KR102324529B1 - 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

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Publication number
KR102324529B1
KR102324529B1 KR1020210095913A KR20210095913A KR102324529B1 KR 102324529 B1 KR102324529 B1 KR 102324529B1 KR 1020210095913 A KR1020210095913 A KR 1020210095913A KR 20210095913 A KR20210095913 A KR 20210095913A KR 102324529 B1 KR102324529 B1 KR 102324529B1
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South Korea
Prior art keywords
mmol
group
formula
sub1
compound
Prior art date
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KR1020210095913A
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Korean (ko)
Inventor
김기원
오경환
윤부용
이형동
신진우
문성윤
이준구
이연화
김미경
서지현
이관희
Original Assignee
덕산네오룩스 주식회사
삼성디스플레이 주식회사
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Application filed by 덕산네오룩스 주식회사, 삼성디스플레이 주식회사 filed Critical 덕산네오룩스 주식회사
Priority to KR1020210095913A priority Critical patent/KR102324529B1/en
Application granted granted Critical
Publication of KR102324529B1 publication Critical patent/KR102324529B1/en
Priority to CN202310097924.7A priority patent/CN116082119A/en
Priority to PCT/KR2022/009054 priority patent/WO2023282511A1/en
Priority to EP22773092.6A priority patent/EP4137474A1/en
Priority to JP2022559772A priority patent/JP2023537800A/en
Priority to EP23157287.6A priority patent/EP4219436A3/en
Priority to CN202310139903.7A priority patent/CN116162015B/en
Priority to CN202280003311.6A priority patent/CN115776979A/en
Priority to EP23157255.3A priority patent/EP4234524A3/en
Priority to JP2023019426A priority patent/JP2023119583A/en
Priority to JP2023019427A priority patent/JP2023123379A/en
Priority to US18/169,524 priority patent/US11856841B2/en
Priority to US18/169,541 priority patent/US11877508B2/en
Priority to JP2024006154A priority patent/JP2024036386A/en

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    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/52—Ortho- or ortho- and peri-condensed systems containing five condensed rings

Abstract

The present invention provides a fluorine containing metal or electrode (cathode) patterning compound, an organic electronic element using the same, and an electronic device thereof. A fluorinated compound is used as a metal or electrode (cathode) patterning material so that micro patterns of an electrode can be formed without use of a shadow mask, and a transparent display having high light transmittance can be easily manufactured, thereby easily applying UDC.

Description

유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치 {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}A compound for an organic electric device, an organic electric device using the same, and an electronic device thereof

본 발명은 불소함유 금속 또는 전극(캐소드) 패터닝용 화합물, 이를 이용한 투명디스플레이 장치에 관한 것이다.The present invention relates to a compound for patterning a fluorine-containing metal or electrode (cathode), and a transparent display device using the same.

디스플레이 기술의 지속적 발전으로 디스플레이 장치에 대한 사용자의 요구가 높아지고 있으며, 단말기 디스플레이 장치(특히, 스마트폰)는 유연성, 풀스크린, 고집적화 방향으로의 발전이 요구되고 있다.With the continuous development of display technology, user demands for display devices are increasing, and terminal display devices (especially, smart phones) are required to develop in the direction of flexibility, full screen, and high integration.

특히 스마트폰 디스플레이의 경우 기술의 발전에 따라 동일한 크기의 스마트폰에도 최대한 화면을 크게 키우려고 노력해 왔으며, 이로 인해 스마트폰의 배젤(Bazel) 사이즈는 화면 크기의 증가에 따라 최대한 작게 하는 개발이 진행되었다. 그 과정에서 스마트폰 전면에 있었던 물리적인 버튼은 화면 속으로 사라져 버렸고, 스마트폰의 카메라 위치도 노치, 홀, 슬라이드 등의 방식으로 지속적으로 변경되고 있다.In particular, in the case of smartphone displays, efforts have been made to make the screen as large as possible even for smartphones of the same size according to the development of technology. . In the process, the physical button on the front of the smartphone disappeared into the screen, and the location of the smartphone's camera is constantly changing in a way such as a notch, a hole, or a slide.

최근에는 배젤이 없는(Bazel-less) 언더 디스플레이(Under Display)의 개발이 빠르게 진행되고 있으며, 이로 인해 투명 디스플레이 기술 개발도 빠르게 진행되고 있는 추세이다.In recent years, the development of a bezel-less under display (Under Display) is progressing rapidly, and as a result, the development of transparent display technology is also rapidly progressing.

이러한 디스플레이 장치의 발전에 따라 최근 들어 차세대 스마트폰 디스플레이 기술인 UDC(Under Display Camera), UPS(Under Panel Sensor) 구현이 높은 관심을 받고 있는 상황이다.With the development of such display devices, the implementation of next-generation smart phone display technologies such as UDC (Under Display Camera) and UPS (Under Panel Sensor) has recently received high attention.

특히 UDC는 디스플레이의 높은 투과도가 담보되어야 UDC 카메라가 정상 작동할 수 있기 때문에, 투과도를 높이기 위해 캐소드의 정밀 패턴화가 필수적으로 요구된다.In particular, since the UDC camera can operate normally only when high transmittance of the display is guaranteed, precise patterning of the cathode is essential to increase transmittance.

일반적으로 전극 패턴 방법으로는 크게 두 가지 방법이 사용되고 있다. 첫째는 섀도 마스크(Shadow Mask)를 이용하여 원하는 부분에 전극을 패터닝하거나, 둘째로 캐소드에 레이저를 조사하여 패턴을 만드는 방법이다.In general, two methods are mainly used as electrode patterning methods. First, an electrode is patterned on a desired part using a shadow mask, or second, a pattern is made by irradiating a laser to the cathode.

그러나 섀도 마스크를 통한 전극 패터닝 방법은 금속 마스크 전형적 재료 특성상 고온 증착 공정 동안 휘어짐 현상이 발생하게 되고, 그로 인해 마스크 형상 및 전극 패턴이 왜곡되는 문제가 발생한다. 이에, 마스크를 유지보수하기 위한 시간 및 비용 발생이 필연적으로 요구됨으로써, 디바이스의 대량생산에 상업적으로 적합하지 않다.However, in the electrode patterning method through the shadow mask, a bending phenomenon occurs during a high-temperature deposition process due to the typical material characteristics of the metal mask, and thereby the mask shape and the electrode pattern are distorted. Accordingly, since time and cost for maintaining the mask are inevitably required, it is not commercially suitable for mass production of the device.

또한, 레이저를 통한 전극 패턴 방식은, 레이저 고유 성질로 인해 전극이 패터닝 되는 방식으로 모재(Substrate)가 손상되지 않도록 레이저의 종류 및 강도를 결정해야 하는 번거로움이 야기된다.In addition, the electrode patterning method through the laser causes the inconvenience of determining the type and intensity of the laser so that the substrate is not damaged in the manner in which the electrode is patterned due to the inherent properties of the laser.

한편 불소화 유기화합물 재료가 유기전기소자에 다양한 용도로 사용되고 있다. 예로 일본공개특허 제1992-206386호에는 서로 대향하는 2개의 전극 사이에 형광성 유기고체로 구성되는 발광층이 개재해서 이루어지는 적층구조체를 갖는 유기 EL 디바이스에 있어서, 클로로트리플루오로에틸렌 단독 중합체, 디클로로플루오로에틸렌 단독 중합체, 클로로트리플루오로에틸렌과 디클로로디플루오렌에틸렌과의 공중합체로 구성되는 군에서 적어도 1종의 중합체를 증착하여 발광층으로의 수분이나 산소의 침입 방지를 더욱 충분하게 한 것으로 밀봉제의 역할을 하는 화합물들을 개시하고 있다. On the other hand, fluorinated organic compound materials are being used for various purposes in organic electric devices. For example, Japanese Laid-Open Patent Publication No. 1992-206386 discloses an organic EL device having a laminate structure formed by a light emitting layer composed of a fluorescent organic solid interposed between two opposing electrodes, chlorotrifluoroethylene homopolymer, dichlorofluoro At least one polymer from the group consisting of an ethylene homopolymer and a copolymer of chlorotrifluoroethylene and dichlorodifluorene ethylene is deposited to further sufficiently prevent the ingress of moisture or oxygen into the light emitting layer. Compounds that play a role are disclosed.

또한 일본공개특허 제2001-247498호 및 J. Am. Chem. Soc., 2000, Vol.122, 1832.에는 불소를 함유하는 물질은 화학적 및 열적 안정성이 높고 또한 전자의 수송성을 향상시킬 수 있기 때문에 유기 EL 소자의 전자 수송층으로서 사용할 수 있고, 정공 차폐기능을 발휘하므로 정공 차폐층으로도 사용할 수 있을 뿐만 아니라 보호막으로도 사용이 가능하여 소자의 수명을 향상시킬 수 있음을 개시하고 있다. In addition, Japanese Patent Laid-Open No. 2001-247498 and J. Am. Chem. Soc., 2000, Vol.122, 1832. shows that fluorine-containing materials have high chemical and thermal stability and can improve electron transport properties, so they can be used as an electron transport layer of organic EL devices and exhibit a hole shielding function. Therefore, it can be used not only as a hole shielding layer but also as a protective film, thereby improving the lifespan of the device.

한국공개특허 KR2000-0000628호에도 불소를 함유하는 물질을 전자 수송층 이외에 발광층의 물질로 사용 가능하다는 것과 한국공개특허 제2000-0000628호에서 전자친화성이 강한 플루오르화 아릴(Fluronated aryl), 즉 펜타플루오로 아릴(Pentafluoro aryl) 또는 옥타플루오로바이페닐(Octafluorobiphenyl)기를 폴리(p-페닐렌비닐렌)에 도입하여 균형된 전자와 정공의 만남을 유도함으로써 전기발광 효율을 향상시킨 녹색 발광 고분자에 대해 개시하고 있으며, 한국공개특허 제2005-0115069호에 고체상태에서 특히 발광효율이 우수한 AIEE(Aggregation Induced Enhanced Emission) 특성을 갖는 불소계 가지체를 포함하는 발광 화합물이 개시되어 있다. 한국등록특허 제10-0846597호에는 제 1전극; 정공수송층; 발광층; 제 2 전극을 구비한 유기발광소자에서 제1전극과 정공수송층 사이에 불소로 치환된 C6yF6y-2n의 방향족 불화 탄소 화합물을 기재하고 있으며, 또한 발광층과 제 2전극 사이에 더 포함하는 것을 특징으로 하는 유기발광소자를 기재하고 있다. 이는 방향족 불화 탄소 화합물을 유기발광소자의 계면을 조절하기 위해 제 1전극(양극)과 정공 주입(정공 수송층) 계면에 불소 함유 화합물을 포함하는 박막을 삽입하여 구동전압 강화를 통한 저소비전력의 유기발광소자를 제공하는 것을 개시하고 있다.Korean Patent Publication No. KR2000-0000628 also states that a material containing fluorine can be used as a material for a light emitting layer other than an electron transport layer, and in Korean Patent Publication No. 2000-0000628, fluorinated aryl with strong electron affinity, that is, pentafluoro A green light-emitting polymer with improved electroluminescence efficiency by introducing a Pentafluoro aryl or Octafluorobiphenyl group to poly(p-phenylenevinylene) to induce balanced electrons and holes to meet and Korean Patent Application Laid-Open No. 2005-0115069 discloses a light-emitting compound including a fluorine-based branch having an AIEE (Aggregation Induced Enhanced Emission) characteristic, which is particularly excellent in luminous efficiency in a solid state. Korean Patent No. 10-0846597 discloses a first electrode; hole transport layer; light emitting layer; Describes an aromatic fluorocarbon compound of C 6y F 6y-2n substituted with fluorine between the first electrode and the hole transport layer in an organic light emitting device having a second electrode, and further comprising between the light emitting layer and the second electrode An organic light emitting diode is described. This is achieved by inserting a thin film containing a fluorine-containing compound at the interface between the first electrode (anode) and the hole injection (hole transport layer) to control the interface of the organic light emitting device with an aromatic fluorocarbon compound, and low power consumption organic light emitting by strengthening the driving voltage. It is disclosed to provide a device.

본 발명은 디스플레이 장치에 있어서, 정밀한 전극 패턴을 형성함과 동시에 패터닝 방식에 소요되는 시간 및 비용을 절감시킬 수 있는 금속 또는 전극(캐소드) 패터닝용 불소화 재료를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a fluorinated material for metal or electrode (cathode) patterning that can reduce the time and cost required for a patterning method while forming a precise electrode pattern in a display device.

본 발명은 하기 화학식 (1)로 표시되는 불소 함유 화합물, 이를 포함하는 금속패터닝용 조성물 및 이를 포함하는 유기전기소자를 제공한다.The present invention provides a fluorine-containing compound represented by the following formula (1), a composition for metal patterning comprising the same, and an organic electric device including the same.

화학식 (1) Formula (1)

Figure 112021084385904-pat00001
Figure 112021084385904-pat00001

본 발명은 상기 화학식 (1)로 표시되는 화합물을 금속 또는 전극(캐소드) 패터닝 재료로 이용함으로써, 쉐도우 마스크의 사용 없이 전극의 미세패턴을 형성할 수 있으며, 높은 광투과율을 갖는 투명 디스플레이의 제작이 용이해져 UDC 적용을 보다 용이하게 할 수 있다.According to the present invention, by using the compound represented by the formula (1) as a metal or electrode (cathode) patterning material, it is possible to form a micropattern of the electrode without the use of a shadow mask, and the production of a transparent display having high light transmittance This makes it easier to apply UDC.

