432.96(C22H12BrNS2=434.37) m / z = 432.96 (C 22 H 12 BrNS 2 = 434.37) Sub 4(5)Sub 4 (5) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 4(6)Sub 4 (6) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 4(7)Sub 4 (7) m/z=387.03(C22H14BrNO=388.26) m / z = 387.03 (C 22 H 14 BrNO = 388.26) Sub 4(8)Sub 4 (8) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32) Sub 4(9)Sub 4 (9) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 4(10)Sub 4 (10) m/z=401.01(C22H12BrNO2=402.24) m / z = 401.01 (C 22 H 12 BrNO 2 = 402.24) Sub 4(11)Sub 4 (11) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 4(12)Sub 4 (12) m/z=413.08(C25H20BrN=414.34) m / z = 413.08 (C 25 H 20 BrN = 414.34) Sub 4(13)Sub 4 (13) m/z=453.11(C28H24BrN=454.40) m / z = 453.11 (C 28 H 24 BrN = 454.40) Sub 4(14)Sub 4 (14) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 4(15)Sub 4 (15) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32) Sub 5(1)Sub 5 (1) m/z=326.97(C16H10BrNS=328.23)m / z = 326.97 (C 16 H 10 BrNS = 328.23) Sub 5(2)Sub 5 (2) m/z=403.00(C22H14BrNS=404.32)m / z = 403.00 (C 22 H 14 BrNS 404.32 =) Sub 5(3)Sub 5 (3) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 5(4)Sub 5 (4) m/z=432.96(C22H12BrNS2=434.37) m / z = 432.96 (C 22 H 12 BrNS 2 = 434.37) Sub 5(5)Sub 5 (5) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 5(6)Sub 5 (6) m/z=310.99(C16H10BrNO=312.16)m / z = 310.99 (C 16 H 10 BrNO = 312.16) Sub 5(7)Sub 5 (7) m/z=387.03(C22H14BrNO=388.26) m / z = 387.03 (C 22 H 14 BrNO = 388.26) Sub 5(8)Sub 5 (8) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32) Sub 5(9)Sub 5 (9) m/z=416.98(C22H12BrNOS=418.3) m / z = 416.98 (C 22 H 12 BrNOS = 418.3) Sub 5(10)Sub 5 (10) m/z=401.01(C22H12BrNO2=402.24) m / z = 401.01 (C 22 H 12 BrNO 2 = 402.24) Sub 5(11)Sub 5 (11) m/z=337.05(C19H16BrN=338.24) m / z = 337.05 (C 19 H 16 BrN = 338.24) Sub 5(12)Sub 5 (12) m/z=413.08(C25H20BrN=414.34) m / z = 413.08 (C 25 H 20 BrN = 414.34) Sub 5(13)Sub 5 (13) m/z=453.11(C28H24BrN=454.40) m / z = 453.11 (C 28 H 24 BrN = 454.40) Sub 5(14)Sub 5 (14) m/z=443.03(C25H18BrNS=444.39)m / z = 443.03 (C 25 H 18 BrNS 444.39 =) Sub 5(15)Sub 5 (15) m/z=427.06(C25H18BrNO=428.32) m / z = 427.06 (C 25 H 18 BrNO = 428.32)

FinalFinal ProductProduct 2, 3, 4의 합성 Synthesis of 2, 3, 4

둥근바닥플라스크에 Sub 3 or Sub 4 or Sub 5화합물 (1.1당량)과, Sub 2 화합물 (1당량), Pd2(dba)3 (0.05당량), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 Product를 얻었다.Sub 3 or Sub 4 or Sub 5 compound (1.1 eq) and, Sub 2 compound (1 eq), Pd 2 (dba) 3 (0.05 eq.), P (t-Bu) 3 (0.1 equiv) in a round bottom flask, NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol) were added thereto, followed by reaction at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain a product.

화합물 2-14의 합성예시Synthesis Example of Compound 2-14

Figure pat00040
Figure pat00040

둥근바닥플라스크에 1-(4-bromophenyl)-1H-benzo[4,5]thieno[2,3-b]pyrrole (7.9g, 24mmol), N-([1,1'-biphenyl]-4-yl)naphthalen-1-amine (5.9g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 7.3g (수율: 67%) 얻었다.To a round bottom flask was added 1- (4-bromophenyl) -lH-benzo [4,5] thieno [2,3-b] pyrrole (7.9 g, yl) naphthalen-1-amine ( 5.9g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 eq.), toluene ( 10.5 mL / 1 mmol), and the reaction is allowed to proceed at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.3 g (yield: 67%) of the product.

화합물 2-31의 합성예시Synthesis Example of Compound 2-31

Figure pat00041
Figure pat00041

둥근바닥플라스크에 2-(4-bromophenyl)-2H-benzo[4,5]thieno[2,3-c]pyrrole (7.9g, 24mmol), di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 7.7g (수율: 68%) 얻었다.A solution of 2- (4-bromophenyl) -2H-benzo [4,5] thieno [2,3-c] pyrrole (7.9 g, 24 mmol), di ([ ), Pd 2 (dba) 3 (0.03-0.05 mmol), P (t-Bu) 3 (0.1 eq.), NaO t -Bu (3 eq.), toluene (10.5 mL / ), And the reaction proceeds at 100 ° C. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.7 g (yield: 68%) of the product.

화합물 2-60의 합성예시Synthesis Example of Compound 2-60

Figure pat00042
Figure pat00042

둥근바닥플라스크에 1-(4'-bromo-[1,1'-biphenyl]-4-yl)-1H-benzofuro[3,2-b]pyrrole (9.3g, 24mmol), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (7.2g, 20mmol), Pd2(dba)3 (0.03~0.05 mmol), P(t-Bu)3 (0.1당량), NaOt-Bu (3당량), toluene (10.5 mL / 1 mmol)을 넣은 후에 100 ℃에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 7.6g (수율: 57%) 얻었다.To a round bottom flask was added 1- (4'-bromo- [1,1'-biphenyl] -4-yl) -1H-benzofuro [3,2- b] pyrrole (9.3 g, 1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (7.2g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 eq.), NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol). After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.6 g (yield: 57%) of the product.

