KR20200040030A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

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

Info

Publication number
KR20200040030A
KR20200040030A KR1020180119765A KR20180119765A KR20200040030A KR 20200040030 A KR20200040030 A KR 20200040030A KR 1020180119765 A KR1020180119765 A KR 1020180119765A KR 20180119765 A KR20180119765 A KR 20180119765A KR 20200040030 A KR20200040030 A KR 20200040030A
Authority
KR
South Korea
Prior art keywords
sub
formula
group
mmol
compound
Prior art date
Application number
KR1020180119765A
Other languages
Korean (ko)
Other versions
KR102654639B1 (en
Inventor
문성윤
이중근
이범성
박정환
이윤석
Original Assignee
덕산네오룩스 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 덕산네오룩스 주식회사 filed Critical 덕산네오룩스 주식회사
Priority to KR1020180119765A priority Critical patent/KR102654639B1/en
Priority to PCT/KR2019/013192 priority patent/WO2020076052A1/en
Publication of KR20200040030A publication Critical patent/KR20200040030A/en
Application granted granted Critical
Publication of KR102654639B1 publication Critical patent/KR102654639B1/en

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/04—Ortho-condensed systems
    • H01L51/0071—
    • H01L51/50—

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)

Abstract

The present invention provides: a novel mixture capable of improving luminous efficiency, stability, and lifespan of an element; an organic electronic element using the same; and an electronic device thereof. By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electronic element, and also significantly improve a lifespan of the element.

Description

유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}Compound for organic electric element, organic electric element using the same, and its electronic device {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

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

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 유기물층은 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, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, 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, 발광재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.Materials used as the organic material layer in the organic electric device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on the function.

헤테로원자를 포함하고 있는 비스타입의 고리화합물의 경우 물질 구조에 따른 특성의 차이가 매우 커서 유기전기소자의 재료로 다양한 층에 적용되고 있다. 특히 환의 개수 및 fused위치, 헤테로원자의 종류와 배열에 따라 밴드 갭(HOMO, LUMO), 전기적 특성, 화학적 특성, 물성 등이 상이한 특징을 갖고 있어, 이를 이용한 다양한 유기전기소자의 층에 대한 적용 개발이 진행되어 왔다.In the case of a bis-type cyclic compound containing a hetero atom, a difference in properties according to a material structure is very large, and thus, it is applied to various layers as a material for an organic electric device. In particular, the band gap (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. have different characteristics depending on the number of rings, fused positions, and the type and arrangement of heteroatoms. This has been going on.

인광 발광 도펀트 재료를 이용하는 인광형 유기전기소자에 있어서 호스트 물질의 LUMO, 및 HOMO level은 유기전기소자의 효울 및 수명에 매우 큰 영향을 주는 요인으로서 발광층 내 전자 및 정공 주입을 효율적으로 조절 가능하냐에 따라 발광층 내 charge balance 조절, 도펀트 ?칭(quenching) 및 정공수송층 계면에서의 발광으로 인한 효율 저하 및 수명 저하를 방지할 수 있다.In a phosphorescent organic electrical device using a phosphorescent dopant material, the LUMO and HOMO levels of the host material are factors that greatly affect the efficiency and lifetime of the organic electrical device. Accordingly, it is possible to control the charge balance in the light-emitting layer, quenching the dopant, and prevent the decrease in efficiency and the life due to light emission at the hole transport layer interface.

형광 및 인광 발광용 호스트 물질의 경우 최근들어 TADF(Thermal activatied delayed fluorescent), Exciplex 등을 이용한 유기전기소자의 효율 증가 및 수명 증가 등을 연구하고 있으며, 특히 호스트 물질에서 도펀트 물질로의 에너지 전달 방법 규명에 많은 연구가 진행되고 있다.In the case of host materials for fluorescence and phosphorescence, recently, research has been conducted on increasing the efficiency and lifetime of organic electric devices using thermal activatied delayed fluorescent (TADF), exciplex, etc., and in particular, identifying energy transfer methods from host materials to dopant materials There is a lot of research going on.

TADF (Thermal activated delayed fluorescent), exciplex에 대한 발광층 내 에너지 전달 규명은 여러 가지 방법들이 있지만, PL lifetime (TRTP) 측정법으로 손쉽게 확인할 수 있다.Although there are several methods for identifying energy transfer in a light emitting layer for TADF (Thermal Activated Delayed Fluorescent), exciplex, it can be easily confirmed by PL lifetime (TRTP) measurement.

TRTP (Time resolved transient PL) 측정법은 펄스 광원을 호스트 박막에 조사한 후, 시간에 따른 스펙트럼의 감소(Decay time)를 관찰하는 방식으로서 에너지 전달 및 발광 지연시간 관찰을 통해 에너지 전달 방식을 규명할 수 있는 측정방법이다. 상기 TRTP 측정은 형광과 인광의 구분 및 mixed 호스트 물질 내에서의 에너지 전달방식, exciplex 에너지 전달방식, TADF 에너지 전달 방식 등을 구분해 줄 수 있는 측정법이다.The TRTP (Time resolved transient PL) measurement method is a method of observing the decay time of the spectrum over time after irradiating a pulsed light source to the host thin film. It is a measurement method. The TRTP measurement is a measurement method capable of distinguishing between fluorescence and phosphorescence, energy transfer method in mixed host material, exciplex energy transfer method, and TADF energy transfer method.

이처럼 호스트 물질로부터 도펀트 물질로 에너지가 전달되는 방식에 따라 효율 및 수명에 영향을 주는 다양한 요인들이 존재하며, 물질에 따라 에너지 전달 방식이 상이하여, 아직까지 안정되고 효율적인 유기전기소자용 호스트 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광층의 호스트 물질에 대한 개발이 절실히 요구되고 있다.As described above, there are various factors affecting efficiency and lifespan depending on the manner in which energy is transferred from the host material to the dopant material, and the energy transmission method is different according to the material, so that the development of a stable and efficient host material for an organic electric device This is not done enough. Therefore, the development of new materials continues to be required, and in particular, the development of the host material of the light emitting layer is urgently required.

KRKR 101170666101170666 B1B1

본 발명은 상기와 같은 인광 호스트 물질의 문제점을 해결하기 위하여 제안된 것으로, 인광 도펀트를 포함하는 인광 발광형 유기전기소자의 호스트 물질에 대한 HOMO level 조절을 통한 발광층 내 charge balance 조절 및 효율, 수명을 향상시킬 수 있는 화합물 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.The present invention has been proposed to solve the problems of the phosphorescent host material as described above, the charge balance in the light emitting layer by adjusting the HOMO level for the host material of the phosphorescent dopant-containing organic electroluminescent device containing a phosphorescent dopant and the efficiency, life span It is an object of the present invention to provide an organic electrical device using the compound and an electronic device thereof.

본 발명은 인광 발광형 유기전기소자의 발광층 내 효율적인 정공 주입을 조절하기 위해 주성분으로서 특정의 제 1호스트 재료에 특정의 제 2호스트 재료를 조합하여 함유함으로써, 발광층과 인접층의 에너지 장벽을 작게 할 수 있고, 발광층 내 charge balance를 최대화 시켜 유기전기소자의 고효율, 고수명을 제공하는 것이다.The present invention is to reduce the energy barrier between the light emitting layer and the adjacent layer by containing a specific first host material in combination with a specific first host material as a main component in order to control efficient hole injection in the light emitting layer of the phosphorescent organic electroluminescent device. It is possible to maximize the charge balance in the light emitting layer to provide high efficiency and high lifespan of the organic electric device.

본 발명은 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광성 발광층으로서 화학식 (1)로 표시되는 제 1호스트 화합물 및 화학식 (2) 표시되는 제 2호스트 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.The present invention is an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer. It provides an organic electric device comprising a first host compound represented by (1) and a second host compound represented by the formula (2).

화학식 (1) 화학식 (2)    Formula (1) Formula (2)

Figure pat00001
Figure pat00002
Figure pat00001
Figure pat00002

또한, 본 발명은 상기 화학식들로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In addition, the present invention provides an organic electric device using the compound represented by the above formulas and an electronic device thereof.

본 발명에 따른 혼합물을 인광 호스트 물질로 이용함으로써, 유기전기소자의 높은 발광효율, 낮은 구동전압을 달성할 수 있으며, 또한 소자의 수명을 크게 향상시킬 수 있다.By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve high luminous efficiency and low driving voltage of the organic electric device, and also significantly improve the life of the device.

도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.1 is an exemplary view of an organic electroluminescent device according to the present invention.

이하, 본 발명의 실시예를 참조하여 상세하게 설명한다. 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.Hereinafter, with reference to the embodiment of the present invention will be described in detail. In describing the present invention, when it is determined that detailed descriptions of related known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

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 구성요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성 요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성 요소에 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 addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다: As used in this specification and the appended claims, unless otherwise stated, the meaning of the following terms is as follows:

본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The terms "halo" or "halogen" as used herein are fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise noted.

본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 사이클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.The term "alkyl" or "alkyl group" used in the present invention has a single bond of 1 to 60 carbon atoms, unless otherwise specified, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cycle. By radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다. The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise specified.

본 발명에 사용된 용어 "헤테로알킬기"는 알킬기를 구성하는 탄소원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.The term "heteroalkyl group" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

본 발명에 사용된 용어 "알켄일기", "알케닐기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다.The terms "alkenyl group", "alkenyl group" or "alkynyl group" used in the present invention have a double or triple bond of 2 to 60 carbon atoms, unless otherwise specified, and include straight or branched chain groups. , But is not limited to this.

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

본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "alkoxyl group", "alkoxy group", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached, and has a carbon number of 1 to 60 unless otherwise specified, and is limited thereto. It is not.

본 발명에 사용된 용어 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has a carbon number of 6 to 60 unless otherwise specified, and 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. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 디메틸플루오렌기, 디페닐플루오렌기, 스파이로플루오렌기일 수 있다.The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multi-ring aromatic, and includes an aromatic ring formed by adjacent substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, dimethylfluorene group, diphenylfluorene group, or spirofluorene group.

접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다. The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has a carbon number described herein.

또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.Also, when the prefix is named in succession, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl 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 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다.The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다.The term “heteroatom” as used herein refers to N, O, S, P or Si, unless otherwise stated.

또한 "헤테로고리기"는 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. In addition, "heterocyclic group" may include a ring containing SO 2 instead of carbon forming a ring. For example, "heterocyclic group" includes the following compounds.

Figure pat00003
Figure pat00003

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 specified, the term "aliphatic" as used herein refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화고리를 포함한다.Unless otherwise specified, the term "ring" used in the present invention refers to an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms or a combination thereof, and It contains a saturated or unsaturated ring.

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-described hetero compounds include one or more hetero atoms, but are not limited thereto.

다른 설명이 없는 한, 본 발명에 사용된 용어 "에스테르(ester)"란 -C(=O)-O-R'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise stated, the term "ester" used in the present invention is represented by -C (= O) -O-R ', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms. It is an aryl group having 30 to 30, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

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 알콕실기, C1~C20의 알킬아민기, C1~C20의 알킬티오펜기, C6~C20의 아릴티오펜기, C2~C20의 알켄일기, C2~C20의 알킨일기, C3~C20의 시클로알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 C2~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxyl group, C 1 ~ C 20 alkylamine group, C 1 ~ C 20 alkylthiophene group, C 6 ~ C 20 arylthiophene group, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 20 aryl group, substituted with deuterium C 6 ~ C 20 aryl group, C 8 ~ C 20 aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C 2 to C 20 heterocyclic groups, and is not limited to these substituents.

또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.In addition, unless otherwise specified, the formula used in the present invention is applied in the same manner as the substituent definition by the exponent definition of the following formula.

Figure pat00004
Figure pat00004

여기서, a가 0의 정수인 경우 치환기 R1은 부존재하는 것을 의미하는데, 즉 a가 0인 경우는 벤젠고리를 형성하는 탄소에 모두 수소가 결합된 것을 의미하며, 이때 탄소에 결합된 수소의 표시를 생략하고 화학식이나 화합물을 기재할 수 있다. a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.Here, when a is an integer of 0, the substituent R 1 means non-existent, that is, when a is 0, it means that hydrogen is bonded to all of the carbons forming the benzene ring. The formula or compound may be omitted. When a is an integer of 1, one substituent R 1 is bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3, each of them is bonded as follows, where R 1 may be the same or different from each other. When a is an integer of 4 to 6, it binds to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bound to the carbon forming the benzene ring is omitted.

Figure pat00005
Figure pat00005

이하, 본 발명의 일 측면에 따른 화합물 및 이를 포함하는 유기전기소자에 대하여 설명한다. Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.

본 발명은 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광성 발광층으로서 화학식 (1)로 표시되는 제 1호스트 화합물 및 화학식 (2) 표시되는 제 2호스트 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.The present invention is an organic electric device including a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer. It provides an organic electric device comprising a first host compound represented by (1) and a second host compound represented by the formula (2).

화학식 (1) 화학식 (2)   Formula (1) Formula (2)

Figure pat00006
Figure pat00007
Figure pat00006
Figure pat00007

{상기 화학식 (1) 및 (2)에서, {In the formulas (1) and (2) above,

1) X, Y 및 W는 각각 독립적으로 NR'; O; S; CR'R"; SiR'R"; 또는 Se;이고,1) X, Y and W are each independently NR '; O; S; CR'R "; SiR'R"; Or Se;

2) a, b, c 및 d는 0 또는 1이고, 단 a+b와 c+d는 1 이상이며,2) a, b, c and d are 0 or 1, provided that a + b and c + d are 1 or more,

3) R' 및 R"는 각각 독립적으로 수소; C1~C50의 알킬기; C6~C60의 아릴기; 및 C2~C60의 헤테로아릴기;로 이루어진 군에서 선택되거나, R' 및 R"은 서로 고리를 형성하여 스파이로(spiro) 고리를 형성하고, 3) R 'and R "are each independently hydrogen; an alkyl group of C 1 to C 50 ; an aryl group of C 6 to C 60 ; and a heteroaryl group of C 2 to C 60 ; or R' And R "form a ring with each other to form a spiro ring,

4) L1, L2 및 L'은 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 또는 C2~C60의 헤테로아릴렌기;이고,4) L 1 , L 2 and L 'are each independently a single bond; C 6 ~ C 60 Arylene group; Or C 2 ~ C 60 heteroarylene group; is,

5) Ar1 및 Ar2는 각각 독립적으로 수소; 중수소; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-NR'R";로 이루어진 군에서 선택되고,5) Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; C 1 ~ C 50 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-NR'R ";

6) Z는 NR', O, S, CR'R", SiR'R", 또는 Se이고,6) Z is NR ', O, S, CR'R ", SiR'R", or Se,

7) R1 내지 R16은 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; C1-C20의 에스테르기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고, 7) R 1 to R 16 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; C 1 -C 20 ester group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; C 1 ~ C 50 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-N (R a ) (R b ); is selected from the group consisting of,

상기 Ra 및 Rb 은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고, R a and R b are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; And O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom; is selected from the group consisting of,

상기 l, n, o 및 p가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 인접한 복수의 R1끼리, 복수의 R3끼리, 복수의 R4끼리, 복수의 R5끼리, 복수의 R16끼리, R6와 R7끼리, R7와 R8끼리, R8와 R9끼리, R10와 R11끼리, R12와 R13끼리, R13과 R14끼리, 또는 R14와 R15끼리는 서로 결합하여 방향족 및 헤테로방향족 고리를 형성할 수 있고, When l, n, o, and p are 2 or more, they are the same as or different from each other as a plurality, and a plurality of adjacent R 1 , a plurality of R 3 , a plurality of R 4 , a plurality of R 5 , a plurality of R 16 , Between R 6 and R 7, between R 7 and R 8, between R 8 and R 9, between R 10 and R 11, between R 12 and R 13, between R 13 and R 14 , or between R 14 and R 15 Can combine with each other to form an aromatic and heteroaromatic ring,

8) A환은 C6~C60의 아릴기; 또는 C2~C60의 헤테로아릴렌기;이고, 8) A ring is C 6 ~ C 60 aryl group; Or C 2 ~ C 60 heteroarylene group; is,

9) n, l, p은 0~4 중 어느 하나의 정수이고, m은 0 또는 1의 정수이고, o는 0 내지 3 중 어느 하나의 정수이고, e는 0 내지 10 중 어느 하나의 정수이며,9) n, l, p is an integer from 0 to 4, m is an integer from 0 or 1, o is an integer from 0 to 3, and e is an integer from 0 to 10 ,

여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 융합고리기, 알킬기, 알케닐기, 알콕시기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group, respectively, deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; Alkoxyl group of C 1 -C 20 ; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 Aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; C 3 -C 20 cycloalkyl group; C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and also these substituents may combine with each other to form a ring, wherein ''Cycle' refers to a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 heterocycle or a fused ring thereof, and includes a saturated or unsaturated ring.}

본 발명에서 상기 화학식 (1)로 나타낸 화합물은 하기 화학식 (3) 또는 (4)로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.The compound represented by the formula (1) in the present invention provides an organic electric device comprising a compound represented by the following formula (3) or (4).

화학식 (3) 화학식 (4)      Formula (3) Formula (4)

Figure pat00008
Figure pat00008

(상기 화학식 (3) 및 (4)에서, X, Y, Z, Ar1, L1, R1, R2, R3, R4, R5, l, m, n, o, 및 p는 상기에서 정의된 바와 동일하다.)(In the formulas (3) and (4), X, Y, Z, Ar 1 , L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , l, m, n, o, and p are Same as defined above.)

또 다른 구체적인 예로, 본 발명은 상기 화학식 (1)로 나타낸 화합물이 하기 화학식 (5) 내지 (12) 중 어느 하나로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.As another specific example, the present invention provides an organic electric device in which the compound represented by the formula (1) includes a compound represented by any one of the following formulas (5) to (12).

화학식 (5) 화학식 (6) 화학식 (7) 화학식 (8)  Formula (5) Formula (6) Formula (7) Formula (8)

Figure pat00009
Figure pat00009

화학식 (9) 화학식 (10) 화학식 (11) 화학식 (12) Formula (9) Formula (10) Formula (11) Formula (12)

Figure pat00010
Figure pat00010

(상기 화학식 (5) 내지 (12)에서, X, Y, Z, Ar1, L1, R1, R2, R3, R4, R5, R', R", l, m, n, o, 및 p는 상기에서 정의된 바와 동일하다.)(In the formulas (5) to (12), X, Y, Z, Ar 1 , L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R ', R ", l, m, n , o, and p are as defined above.)

또한 본 발명은 상기 화학식 (1)에서 상기 l, m, n, o 및 p가 모두 0인 화합물을 포함하는 유기전기소자를 제공한다.In addition, the present invention provides an organic electric device including a compound in which all of l, m, n, o and p are 0 in the formula (1).

또 다른 예로, 본 발명은 상기 화학식 (1)에서 상기 R1, R3, R4 및 R5 중 어느 하나는 이웃한 한 쌍이 서로 결합하여 고리를 형성하는 화합물을 포함하는 유기전기소자를 제공한다.As another example, the present invention provides an organic electroluminescent device including a compound in which any one of the R 1 , R 3 , R 4 and R 5 in the formula (1) combines with each other to form a ring. .

또한, 본 발명은 상기 화학식 (1)에서, 상기 X 및 Y는 S 또는 O인 화합물을 포함하는 유기전기소자를 제공한다.In addition, the present invention in the formula (1), X and Y provides an organic electric device comprising a compound of S or O.

구체적인 예로, 본 발명에서 상기 화학식 (1)은 하기 화합물을 포함한다.As a specific example, the formula (1) in the present invention includes the following compound.

Figure pat00011
Figure pat00011

Figure pat00012
Figure pat00012

Figure pat00013
Figure pat00013

Figure pat00014
Figure pat00014

Figure pat00015
Figure pat00015

Figure pat00016
Figure pat00016

Figure pat00017
Figure pat00017

Figure pat00018
Figure pat00018

Figure pat00019
Figure pat00019

Figure pat00020
Figure pat00020

Figure pat00021
Figure pat00021

Figure pat00022
Figure pat00022

Figure pat00023
Figure pat00023

Figure pat00024
Figure pat00024

Figure pat00025
Figure pat00025

Figure pat00026
Figure pat00026

Figure pat00027
Figure pat00027

Figure pat00028
Figure pat00028

Figure pat00029
Figure pat00029

Figure pat00030
Figure pat00030

Figure pat00031
Figure pat00031

Figure pat00032
Figure pat00032

Figure pat00033
Figure pat00033

Figure pat00034
Figure pat00034

Figure pat00035
Figure pat00035

Figure pat00036
Figure pat00036

Figure pat00037
Figure pat00037

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

Figure pat00040
Figure pat00040

Figure pat00041
Figure pat00041

Figure pat00042
Figure pat00042

Figure pat00043
Figure pat00043

Figure pat00044
Figure pat00044

Figure pat00045
Figure pat00045

Figure pat00046
Figure pat00046

Figure pat00047
Figure pat00047

Figure pat00048
Figure pat00048

Figure pat00049
Figure pat00049

Figure pat00050
Figure pat00050

Figure pat00051
Figure pat00051

Figure pat00052
Figure pat00052

Figure pat00053
Figure pat00053

Figure pat00054
Figure pat00054

Figure pat00055
Figure pat00055

Figure pat00056
Figure pat00056

Figure pat00057
Figure pat00057

Figure pat00058
Figure pat00058

Figure pat00059
Figure pat00059

Figure pat00060
Figure pat00060

Figure pat00061
Figure pat00061

Figure pat00062
Figure pat00062

Figure pat00063
Figure pat00063

Figure pat00064
Figure pat00064

Figure pat00065
Figure pat00065

Figure pat00066
Figure pat00066

한편, 본 발명은 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (13) 또는 (14)로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.On the other hand, the present invention provides an organic electric device in which the compound represented by the formula (2) includes a compound represented by the following formula (13) or (14).

화학식 (13) 화학식 (14)      Formula (13) Formula (14)

Figure pat00067
Figure pat00067

(상기 화학식 (13) 및 (14)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, V, W, c, 및 d는 상기에서 정의한 바와 같다.)(In the formulas (13) and (14), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, V, W, c, and d are as defined above.)

또 다른 예로, 본 발명은 상기 화학식 (2)로 나타낸 화합물의 R6과 R7, R7과 R8, R8과 R9, R10과 R11, R12와 R13, R13과 R14 및 R14와 R15 중 적어도 한 쌍이 서로 결합하여 방향족 또는 헤테로 방향족 고리를 형성하는 화합물을 포함하는 유기전기소자를 제공한다.As another example, the present invention is the compound represented by the formula (2) R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 10 and R 11 , R 12 and R 13 , R 13 and R 14 and R 14 and at least one pair of R 15 are bonded to each other to provide an organic electric device comprising a compound that forms an aromatic or heteroaromatic ring.

또 다른 예로, 본 발명은 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (15) 내지 (38)로 표시되는 것 화합물을 포함한다.As another example, the present invention includes compounds represented by the following formulas (15) to (38).

화학식 (15) 화학식 (16) 화학식 (17) 화학식 (18)Formula (15) Formula (16) Formula (17) Formula (18)

Figure pat00068
Figure pat00068

화학식 (19) 화학식 (20) 화학식 (21) 화학식 (22)Formula (19) Formula (20) Formula (21) Formula (22)

Figure pat00069
Figure pat00069

화학식 (23) 화학식 (24) 화학식 (25) 화학식 (26)Formula (23) Formula (24) Formula (25) Formula (26)

Figure pat00070
Figure pat00070

화학식 (27) 화학식 (28) 화학식 (29) 화학식 (30) Formula (27) Formula (28) Formula (29) Formula (30)

Figure pat00071
Figure pat00071

화학식 (31) 화학식 (32) 화학식 (33) 화학식 (34) Formula (31) Formula (32) Formula (33) Formula (34)

Figure pat00072
Figure pat00072

화학식 (35) 화학식 (36) 화학식 (37) 화학식 (38) Formula (35) Formula (36) Formula (37) Formula (38)

Figure pat00073
Figure pat00073

(상기 화학식 (15) 및 (38)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, V, W, c, 및 d는 상기에서 정의한 바와 같다.)(In the formulas (15) and (38), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, V, W, c, and d are as defined above.)

또한 본 발명은 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (39) 내지 (46) 중 어느 하나인 화합물을 포함하는 유기전기소자를 제공한다.In addition, the present invention provides an organic electric device comprising a compound represented by the formula (2) is any one of the following formulas (39) to (46).

화학식 (39) 화학식 (40) 화학식 (41) 화학식 (42) Formula (39) Formula (40) Formula (41) Formula (42)

Figure pat00074
Figure pat00074

화학식 (43) 화학식 (44) 화학식 (45) 화학식 (46)Formula (43) Formula (44) Formula (45) Formula (46)

Figure pat00075
Figure pat00075

(상기 화학식 (39) 및 (46)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, R' 및 R"는 상기에서 정의한 바와 같다.)(In the formulas (39) and (46), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, R 'and R "are as defined above.)

또 다른 예로, 상기 화학식 (2)의 R6, R7, R8, R9, R10, R12, R13, R14 및 R15가 모두 수소인 화합물을 포함하는 유기전기소자를 제공한다.As another example, to provide an organic electric device comprising a compound in which R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 and R 15 of the formula (2) are all hydrogen. .

또한 본 발명은 상기 화학식 (2)의 A환이 하기 (A-1) 내지 (A-14) 중 어느 하나인 화합물을 포함하는 유기전기소자를 제공한다.In addition, the present invention provides an organic electric device comprising a compound in which the A ring of the formula (2) is any one of the following (A-1) to (A-14).

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)

Figure pat00076
Figure pat00076

(A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14) (A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14)

Figure pat00077
Figure pat00077

(상기 화학식 (A-1) 내지 (A-14)에서, R', R", R16 및 e는 상기에서 정의한 바와 같고, *는 A환의 결합위치를 나타낸다.)(In the formulas (A-1) to (A-14), R ', R ", R 16 and e are as defined above, and * represents the bonding position of the A ring.)

구체적인 예로, 본 발명에서 상기 화학식 (2)는 하기 화합물을 포함한다.As a specific example, the formula (2) in the present invention includes the following compound.

Figure pat00078
Figure pat00078

Figure pat00079
Figure pat00079

Figure pat00080
Figure pat00080

Figure pat00081
Figure pat00081

Figure pat00082
Figure pat00082

Figure pat00083
Figure pat00083

Figure pat00084
Figure pat00084

Figure pat00085
Figure pat00085

Figure pat00086
Figure pat00086

Figure pat00087
Figure pat00087

Figure pat00088
Figure pat00088

Figure pat00089
Figure pat00089

Figure pat00090
Figure pat00090

Figure pat00091
Figure pat00091

Figure pat00092
Figure pat00092

Figure pat00093
Figure pat00093

Figure pat00094
Figure pat00094

Figure pat00095
Figure pat00095

Figure pat00096
Figure pat00096

Figure pat00097
Figure pat00097

Figure pat00098
Figure pat00098

Figure pat00099
Figure pat00099

Figure pat00100
Figure pat00100

Figure pat00101
Figure pat00101

Figure pat00102
Figure pat00102

Figure pat00103
Figure pat00103

Figure pat00104
Figure pat00104

Figure pat00105
Figure pat00105

Figure pat00106
Figure pat00106

Figure pat00107
Figure pat00107

Figure pat00108
Figure pat00108

Figure pat00109
Figure pat00109

Figure pat00110
Figure pat00110

Figure pat00111
Figure pat00111

Figure pat00112
Figure pat00112

Figure pat00113
Figure pat00113

Figure pat00114
Figure pat00114

Figure pat00115
Figure pat00115

Figure pat00116
Figure pat00116

도 1을 참조하여 설명하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(120)과 제 2전극(180) 사이에 화학식 1 및 2로 표시되는 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.Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180 and a first electrode 120 and a second electrode formed on the substrate 110. Between (180) it is provided with an organic layer containing the compound represented by the formula (1) and (2). At this time, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted 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), 발광보조층(151), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 전자수송보조층, 버퍼층(141) 등을 더 포함할 수 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있다.The organic material layer sequentially comprises a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, a light emitting auxiliary layer 151, an electron transport layer 160 and an electron injection layer 170 on the first electrode 120. It can contain. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like may be further included, and the electron transport layer 160, etc. may also serve as a hole blocking layer.

또한, 미도시하였지만 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다. 본 발명의 상기 화학식 1을 포함하는 화합물은 광효율개선층 또는 보호층의 재료로서　사용될수 있다.In addition, although not shown, the organic electric device according to the present invention may further include a protective layer formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode. The compound containing Formula 1 of the present invention may be used as a material for the light efficiency improving layer or the protective layer.

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, even in the same core, the band gap, electrical properties, and interfacial properties may vary depending on which substituents are attached to which positions, so the selection of the core and the combination of sub-substituents coupled thereto are also very good. It is important, especially when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

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 양극을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 또한, 정공수송층(140)과 발광층(150) 사이에 발광보조층(151)을, 발광층(150)과 전자수송층(160) 사이에 전자수송보조층을 추가로 더 형성할 수 있다. The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer 160 are formed thereon. After forming an organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as a cathode thereon. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and the electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.

이에 따라, 본 발명은 상기 화학식 (1) 및 상기 화학식 (2)로 나타내는 화합물이 1:9 내지 9:1 중 어느 하나의 비율로 혼합되어 상기 발광층에 포함되는 유기전기소자를 제공하며, 바람직하게는 1:9 내지 5:5로, 보다 바람직하게는 2:8 내지 3:7 비율로 혼합되어 상기 발광층에 포함된다.Accordingly, the present invention provides a compound represented by the formula (1) and the formula (2) in an ratio of any one of 1: 9 to 9: 1 to provide an organic electric device included in the light emitting layer, preferably Is 1: 9 to 5: 5, more preferably mixed in a ratio of 2: 8 to 3: 7 and included in the light emitting layer.

본 발명은 상기 유기전기소자에서 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율개선층을 더 포함하는 유기전기소자를 제공한다.The present invention further comprises a light efficiency improving layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer from one side of the first electrode in the organic electric device. An organic electric device is provided.

또한 본 발명에서 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되며, 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다. In addition, in the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, and the organic material layer according to the present invention can be formed by various methods Therefore, the scope of the present invention is not limited by the forming method.

본 발명의 일 실시예에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric device according to an embodiment of the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다.WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, the R (Red), G (Green), B (Blue) light emitting units are arranged in a mutually planar side-by-side manner, and the stacking method in which the R, G, and B light-emitting layers are stacked up and down. There is, there is a color conversion material (CCM) method using electroluminescence of the blue (B) organic light-emitting layer and photo-luminescence of the inorganic phosphor using light therefrom, the present invention Can be applied to such WOLED.

또한 본 발명은 상기한 유기전기소자를 포함하는 디스플레이장치 ; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다. In addition, the present invention is a display device comprising the above-described organic electric element; And a control unit for driving the display device.

또 다른 측면에서 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치를 본 발명에서 제공한다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말기일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.In another aspect, the present invention provides an electronic device characterized in that the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game machines, various TVs, and various computers.