도 1 내지 도 3은 불소화합물을 포함하는 디스플레이 적층 구조의 예시도이다.
도 4a는 비교예 1의 SEM 단면도이다.
도 4b는 실시예 3의 SEM 단면도이다.
도 5a는 비교예 1 및 실시예 1의 광 투과율 측정 결과 그래프이다.
도 5b는 비교예 1 및 실시예 2의 광 투과율 측정 결과 그래프이다.
도 5c는 비교예 1 및 실시예 3의 광 투과율 측정 결과 그래프이다.
도 5d는 비교예 1 및 실시예 4의 광 투과율 측정 결과 그래프이다.
도 5e는 비교예 1 및 실시예 5의 광 투과율 측정 결과 그래프이다.
도 5f는 비교예 1 및 실시예 6의 광 투과율 측정 결과 그래프이다.
도 5g는 비교예 1 및 실시예 7의 광 투과율 측정 결과 그래프이다.
도 5h는 비교예 1 및 실시예 8의 광 투과율 측정 결과 그래프이다.
도 6a는 비교예 3 및 실시예 9의 광 투과율 측정 결과 그래프이다.
도 6b는 비교예 4 및 실시예 10의 광 투과율 측정 결과 그래프이다.
도 6c는 비교예 5 및 실시예 11의 광 투과율 측정 결과 그래프이다.
도 7a는 비교예 6 및 실시예 12 내지 실시예 14의 광 투과율 측정 결과 그래프이다.
도 7b는 비교예 6 및 실시예 15 내지 실시예 17의 광 투과율 측정 결과 그래프이다.
도 7c는 비교예 6 및 실시예 18 내지 실시예 20의 광 투과율 측정 결과 그래프이다.
도 7d는 비교예 6 및 실시예 21 내지 실시예 23의 광 투과율 측정 결과 그래프이다.
도 8a는 비교예 7의 접촉각 측정 결과를 나타낸 것이다.
도 8b는 실시예 24의 접촉각 측정 결과를 나타낸 것이다.
도 8c는 실시예 25의 접촉각 측정 결과를 나타낸 것이다.
도 8d는 실시예 26의 접촉각 측정 결과를 나타낸 것이다.
도 8e는 실시예 27의 접촉각 측정 결과를 나타낸 것이다.
도 8f는 실시예 28의 접촉각 측정 결과를 나타낸 것이다.
도 8g는 실시예 29의 접촉각 측정 결과를 나타낸 것이다.
도 8h는 실시예 30의 접촉각 측정 결과를 나타낸 것이다.1 to 3 are exemplary views of a display stacked structure including a fluorine compound.
4A is an SEM cross-sectional view of Comparative Example 1. FIG.
4B is an SEM cross-sectional view of Example 3. FIG.
5A is a graph of light transmittance measurement results of Comparative Examples 1 and 1;
5B is a graph of light transmittance measurement results of Comparative Examples 1 and 2;
5C is a graph of light transmittance measurement results of Comparative Examples 1 and 3;
5D is a graph of light transmittance measurement results of Comparative Examples 1 and 4;
5E is a graph of light transmittance measurement results of Comparative Examples 1 and 5;
5f is a graph of light transmittance measurement results of Comparative Examples 1 and 6;
5g is a graph of light transmittance measurement results of Comparative Examples 1 and 7;
5H is a graph of light transmittance measurement results of Comparative Examples 1 and 8;
6A is a graph of light transmittance measurement results of Comparative Examples 3 and 9;
6B is a graph of light transmittance measurement results of Comparative Examples 4 and 10;
6C is a graph of light transmittance measurement results of Comparative Examples 5 and 11;
7A is a graph of light transmittance measurement results of Comparative Example 6 and Examples 12 to 14;
7B is a graph of light transmittance measurement results of Comparative Example 6 and Examples 15 to 17;
7C is a graph of light transmittance measurement results of Comparative Example 6 and Examples 18 to 20;
7D is a graph of light transmittance measurement results of Comparative Example 6 and Examples 21 to 23;
8A shows a contact angle measurement result of Comparative Example 7. FIG.
8B shows the contact angle measurement result of Example 24.
8C shows the contact angle measurement result of Example 25.
8D shows the contact angle measurement result of Example 26.
8E shows the contact angle measurement result of Example 27.
8f shows the contact angle measurement result of Example 28.
8G shows the contact angle measurement result of Example 29.
8H shows the contact angle measurement result of Example 30.

본 명세서 및 첨부된 청구범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다.As used herein and in the appended claims, unless otherwise stated, the following terms have the following meanings.

본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

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" as used herein, unless otherwise specified, has a single bond having 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

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.As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and include a straight or branched chain group, , but not limited thereto.

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” refers to 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.As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms, unless otherwise specified. it is not

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.As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

본 명세서에 사용된 용어 "알킬싸이오기"는 황 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkylthio group" refers to an alkyl group to which a sulfur radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

본 명세서에 사용된 용어 "아릴싸이오기"는 황 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term “arylthio group” refers to an aryl group to which a sulfur radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

본 명세서에 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, 스파이로플루오렌기일 수 있다.As used herein, the terms “aryl group” and “arylene group” each have 6 to 60 carbon atoms, and are not limited thereto, unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a 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. 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.The prefix “aryl” or “ar” refers to 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 the radical substituted with an aryl group has the number of carbon atoms described herein. Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

본 명세서에 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" as used herein, unless otherwise specified, includes one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, a heteroaliphatic ring and a hetero aromatic rings. It may be formed by combining adjacent functional groups.

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

또한 “헤테로고리기”는 헤테로원자를 포함하는 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 의미한다. 또한, 고리를 형성하는 탄소 대신 하기 화합물과 같이 SO2, P=O 등과 같은 헤테로원자단을 포함하는 화합물도 헤테로고리기에 포함될 수 있다.In addition, "heterocyclic group" refers to a monocyclic group containing a heteroatom, a ring aggregate, a fused multiple ring system, a spiro compound, and the like. In addition, a compound including a heteroatom group such as SO 2 , P=O, etc. may be included in the heterocyclic group, such as the following compounds instead of carbon forming a ring.

Figure 112021084385904-pat00002
Figure 112021084385904-pat00002

본 발명에 사용된 용어 "지방족고리기"는 방향족탄화수소를 제외한 고리형 탄화수소를 의미하며, 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 포함하며, 다른 설명이 없는 한 탄소수 3 내지 60의 고리를 의미하나 여기에 제한되는 것은 아니다. 예컨대, 방향족고리인 벤젠과 비방향족고리인 사이클로헥산이 융합된 경우에도 지방족고리에 해당한다.The term "aliphatic ring group" used in the present invention means a cyclic hydrocarbon other than an aromatic hydrocarbon, and includes a monocyclic ring, a ring aggregate, a fused multiple ring system, a spiro compound, etc., and unless otherwise specified, the number of carbon atoms It means a ring of 3 to 60, but is not limited thereto. For example, even when benzene, which is an aromatic ring, and cyclohexane, which is a non-aromatic ring, are fused, it corresponds to an aliphatic ring.

본 발명에서 사용된 용어 "플루오렌일기", "플루오렌일렌기", "플루오렌트리일기"는 다른 설명이 없는 한 각각 하기 구조에서 R, R' 및 R"이 모두 수소인 1가, 2가 또는 3가의 작용기를 의미하며, "치환된 플루오렌일기", "치환된 플루오렌일렌기" 또는 "치환된 플루오렌트리일기"는 치환기 R, R' 및 R" 중 적어도 하나가 수소 이외의 치환기인 것을 의미하며, R과 R'이 서로 결합되어 이들이 결합된 탄소와 함께 스파이로 화합물을 형성한 경우를 포함한다. 본 명세서에서는 가수와 상관없이 플루오렌일기, 플루오렌일렌기, 플루오렌트리일기를 모두 플루오렌기라고 명명할 수도 있다.As used herein, the terms "fluorenyl group", "fluorenylene group", and "fluorentriyl group" refer to monovalent, 2 It means a valent or trivalent functional group, and "substituted fluorenyl group", "substituted fluorenylene group" or "substituted fluorentriyl group" means that at least one of the substituents R, R' and R" is other than hydrogen. It means a substituent, and includes cases in which R and R' are bonded to each other to form a spiro compound together with the carbon to which they are bonded. In the present specification, the fluorenyl group, fluorenylene group, and fluorentriyl group may all be referred to as fluorene groups regardless of the valence.

Figure 112021084385904-pat00003
Figure 112021084385904-pat00003

본 명세서에서 각 기호 및 그 치환기의 예로 예시되는 아릴기, 아릴렌기, 헤테로고리기 등에 해당하는 '기 이름'은 '가수를 반영한 기의 이름'을 기재할 수도 있지만, '모체화합물 명칭'으로 기재할 수도 있다. 예컨대, 아릴기의 일종인 '페난트렌'의 경우, 1가의 '기'는 '페난트릴'로 2가의 기는 '페난트릴렌' 등과 같이 가수를 구분하여 기의 이름을 기재할 수도 있지만, 가수와 상관없이 모체 화합물 명칭인 '페난트렌'으로 기재할 수도 있다. 유사하게, 피리미딘의 경우에도, 가수와 상관없이 '피리미딘'으로 기재하거나, 1가인 경우에는 피리미딘일기, 2가의 경우에는 피리미딘일렌 등과 같이 해당 가수의 '기의 이름'으로 기재할 수도 있다. 또한, 본 명세서에서는 화합물 명칭이나 치환기 명칭을 기재함에 있어 위치를 표시하는 숫자나 알파벳 등은 생략할 수도 있다. 예컨대, 피리도[4,3-d]피리미딘을 피리도피리미딘으로, 벤조퓨로[2,3-d]피리미딘을 벤조퓨로피리미딘으로, 9,9-다이메틸-9H-플루오렌을 다이메틸플루오렌 등과 같이 기재할 수 있다. 따라서, 벤조[g]퀴녹살린이나 벤조[f]퀴녹살린을 모두 벤조퀴녹살린이라고 기재할 수 있다.In the present specification, the 'group name' corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified as examples of each symbol and its substituents may be described as 'the name of the group reflecting the valence', but is described as 'name of the parent compound' You may. For example, in the case of 'phenanthrene', which is a type of aryl group, the monovalent 'group' is 'phenanthryl' and the divalent group is 'phenanthrylene'. Regardless, it can also be described as the name of the parent compound, 'phenanthrene'. Similarly, in the case of pyrimidine, regardless of the valence, it can be described as 'pyrimidine', or as the 'name of the group' of the valence, such as a pyrimidinyl group in the case of monovalent, or pyrimidinylene in the case of divalent. have. In addition, in the present specification, in describing the compound name or the substituent name, numbers or alphabets indicating positions may be omitted. For example, pyrido[4,3-d]pyrimidine to pyridopyrimidine, benzofuro[2,3-d]pyrimidine to benzofuropyrimidine, 9,9-dimethyl-9H-flu Orene can be described as dimethylfluorene and the like. Therefore, both benzo[g]quinoxaline and benzo[f]quinoxaline can be described as benzoquinoxaline.

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

Figure 112021084385904-pat00004
Figure 112021084385904-pat00004

여기서, a가 0의 정수인 경우 치환기 R1은 부존재하며, 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 is absent, and when a is an integer of 1, one substituent R 1 is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, wherein R 1 may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omitted.

Figure 112021084385904-pat00005
Figure 112021084385904-pat00005

또한, 본 명세서에서 다른 설명이 없는 한, 축합환을 표시할 때 '숫자-축합환'에서 숫자는 축합되는 고리의 개수를 나타낸다. 예컨대, 안트라센, 페난트렌, 벤조퀴나졸린 등과 같이 3개의 고리가 서로 축합한 형태는 3-축합환으로 표기할 수 있다.In addition, unless otherwise specified in the present specification, when representing a condensed ring, the number in 'number-condensed ring' indicates the number of rings to be condensed. For example, a form in which three rings are condensed with each other, such as anthracene, phenanthrene, benzoquinazoline, etc., may be expressed as a 3-condensed ring.

또한, 본 명세서에서 다른 설명이 없는 한, 5원자 고리, 6원자 고리 등과 같이 '숫자원자' 형식으로 고리를 표현한 경우, '숫자-원자'에서 숫자는 고리를 형성하는 원소의 개수를 나타낸다. 예컨대, 싸이오펜이나 퓨란 등은 5원자 고리에 해당할 수 있고, 벤젠이나 피리딘은 6원자 고리에 해당할 수 있다.In addition, unless otherwise specified in the present specification, when a ring is expressed in the form of a 'numeric atom' such as a 5-membered ring, a 6-membered ring, etc., the number in 'number-atom' indicates the number of elements forming the ring. For example, thiophene or furan may correspond to a 5-membered ring, and benzene or pyridine may correspond to a 6-membered ring.

또한, 본 명세서에서 다른 설명이 없는 한, 이웃한 기끼리 서로 결합하여 형성한 고리는 C6~C60의 방향족고리기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C3~C60의 지방족고리기;로 이루어진 군에서 선택될 수 있다.In addition, unless otherwise stated in the present specification, the ring formed by bonding adjacent groups to each other is a C 6 ~ C 60 aromatic ring group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; And C 3 ~ C 60 An aliphatic ring group; may be selected from the group consisting of.

이때, 본 명세서에서 다른 설명이 없는 한, '이웃한 기끼리'라 함은, 하기 화학식을 예로 들어 설명하면, R1과 R2끼리, R2와 R3끼리, R3과 R4끼리, R5와 R6끼리 뿐만 아니라, 하나의 탄소를 공유하는 R7과 R8끼리도 포함되고, R1과 R7끼리, R1과 R8끼리 또는 R4와 R5끼리 등과 같이 바로 인접하지 않은 고리 구성 원소(탄소나 질소 등)에 결합된 치환기도 포함될 수 있다. 즉, 바로 인접한 탄소나 질소 등과 같은 고리 구성 원소에 치환기가 있을 경우에는 이들이 이웃한 기가 될 수 있지만, 바로 인접한 위치의 고리 구성 원소에 그 어떤 치환기도 결합되지 않은 경우에는 그 다음 고리 구성 원소에 결합된 치환기와 이웃한 기가 될 수 있고, 또한 동일 고리 구성 탄소에 결합된 치환기끼리도 이웃한 기라고 할 수 있다.At this time, unless otherwise specified in the present specification, 'neighboring groups' refers to each other when describing the following chemical formula as an example, R 1 and R 2 each other , R 2 and R 3 each other , R 3 and R 4 each other , Not only R 5 and R 6 but also R 7 and R 8 sharing one carbon are included, and not immediately adjacent, such as R 1 and R 7 , R 1 and R 8 , or R 4 and R 5 , etc. Substituents bonded to ring constituents (such as carbon or nitrogen) may also be included. That is, if there is a substituent on a ring constituent element such as carbon or nitrogen immediately adjacent to it, they may be a neighboring group, but if no substituent is bonded to a ring constituent element at the immediately adjacent position, it is bonded to the next ring constituent element It can be a group adjacent to the substituent group, and also the substituents bonded to the same ring constituent carbon can be said to be adjacent groups.

하기 화학식에서 R7과 R8처럼 동일 탄소에 결합된 치환기가 서로 결합하여 고리를 형성할 경우에는 스파이로 모이어티가 포함된 화합물이 형성될 수 있다. When substituents bonded to the same carbon as R 7 and R 8 in the following formula combine with each other to form a ring, a compound including a spiro moiety may be formed.

Figure 112021084385904-pat00006
Figure 112021084385904-pat00006

또한, 본 명세서에서 '이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다'라는 표현은 '이웃한 기끼리 서로 결합하여 선택적으로 고리를 형성한다'라는 것과 동일한 의미로 사용되며, 적어도 한 쌍의 이웃한 기끼리 서로 결합하여 고리를 형성하는 경우를 의미한다.In addition, in the present specification, the expression 'neighboring groups may combine with each other to form a ring' is used in the same meaning as 'neighboring groups combine with each other to selectively form a ring', and at least one pair of It means a case where adjacent groups are bonded to each other to form a ring.

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

본 발명의 일측면에 따르면, 하기 화학식 (1)로 표시되고 분자 내 불소 함량이 30% 이상인 불소화 화합물을 제공한다.According to one aspect of the present invention, there is provided a fluorinated compound represented by the following formula (1) and having an intramolecular fluorine content of 30% or more.