상기와 같은 방법에 의해 생성된 최종 화합물 1-1 내지 2-72의 FD-MS 값은 하기 표 4와 같다.The FD-MS values of the final compounds 1-1 to 2-72 produced by the above method are shown in Table 4 below.

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS 1-11-1 m/z=416.13(C28H20N2S=416.54) m / z = 416.13 (C 28 H 20 N 2 S = 416.54) 1-21-2 m/z=466.15(C32H22N2S=466.60)m / z = 466.15 (C 32 H 22 N 2 S = 466.60) 1-31-3 m/z=466.15(C32H22N2S=466.60)m / z = 466.15 (C 32 H 22 N 2 S = 466.60) 1-41-4 m/z=492.17(C34H24N2S=492.63) m / z = 492.17 (C 34 H 24 N 2 S = 492.63) 1-51-5 m/z=668.23(C48H32N2S=668.85)m / z = 668.23 (C 48 H 32 N 2 S = 668.85) 1-61-6 m/z=674.19(C46H30N2S2=674.87)m / z = 674.19 (C 46 H 30 N 2 S 2 = 674.87) 1-71-7 m/z=733.26(C52H35N3S=733.92)m / z = 733.26 (C 52 H 35 N 3 S = 733.92) 1-81-8 m/z=809.29(C58H39N3S=810.02)m / z = 809.29 (C 58 H 39 N 3 S = 810.02) 1-91-9 m/z=532.20(C37H28N2S=532.70) m / z = 532.20 (C 37 H 28 N 2 S = 532.70) 1-101-10 m/z=656.23(C47H32N2S=656.84)m / z = 656.23 (C 47 H 32 N 2 S = 656.84) 1-111-11 m/z=656.23(C47H32N2S=656.84)m / z = 656.23 (C 47 H 32 N 2 S = 656.84) 1-121-12 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 1-131-13 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 1-141-14 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 1-151-15 m/z=566.18(C40H26N2S=566.71)m / z = 566.18 (C 40 H 26 N 2 S = 566.71) 1-161-16 m/z=572.14(C38H24N2S2=572.74)m / z = 572.14 (C 38 H 24 N 2 S 2 = 572.74) 1-171-17 m/z=633.22(C44H31N3S=633.80)m / z = 633.22 (C 44 H 31 N 3 S = 633.80) 1-181-18 m/z=709.26(C50H35N3S=709.90)m / z = 709.26 (C 50 H 35 N 3 S = 709.90) 1-191-19 m/z=584.23(C41H32N2S=584.77)m / z = 584.23 (C 41 H 32 N 2 S = 584.77) 1-201-20 m/z=708.26(C51H36N2S=708.91)m / z = 708.26 (C 51 H 36 N 2 S = 708.91) 1-211-21 m/z=706.24(C51H34N2S=706.89)m / z = 706.24 (C 51 H 34 N 2 S = 706.89) 1-221-22 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 1-231-23 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 1-241-24 m/z=566.18(C40H26N2S=566.71)m / z = 566.18 (C 40 H 26 N 2 S = 566.71) 1-251-25 m/z=572.14(C38H24N2S2=572.74)m / z = 572.14 (C 38 H 24 N 2 S 2 = 572.74) 1-261-26 m/z=631.21(C44H29N3S=631.79)m / z = 631.21 (C 44 H 29 N 3 S = 631.79) 1-271-27 m/z=707.24(C50H33N3S=707.88)m / z = 707.24 (C 50 H 33 N 3 S = 707.88) 1-281-28 m/z=582.21(C41H30N2S=582.76)m / z = 582.21 (C 41 H 30 N 2 S = 582.76) 1-291-29 m/z=706.24(C51H34N2S=706.89)m / z = 706.24 (C 51 H 34 N 2 S = 706.89) 1-301-30 m/z=706.24(C51H34N2S=706.89)m / z = 706.24 (C 51 H 34 N 2 S = 706.89) 1-311-31 m/z=592.20(C42H28N2S=592.75)m / z = 592.20 (C 42 H 28 N 2 S = 592.75) 1-321-32 m/z=592.20(C42H28N2S=592.75)m / z = 592.20 (C 42 H 28 N 2 S = 592.75) 1-331-33 m/z=598.15(C40H26N2S2=598.78)m / z = 598.15 (C 40 H 26 N 2 S 2 = 598.78) 1-341-34 m/z=657.22(C46H31N3S=657.82)m / z = 657.22 (C 46 H 31 N 3 S = 657.82) 1-351-35 m/z=733.26(C52H35N3S=733.92)m / z = 733.26 (C 52 H 35 N 3 S = 733.92) 1-361-36 m/z=608.23(C43H32N2S=608.79)m / z = 608.23 (C 43 H 32 N 2 S = 608.79) 1-371-37 m/z=733.26(C53H36N2S=732.93)m / z = 733.26 (C 53 H 36 N 2 S = 732.93) 1-381-38 m/z=733.26(C53H36N2S=732.93)m / z = 733.26 (C 53 H 36 N 2 S = 732.93) 1-391-39 m/z=644.23(C46H32N2S=644.82)m / z = 644.23 (C 46 H 32 N 2 S = 644.82) 1-401-40 m/z=593.19(C41H27N3S=593.74)m / z = 593.19 (C 41 H 27 N 3 S = 593.74) 1-411-41 m/z=716.28(C53H36N2O=716.87)m / z = 716.28 (C 53 H 36 N 2 O = 716.87) 1-421-42 m/z=716.28(C53H36N2O=716.87)m / z = 716.28 (C 53 H 36 N 2 O = 716.87) 1-431-43 m/z=628.25(C46H32N2O=628.76)m / z = 628.25 (C 46 H 32 N 2 O = 628.76) 1-441-44 m/z=577.22(C41H27N3O=577.67)m / z = 577.22 (C 41 H 27 N 3 O = 577.67) 1-451-45 m/z=742.33(C56H42N2=742.95)m / z = 742.33 (C 56 H 42 N 2 = 742.95) 1-461-46 m/z=742.33(C56H42N2=742.95)m / z = 742.33 (C 56 H 42 N 2 = 742.95) 1-471-47 m/z=778.33(C59H26N2S=542.69)m / z = 778.33 (C 59 H 26 N 2 S = 542.69) 1-481-48 m/z=725.28(C54H35N3=725.88)m / z = 725.28 (C 54 H 35 N 3 = 725.88) 1-491-49 m/z=492.17(C34H24N2S=492.63) m / z = 492.17 (C 34 H 24 N 2 S = 492.63) 1-501-50 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 1-511-51 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 1-521-52 m/z=568.20(C40H28N2S=568.73)m / z = 568.20 (C 40 H 28 N 2 S = 568.73) 1-531-53 m/z=592.20(C42H28N2S=592.75)m / z = 592.20 (C 42 H 28 N 2 S = 592.75) 1-541-54 m/z=598.15(C40H26N2S2=598.78)m / z = 598.15 (C 40 H 26 N 2 S 2 = 598.78) 1-551-55 m/z=657.22(C46H31N3S=657.82)m / z = 657.22 (C 46 H 31 N 3 S = 657.82) 