이하에서, 본 발명의 상기 화학식 (1) 및 (2)로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, examples of the synthesis of the compounds represented by the formulas (1) and (2) of the present invention and the production examples of the organic electroluminescent device of the present invention will be specifically described with reference to the following examples of the present invention. It is not limited.

[[ 합성예Synthetic example 1] One]

본 발명에 따른 화학식 (1)로 표시되는 화합물(final product 1)은 하기 반응식 1과 같이 Sub 1 또는 Sub 2가 Sub 3과 반응하여 제조된다.The compound represented by the formula (1) according to the present invention (final product 1) is prepared by reacting Sub 1 or Sub 2 with Sub 3 as shown in Reaction Scheme 1 below.

<반응식 1><Scheme 1>

Figure pat00117
Figure pat00117

1. Sub 1의 합성 예시1. Synthesis Example of Sub 1

반응식 1의 sub 1은 하기 반응식 2의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다.Sub 1 of Scheme 1 may be synthesized by the following Reaction Scheme 2, but is not limited thereto.

<반응식 2> (X'= I, Br, Cl)<Reaction Scheme 2> (X '= I, Br, Cl)

Figure pat00118
Figure pat00118

Figure pat00119
Figure pat00119

상기 반응식 2의 Sub 1에 속하는 화합물의 합성예는 다음과 같다.Synthesis examples of compounds belonging to Sub 1 of Scheme 2 are as follows.

1. Sub 1-1의 합성예 (a=1, b= 0, X= S 일 때)1. Synthesis Example of Sub 1-1 (when a = 1, b = 0, X = S)

Figure pat00120
Figure pat00120

(1) Sub 1-I-1의 합성법(1) Synthesis of Sub 1-I-1

둥근바닥플라스크에 2-Chloroaniline (67.2 g, 525 mmol), 1,4-Dibromodibenzothiophene (150 g, 438 mmol),　Pd2(dba)3 (16.2 g, 17.4 mmol), P(t-Bu)3 (15 g, 43.8 mmol), NaO(t-Bu) (126 g, 1317 mmol), Toluene (1.5 L)을 넣는다. 그런 후에 70℃ 상태에서 4시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 1-I-1 (135 g, 79%)을 얻었다.2-Chloroaniline (67.2 g, 525 mmol), 1,4-Dibromodibenzothiophene (150 g, 438 mmol), Pd 2 (dba) 3 in a round bottom flask (16.2 g, 17.4 mmol), P (t-Bu) 3 (15 g, 43.8 mmol), NaO (t-Bu) (126 g, 1317 mmol), Toluene (1.5 L) was added. Then, the mixture was heated to reflux for 4 hours at 70 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 1-I-1 (135 g, 79%).

(2) Sub 1-II-1의 합성법(2) Synthesis of Sub 1-II-1

둥근바닥플라스크에 Sub 1-I-1 (135 g, 348 mmol), PPh3 (228 g, 867 mmol), o-Dichlorobenzene (900 mL)을 넣는다. 그런 후에 180℃ 상태에서 24시간 동안 가열 환류시킨다. 반응이 종결되면 상온으로 식힌 후, 농축한다. 농축되어 생성된 화합물을 silica column 및 재결정하여 생성물 Sub 1-II-1 (91.8 g, 75%)를 얻었다.Round bottom flask with Sub 1-I-1 (135 g, 348 mmol), PPh 3 (228 g, 867 mmol), o -Dichlorobenzene (900 mL) was added. Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 1-II-1 (91.8 g, 75%).

(3) Sub 1-1의 합성법(3) Synthesis of Sub 1-1

둥근바닥플라스크에 Sub 1-II-1 (30.6 g 87 mmol), 1-Bromonaphthalene (21.5 g, 104 mmol), Pd2(dba)3 (3.2 g, 3.5 mmol), P(t-Bu)3 (1.8 g, 8.7 mmol), NaO(t-Bu) (25 g, 261 mmol), Toluene (300 mL)을 넣는다. 그런 후에 110℃ 상태에서 8시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 1-1 (31.6 g, 74%)를 얻었다.Round bottom flask with Sub 1-II-1 (30.6 g 87 mmol), 1-Bromonaphthalene (21.5 g, 104 mmol), Pd 2 (dba) 3 (3.2 g, 3.5 mmol), P (t-Bu) 3 (1.8 g, 8.7 mmol), NaO (t-Bu) (25 g, 261 mmol), Toluene (300 mL) was added. Then, the mixture was heated to reflux for 8 hours at 110 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 1-1 (31.6 g, 74%).

2. Sub 1-2의 합성예 (a=1, b= 0, X= S 일 때)2. Synthesis Example of Sub 1-2 (when a = 1, b = 0, X = S)

Figure pat00121
Figure pat00121

Sub 1-2의 합성법Synthesis of Sub 1-2

둥근바닥플라스크에 Sub 1-II-1 (30 g, 84 mmol), Iodobenzene (20.7 g, 102 mmol), Pd2(dba)3 (3 g, 3.3 mmol), P(t-Bu)3 (1.8 g, 8.4 mmol), NaO(t-Bu) (24.6 g, 255 mmol), Toluene (240 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-2 (28 g, 76%)를 얻었다.In a round bottom flask, Sub 1-II-1 (30 g, 84 mmol), Iodobenzene (20.7 g, 102 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 (3 g, 3.3 mmol), P (t-Bu) 3 (1.8 g, 8.4 mmol), NaO (t-Bu) (24.6 g, 255 mmol), Toluene (240 mL) Using the method, product Sub 1-2 (28 g, 76%) was obtained.

3. Sub 1-3의 합성예 (a=1, b= 0, X= S 일 때)3. Synthesis Example of Sub 1-3 (when a = 1, b = 0, X = S)

Figure pat00122
Figure pat00122

Sub 1-3의 합성법Synthesis of Sub 1-3

둥근바닥플라스크에 Sub 1-II-1 (30.6 g 87 mmol), 4-Iodo-1,1'-biphenyl (29.2 g, 104 mmol), Pd2(dba)3 (3.2 g, 3.5 mmol), P(t-Bu)3 (1.8 g, 8.7 mmol), NaO(t-Bu) (25 g, 261 mmol), Toluene (300 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-3 (32 g, 74%)을 얻었다.Round bottom flask with Sub 1-II-1 (30.6 g 87 mmol), 4-Iodo-1,1'-biphenyl (29.2 g, 104 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 by (3.2 g, 3.5 mmol), P (t-Bu) 3 (1.8 g, 8.7 mmol), NaO (t-Bu) (25 g, 261 mmol), Toluene (300 mL) The product was obtained using the method Sub 1-3 (32 g, 74%).

4. Sub 1-5의 합성예 (a=1, b= 0, X= S 일 때)4. Synthesis Example of Sub 1-5 (when a = 1, b = 0, X = S)

Figure pat00123
Figure pat00123

Sub 1-5의 합성법Synthesis of Sub 1-5

둥근바닥플라스크에 Sub 1-II-1 (30.6 g 87 mmol), 2-Bromonaphthalene (21.5 g, 104 mmol), Pd2(dba)3 (3.2 g, 3.5 mmol), P(t-Bu)3 (1.8 g, 8.7 mmol), NaO(t-Bu) (25 g, 261 mmol), Toluene (300 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-5 (29.1 g, 70%)를 얻었다.Round bottom flask with Sub 1-II-1 (30.6 g 87 mmol), 2-Bromonaphthalene (21.5 g, 104 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 by (3.2 g, 3.5 mmol), P (t-Bu) 3 (1.8 g, 8.7 mmol), NaO (t-Bu) (25 g, 261 mmol), Toluene (300 mL) Using the method, product Sub 1-5 (29.1 g, 70%) was obtained.

5. Sub 1-6의 합성예 (a=1, b= 0, X= S 일 때)5. Synthesis Example of Sub 1-6 (when a = 1, b = 0, X = S)

Figure pat00124
Figure pat00124

(1) Sub 1-I-6의 합성법 (a=1, b= 0, X= S 일 때)(1) Synthesis of Sub 1-I-6 (when a = 1, b = 0, X = S)

둥근바닥플라스크에 2-Chloroaniline (22.4 g, 175 mmol), 2,4-Dibromodibenzothiophene (50 g, 146 mmol),　Pd2(dba)3 (5.4 g, 5.8 mmol), P(t-Bu)3 (5 g, 14.6 mmol), NaO(t-Bu) (42 g, 439 mmol), Toluene (500 mL)을 상기 Sub 1-I-1의 합성방법을 사용하여 생성물 Sub 1-I-6 (46 g, 90%)을 얻었다.Round-bottomed flask 2-Chloroaniline (22.4 g, 175 mmol), 2,4-Dibromodibenzothiophene (50 g, 146 mmol), Pd 2 (dba) 3 (5.4 g, 5.8 mmol), P (t-Bu) 3 (5 g, 14.6 mmol), NaO (t-Bu) (42 g, 439 mmol), Toluene (500 mL) above Sub 1-I-1 Synthesis of to obtain the product Sub 1-I-6 (46 g, 90%).

(2) Sub 1-II-6의 합성법(2) Synthesis of Sub 1-II-6

둥근바닥플라스크에 Sub 1-I-6 (45 g, 116 mmol), PPh3 (76 g, 289 mmol), o-Dichlorobenzene (300 mL)을 상기 Sub 1-II-1의 합성방법을 사용하여 생성물 Sub 1-II-6 (32.6 g, 80%)을 얻었다.Round bottom flask with Sub 1-I-6 (45 g, 116 mmol), PPh 3 (76 g, 289 mmol), o -Dichlorobenzene (300 mL) was obtained using the synthesis method of Sub 1-II-1 to obtain the product Sub 1-II-6 (32.6 g, 80%).

(3) Sub 1-6의 합성법(3) Synthesis of Sub 1-6

둥근바닥플라스크에 Sub 1-II-6 (10 g, 28 mmol), Iodobenzene (6.9 g, 34 mmol), Pd2(dba)3 (1 g, 1.1 mmol), P(t-Bu)3 (0.6 g, 2.8 mmol), NaO(t-Bu) (8.2 g, 85 mmol), Toluene (80 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-6 (10 g, 84%)를 얻었다.Round bottom flask with Sub 1-II-6 (10 g, 28 mmol), Iodobenzene (6.9 g, 34 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 by (1 g, 1.1 mmol), P (t-Bu) 3 (0.6 g, 2.8 mmol), NaO (t-Bu) (8.2 g, 85 mmol), Toluene (80 mL) Method Sub 1-6 (10 g, 84%) was obtained.

6. Sub 1-7의 합성예 (a=1, b= 0, X= S 일 때)6. Synthesis Example of Sub 1-7 (when a = 1, b = 0, X = S)

Figure pat00125
Figure pat00125

Sub 1-7의 합성법Synthesis of Sub 1-7

둥근바닥플라스크에 Sub 1-II-6 (10 g, 28 mmol), 4-Iodo-1,1'-biphenyl (9.5 g, 34 mmol), Pd2(dba)3 (1 g, 1.1 mmol), P(t-Bu)3 (0.6 g, 2.8 mmol), NaO(t-Bu) (8.2 g, 85 mmol), Toluene (80 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-7 (10 g, 71%)를 얻었다.Round bottom flask with Sub 1-II-6 (10 g, 28 mmol), 4-Iodo-1,1'-biphenyl (9.5 g, 34 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 by (1 g, 1.1 mmol), P (t-Bu) 3 (0.6 g, 2.8 mmol), NaO (t-Bu) (8.2 g, 85 mmol), Toluene (80 mL) Using the method the product Sub 1-7 (10 g, 71%) was obtained.

7. Sub 1-14의 합성예 (a=1, b= 0, X= S 일 때)7. Synthesis Example of Sub 1-14 (when a = 1, b = 0, X = S)

Figure pat00126
Figure pat00126

(1) Sub 1-I-14의 합성법(1) Synthesis of Sub 1-I-14

둥근바닥플라스크에 2-Chloronaphthalen-1-amine (31 g, 175 mmol), 2,4-Dibromodibenzothiophene (50 g, 146 mmol),　Pd2(dba)3 (5.4 g, 5.8 mmol), P(t-Bu)3 (5 g, 14.6 mmol), NaO(t-Bu) (42 g, 439 mmol), Toluene (500 mL)을 상기 Sub 1-I-1의 합성방법을 사용하여 생성물 Sub 1-I-14 (48 g, 75%)을 얻었다.2-Chloronaphthalen-1-amine (31 g, 175 mmol), 2,4-Dibromodibenzothiophene (50 g, 146 mmol), Pd 2 (dba) 3 in a round bottom flask (5.4 g, 5.8 mmol), P (t-Bu) 3 (5 g, 14.6 mmol), NaO (t-Bu) (42 g, 439 mmol), Toluene (500 mL) above Sub 1-I-1 Synthesis of to obtain the product Sub 1-I-14 (48 g, 75%).

(2) Sub 1-II-14의 합성법(2) Synthesis of Sub 1-II-14

둥근바닥플라스크에 Sub 1-I-14 (30 g, 68 mmol), PPh3 (45 g, 171 mmol), o-Dichlorobenzene (150 mL)을 넣는다. 그런 후에 180℃ 상태에서 24시간 동안 가열 환류시킨다. 반응이 종결되면 상온으로 식힌 후, 농축한다. 농축되어 생성된 화합물을 silica column 및 재결정하여 생성물 Sub 1-II-14 (25 g, 93%)을 얻었다.Round bottom flask with Sub 1-I-14 (30 g, 68 mmol), PPh 3 (45 g, 171 mmol), o -Dichlorobenzene (150 mL) was added. Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 1-II-14 (25 g, 93%).

(3) Sub 1-14의 합성법(3) Synthesis of Sub 1-14

둥근바닥플라스크에 Sub 1-II-14 (25 g, 62 mmol), Iodobenzene (15 g 75mmo), Pd2(dba)3 (2.g, 2.5 mmol), P(t-Bu)3 (1.3 g (6.2 mmol), NaO(t-Bu) (18 g, 186 mmol), Toluene (300 mL)을 넣는다. 그런 후에 110℃ 상태에서 8시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 1-14 (20 g, 67%)를 얻었다.Round bottom flask with Sub 1-II-14 (25 g, 62 mmol), Iodobenzene (15 g 75mmo), Pd 2 (dba) 3 (2.g, 2.5 mmol), P (t-Bu) 3 (1.3 g (6.2 mmol), NaO (t-Bu) (18 g, 186 mmol), Toluene (300 mL) was added. Heat reflux for 8 hours in the state When the reaction is completed, dilute it with distilled water at room temperature and extract with Methylene chloride and water.The organic layer is concentrated by drying with MgSO 4 , and the resulting compound is recrystallized with Methylene chloride and Hexane to sub 1-14 (20 g, 67%) was obtained.

8. Sub 1-29의 합성예 (a=1, b= 0, X= C 일 때)8. Synthesis Example of Sub 1-29 (when a = 1, b = 0, X = C)

Figure pat00127
Figure pat00127

(1) Sub 1-I-29의 합성법(1) Synthesis of Sub 1-I-29

둥근바닥플라스크에 2-Chloronaphthalen-1-amine (31 g, 175 mmol), 1,4-dibromo-9,9-dimethyl-9H-fluorene (51 g, 146 mmol),　Pd2(dba)3 (5.4 g, 5.8 mmol), P(t-Bu)3 (5 g, 14.6 mmol), NaO(t-Bu) (42 g, 439 mmol), Toluene (500 mL)을 상기 Sub 1-I-1의 합성방법을 사용하여 생성물 Sub 1-I-29 (36 g, 63%)을 얻었다.2-Chloronaphthalen-1-amine (31 g, 175 mmol), 1,4-dibromo-9,9-dimethyl-9H-fluorene (51 g, 146 mmol), Pd 2 (dba) 3 in a round bottom flask (5.4 g, 5.8 mmol), P (t-Bu) 3 (5 g, 14.6 mmol), NaO (t-Bu) (42 g, 439 mmol), Toluene (500 mL) above Sub 1-I-1 Using the synthesis method for obtaining the product Sub 1-I-29 (36 g, 63%).

(2) Sub 1-II-29의 합성법(2) Synthesis of Sub 1-II-29

둥근바닥플라스크에 Sub 1-I-29 (27 g, 68 mmol), PPh3 (45 g, 171 mmol), o-Dichlorobenzene (150 mL)을 상기 Sub 1-II-1의 합성방법을 사용하여 생성물 Sub 1-II-29 (22 g, 92%)을 얻었다.Round bottom flask with Sub 1-I-29 (27 g, 68 mmol), PPh 3 (45 g, 171 mmol), o -Dichlorobenzene (150 mL) was obtained using the synthesis method of Sub 1-II-1 to obtain the product Sub 1-II-29 (22 g, 92%).

(3) Sub 1-29의 합성법(3) Synthesis of Sub 1-29

둥근바닥플라스크에 Sub 1-II-29 (22 g, 62 mmol), 2-Bromonaphthalene (15 g 74mmo), Pd2(dba)3 (2.g, 2.5 mmol), P(t-Bu)3 (1.3 g (6.2 mmol), NaO(t-Bu) (18 g, 186 mmol), Toluene (300 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-29 (20 g, 67%)를 얻었다.Round bottom flask with Sub 1-II-29 (22 g, 62 mmol), 2-Bromonaphthalene (15 g 74mmo), Pd 2 (dba) 3 (2.g, 2.5 mmol), P (t-Bu) 3 (1.3 g (6.2 mmol), NaO (t-Bu) (18 g, 186 mmol), Toluene (300 mL) of Sub 1-1 Using the synthesis method, product Sub 1-29 (20 g, 67%) was obtained.

9. Sub 1-25의 합성예 (a= 1, b= 0, X= O 일 때)9. Synthesis Example of Sub 1-25 (when a = 1, b = 0, X = O)

Figure pat00128
Figure pat00128

(1) Sub 1-I-25의 합성법(1) Synthesis of Sub 1-I-25

둥근바닥플라스크에 2-Chloronaphthalen-1-amine (23.45 g, 183.85 mmol), 1,4-dibromodibenzo[b,d]furan (50 g, 153.4 mmol),　Pd2(dba)3 (5.58 g, 6.1 mmol), P(t-Bu)3 (3.1 g, 15.34 mmol), NaO(t-Bu) (44.32 g, 461.2 mmol), Toluene (340 mL)을 상기 Sub 1-I-1의 합성방법을 이용하여 생성물 Sub 1-I-25 (41.7 g, 73%)을 얻었다.2-Chloronaphthalen-1-amine (23.45 g, 183.85 mmol), 1,4-dibromodibenzo [b, d] furan (50 g, 153.4 mmol), Pd 2 (dba) 3 in a round bottom flask (5.58 g, 6.1 mmol), P (t-Bu) 3 (3.1 g, 15.34 mmol), NaO (t-Bu) (44.32 g, 461.2 mmol), Toluene (340 mL) above Sub 1-I-1 Synthesis of to obtain the product Sub 1-I-25 (41.7 g, 73%).

(2) Sub 1-II-25의 합성법(2) Synthesis of Sub 1-II-25

둥근바닥플라스크에 Sub 1-I-25 (47 g, 126.1 mmol), PPh3 (82.7 g, 315.3 mmol), o-Dichlorobenzene (505 mL)을 상기 Sub 1-II-1의 합성방법을 이용하여 생성물 Sub 1-II-25 (35.62 g, 84 %)을 얻었다.Round bottom flask with Sub 1-I-25 (47 g, 126.1 mmol), PPh 3 (82.7 g, 315.3 mmol), o -Dichlorobenzene (505 mL) was obtained using the synthesis method of Sub 1-II-1 to obtain the product Sub 1-II-25 (35.62 g, 84%).

(3) Sub 1-25의 합성(3) Synthesis of Sub 1-25

둥근바닥플라스크에 Sub 1-II-25 (47 g, 126.13 mmol), Bromobenzene (19.59 g 124.79 mmol), Pd2(dba)3 (3.79 g, 4.14 mmol), P(t-Bu)3 (2.11 g, 10.4 mmol), NaO(t-Bu) (30.08 g, 313.045 mmol), Toluene (230 mL)을 상기 Sub 1-1의 합성방법을 사용하여 생성물 Sub 1-25 (34.77 g, 82 %)를 얻었다.Round bottom flask Sub 1-II-25 (47 g, 126.13 mmol), Bromobenzene (19.59 g 124.79 mmol), Pd 2 (dba) 3 Synthesis of Sub 1-1 (3.79 g, 4.14 mmol), P (t-Bu) 3 (2.11 g, 10.4 mmol), NaO (t-Bu) (30.08 g, 313.045 mmol), Toluene (230 mL) Using the method the product Sub 1-25 (34.77 g, 82%) was obtained.

Sub 1의 예시Sub 1 example

한편, Sub 1에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 1은 Sub 1에 속하는 화합물의 FD-MS 값을 나타낸 것이다.Meanwhile, the compound belonging to Sub 1 may be the following compound, but is not limited thereto, and Table 1 shows the FD-MS value of the compound belonging to Sub 1.

Figure pat00129
Figure pat00129

Figure pat00130
Figure pat00130

Figure pat00131
Figure pat00131

Figure pat00132
Figure pat00132

Figure pat00133
Figure pat00133

Figure pat00134
Figure pat00134

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 1-1Sub 1-1 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 1-2Sub 1-2 m/z=427.00(C24HBrNS=428.34)m / z = 427.00 (C24HBrNS = 428.34) Sub 1-3Sub 1-3 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 1-4Sub 1-4 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 1-5Sub 1-5 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 1-6Sub 1-6 m/z=427.00(C24HBrNS=428.34)m / z = 427.00 (C24HBrNS = 428.34) Sub 1-7Sub 1-7 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 1-8Sub 1-8 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 1-9Sub 1-9 m/z=477.02(C28H16BrNS=478.40))m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 1-10Sub 1-10 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 1-11Sub 1-11 m/z=605.06(C36H20BrN3S =606.53)m / z = 605.06 (C 36 H 20 BrN 3 S = 606.53) Sub 1-12Sub 1-12 m/z=555.04(C32H18BrN3S=556.47)m / z = 555.04 (C 32 H 18 BrN 3 S = 556.47) Sub 1-13Sub 1-13 m/z=603.07(C38H22BrNS=604.56)m / z = 603.07 (C 38 H 22 BrNS = 604.56) Sub 1-14Sub 1-14 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 1-15Sub 1-15 m/z=527.03(C32H18BrNS=528.46)m / z = 527.03 (C 32 H 18 BrNS = 528.46) Sub 1-16Sub 1-16 m/z=629.08(C40H24BrNS=630.59)m / z = 629.08 (C 40 H 24 BrNS = 630.59) Sub 1-17Sub 1-17 m/z=554.05C33H19BrN2S=555.49)m / z = 554.05C 33 H 19 BrN 2 S = 555.49) Sub 1-18Sub 1-18 m/z=734.11(C45H27BrN4S=735.69)m / z = 734.11 (C 45 H 27 BrN 4 S = 735.69) Sub 1-19Sub 1-19 m/z=721.08(C44H24BrN3OS=722.65)m / z = 721.08 (C 44 H 24 BrN 3 OS = 722.65) Sub 1-20Sub 1-20 m/z=629.08(C40H24BrNS=630.59)m / z = 629.08 (C 40 H 24 BrNS = 630.59) Sub 1-21Sub 1-21 m/z=529.02(C30H16BrN3S=530.44)m / z = 529.02 (C 30 H 16 BrN 3 S = 530.44) Sub 1-22Sub 1-22 m/z=555.04(C32H18BrN3S=556.47)m / z = 555.04 (C 32 H 18 BrN 3 S = 556.47) Sub 1-23Sub 1-23 m/z=581.06(C34H20BrN3S=582.51)m / z = 581.06 (C 34 H 20 BrN 3 S = 582.51) Sub 1-24Sub 1-24 m/z=600.06(C33H21BrN4OS=601.52)m / z = 600.06 (C 33 H 21 BrN 4 OS = 601.52) Sub 1-25Sub 1-25 m/z=411.03(C24H14BrNO=412.28)m / z = 411.03 (C 24 H 14 BrNO = 412.28) Sub 1-26Sub 1-26 m/z=671.07(C40H22BrN3OS=672.59)m / z = 671.07 (C 40 H 22 BrN 3 OS = 672.59) Sub 1-27Sub 1-27 m/z=593.04(C36H20BrNOS=594.52)m / z = 593.04 (C 36 H 20 BrNOS = 594.52) Sub 1-28Sub 1-28 m/z=437.08(C27H20BrN=438.36)m / z = 437.08 (C 27 H 20 BrN = 438.36) Sub 1-29Sub 1-29 m/z=487.09(C31H22BrN=488.42)m / z = 487.09 (C 31 H 22 BrN = 488.42) Sub 1-30Sub 1-30 m/z=453.05(C26H20BrNSi=454.43)m / z = 453.05 (C 26 H 20 BrNSi = 454.43) Sub 1-31Sub 1-31 m/z=474.95(C24H14BrNSe=475.24)m / z = 474.95 (C 24 H 14 BrNSe = 475.24)

2. Sub 2의 합성 예시2. Synthesis Example of Sub 2

반응식 1의 sub 2는 하기 반응식 3의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다.Sub 2 of Scheme 1 may be synthesized by the following Reaction Scheme 3, but is not limited thereto.

<반응식 3> (X'= I, Br, Cl)<Scheme 3> (X '= I, Br, Cl)

Figure pat00135
Figure pat00135

Figure pat00136
Figure pat00136

상기 반응식 3의 Sub 2에 속하는 화합물의 합성예는 다음과 같다.Synthesis examples of compounds belonging to Sub 2 of Scheme 3 are as follows.

1. Sub 2-1의 합성예 (a= 0, b=1, Y=S인 경우)1. Synthesis Example of Sub 2-1 (a = 0, b = 1, Y = S)

Figure pat00137
Figure pat00137

Figure pat00138
Figure pat00138

(1) Sub 2-I-1의 합성법(1) Synthesis of Sub 2-I-1

둥근바닥플라스크에 2-Bromodibenzothiophene (100 g, 380 mmol), 2-Nitrophenyl boronic acid (76 g, 456 mmol), Pd(PPh3)4 (18 g, 15 mmol), NaOH (46 g, 1140 mmol), THF (1.2 L)/H2O (0.6 L)을 넣는다. 그런 후에 70℃ 상태에서 4시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 2-I-1 (99 g, 85%)을 얻었다.2-Bromodibenzothiophene (100 g, 380 mmol), 2-Nitrophenyl boronic acid (76 g, 456 mmol), Pd (PPh 3 ) 4 in a round bottom flask 4 (18 g, 15 mmol), NaOH (46 g, 1140 mmol), THF (1.2 L) / H 2 O (0.6 L) are added. Then, the mixture was heated to reflux for 4 hours at 70 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 2-I-1 (99 g, 85%).

(2) Sub 2-II-1의 합성법(2) Synthesis of Sub 2-II-1

둥근바닥플라스크에 Sub 2-I-1 (99 g, 323 mmol), PPh3 (218 g, 808 mmol), o-Dichlorobenzene (1.0 L)을 넣는다. 그런 후에 180℃ 상태에서 24시간 동안 가열 환류시킨다. 반응이 종결되면 상온으로 식힌 후, 농축한다. 농축되어 생성된 화합물을 silica column 및 재결정하여 생성물 Sub 2-II-1 (70 g, 80%)을 얻었다.Round bottom flask Sub 2-I-1 (99 g, 323 mmol), PPh 3 (218 g, 808 mmol), o -Dichlorobenzene (1.0 L) was added. Then, the mixture was heated to reflux for 24 hours at 180 ° C. After the reaction is completed, it is cooled to room temperature and concentrated. The resulting compound was concentrated to silica column and recrystallized to obtain the product Sub 2-II-1 (70 g, 80%).

(3) Sub 2-III-1의 합성법(3) Synthesis of Sub 2-III-1

둥근바닥플라스크에 Sub 2-II-1 (70 g, 293 mmol), N-Bromosuccinimide (52 g, 293 mmol), Methylene chloride (1 L)를 넣는다. 그런 후에 상온에서 4시간 동안 교반한다. 반응이 완료되면 증류수를 넣은 후, Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 2-III-1 (86 g, 83%)을 얻었다.To the round bottom flask, add Sub 2-II-1 (70 g, 293 mmol), N-Bromosuccinimide (52 g, 293 mmol), and Methylene chloride (1 L). Then, the mixture was stirred at room temperature for 4 hours. After the reaction is completed, distilled water is added and then extracted with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain the product Sub 2-III-1 (86 g, 83%).

(4) Sub 2-1의 합성법(4) Sub 2-1 synthesis method

둥근바닥플라스크에 Sub 2-III-1 (30 g, 84 mmol), Iodobenzene (20.7 g, 102 mmol), Pd2(dba)3 (3 g, 3.3 mmol), P(t-Bu)3 (1.8 g, 8.4 mmol), NaO(t-Bu) (24.6 g, 255 mmol), Toluene (240 mL)을 넣는다. 그런 후에 110℃ 상태에서 8시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Methylene chloride와 Hexane으로 재결정하여 생성물 Sub 2-1 (28 g, 76%)를 얻었다.Round bottom flask Sub 2-III-1 (30 g, 84 mmol), Iodobenzene (20.7 g, 102 mmol), Pd 2 (dba) 3 (3 g, 3.3 mmol), P (t-Bu) 3 (1.8 g, 8.4 mmol), NaO (t-Bu) (24.6 g, 255 mmol), Toluene (240 mL) was added. Then, the mixture was heated to reflux for 8 hours at 110 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Methylene chloride and Hexane to obtain product Sub 2-1 (28 g, 76%).

2. Sub 2-2의 합성예 (a= 0, b=1, Y=S인 경우)2. Synthesis Example of Sub 2-2 (a = 0, b = 1, Y = S)

Figure pat00139
Figure pat00139

Sub 2-2의 합성법Synthesis of Sub 2-2

둥근바닥플라스크에 Sub 2-III-1 (30 g, 84 mmol), 4-Iodo-1,1'-biphenyl (28.6 g, 102 mmol), Pd2(dba)3 (3 g, 3.3 mmol), P(t-Bu)3 (1.8 g, 8.4 mmol), NaO(t-Bu) (24.6 g, 255 mmol), Toluene (240 mL)을 상기 Sub 2-1의 합성방법을 사용하여 생성물 Sub 2-2 (32 g, 76%)를 얻었다.In a round bottom flask, Sub 2-III-1 (30 g, 84 mmol), 4-Iodo-1,1'-biphenyl (28.6 g, 102 mmol), Pd 2 (dba) 3 Synthesis of Sub 2-1 (3 g, 3.3 mmol), P (t-Bu) 3 (1.8 g, 8.4 mmol), NaO (t-Bu) (24.6 g, 255 mmol), Toluene (240 mL) The method was used to give the product Sub 2-2 (32 g, 76%).