화학식 (1) Formula (1)

Figure 112021084385904-pat00007
Figure 112021084385904-pat00007

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

Figure 112021084385904-pat00008
Figure 112021084385904-pat00009
Figure 112021084385904-pat00008
Figure 112021084385904-pat00009

상기 화학식 (1), 화학식 (1-1) 및 화학식 (1-2)에서, 각 기호는 하기와 같이 정의될 수 있다.In the above formulas (1), (1-1) and (1-2), each symbol may be defined as follows.

1) Ar1 및 Ar2는 서로 독립적으로 C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택된다.1) Ar 1 and Ar 2 are each independently a C 6 ~ C 60 aryl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; and a C 3 ~ C 60 aliphatic ring and a C 6 ~ C 60 aromatic ring fused ring group; is selected from the group consisting of.

상기 Ar1 및 Ar2가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When Ar 1 and Ar 2 are an aryl group, preferably a C 6 ~ C 30 aryl group, more preferably a C 6 ~ C 20 aryl group, more preferably a C 6 ~ C 18 aryl group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

상기 Ar1 및 Ar2가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When Ar 1 and Ar 2 are a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group. cyclic groups such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

2) A, B, C 및 D는 서로 독립적으로 -CRaRb-; -NRc-; -O-; -S-; -SiRdRe-; C6~C60의 아릴렌기; 플루오렌일렌기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60 헤테로고리기;로 이루어진 군에서 선택된다.2) A, B, C and D are each independently -CR a R b -; -NR c -; -O-; -S-; -SiR d R e -; C 6 ~ C 60 Arylene group; fluorenylene group; And O, N, S, Si, and P including at least one heteroatom C 2 ~ C 60 heterocyclic group; is selected from the group consisting of.

상기 A, B, C 및 D가 아릴렌기인 경우, 바람직하게는 C6~C30의 아릴렌기, 더 바람직하게는 C6~C20의 아릴렌기, 더욱 바람직하게는 C6~C18의 아릴렌기, 예컨대 페닐렌, 바이페닐, 나프틸렌, 터페닐렌 등일 수 있다.When A, B, C and D are an arylene group, preferably a C 6 ~ C 30 arylene group, more preferably a C 6 ~ C 20 arylene group, more preferably a C 6 ~ C 18 aryl group It may be a lene group such as phenylene, biphenyl, naphthylene, terphenylene, and the like.

상기 A, B, C 및 D가 플루오렌일렌기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌일기, 9,9'-스파이로바이플루오렌 등일 수 있다.When A, B, C and D are a fluorenylene group, 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene etc.

상기 A, B, C 및 D가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When A, B, C and D are a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 of a heterocyclic group such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

단, m이 0일 경우 A는 C6~C60의 아릴기; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60 헤테로고리기;이다.However, when m is 0, A is a C 6 ~ C 60 aryl group; Or O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 heterocyclic group;

상기 A가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When A is an aryl group, preferably a C 6 ~ C 30 aryl group, more preferably a C 6 ~ C 20 aryl group, more preferably a C 6 ~ C 18 aryl group, such as phenyl, biphenyl , naphthyl, terphenyl, and the like.

상기 A가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When A is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group, such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

3) R1, R2 및 R3은 각각 동일하거나 상이하고, 서로 독립적으로 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; C1~C50의 알콕실기; C6~C60의 아릴옥시기; -L-NR'R"; 상기 화학식 (1-1)로 표시되는 치환기; 및 상기 화학식 (1-2)로 표시되는 치환기;로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.3) R 1 , R 2 and R 3 are the same or different from each other, and each independently a C 6 ~ C 60 aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; C 3 ~ C 60 A fused ring group of an aliphatic ring and C 6 ~ C 60 aromatic ring; C 1 ~ C 50 Alkyl group; C 1 ~ C 50 Alkoxyl group; C 6 ~ C 60 Aryloxy group; -L-NR'R"; a substituent represented by the formula (1-1); and a substituent represented by the formula (1-2); or adjacent groups are bonded to each other to form a ring can be formed

상기 R1 내지 R3이 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When R 1 to R 3 are an aryl group, preferably a C 6 ~ C 30 aryl group, more preferably a C 6 ~ C 20 aryl group, more preferably a C 6 ~ C 18 aryl group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

상기 R1 내지 R3이 플루오렌일기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌일기, 9,9'-스파이로바이플루오렌 등일 수 있다.When R 1 to R 3 is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene, etc. have.

상기 R1 내지 R3이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When R 1 To R 3 is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group cyclic groups such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

상기 R1 내지 R3이 알킬기인 경우, 바람직하게는 C1~C20의 알킬기, 더 바람직하게는 C1~C10의 알킬기일 수 있고, 예컨대 메틸, t-부틸 등일 수 있다.When R 1 to R 3 is an alkyl group, it may be preferably a C 1 to C 20 alkyl group, more preferably a C 1 to C 10 alkyl group, for example, methyl or t-butyl.

상기 R1 내지 R3이 알콕시기인 경우, 바람직하게는 C1~C20의 알콕실기, 더욱 바람직하게는 C1~C10의 알콕실기, 예컨대 메톡시, t-부톡시 등일 수 있다.When R 1 to R 3 is an alkoxy group, it may be preferably a C 1 to C 20 alkoxyl group, more preferably a C 1 to C 10 alkoxyl group, such as methoxy, t-butoxy, or the like.

상기 R1 내지 R3이 아릴옥시기인 경우, 바람직하게는 C6~C30의 아릴옥시기, 더욱 바람직하게는 C6~C20의 아릴옥시기일 수 있다.When R 1 to R 3 is an aryloxy group, it may be preferably a C 6 ~ C 30 aryloxy group, more preferably a C 6 ~ C 20 aryloxy group.

단, R1, R2 및 R3 중 적어도 하나는 상기 화학식 (1-1)로 표시되는 치환기 또는 상기 화학식 (1-2)로 표시되는 치환기이다.However, at least one of R 1 , R 2 and R 3 is a substituent represented by the formula (1-1) or a substituent represented by the formula (1-2).

4) a, b 및 c는 서로 독립적으로 0 내지 10의 정수이며, 단, a+b+c는 1 이상이고,4) a, b and c are each independently an integer of 0 to 10, with the proviso that a+b+c is 1 or more,

5) m 및 n은 서로 독립적으로 0 내지 50의 정수이다. 여기서, n이 0일 경우, R2는 미존재하며, 이때, a+c는 1 이상이고, m이 0일 경우, R3가 미존재하며, 이때, a+b가 1 이상이고, n 및 m이 모두 0일 경우, R2 및 R3가 미존재하며, 이때, a는 1 내지 10의 정수이다.5) m and n are each independently an integer from 0 to 50; Here, when n is 0, R 2 is absent, wherein a+c is 1 or more, and when m is 0, R 3 is absent, wherein a+b is 1 or more, n and When both m are 0, R 2 and R 3 are absent, where a is an integer from 1 to 10.

6) X1, X2, X3 및 X4는 서로 독립적으로 CRfRg, NRh, O, S 또는 SiRiRj이고,6) X 1 , X 2 , X 3 and X 4 are independently of each other CR f R g , NR h , O, S or SiR i R j ;

7) R' 및 R"은 서로 독립적으로 C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.7) R' and R" are each independently a C 6 -C 60 aryl group; O, N, S, Si and P including a heteroatom of at least one C 2 -C 60 heterocyclic group; and C 3 ~ C 60 A fused ring group of an aliphatic ring and a C 6 ~ C 60 aromatic ring is selected from the group consisting of, or adjacent groups may be bonded to each other to form a ring.

상기 R' 및 R"가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When R' and R" are aryl groups, preferably a C 6 -C 30 aryl group, more preferably a C 6 -C 20 aryl group, more preferably a C 6 -C 18 aryl group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

상기 R' 및 R"가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When R' and R" are a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group cyclic groups such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

8) Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri 및 Rj는 서로 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; 상기 화학식 (1-1)로 표시되는 치환기; 및 상기 화학식 (1-2)로 표시되는 치환기;로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.8) R a , R b , R c , R d , Re e , R f , R g , R h , R i and R j are independently of each other hydrogen; heavy hydrogen; halogen; C 6 ~ C 60 Aryl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; C 3 ~ C 60 A fused ring group of an aliphatic ring and C 6 ~ C 60 aromatic ring; C 1 ~ C 50 Alkyl group; a substituent represented by the above formula (1-1); and a substituent represented by Formula (1-2); or may be selected from the group consisting of, or adjacent groups may be bonded to each other to form a ring.

상기 Ra 내지 Rj가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When R a to R j are an aryl group, preferably a C 6 to C 30 aryl group, more preferably a C 6 to C 20 aryl group, more preferably a C 6 to C 18 aryl group, such as phenyl, biphenyl, naphthyl, terphenyl, and the like.

상기 Ra 내지 Rj가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When R a To R j is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group cyclic groups such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

상기 Ra 내지 Rj가 알킬기인 경우, 바람직하게는 C1~C20의 알킬기, 더 바람직하게는 C1~C10의 알킬기일 수 있고, 예컨대 메틸, t-부틸 등일 수 있다.When R a to R j are an alkyl group, it may be preferably a C 1 to C 20 alkyl group, more preferably a C 1 to C 10 alkyl group, for example, methyl or t-butyl.

9) o, p, q 및 r은 서로 독립적으로 0 또는 1의 정수이다. 이때, 상기 o가 0일 경우 X1은 미존재하며, 상기 p가 0일 경우, X2는 미존재하고, 상기 q가 0일 경우, X3이 미존재하며, 상기 r이 0일 경우, X4가 미존재한다.9) o, p, q and r are each independently an integer of 0 or 1. At this time, when o is 0, X 1 does not exist, when p is 0, X 2 does not exist, when q is 0, X 3 does not exist, and when r is 0, X 4 does not exist.

10) x는 3 내지 50의 정수이다. 또한, y+z는 2x+1, 2x 또는 2x-2의 정수이다. 예컨대, y는 0이고 z가 2x+1, 2x 또는 2x-2일 수 있다.10) x is an integer from 3 to 50; In addition, y+z is an integer of 2x+1, 2x, or 2x-2. For example, y may be 0 and z may be 2x+1, 2x or 2x-2.

이때, x는 바람직하게는 3 내지 20의 정수이고, 더 바람직하게는 5 내지 15의 정수이며, 더욱 바람직하게는 5 내지 12의 정수이다. x가 상기 범위를 초과하는 경우 진공증착시 Td가 높아질 수 있는 문제점이 있고, 상기 범위 미만인 경우, 화합물이 액체가 될 가능성이 크다.In this case, x is preferably an integer of 3 to 20, more preferably an integer of 5 to 15, and still more preferably an integer of 5 to 12. When x exceeds the above range, there is a problem that Td may be increased during vacuum deposition, and if it is less than the above range, the compound is highly likely to become a liquid.

11) i, t 및 v는 서로 독립적으로 0 내지 20의 정수이고, s, u 및 w는 서로 독립적으로 1 내지 20의 정수이다. 여기서, i 또는 t가 0일 경우, B 및 C가 단일결합을 의미하며, 이때 s 또는 u는 1이다.11) i, t and v are independently integers from 0 to 20, and s, u and w are independently integers from 1 to 20. Here, when i or t is 0, B and C mean a single bond, where s or u is 1.

12) L은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C1~C50의 알킬렌기; 및 C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기;로 이루어진 군에서 선택된다.12) L is a single bond; C 6 ~ C 60 Arylene group; fluorenylene group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; C 1 ~ C 50 alkylene group; and a C 3 ~ C 60 aliphatic ring and a C 6 ~ C 60 aromatic ring fused ring group; is selected from the group consisting of.

상기 L이 아릴렌기인 경우, 바람직하게는 C6~C30의 아릴렌기, 더 바람직하게는 C6~C20의 아릴렌기, 더욱 바람직하게는 C6~C18의 아릴렌기, 예컨대 페닐렌, 바이페닐, 나프틸렌, 터페닐렌 등일 수 있다.When L is an arylene group, preferably a C 6 ~ C 30 arylene group, more preferably a C 6 ~ C 20 arylene group, more preferably a C 6 ~ C 18 arylene group, such as phenylene; biphenyl, naphthylene, terphenylene, and the like.

상기 L이 플루오렌일렌기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌일기, 9,9'-스파이로바이플루오렌 등일 수 있다.When L is a fluorenylene group, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene, or the like.

상기 L이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When L is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group, such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

상기 L이 알킬렌기인 경우, 바람직하게는 C1~C20의 알킬렌기, 더 바람직하게는 C1~C10의 알킬렌기일 수 있고, 예컨대 메틸렌, 부틸렌 등일 수 있다.When L is an alkylene group, it may be preferably a C 1 to C 20 alkylene group, more preferably a C 1 to C 10 alkylene group, such as methylene or butylene.

13) 여기서, 상기 아릴기, 아릴렌기, 헤테로고리기, 플루오렌일기, 플루오렌일렌기, 융합고리기, 알킬기, 알콕실기, 아릴옥시기 및 이웃한 기끼리 서로 결합하여 형성한 고리는 각각 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1~C20의 알킬싸이오기; C1~C20의 알콕실기; C6~C20의 아릴옥시기; C1~C20의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; 할로겐으로 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.13) Here, the aryl group, the arylene group, the heterocyclic group, the fluorenyl group, the fluorenylene group, the fused ring group, the alkyl group, the alkoxyl group, the aryloxy group, and the rings formed by bonding the neighboring groups are each deuterium ; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C 1 ~ C 20 Alkylthio group; C 1 ~ C 20 An alkoxyl group; C 6 ~ C 20 Aryloxy group; C 1 ~ C 20 Alkyl group; C 2 ~ C 20 Alkenyl group; C 2 ~ C 20 Alkynyl group; C 6 ~ C 20 Aryl group; C 6 ~ C 20 Aryl group substituted with deuterium; a halogen-substituted C 6 ~ C 20 aryl group; fluorenyl group; C 2 ~ C 20 A heterocyclic group; C 3 ~ C 20 Cycloalkyl group; C 7 ~ C 20 Arylalkyl group; And C 8 ~ C 20 Aryl alkenyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be combined with each other to form a ring, where 'ring' means C 3 ~ C 60 of an aliphatic ring or C 6 ~ C 60 aromatic ring or C 2 ~ C 60 heterocyclic ring or a fused ring consisting of a combination thereof, and includes a saturated or unsaturated ring.

상기 화학식 (1)은 하기 화학식 (2)로 표시될 수 있다.The formula (1) may be represented by the following formula (2).