1-561-56 m/z=733.26(C52H35N3S=733.92)m / z = 733.26 (C 52 H 35 N 3 S = 733.92) 1-571-57 m/z=658.24(C47H34N2S=658.85)m / z = 658.24 (C 47 H 34 N 2 S = 658.85) 1-581-58 m/z=782.28(C57H38N2S=782.99)m / z = 782.28 (C 57 H 38 N 2 S = 782.99) 1-591-59 m/z=782.28(C57H38N2S=782.99)m / z = 782.28 (C 57 H 38 N 2 S = 782.99) 1-601-60 m/z=642.21(C46H30N2S=642.81)m / z = 642.21 (C 46 H 30 N 2 S = 642.81) 1-611-61 m/z=642.21(C46H30N2S=642.81)m / z = 642.21 (C 46 H 30 N 2 S = 642.81) 1-621-62 m/z=668.23(C48H32N2S=668.85)m / z = 668.23 (C 48 H 32 N 2 S = 668.85) 1-631-63 m/z=692.23(C50H32N2S=692.87)m / z = 692.23 (C 50 H 32 N 2 S = 692.87) 1-641-64 m/z=692.19(C48H30N2S2=698.90)m / z = 692.19 (C 48 H 30 N 2 S 2 = 698.90) 1-651-65 m/z=783.27(C53H37N3S=783.98)m / z = 783.27 (C 53 H 37 N 3 S = 783.98) 1-661-66 m/z=859.30(C62H41N3S=860.07)m / z = 859.30 (C 62 H 41 N 3 S = 860.07) 1-671-67 m/z=734.28(C53H38N2S=734.95)m / z = 734.28 (C 53 H 38 N 2 S = 734.95) 1-681-68 m/z=858.31(C63H42N2S=859.09)m / z = 858.31 (C 63 H 42 N 2 S = 859.09) 1-691-69 m/z=858.31(C63H42N2S=859.09)m / z = 858.31 (C 63 H 42 N 2 S = 859.09) 1-701-70 m/z=668.23(C48H32N2S=668.85)m / z = 668.23 (C 48 H 32 N 2 S = 668.85) 1-711-71 m/z=694.24(C50H34N2S=694.88) m / z = 694.24 (C 50 H 34 N 2 S = 694.88) 1-721-72 m/z=718.24(C52H34N2S=718.90)m / z = 718.24 (C 52 H 34 N 2 S = 718.90) 1-731-73 m/z=764.23(C53H36N2S2=765.00)m / z = 764.23 (C 53 H 36 N 2 S 2 = 765.00) 1-741-74 m/z=823.30(C59H41N3S=824.04)m / z = 823.30 (C 59 H 41 N 3 S = 824.04) 1-751-75 m/z=684.26(C49H36N2S=684.89)m / z = 684.26 (C 49 H 36 N 2 S = 684.89) 1-761-76 m/z=644.23(C46H32N2S=644.82)m / z = 644.23 (C 46 H 32 N 2 S = 644.82) 1-771-77 m/z=1022.37(C76H50N2S=1023.29)m / z = 1022.37 (C 76 H 50 N 2 S = 1023.29) 1-781-78 m/z=1022.37(C76H50N2S=1023.29)m / z = 1022.37 (C 76 H 50 N 2 S = 1023.29) 1-791-79 m/z=702.26(C52H36N2S=720.92)m / z = 702.26 (C 52 H 36 N 2 S = 720.92) 1-801-80 m/z=906.31(C67H47N2S=907.13)m / z = 906.31 (C 67 H 47 N 2 S = 907.13) 1-811-81 m/z=780.17(C52H32N2S3=781.02)m / z = 780.17 (C 52 H 32 N 2 S 3 = 781.02) 1-821-82 m/z=839.24(C58H37N3S2=840.06)m / z = 839.24 (C 58 H 37 N 3 S 2 = 840.06) 1-831-83 m/z=915.27(C64H41N2S2=916.16)m / z = 915.27 (C 64 H 41 N 2 S 2 = 916.16) 1-841-84 m/z=790.25(C55H38N2S2=791.03)m / z = 790.25 (C 55 H 38 N 2 S 2 = 791.03) 1-851-85 m/z=898.30(C65H42N2OS=899.11)m / z = 898.30 (C 65 H 42 N 2 OS = 899.11) 1-861-86 m/z=898.30(C65H42N2OS=899.11)m / z = 898.30 (C 65 H 42 N 2 OS = 899.11) 1-871-87 m/z=720.26(C52H36N2S=720.92)m / z = 720.26 (C 52 H 36 N 2 S = 720.92) 1-881-88 m/z=775.21(C53H33N3S2=775.98)m / z = 775.21 (C 53 H 33 N 3 S 2 = 775.98) 1-891-89 m/z=732.31(C59H40N2O=792.96)m / z = 732.31 (C 59 H 40 N 2 O = 792.96) 1-901-90 m/z=792.31(C59H40N2O=792.96)m / z = 792.31 (C 59 H 40 N 2 O = 792.96) 1-911-91 m/z=704.28(C52H36N2O=704.86)m / z = 704.28 (C 52 H 36 N 2 O = 704.86) 1-921-92 m/z=653.25(C47H31N3O=653.77)m / z = 653.25 (C 47 H 31 N 3 O = 653.77) 1-931-93 m/z=818.37(C62H46N2=819.04)m / z = 818.37 (C 62 H 46 N 2 = 819.04) 1-941-94 m/z=818.37(C62H46N2=819.04)m / z = 818.37 (C 62 H 46 N 2 = 819.04) 1-951-95 m/z=854.37(C65H46N2=855.07)m / z = 854.37 (C 65 H 46 N 2 = 855.07) 1-961-96 m/z=801.31(C60H39N3=801.97)m / z = 801.31 (C 60 H 39 N 3 = 801.97) 2-12-1 m/z=416.13(C28H20N2S=416.54) m / z = 416.13 (C 28 H 20 N 2 S = 416.54) 2-22-2 m/z=466.15(C32H22N2S=466.60)m / z = 466.15 (C 32 H 22 N 2 S = 466.60) 2-32-3 m/z=466.15(C32H22N2S=466.60)m / z = 466.15 (C 32 H 22 N 2 S = 466.60) 2-42-4 m/z=492.17(C34H24N2S=492.63) m / z = 492.17 (C 34 H 24 N 2 S = 492.63) 2-52-5 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 2-62-6 m/z=522.12(C34H22N2S2=522.68) m / z = 522.12 (C 34 H 22 N 2 S 2 = 522.68) 2-72-7 m/z=581.19(C40H27N3S=581.73)m / z = 581.19 (C 40 H 27 N 3 S = 581.73) 2-82-8 m/z=657.22(C46H31N3S=657.82)m / z = 657.22 (C 46 H 31 N 3 S = 657.82) 2-92-9 m/z=532.20(C37H28N2S=532.70) m / z = 532.20 (C 37 H 28 N 2 S = 532.70) 2-102-10 m/z=656.23(C47H32N2S=656.84)m / z = 656.23 (C 47 H 32 N 2 S = 656.84) 2-112-11 m/z=654.21(C47H30N2S=654.82)m / z = 654.21 (C 47 H 30 N 2 S = 654.82) 2-122-12 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 2-132-13 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 2-142-14 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 2-152-15 m/z=566.18(C40H26N2S=566.71)m / z = 566.18 (C 40 H 26 N 2 S = 566.71) 2-162-16 m/z=572.14(C38H24N2S2=572.74)m / z = 572.14 (C 38 H 24 N 2 S 2 = 572.74) 