3. Sub 2-3의 합성예 (a= 0, b=1, Y=S인 경우)3. Synthesis Example of Sub 2-3 (when a = 0, b = 1, Y = S)

Figure pat00140
Figure pat00140

Sub 2-3의 합성법Synthesis of Sub 2-3

둥근바닥플라스크에 Sub 2-III-1 (30 g, 84 mmol), 3-Bromo-1,1'-biphenyl (23.8 g, 102 mmol), Pd2(dba)3 (3 g, 3.3 mmol), P(t-Bu)3 (1.8 g, 8.4 mmol), NaO(t-Bu) (24.6 g, 255 mmol), Toluene (240 mL)을 상기 Sub 2-1의 합성방법을 사용하여 생성물 Sub 2-3 (34 g, 80%)를 얻었다.Round bottom flask Sub 2-III-1 (30 g, 84 mmol), 3-Bromo-1,1'-biphenyl (23.8 g, 102 mmol), Pd 2 (dba) 3 Synthesis of Sub 2-1 (3 g, 3.3 mmol), P (t-Bu) 3 (1.8 g, 8.4 mmol), NaO (t-Bu) (24.6 g, 255 mmol), Toluene (240 mL) Using the method, product Sub 2-3 (34 g, 80%) was obtained.

4. Sub 2-37의 합성예 (a= 0, b=1, Y=O인 경우)4. Synthesis Example of Sub 2-37 (a = 0, b = 1, Y = O)

Figure pat00141
Figure pat00141

Figure pat00142
Figure pat00142

(1) Sub 2-I-37의 합성법(1) Synthesis of Sub 2-I-37

둥근바닥플라스크에 2-Bromodibenzofuran (50 g, 202 mmol), 2-Nitrophenyl boronic acid (40.5 g, 242 mmol), Pd(PPh3)4 (9.3 g, 8 mmol), NaOH (24 g, 606 mmol), THF (600 mL)/H2O (300 mL)을 상기 Sub 2-I-1의 합성방법을 사용하여 생성물 Sub 2-I-37 (43 g, 74%)을 얻었다.2-Bromodibenzofuran (50 g, 202 mmol), 2-Nitrophenyl boronic acid (40.5 g, 242 mmol), Pd (PPh 3 ) 4 in a round bottom flask 4 (9.3 g, 8 mmol), NaOH (24 g, 606 mmol), THF (600 mL) / H 2 O (300 mL) using the synthesis method of Sub 2-I-1 above, Sub 2-I- 37 (43 g, 74%).

(2) Sub 2-II-37의 합성법(2) Synthesis of Sub 2-II-37

둥근바닥플라스크에 Sub 2-I-37 (43 g, 110 mmol), PPh3 (72 g, 276 mmol), o-Dichlorobenzene (350 mL)을 상기 Sub 2-II-1의 합성방법을 사용하여 생성물 Sub 2-II-37 (23 g, 82%)을 얻었다.Round bottom flask Sub 2-I-37 (43 g, 110 mmol), PPh 3 (72 g, 276 mmol), o -Dichlorobenzene (350 mL) was obtained using the synthesis method of Sub 2-II-1 to obtain the product Sub 2-II-37 (23 g, 82%).

(3) Sub 2-III-37의 합성법(3) Synthesis of Sub 2-III-37

둥근바닥플라스크에 Sub 2-II-37 (23 g, 89 mmol), N-Bromosuccinimide (16 g, 89 mmol), Methylene chloride (300 mL)를 상기 Sub 2-III-1의 합성방법을 사용하여 생성물 Sub 2-III-37 (21 g, 70%)을 얻었다.Sub-II-37 (23 g, 89 mmol), N-Bromosuccinimide (16 g, 89 mmol) and Methylene chloride (300 mL) were added to the round bottom flask using the synthesis method of Sub 2-III-1. Sub 2-III-37 (21 g, 70%) was obtained.

(4) Sub 2-37의 합성법(4) Synthesis of Sub 2-37

둥근바닥플라스크에 Sub 2-III-37 (21 g, 62 mmol), Iodobenzene (15.3 g, 75 mmol), Pd2(dba)3 (2.3 g, 2.5 mmol), P(t-Bu)3 (1.3 g, 6.2 mmol), NaO(t-Bu) (18 g, 187 mmol), Toluene (200 mL)을 상기 Sub 2-1의 합성방법을 사용하여 생성물 Sub 2-37 (16 g, 63%)를 얻었다.Round-bottomed flask Sub 2-III-37 (21 g, 62 mmol), Iodobenzene (15.3 g, 75 mmol), Pd 2 (dba) 3 Synthesis of Sub 2-1 (2.3 g, 2.5 mmol), P (t-Bu) 3 (1.3 g, 6.2 mmol), NaO (t-Bu) (18 g, 187 mmol), Toluene (200 mL) The method was used to give the product Sub 2-37 (16 g, 63%).

5. Sub 2-144의 합성예 (a= 0, b=1, Y=C인 경우)5. Synthesis Example of Sub 2-144 (a = 0, b = 1, Y = C)

Figure pat00143
Figure pat00143

Figure pat00144
Figure pat00144

(1) Sub 2-I-144의 합성법(1) Synthesis of Sub 2-I-144

둥근바닥플라스크에 3-bromo-9,9-dimethyl-9H-fluorene (50 g, 183.04 mmol), 2-Nitrophenyl boronic acid (36.6 g, 219.28 mmol), Pd(PPh3)4 (8.4 g, 7.25 mmol), NaOH (22 g, 549.11 mmol), THF (805 mL)/H2O (402 mL)을 상기 Sub 2-I-1 합성방법을 사용하여 생성물 Sub 2-I-144 (47.72 g, 69 %)을 얻었다.3-bromo-9,9-dimethyl-9H-fluorene (50 g, 183.04 mmol), 2-Nitrophenyl boronic acid (36.6 g, 219.28 mmol), Pd (PPh 3 ) 4 in a round bottom flask 4 (8.4 g, 7.25 mmol), NaOH (22 g, 549.11 mmol), THF (805 mL) / H 2 O (402 mL) using the above Sub 2-I-1 synthesis method, product Sub 2-I-144 (47.72 g, 69%).

(2) Sub 2-II-144의 합성법(2) Synthesis of Sub 2-II-144

둥근바닥플라스크에 Sub 2-I-144 (47 g, 149 mmol), PPh3 (97.7 g, 372.48 mmol), o-Dichlorobenzene (596 mL)을 상기 Sub 2-II-1의 합성방법을 사용하여 생성물 Sub 2-II-144 (30.41 g, 72 %)을 얻었다.Round bottom flask Sub 2-I-144 (47 g, 149 mmol), PPh 3 (97.7 g, 372.48 mmol), o -Dichlorobenzene (596 mL) was obtained using the synthesis method of Sub 2-II-1 to obtain the product Sub 2-II-144 (30.41 g, 72%).

(3) Sub 2-III-144의 합성법(3) Synthesis of Sub 2-III-144

둥근바닥플라스크에 Sub 2-II-144 (30 g, 89 mmol), N-Bromosuccinimide (18.8 g, 105.9 mmol), Methylene chloride (318 mL)를 상기 Sub 2-III-1의 합성방법을 이용하여 생성물 Sub 2-III-144 (18.24 g, 53 %)을 얻었다.To the round bottom flask, Sub 2-II-144 (30 g, 89 mmol), N-Bromosuccinimide (18.8 g, 105.9 mmol), Methylene chloride (318 mL) were prepared using the synthesis method of Sub 2-III-1. Sub 2-III-144 (18.24 g, 53%) was obtained.

(4) Sub 2-144의 합성법(4) Synthesis of Sub 2-144

둥근바닥플라스크에 Sub 2-III-144 (18 g, 49.7 mmol), Iodobenzene (12.26 g, 60.1 mmol), Pd2(dba)3 (1.83 g, 2 mmol), P(t-Bu)3 (1.01 g, 4.97 mmol), NaO(t-Bu) (14.4 g, 149.9 mmol), Toluene (109 mL)을 상기 Sub 2-1의 합성방법을 사용하여 생성물 Sub 2-144 (15.03 g, 69%)를 얻었다.In a round bottom flask, Sub 2-III-144 (18 g, 49.7 mmol), Iodobenzene (12.26 g, 60.1 mmol), Pd 2 (dba) 3 Synthesis of Sub 2-1 (1.83 g, 2 mmol), P (t-Bu) 3 (1.01 g, 4.97 mmol), NaO (t-Bu) (14.4 g, 149.9 mmol), Toluene (109 mL) The method was used to give the product Sub 2-144 (15.03 g, 69%).

Sub 2의 예시Sub 2 example

한편, Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 2는 Sub 2에 속하는 화합물의 FD-MS 값을 나타낸 것이다.Meanwhile, the compound belonging to Sub 2 may be the following compound, but is not limited thereto, and Table 2 shows the FD-MS value of the compound belonging to Sub 2.

Figure pat00145
Figure pat00145

Figure pat00146
Figure pat00146

Figure pat00147
Figure pat00147

Figure pat00148
Figure pat00148

Figure pat00149
Figure pat00149

Figure pat00150
Figure pat00150

Figure pat00151
Figure pat00151

Figure pat00152
Figure pat00152

Figure pat00153
Figure pat00153

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 2-1Sub 2-1 m/z=427.00(C24HBrNS=428.34)m / z = 427.00 (C24HBrNS = 428.34) Sub 2-2Sub 2-2 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-3Sub 2-3 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-4Sub 2-4 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 2-5Sub 2-5 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 2-6Sub 2-6 m/z=483.07(C28H22BrNS=484.45)m / z = 483.07 (C 28 H 22 BrNS = 484.45) Sub 2-7Sub 2-7 m/z=507.03(C29H18BrNOS=508.43)m / z = 507.03 (C 29 H 18 BrNOS = 508.43) Sub 2-8Sub 2-8 m/z=467.03(C27H18BrNS=468.41)m / z = 467.03 (C 27 H 18 BrNS = 468.41) Sub 2-9Sub 2-9 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-10Sub 2-10 m/z=427.00(C24HBrNS=428.34)m / z = 427.00 (C24HBrNS = 428.34) Sub 2-11Sub 2-11 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-12Sub 2-12 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-13Sub 2-13 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 2-14Sub 2-14 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 2-15Sub 2-15 m/z=582.05(C33H19BrN4S=583.50)m / z = 582.05 (C 33 H 19 BrN 4 S = 583.50) Sub 2-16Sub 2-16 m/z=581.06(C34H20BrN3S=582.51)m / z = 581.06 (C 34 H 20 BrN 3 S = 582.51) Sub 2-17Sub 2-17 m/z=581.06(C34H20BrN3S=582.51)m / z = 581.06 (C 34 H 20 BrN 3 S = 582.51) Sub 2-18Sub 2-18 m/z=581.06(C34H20BrN3S=582.51)m / z = 581.06 (C 34 H 20 BrN 3 S = 582.51) Sub 2-19Sub 2-19 m/z=555.04(C32H18BrN3S=556.47)m / z = 555.04 (C 32 H 18 BrN 3 S = 556.47) Sub 2-20Sub 2-20 m/z=611.01(C34H18BrN3S2=612.56)m / z = 611.01 (C 34 H 18 BrN 3 S 2 = 612.56) Sub 2-21Sub 2-21 m/z=681.09(C42H24BrN3S=682.63)m / z = 681.09 (C 42 H 24 BrN 3 S = 682.63) Sub 2-22Sub 2-22 m/z=542.05(C32H19BrN2S=543.48)m / z = 542.05 (C 32 H 19 BrN 2 S = 543.48) Sub 2-23Sub 2-23 m/z=665.08(C43H24BrNS=666.63)m / z = 665.08 (C 43 H 24 BrNS = 666.63) Sub 2-24Sub 2-24 m/z=599.11(C36H18D5BrN2S=600.58)m / z = 599.11 (C 36 H 18 D 5 BrN 2 S = 600.58) Sub 2-25Sub 2-25 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-26Sub 2-26 m/z=502.01(C29H15BrN2S=503.41)m / z = 502.01 (C 29 H 15 BrN 2 S = 503.41) Sub 2-27Sub 2-27 m/z=629.08(C40H24BrNS=630.59)m / z = 629.08 (C 40 H 24 BrNS = 630.59) Sub 2-28Sub 2-28 m/z=605.06(C36H20BrN3S =606.53)m / z = 605.06 (C 36 H 20 BrN 3 S = 606.53) Sub 2-29Sub 2-29 m/z=657.09(C40H24BrN3S=658.61)m / z = 657.09 (C 40 H 24 BrN 3 S = 658.61) Sub 2-30Sub 2-30 m/z=631.07(C38H22BrN3S=632.57)m / z = 631.07 (C 38 H 22 BrN 3 S = 632.57) Sub 2-31Sub 2-31 m/z=720.09(C45H25BrN2OS=721.66)m / z = 720.09 (C 45 H 25 BrN 2 OS = 721.66) Sub 2-32Sub 2-32 m/z=593.08(C37H24BrNS=594.56)m / z = 593.08 (C 37 H 24 BrNS = 594.56) Sub 2-33Sub 2-33 m/z=471.99(C24H13BrN2O2S=473.34)m / z = 471.99 (C 24 H 13 BrN 2 O 2 S = 473.34) Sub 2-34Sub 2-34 m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) Sub 2-35Sub 2-35 m/z=477.02(C28H16BrNS=478.40)m / z = 477.02 (C 28 H 16 BrNS = 478.40) Sub 2-36Sub 2-36 m/z=508.07(C30H13D5BrNS=509.47)m / z = 508.07 (C 30 H 13 D 5 BrNS = 509.47) Sub 2-37Sub 2-37 m/z=411.03(C24H14BrNO=412.28)m / z = 411.03 (C 24 H 14 BrNO = 412.28) Sub 2-38Sub 2-38 m/z=655.09(C40H22BrN3O2=656.53)m / z = 655.09 (C 40 H 22 BrN 3 O 2 = 656.53) Sub 2-39Sub 2-39 m/z=539.06(C32H18BrN3O=540.41)m / z = 539.06 (C 32 H 18 BrN 3 O = 540.41) Sub 2-40Sub 2-40 m/z=645.05(C38H20BrN3OS=646.55)m / z = 645.05 (C 38 H 20 BrN 3 OS = 646.55) Sub 2-41Sub 2-41 m/z=461.04(C28H16BrNO=462.34)m / z = 461.04 (C 28 H 16 BrNO = 462.34) Sub 2-42Sub 2-42 m/z=487.06(C30H18BrNO=488.37)m / z = 487.06 (C 30 H 18 BrNO = 488.37) Sub 2-43Sub 2-43 m/z=537.07(C34H20BrNO=538.43)m / z = 537.07 (C 34 H 20 BrNO = 538.43) Sub 2-44Sub 2-44 m/z=437.08(C27H20BrN=438.36)m / z = 437.08 (C 27 H 20 BrN = 438.36) Sub 2-45Sub 2-45 m/z=453.05(C20H20BrNSi=453.43)m / z = 453.05 (C 20 H 20 BrNSi = 453.43) Sub 2-46Sub 2-46 m/z=474.95(C24H14BrNSi=478.24)m / z = 474.95 (C 24 H 14 BrNSi = 478.24)

Sub 3의 예시Sub 3 example

한편, Sub 3에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 3은 Sub 3에 속하는 화합물의 FD-MS 값을 나타낸 것이다.Meanwhile, the compound belonging to Sub 3 may be the following compound, but is not limited thereto, and Table 3 shows the FD-MS value of the compound belonging to Sub 3.

Figure pat00154
Figure pat00154

Figure pat00155
Figure pat00155

Figure pat00156
Figure pat00156

Figure pat00157
Figure pat00157

Figure pat00158
Figure pat00158

Figure pat00159
Figure pat00159

Figure pat00160
Figure pat00160

Figure pat00161
Figure pat00161

Figure pat00162
Figure pat00162

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 3-1Sub 3-1 m/z=287.11(C18H14BNO2=287.12)m / z = 287.11 (C 18 H 14 BNO 2 = 287.12) Sub 3-2Sub 3-2 m/z=287.11(C18H14BNO2=287.12)m / z = 287.11 (C 18 H 14 BNO 2 = 287.12) Sub 3-3Sub 3-3 m/z=287.11(C18H14BNO2=287.12)m / z = 287.11 (C 18 H 14 BNO 2 = 287.12) Sub 3-4Sub 3-4 m/z=287.11(C18H14BNO2=287.12)m / z = 287.11 (C 18 H 14 BNO 2 = 287.12) Sub 3-5Sub 3-5 m/z=337.13(C22H16BNO2=337.18)m / z = 337.13 (C 22 H 16 BNO 2 = 337.18) Sub 3-6Sub 3-6 m/z=337.13(C22H16BNO2=337.18)m / z = 337.13 (C 22 H 16 BNO 2 = 337.18) Sub 3-7Sub 3-7 m/z=337.13(C22H16BNO2=337.18)m / z = 337.13 (C 22 H 16 BNO 2 = 337.18) Sub 3-8Sub 3-8 m/z=337.13(C22H16BNO2=337.18)m / z = 337.13 (C 22 H 16 BNO 2 = 337.18) Sub 3-9Sub 3-9 m/z=337.13(C22H16BNO2=337.18)m / z = 337.13 (C 22 H 16 BNO 2 = 337.18) Sub 3-10Sub 3-10 m/z=363.14(C24H18BNO2=363.22)m / z = 363.14 (C 24 H 18 BNO 2 = 363.22) Sub 3-11Sub 3-11 m/z=363.14(C24H18BNO2=363.22)m / z = 363.14 (C 24 H 18 BNO 2 = 363.22) Sub 3-12Sub 3-12 m/z=368.17(C24H13D5BNO2=368.25)m / z = 368.17 (C 24 H 13 D 5 BNO 2 = 368.25) Sub 3-13Sub 3-13 m/z=387.14(C26H18BNO2=387.24)m / z = 387.14 (C 26 H 18 BNO 2 = 387.24) Sub 3-14Sub 3-14 m/z=437.16(C30H20BNO2=437.30)m / z = 437.16 (C 30 H 20 BNO 2 = 437.30) Sub 3-15Sub 3-15 m/z=413.16(C28H20BNO2=413.27)m / z = 413.16 (C 28 H 20 BNO 2 = 413.27) Sub 3-16Sub 3-16 m/z=429.13(C28H17BFNO2=429.25)m / z = 429.13 (C 28 H 17 BFNO 2 = 429.25) Sub 3-17Sub 3-17 m/z=368.17(C24H13D5BNO2=368.25)m / z = 368.17 (C 24 H 13 D 5 BNO 2 = 368.25) Sub 3-18Sub 3-18 m/z=482.18(C31H23BNO3=482.34)m / z = 482.18 (C 31 H 23 BNO 3 = 482.34) Sub 3-19Sub 3-19 m/z=452.17(C30H21BN2O2=452.31)m / z = 452.17 (C 30 H 21 BN 2 O 2 = 452.31) Sub 3-20Sub 3-20 m/z=364.14(C23H17BN2O2=364.20)m / z = 364.14 (C 23 H 17 BN 2 O 2 = 364.20) Sub 3-21Sub 3-21 m/z=442.16(C27H19BN4O2=442.28)m / z = 442.16 (C 27 H 19 BN 4 O 2 = 442.28) Sub 3-22Sub 3-22 m/z=441.16(C28H20BN3O2=441.29)m / z = 441.16 (C 28 H 20 BN 3 O 2 = 441.29) Sub 3-23Sub 3-23 m/z=441.26(C28H20BN3O2=441.29)m / z = 441.26 (C 28 H 20 BN 3 O 2 = 441.29) Sub 3-24Sub 3-24 m/z=442.16(C27H19BN4O2=442.28)m / z = 442.16 (C 27 H 19 BN 4 O 2 = 442.28) Sub 3-25Sub 3-25 m/z=441.16(C28H20BN3O2=441.29)m / z = 441.16 (C 28 H 20 BN 3 O 2 = 441.29) Sub 3-26Sub 3-26 m/z=517.20(C34H24BN3O2=517.38)m / z = 517.20 (C 34 H 24 BN 3 O 2 = 517.38) Sub 3-27Sub 3-27 m/z=528.25(C33H13D10BN4O2=528.43)m / z = 528.25 (C 33 H 13 D 10 BN 4 O 2 = 528.43) Sub 3-28Sub 3-28 m/z=455.14(C28H18BN3O3=455.27)m / z = 455.14 (C 28 H 18 BN 3 O 3 = 455.27) Sub 3-29Sub 3-29 m/z=505.16(C32H20BN3O3=505.33)m / z = 505.16 (C 32 H 20 BN 3 O 3 = 505.33) Sub 3-30Sub 3-30 m/z=444.11(C27H17BN2O2S=444.31)m / z = 444.11 (C 27 H 17 BN 2 O 2 S = 444.31) Sub 3-31Sub 3-31 m/z=547.15(C34H22BN3O2S=547.43)m / z = 547.15 (C 34 H 22 BN 3 O 2 S = 547.43) Sub 3-32Sub 3-32 m/z=415.15(C26H18BN3O2=415.25)m / z = 415.15 (C 26 H 18 BN 3 O 2 = 415.25) Sub 3-33Sub 3-33 m/z=465.16(C30H20BN3O2=465.31)m / z = 465.16 (C 30 H 20 BN 3 O 2 = 465.31) Sub 3-34Sub 3-34 m/z=565.20(C38H24BN3O2=565.43)m / z = 565.20 (C 38 H 24 BN 3 O 2 = 565.43) Sub 3-35Sub 3-35 m/z=465.16(C30H20BN3O2=465.31)m / z = 465.16 (C 30 H 20 BN 3 O 2 = 465.31) Sub 3-36Sub 3-36 m/z=228.04(C12H9BO2S=228.07)m / z = 228.04 (C 12 H 9 BO 2 S = 228.07) Sub 3-37Sub 3-37 m/z=228.04(C12H9BO2S=228.07)m / z = 228.04 (C 12 H 9 BO 2 S = 228.07) Sub 3-38Sub 3-38 m/z=228.04(C12H9BO2S=228.07)m / z = 228.04 (C 12 H 9 BO 2 S = 228.07) Sub 3-39Sub 3-39 m/z=278.06(C16H11BN2S=278.13)m / z = 278.06 (C 16 H 11 BN 2 S = 278.13) Sub 3-40Sub 3-40 m/z=278.06(C16H11BO2S=278.13)m / z = 278.06 (C 16 H 11 BO 2 S = 278.13) Sub 3-41Sub 3-41 m/z=278.06(C16H11BO2S=278.13)m / z = 278.06 (C 16 H 11 BO 2 S = 278.13) Sub 3-42Sub 3-42 m/z=305.07(C17H12BNO2S=305.16)m / z = 305.07 (C 17 H 12 BNO 2 S = 305.16) Sub 3-43Sub 3-43 m/z=212.06(C12H9BO3=212.01)m / z = 212.06 (C 12 H 9 BO 3 = 212.01) Sub 3-44Sub 3-44 m/z=212.06(C12H9BO3=212.01)m / z = 212.06 (C 12 H 9 BO 3 = 212.01) Sub 3-45Sub 3-45 m/z=212.06(C12H9BO3=212.01)m / z = 212.06 (C 12 H 9 BO 3 = 212.01) Sub 3-46Sub 3-46 m/z=262.08(C16H11BO3=262.07)m / z = 262.08 (C 16 H 11 BO 3 = 262.07) Sub 3-47Sub 3-47 m/z=312.10(C20H13BO3=312.13)m / z = 312.10 (C 20 H 13 BO 3 = 312.13) Sub 3-48Sub 3-48 m/z=289.09(C17H12BNO3=289.09)m / z = 289.09 (C 17 H 12 BNO 3 = 289.09) Sub 3-49Sub 3-49 m/z=238.12(C15H15BO2=238.09)m / z = 238.12 (C 15 H 15 BO 2 = 238.09) Sub 3-50Sub 3-50 m/z=238.12(C15H15BO2=238.09)m / z = 238.12 (C 15 H 15 BO 2 = 238.09) Sub 3-51Sub 3-51 m/z=266.15(C17H19BO2=266.14)m / z = 266.15 (C 17 H 19 BO 2 = 266.14) Sub 3-52Sub 3-52 m/z=362.15(C25H19BO2=362.23)m / z = 362.15 (C 25 H 19 BO 2 = 362.23) Sub 3-53Sub 3-53 m/z=438.18(C31H23BO2=438.32)m / z = 438.18 (C 31 H 23 BO 2 = 438.32) Sub 3-54Sub 3-54 m/z=360.13(C24H17BO2=360.21)m / z = 360.13 (C 24 H 17 BO 2 = 360.21) Sub 3-55Sub 3-55 m/z=410.15(C29H19BO2=410.27)m / z = 410.15 (C 29 H 19 BO 2 = 410.27) Sub 3-56Sub 3-56 m/z=254.09(C14H15BO2Si=254.16)m / z = 254.09 (C 14 H 15 BO 2 Si = 254.16) Sub 3-57Sub 3-57 m/z=254.09(C14H15BO2Si=254.16)m / z = 254.09 (C 14 H 15 BO 2 Si = 254.16) Sub 3-58Sub 3-58 m/z=282.12(C16H19BO2Si=282.22)m / z = 282.12 (C 16 H 19 BO 2 Si = 282.22) Sub 3-59Sub 3-59 m/z=378.12(C24H19BO2Si=387.30)m / z = 378.12 (C 24 H 19 BO 2 Si = 387.30) Sub 3-60Sub 3-60 m/z=378.12(C24H19BO2Si=378.30)m / z = 378.12 (C 24 H 19 BO 2 Si = 378.30) Sub 3-61Sub 3-61 m/z=376.11(C24H17BO2Si=376.29)m / z = 376.11 (C 24 H 17 BO 2 Si = 376.29) Sub 3-62Sub 3-62 m/z=275.99(C12H9BO2Se=274.97)m / z = 275.99 (C 12 H 9 BO 2 Se = 274.97) Sub 3-63Sub 3-63 m/z=275.99(C12H9BO2Se=274.97)m / z = 275.99 (C 12 H 9 BO 2 Se = 274.97) Sub 3-64Sub 3-64 m/z=326.00(C16H11BO2Se=325.03)m / z = 326.00 (C 16 H 11 BO 2 Se = 325.03)

3. 화학식 1의 Product의 합성 예시3. Synthesis Example of Product of Formula 1

둥근바닥플라스크에 Sub 1 또는 Sub 2 화합물 (1 당량)을 넣고, Sub 3 화합물을 (1 당량), Pd(PPh3)4 (0.03~0.05 당량), NaOH (3 당량), THF (3 mL / 1 mmol), 물 (1.5 mL / 1 mmol)을 넣는다. 그런 후에 80℃ 상태에서 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Toluene과 Acetone으로 재결정하여 생성물을 얻었다.Put the Sub 1 or Sub 2 compound (1 eq) into the round bottom flask, and add the Sub 3 compound (1 eq), Pd (PPh 3 ) 4 (0.03 ~ 0.05 eq), NaOH (3 eq), THF (3 mL / 1 mmol) and water (1.5 mL / 1 mmol). Then, the mixture was heated to reflux at 80 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Toluene and Acetone to obtain a product.

1. 화합물 1-2의 합성예1. Synthesis Example of Compound 1-2

Figure pat00163
Figure pat00163

둥근바닥플라스크에 Sub 1-2 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 넣는다. 그런 후에 80℃ 상태에서 8시간 동안 가열 환류시킨다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 Methylene chloride와 물로 추출한다. 유기층을 MgSO4로 건조하여 농축한 후 생성된 화합물을 Toluene과 Acetone으로 재결정하여 생성물 1-2 (5.4 g, 80%)을 얻었다.Round bottom flask Sub 1-2 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) is added. Then, the mixture was heated to reflux for 8 hours at 80 ° C. When the reaction is complete, dilute it with distilled water at room temperature and extract with Methylene chloride and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was recrystallized from Toluene and Acetone to obtain product 1-2 (5.4 g, 80%).

2. 화합물 1-7의 합성예2. Synthesis Example of Compound 1-7

Figure pat00164
Figure pat00164

Sub 1-3 (10 g, 20 mmol), Sub 3-3 (5.7 g, 20 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-7 (11.3 g, 85%)을 얻었다.Sub 1-3 (10 g, 20 mmol), Sub 3-3 (5.7 g, 20 mmol), Pd (PPh 3 ) 4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL) / H 2 O (20 mL) using the 1-2 synthesis method described above for product 1-7 (11.3 g, 85%) ).

3. 화합물 1-14의 합성예3. Synthesis Example of Compound 1-14

Figure pat00165
Figure pat00165

Sub 1-5 (10 g, 21 mmol), Sub 3-10 (7.6 g, 21 mmol), Pd(PPh3)4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-14 (12.3 g, 82%)을 얻었다.Sub 1-5 (10 g, 21 mmol), Sub 3-10 (7.6 g, 21 mmol), Pd (PPh 3 ) 4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL) / H 2 O (20 mL) using the above 1-2 synthesis method to give products 1-14 (12.3 g, 82%) ).

4. 화합물 1-20의 합성예4. Synthesis Example of Compound 1-20

Figure pat00166
Figure pat00166

Sub 1-1 (10 g, 21 mmol), Sub 3-11 (7.6 g, 21 mmol), Pd(PPh3)4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-20 (12.5 g, 83%)을 얻었다.Sub 1-1 (10 g, 21 mmol), Sub 3-11 (7.6 g, 21 mmol), Pd (PPh 3 ) 4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL) / H 2 O (20 mL) using the 1-2 synthesis method described above for product 1-20 (12.5 g, 83%) ).

5. 화합물 1-26의 합성예5. Synthesis Example of Compound 1-26

Figure pat00167
Figure pat00167

Sub 1-6 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-26 (4.9 g, 72%)을 얻었다.Sub 1-6 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the above 1-2 synthesis method, product 1-26 (4.9 g, 72%) ).

6. 화합물 1-27의 합성예6. Synthesis Example of Compound 1-27

Figure pat00168
Figure pat00168

Sub 1-6 (5 g, 11.5 mmol), Sub 3-10 (4.2 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-27 (6.5 g, 85%)을 얻었다.Sub 1-6 (5 g, 11.5 mmol), Sub 3-10 (4.2 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using 1-2 synthesis method above, product 1-27 (6.5 g, 85%) ).

7. 화합물 1-33의 합성예7. Synthesis Example of Compound 1-33

Figure pat00169
Figure pat00169

Sub 1-7 (10 g, 20 mmol), Sub 3-11 (7.3 g, 20 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-33 (13.5 g, 91%)을 얻었다.Sub 1-7 (10 g, 20 mmol), Sub 3-11 (7.3 g, 20 mmol), Pd (PPh 3 ) 4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL) / H 2 O (20 mL) using 1-3 synthesis method above 1-33 (13.5 g, 91%) ).

8. 화합물 1-51의 합성예8. Synthesis Example of Compound 1-51

Figure pat00170
Figure pat00170

Sub 1-6 (5 g, 11.5 mmol), Sub 3-1 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-51 (3.5 g, 51%)을 얻었다.Sub 1-6 (5 g, 11.5 mmol), Sub 3-1 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the 1-2 synthesis method above, product 1-51 (3.5 g, 51%) ).