화학식 (2) Formula (2)

Figure 112021084385904-pat00010
Figure 112021084385904-pat00010

{상기 화학식 (2)에서, Ar1, Ar2, R1, R2, R3, A, a, b, c, m 및 n은 상기 화학식 (1)에서 정의된 바와 동일하다.}{In Formula (2), Ar 1 , Ar 2 , R 1 , R 2 , R 3 , A, a, b, c, m and n are the same as defined in Formula (1).}

바람직하게는, 상기 화학식 (1)은 하기 화학식 (2-1) 내지 화학식 (2-5) 중 어느 하나로 표시될 수 있다.Preferably, the formula (1) may be represented by any one of the following formulas (2-1) to (2-5).

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

Figure 112021084385904-pat00011
Figure 112021084385904-pat00011

화학식 (2-3) 화학식 (2-4) Formula (2-3) Formula (2-4)

Figure 112021084385904-pat00012
Figure 112021084385904-pat00012

화학식 (2-5) Formula (2-5)

Figure 112021084385904-pat00013
Figure 112021084385904-pat00013

{상기 화학식 (2-1) 내지 화학식 (2-5)에서, Ar1, Ar2, R1, R3, Ra, Rb, Rc, Rd, Re, a 및 c는 상기 화학식 (1)에서 정의된 바와 동일하다.}{In Formulas (2-1) to (2-5), Ar 1 , Ar 2 , R 1 , R 3 , R a , R b , R c , R d , R e , a and c are the formulas Same as defined in (1).}

또한, 바람직하게는 상기 화학식 (1)은 하기 화학식 (2-6)으로 표시될 수 있다.In addition, preferably, the formula (1) may be represented by the following formula (2-6).

화학식 (2-6) Formula (2-6)

Figure 112021084385904-pat00014
Figure 112021084385904-pat00014

상기 화학식 (2-6)에서, 각 기호는 하기와 같이 정의될 수 있다.In the above formula (2-6), each symbol may be defined as follows.

1) Ar1, Ar2, R1, R2, R3, a, b 및 c는 상기 화학식 (1)에서 정의된 바와 동일하며,1) Ar 1 , Ar 2 , R 1 , R 2 , R 3 , a, b and c are the same as defined in Formula (1) above,

2) A'은 C6~C60의 아릴렌기; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60 헤테로고리기;이다.2) A' is a C 6 ~ C 60 arylene group; Or O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 heterocyclic group;

상기 A'이 아릴렌기인 경우, 바람직하게는 C6~C30의 아릴렌기, 더 바람직하게는 C6~C20의 아릴렌기, 더욱 바람직하게는 C6~C18의 아릴렌기, 예컨대 페닐렌, 바이페닐, 나프틸렌, 터페닐렌, 트리페닐렌 등일 수 있다.When A' is an arylene group, preferably a C 6 ~ C 30 arylene group, more preferably a C 6 ~ C 20 arylene group, more preferably a C 6 ~ C 18 arylene group, such as phenylene , biphenyl, naphthylene, terphenylene, triphenylene, and the like.

상기 A'이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린 등일 수 있다.When A' is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group, For example, it may be pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, and the like.

더 바람직하게는 상기 화학식 (1)은 하기 화학식 (2-7)로 표시될 수 있다.More preferably, the formula (1) may be represented by the following formula (2-7).

화학식 (2-7) Formula (2-7)

Figure 112021084385904-pat00015
Figure 112021084385904-pat00015

{상기 화학식 (2-7)에서,{In the above formula (2-7),

1) R1, R2, R3 및 b는 상기 화학식 (1)에서 정의된 바와 동일하며,1) R 1 , R 2 , R 3 and b are the same as defined in Formula (1) above,

2) A'은 상기 화학식 (2-6)에서 정의된 바와 동일하고,2) A' is the same as defined in Formula (2-6) above,

3) a' 및 c'은 서로 독립적으로 0 내지 5의 정수이다.}3) a' and c' are each independently an integer from 0 to 5.}

더욱 바람직하게는 상기 화학식 (1)은 하기 화학식 (2-8) 또는 화학식 (2-9)로 표시될 수 있다.More preferably, the formula (1) may be represented by the following formula (2-8) or (2-9).

화학식 (2-8) 화학식 (2-9) Formula (2-8) Formula (2-9)

Figure 112021084385904-pat00016
Figure 112021084385904-pat00016

상기 화학식 (2-8) 및 화학식 (2-9)에서, 각 기호는 하기와 같이 정의될 수 있다.In the above formulas (2-8) and (2-9), each symbol may be defined as follows.

1) b, B, i, x, y, z 및 s는 상기 화학식 (1)에서 정의된 바와 동일하며,1) b, B, i, x, y, z and s are the same as defined in the above formula (1),

2) A'은 상기 화학식 (2-6)에서 정의된 바와 동일하고,2) A' is the same as defined in Formula (2-6) above,

3) R4는 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; C1~C50의 알콕실기; C6~C60의 아릴옥시기; 및 -L-NR'R";로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있으며,3) R 4 is a C 6 ~ C 60 aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 60 A heterocyclic group; C 3 ~ C 60 A fused ring group of an aliphatic ring and C 6 ~ C 60 aromatic ring; C 1 ~ C 50 Alkyl group; C 1 ~ C 50 Alkoxyl group; C 6 ~ C 60 Aryloxy group; And -L-NR'R"; is selected from the group consisting of, or adjacent groups may combine with each other to form a ring,

상기 L, R' 및 R"은 상기 화학식 (1)에서 정의된 바와 동일하다.L, R' and R" are the same as defined in the above formula (1).

상기 R4가 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When R 4 is an aryl group, preferably a C 6 ~ C 30 aryl group, more preferably a C 6 ~ C 20 aryl group, more preferably a C 6 ~ C 18 aryl group, such as phenyl, bi phenyl, naphthyl, terphenyl, and the like.

상기 R4가 플루오렌일기인 경우, 9,9-다이메틸-9H-플루오렌, 9,9-다이페닐-9H-플루오렌일기, 9,9'-스파이로바이플루오렌 등일 수 있다.When R 4 is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorenyl group, 9,9'-spirobifluorene, or the like.

상기 R4가 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린, 다이벤조퓨란, 다이벤조싸이오펜, 나프토벤조싸이오펜, 나프토벤조퓨란 등일 수 있다.When R 4 is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group, For example, it may be pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, dibenzofuran, dibenzothiophene, naphthobenzothiophene, naphthobenzofuran, and the like.

상기 R4가 알킬기인 경우, 바람직하게는 C1~C20의 알킬기, 더 바람직하게는 C1~C10의 알킬기일 수 있고, 예컨대 메틸, t-부틸 등일 수 있다.When R 4 is an alkyl group, it may be preferably a C 1 to C 20 alkyl group, more preferably a C 1 to C 10 alkyl group, for example, methyl or t-butyl.

상기 R4가 알콕시기인 경우, 바람직하게는 C1~C20의 알콕실기, 더욱 바람직하게는 C1~C10의 알콕실기, 예컨대 메톡시, t-부톡시 등일 수 있다.When R 4 is an alkoxy group, it may be preferably a C 1 to C 20 alkoxyl group, more preferably a C 1 to C 10 alkoxyl group, such as methoxy, t-butoxy, or the like.

상기 R4가 아릴옥시기인 경우, 바람직하게는 C6~C30의 아릴옥시기, 더욱 바람직하게는 C6~C20의 아릴옥시기일 수 있다.When R 4 is an aryloxy group, it may be preferably a C 6 ~ C 30 aryloxy group, more preferably a C 6 ~ C 20 aryloxy group.

가장 바람직하게는 상기 화학식 (1)은 하기 화학식 (2-10) 또는 화학식 (2-11)로 표시될 수 있다.Most preferably, Chemical Formula (1) may be represented by the following Chemical Formula (2-10) or Chemical Formula (2-11).

화학식 (2-10) 화학식 (2-11) Formula (2-10) Formula (2-11)

Figure 112021084385904-pat00017
Figure 112021084385904-pat00017

{상기 화학식 (2-10) 및 화학식 (2-11)에서,{In the above formulas (2-10) and (2-11),

1) b, x, y 및 z는 상기 화학식 (1)에서 정의된 바와 동일하며,1) b, x, y and z are the same as defined in the above formula (1),

2) A'은 상기 화학식 (2-6)에서 정의된 바와 동일하고,2) A' is the same as defined in Formula (2-6) above,

3) R4는 상기 화학식 (2-8) 및 화학식 (2-9)에서 정의된 바와 동일하다.}3) R 4 is the same as defined in Formulas (2-8) and (2-9) above.}

또한, 상기 화학식 (1)은 하기 화학식 (3)으로 표시될 수 있다.In addition, the formula (1) may be represented by the following formula (3).

화학식 (3) Formula (3)

Figure 112021084385904-pat00018
Figure 112021084385904-pat00018

{상기 화학식 (3)에서, Ar1, Ar2, R1, R3, a, c 및 m은 상기 화학식 (1)에서 정의된 바와 동일하다.}{In Formula (3), Ar 1 , Ar 2 , R 1 , R 3 , a, c and m are the same as defined in Formula (1).}

바람직하게는 상기 화학식 (1)은 하기 화학식 (3-1)로 표시될 수 있다.Preferably, the formula (1) may be represented by the following formula (3-1).

화학식 (3-1) Formula (3-1)

Figure 112021084385904-pat00019
Figure 112021084385904-pat00019

{상기 화학식 (3-1)에서,{In the above formula (3-1),

1) R1, R3 및 m은 상기 화학식 (1)에서 정의된 바와 동일하며,1) R 1 , R 3 and m are the same as defined in Formula (1) above,

2) a' 및 c'은 서로 독립적으로 0 내지 5의 정수이다.}2) a' and c' are each independently an integer from 0 to 5.}

또한, 상기 화학식 (1)은 하기 화학식 (4)로 표시될 수 있다. In addition, the formula (1) may be represented by the following formula (4).

화학식 (4) Formula (4)

Figure 112021084385904-pat00020
Figure 112021084385904-pat00020

상기 화학식 (4)에서, 각 기호는 하기와 같이 정의될 수 있다.In the formula (4), each symbol may be defined as follows.

1) Ar1, X1, X3, R1, R2, a 및 b은 상기 화학식 (1)에서 정의된 바와 동일하며,1) Ar 1 , X 1 , X 3 , R 1 , R 2 , a and b are the same as defined in Formula (1) above,

2) o' 및 p'은 서로 독립적으로 0 또는 1이고, o'+p'은 1 이상이며,2) o' and p' are each independently 0 or 1, o'+p' is 1 or more,

3) A"은 C6~C60의 아릴기; 또는 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60 헤테로고리기;이다.3) A" is a C 6 ~ C 60 aryl group; or a C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P;

상기 A''이 아릴기인 경우, 바람직하게는 C6~C30의 아릴기, 더 바람직하게는 C6~C20의 아릴기, 더욱 바람직하게는 C6~C18의 아릴기, 예컨대 페닐, 바이페닐, 나프틸, 터페닐 등일 수 있다.When A'' is an aryl group, preferably a C 6 ~ C 30 aryl group, more preferably a C 6 ~ C 20 aryl group, more preferably a C 6 ~ C 18 aryl group, such as phenyl; biphenyl, naphthyl, terphenyl, and the like.

상기 A''이 헤테로고리기인 경우, 바람직하게는 C2~C30의 헤테로고리기, 더 바람직하게는 C2~C20의 헤테로고리기, 더욱 바람직하게는 C2~C16의 헤테로고리기, 예컨대 피리딘, 피리미딘, 퀴놀린, 퀴나졸린, 퀴녹살린 등일 수 있다.When A'' is a heterocyclic group, preferably a C 2 ~ C 30 heterocyclic group, more preferably a C 2 ~ C 20 heterocyclic group, more preferably a C 2 ~ C 16 heterocyclic group , such as pyridine, pyrimidine, quinoline, quinazoline, quinoxaline, and the like.

바람직하게는 상기 화학식 (1)은 하기 화학식 (4-1)로 표시될 수 있다.Preferably, the formula (1) may be represented by the following formula (4-1).

화학식 (4-1) Formula (4-1)

Figure 112021084385904-pat00021
Figure 112021084385904-pat00021

{상기 화학식 (4-1)에서,{In the formula (4-1),

1) Ar1, R1, R2, X1, a 및 b는 상기 화학식 (1)에서 정의된 바와 동일하며,1) Ar 1 , R 1 , R 2 , X 1 , a and b are the same as defined in Formula (1) above,

2) A"은 상기 화학식 (4)에서 정의된 바와 동일하다.}2) A" is the same as defined in formula (4) above.}

더 바람직하게는 상기 화학식 (1)은 하기 화학식 (4-2) 내지 화학식 (4-6) 중 어느 하나로 표시될 수 있다.More preferably, the formula (1) may be represented by any one of the following formulas (4-2) to (4-6).

화학식 (4-2) 화학식 (4-3) Formula (4-2) Formula (4-3)

Figure 112021084385904-pat00022
Figure 112021084385904-pat00022

화학식 (4-4) 화학식 (4-5) Formula (4-4) Formula (4-5)

Figure 112021084385904-pat00023
Figure 112021084385904-pat00023

화학식 (4-6) Formula (4-6)

Figure 112021084385904-pat00024
Figure 112021084385904-pat00024

{상기 화학식 (4-2) 내지 화학식 (4-6)에서, {In the above formulas (4-2) to (4-6),

1) Ar1, R1, R2, Rf, Rg, Rh, Ri, Rj, a 및 b는 상기 화학식 (1)에서 정의된 바와 동일하며,1) Ar 1 , R 1 , R 2 , R f , R g , R h , R i , R j , a and b are the same as defined in Formula (1) above,

2) A"은 상기 화학식 (4)에서 정의된 바와 동일하다.}2) A" is the same as defined in formula (4) above.}

또한, 더 바람직하게는 상기 화학식 (1)은 하기 화학식 (4-7)로 표시될 수 있다.In addition, more preferably, the formula (1) may be represented by the following formula (4-7).

화학식 (4-7) Formula (4-7)

Figure 112021084385904-pat00025
Figure 112021084385904-pat00025

{상기 화학식 (4-7)에서,{In the above formula (4-7),

1) X1, R1 및 R2는 상기 화학식 (1)에서 정의된 바와 동일하며,1) X 1 , R 1 and R 2 are the same as defined in Formula (1) above,

2) a" 및 b'은 서로 독립적으로 0 내지 4의 정수이다.}2) a" and b' are each independently an integer from 0 to 4.}

또한, 상기 화학식 (1)은 하기 화학식 (5) 또는 화학식 (6)으로 표시될 수 있다.In addition, the formula (1) may be represented by the following formula (5) or (6).