2-172-17 m/z=631.21(C44H29N3S=631.79)m / z = 631.21 (C 44 H 29 N 3 S = 631.79) 2-182-18 m/z=707.24(C50H33N3S=707.88)m / z = 707.24 (C 50 H 33 N 3 S = 707.88) 2-192-19 m/z=582.21(C41H30N2S=582.76)m / z = 582.21 (C 41 H 30 N 2 S = 582.76) 2-202-20 m/z=706.24(C51H34N2S=706.89)m / z = 706.24 (C 51 H 34 N 2 S = 706.89) 2-212-21 m/z=704.23(C51H32N2S=704.88)m / z = 704.23 (C 51 H 32 N 2 S = 704.88) 2-222-22 m/z=516.17(C36H24N2S=516.65) m / z = 516.17 (C 36 H 24 N 2 S = 516.65) 2-232-23 m/z=542.18(C38H26N2S=542.69)m / z = 542.18 (C 38 H 26 N 2 S = 542.69) 2-242-24 m/z=566.18(C40H26N2S=566.71)m / z = 566.18 (C 40 H 26 N 2 S = 566.71) 2-252-25 m/z=572.14(C38H24N2S2=572.74)m / z = 572.14 (C 38 H 24 N 2 S 2 = 572.74) 2-262-26 m/z=631.21(C44H29N3S=631.79)m / z = 631.21 (C 44 H 29 N 3 S = 631.79) 2-272-27 m/z=707.24(C50H33N3S=707.88)m / z = 707.24 (C 50 H 33 N 3 S = 707.88) 2-282-28 m/z=582.21(C41H30N2S=582.76)m / z = 582.21 (C 41 H 30 N 2 S = 582.76) 2-292-29 m/z=706.24(C51H34N2S=706.89)m / z = 706.24 (C 51 H 34 N 2 S = 706.89) 2-302-30 m/z=704.23(C51H32N2S=704.88)m / z = 704.23 (C 51 H 32 N 2 S = 704.88) 2-312-31 m/z=568.20(C40H28N2S=568.73)m / z = 568.20 (C 40 H 28 N 2 S = 568.73) 2-322-32 m/z=592.20(C42H28N2S=592.75)m / z = 592.20 (C 42 H 28 N 2 S = 592.75) 2-332-33 m/z=598.15(C40H26N2S2=598.78)m / z = 598.15 (C 40 H 26 N 2 S 2 = 598.78) 2-342-34 m/z=657.22(C46H31N3S=657.82)m / z = 657.22 (C 46 H 31 N 3 S = 657.82) 2-352-35 m/z=733.26(C52H35N3S=733.92)m / z = 733.26 (C 52 H 35 N 3 S = 733.92) 2-362-36 m/z=608.23(C43H32N2S=608.79)m / z = 608.23 (C 43 H 32 N 2 S = 608.79) 2-372-37 m/z=732.26(C53H36N2S=732.93)m / z = 732.26 (C 53 H 36 N 2 S = 732.93) 2-382-38 m/z=730.24(C53H34N2S=730.92)m / z = 730.24 (C 53 H 34 N 2 S = 730.92) 2-392-39 m/z=644.23(C46H32N2S=644.82)m / z = 644.23 (C 46 H 32 N 2 S = 644.82) 2-402-40 m/z=668.23(C48H32N2S=668.85)m / z = 668.23 (C 48 H 32 N 2 S = 668.85) 2-412-41 m/z=674.19(C46H30N2S2=674.87)m / z = 674.19 (C 46 H 30 N 2 S 2 = 674.87) 2-422-42 m/z=733.26(C52H35N3S=733.92)m / z = 733.26 (C 52 H 35 N 3 S = 733.92) 2-432-43 m/z=809.29(C58H39N3S=810.02)m / z = 809.29 (C 58 H 39 N 3 S = 810.02) 2-442-44 m/z=684.26(C49H36N2S=684.89)m / z = 684.26 (C 49 H 36 N 2 S = 684.89) 2-452-45 m/z=808.29(C59H40N2S=809.03)m / z = 808.29 (C 59 H 40 N 2 S = 809.03) 2-462-46 m/z=806.28(C59H38N2S=807.01)m / z = 806.28 (C 59 H 38 N 2 S = 807.01) 2-472-47 m/z=674.19(C46H30N2S2=674.87)m / z = 674.19 (C 46 H 30 N 2 S 2 = 674.87) 2-482-48 m/z=698.19(C48H30N2S2=698.90)m / z = 698.19 (C 48 H 30 N 2 S 2 = 698.90) 2-492-49 m/z=704.14(C46H28N2S3=704.92)m / z = 704.14 (C 46 H 28 N 2 S 3 = 704.92) 2-502-50 m/z=773.29(C55H39N3S=773.98)m / z = 773.29 (C 55 H 39 N 3 S = 773.98) 2-512-51 m/z=849.32(C61H43N3S=850.08)m / z = 849.32 (C 61 H 43 N 3 S = 850.08) 2-522-52 m/z=848.32(C62H44N2S=849.09)m / z = 848.32 (C 62 H 44 N 2 S = 849.09) 2-532-53 m/z=822.27(C59H38N2OS=823.01)m / z = 822.27 (C 59 H 38 N 2 OS = 823.01) 2-542-54 m/z=820.25(C59H36N2OS=820.99)m / z = 820.25 (C 59 H 36 N 2 OS = 820.99) 2-552-55 m/z=628.25(C46H32N2O=628.76)m / z = 628.25 (C 46 H 32 N 2 O = 628.76) 2-562-56 m/z=652.25(C48H32N2O=652.78)m / z = 652.25 (C 48 H 32 N 2 O = 652.78) 2-572-57 m/z=658.21(C46H30N2OS=658.81)m / z = 658.21 (C 46 H 30 N 2 OS = 658.81) 2-582-58 m/z=717.28(C52H35N3O=717.85)m / z = 717.28 (C 52 H 35 N 3 O = 717.85) 2-592-59 m/z=793.31(C58H39N3O=793.95)m / z = 793.31 (C 58 H 39 N 3 O = 793.95) 2-602-60 m/z=668.28(C49H36N2O=668.82)m / z = 668.28 (C 49 H 36 N 2 O = 668.82) 2-612-61 m/z=818.37(C62H46N2=819.04)m / z = 818.37 (C 62 H 46 N 2 = 819.04) 2-622-62 m/z=816.35(C62H44N2=817.03)m / z = 816.35 (C 62 H 44 N 2 = 817.03) 2-632-63 m/z=684.26(C49H36N2S=684.89)m / z = 684.26 (C 49 H 36 N 2 S = 684.89) 2-642-64 m/z=708.26(C51H36N2S=708.91)m / z = 708.26 (C 51 H 36 N 2 S = 708.91) 2-652-65 m/z=688.16(C46H28N2OS2=688.86)m / z = 688.16 (C 46 H 28 N 2 OS 2 = 688.86) 2-662-66 m/z=757.31(C55H39N3O=757.92)m / z = 757.31 (C 55 H 39 N 3 O = 757.92) 2-672-67 m/z=833.34(C61H43N3O=834.01)m / z = 833.34 (C 61 H 43 N 3 O = 834.01) 2-682-68 m/z=832.35(C62H44N2O=833.03)m / z = 832.35 (C 62 H 44 N 2 O = 833.03) 2-692-69 m/z=806.29(C59H38N2O2=806.95)m / z = 806.29 (C 59 H 38 N 2 O 2 = 806.95) 2-702-70 m/z=804.28(C59H36N2O2=804.93)m / z = 804.28 (C 59 H 36 N 2 O 2 = 804.93) 2-712-71 m/z=552.22(C40H28N2O=552.66)m / z = 552.22 (C 40 H 28 N 2 O = 552.66) 2-722-72 m/z=552.22(C40H28N2O=552.66)m / z = 552.22 (C 40 H 28 N 2 O = 552.66)