9. 화합물 1-52의 합성예9. Synthesis Example of Compound 1-52

Figure pat00171
Figure pat00171

Sub 1-6 (5 g, 11.5 mmol), Sub 3-2 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-52 (3.8 g, 56%)을 얻었다.Sub 1-6 (5 g, 11.5 mmol), Sub 3-2 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the 1-2 synthesis method described above for product 1-52 (3.8 g, 56%) ).

10. 화합물 1-53의 합성예10. Synthesis Example of Compound 1-53

Figure pat00172
Figure pat00172

Sub 1-6 (5 g, 11.5 mmol), Sub 3-4 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-53 (4.2 g, 62%)을 얻었다.Sub 1-6 (5 g, 11.5 mmol), Sub 3-4 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using 1-2 synthesis methods above, product 1-53 (4.2 g, 62%) ).

11. 화합물 1-66의 합성예11. Synthesis Example of Compound 1-66

Figure pat00173
Figure pat00173

Sub 1-14 (10 g, 21 mmol), Sub 3-3 (7.6 g, 21 mmol), Pd(PPh3)4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-66 (8.5 g, 63%)을 얻었다.Sub 1-14 (10 g, 21 mmol), Sub 3-3 (7.6 g, 21 mmol), Pd (PPh 3 ) 4 (1 g, 0.8 mmol), NaOH (2.5 g, 63 mmol), THF (40 mL) / H 2 O (20 mL) using the 1-2 synthesis method described above for product 1-66 (8.5 g, 63%) ).

12. 화합물 1-71의 합성예12. Synthesis Example of Compound 1-71

Figure pat00174
Figure pat00174

둥근바닥플라스크에 Sub 1-1 (5 g, 11.5 mmol), Sub 3-46 (3.0 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-71 (4.7 g, 73%)을 얻었다.Round bottom flask Sub 1-1 (5 g, 11.5 mmol), Sub 3-46 (3.0 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the 1-2 synthesis method described above for product 1-71 (4.7 g, 73%) ).

13. 화합물 1-78의 합성예13. Synthesis Example of Compound 1-78

Figure pat00175
Figure pat00175

둥근바닥플라스크에 Sub 1-4 (5 g, 9.9 mmol), Sub 3-53 (4.3 g, 9.9 mmol), Pd(PPh3)4 (0.5 g, 0.4 mmol), NaOH (1.2 g, 29.7 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-78 (5.3 g, 65%)을 얻었다.In a round bottom flask, Sub 1-4 (5 g, 9.9 mmol), Sub 3-53 (4.3 g, 9.9 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.4 mmol), NaOH (1.2 g, 29.7 mmol) , THF (40 mL) / H 2 O (20 mL) was obtained product 1-78 (5.3 g, 65%) using the above 1-2 synthesis method.

14. 화합물 1-90의 합성예14. Synthesis Example of Compound 1-90

Figure pat00176
Figure pat00176

둥근바닥플라스크에 Sub 1-39 (10 g, 20.5 mmol), Sub 3-38 (5.9 g, 20.5 mmol), Pd(PPh3)4 (1 g, 0.8 mmol), NaOH (2.5 g, 61 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 1-90 (5.8 g, 48%)을 얻었다.Round bottom flask Sub 1-39 (10 g, 20.5 mmol), Sub 3-38 (5.9 g, 20.5 mmol), Pd (PPh 3 ) 4 (1 g, 0.8 mmol), NaOH (2.5 g, 61 mmol), THF (40 mL) / H 2 O (20 mL) using 1-2 synthesis methods above, product 1-90 (5.8 g, 48%) ).

15. 화합물 2-1의 합성예15. Synthesis Example of Compound 2-1

Figure pat00177
Figure pat00177

둥근바닥플라스크에 Sub 2-1 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-1 (5.5 g, 81%)을 얻었다.Round bottom flask Sub 2-1 (5 g, 11.5 mmol), Sub 3-3 (3.9 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the above 1-2 synthesis method, product 2-1 (5.5 g, 81%) ).

16. 화합물 2-2의 합성예16. Synthesis Example of Compound 2-2

Figure pat00178
Figure pat00178

둥근바닥플라스크에 Sub 2-1 (5 g, 11.5 mmol), Sub 3-10 (4.2 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-2 (6.1 g, 80%)를 얻었다.Round bottom flask Sub 2-1 (5 g, 11.5 mmol), Sub 3-10 (4.2 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the above 1-2 synthesis method, product 2-2 (6.1 g, 80%) ).

17. 화합물 2-3의 합성예17. Synthesis Example of Compound 2-3

Figure pat00179
Figure pat00179

둥근바닥플라스크에 Sub 2-1 (5 g, 11.5 mmol), Sub 3-11 (4.2 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-3 (5.8 g, 76%)을 얻었다.Round bottom flask Sub 2-1 (5 g, 11.5 mmol), Sub 3-11 (4.2 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the above 1-2 synthesis method, product 2-3 (5.8 g, 76%) ).

18. 화합물 2-6의 합성예18. Synthesis Example of Compound 2-6

Figure pat00180
Figure pat00180

둥근바닥플라스크에 Sub 2-2 (10 g, 20 mmol), Sub 3-3 (5.7 g, 20 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-6 (10.3 g, 81%)을 얻었다.In a round bottom flask, Sub 2-2 (10 g, 20 mmol), Sub 3-3 (5.7 g, 20 mmol), Pd (PPh 3 ) 4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol) , THF (40 mL) / H 2 O (20 mL) was obtained product 2-6 (10.3 g, 81%) using the above 1-2 synthesis method.

19. 화합물 2-7의 합성예19. Synthesis Example of Compound 2-7

Figure pat00181
Figure pat00181

둥근바닥플라스크에 Sub 2-2 (10 g, 20 mmol), Sub 3-10 (7.3 g, 20 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-7 (11 g, 74%)을 얻었다.In a round bottom flask, Sub 2-2 (10 g, 20 mmol), Sub 3-10 (7.3 g, 20 mmol), Pd (PPh 3 ) 4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol) , THF (40 mL) / H 2 O (20 mL) was obtained using the 1-2 synthesis method above to obtain product 2-7 (11 g, 74%).

20. 화합물 2-8의 합성예20. Synthesis Example of Compound 2-8

Figure pat00182
Figure pat00182

둥근바닥플라스크에 Sub 2-2 (10 g, 20 mmol), Sub 3-11 (7.3 g, 20 mmol), Pd(PPh3)4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol), THF (40 mL)/H2O (20 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-8 (12 g, 81%)을 얻었다.In a round bottom flask, Sub 2-2 (10 g, 20 mmol), Sub 3-11 (7.3 g, 20 mmol), Pd (PPh 3 ) 4 (0.9 g, 0.8 mmol), NaOH (2.4 g, 59 mmol) , THF (40 mL) / H 2 O (20 mL) was obtained product 2-8 (12 g, 81%) using the above 1-2 synthesis method.

21. 화합물 2-33의 합성예21. Synthesis Example of Compound 2-33

Figure pat00183
Figure pat00183

둥근바닥플라스크에 Sub 2-1 (5 g, 11.5 mmol), Sub 3-38 (2.6 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-33 (5.0 g, 82%)을 얻었다.Round bottom flask Sub 2-1 (5 g, 11.5 mmol), Sub 3-38 (2.6 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the above 1-2 synthesis method, product 2-33 (5.0 g, 82%) ).

22. 화합물 2-38의 합성예22. Synthesis Example of Compound 2-38

Figure pat00184
Figure pat00184

둥근바닥플라스크에 Sub 2-1 (5 g, 11.5 mmol), Sub 3-45 (2.4 g, 11.5 mmol), Pd(PPh3)4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-38 (4.4 g, 74%)을 얻었다.In a round bottom flask, Sub 2-1 (5 g, 11.5 mmol), Sub 3-45 (2.4 g, 11.5 mmol), Pd (PPh 3 ) 4 (0.5 g, 0.5 mmol), NaOH (1.4 g, 35 mmol), THF (30 mL) / H 2 O (15 mL) using the 1-2 synthesis method above, 2-38 (4.4 g, 74%) ).

23. 화합물 2-133의 합성예23. Synthesis Example of Compound 2-133

Figure pat00185
Figure pat00185

둥근바닥플라스크에 Sub 2-37 (5 g, 12 mmol), Sub 3-10 (4.4 g, 12 mmol), Pd(PPh3)4 (0.6 g, 0.5 mmol), NaOH (1.5 g, 36 mmol), THF (30 mL)/H2O (15 mL)을 상기 1-2 합성방법을 사용하여 생성물 2-133 (5.6 g, 72%)을 얻었다.Round bottom flask Sub 2-37 (5 g, 12 mmol), Sub 3-10 (4.4 g, 12 mmol), Pd (PPh 3 ) 4 (0.6 g, 0.5 mmol), NaOH (1.5 g, 36 mmol) , THF (30 mL) / H 2 O (15 mL) was obtained using the 1-2 synthesis method above to obtain 2-133 (5.6 g, 72%).

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS 1-11-1 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-21-2 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-31-3 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-41-4 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-51-5 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-61-6 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-71-7 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-81-8 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-91-9 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-101-10 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-111-11 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-121-12 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-131-13 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-141-14 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-151-15 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-161-16 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-171-17 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-181-18 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-191-19 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-201-20 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-211-21 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-221-22 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-231-23 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-241-24 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-251-25 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-261-26 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-271-27 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-281-28 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-291-29 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-301-30 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-311-31 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-321-32 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-331-33 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-341-34 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-351-35 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-361-36 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 1-371-37 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-381-38 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 1-391-39 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-401-40 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-411-41 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-421-42 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-431-43 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-441-44 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-451-45 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-461-46 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-471-47 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-481-48 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 1-491-49 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-501-50 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 1-511-51 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-521-52 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-531-53 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 1-541-54 m/z=531.11(C36H21NS2=531.69)m / z = 531.11 (C 36 H 21 NS 2 = 531.69) 1-551-55 m/z=531.11(C36H21NS2=531.69)m / z = 531.11 (C 36 H 21 NS 2 = 531.69) 1-561-56 m/z=515.13(C36H21NOS=515.62)m / z = 515.13 (C 36 H 21 NOS = 515.62) 1-571-57 m/z=744.23(C52H32N4S=743.90)m / z = 744.23 (C 52 H 32 N 4 S = 743.90) 1-581-58 m/z=870.28(C62H38N4S=871.06)m / z = 870.28 (C 62 H 38 N 4 S = 871.06) 1-591-59 m/z=768.23(C54H32N4S=768.92)m / z = 768.23 (C 54 H 32 N 4 S = 768.92) 1-601-60 m/z=718.22(C50H30N4S=718.87)m / z = 718.22 (C 50 H 30 N 4 S = 718.87) 1-611-61 m/z=931.30(C68H41N3S=932.14)m / z = 931.30 (C 68 H 41 N 3 S = 932.14) 1-621-62 m/z=808.23(C56H32N4OS=808.94)m / z = 808.23 (C 56 H 32 N 4 OS = 808.94) 1-631-63 m/z=850.22(C58H34N4S2=851.05)m / z = 850.22 (C 58 H 34 N 4 S 2 = 851.05) 1-641-64 m/z=831.32(C57H25D10N5S=832.05)m / z = 831.32 (C 57 H 25 D 10 N 5 S = 832.05) 1-651-65 m/z=768.23(C54H32N4S=768.92)m / z = 768.23 (C 54 H 32 N 4 S = 768.92) 1-661-66 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 1-671-67 m/z=531.11(C36H21NS2=531.69)m / z = 531.11 (C 36 H 21 NS 2 = 531.69) 1-681-68 m/z=708.17(C49H28N2S2=708.89)m / z = 708.17 (C 49 H 28 N 2 S 2 = 708.89) 1-691-69 m/z=733.19(C52H31NS2=733.94)m / z = 733.19 (C 52 H 31 NS 2 = 733.94) 1-701-70 m/z=708.17(C49H28N2S2=708.89)m / z = 708.17 (C 49 H 28 N 2 S 2 = 708.89) 1-711-71 m/z=565.15(C40H23NOS=565.68)m / z = 565.15 (C 40 H 23 NOS = 565.68) 1-721-72 m/z=822.25(C57H34N4OS=822.97)m / z = 822.25 (C 57 H 34 N 4 OS = 822.97) 1-731-73 m/z=809.21(C56H31N3O2S=809.93)m / z = 809.21 (C 56 H 31 N 3 O 2 S = 809.93) 1-741-74 m/z=781.13(C52H31NSSe=780.83)m / z = 781.13 (C 52 H 31 NSSe = 780.83) 1-751-75 m/z=681.08(C42H23N3SSe=680.68)m / z = 681.08 (C4 2 H 23 N 3 SSe = 680.68) 1-761-76 m/z=585.19(C40H31NSSi=585.83)m / z = 585.19 (C 40 H 31 NSSi = 585.83) 1-771-77 m/z=809.23(C56H35N3SSi=810.05)m / z = 809.23 (C 56 H 35 N 3 SSi = 810.05) 1-781-78 m/z=817.28(C61H39NS=818.03)m / z = 817.28 (C 61 H 39 NS = 818.03) 1-791-79 m/z=817.26(C59H35N3S=817.99)m / z = 817.26 (C 59 H 35 N 3 S = 817.99) 1-801-80 m/z=742.28(C50H30N4OS=742.93)m / z = 742.28 (C 50 H 30 N 4 OS = 742.93) 1-811-81 m/z=574.20(C42H26N2O=574.67)m / z = 574.20 (C 42 H 26 N 2 O = 574.67) 1-821-82 m/z=624.22(C46H28N2O=624.73)m / z = 624.22 (C 46 H 28 N 2 O = 624.73) 1-831-83 m/z=852.29(C62H36N4O=852.98)m / z = 852.29 (C 62 H 36 N 4 O = 852.98) 1-841-84 m/z=834.25(C58H34N4OS=834.98)m / z = 834.25 (C 58 H 34 N 4 OS = 834.98) 1-851-85 m/z=649.24(C49H31NO=649.78)m / z = 649.24 (C 49 H 31 NO = 649.78) 1-861-86 m/z=829.24(C61H35NOS=830.00)m / z = 829.24 (C 61 H 35 NOS = 830.00) 1-871-87 m/z=665.22(C48H31NOSi=665.85)m / z = 665.22 (C 48 H 31 NOSi = 665.85) 1-881-88 m/z=563.08(C36H21NOSe=562.52)m / z = 563.08 (C 36 H 21 NOSe = 562.52) 1-891-89 m/z=600.26(C45H32N2=600.75)m / z = 600.26 (C 45 H 32 N 2 = 600.75) 1-901-90 m/z=591.20(C43H29NS=591.76)m / z = 591.20 (C 43 H 29 NS = 591.76) 1-911-91 m/z=525.21(C39H27NO=525.64)m / z = 525.21 (C 39 H 27 NO = 525.64) 1-921-92 m/z=551.26(C42H33N=551.72)m / z = 551.26 (C 42 H 33 N = 551.72) 1-931-93 m/z=616.23(C44H32N2Si=616.82)m / z = 616.23 (C 44 H 32 N 2 Si = 616.82) 1-941-94 m/z=541.19(C38H27NOSi=541.71)m / z = 541.19 (C 38 H 27 NOSi = 541.71) 1-951-95 m/z=557.16(C38H27NSSi=557.78)m / z = 557.16 (C 38 H 27 NSSi = 557.78) 1-961-96 m/z=638.13(C42H26N2Se=637.63)m / z = 638.13 (C 42 H 26 N 2 Se = 637.63) 1-971-97 m/z=563.08(C36H21NOSe=562.52)m / z = 563.08 (C 36 H 21 NOSe = 562.52) 1-981-98 m/z=589.13(C39H27NSe=588.60)m / z = 589.13 (C 39 H 27 NSe = 588.60) 2-12-1 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-22-2 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-32-3 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-42-4 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-52-5 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-62-6 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-72-7 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-82-8 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-92-9 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-102-10 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-112-11 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-122-12 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-132-13 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-142-14 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-152-15 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-162-16 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-172-17 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-182-18 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-192-19 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-202-20 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-212-21 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-222-22 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-232-23 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-242-24 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-252-25 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-262-26 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-272-27 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-282-28 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-292-29 m/z=746.28(C54H38N2S=746.96)m / z = 746.28 (C 54 H 38 N 2 S = 746.96) 2-302-30 m/z=796.25(C57H36N2OS=796.97)m / z = 796.25 (C 57 H 36 N 2 OS = 796.97) 2-312-31 m/z=780.26(C57H36N2S=780.97)m / z = 780.26 (C 57 H 36 N 2 S = 780.97) 2-322-32 m/z=743.24(C53H33N3S=743.91)m / z = 743.24 (C 53 H 33 N 3 S = 743.91) 2-332-33 m/z=531.11(C36H21NS2=531.69)m / z = 531.11 (C 36 H 21 NS 2 = 531.69) 2-342-34 m/z=607.14(C42H25NS2=607.78)m / z = 607.14 (C 42 H 25 NS 2 = 607.78) 2-352-35 m/z=607.14(C42H25NS2=607.78)m / z = 607.14 (C 42 H 25 NS 2 = 607.78) 2-362-36 m/z=581.13(C40H23NS2=581.75)m / z = 581.13 (C 40 H 23 NS 2 = 581.75) 2-372-37 m/z=581.13(C40H23NS2=581.75)m / z = 581.13 (C 40 H 23 NS 2 = 581.75) 2-382-38 m/z=515.13(C36H21NOS=515.62)m / z = 515.13 (C 36 H 21 NOS = 515.62) 2-392-39 m/z=591.17(C42H25NOS=591.72)m / z = 591.17 (C 42 H 25 NOS = 591.72) 2-402-40 m/z=591.17(C42H25NOS=591.72)m / z = 591.17 (C 42 H 25 NOS = 591.72) 2-412-41 m/z=565.15(C40H23NOS=565.68)m / z = 565.15 (C 40 H 23 NOS = 565.68) 2-422-42 m/z=565.15(C40H23NOS=565.68)m / z = 565.15 (C 40 H 23 NOS = 565.68) 2-432-43 m/z=541.19(C39H27NS=541.70)m / z = 541.19 (C 39 H 27 NS = 541.70) 2-442-44 m/z=617.21(C45H31NS=617.80)m / z = 617.21 (C 45 H 31 NS = 617.80) 2-452-45 m/z=617.21(C45H31NS=617.80)m / z = 617.21 (C 45 H 31 NS = 617.80) 2-462-46 m/z=591.20(C43H29NS=591.76)m / z = 591.20 (C 43 H 29 NS = 591.76) 2-472-47 m/z=591.20(C43H29NS=591.76)m / z = 591.20 (C 43 H 29 NS = 591.76) 2-482-48 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-492-49 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-502-50 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-512-51 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-522-52 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-532-53 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-542-54 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-552-55 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-562-56 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-572-57 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-582-58 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-592-59 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-602-60 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-612-61 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-622-62 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-632-63 m/z=742.24(C54H34N2S=742.93)m / z = 742.24 (C 54 H 34 N 2 S = 742.93) 2-642-64 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-652-65 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-662-66 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-672-67 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-682-68 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-692-69 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-702-70 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-712-71 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-722-72 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-732-73 m/z=716.23(C52H32N2S=716.89)m / z = 716.23 (C 52 H 32 N 2 S = 716.89) 2-742-74 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-752-75 m/z=690.21(C50H30N2S=690.85)m / z = 690.21 (C 50 H 30 N 2 S = 690.85) 2-762-76 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-772-77 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-782-78 m/z=590.18(C42H26N2S=590.73)m / z = 590.18 (C 42 H 26 N 2 S = 590.73) 2-792-79 m/z=581.13(C40H23NS2=581.75)m / z = 581.13 (C 40 H 23 NS 2 = 581.75) 2-802-80 m/z=581.13(C40H23NS2=581.75)m / z = 581.13 (C 40 H 23 NS 2 = 581.75) 2-812-81 m/z=515.13(C36H21NOS=515.62)m / z = 515.13 (C 36 H 21 NOS = 515.62) 2-822-82 m/z=591.17(C42H25NOS=591.72)m / z = 591.17 (C 42 H 25 NOS = 591.72) 2-832-83 m/z=591.17(C42H25NOS=591.72)m / z = 591.17 (C 42 H 25 NOS = 591.72) 2-842-84 m/z=565.15(C40H23NOS=565.68)m / z = 565.15 (C 40 H 23 NOS = 565.68) 2-852-85 m/z=565.15(C40H23NOS=565.68)m / z = 565.15 (C 40 H 23 NOS = 565.68) 2-862-86 m/z=541.19(C39H27NS=541.70)m / z = 541.19 (C 39 H 27 NS = 541.70) 2-872-87 m/z=617.21(C45H31NS=617.80)m / z = 617.21 (C 45 H 31 NS = 617.80) 2-882-88 m/z=617.21(C45H31NS=617.80)m / z = 617.21 (C 45 H 31 NS = 617.80) 2-892-89 m/z=531.11(C36H21NS2=531.69)m / z = 531.11 (C 36 H 21 NS 2 = 531.69) 2-902-90 m/z=607.14(C42H25NS2=607.78)m / z = 607.14 (C 42 H 25 NS 2 = 607.78) 2-912-91 m/z=607.14(C42H25NS2=607.78)m / z = 607.14 (C 42 H 25 NS 2 = 607.78) 2-922-92 m/z=591.20(C43H29NS=591.76)m / z = 591.20 (C 43 H 29 NS = 591.76) 2-932-93 m/z=591.20(C43H29NS=591.76)m / z = 591.20 (C 43 H 29 NS = 591.76) 2-942-94 m/z=745.23(C51H31N5S=745.89)m / z = 745.23 (C 51 H 31 N 5 S = 745.89) 2-952-95 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-962-96 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-972-97 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-982-98 m/z=718.22(C50H30N4S=718.87)m / z = 718.22 (C 50 H 30 N 4 S = 718.87) 2-992-99 m/z=745.23(C51H31N5S=745.89)m / z = 745.23 (C 51 H 31 N 5 S = 745.89) 2-1002-100 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-1012-101 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-1022-102 m/z=744.23(C52H32N4S=744.90)m / z = 744.23 (C 52 H 32 N 4 S = 744.90) 2-1032-103 m/z=718.22(C50H30N4S=718.87)m / z = 718.22 (C 50 H 30 N 4 S = 718.87) 2-1042-104 m/z=768.24(C54H32N4S=768.92)m / z = 768.24 (C 54 H 32 N 4 S = 768.92) 2-1052-105 m/z=834.25(C58H34N4OS=834.98)m / z = 834.25 (C 58 H 34 N 4 OS = 834.98) 2-1062-106 m/z=900.24(C62H36N4S2=901.11)m / z = 900.24 (C 62 H 36 N 4 S 2 = 901.11) 2-1072-107 m/z=844.27(C60H36N4S=845.02)m / z = 844.27 (C 60 H 36 N 4 S = 845.02) 2-1082-108 m/z=847.25(C60H3FN3S=848.00)m / z = 847.25 (C 60 H 3 FN 3 S = 848.00) 2-1092-109 m/z=745.23(C51H31N5S=745.89)m / z = 745.23 (C 51 H 31 N 5 S = 745.89) 2-1102-110 m/z=909.32(C67H35D5N2S=910.14)m / z = 909.32 (C 67 H 35 D 5 N 2 S = 910.14) 2-1112-111 m/z=747.18(C51H29N3S2=747.93)m / z = 747.18 (C 51 H 29 N 3 S 2 = 747.93) 2-1122-112 m/z=762.29(C54H30D5N3S=762.97)m / z = 762.29 (C 54 H 30 D 5 N 3 S = 762.97) 2-1132-113 m/z=789.25(C59H35NS=789.98)m / z = 789.25 (C 59 H 35 NS = 789.98) 2-1142-114 m/z=860.26(C60H36N4OS=861.02)m / z = 860.26 (C 60 H 36 N 4 OS = 861.02) 2-1152-115 m/z=515.13(C36H21NOS=515.62)m / z = 515.13 (C 36 H 21 NOS = 515.62) 2-1162-116 m/z=717.21(C52H31NOS=717.87)m / z = 717.21 (C 52 H 31 NOS = 717.87) 2-1172-117 m/z=770.21(C53H30N4S=770.90)m / z = 770.21 (C 53 H 30 N 4 S = 770.90) 2-1182-118 m/z=845.25(C60H35N3OS=846.00)m / z = 845.25 (C 60 H 35 N 3 OS = 846.00) 2-1192-119 m/z=699.14(C46H25N3S2=699.84)m / z = 699.14 (C 46 H 25 N 3 S 2 = 699.84) 2-1202-120 m/z=581.13(C40H23NS2=581.75)m / z = 581.13 (C 40 H 23 NS 2 = 581.75) 2-1212-121 m/z=785.20(C54H31N3S2=785.97)m / z = 785.20 (C 54 H 31 N 3 S 2 = 785.97) 2-1222-122 m/z=824.20(C57H32N2OS2=825.01)m / z = 824.20 (C 57 H 32 N 2 OS 2 = 825.01) 2-1232-123 m/z=697.19(C49H31NS2=697.91)m / z = 697.19 (C 49 H 31 NS 2 = 697.91) 2-1242-124 m/z=624.04(C36H20N2O2SSe=623.58)m / z = 624.04 (C 36 H 20 N 2 O 2 SSe = 623.58) 2-1252-125 m/z=666.21(C48H30N2S=666.83)m / z = 666.21 (C 48 H 30 N 2 S = 666.83) 2-1262-126 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-1272-127 m/z=640.20(C46H28N2S=640.79)m / z = 640.20 (C 46 H 28 N 2 S = 640.79) 2-1282-128 m/z=671.24(C48H25D5N2S=671.86)m / z = 671.24 (C 48 H 25 D 5 N 2 S = 671.86) 2-1292-129 m/z=671.24(C48H25D5N2S=671.86)m / z = 671.24 (C 48 H 25 D 5 N 2 S = 671.86) 2-1302-130 m/z=557.16(C38H27NSSi=557.78)m / z = 557.16 (C 38 H 27 NSSi = 557.78) 2-1312-131 m/z=579.06(C36H21NSSe=579.58)m / z = 579.06 (C 36 H 21 NSSe = 579.58) 2-1322-132 m/z=681.19(C48H31NSSi=681.92)m / z = 681.19 (C 48 H 31 NSSi = 681.92) 2-1332-133 m/z=574.20(C42H26N2O=574.67)m / z = 574.20 (C 42 H 26 N 2 O = 574.67) 2-1342-134 m/z=650.24(C48H30N2O=650.76)m / z = 650.24 (C 48 H 30 N 2 O = 650.76) 2-1352-135 m/z=664.22(C48H28N2O2=664.75)m / z = 664.22 (C 48 H 28 N 2 O 2 = 664.75) 2-1362-136 m/z=818.27(C58H34N4O2=818.92)m / z = 818.27 (C 58 H 34 N 4 O 2 = 818.92) 2-1372-137 m/z=758.21(C52H30N4OS=758.89)m / z = 758.21 (C 52 H 30 N 4 OS = 758.89) 2-1382-138 m/z=702.24(C50H30N4O=702.80)m / z = 702.24 (C 50 H 30 N 4 O = 702.80) 2-1392-139 m/z=729.25(C51H31N5O=729.82)m / z = 729.25 (C 51 H 31 N 5 O = 729.82) 2-1402-140 m/z=759.23(C53H33N3OS=759.91)m / z = 759.23 (C 53 H 33 N 3 OS = 759.91) 2-1412-141 m/z=697.24(C53H31NO=697.82)m / z = 697.24 (C 53 H 31 NO = 697.82) 2-1422-142 m/z=739.23(C54H33NOSi=739.93)m / z = 739.23 (C 54 H 33 NOSi = 739.93) 2-1432-143 m/z=739.14(C50H29NOSe=738.73)m / z = 739.14 (C 50 H 29 NOSe = 738.73) 2-1442-144 m/z=650.27(C49H34N2=650.81)m / z = 650.27 (C 49 H 34 N 2 = 650.81) 2-1452-145 m/z=591.20(C43H29NO=591.76)m / z = 591.20 (C 43 H 29 NO = 591.76) 2-1462-146 m/z=525.21(C39H27NO=525.64)m / z = 525.21 (C 39 H 27 NO = 525.64) 2-1472-147 m/z=551.26(C42H33=551.72)m / z = 551.26 (C 42 H 33 = 551.72) 2-1482-148 m/z=616.23(C44H32N2Si=616.82)m / z = 616.23 (C 44 H 32 N 2 Si = 616.82) 2-1492-149 m/z=557.16(C38H27NSSi=557.78)m / z = 557.16 (C 38 H 27 NSSi = 557.78) 2-1502-150 m/z=541.19(C38H27NOSi=541.71)m / z = 541.19 (C 38 H 27 NOSi = 541.71) 2-1512-151 m/z=583.22(C40H33NSi2=583.87)m / z = 583.22 (C 40 H 33 NSi 2 = 583.87) 2-1522-152 m/z=638.13(C42H26N2Se=637.63)m / z = 638.13 (C 42 H 26 N 2 Se = 637.63) 2-1532-153 m/z=579.06(C36H21NSSe=578.58)m / z = 579.06 (C 36 H 21 NSSe = 578.58) 2-1542-154 m/z=589.13(C39H27NSe=588.60)m / z = 589.13 (C 39 H 27 NSe = 588.60)

[[ 합성예Synthetic example 2] 2]

본 발명에 따른 화학식 (2)로 표시되는 화합물(final product 2)은 하기 반응식 4와 같이 Sub 4와 Sub 5가 반응하여 제조된다.The compound represented by the formula (2) according to the present invention (final product 2) is prepared by reacting Sub 4 and Sub 5 as shown in Reaction Scheme 4 below.

<반응식 4><Reaction Scheme 4>

Figure pat00186
Figure pat00186

4. Sub 4의 합성 예시4. Synthesis Example of Sub 4

반응식 4의 Sub 4는 하기 반응식 5의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다.Sub 4 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below, but is not limited thereto.

<반응식 5><Scheme 5>

Figure pat00187
Figure pat00187

Figure pat00188
Figure pat00188

1. Sub 4-1의 합성예1. Synthesis Example of Sub 4-1

Figure pat00189
Figure pat00189

(1) Sub 4-1a의 합성법(1) Synthesis of Sub 4-1a

1-bromodibenzo[b,d]furan (50.0 g, 202 mmol)를 DMF (1012 mL)에 녹인 후, bis(pinacolato)diboron (56.2 g, 223 mmol), KOAc (59.6 g, 607 mmol), PdCl2(dppf) (4.44 g, 6.07 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 45.2 g (수율: 76%)을 얻었다.After dissolving 1-bromodibenzo [b, d] furan (50.0 g, 202 mmol) in DMF (1012 mL), bis (pinacolato) diboron (56.2 g, 223 mmol), KOAc (59.6 g, 607 mmol), PdCl 2 (dppf) (4.44 g, 6.07 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 45.2 g (yield: 76%) of the product.