화학식 (5) Formula (5)

Figure 112021084385904-pat00026
Figure 112021084385904-pat00026

화학식 (6) Formula (6)

Figure 112021084385904-pat00027
Figure 112021084385904-pat00027

{상기 화학식 (5) 및 화학식 (6)에서, {In the above formulas (5) and (6),

1) Ar1, Ar2, X1, X2, X4, R1, R2, R3, a, b 및 c는 상기 화학식 (1)에서 정의된 바와 동일하며,1) Ar 1 , Ar 2 , X 1 , X 2 , X 4 , R 1 , R 2 , R 3 , a, b and c are the same as defined in Formula (1) above,

2) A'은 상기 화학식 (2-6)에서 정의된 바와 동일하다.}2) A' is the same as defined in Formula (2-6) above.}

바람직하게는 상기 화학식 (1)은 하기 화학식 (5-1) 내지 화학식 (5-3) 중 어느 하나로 표시될 수 있다.Preferably, the formula (1) may be represented by any one of the following formulas (5-1) to (5-3).

화학식 (5-1) 화학식 (5-2) Formula (5-1) Formula (5-2)

Figure 112021084385904-pat00028
Figure 112021084385904-pat00029
Figure 112021084385904-pat00028
Figure 112021084385904-pat00029

화학식 (5-3) Formula (5-3)

Figure 112021084385904-pat00030
Figure 112021084385904-pat00030

{상기 화학식 (5-1) 내지 화학식 (5-3)에서,{In the above formulas (5-1) to (5-3),

1) X1, X2, R1, R2 및 R3은 상기 화학식 (1)에서 정의된 바와 동일하며,1) X 1 , X 2 , R 1 , R 2 and R 3 are the same as defined in Formula (1) above,

2) a" 및 c"은 서로 독립적으로 0 내지 4의 정수이고, b"은 0 내지 2의 정수이다.}2) a" and c" are each independently an integer from 0 to 4, and b" is an integer from 0 to 2.}

또한, 바람직하게는 상기 화학식 (1)은 하기 화학식 (6-1) 또는 화학식 (6-2)로 표시될 수 있다.Also, preferably, the formula (1) may be represented by the following formula (6-1) or (6-2).

화학식 (6-1) 화학식 (6-2) Formula (6-1) Formula (6-2)

Figure 112021084385904-pat00031
Figure 112021084385904-pat00032
Figure 112021084385904-pat00031
Figure 112021084385904-pat00032

{상기 화학식 (6-1) 및 (6-2)에서,{In the above formulas (6-1) and (6-2),

1) X1, X4, R1, R2 및 R3은 상기 화학식 (1)에서 정의된 바와 동일하며,1) X 1 , X 4 , R 1 , R 2 and R 3 are the same as defined in Formula (1) above,

2) a" 및 c"은 서로 독립적으로 0 내지 4의 정수이고, b"은 0 내지 2의 정수이다.}2) a" and c" are each independently an integer from 0 to 4, and b" is an integer from 0 to 2.}

또한, 상기 화학식 (1-1)은 하기 화학식 (1-1-a) 또는 화학식 (1-1-b)로 표시될 수 있다.In addition, the formula (1-1) may be represented by the following formula (1-1-a) or (1-1-b).

화학식 (1-1-a) 화학식 (1-1-b)Formula (1-1-a) Formula (1-1-b)

Figure 112021084385904-pat00033
Figure 112021084385904-pat00034
Figure 112021084385904-pat00033
Figure 112021084385904-pat00034

{상기 화학식 (1-1-a) 또는 화학식 (1-1-b)에서,{In the formula (1-1-a) or (1-1-b),

1) x, y, z, s 및 B는 화학식 (1)에서 정의된 바와 동일하며, 1) x, y, z, s and B are the same as defined in formula (1),

2) i'은 1 내지 20의 정수이다.}2) i' is an integer from 1 to 20.}

한편, 상기 화학식 (1-1-b)는 하기 화학식 (1-1-c)일 수 있다.Meanwhile, the formula (1-1-b) may be the following formula (1-1-c).

화학식 (1-1-c) Formula (1-1-c)

Figure 112021084385904-pat00035
Figure 112021084385904-pat00035

{상기 화학식 (1-1-c)에서,{In the above formula (1-1-c),

1) x, y, z 및 s는 상기 화학식 (1)에서 정의된 바와 동일하고,1) x, y, z and s are the same as defined in the above formula (1),

2) i'은 1 내지 20의 정수이며, d는 0 내지 4의 정수이고,2) i' is an integer from 1 to 20, d is an integer from 0 to 4,

3) R5는 중수소; 할로겐; C6~C20의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C20의 헤테로고리기; C3~C20의 지방족고리와 C6~C20의 방향족고리의 융합고리기; C1~C20의 알킬기;로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있다.}3) R 5 is deuterium; halogen; C 6 ~ C 20 Aryl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 20 A heterocyclic group; C 3 ~ C 20 A fused ring group of an aliphatic ring and a C 6 ~ C 20 aromatic ring; C 1 ~ C 20 Alkyl group; selected from the group consisting of, or adjacent groups may combine with each other to form a ring.}

또한, 상기 화학식 (1-2)는 하기 화학식 (1-2-a) 또는 화학식 (1-2-b)로 표시될 수 있다.In addition, the formula (1-2) may be represented by the following formula (1-2-a) or (1-2-b).

화학식 (1-2-a) 화학식 (1-2-b) Formula (1-2-a) Formula (1-2-b)

Figure 112021084385904-pat00036
Figure 112021084385904-pat00036

{상기 화학식 (1-2-a) 또는 화학식 (1-2-b)에서,{In the above formula (1-2-a) or formula (1-2-b),

1) x, y, z, C, D, u, v 및 w는 화학식 (1)에서 정의된 바와 동일하고,1) x, y, z, C, D, u, v and w are the same as defined in formula (1),

2) t'은 1 내지 20의 정수이다.}2) t' is an integer from 1 to 20.}

구체적으로 상기 화학식 (1-1) 및 화학식 (1-2)는 하기 화합물 중 하나일 수 있으나, 이에 한정된 것은 아니다.Specifically, Chemical Formulas (1-1) and (1-2) may be one of the following compounds, but are not limited thereto.

Figure 112021084385904-pat00037
Figure 112021084385904-pat00037

Figure 112021084385904-pat00038
Figure 112021084385904-pat00038

Figure 112021084385904-pat00039
Figure 112021084385904-pat00039

Figure 112021084385904-pat00040
Figure 112021084385904-pat00040

Figure 112021084385904-pat00041
Figure 112021084385904-pat00041

Figure 112021084385904-pat00042
Figure 112021084385904-pat00042

Figure 112021084385904-pat00043
Figure 112021084385904-pat00043

Figure 112021084385904-pat00044
Figure 112021084385904-pat00044

Figure 112021084385904-pat00045
Figure 112021084385904-pat00045

Figure 112021084385904-pat00046
Figure 112021084385904-pat00046

Figure 112021084385904-pat00047
Figure 112021084385904-pat00047

Figure 112021084385904-pat00048
Figure 112021084385904-pat00048

Figure 112021084385904-pat00049
Figure 112021084385904-pat00049

Figure 112021084385904-pat00050
Figure 112021084385904-pat00050

Figure 112021084385904-pat00051
Figure 112021084385904-pat00051

Figure 112021084385904-pat00052
Figure 112021084385904-pat00052

Figure 112021084385904-pat00053
Figure 112021084385904-pat00053

Figure 112021084385904-pat00054
Figure 112021084385904-pat00054

Figure 112021084385904-pat00055
Figure 112021084385904-pat00055

Figure 112021084385904-pat00056
Figure 112021084385904-pat00056

한편, 구체적으로, 상기 화학식 (1)로 표시되는 화합물은 하기 화합물 중 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.On the other hand, specifically, the compound represented by the formula (1) may be any one of the following compounds, but is not limited thereto.

Figure 112021084385904-pat00057
Figure 112021084385904-pat00057

Figure 112021084385904-pat00058
Figure 112021084385904-pat00058

Figure 112021084385904-pat00059
Figure 112021084385904-pat00059

Figure 112021084385904-pat00060
Figure 112021084385904-pat00060

Figure 112021084385904-pat00061
Figure 112021084385904-pat00061

Figure 112021084385904-pat00062
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Figure 112021084385904-pat00063
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Figure 112021084385904-pat00064
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Figure 112021084385904-pat00065
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Figure 112021084385904-pat00066
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Figure 112021084385904-pat00067
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Figure 112021084385904-pat00068
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Figure 112021084385904-pat00069
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Figure 112021084385904-pat00070
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Figure 112021084385904-pat00071
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Figure 112021084385904-pat00072
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Figure 112021084385904-pat00073
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Figure 112021084385904-pat00076
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Figure 112021084385904-pat00078
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Figure 112021084385904-pat00080
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Figure 112021084385904-pat00081
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Figure 112021084385904-pat00082
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Figure 112021084385904-pat00084
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Figure 112021084385904-pat00086
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Figure 112021084385904-pat00087
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Figure 112021084385904-pat00088
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Figure 112021084385904-pat00089
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Figure 112021084385904-pat00090
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Figure 112021084385904-pat00091
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Figure 112021084385904-pat00092
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Figure 112021084385904-pat00093
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Figure 112021084385904-pat00094
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Figure 112021084385904-pat00095
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Figure 112021084385904-pat00096
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Figure 112021084385904-pat00097
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Figure 112021084385904-pat00098
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Figure 112021084385904-pat00099
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Figure 112021084385904-pat00100
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Figure 112021084385904-pat00101
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Figure 112021084385904-pat00102
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Figure 112021084385904-pat00103
Figure 112021084385904-pat00103

Figure 112021084385904-pat00104
Figure 112021084385904-pat00104

Figure 112021084385904-pat00105
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Figure 112021084385904-pat00106
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Figure 112021084385904-pat00107
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Figure 112021084385904-pat00108
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Figure 112021084385904-pat00109
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Figure 112021084385904-pat00110
Figure 112021084385904-pat00110

Figure 112021084385904-pat00111
Figure 112021084385904-pat00111

Figure 112021084385904-pat00112
Figure 112021084385904-pat00112

Figure 112021084385904-pat00113
Figure 112021084385904-pat00113

Figure 112021084385904-pat00114
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Figure 112021084385904-pat00115
Figure 112021084385904-pat00115

Figure 112021084385904-pat00116
Figure 112021084385904-pat00116

Figure 112021084385904-pat00117
Figure 112021084385904-pat00117

여기서, 상기 화학식 (1)로 표시되는 화합물의 불소함량은 30% 이상일 수 있다. 바람직하게는 30% 내지 80%일 수 있고, 더 바람직하게는 30% 내지 60%일 수 있다.Here, the fluorine content of the compound represented by Formula (1) may be 30% or more. Preferably it may be 30% to 80%, and more preferably 30% to 60%.

본 명세서에서 기재하고 있는 화합물의 불소 함량은 하기 식(A)로 표현된다.The fluorine content of the compounds described herein is represented by the following formula (A).

[식(A)][Formula (A)]

불소 함량 = 화합물의 불소 원자 수 / 화합물의 전체 원자 수 × 100Fluorine content = number of fluorine atoms in compound / total number of atoms in compound × 100

여기서 화합물의 불소 원자 수는 화합물에 함유된 불소 원자의 개수를 의미하며, 화합물의 전체 원자 수는 불소를 포함한 화합물의 전체 원자의 개수를 의미한다.Here, the number of fluorine atoms in the compound means the number of fluorine atoms contained in the compound, and the total number of atoms in the compound means the total number of atoms in the compound including fluorine.

본 발명의 다른 측면에서, 본 발명은 양극, 상기 양극 상에 형성된 유기물층, 상기 유기물층 상에 형성된 금속패터닝층을 포함하는 유기전기소자를 제공하고, 이때 상기 금속패터닝층은 상기 화학식 (1)로 표시되는 1종의 단독화합물 또는 2종 이상의 화합물을 포함한다.In another aspect of the present invention, the present invention provides an organic electric device comprising an anode, an organic material layer formed on the anode, and a metal patterning layer formed on the organic material layer, wherein the metal patterning layer is represented by the formula (1) It includes one single compound or two or more compounds.

상기 유기물층은 정공주입층, 정공수송층, 발광보조층, 전자수송보조층, 전자수송층 및 전자주입층 중 적어도 하나의 층을 포함할 수 있다.The organic material layer may include at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.

본 발명의 또 다른 측면에서, 본 발명은 상기 화학식 (1)로 표시되는 유기전기소자를 포함하는 디스플레이 장치와, 상기 디스플레이 장치를 구동하는 제어부를 포함하는 전자장치를 제공한다.In another aspect of the present invention, the present invention provides an electronic device including a display device including the organic electric device represented by the formula (1), and a control unit for driving the display device.

이하, 본 발명의 화합물이 포함된 유기전기소자의 적층구조에 대하여 도 1 내지 도 3를 참조하여 설명한다.Hereinafter, the laminated structure of the organic electric device containing the compound of the present invention will be described with reference to FIGS. 1 to 3 .

각 도면의 구성요소들에 참조부호를 부가함에 있어, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same components are given the same reference numerals as much as possible even though they are indicated on different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

본 명세서 상에서 언급된 "포함한다", "갖는다", "이루어진다" 등이 사용되는 경우 "~만"이 사용되지 않는 이상 다른 부분이 추가될 수 있다. 구성 요소를 단수로 표현한 경우에 특별한 명시적인 기재 사항이 없는 한 복수를 포함하는 경우를 포함할 수 있다.When "includes", "has", "consisting of", etc. mentioned in this specification are used, other parts may be added unless "only" is used. When a component is expressed in a singular, it may include a case in which the plural is included unless otherwise explicitly stated.

또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 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), (b), etc. may be used. These terms are only for distinguishing the components from other components, and the essence, order, or order of the components are not limited by the terms. When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is between each component. It should be understood that elements may be “connected,” “coupled,” or “connected.”

또한, 층, 막, 영역, 판 등의 구성 요소가 다른 구성 요소 "위에" 또는 "상에" 있다고 하는 경우, 이는 다른 구성 요소 "바로 위에" 있는 경우뿐만 아니라 그 중간에 또 다른 구성 요소가 있는 경우도 포함할 수 있다고 이해되어야 할 것이다. 반대로, 어떤 구성 요소가 다른 부분 "바로 위에" 있다고 하는 경우에는 중간에 또 다른 부분이 없는 것을 뜻한다고 이해되어야 할 것이다.Also, when a component, such as a layer, membrane, region, plate, etc., is said to be “on” or “on” another component, this means not only when it is “directly above” the other component, but also when there is another component in between. It should be understood that cases may be included. Conversely, it should be understood that when an element is said to be "on top of" another part, it means that there is no other part in the middle.

도 1, 도 2 및 도 3은 본 발명의 실시예에 따른 유기전기소자의 예시도이다.1, 2 and 3 are exemplary views of an organic electric device according to an embodiment of the present invention.

도 1을 참조하면, 본 발명의 일 실시예에 따른 유기전기소자(100)는 기판(미도시) 상에 형성된 제1 전극(110)과 제1 전극(110)상에 형성된 유기물층(120, 130, 140, 150), 그리고 유기물층 상에 형성된 금속패터닝층(170)을 포함한다.Referring to FIG. 1 , an organic electric device 100 according to an embodiment of the present invention includes a first electrode 110 formed on a substrate (not shown) and organic material layers 120 and 130 formed on the first electrode 110 . , 140 , 150 ), and a metal patterning layer 170 formed on the organic material layer.