유기전기소자의 제조평가Evaluation of manufacturing of organic electric device

[[ 실험예Experimental Example 1]  One] 정공수송층에On the hole transport layer 적용(그린유기발광소자) Application (Green organic light emitting device)

합성을 통해 얻은 화합물을 정공수송층 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유기 기판에 형성된 ITO층(양극)위에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60nm 두께의 정공주입층을 형성하하고, 본 발명의 화합물을 20nm 두께로 진공 증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 상에 CBP[4,4'-N,N'-dicarbazole-biphenyl]를 발광 호스트 물질로, Ir(ppy)3 [tris(2-phenylpyridine)-iridium] 을 도펀트 물질로 사용하여 90:10 중량으로 도핑하여 30nm 두께의 발광층을 증착하였다. 그리고, 상기 발광층 상에 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하여 홀저지층을 형성하고, 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약칭함)을 상기 홀저지층 상에 40 nm 두께로 성막하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 전자수송층 상에 0.2 nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150 nm의 두께로 증착하여 음극을 형성하였다.An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a hole transport layer material. First, N 1 on the ITO layer (anode) formed on an organic substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 - phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was vacuum deposited to form a hole injection layer having a thickness of 60 nm, and the compound of the present invention was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Subsequently, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a light emitting host material and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] was used as a dopant material on the hole transport layer Lt; RTI ID = 0.0 &gt; 90 &lt; / RTI &gt; (1, 1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light- And a tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited on the hole blocking layer to a thickness of 40 nm to form an electron transporting layer. LiF, which is an alkali metal halide, was then deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, followed by deposition of Al to a thickness of 150 nm to form a cathode.