(2) Sub 4-1b의 합성법(2) Synthesis of Sub 4-1b

상기 합성에서 얻어진 Sub 4-1a (45.2 g, 154 mmol)를 THF (758 mL)에 녹인 후, 1-bromo-2-nitrobenzene (31.0 g, 154 mmol), K2CO3 (63.7 g, 461 mmol), Pd(PPh3)4 (10.7 g, 9.22 mmol), 물 (379 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 33.6 g (수율: 85%)을 얻었다.After dissolving Sub 4-1a (45.2 g, 154 mmol) obtained in the above synthesis in THF (758 mL), 1-bromo-2-nitrobenzene (31.0 g, 154 mmol), K 2 CO 3 (63.7 g, 461 mmol) ), Pd (PPh 3 ) 4 (10.7 g, 9.22 mmol), water (379 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 33.6 g (yield: 85%) of the product.

(3) Sub 4-1의 합성법(3) Sub 4-1 synthesis method

상기 합성에서 얻어진 Sub 4-1b (38.6 g, 116 mmol)을 o-dichlorobenzene (617 mL)으로 녹인 후, triphenylphosphine (76.2 g, 290 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 25.1 g (수율: 84%)을 얻었다.Sub 4-1b (38.6 g, 116 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (617 mL), triphenylphosphine (76.2 g, 290 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 25.1 g (yield: 84%) of the product.

2. Sub 4-8의 합성예2. Synthesis Example of Sub 4-8

Figure pat00190
Figure pat00190

(1) Sub 4-8a의 합성법(1) Synthesis of Sub 4-8a

7-bromonaphtho[1,2-b]benzofuran (50.0 g, 168 mmol)를 DMF (841 mL)에 녹인 후, bis(pinacolato)diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl2(dppf) (3.69 g, 5.05 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 47.5 g (수율: 82%)을 얻었다.After 7-bromonaphtho [1,2-b] benzofuran (50.0 g, 168 mmol) was dissolved in DMF (841 mL), bis (pinacolato) diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl 2 (dppf) (3.69 g, 5.05 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 47.5 g (yield: 82%) of the product.

(2) Sub 4-8b의 합성법(2) Synthesis of Sub 4-8b

상기 합성에서 얻어진 Sub 4-8a (47.5 g, 138 mmol)를 THF (690 mL)에 녹인 후, 1-bromo-2-nitrobenzene (27.9 g, 138 mmol), K2CO3 (57.2 g, 414 mmol), Pd(PPh3)4 (9.57 g, 8.28 mmol), 물 (345 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 39.8 g (수율: 86%)을 얻었다.After dissolving Sub 4-8a (47.5 g, 138 mmol) obtained in the above synthesis in THF (690 mL), 1-bromo-2-nitrobenzene (27.9 g, 138 mmol), K 2 CO 3 (57.2 g, 414 mmol) ), Pd (PPh 3 ) 4 (9.57 g, 8.28 mmol), water (345 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the produced compound was recrystallized after applying a silica gel column to obtain 39.8 g (yield: 86%) of the product.

(3) Sub 4-8의 합성법(3) Synthesis of Sub 4-8

상기 합성에서 얻어진 Sub 4-8b (39.8 g, 117 mmol)을 o-dichlorobenzene (586 mL)으로 녹인 후, triphenylphosphine (76.9 g, 293 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 31.4 g (수율: 87%)을 얻었다.Sub 4-8b (39.8 g, 117 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (586 mL), triphenylphosphine (76.9 g, 293 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 31.4 g (yield: 87%) of the product.

3. Sub 4-17의 합성예3. Synthesis Example of Sub 4-17

Figure pat00191
Figure pat00191

(1) Sub 4-17a의 합성법(1) Synthesis of Sub 4-17a

6-bromonaphtho[2,1-b]benzofuran (50.0 g, 168 mmol)를 DMF (841 mL)에 녹인 후, bis(pinacolato)diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl2(dppf) (3.69 g, 5.05 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 46.9 g (수율: 81%)을 얻었다.6-bromonaphtho [2,1-b] benzofuran (50.0 g, 168 mmol) was dissolved in DMF (841 mL), followed by bis (pinacolato) diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl 2 (dppf) (3.69 g, 5.05 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 46.9 g (yield: 81%) of the product.

(2) Sub 4-17b의 합성법(2) Synthesis of Sub 4-17b

상기 합성에서 얻어진 Sub 4-17a (46.9 g, 136 mmol)를 THF (681 mL)에 녹인 후, 1-bromo-2-nitrobenzene (27.5 g, 136 mmol), K2CO3 (56.5 g, 409 mmol), Pd(PPh3)4 (9.45 g, 8.18 mmol), 물 (341 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 38.4 g (수율: 86%)을 얻었다.Sub 4-17a (46.9 g, 136 mmol) obtained in the above synthesis was dissolved in THF (681 mL), and then 1-bromo-2-nitrobenzene (27.5 g, 136 mmol), K 2 CO 3 (56.5 g, 409 mmol) ), Pd (PPh 3 ) 4 (9.45 g, 8.18 mmol), water (341 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 38.4 g (yield: 86%) of the product.

(3) Sub 4-17의 합성법(3) Synthesis of Sub 4-17

상기 합성에서 얻어진 Sub 4-17b (38.4 g, 113 mmol)을 o-dichlorobenzene (566 mL)으로 녹인 후, triphenylphosphine (74.2 g, 283 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 29.9 g (수율: 86%)을 얻었다.Sub 4-17b (38.4 g, 113 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (566 mL), triphenylphosphine (74.2 g, 283 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 29.9 g of product (yield: 86%).

4. Sub 4-22의 합성예4. Synthesis Example of Sub 4-22

Figure pat00192
Figure pat00192

(1) Sub 4-22a의 합성법(1) Synthesis of Sub 4-22a

8-bromonaphtho[2,1-b]benzofuran (50.0 g, 168 mmol)를 DMF (841 mL)에 녹인 후, bis(pinacolato)diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl2(dppf) (3.69 g, 5.05 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 45.2 g (수율: 78%)을 얻었다.After dissolving 8-bromonaphtho [2,1-b] benzofuran (50.0 g, 168 mmol) in DMF (841 mL), bis (pinacolato) diboron (47.0 g, 185 mmol), KOAc (49.5 g, 505 mmol), PdCl 2 (dppf) (3.69 g, 5.05 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 45.2 g (yield: 78%) of the product.

(2) Sub 4-22b의 합성법(2) Synthesis of Sub 4-22b

상기 합성에서 얻어진 Sub 4-22a (45.2 g, 131 mmol)를 THF (657 mL)에 녹인 후, 1-bromo-2-nitronaphthalene (33.1 g, 131 mmol), K2CO3 (54.4 g, 394 mmol), Pd(PPh3)4 (9.10 g, 7.88 mmol), 물 (328 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 41.9 g (수율: 82%)을 얻었다.After dissolving Sub 4-22a (45.2 g, 131 mmol) obtained in the above synthesis in THF (657 mL), 1-bromo-2-nitronaphthalene (33.1 g, 131 mmol), K 2 CO 3 (54.4 g, 394 mmol) ), Pd (PPh 3 ) 4 (9.10 g, 7.88 mmol), water (328 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 41.9 g (yield: 82%) of the product.

(3) Sub 4-22의 합성법(3) Synthesis of Sub 4-22

상기 합성에서 얻어진 Sub 4-22b (41.9 g, 108 mmol)을 o-dichlorobenzene (538 mL)으로 녹인 후, triphenylphosphine (70.6 g, 269 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 32.3 g (수율: 84%)을 얻었다.Sub 4-22b (41.9 g, 108 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (538 mL), triphenylphosphine (70.6 g, 269 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 32.3 g of product (yield: 84%).

5. Sub 4-30의 합성예5. Synthesis Example of Sub 4-30

Figure pat00193
Figure pat00193

(1) Sub 4-30a의 합성법(1) Synthesis of Sub 4-30a

1-bromodibenzo[b,d]thiophene (50.0 g, 190 mmol)를 DMF (950 mL)에 녹인 후, bis(pinacolato)diboron (53.1 g, 209 mmol), KOAc (55.9 g, 570 mmol), PdCl2(dppf) (4.17 g, 5.70 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 47.7 g (수율: 81%)을 얻었다.After dissolving 1-bromodibenzo [b, d] thiophene (50.0 g, 190 mmol) in DMF (950 mL), bis (pinacolato) diboron (53.1 g, 209 mmol), KOAc (55.9 g, 570 mmol), PdCl 2 (dppf) (4.17 g, 5.70 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulted compound was recrystallized after applying a silica gel column to obtain 47.7 g (yield: 81%) of the product.

(2) Sub 4-30b의 합성법(2) Synthesis of Sub 4-30b

상기 합성에서 얻어진 Sub 4-30a (47.7 g, 153 mmol)를 THF (769 mL)에 녹인 후, 1-bromo-2-nitrobenzene (31.1 g, 153 mmol), K2CO3 (63.7 g, 461 mmol), Pd(PPh3)4 (10.2 g, 9.22 mmol), 물 (384 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 40.4 g (수율: 86%)을 얻었다.After dissolving Sub 4-30a (47.7 g, 153 mmol) obtained in the above synthesis in THF (769 mL), 1-bromo-2-nitrobenzene (31.1 g, 153 mmol), K 2 CO 3 (63.7 g, 461 mmol) ), Pd (PPh 3 ) 4 (10.2 g, 9.22 mmol), water (384 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 40.4 g (yield: 86%) of the product.

(3) Sub 4-30의 합성법(3) Synthesis of Sub 4-30

상기 합성에서 얻어진 Sub 4-30b (40.4 g, 132 mmol)을 o-dichlorobenzene (662 mL)으로 녹인 후, triphenylphosphine (86.8 g, 331 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 31.5 g (수율: 87%)을 얻었다.Sub 4-30b (40.4 g, 132 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (662 mL), triphenylphosphine (86.8 g, 331 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 31.5 g of product (yield: 87%).

6. Sub 4-34의 합성예6. Synthesis Example of Sub 4-34

Figure pat00194
Figure pat00194

(1) Sub 4-34a의 합성법(1) Synthesis of Sub 4-34a

11-bromobenzo[b]naphtho[1,2-d]thiophene (50.0 g, 160 mmol)를 DMF (798 mL)에 녹인 후, bis(pinacolato)diboron (44.6 g, 254 mmol), KOAc (47.0 g, 479 mmol), PdCl2(dppf) (3.50 g, 4.79 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 47.7 g (수율: 83%)을 얻었다.After dissolving 11-bromobenzo [b] naphtho [1,2-d] thiophene (50.0 g, 160 mmol) in DMF (798 mL), bis (pinacolato) diboron (44.6 g, 254 mmol), KOAc (47.0 g, 479 mmol), PdCl 2 (dppf) (3.50 g, 4.79 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 47.7 g (yield: 83%) of the product.

(2) Sub 4-34b의합성법(2) Synthesis of Sub 4-34b

상기 합성에서 얻어진 Sub 4-34a (47.7 g, 132 mmol)를 THF (662 mL)에 녹인 후, 2-bromo-1-nitronaphthalene (33.4 g, 132 mmol), K2CO3 (54.9 g, 397 mmol), Pd(PPh3)4 (9.18 g, 7.94 mmol), 물 (331 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 44.0 g (수율: 82%)을 얻었다.Sub 4-34a (47.7 g, 132 mmol) obtained in the above synthesis was dissolved in THF (662 mL), 2-bromo-1-nitronaphthalene (33.4 g, 132 mmol), K 2 CO 3 (54.9 g, 397 mmol) ), Pd (PPh 3 ) 4 (9.18 g, 7.94 mmol), water (331 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the produced compound was recrystallized after applying a silica gel column to obtain 44.0 g (yield: 82%) of the product.

(3) Sub 4-34의 합성법(3) Synthesis of Sub 4-34

상기 합성에서 얻어진 Sub 4-34b (44.0 g, 109 mmol)을 o-dichlorobenzene (543 mL)으로 녹인 후, triphenylphosphine (71.2 g, 271 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 34.4 g (수율: 85%)을 얻었다.Sub 4-34b (44.0 g, 109 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (543 mL), triphenylphosphine (71.2 g, 271 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 34.4 g (yield: 85%) of the product.

7. Sub 4-53의 합성예7. Synthesis Example of Sub 4-53

Figure pat00195
Figure pat00195

(1) Sub 4-53a의 합성법(1) Synthesis of Sub 4-53a

6-bromodinaphtho[1,2-b:1',2'-d]thiophene (50.0 g, 138 mmol)를 DMF (688 mL)에 녹인 후, bis(pinacolato)diboron (38.4 g, 151 mmol), KOAc (40.5 g, 413 mmol), PdCl2(dppf) (3.02 g, 4.13 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 44.1 g (수율: 78%)을 얻었다.After dissolving 6-bromodinaphtho [1,2-b: 1 ', 2'-d] thiophene (50.0 g, 138 mmol) in DMF (688 mL), bis (pinacolato) diboron (38.4 g, 151 mmol), KOAc (40.5 g, 413 mmol), PdCl 2 (dppf) (3.02 g, 4.13 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 44.1 g (yield: 78%) of the product.

(2) Sub 4-53b의 합성법(2) Synthesis of Sub 4-53b

상기 합성에서 얻어진 Sub 4-53a (44.1 g, 107 mmol)를 THF (537 mL)에 녹인 후, 1-bromo-2-nitrobenzene (21.7 g, 107 mmol), K2CO3 (44.6 g, 323 mmol), Pd(PPh3)4 (7.56 g, 6.45 mmol), 물 (269 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 34.9 g (수율: 80%)을 얻었다.After dissolving Sub 4-53a (44.1 g, 107 mmol) obtained in the above synthesis in THF (537 mL), 1-bromo-2-nitrobenzene (21.7 g, 107 mmol), K 2 CO 3 (44.6 g, 323 mmol) ), Pd (PPh 3 ) 4 (7.56 g, 6.45 mmol), water (269 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 34.9 g (yield: 80%) of the product.

(3) Sub 4-53의 합성법(3) Synthesis of Sub 4-53

상기 합성에서 얻어진 Sub 4-53b (34.9 g, 86 mmol)을 o-dichlorobenzene (430 mL)으로 녹인 후, triphenylphosphine (56.4 g, 215 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 26.7 g (수율: 83%)을 얻었다.Sub 4-53b (34.9 g, 86 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (430 mL), triphenylphosphine (56.4 g, 215 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulted compound was recrystallized after applying a silica gel column to obtain 26.7 g of product (yield: 83%).

8. Sub 4-56의 합성예8. Synthesis Example of Sub 4-56

Figure pat00196
Figure pat00196

(1) Sub 4-56a의 합성법(1) Synthesis of Sub 4-56a

4-bromodibenzo[b,d]thiophene (50.0 g, 190 mmol)를 DMF (950 mL)에 녹인 후, bis(pinacolato)diboron (53.1 g, 209 mmol), KOAc (55.9 g, 570 mmol), PdCl2(dppf) (4.17 g, 5.70 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 47.1 g (수율: 80%)을 얻었다.After 4-bromodibenzo [b, d] thiophene (50.0 g, 190 mmol) was dissolved in DMF (950 mL), bis (pinacolato) diboron (53.1 g, 209 mmol), KOAc (55.9 g, 570 mmol), PdCl 2 (dppf) (4.17 g, 5.70 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 47.1 g (yield: 80%) of the product.

(2) Sub 4-56b의 합성법(2) Synthesis of Sub 4-56b

상기 합성에서 얻어진 Sub 4-56a (47.1 g, 152 mmol)를 THF (759 mL)에 녹인 후2-bromo-1-nitronaphthalene (38.3 g, 152 mmol), K2CO3 (63.0 g, 456 mmol), Pd(PPh3)4 (10.5 g, 9.12 mmol), 물 (380 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 42.7 g (수율: 79%)을 얻었다.After dissolving Sub 4-56a (47.1 g, 152 mmol) obtained in the above synthesis in THF (759 mL), 2-bromo-1-nitronaphthalene (38.3 g, 152 mmol), K 2 CO 3 (63.0 g, 456 mmol) , Pd (PPh 3 ) 4 (10.5 g, 9.12 mmol), water (380 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 42.7 g of product (yield: 79%).

(3) Sub 4-56의 합성법(3) Synthesis of Sub 4-56

상기 합성에서 얻어진 Sub 4-56b (42.7 g, 120 mmol)을 o-dichlorobenzene (601 mL)으로 녹인 후, triphenylphosphine (78.8 g, 300 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 32.6 g (수율: 84%)을 얻었다.Sub 4-56b (42.7 g, 120 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (601 mL), triphenylphosphine (78.8 g, 300 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resultant compound was recrystallized after applying a silica gel column to obtain 32.6 g (yield: 84%) of the product.

9. Sub 4-70 합성예9. Sub 4-70 Synthesis Example

Figure pat00197
Figure pat00197

(1) Sub 4-70a의 합성법(1) Synthesis of Sub 4-70a

4-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol)를 DMF (915 mL)에 녹인 후, bis(pinacolato)diboron (51.1 g, 201 mmol), KOAc (53.9 g, 549 mmol), PdCl2(dppf) (4.02 g, 5.49 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 45.1 g (수율: 77%)을 얻었다.After 4-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) was dissolved in DMF (915 mL), bis (pinacolato) diboron (51.1 g, 201 mmol), KOAc (53.9 g, 549 mmol) ), PdCl 2 (dppf) (4.02 g, 5.49 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 45.1 g (yield: 77%) of the product.

(2) Sub 4-70b의 합성법(2) Synthesis of Sub 4-70b

상기 합성에서 얻어진 Sub 4-70a (45.1 g, 141 mmol)를 THF (740 mL)에 녹인 후, 9-bromo-10-nitrophenanthrene (42.5 g, 141 mmol), K2CO3 (58.4 g, 422 mmol), Pd(PPh3)4 (9.76 g, 8.45 mmol), 물 (352 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 36.3 g (수율: 62%)을 얻었다.After dissolving Sub 4-70a (45.1 g, 141 mmol) obtained in the above synthesis in THF (740 mL), 9-bromo-10-nitrophenanthrene (42.5 g, 141 mmol), K 2 CO 3 (58.4 g, 422 mmol) ), Pd (PPh 3 ) 4 (9.76 g, 8.45 mmol), water (352 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 36.3 g (yield: 62%) of the product.

(3) Sub 4-70의 합성법(3) Synthesis of Sub 4-70

상기 합성에서 얻어진 Sub 4-70b (36.3 g, 87 mmol)을 o-dichlorobenzene (437 mL)으로 녹인 후, triphenylphosphine (57.3 g, 218 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 27.1 g (수율: 81%)을 얻었다.Sub 4-70b (36.3 g, 87 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (437 mL), triphenylphosphine (57.3 g, 218 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 27.1 g (yield: 81%) of the product.

10. Sub 4-75의 합성예10. Synthesis Example of Sub 4-75

Figure pat00198
Figure pat00198

(1) Sub 4-75a의 합성법(1) Synthesis of Sub 4-75a

4-bromo-9,9'-spirobi[fluorene] (50.0 g, 126 mmol)를 DMF (632 mL)에 녹인 후, bis(pinacolato)diboron (35.3 g, 139 mmol), KOAc (37.2 g, 379 mmol), PdCl2(dppf) (2.78 g, 3.79 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 39.7 g (수율: 71%)을 얻었다.After 4-bromo-9,9'-spirobi [fluorene] (50.0 g, 126 mmol) was dissolved in DMF (632 mL), bis (pinacolato) diboron (35.3 g, 139 mmol), KOAc (37.2 g, 379 mmol) ), PdCl 2 (dppf) (2.78 g, 3.79 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 39.7 g (yield: 71%) of the product.

(2) Sub 4-75b의 합성법(2) Synthesis of Sub 4-75b

상기 합성에서 얻어진 Sub 4-75a (39.8 g, 90 mmol)를 THF (450 mL)에 녹인 후, 1-bromo-2-nitrobenzene (18.2 g, 90 mmol), K2CO3 (37.3 g, 270 mmol), Pd(PPh3)4 (6.24 g, 5.40 mmol), 물 (225 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 25.6 g (수율: 65%)을 얻었다.After dissolving Sub 4-75a (39.8 g, 90 mmol) obtained in the above synthesis in THF (450 mL), 1-bromo-2-nitrobenzene (18.2 g, 90 mmol), K 2 CO 3 (37.3 g, 270 mmol) ), Pd (PPh 3 ) 4 (6.24 g, 5.40 mmol), water (225 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resultant compound was recrystallized after applying a silica gel column to obtain 25.6 g of a product (yield: 65%).

(3) Sub 4-75의 합성법(3) Synthesis of Sub 4-75

상기 합성에서 얻어진 Sub 4-75b (25.6 g, 58 mmol)을 o-dichlorobenzene (293 mL)으로 녹인 후, triphenylphosphine (38.4 g, 146 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 19.2 g (수율: 81%)을 얻었다.Sub 4-75b (25.6 g, 58 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (293 mL), triphenylphosphine (38.4 g, 146 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 19.2 g (yield: 81%) of the product.

11. Sub 4-88의 합성예11. Synthesis Example of Sub 4-88

Figure pat00199
Figure pat00199

(1) Sub 4-88a의 합성법(1) Synthesis of Sub 4-88a

1-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol)를 DMF (915 mL)에 녹인 후, bis(pinacolato)diboron (58.9 g, 232 mmol), KOAc (62.1 g, 632 mmol), PdCl2(dppf) (4.63 g, 6.32 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 42.5 g (수율: 63%)을 얻었다.After dissolving 1-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in DMF (915 mL), bis (pinacolato) diboron (58.9 g, 232 mmol), KOAc (62.1 g, 632 mmol) ), PdCl 2 (dppf) (4.63 g, 6.32 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 42.5 g of product (yield: 63%).

(2) Sub 4-88b의 합성법(2) Synthesis of Sub 4-88b

상기 합성에서 얻어진 Sub 4-88a (42.5 g, 133 mmol)를 THF (664 mL)에 녹인 후2-bromo-3-nitronaphthalene (33.5 g, 133 mmol), K2CO3 (55.0 g, 398 mmol), Pd(PPh3)4 (9.20 g, 7.96 mmol), 물 (332 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 30.1 g (수율: 62%)을 얻었다.After dissolving Sub 4-88a (42.5 g, 133 mmol) obtained in the above synthesis in THF (664 mL), 2-bromo-3-nitronaphthalene (33.5 g, 133 mmol), K 2 CO 3 (55.0 g, 398 mmol) , Pd (PPh 3 ) 4 (9.20 g, 7.96 mmol), water (332 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 30.1 g (yield: 62%) of the product.

(3) Sub 4-88의 합성법(3) Synthesis of Sub 4-88

상기 합성에서 얻어진 Sub 4-88b (30.1 g, 82 mmol)을 o-dichlorobenzene (412 mL)으로 녹인 후, triphenylphosphine (54.0 g, 206 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 22.5 g (수율: 82%)을 얻었다.Sub 4-88b (30.1 g, 82 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (412 mL), triphenylphosphine (54.0 g, 206 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 22.5 g of product (yield: 82%).

12. Sub 4-90의 합성예12. Synthesis Example of Sub 4-90

Figure pat00200
Figure pat00200

(1) Sub 4-90a의 합성법(1) Synthesis of Sub 4-90a

1-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 155 mmol)를 DMF (773 mL)에 녹인 후, bis(pinacolato)diboron (43.2 g, 170 mmol), KOAc (45.5 g, 464 mmol), PdCl2(dppf) (3.40 g, 4.64 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 34.4 g (수율: 60%)을 얻었다.After dissolving 1-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 155 mmol) in DMF (773 mL), bis (pinacolato) diboron (43.2 g, 170 mmol), KOAc (45.5 g, 464 mmol) ), PdCl 2 (dppf) (3.40 g, 4.64 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 34.4 g (yield: 60%) of the product.

(2) Sub 4-90b의 합성법(2) Synthesis of Sub 4-90b

상기 합성에서 얻어진 Sub 4-90a (34.4 g, 93 mmol)를 THF (464 mL)에 녹인 후2-bromo-1-nitronaphthalene (23.4 g, 93 mmol), K2CO3 (38.5 g, 279 mmol), Pd(PPh3)4 (6.44 g, 5.57 mmol), 물 (232 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 23.5 g (수율: 61%)을 얻었다.After dissolving Sub 4-90a (34.4 g, 93 mmol) obtained in the above synthesis in THF (464 mL), 2-bromo-1-nitronaphthalene (23.4 g, 93 mmol), K 2 CO 3 (38.5 g, 279 mmol) , Pd (PPh 3 ) 4 (6.44 g, 5.57 mmol), water (232 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resultant compound was recrystallized after applying a silica gel column to obtain 23.5 g (yield: 61%) of the product.

(3) Sub 4-90의 합성법(3) Synthesis of Sub 4-90

상기 합성에서 얻어진 Sub 4-90b (23.5 g, 57 mmol)을 o-dichlorobenzene (283 mL)으로 녹인 후, triphenylphosphine (37.1 g, 141 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 17.4 g (수율: 81%)을 얻었다.Sub 4-90b (23.5 g, 57 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (283 mL), triphenylphosphine (37.1 g, 141 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 17.4 g (yield: 81%) of the product.

13. Sub 4-100의 합성예13. Synthesis Example of Sub 4-100

Figure pat00201
Figure pat00201

(1) Sub 4-100a의 합성법(1) Synthesis of Sub 4-100a

4-bromo-9-phenyl-9H-carbazole (50.0 g, 155 mmol)를 DMF (776 mL)에 녹인 후, bis(pinacolato)diboron (43.3 g, 171 mmol), KOAc (45.7 g, 466 mmol), PdCl2(dppf) (3.41 g, 4.65 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 48.1 g (수율: 84%)을 얻었다.After 4-bromo-9-phenyl-9H-carbazole (50.0 g, 155 mmol) was dissolved in DMF (776 mL), bis (pinacolato) diboron (43.3 g, 171 mmol), KOAc (45.7 g, 466 mmol), PdCl 2 (dppf) (3.41 g, 4.65 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 48.1 g (yield: 84%) of the product.

(2) Sub 4-100b의 합성법(2) Synthesis of Sub 4-100b

상기 합성에서 얻어진 Sub 4-100a (48.1 g, 130 mmol)를 THF (651 mL)에 녹인 후1-bromo-2-nitrobenzene (26.3 g, 130 mmol), K2CO3 (54.0 g, 391 mmol), Pd(PPh3)4 (9.03 g, 7.82 mmol), 물 (326 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 38.9 g (수율: 82%)을 얻었다.After dissolving Sub 4-100a (48.1 g, 130 mmol) obtained in the above synthesis in THF (651 mL), 1-bromo-2-nitrobenzene (26.3 g, 130 mmol), K 2 CO 3 (54.0 g, 391 mmol) , Pd (PPh 3 ) 4 (9.03 g, 7.82 mmol), water (326 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resultant compound was recrystallized after applying a silica gel column to obtain 38.9 g (yield: 82%) of the product.

(3) Sub 4-100의 합성법(3) Synthesis of Sub 4-100

상기 합성에서 얻어진 Sub 4-100b (38.9 g, 107 mmol)을 o-dichlorobenzene (534 mL)으로 녹인 후, triphenylphosphine (70.0 g, 267 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 30.5 g (수율: 86%)을 얻었다.Sub 4-100b (38.9 g, 107 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (534 mL), triphenylphosphine (70.0 g, 267 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 30.5 g of product (yield: 86%).

14. Sub 4-104의 합성예14. Synthesis Example of Sub 4-104

Figure pat00202
Figure pat00202

(1) Sub 4-104a의 합성법(1) Synthesis of Sub 4-104a

6-bromo-7-phenyl-7H-benzo[c]carbazole (50.0 g, 134 mmol)를 DMF (672 mL)에 녹인 후, bis(pinacolato)diboron (37.5 g, 148 mmol), KOAc (39.5 g, 403 mmol), PdCl2(dppf) (2.95 g, 4.03 mmol)를 첨가하고 120℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출한다. 추출이 완료되면 유기층을 MgSO4로 건조하고 농축한다. 이후, 생성된 화합물을 실리카겔 컬럼을 적용한 후 재결정하여 생성물 42.8 g (수율: 76%)을 얻었다.After dissolving 6-bromo-7-phenyl-7H-benzo [c] carbazole (50.0 g, 134 mmol) in DMF (672 mL), bis (pinacolato) diboron (37.5 g, 148 mmol), KOAc (39.5 g, 403 mmol), PdCl 2 (dppf) (2.95 g, 4.03 mmol) was added and stirred at 120 ° C. When the reaction is complete, DMF is removed by distillation and extracted with CH 2 Cl 2 and water. When extraction is completed, the organic layer is dried over MgSO 4 and concentrated. Thereafter, the resultant compound was recrystallized after applying a silica gel column to obtain 42.8 g (yield: 76%) of the product.

(2) Sub 4-104b의 합성법(2) Synthesis of Sub 4-104b

상기 합성에서 얻어진 Sub 4-104a (42.8 g, 102 mmol)를 THF (510 mL)에 녹인 후1-bromo-2-nitrobenzene (20.6 g, 102 mmol), K2CO3 (42.3 g, 306 mmol), Pd(PPh3)4 (7.08 g, 6.12 mmol), 물 (255 mL)을 첨가하고 80℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 29.2 g (수율: 69%)을 얻었다.After dissolving Sub 4-104a (42.8 g, 102 mmol) obtained in the above synthesis in THF (510 mL), 1-bromo-2-nitrobenzene (20.6 g, 102 mmol), K 2 CO 3 (42.3 g, 306 mmol) , Pd (PPh 3 ) 4 (7.08 g, 6.12 mmol), water (255 mL) was added and stirred at 80 ° C. After the reaction was completed, extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated. Thereafter, the produced compound was recrystallized after applying a silica gel column to obtain 29.2 g (yield: 69%) of the product.

(3) Sub 4-104의 합성법(3) Synthesis of Sub 4-104

상기 합성에서 얻어진 Sub 4-104b (29.2 g, 70 mmol)을 o-dichlorobenzene (352 mL)으로 녹인 후, triphenylphosphine (46.2 g, 176 mmol)을 첨가하고 200℃에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 22.1 g (수율: 82%)을 얻었다.Sub 4-104b (29.2 g, 70 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene (352 mL), triphenylphosphine (46.2 g, 176 mmol) was added and stirred at 200 ° C. When the reaction was completed, o- dichlorobenzene was removed through distillation, and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 22.1 g of product (yield: 82%).

Sub 4의 예시는 다음과 같으나, 이에 한정되는 것은 아니며, 표 5는 Sub 4에 속하는 화합물의 FD-MS (Field Desorption-Mass Spectrometry) 값을 나타낸 것이다.Examples of Sub 4 are as follows, but are not limited thereto, and Table 5 shows FD-MS (Field Desorption-Mass Spectrometry) values of compounds belonging to Sub 4.