유기물층은 제 1전극(110) 상에 순차적으로 정공주입층(120), 정공수송층(130), 발광층(140) 및 전자수송층(150)을 포함할 수 있다. 정공저지층, 전자저지층, 발광보조층(220), 버퍼층(210), 전자주입층 등을 더 포함할 수도 있고, 전자수송층(150) 등이 정공저지층의 역할을 할 수도 있을 것이다. 상기 전자수송층(150) 상에는 전자주입층이 형성될 수도 있고 필요에 따라 제외할 수 있으나, 이에 제한되지는 않는다.The organic material layer may sequentially include a hole injection layer 120 , a hole transport layer 130 , a light emitting layer 140 , and an electron transport layer 150 on the first electrode 110 . It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 220 , a buffer layer 210 , an electron injection layer, and the like, and the electron transport layer 150 and the like may serve as a hole blocking layer. An electron injection layer may be formed on the electron transport layer 150 or may be excluded as necessary, but is not limited thereto.

상기 화학식 (1)로 표시되는 화합물을 포함하는 금속패터닝층(190)은 상기 유기물층에 상에 형성되며 금속패터닝층이 형성된 부분에는 제 2전극(170)이 형성되지 않는다. 즉 본 발명에 따른 화학식 (1)로 표시되는 화합물을 금속패터닝층(170)의 재료로 사용함으로써, 제 2전극 재료를 형성시키고자 하는 부분 또는 선택적 부위 만을 형성시킬 수 있다. 또는 도 3과 같이 유기물층 상에 금속패터닝층을 형성시킴으로써 제 2전극이 형성되는 것을 억제할 수 있다. The metal patterning layer 190 including the compound represented by Formula (1) is formed on the organic material layer, and the second electrode 170 is not formed on the portion where the metal patterning layer is formed. That is, by using the compound represented by Formula (1) according to the present invention as a material of the metal patterning layer 170, only a portion or a selective portion to be formed of the second electrode material can be formed. Alternatively, the formation of the second electrode may be suppressed by forming a metal patterning layer on the organic material layer as shown in FIG. 3 .

금속패터닝층이 코팅되면 금속패터닝층에 들어가는 화합물의 구조 및 불소의 함량에 따라 금속패터닝층 위에 음극이 깔리는 것이 억제되고 최종적으로 음극이 극소량으로 깔리거나 깔리지 않게 된다.When the metal patterning layer is coated, the cathode is suppressed from being spread on the metal patterning layer depending on the structure of the compound entering the metal patterning layer and the content of fluorine, and finally the cathode is spread in a very small amount or not.

이때, 전극(전기 전도성 물질)의 코팅과 관련하여 어느 표면 위에 존재하는 전극 물질의 양을 알아보는데 사용되는 것이 광 투과율이다. 그 이유는 전극 물질은 금속을 포함하고 있으며, 금속과 같은 전기전도성 물질은 빛을 감쇠 및/또는 흡수하기 때문이다. 따라서 전자기 스펙트럼의 가시광선 영역에서 광 투과율이 90%를 초과할 경우의 표면은 전기 전도성 물질을 실질적으로 갖고 있지 않은 것으로 간주 될 수 있다.At this time, the light transmittance is used to determine the amount of the electrode material present on a certain surface in relation to the coating of the electrode (electrically conductive material). The reason is that the electrode material contains a metal, and an electrically conductive material such as a metal attenuates and/or absorbs light. Therefore, when the light transmittance exceeds 90% in the visible region of the electromagnetic spectrum, the surface can be considered to be substantially free of an electrically conductive material.

이를 통해 금속패터닝이 포함된 유기전기소자의 픽셀은 투과도가 높고 빛이 나지 않아 블랭크로 작용하게 되며, 높은 투과도로 인해 기판 아래에 있는(TFT 기판) 여러 가지 광각센서(광학센서)에 광노이즈 없이 전달해 줄 수 있게 된다.Through this, the pixel of the organic electric device with metal patterning has high transmittance and does not emit light, so it acts as a blank. be able to deliver it.

따라서 금속패터닝층이 포함된 유기전기소자에 있어서(도 3 참조), 기판(ITO) 상에 유기층을 형성함에 있어 발광층(140)이 있을 수도 있고 없을 수도 있으며, 금속패터닝층 상에 제 2전극(음극)이 없으므로 전기가 통하지 않아 빛은 나지 않게 된다.Therefore, in the organic electric device including the metal patterning layer (see FIG. 3), the light emitting layer 140 may or may not be present in forming the organic layer on the substrate ITO, and the second electrode ( Because there is no cathode), electricity does not pass through, so there is no light.

한편 본 발명은 상기 화학식 (1)로 표시되는 화합물의 동종 또는 구조가 서로 상이한 둘 이상의 화합물을 포함하는 금속패터닝용 조성물을 제공한다.Meanwhile, the present invention provides a composition for metal patterning comprising two or more compounds having the same type or structure different from each other of the compound represented by Formula (1).

또한 본 발명은 상기 화학식 (1)로 표시되는 화합물을 포함하는 금속패터닝층을 포함하는 유기전기소자를 제공한다.In addition, the present invention provides an organic electric device comprising a metal patterning layer containing the compound represented by the formula (1).

또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정, 닥터 블레이딩 공정, 스크린 프린팅 공정, 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic layer is a solution process or a solvent process rather than a deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, a doctor It can be manufactured with a smaller number of layers by a method such as a blading process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the formation method.

또한, 본 발명의 일 실시예에 따른 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 단색 조명용 소자 및 퀀텀닷 디스플레이용 소자로 이루어진 군에서 선택될 수 있다.In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a device for monochromatic lighting, and a device for a quantum dot display.

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

이하에서, 본 발명의 상기 화학식 (1)로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, a synthesis example of the compound represented by the formula (1) of the present invention and a manufacturing example of an organic electric device of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

합성예Synthesis example

본 발명에 따른 화학식 (1)로 표시되는 화합물(Final Product)은 하기 반응식 1과 같이 합성되며 이에 한정되는 것은 아니다. The compound (Final Product) represented by Formula (1) according to the present invention is synthesized as shown in Scheme 1 below, but is not limited thereto.

<반응식 1><Scheme 1>

Figure 112021084385904-pat00118
Figure 112021084385904-pat00118

Figure 112021084385904-pat00119
Figure 112021084385904-pat00119

{상기 반응식 1에서,{In Scheme 1,

1) Hal1, Hal2, Hal3 및 Hal4는 서로 독립적으로 Cl, Br 또는 I이며,1) Hal 1 , Hal 2 , Hal 3 and Hal 4 are each independently Cl, Br or I;

2) a'+a"은 a이고, b'+b"은 b이며, c'+c"은 c이고,2) a'+a" is a, b'+b" is b, c'+c" is c,

단, a", b" 및 c" 중 적어도 하나는 1 이상이며,provided that at least one of a", b" and c" is 1 or more,

3) Y는 -[CxHyFz] 또는 -[CxHyFz]-[D]v-[CxHyFz]w이고, 3) Y is -[C x H y F z ] or -[C x H y F z ]-[D] v -[C x H y F z ] w ,

4) Y'은 -[B]i'-[CxHyFz]s 또는 -[C]t'-[CxHyFz]u-[D]v-[CxHyFz]w이다.4) Y' is -[B] i' -[C x H y F z ] s or -[C] t' -[C x H y F z ] u -[D] v -[C x H y F z ] w .

5) X1, X2, X3, X4, o, p, q, r, R1, R2, R3, a, b, c, Ar1, Ar2, A, D, m, n, i', t', u, v, w, x, y, z는 상기에서 정의된 바와 동일하다.}5) X 1 , X 2 , X 3 , X 4 , o, p, q, r, R 1 , R 2 , R 3 , a, b, c, Ar 1 , Ar 2 , A, D, m, n , i', t', u, v, w, x, y, z are the same as defined above.}

I. Sub1의 합성I. Synthesis of Sub1

1. Sub1-9 합성예1. Sub1-9 Synthesis Example

Figure 112021084385904-pat00120
Figure 112021084385904-pat00120

둥근바닥플라스크에 1,4-dibromo-2-iodobenzene (10.0 g, 27.6 mmol)을 THF (Tetrahydrofuran) (138 mL)에 녹인 후, naphthalen-1-ylboronic acid (5.2 g, 30.4 mmol), K2CO3 (11.5 g, 82.9 mmol), Pd(PPh3)4 (1.92 g, 1.66 mmol), 물 (69 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 7.5 g (수율: 75%)을 얻었다.After dissolving 1,4-dibromo-2-iodobenzene (10.0 g, 27.6 mmol) in THF (Tetrahydrofuran) (138 mL) in a round-bottom flask, naphthalen-1-ylboronic acid (5.2 g, 30.4 mmol), K 2 CO 3 (11.5 g, 82.9 mmol), Pd(PPh 3 ) 4 (1.92 g, 1.66 mmol), water (69 mL) were added and stirred at 80°C. Upon completion of the reaction , the mixture was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 7.5 g (yield: 75%) of the product.

2. Sub1-12 합성예2. Sub1-12 Synthesis Example

Figure 112021084385904-pat00121
Figure 112021084385904-pat00121

4-bromo-1-chloro-2-iodobenzene (5.0 g, 15.8 mmol), THF (79 mL), naphtho[2,3-b]benzofuran-3-ylboronic acid (4.5 g, 17.3 mmol), K2CO3 (6.5 g, 47.3 mmol), Pd(PPh3)4 (1.09 g, 0.95 mmol), 물 (39 mL)을 상기 Sub1-9의 합성법을 이용하여 생성물 4.9 g (수율: 77%)을 얻었다.4-bromo-1-chloro-2-iodobenzene (5.0 g, 15.8 mmol), THF (79 mL), naphtho[2,3-b]benzofuran-3-ylboronic acid (4.5 g, 17.3 mmol), K 2 CO 3 (6.5 g, 47.3 mmol), Pd(PPh 3 ) 4 (1.09 g, 0.95 mmol), and water (39 mL) were used for the synthesis of Sub1-9 to obtain 4.9 g (yield: 77%) of the product.

3. Sub1-46 합성예3. Sub1-46 Synthesis Example

Figure 112021084385904-pat00122
Figure 112021084385904-pat00122

3-bromo-1-iodonaphthalene (5.0 g, 15.0 mmol), THF (75 mL), (3-bromophenyl)boronic acid (3.3 g, 16.5 mmol), K2CO3 (6.2 g, 45.0 mmol), Pd(PPh3)4 (1.04 g, 0.90 mmol), 물 (38 mL)을 상기 Sub1-9의 합성법을 이용하여 생성물 4.4 g (수율: 81%)을 얻었다.3-bromo-1-iodonaphthalene (5.0 g, 15.0 mmol), THF (75 mL), (3-bromophenyl)boronic acid (3.3 g, 16.5 mmol), K 2 CO 3 (6.2 g, 45.0 mmol), Pd ( PPh 3 ) 4 (1.04 g, 0.90 mmol) and water (38 mL) were used for the synthesis of Sub1-9 to obtain 4.4 g (yield: 81%) of the product.

4. Sub1-58 합성예4. Sub1-58 Synthesis Example

Figure 112021084385904-pat00123
Figure 112021084385904-pat00123

둥근바닥플라스크에 dibenzo[b,d]thiophen-3-amine (5.0 g, 25.1 mmol), Toluene (250 mL), 1-bromo-4-chlorobenzene (10.6 g, 55.2 mmol), Pd2(dba)3 (1.38 g, 1.51 mmol), P(t-Bu)3 (0.61 g, 3.01 mmol), NaOt-Bu (9.6 g, 100 mmol)을 첨가하고 100℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 7.5 g (수율: 71%)을 얻었다.Dibenzo[b,d]thiophen-3-amine (5.0 g, 25.1 mmol), Toluene (250 mL), 1-bromo-4-chlorobenzene (10.6 g, 55.2 mmol), Pd 2 (dba) 3 in a round-bottom flask (1.38 g, 1.51 mmol), P(t-Bu) 3 (0.61 g, 3.01 mmol), NaOt-Bu (9.6 g, 100 mmol) were added and stirred at 100°C. Upon completion of the reaction , the mixture was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 7.5 g (yield: 71%) of the product.

5. Sub1-63 합성예5. Sub1-63 Synthesis Example

Figure 112021084385904-pat00124
Figure 112021084385904-pat00124

둥근바닥플라스크에 4-bromonaphthalen-1-ol (5.0 g, 22.4 mmol), 1-bromo-4-iodobenzene (12.7 g, 44.8 mmol) 및 DMSO (22 mL)를 넣고 5분간 교반하였다. 이후, t-BuOK (6.29 g, 56.0 mmol)을 천천히 적가한 후 45℃에서 8시간 동안 교반하였다. 반응이 완료되면 EA (ethyl acetate)와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 4.9 g (수율: 58%)을 얻었다.4-bromonaphthalen-1-ol (5.0 g, 22.4 mmol), 1-bromo-4-iodobenzene (12.7 g, 44.8 mmol) and DMSO (22 mL) were added to a round-bottom flask and stirred for 5 minutes. Thereafter, t-BuOK (6.29 g, 56.0 mmol) was slowly added dropwise, followed by stirring at 45° C. for 8 hours. When the reaction was completed, the mixture was extracted with EA (ethyl acetate) and water, and the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 4.9 g (yield: 58%) of the product.

6. Sub1-69 합성예6. Sub1-69 Synthesis Example

Figure 112021084385904-pat00125
Figure 112021084385904-pat00125

(2-bromo-4-chlorophenyl)(4-chlorophenyl)sulfane (6.0 g, 18.0 mmol), THF (90 mL), phenylboronic acid (2.4 g, 19.8 mmol), K2CO3 (7.4 g, 53.9 mmol), Pd(PPh3)4 (1.25 g, 1.08 mmol), 물 (45 mL)을 상기 Sub1-9의 합성법을 이용하여 생성물 4.4 g (수율: 74%)을 얻었다.(2-bromo-4-chlorophenyl)(4-chlorophenyl)sulfane (6.0 g, 18.0 mmol), THF (90 mL), phenylboronic acid (2.4 g, 19.8 mmol), K 2 CO 3 (7.4 g, 53.9 mmol) , Pd(PPh 3 ) 4 (1.25 g, 1.08 mmol) and water (45 mL) were used for the synthesis of Sub1-9 to obtain 4.4 g (yield: 74%) of the product.