[[ 비교예Comparative Example 1] 및 [ 1] and [ 비교예Comparative Example 2] 2]

상기 실험예와 동일하게 유기전기발광소자를 제작하되, 비교예 1은 하기 비교화합물 1을, 비교예 2는 하기 비교화합물 2를 정공수송층 물질로 사용하였다.An organic electroluminescent device was fabricated in the same manner as in the Experimental Example, except that Comparative Example 1 was used as the comparative compound 1 and Comparative Example 2 was used as the hole transport layer material.

<비교예 1> <비교예 2>       &Lt; Comparative Example 1 > < Comparative Example 2 &

Figure pat00043
Figure pat00043

상기 실험예 1, 비교예 1 및 비교예 2에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T90 수명을 측정하였다. 하기 표 5는 측정 결과를 나타낸 것이다.Electroluminescence (EL) characteristics of the organic electroluminescent devices prepared according to Experimental Example 1, Comparative Example 1 and Comparative Example 2 were measured with a photoresist PR-650 by applying a forward bias DC voltage, Results The T90 lifetime was measured with a lifetime measuring device manufactured by Mac Science Inc. at a luminance of 300 cd / m 2. Table 5 shows the measurement results.

Figure pat00044
Figure pat00044

상기 표 5의 결과로부터 알 수 있듯이, 본 발명의 화합물을 유기전기발광소자의 정공수송층 재료로 사용할 경우, 높은 발광효율, 낮은 구동전압을 얻을 수 있고 수명을 현저히 개선시킬 수 있다. As can be seen from the results of Table 5, when the compound of the present invention is used as a hole transporting layer material of an organic electroluminescent device, it is possible to obtain a high luminous efficiency, a low driving voltage and a remarkably improved lifetime.

비스다이아릴아민 타입인 비교화합물 1 보다 thieno indole이 코어인 비교화합물 2가 더 좋은 결과를 나타내었고, 비교화합물 2와 자사발명화합물의 결과를 비교해보면 thieno indole 코어에 헤테로 고리가 치환된 비교화합물 2보다 thieno pyrrole에 3차 아민기가 치환된 본 발명의 화합물이 더 좋은 결과를 나타낸다는 것을 알 수 있다. 이는 thieno pyrrole에 3차 아민기가 치환된 경우 thieno indole 헤테로 고리가 치환된 경우보다 LUMO값이 높아지고, 이로 인해 전자를 blocking 하는 능력이 좋아져 소자의 효율을 높이는 것으로 설명할 수 있을 것이다. 또한 thieno pyrrole에 3차 아민기가 치환된 경우 이웃한 층과의 charge balance가 좋아지므로, 전자의 mobility가 빨라지고 그로 인해 구동전압이 낮아지게 된다. 이와 같이 구동전압이 낮아짐으로 인해 소자의 수명을 향상시킬 수 있는 것이다.
Comparative Compound 2, which is thieno indole core, showed better results than Comparative Compound 1 which is bisdiarylamine type. Comparing the results of Comparative Compound 2 with those of the inventive compounds, it was found that Comparative Compound 2 substituted with a heterocycle in the thieno indole core It can be seen that compounds of the present invention in which thieno pyrrole is substituted with a tertiary amine group show better results. It can be explained that when tertiary amine group is substituted for thieno pyrrole, the LUMO value is higher than that of thieno indole heteroleptide, thereby improving the device efficiency by improving the blocking ability of electrons. When thieno pyrrole is substituted with a tertiary amine group, the charge balance with neighboring layers is improved, so that the mobility of the electrons is enhanced and the driving voltage is lowered. Thus, the lifetime of the device can be improved by lowering the driving voltage.

[[ 실험예Experimental Example 2]  2] 발광보조층에On the light-emitting auxiliary layer 적용( apply( 레드Red 유기 발광 소자) Organic light emitting device)

합성을 통해 얻은 본 발명의 화합물을 발광보조층 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 2-TNATA 막을 진공증착하여 60 nm 두께의 홀주입층을 형성하고, 홀주입층상에 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐(이하 -NPD로 약기함)을 20 nm 두께로 진공증착하여 홀수송층을 형성하였다. 이어서, 홀수송층 상에 본 발명의 화합물을 20nm의 두께로 진공증착하여 발광보조층을 형성하였다. 이후, 발광보조층 상에, CBP[4,4'-N,N'-dicarbazole-biphenyl]를 호스트물질로, (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate]를 도펀트 물질로 95:5 중량으로 도핑하여 30nm 두께의 발광층을 증착하였다. 이어서, 상기 발광층 상에, BAlq를 10nm 두께로 진공증착하여 홀저지층을 형성하고, 홀저지층 상에 Alq3를 40 nm 두께로 성막하여 전자수송층을 형성하였다. 이후, 전자수송층 상에 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150 nm의 두께로 증착하여 음극을 형성하였다.An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting auxiliary layer material. First, a 2-TNATA film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to form a 60 nm thick hole injection layer, and 4,4-bis [N- (1-naphthyl) -N -Phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 20 nm to form a hole transporting layer. Subsequently, the compound of the present invention was vacuum-deposited on the hole transporting layer to a thickness of 20 nm to form a light emitting auxiliary layer. Then, CBP [4,4'-N, N'-dicarbazole-biphenyl] was added to the luminescent auxiliary layer as a host material and (piq) 2 Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate ] Was doped with a dopant material to a weight ratio of 95: 5 to deposit a light emitting layer with a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq 3 was formed to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, an alkali metal halide, was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, followed by deposition of Al to a thickness of 150 nm to form a cathode.