Figure pat00203
Figure pat00203

Figure pat00204
Figure pat00204

Figure pat00205
Figure pat00205

Figure pat00206
Figure pat00206

Figure pat00207
Figure pat00207

Figure pat00208
Figure pat00208

Figure pat00209
Figure pat00209

Figure pat00210
Figure pat00210

Figure pat00211
Figure pat00211

Figure pat00212
Figure pat00212

Figure pat00213
Figure pat00213

Figure pat00214
Figure pat00214

Figure pat00215
Figure pat00215

Figure pat00216
Figure pat00216

Figure pat00217
Figure pat00217

Figure pat00218
Figure pat00218

Figure pat00219
Figure pat00219

Figure pat00220
Figure pat00220

Figure pat00221
Figure pat00221

Figure pat00222
Figure pat00222

Figure pat00223
Figure pat00223

Figure pat00224
Figure pat00224

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 4-1Sub 4-1 m/z=257.08(C18H11NO=257.29)m / z = 257.08 (C 18 H 11 NO = 257.29) Sub 4-2Sub 4-2 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-3Sub 4-3 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-4Sub 4-4 m/z=357.12(C26H15NO=357.41)m / z = 357.12 (C 26 H 15 NO = 357.41) Sub 4-5Sub 4-5 m/z=357.12(C26H15NO=357.41)m / z = 357.12 (C 26 H 15 NO = 357.41) Sub 4-6Sub 4-6 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-7Sub 4-7 m/z=407.13(C30H17NO=407.47)m / z = 407.13 (C 30 H 17 NO = 407.47) Sub 4-8Sub 4-8 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-9Sub 4-9 m/z=282.08(C19H10N2O=282.30)m / z = 282.08 (C 19 H 10 N 2 O = 282.30) Sub 4-10Sub 4-10 m/z=325.09(C22H12FNO=325.34)m / z = 325.09 (C 22 H 12 FNO = 325.34) Sub 4-11Sub 4-11 m/z=297.12(C21H15NO=297.36)m / z = 297.12 (C 21 H 15 NO = 297.36) Sub 4-12Sub 4-12 m/z=349.15(C25H19NO=349.43)m / z = 349.15 (C 25 H 19 NO = 349.43) Sub 4-13Sub 4-13 m/z=334.11(C23H14N2O=334.38)m / z = 334.11 (C 23 H 14 N 2 O = 334.38) Sub 4-14Sub 4-14 m/z=654.21(C45H26N4O2=654.73)m / z = 654.21 (C 45 H 26 N 4 O 2 = 654.73) Sub 4-15Sub 4-15 m/z=257.08(C18H11NO=257.29)m / z = 257.08 (C 18 H 11 NO = 257.29) Sub 4-16Sub 4-16 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-17Sub 4-17 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-18Sub 4-18 m/z=357.12(C26H15NO=357.41)m / z = 357.12 (C 26 H 15 NO = 357.41) Sub 4-19Sub 4-19 m/z=357.12(C26H15NO=357.41)m / z = 357.12 (C 26 H 15 NO = 357.41) Sub 4-20Sub 4-20 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-21Sub 4-21 m/z=307.10(C22H13NO=307.35)m / z = 307.10 (C 22 H 13 NO = 307.35) Sub 4-22Sub 4-22 m/z=357.12(C26H15NO=357.41)m / z = 357.12 (C 26 H 15 NO = 357.41) Sub 4-23Sub 4-23 m/z=282.08(C19H10N2O=282.30)m / z = 282.08 (C 19 H 10 N 2 O = 282.30) Sub 4-24Sub 4-24 m/z=325.09(C22H12FNO=325.34)m / z = 325.09 (C 22 H 12 FNO = 325.34) Sub 4-25Sub 4-25 m/z=337.15(C24H19NO=337.42)m / z = 337.15 (C 24 H 19 NO = 337.42) Sub 4-26Sub 4-26 m/z=349.15(C25H19NO=349.43)m / z = 349.15 (C 25 H 19 NO = 349.43) Sub 4-27Sub 4-27 m/z=334.11(C23H14N2O=334.38)m / z = 334.11 (C 23 H 14 N 2 O = 334.38) Sub 4-28Sub 4-28 m/z=407.13(C30H17NO=407.47)m / z = 407.13 (C 30 H 17 NO = 407.47) Sub 4-29Sub 4-29 m/z=654.21(C30H17NO=407.47)m / z = 654.21 (C 30 H 17 NO = 407.47) Sub 4-30Sub 4-30 m/z=273.06(C18H11NS=257.35)m / z = 273.06 (C 18 H 11 NS = 257.35) Sub 4-31Sub 4-31 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-32Sub 4-32 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-33Sub 4-33 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-34Sub 4-34 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-35Sub 4-35 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-36Sub 4-36 m/z=423.11(C30H17NS=423.53)m / z = 423.11 (C 30 H 17 NS = 423.53) Sub 4-37Sub 4-37 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-38Sub 4-38 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-39Sub 4-39 m/z=423.11(C30H17NS=423.53)m / z = 423.11 (C 30 H 17 NS = 423.53) Sub 4-40Sub 4-40 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-41Sub 4-41 m/z=298.06(C19H10N2S=298.36)m / z = 298.06 (C 19 H 10 N 2 S = 298.36) Sub 4-42Sub 4-42 m/z=299.08(C20H13NS=299.39)m / z = 299.08 (C 20 H 13 NS = 299.39) Sub 4-43Sub 4-43 m/z=331.07(C20H13NO2S=331.39)m / z = 331.07 (C 20 H 13 NO 2 S = 331.39) Sub 4-44Sub 4-44 m/z=452.13(C31H20N2S=452.58)m / z = 452.13 (C 31 H 20 N 2 S = 452.58) Sub 4-45Sub 4-45 m/z=514.15(C36H22N2S=514.65)m / z = 514.15 (C 36 H 22 N 2 S = 514.65) Sub 4-46Sub 4-46 m/z=439.10(C30H17NOS=439.53)m / z = 439.10 (C 30 H 17 NOS = 439.53) Sub 4-47Sub 4-47 m/z=273.06(C18H11NS=257.35)m / z = 273.06 (C 18 H 11 NS = 257.35) Sub 4-48Sub 4-48 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-49Sub 4-49 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-50Sub 4-50 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-51Sub 4-51 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-52Sub 4-52 m/z=423.11(C30H17NS=423.53)m / z = 423.11 (C 30 H 17 NS = 423.53) Sub 4-53Sub 4-53 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-54Sub 4-54 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-55Sub 4-55 m/z=423.11(C30H17NS=423.53)m / z = 423.11 (C 30 H 17 NS = 423.53) Sub 4-56Sub 4-56 m/z=323.08(C22H13NS=323.41)m / z = 323.08 (C 22 H 13 NS = 323.41) Sub 4-57Sub 4-57 m/z=373.09(C26H15NS=373.47)m / z = 373.09 (C 26 H 15 NS = 373.47) Sub 4-58Sub 4-58 m/z=298.06(C19H10N2S=298.36)m / z = 298.06 (C 19 H 10 N 2 S = 298.36) Sub 4-59Sub 4-59 m/z=299.08(C20H13NS=299.39)m / z = 299.08 (C 20 H 13 NS = 299.39) Sub 4-60Sub 4-60 m/z=331.07(C20H13NO2S=331.39)m / z = 331.07 (C 20 H 13 NO 2 S = 331.39) Sub 4-61Sub 4-61 m/z=514.15(C36H22N2S=514.65)m / z = 514.15 (C 36 H 22 N 2 S = 514.65) Sub 4-62Sub 4-62 m/z=439.10(C30H17NOS=439.53)m / z = 439.10 (C 30 H 17 NOS = 439.53) Sub 4-63Sub 4-63 m/z=452.13(C31H20N2S=452.58)m / z = 452.13 (C 31 H 20 N 2 S = 452.58) Sub 4-64Sub 4-64 m/z=455.08(C30H17NS2=455.59)m / z = 455.08 (C 30 H 17 NS 2 = 455.59) Sub 4-65Sub 4-65 m/z=283.14(C21H17N=283.37)m / z = 283.14 (C 21 H 17 N = 283.37) Sub 4-66Sub 4-66 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-67Sub 4-67 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-68Sub 4-68 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-69Sub 4-69 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-70Sub 4-70 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-71Sub 4-71 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-72Sub 4-72 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-73Sub 4-73 m/z=345.15(C26H19N=345.45)m / z = 345.15 (C 26 H 19 N = 345.45) Sub 4-74Sub 4-74 m/z=407.17(C31H21N=407.52)m / z = 407.17 (C 31 H 21 N = 407.52) Sub 4-75Sub 4-75 m/z=405.15(C31H19N=405.50)m / z = 405.15 (C 31 H 19 N = 405.50) Sub 4-76Sub 4-76 m/z=301.13(C21H16FN=301.36)m / z = 301.13 (C 21 H 16 FN = 301.36) Sub 4-77Sub 4-77 m/z=323.17(C24H21N=323.44)m / z = 323.17 (C 24 H 21 N = 323.44) Sub 4-78Sub 4-78 m/z=359.17(C27H21N=359.47)m / z = 359.17 (C 27 H 21 N = 359.47) Sub 4-79Sub 4-79 m/z=313.15(C22H19NO=313.40)m / z = 313.15 (C 22 H 19 NO = 313.40) Sub 4-80Sub 4-80 m/z=514.22(C36H26N4=514.63)m / z = 514.22 (C 36 H 26 N 4 = 514.63) Sub 4-81Sub 4-81 m/z=449.18(C33H23NO=449.55)m / z = 449.18 (C 33 H 23 NO = 449.55) Sub 4-82Sub 4-82 m/z=283.14(C21H17N=283.37)m / z = 283.14 (C 21 H 17 N = 283.37) Sub 4-83Sub 4-83 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-84Sub 4-84 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-85Sub 4-85 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-86Sub 4-86 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-87Sub 4-87 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-88Sub 4-88 m/z=333.15(C25H19N=333.43)m / z = 333.15 (C 25 H 19 N = 333.43) Sub 4-89Sub 4-89 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-90Sub 4-90 m/z=383.17(C29H21N=383.49)m / z = 383.17 (C 29 H 21 N = 383.49) Sub 4-91Sub 4-91 m/z=345.15(C26H19N=345.45)m / z = 345.15 (C 26 H 19 N = 345.45) Sub 4-92Sub 4-92 m/z=407.17(C31H21N=407.52)m / z = 407.17 (C 31 H 21 N = 407.52) Sub 4-93Sub 4-93 m/z=405.15(C31H19N=405.50)m / z = 405.15 (C 31 H 19 N = 405.50) Sub 4-94Sub 4-94 m/z=301.13(C21H16FN=301.36)m / z = 301.13 (C 21 H 16 FN = 301.36) Sub 4-95Sub 4-95 m/z=323.17(C24H21N=323.44)m / z = 323.17 (C 24 H 21 N = 323.44) Sub 4-96Sub 4-96 m/z=359.17(C27H21N=359.47)m / z = 359.17 (C 27 H 21 N = 359.47) Sub 4-97Sub 4-97 m/z=313.15(C22H19NO=313.40)m / z = 313.15 (C 22 H 19 NO = 313.40) Sub 4-98Sub 4-98 m/z=465.16(C33H23NS=465.61)m / z = 465.16 (C 33 H 23 NS = 465.61) Sub 4-99Sub 4-99 m/z=620.20(C42H28N4S=620.77)m / z = 620.20 (C 42 H 28 N 4 S = 620.77) Sub 4-100Sub 4-100 m/z=332.13(C24H16N2=332.41)m / z = 332.13 (C 24 H 16 N 2 = 332.41) Sub 4-101Sub 4-101 m/z=432.16(C32H20N2=432.53)m / z = 432.16 (C 32 H 20 N 2 = 432.53) Sub 4-102Sub 4-102 m/z=422.14(C30H18N2O=422.49)m / z = 422.14 (C 30 H 18 N 2 O = 422.49) Sub 4-103Sub 4-103 m/z=487.18(C33H21N5=487.57)m / z = 487.18 (C 33 H 21 N 5 = 487.57) Sub 4-104Sub 4-104 m/z=382.15(C28H18N2=382.47)m / z = 382.15 (C 28 H 18 N 2 = 382.47) Sub 4-105Sub 4-105 m/z=432.16(C32H20N2=432.53)m / z = 432.16 (C 32 H 20 N 2 = 432.53) Sub 4-106Sub 4-106 m/z=460.17(C32H20N4=460.54)m / z = 460.17 (C 32 H 20 N 4 = 460.54) Sub 4-107Sub 4-107 m/z=408.16(C30H20N2=408.50)m / z = 408.16 (C 30 H 20 N 2 = 408.50)

Sub 5의 예시Sub 5 example

반응식 4의 Sub 5의 예시는 하기와 같으며 이에 한정된 것은 아니다.Examples of Sub 5 of Scheme 4 are as follows and are not limited thereto.

Figure pat00225
Figure pat00225

Figure pat00226
Figure pat00226

Figure pat00227
Figure pat00227

Figure pat00228
Figure pat00228

Figure pat00229
Figure pat00229

Figure pat00230
Figure pat00230

Figure pat00231
Figure pat00231

Figure pat00232
Figure pat00232

Figure pat00233
Figure pat00233

Figure pat00234
Figure pat00234

Figure pat00235
Figure pat00235

Figure pat00236
Figure pat00236

Figure pat00237
Figure pat00237

Figure pat00238
Figure pat00238

Figure pat00239
Figure pat00239

Figure pat00240
Figure pat00240

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub 5-1Sub 5-1 m/z=240.05(C14H9ClN2=240.69)m / z = 240.05 (C 14 H 9 ClN 2 = 240.69) Sub 5-2Sub 5-2 m/z=290.06(C18H11ClN2=290.75)m / z = 290.06 (C 18 H 11 ClN 2 = 290.75) Sub 5-3Sub 5-3 m/z=290.06(C18H11ClN2=290.75)m / z = 290.06 (C 18 H 11 ClN 2 = 290.75) Sub 5-4Sub 5-4 m/z=316.08(C20H13ClN2=316.79)m / z = 316.08 (C 20 H 13 ClN 2 = 316.79) Sub 5-5Sub 5-5 m/z=316.08(C20H13ClN2=316.79)m / z = 316.08 (C 20 H 13 ClN 2 = 316.79) Sub 5-6Sub 5-6 m/z=316.08(C20H13ClN2=316.79)m / z = 316.08 (C 20 H 13 ClN 2 = 316.79) Sub 5-7Sub 5-7 m/z=360.03(C20H13BrN2=361.24)m / z = 360.03 (C 20 H 13 BrN 2 = 361.24) Sub 5-8Sub 5-8 m/z=436.06(C26H17BrN2=437.34)m / z = 436.06 (C 26 H 17 BrN 2 = 437.34) Sub 5-9Sub 5-9 m/z=410.04(C24H15BrN2=411.30)m / z = 410.04 (C 24 H 15 BrN 2 = 411.30) Sub 5-10Sub 5-10 m/z=486.07(C30H19BrN2=487.40)m / z = 486.07 (C 30 H 19 BrN 2 = 487.40) Sub 5-11Sub 5-11 m/z=340.08(C22H13ClN2=340.81)m / z = 340.08 (C 22 H 13 ClN 2 = 340.81) Sub 5-12Sub 5-12 m/z=508.17(C35H25ClN2=509.05)m / z = 508.17 (C 35 H 25 ClN 2 = 509.05) Sub 5-13Sub 5-13 m/z=460.06(C28H17BrN2=461.36)m / z = 460.06 (C 28 H 17 BrN 2 = 461.36) Sub 5-14Sub 5-14 m/z=478.12(C33H19ClN2=478.98)m / z = 478.12 (C 33 H 19 ClN 2 = 478.98) Sub 5-15Sub 5-15 m/z=440.11(C30H17ClN2=440.93)m / z = 440.11 (C 30 H 17 ClN 2 = 440.93) Sub 5-16Sub 5-16 m/z=390.09(C26H15ClN2=390.87)m / z = 390.09 (C 26 H 15 ClN 2 = 390.87) Sub 5-17Sub 5-17 m/z=576.12(C37H25BrN2=577.53)m / z = 576.12 (C 37 H 25 BrN 2 = 577.53) Sub 5-18Sub 5-18 m/z=241.04(C13H8ClN3=241.68)m / z = 241.04 (C 13 H 8 ClN 3 = 241.68) Sub 5-19Sub 5-19 m/z=361.02(C19H12BrN3=362.23)m / z = 361.02 (C 19 H 12 BrN 3 = 362.23) Sub 5-20Sub 5-20 m/z=317.07(C19H12ClN3=317.78)m / z = 317.07 (C 19 H 12 ClN 3 = 317.78) Sub 5-21Sub 5-21 m/z=444.11(C28H17ClN4=444.92)m / z = 444.11 (C 28 H 17 ClN 4 = 444.92) Sub 5-22Sub 5-22 m/z=317.07(C19H12ClN3=317.78)m / z = 317.07 (C 19 H 12 ClN 3 = 317.78) Sub 5-23Sub 5-23 m/z=318.07(C18H11ClN4=318.76)m / z = 318.07 (C 18 H 11 ClN 4 = 318.76) Sub 5-24Sub 5-24 m/z=362.02(C18H11BrN4=363.22)m / z = 362.02 (C 18 H 11 BrN 4 = 363.22) Sub 5-25Sub 5-25 m/z=480.14(C33H21ClN2=481.00)m / z = 480.14 (C 33 H 21 ClN 2 = 481.00) Sub 5-26Sub 5-26 m/z=340.08(C22H13ClN2=340.81)m / z = 340.08 (C 22 H 13 ClN 2 = 340.81) Sub 5-27Sub 5-27 m/z=390.06(C18H11ClN2=290.75)m / z = 390.06 (C 18 H 11 ClN 2 = 290.75) Sub 5-28Sub 5-28 m/z=430.09(C28H15ClN2O=430.89)m / z = 430.09 (C 28 H 15 ClN 2 O = 430.89) Sub 5-29Sub 5-29 m/z=314.06(C20H11ClN2=314.77)m / z = 314.06 (C 20 H 11 ClN 2 = 314.77) Sub 5-30Sub 5-30 m/z=290.06(C18H11ClN2=290.75)m / z = 290.06 (C 18 H 11 ClN 2 = 290.75) Sub 5-31Sub 5-31 m/z=390.09(C26H15ClN2=390.87)m / z = 390.09 (C 26 H 15 ClN 2 = 390.87) Sub 5-32Sub 5-32 m/z=446.06(C28H15ClN2S=446.95)m / z = 446.06 (C 28 H 15 ClN 2 S = 446.95) Sub 5-33Sub 5-33 m/z=429.10(C28H16ClN3=429.91)m / z = 429.10 (C 28 H 16 ClN 3 = 429.91) Sub 5-34Sub 5-34 m/z=462.10(C29H19ClN2S=463.00)m / z = 462.10 (C 29 H 19 ClN 2 S = 463.00) Sub 5-35Sub 5-35 m/z=446.12(C29H19ClN2O=446.93)m / z = 446.12 (C 29 H 19 ClN 2 O = 446.93) Sub 5-36Sub 5-36 m/z=422.06(C26H15ClN2S=422.93)m / z = 422.06 (C 26 H 15 ClN 2 S = 422.93) Sub 5-37Sub 5-37 m/z=330.06(C20H11ClN2O=330.77)m / z = 330.06 (C 20 H 11 ClN 2 O = 330.77) Sub 5-38Sub 5-38 m/z=432.14(C29H21ClN2=432.95)m / z = 432.14 (C 29 H 21 ClN 2 = 432.95) Sub 5-39Sub 5-39 m/z=450.04(C26H15BrN2O=451.32)m / z = 450.04 (C 26 H 15 BrN 2 O = 451.32) Sub 5-40Sub 5-40 m/z=476.09(C29H21BrN2=477.41)m / z = 476.09 (C 29 H 21 BrN 2 = 477.41) Sub 5-41Sub 5-41 m/z=508.17(C35H25ClN2=509.05)m / z = 508.17 (C 35 H 25 ClN 2 = 509.05) Sub 5-42Sub 5-42 m/z=346.03(C20H11ClN2S=346.83)m / z = 346.03 (C 20 H 11 ClN 2 S = 346.83) Sub 5-43Sub 5-43 m/z=466.01(C26H15BrN2S=467.38)m / z = 466.01 (C 26 H 15 BrN 2 S = 467.38) Sub 5-44Sub 5-44 m/z=615.09(C38H22BrN3O=616.52)m / z = 615.09 (C 38 H 22 BrN 3 O = 616.52) Sub 5-45Sub 5-45 m/z=449.05(C26H16BrN3=450.34)m / z = 449.05 (C 26 H 16 BrN 3 = 450.34) Sub 5-46Sub 5-46 m/z=329.07(C20H12ClN3=329.79)m / z = 329.07 (C 20 H 12 ClN 3 = 329.79) Sub 5-47Sub 5-47 m/z=540.05(C32H17BrN2O2=541.40)m / z = 540.05 (C 32 H 17 BrN 2 O 2 = 541.40) Sub 5-48Sub 5-48 m/z=260.09(C17H12N2O=260.30)m / z = 260.09 (C 17 H 12 N 2 O = 260.30) Sub 5-49Sub 5-49 m/z=386.14(C27H18N2O=386.45)m / z = 386.14 (C 27 H 18 N 2 O = 386.45) Sub 5-50Sub 5-50 m/z=387.14(C26H17N3O=387.44)m / z = 387.14 (C 26 H 17 N 3 O = 387.44) Sub 5-51Sub 5-51 m/z=480.11(C31H17ClN4=480.96)m / z = 480.11 (C 31 H 17 ClN 4 = 480.96) Sub 5-52Sub 5-52 m/z=380.07(C24H13ClN2O=380.83)m / z = 380.07 (C 24 H 13 ClN 2 O = 380.83) Sub 5-53Sub 5-53 m/z=396.05(C24H13ClN2S=396.89)m / z = 396.05 (C 24 H 13 ClN 2 S = 396.89) Sub 5-54Sub 5-54 m/z=406.09(C26H15ClN2O=406.87)m / z = 406.09 (C 26 H 15 ClN 2 O = 406.87) Sub 5-55Sub 5-55 m/z=416.11(C28H17ClN2=416.91)m / z = 416.11 (C 28 H 17 ClN 2 = 416.91) Sub 5-56Sub 5-56 m/z=356.07(C22H13ClN2O=356.81)m / z = 356.07 (C 22 H 13 ClN 2 O = 356.81) Sub 5-57Sub 5-57 m/z=356.07(C22H13ClN2O=356.81)m / z = 356.07 (C 22 H 13 ClN 2 O = 356.81) Sub 5-58Sub 5-58 m/z=400.02(C22H13BrN2O=401.26)m / z = 400.02 (C 22 H 13 BrN 2 O = 401.26) Sub 5-59Sub 5-59 m/z=370.05(C22H11ClN2O2=370.79)m / z = 370.05 (C 22 H 11 ClN 2 O 2 = 370.79) Sub 5-60Sub 5-60 m/z=490.03(C28H15BrN2O2=491.34)m / z = 490.03 (C 28 H 15 BrN 2 O 2 = 491.34) Sub 5-61Sub 5-61 m/z=445.10(C28H16ClN3O=445.91)m / z = 445.10 (C 28 H 16 ClN 3 O = 445.91) Sub 5-62Sub 5-62 m/z=565.08(C34H20BrN3O=566.46)m / z = 565.08 (C 34 H 20 BrN 3 O = 566.46) Sub 5-63Sub 5-63 m/z=296.02(C16H9ClN2S=296.77)m / z = 296.02 (C 16 H 9 ClN 2 S = 296.77) Sub 5-64Sub 5-64 m/z=372.05(C22H13ClN2S=372.87)m / z = 372.05 (C 22 H 13 ClN 2 S = 372.87) Sub 5-65Sub 5-65 m/z=372.05(C22H13ClN2S=372.87)m / z = 372.05 (C 22 H 13 ClN 2 S = 372.87) Sub 5-66Sub 5-66 m/z=372.05(C22H13ClN2S=372.87)m / z = 372.05 (C 22 H 13 ClN 2 S = 372.87) Sub 5-67Sub 5-67 m/z=422.06(C26H15ClN2S=422.93)m / z = 422.06 (C 26 H 15 ClN 2 S = 422.93) Sub 5-68Sub 5-68 m/z=386.03(C22H11ClN2OS=386.85)m / z = 386.03 (C 22 H 11 ClN 2 OS = 386.85) Sub 5-69Sub 5-69 m/z=461.08(C28H16ClN3S=461.97)m / z = 461.08 (C 28 H 16 ClN 3 S = 461.97) Sub 5-70Sub 5-70 m/z=467.01(C25H14BrN3S=468.37)m / z = 467.01 (C 25 H 14 BrN 3 S = 468.37) Sub 5-71Sub 5-71 m/z=405.10(C26H16ClN3=405.89)m / z = 405.10 (C 26 H 16 ClN 3 = 405.89) Sub 5-72Sub 5-72 m/z=596.18(C40H25ClN4=597.12)m / z = 596.18 (C 40 H 25 ClN 4 = 597.12) Sub 5-73Sub 5-73 m/z=561.14(C35H20ClN5O=562.03)m / z = 561.14 (C 35 H 20 ClN 5 O = 562.03) Sub 5-74Sub 5-74 m/z=577.11(C35H20ClN5S=578.09)m / z = 577.11 (C 35 H 20 ClN 5 S = 578.09) Sub 5-75Sub 5-75 m/z=258.04(C14H8ClFN2=258.68)m / z = 258.04 (C 14 H 8 ClFN 2 = 258.68) Sub 5-76Sub 5-76 m/z=265.04(C15H8ClN3=265.70)m / z = 265.04 (C 15 H 8 ClN 3 = 265.70) Sub 5-77Sub 5-77 m/z=245.08(C14H4D5ClN2=245.72)m / z = 245.08 (C 14 H 4 D 5 ClN 2 = 245.72) Sub 5-78Sub 5-78 m/z=376.13(C23H21ClN2O=376.88)m / z = 376.13 (C 23 H 21 ClN 2 O = 376.88)

5. 화학식 2의 Product의 합성 예시5. Synthesis Example of Product of Formula 2

둥근바닥플라스크에 Sub 4 (1 당량)을 Toluene으로 녹인 후에, Sub 5 (1 당량), Pd2(dba)3 (0.03 당량), P(t-Bu)3 (0.06 당량), NaOt-Bu (2 당량)을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Final product 2를 얻었다.After dissolving Sub 4 (1 eq) in a round bottom flask with Toluene, Sub 5 (1 eq), Pd 2 (dba) 3 (0.03 eq), P ( t -Bu) 3 (0.06 eq), NaO t -Bu (2 eq.) Was added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was silicagel column and recrystallized to obtain Final product 2.

1. 3-25의 합성예1. Synthesis Example of 3-25

Figure pat00241
Figure pat00241

Sub 4-1 (25.1 g, 97.6 mmol), Toluene (488 mL), Sub 5-63 (29.0 g, 97.6 mmol), Pd2(dba)3 (2.68 g, 2.93 mmol), P(t-Bu)3 (1.18 g, 5.85 mmol), NaOt-Bu (18.8 g, 195 mmol)을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 35.3 g (수율: 70%)를 얻었다.Sub 4-1 (25.1 g, 97.6 mmol), Toluene (488 mL), Sub 5-63 (29.0 g, 97.6 mmol), Pd 2 (dba) 3 (2.68 g, 2.93 mmol), P ( t -Bu) 3 (1.18 g, 5.85 mmol), NaO t -Bu (18.8 g, 195 mmol) was added and stirred at 100 ° C. After the reaction was completed, the organic layer was extracted with CH 2 Cl 2 and water, dried over MgSO 4 and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 35.3 g of product (yield: 70%).

2. 3-36의 합성예2. Synthesis Example of 3-36

Figure pat00242
Figure pat00242

Sub 4-30 (31.5 g, 115 mmol), Toluene (576 mL), Sub 5-28 (49.7 g, 115 mmol), Pd2(dba)3 (3.17 g, 3.46 mmol), P(t-Bu)3 (1.40 g, 6.91 mmol), NaOt-Bu (22.2 g, 231 mmol)을 상기 3-25의 합성방법을 이용하여 최종 생성물 52.3 g (수율: 68%)를 얻었다.Sub 4-30 (31.5 g, 115 mmol), Toluene (576 mL), Sub 5-28 (49.7 g, 115 mmol), Pd 2 (dba) 3 (3.17 g, 3.46 mmol), P ( t -Bu) 3 (1.40 g, 6.91 mmol), NaO t -Bu (22.2 g, 231 mmol) was obtained using the synthesis method of 3-25 above to obtain 52.3 g of the final product (yield: 68%).

3. 3-74의 합성예3. Synthesis Example of 3-74

Figure pat00243
Figure pat00243

Sub 4-100 (30.5 g, 91.8 mmol), Toluene (459 mL), Sub 5-58 (36.8 g, 91.8 mmol), Pd2(dba)3 (2.52 g, 2.75 mmol), P(t-Bu)3 (1.11 g, 5.51 mmol), NaOt-Bu (17.6 g, 184 mmol )을 상기 3-25의 합성방법을 이용하여 최종 생성물 43.7 g (수율: 73%)를 얻었다.Sub 4-100 (30.5 g, 91.8 mmol), Toluene (459 mL), Sub 5-58 (36.8 g, 91.8 mmol), Pd 2 (dba) 3 (2.52 g, 2.75 mmol), P ( t -Bu) 3 (1.11 g, 5.51 mmol), NaO t -Bu (17.6 g, 184 mmol) was obtained using the synthesis method of 3-25 above to obtain 43.7 g (yield: 73%) of the final product.

4. 4-37의 합성예4. Synthesis Example of 4-37

Figure pat00244
Figure pat00244

Sub 4-53 (26.7 g, 71.5 mmol), Toluene (357 mL), Sub 5-1 (17.2 g, 71.5 mmol), Pd2(dba)3 (1.96 g, 2.14 mmol), P(t-Bu)3 (0.87 g, 4.29 mmol), NaOt-Bu (13.7 g, 143 mmol )을 상기 3-25의 합성방법을 이용하여 최종 생성물 28.5 g (수율: 69%)를 얻었다.Sub 4-53 (26.7 g, 71.5 mmol), Toluene (357 mL), Sub 5-1 (17.2 g, 71.5 mmol), Pd 2 (dba) 3 (1.96 g, 2.14 mmol), P ( t -Bu) 3 (0.87 g, 4.29 mmol), NaO t -Bu (13.7 g, 143 mmol) was obtained using the synthesis method of 3-25 to obtain 28.5 g of the final product (yield: 69%).

5. 4-38의 합성예5. Synthesis Example of 4-38

Figure pat00245
Figure pat00245

Sub 4-88 (22.5 g, 67.5 mmol), Toluene (337 mL), Sub 5-7 (24.4 g, 67.5 mmol), Pd2(dba)3 (1.85 g, 2.02 mmol), P(t-Bu)3 (0.82 g, 4.05 mmol), NaOt-Bu (13.0 g, 135 mmol )을 상기 3-25의 합성방법을 이용하여 최종 생성물 29.8 g (수율: 72%)를 얻었다.Sub 4-88 (22.5 g, 67.5 mmol), Toluene (337 mL), Sub 5-7 (24.4 g, 67.5 mmol), Pd 2 (dba) 3 (1.85 g, 2.02 mmol), P ( t -Bu) 3 (0.82 g, 4.05 mmol), NaO t -Bu (13.0 g, 135 mmol) was obtained using the synthesis method of 3-25 to obtain a final product 29.8 g (yield: 72%).