7. Sub1-78 합성예7. Sub1-78 Synthesis Example

Figure 112021084385904-pat00126
Figure 112021084385904-pat00126

3,6-dibromo-9H-carbazole (5.0 g, 15.4 mmol), Toluene (154 mL), 4'-bromo-2,3,4,5,6-pentafluoro-1,1'-biphenyl (10.9 g, 33.8 mmol), Pd2(dba)3 (0.85 g, 0.92 mmol), P(t-Bu)3 (0.37 g, 1.85 mmol), NaOt-Bu (5.9 g, 61.5 mmol)을 상기 Sub1-58의 합성법을 이용하여 생성물 6.8 g (수율: 78%)을 얻었다.3,6-dibromo-9H-carbazole (5.0 g, 15.4 mmol), Toluene (154 mL), 4'-bromo-2,3,4,5,6-pentafluoro-1,1'-biphenyl (10.9 g, 33.8 mmol), Pd 2 (dba) 3 (0.85 g, 0.92 mmol), P(t-Bu) 3 (0.37 g, 1.85 mmol), NaOt-Bu (5.9 g, 61.5 mmol) was synthesized by the above method for the synthesis of Sub1-58. was used to obtain 6.8 g (yield: 78%) of the product.

8. Sub1-83 합성예8. Sub1-83 Synthesis Example

Figure 112021084385904-pat00127
Figure 112021084385904-pat00127

7-bromo-2-chlorodibenzo[b,d]furan (5.0 g, 17.8 mmol), THF (89 mL), Sub3-2 (10.2 g, 19.5 mmol), K2CO3 (7.4 g, 53.3 mmol), Pd(PPh3)4 (1.23 g, 1.07 mmol), 물 (44 mL)을 상기 Sub1-9의 합성법을 이용하여 생성물 8.3 g (수율: 78%)을 얻었다.7-bromo-2-chlorodibenzo[b,d]furan (5.0 g, 17.8 mmol), THF (89 mL), Sub3-2 (10.2 g, 19.5 mmol), K 2 CO 3 (7.4 g, 53.3 mmol), Pd(PPh 3 ) 4 (1.23 g, 1.07 mmol) and water (44 mL) were used for the synthesis of Sub1-9 to obtain 8.3 g (yield: 78%) of the product.

9. Sub1-112 합성예9. Sub1-112 Synthesis Example

Figure 112021084385904-pat00128
Figure 112021084385904-pat00128

2-chloro-8,8-dimethyl-5,8-dihydroindeno[2,1-c]carbazole (5.0 g, 15.7 mmol, CAS#: 2376527-04-5), Toluene (79 mL), bromobenzene (2.7 g, 17.3 mmol), Pd2(dba)3 (0.43 g, 0.47 mmol), P(t-Bu)3 (0.19 g, 0.94 mmol), NaOt-Bu (3.0 g, 31.5 mmol)을 상기 Sub1-58의 합성법을 이용하여 생성물 4.7 g (수율: 76%)을 얻었다.2-chloro-8,8-dimethyl-5,8-dihydroindeno[2,1-c]carbazole (5.0 g, 15.7 mmol, CAS#: 2376527-04-5), Toluene (79 mL), bromobenzene (2.7 g , 17.3 mmol), Pd 2 (dba) 3 (0.43 g, 0.47 mmol), P(t-Bu) 3 (0.19 g, 0.94 mmol), NaOt-Bu (3.0 g, 31.5 mmol) of Sub1-58 4.7 g (yield: 76%) of the product was obtained by the synthetic method.

한편, Sub1에 속하는 화합물은 하기와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 하기 표 1은 하기 화합물의 FD-MS (Field Desorption-Mass Spectrometry) 값 또는 CAS number (이하, CAS#로 표기함)를 나타낸 것이다. 하기 표 1에서 기공지된 화합물의 경우 CAS#로 나타내었고, 공지되지 않은 화합물의 경우 FD-MS로 나타내었다.On the other hand, the compound belonging to Sub1 may be a compound as follows, but is not limited thereto, and Table 1 below shows FD-MS (Field Desorption-Mass Spectrometry) values or CAS number (hereinafter, denoted as CAS#) of the following compounds. ) is shown. In the case of known compounds in Table 1 below, it is indicated by CAS#, and in the case of unknown compounds, it is indicated by FD-MS.

Figure 112021084385904-pat00129
Figure 112021084385904-pat00129

Figure 112021084385904-pat00130
Figure 112021084385904-pat00130

Figure 112021084385904-pat00131
Figure 112021084385904-pat00131

Figure 112021084385904-pat00132
Figure 112021084385904-pat00132

Figure 112021084385904-pat00133
Figure 112021084385904-pat00133

Figure 112021084385904-pat00134
Figure 112021084385904-pat00134

Figure 112021084385904-pat00135
Figure 112021084385904-pat00135

Figure 112021084385904-pat00136
Figure 112021084385904-pat00136

Figure 112021084385904-pat00137
Figure 112021084385904-pat00137

Figure 112021084385904-pat00138
Figure 112021084385904-pat00138

Figure 112021084385904-pat00139
Figure 112021084385904-pat00139

Figure 112021084385904-pat00140
Figure 112021084385904-pat00140

Figure 112021084385904-pat00141
Figure 112021084385904-pat00141

Figure 112021084385904-pat00142
Figure 112021084385904-pat00142

Figure 112021084385904-pat00143
Figure 112021084385904-pat00143

Figure 112021084385904-pat00144
Figure 112021084385904-pat00144

Figure 112021084385904-pat00145
Figure 112021084385904-pat00145

Figure 112021084385904-pat00146
Figure 112021084385904-pat00146

Figure 112021084385904-pat00147
Figure 112021084385904-pat00147

Figure 112021084385904-pat00148
Figure 112021084385904-pat00148

Figure 112021084385904-pat00149
Figure 112021084385904-pat00149

Figure 112021084385904-pat00150
Figure 112021084385904-pat00150

Figure 112021084385904-pat00151
Figure 112021084385904-pat00151

Figure 112021084385904-pat00152
Figure 112021084385904-pat00152

Figure 112021084385904-pat00153
Figure 112021084385904-pat00153

Figure 112021084385904-pat00154
Figure 112021084385904-pat00154

Figure 112021084385904-pat00155
Figure 112021084385904-pat00155

Figure 112021084385904-pat00156
Figure 112021084385904-pat00156

화합물compound CAS# or FD-MSCAS# or FD-MS 화합물compound CAS# or FD-MSCAS# or FD-MS Sub1-1Sub1-1 CAS#: 106-39-8CAS#: 106-39-8 Sub1-2Sub1-2 CAS#: 106-37-6CAS#: 106-37-6 Sub1-3Sub1-3 CAS#: 108-37-2CAS#: 108-37-2 Sub1-4Sub1-4 CAS#: 108-36-1CAS#: 108-36-1 Sub1-5Sub1-5 CAS#: 22875-47-4CAS#: 22875-47-4 Sub1-6Sub1-6 CAS#: 103431-11-4CAS#: 103431-11-4 Sub1-7Sub1-7 CAS#: 2375-96-4CAS#: 2375-96-4 Sub1-8Sub1-8 CAS#: 344-03-6CAS#: 344-03-6 Sub1-9Sub1-9 m/z=359.91(C16H10Br2=362.06)m/z=359.91 (C 16 H 10 Br 2 =362.06) Sub1-10Sub1-10 m/z=365.98(C20H12BrCl=367.67)m/z=365.98 (C 20 H 12 BrCl=367.67) Sub1-11Sub1-11 m/z=365.96(C16H16Br2=368.11)m/z=365.96 (C 16 H 16 Br 2 =368.11) Sub1-12Sub1-12 m/z=405.98(C22H12BrClO=407.69)m/z=405.98 (C 22 H 12 BrClO=407.69) Sub1-13Sub1-13 CAS#: 1161501-90-1CAS#: 1161501-90-1 Sub1-14Sub1-14 m/z=421.95(C22H12BrClS=423.75)m/z=421.95 (C 22 H 12 BrClS=423.75) Sub1-15Sub1-15 m/z=465.9(C22H12Br2S=468.21)m/z=465.9 (C 22 H 12 Br 2 S=468.21) Sub1-16Sub1-16 m/z=386.93(C17H11Br2N=389.09)m/z=386.93 (C 17 H 11 Br 2 N=389.09) Sub1-17Sub1-17 CAS#: 1656247-96-9CAS#: 1656247-96-9 Sub1-18Sub1-18 CAS#: 1369931-75-8CAS#: 1369931-75-8 Sub1-19Sub1-19 CAS#: 46438-88-4CAS#: 46438-88-4 Sub1-20Sub1-20 CAS#: 14862-52-3CAS#: 14862-52-3 Sub1-21Sub1-21 CAS#: 18282-59-2CAS#: 18282-59-2 Sub1-22Sub1-22 CAS#: 23055-77-8CAS#: 23055-77-8 Sub1-23Sub1-23 CAS#: 92-86-4CAS#: 92-86-4 Sub1-24Sub1-24 CAS#: 16400-51-4CAS#: 16400-51-4 Sub1-25Sub1-25 CAS#: 49602-90-6CAS#: 49602-90-6 Sub1-26Sub1-26 CAS#: 16372-96-6CAS#: 16372-96-6 Sub1-27Sub1-27 CAS#: 72416-87-6CAS#: 72416-87-6 Sub1-28Sub1-28 CAS#: 16400-50-3CAS#: 16400-50-3 Sub1-29Sub1-29 CAS#: 2162961-53-5CAS#: 2162961-53-5 Sub1-30Sub1-30 m/z=465.83(C16H9Br3N2=468.97)m/z=465.83 (C 16 H 9 Br 3 N 2 =468.97) Sub1-31Sub1-31 m/z=382.97(C19H11BrClNO=384.66)m/z=382.97 (C 19 H 11 BrClNO=384.66) Sub1-32Sub1-32 m/z=507.04(C30H19BrClN=508.84)m/z=507.04 (C 30 H 19 BrClN=508.84) Sub1-33Sub1-33 CAS#: 29510-41-6CAS#: 29510-41-6 Sub1-34Sub1-34 CAS#: 1762-84-1CAS#: 1762-84-1 Sub1-35Sub1-35 CAS#: 1290039-62-1CAS#: 1290039-62-1 Sub1-36Sub1-36 CAS#: 17788-94-2CAS#: 17788-94-2 Sub1-37Sub1-37 CAS#: 24253-43-8CAS#: 24253-43-8 Sub1-38Sub1-38 CAS#: 1612879-37-4CAS#: 1612879-37-4 Sub1-39Sub1-39 CAS#: 7511-49-1CAS#: 7511-49-1 Sub1-40Sub1-40 CAS#: 96761-85-2CAS#: 96761-85-2 Sub1-41Sub1-41 CAS#: 83-53-4CAS#: 83-53-4 Sub1-42Sub1-42 CAS#: 17135-74-9CAS#: 17135-74-9 Sub1-43Sub1-43 CAS#: 7351-74-8CAS#: 7351-74-8 Sub1-44Sub1-44 CAS#: 13720-06-4CAS#: 13720-06-4 Sub1-45Sub1-45 CAS#: 952604-26-1CAS#: 952604-26-1 Sub1-46Sub1-46 m/z=359.91(C16H10Br2=362.06)m/z=359.91 (C 16 H 10 Br 2 =362.06) Sub1-47Sub1-47 CAS#: 523-27-3CAS#: 523-27-3 Sub1-48Sub1-48 CAS#: 359435-47-5CAS#: 359435-47-5 Sub1-49Sub1-49 CAS#: 1821394-50-6CAS#: 1821394-50-6 Sub1-50Sub1-50 CAS#: 62325-30-8CAS#: 62325-30-8 Sub1-51Sub1-51 CAS#: 1316311-32-6CAS#: 1316311-32-6 Sub1-52Sub1-52 CAS#: 888041-37-0CAS#: 888041-37-0 Sub1-53Sub1-53 CAS#: 53939-30-3CAS#: 53939-30-3 Sub1-54Sub1-54 CAS#: 2408-70-0CAS#: 2408-70-0 Sub1-55Sub1-55 CAS#: 14921-00-7CAS#: 14921-00-7 Sub1-56Sub1-56 CAS#: 4316-58-9CAS#: 4316-58-9 Sub1-57Sub1-57 m/z=604.15(C40H26Cl2N2=605.56)m/z=604.15 (C 40 H 26 Cl 2 N 2 =605.56) Sub1-58Sub1-58 m/z=419.03(C24H15Cl2NS=420.35)m/z=419.03 (C 24 H 15 Cl 2 NS=420.35) Sub1-59Sub1-59 m/z=617(C34H21Br2NO=619.36)m/z=617 (C 34 H 21 Br 2 NO=619.36) Sub1-60Sub1-60 m/z=737.06(C26H12F21N=737.36)m/z=737.06 (C 26 H 12 F 21 N=737.36) Sub1-61Sub1-61 m/z=537.08(C22H12F13N=537.32)m/z=537.08 (C 22 H 12 F 13 N=537.32) Sub1-62Sub1-62 CAS#: 2050-47-7CAS#: 2050-47-7 Sub1-63Sub1-63 m/z=375.91(C16H10Br2O=378.06)m/z=375.91 (C 16 H 10 Br 2 O=378.06) Sub1-64Sub1-64 CAS#: 25147-71-1CAS#: 25147-71-1 Sub1-65Sub1-65 m/z=430.09(C27H20Cl2O=431.36)m/z=430.09 (C 27 H 20 Cl 2 O=431.36) Sub1-66Sub1-66 m/z=454.01(C22H18Cl4O2=456.18)m/z=454.01 (C 22 H 18 Cl 4 O 2 =456.18) Sub1-67Sub1-67 CAS#: 3393-78-0CAS#: 3393-78-0 Sub1-68Sub1-68 m/z=391.89(C16H10Br2S=394.12)m/z=391.89 (C 16 H 10 Br 2 S=394.12) Sub1-69Sub1-69 m/z=330(C18H12Cl2S=331.25)m/z=330 (C 18 H 12 Cl 2 S=331.25) Sub1-70Sub1-70 CAS#: 906069-09-8CAS#: 906069-09-8 Sub1-71Sub1-71 CAS#: 1186383-49-2CAS#: 1186383-49-2 Sub1-72Sub1-72 CAS#: 1931951-30-2CAS#: 1931951-30-2 Sub1-73Sub1-73 CAS#: 18733-91-0CAS#: 18733-91-0 Sub1-74Sub1-74 CAS#: 1111070-90-6CAS#: 1111070-90-6 Sub1-75Sub1-75 CAS#: 2448385-13-3CAS#: 2448385-13-3 Sub1-76Sub1-76 CAS#: 57103-20-5CAS#: 57103-20-5 Sub1-77Sub1-77 CAS#: 597570-70-2CAS#: 597570-70-2 Sub1-78Sub1-78 m/z=564.91(C24H10Br2F5N=567.15)m/z=564.91 (C 24 H 10 Br 2 F 5 N=567.15) Sub1-79Sub1-79 m/z=643(C30H9Cl2F10N=644.29)m/z=643 (C 30 H 9 Cl 2 F 10 N=644.29) Sub1-80Sub1-80 m/z=575.21(C38H35Cl2N=576.61)m/z=575.21 (C 38 H 35 Cl 2 N=576.61) Sub1-81Sub1-81 CAS#: 10016-52-1CAS#: 10016-52-1 Sub1-82Sub1-82 CAS#: 67019-91-4CAS#: 67019-91-4 Sub1-83Sub1-83 m/z=596.02(C24H10ClF13O=596.77)m/z=596.02 (C 24 H 10 ClF 13 O=596.77) Sub1-84Sub1-84 CAS#: 31574-87-5CAS#: 31574-87-5 Sub1-85Sub1-85 CAS#: 83834-10-0CAS#: 83834-10-0 Sub1-86Sub1-86 m/z=612(C24H10ClF13S=612.83)m/z=612 (C 24 H 10 ClF 13 S=612.83) Sub1-87Sub1-87 m/z=478.03(C30H16Cl2S=479.42)m/z=478.03 (C 30 H 16 Cl 2 S=479.42) Sub1-88Sub1-88 m/z=375.09(C24H10D5ClS=375.92)m/z=375.09 (C 24 H 10 D 5 ClS=375.92) Sub1-89Sub1-89 CAS#: 28320-32-3CAS#: 28320-32-3 Sub1-90Sub1-90 CAS#: 865702-19-8CAS#: 865702-19-8 Sub1-91Sub1-91 CAS#: 186259-63-2CAS#: 186259-63-2 Sub1-92Sub1-92 CAS#: 474918-32-6CAS#: 474918-32-6 Sub1-93Sub1-93 CAS#: 128406-10-0CAS#: 128406-10-0 Sub1-94Sub1-94 CAS#: 171408-84-7CAS#: 171408-84-7 Sub1-95Sub1-95 CAS#: 198142-65-3CAS#: 198142-65-3 Sub1-96Sub1-96 CAS#: 1637301-23-5CAS#: 1637301-23-5 Sub1-97Sub1-97 CAS#: 880800-04-4CAS#: 880800-04-4 Sub1-98Sub1-98 CAS#: 1228595-79-6CAS#: 1228595-79-6 Sub1-99Sub1-99 CAS#: 1315321-81-3CAS#: 1315321-81-3 Sub1-100Sub1-100 CAS#: 1262507-19-6CAS#: 1262507-19-6 Sub1-101Sub1-101 m/z=535.12(C36H22ClNS=536.09)m/z=535.12 (C 36 H 22 ClNS=536.09) Sub1-102Sub1-102 CAS#: 2416751-27-2CAS#: 2416751-27-2 Sub1-103Sub1-103 CAS#: 885318-49-0CAS#: 885318-49-0 Sub1-104Sub1-104 CAS#: 1882117-91-0CAS#: 1882117-91-0 Sub1-105Sub1-105 m/z=500.98(C24H9BrF5NO=502.24)m/z=500.98 (C 24 H 9 BrF 5 NO=502.24) Sub1-106Sub1-106 CAS#: 1959627-18-9CAS#: 1959627-18-9 Sub1-107Sub1-107 CAS#: 1199616-46-0CAS#: 1199616-46-0 Sub1-108Sub1-108 CAS#: 2129175-93-3CAS#: 2129175-93-3 Sub1-109Sub1-109 CAS#: 1627726-96-8CAS#: 1627726-96-8 Sub1-110Sub1-110 CAS#: 2489751-47-3CAS#: 2489751-47-3 Sub1-111Sub1-111 CAS#: 2403759-27-1CAS#: 2403759-27-1 Sub1-112Sub1-112 m/z=393.13(C27H20ClN=393.91)m/z=393.13 (C 27 H 20 ClN=393.91) Sub1-113Sub1-113 CAS#: 1350842-19-1CAS#: 1350842-19-1 Sub1-114Sub1-114 CAS#: 1639155-80-8CAS#: 1639155-80-8 Sub1-115Sub1-115 CAS#: 2491751-07-4CAS#: 2491751-07-4 Sub1-116Sub1-116 CAS#: 2341893-65-8CAS#: 2341893-65-8 Sub1-117Sub1-117 CAS#: 6336-32-9CAS#: 6336-32-9 Sub1-118Sub1-118 CAS#: 2125489-31-6CAS#: 2125489-31-6 Sub1-119Sub1-119 CAS#: 2125520-08-1CAS#: 2125520-08-1 Sub1-120Sub1-120 CAS#: 2299231-59-5CAS#: 2299231-59-5