[[ 비교예Comparative Example 3] 및 [ 3] and [ 비교예Comparative Example 4] 4]

실험예 2와 동일하게 유기전기발광소자를 제작하되, 비교예 3은 발광보조층없이, 비교예 4는 비교화합물 2를 발광보조층 재료로 사용하였다.The organic electroluminescent device was fabricated in the same manner as in Experimental Example 2, except that the luminescent auxiliary layer was not used in Comparative Example 3 and the luminescent auxiliary layer material was used in Comparative Example 4.

상기 실험예 2, 비교예 3 및 비교예 4에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T90 수명을 측정하였다. 하기 표 6은 측정 결과를 나타낸 것이다.Electroluminescence (EL) characteristics of the organic electroluminescent devices prepared in Experimental Example 2, Comparative Example 3, and Comparative Example 4 were measured by applying a forward bias DC voltage to a PR-650 manufactured by photoresearch, Results The T90 lifetime was measured with a lifetime measuring device manufactured by Mac Science Inc. at a luminance of 300 cd / m 2. Table 6 shows the measurement results.

Figure pat00045
Figure pat00045

Figure pat00046
Figure pat00046

Figure pat00047
Figure pat00047

Figure pat00048
Figure pat00048

Figure pat00049
Figure pat00049

상기 표 6의 의 결과로부터 알 수 있듯이, 본 발명의 화합물을 발광보조층 재료로 사용할 경우, 발광보조층이 형성되지 않은 비교예 3과 비교화합물 2를 이용한 비교예 4에 비해 낮은 구동전압, 높은 발광효율 및 장수명을 나타내므로, 소자특성이 현저히 개선됨을 확인할 수 있다. 이는 본 발명의 화합물을 단독으로 발광보조층으로 사용할 경우 높은 T1 에너지 레벨을 가지며, 깊은 HOMO 에너지 레벨로 인해 유기전기발광소자의 낮은 전압, 높은 발광효율 및 소자수명을 향상시키는 것으로 설명할 수 있다.As can be seen from the results of Table 6, when the compound of the present invention is used as the light-emitting auxiliary layer material, compared with Comparative Example 3 in which no luminescent auxiliary layer is formed and Comparative Example 4 using Comparative Compound 2, The light emitting efficiency and the longevity are shown, it is confirmed that the device characteristics are remarkably improved. It can be explained that when the compound of the present invention is used singly as a light emitting auxiliary layer, it has a high T1 energy level and the deep HOMO energy level improves the low voltage of the organic electroluminescent device, high luminous efficiency and device life.

본 발명의 화합물들을 유기전기발광소자의 다른 유기물층들, 예를 들어 발광 The compounds of the present invention may be combined with other organic layers of an organic electroluminescent device,

보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있을 것이다.The same effect can be obtained even if it is used for the auxiliary layer, the electron injection layer, the electron transporting layer, and the hole injection layer.

이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: 유기전기소자 110: 기판
120: 제 1전극 130: 정공주입층
140: 정공수송층 141: 버퍼층
150: 발광층 151: 발광보조층
160: 전자수송층 170: 전자주입층
180: 제 2전극100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (8)

하기 화학식 1과 화학식 2의 조합으로 표시되는 화합물.
<화학식 1> <화학식 2>
Figure pat00050
,
Figure pat00051

[상기 화학식에서, Y를 포함하는 오각형의 환이 형성되도록 화학식 2는 화학식 1의 이웃한 두 탄소에 결합되며,
R1~R5 및 R11은 서로 독립적으로, 수소; C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; C1~C50의 알킬기; 플루오렌일기; 및 -L-N(Ar1)(Ar2)로 이루어진 군에서 선택되고, n은 1 또는 2의 정수이며, 단 상기 R1~R4 중 적어도 하나 또는 R11이 -L-N(Ar1)(Ar2)이거나, R1~R4 중 적어도 하나와 R11이 -L-N(Ar1)(Ar2)이며,
Y는 S, O 또는 CR'R"이며, 여기서 R' 및 R"은 ⅰ) 서로 독립적으로, 수소; C1~C50의 알킬기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; 및 -L-N(Ar1)(Ar2)로 이루어진 군에서 선택되거나, 또는 ⅱ) 서로 결합하여 스피로 화합물을 형성하며,
상기 L은 C6~C60의 직접결합; 아릴렌기; O, N, S, Si, P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; 및 플루오레닐렌기;로 이루어진 군에서 선택되고 (단, 이들 각각은 니트로기, 시아노기, 할로겐기, C1~C20의 알킬기, C6~C20의 아릴기, C2~C20의 헤테로고리기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환될 수 있음),
상기 Ar1, Ar2는 C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C3~C60의 헤테로고리기; C1~C50의 알킬기; 및 플루오렌일기;로 이루어진 군에서 선택된다.
(상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 아릴기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,
상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 헤테로고리기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, 니트로기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,
상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 플루오렌일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,
상기 R1~R5, R11, R' 및 R", Ar1 및 Ar2가 알킬기인 경우, 이는 할로겐, 실란기, 붕소기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다)]A compound represented by the following formula (1) and (2):
&Lt; Formula 1 >< EMI ID =
Figure pat00050
,
Figure pat00051