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS 3-13-1 m/z=461.15(C32H19N3O=461.52)m / z = 461.15 (C 32 H 19 N 3 O = 461.52) 3-23-2 m/z=527.15(C36H21N3S=527.65)m / z = 527.15 (C 36 H 21 N 3 S = 527.65) 3-33-3 m/z=537.22(C39H27N3=537.67)m / z = 537.22 (C 39 H 27 N 3 = 537.67) 3-43-4 m/z=537.18(C38H23N3O=537.62)m / z = 537.18 (C 38 H 23 N 3 O = 537.62) 3-53-5 m/z=477.13(C32H19N3S=477.59)m / z = 477.13 (C 32 H 19 N 3 S = 477.59) 3-63-6 m/z=487.2(C35H25N3=487.61)m / z = 487.2 (C 35 H 25 N 3 = 487.61) 3-73-7 m/z=603.18(C42H25N3S=603.74)m / z = 603.18 (C 42 H 25 N 3 S = 603.74) 3-83-8 m/z=613.25(C45H31N3=613.76)m / z = 613.25 (C 45 H 31 N 3 = 613.76) 3-93-9 m/z=511.17(C36H21N3O=511.58)m / z = 511.17 (C 36 H 21 N 3 O = 511.58) 3-103-10 m/z=528.14(C35H20N4S=528.63)m / z = 528.14 (C 35 H 20 N 4 S = 528.63) 3-113-11 m/z=614.25(C44H30N4=614.75)m / z = 614.25 (C 44 H 30 N 4 = 614.75) 3-123-12 m/z=601.18(C42H23N3O2=601.67)m / z = 601.18 (C 42 H 23 N 3 O 2 = 601.67) 3-133-13 m/z=709.16(C48H27N3S2=709.89)m / z = 709.16 (C 48 H 27 N 3 S 2 = 709.89) 3-143-14 m/z=741.31(C55H39N3=741.94)m / z = 741.31 (C 55 H 39 N 3 = 741.94) 3-153-15 m/z=638.21(C45H26N4O=638.73)m / z = 638.21 (C 45 H 26 N 4 O = 638.73) 3-163-16 m/z=629.19(C44H27N3S=629.78)m / z = 629.19 (C 44 H 27 N 3 S = 629.78) 3-173-17 m/z=713.28(C53H35N3=713.88)m / z = 713.28 (C 53 H 35 N 3 = 713.88) 3-183-18 m/z=727.23(C52H29N3O2=727.82)m / z = 727.23 (C 52 H 29 N 3 O 2 = 727.82) 3-193-19 m/z=769.26(C55H35N3S=769.79)m / z = 769.26 (C 55 H 35 N 3 S = 769.79) 3-203-20 m/z=637.25(C47H31N3=637.79)m / z = 637.25 (C 47 H 31 N 3 = 637.79) 3-213-21 m/z=588.2(C41H24N4O=588.67)m / z = 588.2 (C 41 H 24 N 4 O = 588.67) 3-223-22 m/z=677.19(C48H27N3S=677.83)m / z = 677.19 (C 48 H 27 N 3 S = 677.83) 3-233-23 m/z=543.18(C37H25N3S=543.69)m / z = 543.18 (C 37 H 25 N 3 S = 543.69) 3-243-24 m/z=593.16(C40H23N3OS=593.70)m / z = 593.16 (C 40 H 23 N 3 OS = 593.70) 3-253-25 m/z=517.12(C34H19N3OS=517.61)m / z = 517.12 (C 34 H 19 N 3 OS = 517.61) 3-263-26 m/z=533.1(C34H19N3S2=533.67)m / z = 533.1 (C 34 H 19 N 3 S 2 = 533.67) 3-273-27 m/z=649.22(C47H27N3O=649.75)m / z = 649.22 (C 47 H 27 N 3 O = 649.75) 3-283-28 m/z=627.19(C44H25N3O2=627.70)m / z = 627.19 (C 44 H 25 N 3 O 2 = 627.70) 3-293-29 m/z=644.17(C43H24N4OS=644.75)m / z = 644.17 (C 43 H 24 N 4 OS = 644.75) 3-303-30 m/z=743.24(C53H33N3S=743.93)m / z = 743.24 (C 53 H 33 N 3 S = 743.93) 3-313-31 m/z=732.20(C50H28N4OS=732.86)m / z = 732.20 (C 50 H 28 N 4 OS = 732.86) 3-323-32 m/z=708.23(C49H32N4S=708.88)m / z = 708.23 (C 49 H 32 N 4 S = 708.88) 3-333-33 m/z=641.17(C44H23N3O3=641.69)m / z = 641.17 (C 44 H 23 N 3 O 3 = 641.69) 3-343-34 m/z=759.18(C52H29N3S2=759.95)m / z = 759.18 (C 52 H 29 N 3 S 2 = 759.95) 3-353-35 m/z=743.26(C53H33N3O2=743.87)m / z = 743.26 (C 53 H 33 N 3 O 2 = 743.87) 3-363-36 m/z=667.17(C46H25N3OS=667.79)m / z = 667.17 (C 46 H 25 N 3 OS = 667.79) 3-373-37 m/z=733.16(C50H27N3S2=733.91)m / z = 733.16 (C 50 H 27 N 3 S 2 = 733.91) 3-383-38 m/z=808.30(C56H36N6O=808.95)m / z = 808.30 (C 56 H 36 N 6 O = 808.95) 3-393-39 m/z=742.24(C52H30N4O2=742.84)m / z = 742.24 (C 52 H 30 N 4 O 2 = 742.84) 3-403-40 m/z=692.20(C48H28N4S=692.84)m / z = 692.20 (C 48 H 28 N 4 S = 692.84) 3-413-41 m/z=677.25(C49H31N3O=677.81)m / z = 677.25 (C 49 H 31 N 3 O = 677.81) 3-423-42 m/z=667.23(C47H29N3O2=667.77)m / z = 667.23 (C 47 H 29 N 3 O 2 = 667.77) 3-433-43 m/z=677.19(C48H27N3S=677.83)m / z = 677.19 (C 48 H 27 N 3 S = 677.83) 3-443-44 m/z=773.32(C56H40FN3=773.96)m / z = 773.32 (C 56 H 40 FN 3 = 773.96) 3-453-45 m/z=504.14(C33H17FN4O=504.52)m / z = 504.14 (C 33 H 17 FN 4 O = 504.52) 3-463-46 m/z=653.19(C46H27N3S=653.80)m / z = 653.19 (C 46 H 27 N 3 S = 653.80) 3-473-47 m/z=737.28(C55H35N3=737.91)m / z = 737.28 (C 55 H 35 N 3 = 737.91) 3-483-48 m/z=466.18(C32H14D5N3O=466.55)m / z = 466.18 (C 32 H 14 D 5 N 3 O = 466.55) 3-493-49 m/z=535.14(C34H21N3O2S=535.62)m / z = 535.14 (C 34 H 21 N 3 O 2 S = 535.62) 3-503-50 m/z=588.23(C42H28N4=588.71)m / z = 588.23 (C 42 H 28 N 4 = 588.71) 3-513-51 m/z=529.16(C36H20FN3O=529.57)m / z = 529.16 (C 36 H 20 FN 3 O = 529.57) 3-523-52 m/z=591.15(C39H21N5S=591.69)m / z = 591.15 (C 39 H 21 N 5 S = 591.69) 3-533-53 m/z=717.28(C52H35N3O=717.87)m / z = 717.28 (C 52 H 35 N 3 O = 717.87) 3-543-54 m/z=665.22(C46H27N5O=665.76)m / z = 665.22 (C 46 H 27 N 5 O = 665.76) 3-553-55 m/z=656.20(C45H28N4S=656.81)m / z = 656.20 (C 45 H 28 N 4 S = 656.81) 3-563-56 m/z=725.28(C54H35N3=725.90)m / z = 725.28 (C 54 H 35 N 3 = 725.90) 3-573-57 m/z=651.23(C47H29N3O=651.77)m / z = 651.23 (C 47 H 29 N 3 O = 651.77) 3-583-58 m/z=603.18(C42H25N3S=603.74)m / z = 603.18 (C 42 H 25 N 3 S = 603.74) 3-593-59 m/z=451.20(C32H25N3=451.57)m / z = 451.20 (C 32 H 25 N 3 = 451.57) 3-603-60 m/z=689.30(C48H39N3O2=689.86)m / z = 689.30 (C 48 H 39 N 3 O 2 = 689.86) 3-613-61 m/z=845.25(C60H35N3OS=846.02)m / z = 845.25 (C 60 H 35 N 3 OS = 846.02) 3-623-62 m/z=843.29(C61H37N3O2=843.99)m / z = 843.29 (C 61 H 37 N 3 O 2 = 843.99) 3-633-63 m/z=851.29(C63H37N3O=852.01)m / z = 851.29 (C 63 H 37 N 3 O = 852.01) 3-643-64 m/z=742.22(C52H30N4S=742.90)m / z = 742.22 (C 52 H 30 N 4 S = 742.90) 3-653-65 m/z=870.35(C62H42N6=871.06)m / z = 870.35 (C 62 H 42 N 6 = 871.06) 3-663-66 m/z=792.25(C56H32N4O2=792.90)m / z = 792.25 (C 56 H 32 N 4 O 2 = 792.90) 3-673-67 m/z=666.19(C46H26N4S=666.80)m / z = 666.19 (C 46 H 26 N 4 S = 666.80) 3-683-68 m/z=843.34(C61H41N5=844.03)m / z = 843.34 (C 61 H 41 N 5 = 844.03) 3-693-69 m/z=538.18(C37H22N4O=538.61)m / z = 538.18 (C 37 H 22 N 4 O = 538.61) 3-703-70 m/z=718.22(C50H30N4S=718.88)m / z = 718.22 (C 50 H 30 N 4 S = 718.88) 3-713-71 m/z=353.25(C47H31N3O=356.79)m / z = 353.25 (C 47 H 31 N 3 O = 356.79) 3-723-72 m/z=858.27(C59H34N6O2=858.96)m / z = 858.27 (C 59 H 34 N 6 O 2 = 858.96) 3-733-73 m/z=626.21(C44H26N4O=626.72)m / z = 626.21 (C 44 H 26 N 4 O = 626.72) 3-743-74 m/z=652.23(C46H28N4O=652.76)m / z = 652.23 (C 46 H 28 N 4 O = 652.76) 3-753-75 m/z=636.23(C46H28N4=636.76)m / z = 636.23 (C 46 H 28 N 4 = 636.76) 3-763-76 m/z=691.25(C47H29N7=691.80)m / z = 691.25 (C 47 H 29 N 7 = 691.80) 4-14-1 m/z=461.15(C32H19N3O=461.52)m / z = 461.15 (C 32 H 19 N 3 O = 461.52) 4-24-2 m/z=527.15(C36H21N3S=527.65)m / z = 527.15 (C 36 H 21 N 3 S = 527.65) 4-34-3 m/z=537.22(C39H27N3=537.67)m / z = 537.22 (C 39 H 27 N 3 = 537.67) 4-44-4 m/z=537.18(C38H23N3O=537.62)m / z = 537.18 (C 38 H 23 N 3 O = 537.62) 4-54-5 m/z=477.13(C32H19N3S=477.59)m / z = 477.13 (C 32 H 19 N 3 S = 477.59) 4-64-6 m/z=487.20(C35H25N3=487.61)m / z = 487.20 (C 35 H 25 N 3 = 487.61) 4-74-7 m/z=587.20(C42H25N3O=587.68)m / z = 587.20 (C 42 H 25 N 3 O = 587.68) 4-84-8 m/z=613.25(C45H31N3=613.76)m / z = 613.25 (C 45 H 31 N 3 = 613.76) 4-94-9 m/z=511.17(C36H21N3O=511.58)m / z = 511.17 (C 36 H 21 N 3 O = 511.58) 4-104-10 m/z=528.14(C35H20N4S=528.63)m / z = 528.14 (C 35 H 20 N 4 S = 528.63) 4-114-11 m/z=615.24(C43H29N5=615.74)m / z = 615.24 (C 43 H 29 N 5 = 615.74) 4-124-12 m/z=617.16(C42H23N3OS=617.73)m / z = 617.16 (C 42 H 23 N 3 OS = 617.73) 4-134-13 m/z=709.16(C48H27N3S2=709.89)m / z = 709.16 (C 48 H 27 N 3 S 2 = 709.89) 4-144-14 m/z=741.31(C55H39N3=741.94)m / z = 741.31 (C 55 H 39 N 3 = 741.94) 4-154-15 m/z=638.21(C45H26N4O=638.73)m / z = 638.21 (C 45 H 26 N 4 O = 638.73) 4-164-16 m/z=629.19(C44H27N3S=629.78)m / z = 629.19 (C 44 H 27 N 3 S = 629.78) 4-174-17 m/z=713.28(C53H35N3=713.88)m / z = 713.28 (C 53 H 35 N 3 = 713.88) 4-184-18 m/z=743.20(C52H29N3OS=743.88)m / z = 743.20 (C 52 H 29 N 3 OS = 743.88) 4-194-19 m/z=869.29(C63H39N3S=870.09)m / z = 869.29 (C 63 H 39 N 3 S = 870.09) 4-204-20 m/z=637.25(C47H31N3=637.79)m / z = 637.25 (C 47 H 31 N 3 = 637.79) 4-214-21 m/z=589.19(C40H23N5O=589.66)m / z = 589.19 (C 40 H 23 N 5 O = 589.66) 4-224-22 m/z=677.19(C48H27N3S=677.83)m / z = 677.19 (C 48 H 27 N 3 S = 677.83) 4-234-23 m/z=543.18(C37H25N3S=543.69)m / z = 543.18 (C 37 H 25 N 3 S = 543.69) 4-244-24 m/z=653.21(C46H27N3O2=653.74)m / z = 653.21 (C 46 H 27 N 3 O 2 = 653.74) 4-254-25 m/z=517.12(C34H19N3OS=517.61)m / z = 517.12 (C 34 H 19 N 3 OS = 517.61) 4-264-26 m/z=533.10(C34H19N3S2=533.67)m / z = 533.10 (C 34 H 19 N 3 S 2 = 533.67) 4-274-27 m/z=665.19(C47H27N3S=665.81)m / z = 665.19 (C 47 H 27 N 3 S = 665.81) 4-284-28 m/z=643.17(C44H25N3OS=643.76)m / z = 643.17 (C 44 H 25 N 3 OS = 643.76) 4-294-29 m/z=660.14(C43H24N4S2=660.81)m / z = 660.14 (C 43 H 24 N 4 S 2 = 660.81) 4-304-30 m/z=743.24(C53H33N3S=743.93)m / z = 743.24 (C 53 H 33 N 3 S = 743.93) 4-314-31 m/z=732.20(C50H28N4OS=732.86)m / z = 732.20 (C 50 H 28 N 4 OS = 732.86) 4-324-32 m/z=682.18(C46H26N4OS=682.80)m / z = 682.18 (C 46 H 26 N 4 OS = 682.80) 4-334-33 m/z=657.15(C44H23N3O2S=657.75)m / z = 657.15 (C 44 H 23 N 3 O 2 S = 657.75) 4-344-34 m/z=743.20(C52H29N3OS=743.88)m / z = 743.20 (C 52 H 29 N 3 OS = 743.88) 4-354-35 m/z=743.26(C53H33N3O2=743.87)m / z = 743.26 (C 53 H 33 N 3 O 2 = 743.87) 4-364-36 m/z=667.17(C46H25N3OS=667.79)m / z = 667.17 (C 46 H 25 N 3 OS = 667.79) 4-374-37 m/z=577.16(C40H23N3S=577.71)m / z = 577.16 (C 40 H 23 N 3 S = 577.71) 4-384-38 m/z=613.25(C45H31N3=613.76)m / z = 613.25 (C 45 H 31 N 3 = 613.76) 4-394-39 m/z=601.18(C42H23N3O2=601.67)m / z = 601.18 (C 42 H 23 N 3 O 2 = 601.67) 4-404-40 m/z=663.27(C49H33N3=663.82)m / z = 663.27 (C 49 H 33 N 3 = 663.82) 4-414-41 m/z=733.16(C50H27N3S2=733.91)m / z = 733.16 (C 50 H 27 N 3 S 2 = 733.91) 4-424-42 m/z=824.27(C56H36N6S=825.01)m / z = 824.27 (C 56 H 36 N 6 S = 825.01) 4-434-43 m/z=742.24(C52H30N4O2=742.84)m / z = 742.24 (C 52 H 30 N 4 O 2 = 742.84) 4-444-44 m/z=692.20(C48H28N4S=692.80)m / z = 692.20 (C 48 H 28 N 4 S = 692.80) 4-454-45 m/z=677.25(C49H31N3O=677.81)m / z = 677.25 (C 49 H 31 N 3 O = 677.81) 4-464-46 m/z=683.20(C47H29N3OS=683.83)m / z = 683.20 (C 47 H 29 N 3 OS = 683.83) 4-474-47 m/z=677.19(C48H27N3S=677.83)m / z = 677.19 (C 48 H 27 N 3 S = 677.83) 4-484-48 m/z=773.32(C56H40FN3=773.96)m / z = 773.32 (C 56 H 40 FN 3 = 773.96) 4-494-49 m/z=504.14(C33H17FN4O=504.52)m / z = 504.14 (C 33 H 17 FN 4 O = 504.52) 4-504-50 m/z=653.19(C46H27N3S=653.80)m / z = 653.19 (C 46 H 27 N 3 S = 653.80) 4-514-51 m/z=737.28(C55H35N3=737.91)m / z = 737.28 (C 55 H 35 N 3 = 737.91) 4-524-52 m/z=466.18(C32H14D5N3O=466.55)m / z = 466.18 (C 32 H 14 D 5 N 3 O = 466.55) 4-534-53 m/z=535.14(C34H21N3O2S=535.62)m / z = 535.14 (C 34 H 21 N 3 O 2 S = 535.62) 4-544-54 m/z=588.23(C42H28N4=588.71)m / z = 588.23 (C 42 H 28 N 4 = 588.71) 4-554-55 m/z=529.16(C36H20FN3O=529.57)m / z = 529.16 (C 36 H 20 FN 3 O = 529.57) 4-564-56 m/z=591.15(C39H21N5S=591.69)m / z = 591.15 (C 39 H 21 N 5 S = 591.69) 4-574-57 m/z=717.28(C52H35N3O=717.87)m / z = 717.28 (C 52 H 35 N 3 O = 717.87) 4-584-58 m/z=665.2(C46H27N5O=665.76)m / z = 665.2 (C 46 H 27 N 5 O = 665.76) 4-594-59 m/z=656.20(C45H28N4S=656.81)m / z = 656.20 (C 45 H 28 N 4 S = 656.81) 4-604-60 m/z=725.28(C54H35N3=725.09)m / z = 725.28 (C 54 H 35 N 3 = 725.09) 4-614-61 m/z=691.26(C50H33N3O=691.83)m / z = 691.26 (C 50 H 33 N 3 O = 691.83) 4-624-62 m/z=603.18(C42H25N3S=603.74)m / z = 603.18 (C 42 H 25 N 3 S = 603.74) 4-634-63 m/z=451.20(C32H25N3=451.57)m / z = 451.20 (C 32 H 25 N 3 = 451.57) 4-644-64 m/z=689.30(C48H39N3O2=689.86)m / z = 689.30 (C 48 H 39 N 3 O 2 = 689.86) 4-654-65 m/z=845.25(C60H35N3OS=846.02)m / z = 845.25 (C 60 H 35 N 3 OS = 846.02) 4-664-66 m/z=843.29(C61H37N3O2=843.99)m / z = 843.29 (C 61 H 37 N 3 O 2 = 843.99) 4-674-67 m/z=851.29(C63H37N3O=852.01)m / z = 851.29 (C 63 H 37 N 3 O = 852.01) 4-684-68 m/z=742.22(C52H30N4S=742.90)m / z = 742.22 (C 52 H 30 N 4 S = 742.90) 4-694-69 m/z=976.33(C68H44N6S=977.20)m / z = 976.33 (C 68 H 44 N 6 S = 977.20) 4-704-70 m/z=792.25(C56H32N4O2=792.90)m / z = 792.25 (C 56 H 32 N 4 O 2 = 792.90) 4-714-71 m/z=666.19(C46H26N4S=666.80)m / z = 666.19 (C 46 H 26 N 4 S = 666.80) 4-724-72 m/z=843.34(C61H41N5=844.03)m / z = 843.34 (C 61 H 41 N 5 = 844.03) 4-734-73 m/z=538.18(C37H22N4O=538.61)m / z = 538.18 (C 37 H 22 N 4 O = 538.61) 4-744-74 m/z=718.22(C50H30N4S=718.88)m / z = 718.22 (C 50 H 30 N 4 S = 718.88) 4-754-75 m/z=669.22(C47H31N3S=669.85)m / z = 669.22 (C 47 H 31 N 3 S = 669.85) 4-764-76 m/z=858.27(C59H34N6O2=858.96)m / z = 858.27 (C 59 H 34 N 6 O 2 = 858.96) 4-774-77 m/z=664.24(C46H28N6=664.77)m / z = 664.24 (C 46 H 28 N 6 = 664.77) 4-784-78 m/z=692.20(C48H28N4S=692.84)m / z = 692.20 (C 48 H 28 N 4 S = 692.84) 4-794-79 m/z=612.23(C44H28N4=612.74)m / z = 612.23 (C 44 H 28 N 4 = 612.74) 4-804-80 m/z=663.24(C47H29N5=663.78)m / z = 663.24 (C 47 H 29 N 5 = 663.78)

유기전기소자의 제조평가Manufacturing evaluation of organic electric devices

실시예 1) Example 1) 레드Red 유기 발광 소자의 제작 및 시험 Fabrication and testing of organic light emitting devices

먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, N,N'-Bis(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine (이하 NPB로 약기함)을 60 nm 두께로 진공증착하여 홀 수송층을 형성하였다. 정공수송층 상부에 호스트로서 화학식 (1)과 화학식 (2)로 표시되는 상기 발명화합물을 50:50으로 혼합한 혼합물을 사용하였으며, 도판트로서는 (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate]을 95:5 중량으로 도핑함으로써 상기 정공수송층 위에 30 nm 두께의 발광층을 증착하였다. 홀 저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 약칭함)을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로써 유기전기발광소자를 제조하였다.First, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl as a hole injection layer first on the ITO layer (anode) formed on the glass substrate. ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a thickness of 60 nm. Subsequently, N, N'-Bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'-diamine (hereinafter abbreviated as NPB) to a thickness of 60 nm. Vacuum-deposited to form a hole transport layer. As a host on the hole transport layer, a mixture of the above-described compounds represented by Chemical Formulas (1) and (2) in a ratio of 50:50 was used, and as a dopant, (piq) 2 Ir (acac) [bis- (1- phenylisoquinolyl) iridium (III) acetylacetonate] was doped with a weight of 95: 5 to deposit a 30 nm thick light emitting layer on the hole transport layer. As the hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) is vacuum deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, an alkali metal halide as an electron injection layer, to a thickness of 0.2 nm, and then depositing Al to a thickness of 150 nm to use as a cathode.

이와 같이 제조된 실시예 및 비교예 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch)사의 PR-650으로 전기발광 (EL) 특성을 측정하였으며, 그 측정 결과 2500cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표는 소자제작 및 평가한 결과를 나타낸다.The electroluminescence (EL) characteristics were measured by the PR-650 of photoresearch by applying a net bias DC voltage to the organic electroluminescent elements of the examples and comparative examples prepared as described above, and the measurement result showed a luminance of 2500 cd / m 2 In the T95 life was measured by a life measurement equipment manufactured by Max Science. The following table shows the results of device fabrication and evaluation.

[[ 비교예Comparative example 1~3] 1 ~ 3]

화학식 1로 표시되는 화합물을 단독으로 호스트로 사용하는 것을 제외하고는 상기 실시예와 동일한 방법으로 유기전기발광소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 1 was used alone as a host.

[[ 비교예Comparative example 4~6] 4 ~ 6]

화학식 2로 표시되는 화합물을 단독으로 호스트로 사용하는 것을 제외하고는 상기 실시예와 동일한 방법으로 유기전기발광소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 2 was used alone as a host.

[[ 비교예Comparative example 7] 7]

화학식 1로 표시되는 화합물과 비교화합물 1을 혼합물로 사용하는 것을 제외하고는 상기 실시예와 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 1 and Comparative Compound 1 were used as a mixture.

[[ 비교예Comparative example 8] 8]

화학식 2로 표시되는 화합물과 비교화합물 2를 혼합물로 사용하는 것을 제외하고는 상기 실시예와 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in the above Example, except that the compound represented by Chemical Formula 2 and Comparative Compound 2 were used as a mixture.

[[ 비교예Comparative example 9~11] 9 ~ 11]

화학식 1로 표시되는 화합물과 비교화합물 3 내지 비교화합물 5를 혼합물로 사용하는 것을 제외하고는 상기 실시예와 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in the above example, except that the compound represented by Chemical Formula 1 and Comparative Compound 3 to Comparative Compound 5 were used as a mixture.

비교화합물 1 비교화합물 2 비교화합물 3 비교화합물 4 비교화합물 5    Comparative Compound 1 Comparative Compound 2 Comparative Compound 3 Comparative Compound 4 Comparative Compound 5

Figure pat00246
Figure pat00246

제 1호스트Host 1 제 2호스트Host 2 VoltageVoltage Current DensityCurrent Density Brightness
(cd/m2)Brightness
(cd / m2) EfficiencyEfficiency Lifetime
T(95)Lifetime
T (95) 비교예(1)Comparative Example (1) 화합물(1-56)Compound (1-56) -- 5.15.1 19.5 19.5 2500.0 2500.0 12.8 12.8 90.7 90.7 비교예(2)Comparative Example (2) 화합물(2-43)Compound (2-43) -- 5.25.2 22.2 22.2 2500.0 2500.0 11.3 11.3 90.4 90.4 비교예(3)Comparative Example (3) 화합물(2-133)Compound (2-133) -- 5.05.0 18.5 18.5 2500.0 2500.0 13.5 13.5 95.0 95.0 비교예(4)Comparative Example (4) 화합물 (3-36)Compound (3-36) -- 4.44.4 13.413.4 2500.0 2500.0 18.6 18.6 95.2 95.2 비교예(5)Comparative Example (5) 화합물 (3-74)Compound (3-74) -- 4.14.1 17.417.4 2500.0 2500.0 14.414.4 92.8 92.8 비교예(6)Comparative Example (6) 화합물 (4-37)Compound (4-37) -- 4.24.2 16.316.3 2500.0 2500.0 15.3 15.3 94.694.6 비교예(7)Comparative Example (7) 화합물(2-133)Compound (2-133) 비교화합물 1Comparative Compound 1 4.74.7 11.3 11.3 2500.0 2500.0 22.1 22.1 100.0 100.0 비교예(8)Comparative Example (8) 화합물 (3-36)Compound (3-36) 비교화합물 2Comparative Compound 2 4.24.2 12.212.2 2500.0 2500.0 20.5 20.5 105.7 105.7 비교예(9)Comparative Example (9) 화합물(2-133)Compound (2-133) 비교화합물 3Comparative Compound 3 4.6 4.6 9.4 9.4 2500.0 2500.0 26.6 26.6 110.4 110.4 비교예(10)Comparative Example (10) 화합물(2-133)Compound (2-133) 비교화합물 4Comparative Compound 4 4.5 4.5 9.4 9.4 2500.0 2500.0 26.6 26.6 112.7 112.7 비교예(11)Comparative Example (11) 화합물(2-133)Compound (2-133) 비교화합물 5Comparative Compound 5 4.6 4.6 9.2 9.2 2500.0 2500.0 27.2 27.2 111.0 111.0 실시예(1)Example (1) 화합물(1-56)Compound (1-56) 화합물 (3-25)Compound (3-25) 4.14.1 6.76.7 2500.02500.0 37.337.3 124.5124.5 실시예(2)Example (2) 화합물(2-43)Compound (2-43) 화합물 (3-25)Compound (3-25) 3.93.9 6.56.5 2500.02500.0 38.638.6 128.3128.3 실시예(3)Example (3) 화합물(2-133)Compound (2-133) 화합물 (3-25)Compound (3-25) 3.93.9 6.36.3 2500.02500.0 39.539.5 133.6133.6 실시예(4)Example (4) 화합물(1-56)Compound (1-56) 화합물 (3-36)Compound (3-36) 4.04.0 6.46.4 2500.02500.0 39.239.2 121.4121.4 실시예(5)Example (5) 화합물(2-43)Compound (2-43) 화합물 (3-36)Compound (3-36) 4.04.0 6.26.2 2500.02500.0 40.540.5 126.1126.1 실시예(6)Example (6) 화합물(2-133)Compound (2-133) 화합물 (3-36)Compound (3-36) 3.83.8 6.16.1 2500.02500.0 41.241.2 130.7130.7 실시예(7)Example (7) 화합물(1-56)Compound (1-56) 화합물 (3-74)Compound (3-74) 3.93.9 7.67.6 2500.02500.0 32.832.8 109.8109.8 실시예(8)Example (8) 화합물(2-43)Compound (2-43) 화합물 (3-74)Compound (3-74) 3.83.8 7.37.3 2500.02500.0 34.334.3 113.4113.4 실시예(9)Example (9) 화합물(2-133)Compound (2-133) 화합물 (3-74)Compound (3-74) 3.73.7 7.17.1 2500.02500.0 35.235.2 118.2118.2 실시예(10)Example (10) 화합물(1-56)Compound (1-56) 화합물 (4-37)Compound (4-37) 4.14.1 6.56.5 2500.02500.0 38.738.7 115.5115.5 실시예(11)Example (11) 화합물(2-43)Compound (2-43) 화합물 (4-37)Compound (4-37) 4.04.0 6.36.3 2500.02500.0 39.639.6 119.4119.4 실시예(12)Example (12) 화합물(2-133)Compound (2-133) 화합물 (4-37)Compound (4-37) 3.83.8 6.16.1 2500.02500.0 40.840.8 123.2123.2 실시예(13)Example (13) 화합물(1-56)Compound (1-56) 화합물 (4-38)Compound (4-38) 3.83.8 8.08.0 2500.02500.0 31.431.4 103.2103.2 실시예(14)Example (14) 화합물(2-43)Compound (2-43) 화합물 (4-38)Compound (4-38) 3.73.7 7.77.7 2500.02500.0 32.632.6 106.5106.5 실시예(15)Example (15) 화합물(2-133)Compound (2-133) 화합물 (4-38)Compound (4-38) 3.73.7 7.37.3 2500.02500.0 34.434.4 110.7110.7

상기 표 8 결과로부터 알 수 있듯이, 화학식 (1)과 화학식 (2)로 표시되는 본 발명의 유기전기발광소자용 재료를 혼합하여 인광호스트로 사용할 경우 (실시예 1~15), 단일물질을 사용한 소자 (비교예 1~6)와 비교화합물을 혼합하여 사용한 소자 (비교예 7~11)에 비해 구동전압, 효율 및 수명을 현저히 개선시키는 것을 확인할 수 있었다. 다시 말해, 화학식 (1)과 화학식 (2)로 표시되는 본 발명의 화합물을 단독으로 인광호스트로 쓴 경우 (비교예 1~6)보다 화학식 (1) 또는 화학식 (2)로 표시되는 화합물과 비교화합물 1 내지 비교화합물 5를 혼합하여 인광호스트로 사용한 비교예 7~11의 결과가 효율 및 수명 면에서 대체적으로 우수했고, 이보다는 화학식 (1)과 화학식 (2)로 표시되는 본 발명의 화합물을 혼합한 실시예 1~15가 구동전압, 효율 및 수명 면에서 현저히 우수한 효과를 나타냄을 알 수 있다.As can be seen from the results of Table 8, when the material for the organic electroluminescent device of the present invention represented by Formula (1) and Formula (2) is mixed and used as a phosphorescent host (Examples 1 to 15), a single substance is used. It was confirmed that the driving voltage, efficiency and lifespan were significantly improved compared to the devices (Comparative Examples 7 to 11) used by mixing the devices (Comparative Examples 1 to 6) and the comparative compound. In other words, when the compounds of the present invention represented by Formulas (1) and (2) are used alone as phosphorescent hosts, they are compared with compounds represented by Formulas (1) or (2) rather than (Comparative Examples 1-6). The results of Comparative Examples 7-11 used as a phosphorescent host by mixing Compound 1 to Comparative Compound 5 were generally excellent in terms of efficiency and lifetime, rather than the compounds of the present invention represented by Formulas (1) and (2). It can be seen that the mixed examples 1 to 15 show remarkably excellent effects in terms of driving voltage, efficiency and life.