In the above formula, the formula (2) is bonded to two neighboring carbons of the formula (1) so that a pentagonal ring containing Y is formed,
R 1 to R 5 and R 11 independently from each other are hydrogen; A C 6 to C 60 aryl group; O, N, S, Si and P, A C 3 to C 60 heterocyclic group; A C 1 to C 50 alkyl group; A fluorenyl group; And -LN (Ar 1 ) (Ar 2 ), and n is an integer of 1 or 2, provided that at least one of R 1 to R 4 or R 11 is -LN (Ar 1 ) (Ar 2 Or at least one of R 1 to R 4 and R 11 is -LN (Ar 1 ) (Ar 2 )
Y is S, O or CR'R &quot;, wherein R 'and R "are independently selected from the group consisting of: i) independently of each other hydrogen; A C 1 to C 50 alkyl group; A C 6 to C 60 aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si, and C 3 ~ containing at least one hetero atom in the P C 60; And -LN (Ar 1 ) (Ar 2 ), or ii) bonded to each other to form a spiro compound,
L is a direct bond of C 6 to C 60 ; An arylene group; Containing at least one heteroatom selected from O, N, S, Si, P A C 3 to C 60 heterocyclic group; And a fluorenylene group, provided that each of these is selected from the group consisting of a nitro group, a cyano group, a halogen group, a C 1 to C 20 alkyl group, a C 6 to C 20 aryl group, a C 2 to C 20 A heterocyclic group, a C 1 to C 20 alkoxy group, and an amino group,
Ar 1 and Ar 2 are C 6 to C 60 aryl groups; O, N, S, Si and P, A C 3 to C 60 heterocyclic group; A C 1 to C 50 alkyl group; And a fluorenyl group.
(Wherein R 1 ~ R 5, R 11 , R ' and R ", Ar 1 and Ar 2 are aryl groups cases, this heavy hydrogen, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C 1 ~ for C 20 come alkylthio, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkyl group, C 2 ~ C 20 of alkenyl groups (alkenyl), C 2 ~ C 20 of the alkynyl group (alkynyl), C of the of 6 ~ C 20 aryl group, of a C 6 ~ C 20 aryl group substituted with a heavy hydrogen, C 2 ~ C 20 heterocyclic group, C 3 ~ C 20 cycloalkyl group, C 7 ~ C 20 of the An arylalkyl group, and an arylalkenyl group having 8 to 20 carbon atoms,
Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 a heterocyclic group, which is heavy hydrogen, an alkoxyl group, a halogen, a silane group, a cyano group, a nitro group, C 1 ~ C 20, C 1 ~ C 20 alkyl group, C 2 ~ C 20 of alkenyl groups (alkenyl), C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, a C 2 ~ heterocycle of the C 20 Group, a C 3 to C 20 cycloalkyl group, a C 7 to C 20 An arylalkyl group, and an arylalkenyl group having 8 to 20 carbon atoms,
Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 fluorene group in which heavy hydrogen, a halogen, a silane group, a cyano group, C alkyl group of 1 ~ C 20, C 2 ~ An alkenyl group of C 20 , a C 6 to C 20 aryl group, a C 6 to C 20 aryl group substituted by deuterium, a C 2 to C 20 heterocyclic group, and a C 3 to C 20 cycloalkyl group Lt; / RTI &gt; may be substituted with one or more substituents selected from the group consisting &lt; RTI ID =
Wherein R 1 ~ R 5, R 11 , R ' and R ", when the Ar 1 and Ar 2 is an alkyl group, which is a halogen, a silane group, a boron group, cyano group, C 1 ~ C 20 alkoxy group, C 1 ~ of alkyl group of C 20, C 2 ~ C 20 of alkenyl groups (alkenyl), C 6 ~ C 20 aryl group, of a C 6 ~ C 20 substituted by deuterium aryl group, C 2 ~ C 20 heterocyclic group, C of 7 to C 20 An arylalkyl group and an arylalkenyl group having 8 to 20 carbon atoms, 제 1항에 있어서,
하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.
<화학식 3> <화학식 4> <화학식 5>
Figure pat00052
Figure pat00053

<화학식 6> <화학식 7> <화학식 8>
Figure pat00054

<화학식 9> <화학식 10> <화학식 11>
Figure pat00055

(여기서, R1~R5, R11, Y, L, Ar1, Ar2 및 n은 제1항에서 정의된 것과 같다)The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
&Lt; Formula 3 &gt;&lt; EMI ID =
Figure pat00052
Figure pat00053

&Lt; Formula 6 >< EMI ID =
Figure pat00054

&Lt; Formula 9 &gt;&lt; EMI ID =
Figure pat00055

(Wherein R 1 to R 5 , R 11 , Y, L, Ar 1 , Ar 2 and n are the same as defined in claim 1) 제 1항에 있어서,
하기 화합물 중 하나로 표시되는 것을 특징으로 하는 화합물.
Figure pat00056

Figure pat00057

Figure pat00058

Figure pat00059

Figure pat00060

Figure pat00061

Figure pat00062

Figure pat00063

Figure pat00064

Figure pat00065

Figure pat00066

Figure pat00067

Figure pat00068
The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
Figure pat00056

Figure pat00057

Figure pat00058

Figure pat00059

Figure pat00060

Figure pat00061

Figure pat00062

Figure pat00063

Figure pat00064

Figure pat00065

Figure pat00066

Figure pat00067

Figure pat00068
 제 1전극, 제 2전극, 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층을 포함하는 유기전기소자에 있어서,
상기 유기물층은 제 1항 내지 제 3항 중 어느 한 항의 화합물을 함유하는 것을 특징으로 하는 유기전기소자.An organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode,
Wherein the organic material layer contains the compound of any one of claims 1 to 3. 제 4항에 있어서,
상기 화합물을 용액공정(soluble process)에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자. 5. The method of claim 4,
Wherein said compound is formed into said organic material layer by a soluble process. 제 4항에 있어서,
상기 유기물층은 발광층, 발광보조층, 정공수송층, 정공주입층, 전자수송층 및 전자주입층을 포함하며,
상기 화합물은 상기 정공수송층 및 발광보조층 중 적어도 일층에 함유된 것을 특징으로 하는 유기전기소자.5. The method of claim 4,
The organic material layer includes a light emitting layer, a light emitting auxiliary layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, and an electron injecting layer,
Wherein the compound is contained in at least one layer of the hole transporting layer and the light emission-assisting layer. 제 4항의 유기전기소자를 포함하는 디스플레이장치; 및
상기 디스플레이장치를 구동하는 제어부; 를 포함하는 전자장치.A display device including the organic electroluminescent device of claim 4; And
A controller for driving the display device; &Lt; / RTI &gt; 제 7항에 있어서,
상기 유기전기소자는 유기전기발광소자(OLED ), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.8. The method of claim 7,
Wherein the organic electronic device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.
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