본 발명자들은 상기 실험결과를 근거로 화학식 (1)의 물질과 화학식 (2)의 물질을 혼합한 물질의 경우 각각 물질에 대한 특성 이외의 다른 신규한 특성을 갖는다고 판단하여, 화학식 (1)의 물질, 화학식 (2)의 물질, 본 발명 혼합물을 각각 사용하여 PL lifetime을 측정하였다. 그 결과 본 발명 화합물인 화학식 (1)과 화학식 (2)를 혼합하였을 경우 단독 화합물일 때와 달리 새로운 PL 파장이 형성되는 것을 확인할 수 있었으며, 새롭게 형성된 PL 파장의 감소 및 소멸 시간은 화학식 (1) 및 화학식 (1) 물질 각각의 감소 및 소멸시간보다 증가하는 것을 확인할 수 있었다. 이는 본 발명화합물을 혼합하여 사용할 경우 각각의 물질이 갖는 에너지 준위를 통해 전자와 정공이 이동되는 것뿐만 아니라, 혼합으로 인하여 형성된 새로운 에너지 준위를 갖는 신규 영역에 (exciplex) 의한 전자, 정공 이동 또는 에너지 전달로 효율 및 수명이 증가하는 것으로 판단된다. 이는 결과적으로 상기 본 발명 혼합물을 사용할 경우 혼합 박막이 exciplex 에너지 전달 및 발광 프로세스를 보이는 중요한 예라고 할 수 있다.Based on the results of the above experiment, the present inventors determined that, in the case of a substance in which the substance of formula (1) and the substance of formula (2) were mixed, they had novel characteristics other than the characteristics of each substance. PL lifetime was measured using a substance, a substance of formula (2), and a mixture of the present invention. As a result, when the compounds of the present invention, the formula (1) and the formula (2) were mixed, it was confirmed that a new PL wavelength was formed unlike the single compound, and the newly formed PL wavelength was reduced and extinction time was expressed by the formula (1). And it was confirmed that the increase in each of the reduction and extinction time of each of the formula (1) material. When the compound of the present invention is used in combination, not only electrons and holes are moved through the energy level of each substance, but also electrons, hole movement, or energy due to exciplex to a new region having a new energy level formed due to mixing. It is judged that the efficiency and life of the furnace are increased. As a result, when using the mixture of the present invention, it can be said that the mixed thin film is an important example of exciplex energy transfer and luminescence processes.

또한 비교화합물을 혼합한 인광호스트로 사용한 비교예 7 내지 비교예 11보다 본 발명의 조합이 우수한 이유는 electron 뿐만 아니라 hole에 대한 안정성, 높은 T1 등의 특징이 있는 화학식 (2)로 표시되는 다환 고리화합물에 hole 특성이 강한 화학식 (1)로 표시되는 화합물을 혼합할 경우, 높은 T1과 높은 LUMO 에너지 값으로 인해 전자 블로킹 능력이 향상되고, 발광층에 더 많은 hole이 빠르고 쉽게 이동하게 된다. 이에 따라 정공과 전자의 발광층 내 charge balance가 증가되어 정공수송층 계면이 아닌 발광층 내부에서 발광이 잘 이루어지고, 그로 인해 HTL 계면에 열화 또한 감소하여 소자 전체의 구동 전압, 효율 그리고 수명이 극대화 된다고 판단된다. 즉, 화학식 (1)과 화학식 (2)의 조합이 전기화학적으로 시너지 작용을 하여 소자 전체의 성능을 향상된 것으로 사료된다.In addition, the reason why the combination of the present invention is superior to Comparative Examples 7 to 11 used as a phosphorescent host in which a comparative compound is mixed is a polycyclic ring represented by Chemical Formula (2) having not only electron but also stability to hole, high T1, etc. When the compound represented by the formula (1) having strong hole characteristics is mixed with the compound, the electron blocking ability is improved due to the high T1 and high LUMO energy values, and more holes are quickly and easily moved in the light emitting layer. Accordingly, it is judged that the charge balance in the light emitting layer of holes and electrons is increased, so that light emission is performed well inside the light emitting layer rather than the hole transport layer interface, thereby reducing deterioration at the HTL interface, thereby maximizing the driving voltage, efficiency, and lifetime of the entire device. . That is, the combination of the formula (1) and the formula (2) is thought to improve the performance of the entire device by synergistically electrochemically.

실시예 2) Example 2) 혼합비율 별By mixing ratio 레드Red 유기 발광 소자의 제작 및 시험 Fabrication and testing of organic light emitting devices

제 1호스트Host 1 제 2호스트Host 2 혼합 비율
(제 1 호스트 : 제 2호스트)Mixing ratio
(1st host: 2nd host) VoltageVoltage Current DensityCurrent Density Brightness
(cd/m2)Brightness
(cd / m 2 ) EfficiencyEfficiency Lifetime
T(95)Lifetime
T (95) 실시예(16)Example (16) 화합물(1-56)Compound (1-56) 화합물(3-25)Compound (3-25) 2:82: 8 3.93.9 7.87.8 2500.02500.0 31.931.9 110.3110.3 실시예(17)Example (17) 화합물(1-56)Compound (1-56) 화합물(3-25)Compound (3-25) 3:73: 7 4.14.1 7.57.5 2500.02500.0 33.433.4 115.1115.1 실시예(18)Example (18) 화합물(1-56)Compound (1-56) 화합물(3-25)Compound (3-25) 4:64: 6 4.24.2 7.07.0 2500.02500.0 35.835.8 120.2120.2 실시예(20)Example (20) 화합물(2-133)Compound (2-133) 화합물(4-37)Compound (4-37) 2:82: 8 3.63.6 7.17.1 2500.02500.0 35.335.3 106.6106.6 실시예(21)Example (21) 화합물(2-133)Compound (2-133) 화합물(4-37)Compound (4-37) 3:73: 7 3.73.7 6.66.6 2500.02500.0 37.737.7 112.4112.4 실시예(22)Example (22) 화합물(2-133)Compound (2-133) 화합물(4-37)Compound (4-37) 4:64: 6 3.83.8 6.36.3 2500.02500.0 40.040.0 119.6119.6

상기 표 9와 같이 본 발명의 화합물의 혼합물을 비율별 (2:8, 3:7, 4:6)로 소자를 제작하여 측정하였다.As shown in Table 9, the mixture of the compounds of the present invention was measured by fabricating the device by ratio (2: 8, 3: 7, 4: 6).

결과를 자세히 설명하면, 제 2호스트 비율이 증가할수록 구동전압의 결과가 더 향상되는 것을 확인하였지만 반대로 효율 및 수명에 있어서는 반대의 경향을 띄는 것을 확인하였다. 따라서 혼합물의 경우 혼합 비율의 양이 특성에 영향을 미치기 때문에 발광층 내 charge balance가 극대화되는 혼합비율을 도출하는 것이 매우 중요한 과제라고 판단된다.When the results were described in detail, it was confirmed that as the second host ratio increased, the result of the driving voltage was further improved. Therefore, in the case of a mixture, it is judged that it is a very important task to derive a mixing ratio in which the charge balance in the light emitting layer is maximized because the amount of the mixing ratio affects the properties.

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 실시 예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시 예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein are not intended to limit the present invention, but to explain the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the equivalent range should be interpreted as being included in the scope of the present invention.

100 : 유기전기소자 110 : 기판
120 : 제 1전극(양극) 130 : 정공주입층
140 : 정공수송층 141 : 버퍼층
150 : 발광층 151 : 발광보조층
160 : 전자수송층 170 : 전자주입층
180 : 제 2전극(음극)100: organic electrical element 110: substrate
120: first electrode (anode) 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 (cathode)

Claims (19)

제 1전극, 제 2전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 인광성 발광층으로서 하기 화학식 (1)로 표시되는 제 1호스트 및 하기 화학식 (2)로 표시되는 제 2호스트를 포함하는 것을 특징으로 하는 유기전기소자
화학식 (1) 화학식 (2)
Figure pat00247
Figure pat00248

{상기 화학식 (1) 및 (2)에서,
1) X, Y 및 W는 각각 독립적으로 NR'; O; S; CR'R"; SiR'R"; 또는 Se;이고,
2) a, b, c 및 d는 0 또는 1이고, 단 a+b와 c+d는 1 이상이며,
3) R' 및 R"는 각각 독립적으로 수소; C1~C50의 알킬기; C6~C60의 아릴기; 및 C2~C60의 헤테로아릴기;로 이루어진 군에서 선택되거나, R' 및 R"은 서로 고리를 형성하여 스파이로(spiro) 고리를 형성하고,
4) L1, L2 및 L'은 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 또는 C2~C60의 헤테로아릴렌기;이고,
5) Ar1 및 Ar2는 각각 독립적으로 수소; 중수소; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-NR'R";로 이루어진 군에서 선택되고,
6) Z는 NR', O, S, CR'R", SiR'R", 또는 Se이고,
7) R1 내지 R16은 각각 독립적으로 수소; 중수소; 할로겐; 시아노기; C1-C20의 에스테르기; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고,
상기 Ra 및 Rb 은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,
상기 l, n, o 및 p가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 인접한 복수의 R1끼리, 복수의 R3끼리, 복수의 R4끼리, 복수의 R5끼리, 복수의 R16끼리, R6와 R7끼리, R7와 R8끼리, R8와 R9끼리, R10와 R11끼리, R12와 R13끼리, R13과 R14끼리, 또는 R14와 R15끼리는 서로 결합하여 방향족 및 헤테로방향족 고리를 형성할 수 있고,
8) A환은 C6~C60의 아릴기; 또는 C2~C60의 헤테로아릴렌기;이고,
9) n, l, p은 0~4 중 어느 하나의 정수이고, m은 0 또는 1의 정수이고, o는 0 내지 3 중 어느 하나의 정수이고, e는 0 내지 10 중 어느 하나의 정수이며,
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 플루오렌일렌기, 융합고리기, 알킬기, 알케닐기, 알콕시기 및 아릴옥시기는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기;로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 C3-C60의 지방족고리 또는 C6-C60의 방향족고리 또는 C2-C60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}
In an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the organic material layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer represented by the following formula (1). An organic electric device comprising a first host represented by) and a second host represented by the following formula (2)
Formula (1) Formula (2)
Figure pat00247
Figure pat00248

{In the formulas (1) and (2) above,
1) X, Y and W are each independently NR ';O;S;CR'R";SiR'R"; Or Se;
2) a, b, c and d are 0 or 1, provided that a + b and c + d are 1 or more,
3) R 'and R "are each independently hydrogen; an alkyl group of C 1 to C 50 ; an aryl group of C 6 to C 60 ; and a heteroaryl group of C 2 to C 60 ; or R' And R "form a ring with each other to form a spiro ring,
4) L 1 , L 2 and L 'are each independently a single bond; C 6 ~ C 60 Arylene group; Or C 2 ~ C 60 heteroarylene group; is,
5) Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; C 1 ~ C 50 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-NR'R ";
6) Z is NR ', O, S, CR'R ", SiR'R", or Se,
7) R 1 to R 16 are each independently hydrogen; heavy hydrogen; halogen; Cyano group; C 1 -C 20 ester group; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; C 1 ~ C 50 alkyl group; C 2 ~ C 20 alkenyl group; C 2 ~ C 20 alkynyl group; C 1 ~ C 30 Alkoxy group; C 6 ~ C 30 Aryloxy group; And -L'-N (R a ) (R b ); is selected from the group consisting of,
R a and R b are independently of each other C 6 ~ C 60 aryl group; Fluorenyl group; C 3 ~ C 60 aliphatic ring and C 6 ~ C 60 aromatic ring fused ring group; And O, N, S, Si, and C 2 ~ C 60 heterocyclic group containing at least one heteroatom; is selected from the group consisting of,
When l, n, o, and p are 2 or more, they are the same as or different from each other as a plurality, and a plurality of adjacent R 1 , a plurality of R 3 , a plurality of R 4 , a plurality of R 5 , a plurality of R 16 , Between R 6 and R 7, between R 7 and R 8, between R 8 and R 9, between R 10 and R 11, between R 12 and R 13, between R 13 and R 14 , or between R 14 and R 15 Can combine with each other to form an aromatic and heteroaromatic ring,
8) A ring is C 6 ~ C 60 aryl group; Or C 2 ~ C 60 heteroarylene group; is,
9) n, l, p is an integer from 0 to 4, m is an integer from 0 or 1, o is an integer from 0 to 3, and e is an integer from 0 to 10 ,
Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkoxy group and aryloxy group, respectively, deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C 1 -C 20 alkylthio; Alkoxyl group of C 1 -C 20 ; C 1 -C 20 alkyl group; Alkenyl group of C 2 -C 20 ; Alkynyl group of C 2 -C 20 ; C 6 -C 20 Aryl group; A C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; C 3 -C 20 cycloalkyl group; C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and also these substituents may combine with each other to form a ring, wherein ''Cycle' refers to a C 3 -C 60 aliphatic ring or a C 6 -C 60 aromatic ring or a C 2 -C 60 heterocycle or a fused ring thereof, and includes a saturated or unsaturated ring.}
제 1항에 있어서, 상기 화학식 (1)로 나타낸 화합물이 하기 화학식 (3) 또는 (4)로 표시되는 것을 특징으로 하는 유기전기소자
화학식 (3) 화학식 (4)
Figure pat00249

(상기 화학식 (3) 및 (4)에서, X, Y, Z, Ar1, L1, R1, R2, R3, R4, R5, l, m, n, o, 및 p는 상기 청구항 1에서 정의된 바와 동일하다.)
The organic electric device according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (3) or (4).
Formula (3) Formula (4)
Figure pat00249

(In the formulas (3) and (4), X, Y, Z, Ar 1 , L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , l, m, n, o, and p are It is the same as defined in claim 1 above.)
제 1항에 있어서, 상기 화학식 (1)로 나타낸 화합물이 하기 화학식 (5) 내지 (12) 중 어느 하나로 표시되는 것을 특징으로 하는 유기전기소자
화학식 (5) 화학식 (6) 화학식 (7) 화학식 (8)
Figure pat00250

화학식 (9) 화학식 (10) 화학식 (11) 화학식 (12)
Figure pat00251

(상기 화학식 (5) 내지 (12)에서, X, Y, Z, Ar1, L1, R1, R2, R3, R4, R5, R', R", l, m, n, o, 및 p는 상기 청구항 1에서 정의된 바와 동일하다.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) is represented by any one of the following formulas (5) to (12).
Formula (5) Formula (6) Formula (7) Formula (8)
Figure pat00250

Formula (9) Formula (10) Formula (11) Formula (12)
Figure pat00251

(In the formulas (5) to (12), X, Y, Z, Ar 1 , L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R ', R ", l, m, n , o, and p are as defined in claim 1 above.)
제 1항에 있어서, 상기 l, m, n, o 및 p가 모두 0인 것을 특징으로 하는 유기전기소자
The method of claim 1, wherein the l, m, n, o and p are all 0 organic electric device characterized in that
제 1항에 있어서, 상기 R1, R3, R4 및 R5 중 어느 하나는 이웃한 한 쌍이 서로 결합하여 고리를 형성하는 것을 특징으로 하는 유기전기소자
The method according to claim 1, wherein any one of R 1 , R 3 , R 4 and R 5 is an organic electric device characterized in that a pair of adjacent ones combine with each other to form a ring.
제 1항에 있어서, 상기 X 또는 Y는 S 또는 O인 것을 특징으로 하는 유기전기소자
According to claim 1, wherein the X or Y is an organic electric device, characterized in that S or O
제 1항에 있어서, 상기 화학식 (1)은 하기 화합물 중 어느 하나인 것을 특징으로 하는 유기전기소자
Figure pat00252

Figure pat00253

Figure pat00254

Figure pat00255

Figure pat00256

Figure pat00257

Figure pat00258

Figure pat00259

Figure pat00260

Figure pat00261

Figure pat00262

Figure pat00263

Figure pat00264

Figure pat00265

Figure pat00266

Figure pat00267

Figure pat00268

Figure pat00269

Figure pat00270

Figure pat00271

Figure pat00272

Figure pat00273

Figure pat00274

Figure pat00275

Figure pat00276

Figure pat00277

Figure pat00278

Figure pat00279

Figure pat00280

Figure pat00281

Figure pat00282

Figure pat00283

Figure pat00284

Figure pat00285

Figure pat00286

Figure pat00287

Figure pat00288

Figure pat00289

Figure pat00290

Figure pat00291

Figure pat00292

Figure pat00293

Figure pat00294

Figure pat00295

Figure pat00296

Figure pat00297

Figure pat00298

Figure pat00299

Figure pat00300

Figure pat00301

Figure pat00302

Figure pat00303

Figure pat00304

Figure pat00305

Figure pat00306

Figure pat00307

The method of claim 1, wherein the formula (1) is an organic electric device, characterized in that any one of the following compounds
Figure pat00252

Figure pat00253

Figure pat00254

Figure pat00255

Figure pat00256

Figure pat00257

Figure pat00258

Figure pat00259

Figure pat00260

Figure pat00261

Figure pat00262

Figure pat00263

Figure pat00264

Figure pat00265

Figure pat00266

Figure pat00267

Figure pat00268

Figure pat00269

Figure pat00270

Figure pat00271

Figure pat00272

Figure pat00273

Figure pat00274

Figure pat00275

Figure pat00276

Figure pat00277

Figure pat00278

Figure pat00279

Figure pat00280

Figure pat00281

Figure pat00282

Figure pat00283

Figure pat00284

Figure pat00285

Figure pat00286

Figure pat00287

Figure pat00288

Figure pat00289

Figure pat00290

Figure pat00291

Figure pat00292

Figure pat00293

Figure pat00294

Figure pat00295

Figure pat00296

Figure pat00297

Figure pat00298

Figure pat00299

Figure pat00300

Figure pat00301

Figure pat00302

Figure pat00303

Figure pat00304

Figure pat00305

Figure pat00306

Figure pat00307

 제1항에 있어서, 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (13) 또는 (14)로 표시되는 것을 특징으로 하는 유기전기소자
화학식 (13) 화학식 (14)
Figure pat00308

(상기 화학식 (13) 및 (14)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, V, W, c, 및 d는 상기 청구항 1에서 정의한 바와 같다.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (2) is represented by the following formula (13) or (14).
Formula (13) Formula (14)
Figure pat00308

(In the formulas (13) and (14), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, V, W, c, and d are as defined in claim 1 above.)
제 1항에 있어서, 상기 화학식 (2)로 나타낸 화합물의 R6과 R7, R7과 R8, R8과 R9, R10과 R11, R12와 R13, R13과 R14 및 R14와 R15 중 적어도 한 쌍이 서로 결합하여 방향족 또는 헤테로 방향족 고리를 형성하는 것을 특징으로 하는 유기전기소자
According to claim 1, R 6 and R 7 of the compound represented by the formula (2), R 7 and R 8 , R 8 and R 9 , R 10 and R 11 , R 12 and R 13 , R 13 and R 14 And at least one pair of R 14 and R 15 combine with each other to form an aromatic or heteroaromatic ring.
제1항에 있어서, 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (15) 내지 (38)로 표시되는 것 중 어느 하나인 것을 특징으로 하는 유기전기소자
화학식 (15) 화학식 (16) 화학식 (17) 화학식 (18)
Figure pat00309

화학식 (19) 화학식 (20) 화학식 (21) 화학식 (22)
Figure pat00310

화학식 (23) 화학식 (24) 화학식 (25) 화학식 (26)
Figure pat00311

화학식 (27) 화학식 (28) 화학식 (29) 화학식 (30)
Figure pat00312

화학식 (31) 화학식 (32) 화학식 (33) 화학식 (34)
Figure pat00313

화학식 (35) 화학식 (36) 화학식 (37) 화학식 (38)
Figure pat00314

(상기 화학식 (15) 및 (38)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, V, W, c, 및 d는 상기 청구항 1에서 정의한 바와 같다.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (2) is any one of the following formulas (15) to (38).
Formula (15) Formula (16) Formula (17) Formula (18)
Figure pat00309

Formula (19) Formula (20) Formula (21) Formula (22)
Figure pat00310

Formula (23) Formula (24) Formula (25) Formula (26)
Figure pat00311

Formula (27) Formula (28) Formula (29) Formula (30)
Figure pat00312

Formula (31) Formula (32) Formula (33) Formula (34)
Figure pat00313

Formula (35) Formula (36) Formula (37) Formula (38)
Figure pat00314

(In the formulas (15) and (38), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, V, W, c, and d are as defined in claim 1 above.)
제1항에 있어서, 상기 화학식 (2)로 나타낸 화합물이 하기 화학식 (39) 내지 (46) 중 어느 하나인 것을 특징으로 하는 유기전기소자
화학식 (39) 화학식 (40) 화학식 (41) 화학식 (42)
Figure pat00315

화학식 (43) 화학식 (44) 화학식 (45) 화학식 (46)
Figure pat00316

(상기 화학식 (39) 및 (46)에서, Ar2, L2, R16, e, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, A, R' 및 R"는 상기 청구항 1에서 정의한 바와 같다.)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (2) is any one of the following formulas (39) to (46).
Formula (39) Formula (40) Formula (41) Formula (42)
Figure pat00315

Formula (43) Formula (44) Formula (45) Formula (46)
Figure pat00316

(In the formulas (39) and (46), Ar 2 , L 2 , R 16 , e, R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , A, R 'and R "are as defined in claim 1 above.)
제 1항에 있어서, 상기 화학식 (2)의 R6, R7, R8, R9, R10, R12, R13, R14 및 R15가 모두 수소인 것을 특징으로 하는 유기전기소자
The method according to claim 1, wherein R 6 , R 7 , R 8 , R 9 , R 10 of Formula (2), R 12 , R 13 , R 14 and R 15 are all organic electric devices characterized in that they are hydrogen.
제1항에 있어서, 상기 화학식 (2)의 A환이 하기 (A-1) 내지 (A-14) 중 어느 하나인 것을 특징으로 하는 유기전기소자
(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)
Figure pat00317

(A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14)
Figure pat00318

(상기 화학식 (A-1) 내지 (A-14)에서, R', R", R16 및 e는 상기 청구항 1에서 정의한 바와 같고, *는 A환의 결합위치를 나타낸다.)
The organic electric device according to claim 1, wherein the A ring of the formula (2) is any one of the following (A-1) to (A-14).
(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7)
Figure pat00317

(A-8) (A-9) (A-10) (A-11) (A-12) (A-13) (A-14)
Figure pat00318

(In the formulas (A-1) to (A-14), R ', R ", R 16 and e are as defined in claim 1 above, and * represents the bonding position of the A ring.)
제1항에 있어서, 상기 화학식 (2)는 하기 화합물 중 하나인 것을 특징으로 하는 유기전기소자
Figure pat00319

Figure pat00320

Figure pat00321

Figure pat00322

Figure pat00323

Figure pat00324

Figure pat00325

Figure pat00326

Figure pat00327

Figure pat00328

Figure pat00329

Figure pat00330

Figure pat00331

Figure pat00332

Figure pat00333

Figure pat00334

Figure pat00335

Figure pat00336

Figure pat00337

Figure pat00338

Figure pat00339

Figure pat00340

Figure pat00341

Figure pat00342

Figure pat00343

Figure pat00344

Figure pat00345

Figure pat00346

Figure pat00347

Figure pat00348

Figure pat00349

Figure pat00350

Figure pat00351

Figure pat00352

Figure pat00353

Figure pat00354

Figure pat00355

Figure pat00356

Figure pat00357

The method of claim 1, wherein the formula (2) is an organic electric device, characterized in that one of the following compounds
Figure pat00319

Figure pat00320

Figure pat00321

Figure pat00322

Figure pat00323

Figure pat00324

Figure pat00325

Figure pat00326

Figure pat00327

Figure pat00328

Figure pat00329

Figure pat00330

Figure pat00331

Figure pat00332

Figure pat00333

Figure pat00334

Figure pat00335

Figure pat00336

Figure pat00337

Figure pat00338

Figure pat00339

Figure pat00340

Figure pat00341

Figure pat00342

Figure pat00343

Figure pat00344

Figure pat00345

Figure pat00346

Figure pat00347

Figure pat00348

Figure pat00349

Figure pat00350

Figure pat00351

Figure pat00352

Figure pat00353

Figure pat00354

Figure pat00355

Figure pat00356

Figure pat00357

 제1항에 있어서, 상기 화학식 (1) 및 상기 화학식 (2)로 나타내는 화합물이 중량비 1:9 내지 9:1 중 어느 하나의 비율로 혼합되는 것을 특징으로 하는 유기전기소자.The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a ratio of any one of 1: 9 to 9: 1 by weight. 제1항에 있어서, 상기 화학식 (1) 및 상기 화학식 (2)로 나타내는 화합물이 중량비 1:9 내지 5:5로 혼합되는 것을 특징으로 하는 유기전기소자.The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a weight ratio of 1: 9 to 5: 5. 제1항에 있어서, 상기 화학식 (1) 및 상기 화학식 (2)로 나타내는 화합물이 중량비 2:8 내지 3:7로 혼합되는 것을 특징으로 하는 유기전기소자.The organic electroluminescent device according to claim 1, wherein the compounds represented by the formula (1) and the formula (2) are mixed in a weight ratio of 2: 8 to 3: 7. 제1항에 따른 유기전기소자를 포함하는 디스플레이장치: 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치.An electronic device comprising: a display device comprising the organic electroluminescent device according to claim 1 and a control unit driving the display device. 제18항에 있어서, 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용소자 중 적어도 하나인 것을 특징으로 하는 전자장치.
19. The electronic device according to claim 18, wherein the organic electric element is at least one of an organic electroluminescent element, an organic solar cell, an organic photoreceptor, an organic transistor, and a monochromatic or white lighting element.
KR1020180119765A 2018-10-08 2018-10-08 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof KR102654639B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020180119765A KR102654639B1 (en) 2018-10-08 2018-10-08 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
PCT/KR2019/013192 WO2020076052A1 (en) 2018-10-08 2019-10-08 Compound for organic electric device, organic electric device using same, and electronic apparatus thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020180119765A KR102654639B1 (en) 2018-10-08 2018-10-08 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Publications (2)

Publication Number Publication Date
KR20200040030A true KR20200040030A (en) 2020-04-17
KR102654639B1 KR102654639B1 (en) 2024-04-04

Family

ID=70164002

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020180119765A KR102654639B1 (en) 2018-10-08 2018-10-08 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Country Status (2)

Country Link
KR (1) KR102654639B1 (en)
WO (1) WO2020076052A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220251077A1 (en) * 2021-02-08 2022-08-11 Luminescence Technology Corp. Organic compound and organic electroluminescence device using the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101170666B1 (en) 2009-03-03 2012-08-07 덕산하이메탈(주) Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof
KR20150127548A (en) * 2014-05-07 2015-11-17 롬엔드하스전자재료코리아유한회사 Multi-component host material and organic electroluminescent device comprising the same
KR20170052487A (en) * 2015-11-03 2017-05-12 롬엔드하스전자재료코리아유한회사 A plurality of host materials and organic electroluminescent device comprising the same
KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
KR20170092406A (en) * 2016-02-03 2017-08-11 삼성에스디아이 주식회사 Organic compound and organic optoelectronic device and display device
KR20180008286A (en) * 2016-07-14 2018-01-24 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101170666B1 (en) 2009-03-03 2012-08-07 덕산하이메탈(주) Bis-carbazole chemiclal and organic electroric element using the same, terminal thererof
KR20150127548A (en) * 2014-05-07 2015-11-17 롬엔드하스전자재료코리아유한회사 Multi-component host material and organic electroluminescent device comprising the same
KR20170052487A (en) * 2015-11-03 2017-05-12 롬엔드하스전자재료코리아유한회사 A plurality of host materials and organic electroluminescent device comprising the same
KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
KR20170092406A (en) * 2016-02-03 2017-08-11 삼성에스디아이 주식회사 Organic compound and organic optoelectronic device and display device
KR20180008286A (en) * 2016-07-14 2018-01-24 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Also Published As

Publication number Publication date
KR102654639B1 (en) 2024-04-04
WO2020076052A1 (en) 2020-04-16

Similar Documents

Publication Publication Date Title
KR102329806B1 (en) Display device using a composition for organic electronic element, and an organic electronic element thereof
KR102293436B1 (en) Display device using a composition for organic electronic element, and an organic electronic element thereof
KR102329807B1 (en) Display device using a composition for organic electronic element, and an organic electronic element thereof
KR102170190B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102342493B1 (en) Display device using a composition for organic electronic element, and an organic electronic element thereof
KR102152194B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102211338B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
US10717744B2 (en) Compound for organic electric element, organic electric element comprising the same and electronic device thereof
US11367839B2 (en) Compound for organic electric element, organic electric element using the same, and an electronic device thereof
KR102292572B1 (en) Display device using a composition for organic electronic element, and an organic electronic element thereof
KR102501667B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102502430B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20130096334A (en) Organic electronic element, and a compound for the same
KR20180013713A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20180008286A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102543685B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20200081771A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20190127554A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20190105437A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20200037542A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20200084172A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20200043076A (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR20220007033A (en) An organic electronic element comprising compound for organic electronic element and an electronic device thereof
KR101926340B1 (en) Organic electronic element, and a compound for the same
KR102654639B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
AMND Amendment
E601 Decision to refuse application
X091 Application refused [patent]
AMND Amendment
X701 Decision to grant (after re-examination)
GRNT Written decision to grant