II. Sub 2의 합성II. Synthesis of Sub 2

1. Sub2-12 합성예1. Sub2-12 Synthesis Example

Figure 112021084385904-pat00157
Figure 112021084385904-pat00157

Figure 112021084385904-pat00158
Figure 112021084385904-pat00158

Figure 112021084385904-pat00159
Figure 112021084385904-pat00159

(1) Sub2-12-a 합성예시(1) Sub2-12-a synthesis example

둥근바닥플라스크에 4-iodoaniline (30.0 g, 137 mmol), Cu (34.8 g, 548 mmol) 및 DMSO (274 mL)을 넣고 70℃에서 녹인 후 30분 동안 교반하였다. 그 후 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1-iodo-8-((perfluoropropan-2-yl)oxy)octane (117 g, 164 mmol)을 1시간 동안 천천히 적가한 뒤 120℃에서 24시간 동안 교반하였다. 반응이 완료되면 증류수를 넣은 후 생성된 고체를 감압여과하였다. 그 후 여과액은 Ethyl acetate를 이용하여 추출한 후 유기층을 MgSO4로 건조하고 농축한 뒤 생성된 화합물을 실리카겔 칼럼으로 분리하여 생성물 63.0 g (수율: 68%)을 얻었다.In a round-bottom flask, 4-iodoaniline (30.0 g, 137 mmol), Cu (34.8 g, 548 mmol) and DMSO (274 mL) were added and dissolved at 70°C, followed by stirring for 30 minutes. Then 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1-iodo-8-((perfluoropropan-2-yl) oxy)octane (117 g, 164 mmol) was slowly added dropwise over 1 hour, followed by stirring at 120° C. for 24 hours. When the reaction was completed, distilled water was added and the resulting solid was filtered under reduced pressure. After that, the filtrate was extracted with ethyl acetate, and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was separated by a silica gel column to obtain 63.0 g (yield: 68%) of the product.

(2) Sub2-12-b 합성예시(2) Sub2-12-b synthesis example

둥근바닥플라스크에 상기에서 합성된 Sub2-12-a (50.0 g, 73.8 mmol), 35% HCl (6.84 mL, 222 mmol)을 넣고 1시간 동안 교반한다. 이후, Ice bath로 냉각시키고, NaNO2 (7.13 g, 103 mmol)을 녹인 수용액을 30분 동안 적가하고, 증류수 (60 mL)에 녹인 KI (17.2 g, 103 mmol)을 추가적으로 적가한다. 이후 THF (80 mL)를 투입한 후, 상온에서 밤새 교반시킨다. 반응이 완료되면, NaOH 수용액으로 중화시키고 Diethylether로 추출한 후 유기층을 MgSO4로 건조하고 농축한 뒤 생성된 화합물을 실리카겔 칼럼으로 분리하여 생성물 47.0 g (수율: 81%)을 얻었다.Sub2-12-a (50.0 g, 73.8 mmol) and 35% HCl (6.84 mL, 222 mmol) synthesized above were added to a round-bottom flask and stirred for 1 hour. Then, cooled with an ice bath, an aqueous solution in which NaNO 2 (7.13 g, 103 mmol) was dissolved was added dropwise for 30 minutes, and KI (17.2 g, 103 mmol) dissolved in distilled water (60 mL) was additionally added dropwise. After adding THF (80 mL), the mixture was stirred at room temperature overnight. After completion of the reaction, neutralized with aqueous NaOH solution, extracted with diethylether, the organic layer was dried over MgSO 4 , concentrated, and the resulting compound was separated by a silica gel column to obtain 47.0 g (yield: 81%) of the product.

(3) Sub2-12 합성예시(3) Sub2-12 Synthesis Example

둥근바닥플라스크에 상기에서 합성된 Sub2-12-b (40.0 g, 50.8 mmol), Cu (7.10 g, 112 mmol) 및 DMSO (102 mL)을 넣고 70℃에서 녹인 후 30분 동안 교반하였다. 그 후 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane (33.7 g, 60.9 mmol)을 1시간 동안 천천히 적가한 뒤 120℃에서 24시간 동안 교반하였다. 반응이 완료되면 증류수를 넣은 후 생성된 고체를 감압여과하였다. 그 후 여과액은 Ethyl acetate를 이용하여 추출한 후 유기층을 MgSO4로 건조하고 농축한 뒤 생성된 화합물을 실리카겔 칼럼으로 분리하여 생성물 11.0 g (수율: 20%)을 얻었다.Sub2-12-b (40.0 g, 50.8 mmol), Cu (7.10 g, 112 mmol) and DMSO (102 mL) synthesized above were added to a round-bottom flask and dissolved at 70°C, followed by stirring for 30 minutes. After that, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane (33.7 g, 60.9 mmol) was slowly added dropwise for 1 hour, and then at 120°C. was stirred for 24 hours. When the reaction was completed, distilled water was added and the resulting solid was filtered under reduced pressure. After that, the filtrate was extracted with ethyl acetate, and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was separated by a silica gel column to obtain 11.0 g (yield: 20%) of the product.

2. Sub2-13 합성예2. Sub2-13 Synthesis Example

Figure 112021084385904-pat00160
Figure 112021084385904-pat00160

1-iodo-4-(trifluoromethyl)benzene (40.0 g, 147 mmol), Cu (20.6 g, 324 mmol), 1,1,2,2-tetrafluoro-1,2-diiodoethane (62.4 g, 176 mmol), DMSO (294 mL)을 상기 Sub2-12의 합성법을 통해 생성물 9.3 g (수율: 17%)을 얻었다.1-iodo-4-(trifluoromethyl)benzene (40.0 g, 147 mmol), Cu (20.6 g, 324 mmol), 1,1,2,2-tetrafluoro-1,2-diiodoethane (62.4 g, 176 mmol), DMSO (294 mL) was used for the synthesis of Sub2-12 to obtain 9.3 g (yield: 17%) of the product.

3. Sub2-15 합성예3. Sub2-15 Synthesis Example

Figure 112021084385904-pat00161
Figure 112021084385904-pat00161

1-iodo-4-(perfluorohexyl)benzene (40.0 g, 76.6 mmol), Cu (10.7 g, 169 mmol), 1,1,2,2-tetrafluoro-1,2-diiodoethane (32.5 g, 92.0 mmol), DMSO (153 mL)을 상기 Sub2-12의 합성법을 통해 생성물 9.1 g (수율: 19%)을 얻었다.1-iodo-4-(perfluorohexyl)benzene (40.0 g, 76.6 mmol), Cu (10.7 g, 169 mmol), 1,1,2,2-tetrafluoro-1,2-diiodoethane (32.5 g, 92.0 mmol), DMSO (153 mL) was used for the synthesis of Sub2-12 to obtain 9.1 g (yield: 19%) of the product.

4. Sub2-16 합성예4. Sub2-16 Synthesis Example

Figure 112021084385904-pat00162
Figure 112021084385904-pat00162

1-iodo-4-(perfluorohexyl)benzene (40.0 g, 76.6 mmol), Cu (10.7 g, 169 mmol), 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-1,6-diiodohexane (50.9 g, 92.0 mmol), DMSO (153 mL)을 상기 Sub2-12의 합성법을 통해 생성물 13.2 g (수율: 21%)을 얻었다.1-iodo-4-(perfluorohexyl)benzene (40.0 g, 76.6 mmol), Cu (10.7 g, 169 mmol), 1,1,2,2,3,3,4,4,5,5,6,6 -dodecafluoro-1,6-diiodohexane (50.9 g, 92.0 mmol) and DMSO (153 mL) were used for the synthesis of Sub2-12 to obtain 13.2 g (yield: 21%) of the product.

한편, Sub2에 속하는 화합물은 하기와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 하기 표 2는 하기 화합물의 FD-MS 값 또는 CAS#를 나타낸 것이다. 하기 표 2에서 기공지된 화합물의 경우 CAS#로 나타내었고, 공지되지 않은 화합물의 경우 FD-MS로 나타내었다.On the other hand, the compound belonging to Sub2 may be a compound as follows, but is not limited thereto, and Table 2 below shows FD-MS values or CAS# of the following compounds. In the case of known compounds in Table 2 below, it is indicated by CAS#, and in the case of unknown compounds, it is indicated by FD-MS.

Figure 112021084385904-pat00163
Figure 112021084385904-pat00163

Figure 112021084385904-pat00164
Figure 112021084385904-pat00164

Figure 112021084385904-pat00165
Figure 112021084385904-pat00165

Figure 112021084385904-pat00166
Figure 112021084385904-pat00166

화합물compound CAS# or FD-MSCAS# or FD-MS 화합물compound CAS# or FD-MSCAS# or FD-MS Sub2-1Sub2-1 CAS#: 355-43-1CAS#: 355-43-1 Sub2-2Sub2-2 CAS#: 355-58-0CAS#: 355-58-0 Sub2-3Sub2-3 CAS#: 507-63-1CAS#: 507-63-1 Sub2-4Sub2-4 CAS#: 423-62-1CAS#: 423-62-1 Sub2-5Sub2-5 CAS#: 213014-41-6CAS#: 213014-41-6 Sub2-6Sub2-6 CAS#: 1146953-90-3CAS#: 1146953-90-3 Sub2-7Sub2-7 CAS#: 2043-57-4CAS#: 2043-57-4 Sub2-8Sub2-8 CAS#: 677-69-0CAS#: 677-69-0 Sub2-9Sub2-9 CAS#: 375-51-9CAS#: 375-51-9 Sub2-10Sub2-10 CAS#: 212563-43-4CAS#: 212563-43-4 Sub2-11Sub2-11 CAS#: 25080-19-7CAS#: 25080-19-7 Sub2-12Sub2-12 m/z=1087.87(C23H4F35IO=1088.13)m/z=1087.87 (C 23 H 4 F 35 IO=1088.13) Sub2-13Sub2-13 m/z=371.92(C9H4F7I=372.02)m/z=371.92 (C 9 H 4 F 7 I=372.02) Sub2-14Sub2-14 CAS#: 155367-62-7CAS#: 155367-62-7 Sub2-15Sub2-15 m/z=621.91(C14H4F17I=622.06)m/z=621.91 (C 14 H 4 F 17 I=622.06) Sub2-16Sub2-16 m/z=821.9(C18H4F25I=822.09)m/z=821.9 (C 18 H 4 F 25 I=822.09) Sub2-17Sub2-17 CAS#: 7057-81-0CAS#: 7057-81-0 Sub2-18Sub2-18 CAS#: 678-39-7CAS#: 678-39-7 Sub2-19Sub2-19 m/z=499.99(C10H3F19O=500.1)m/z=499.99 (C 10 H 3 F 19 O=500.1) Sub2-20Sub2-20 CAS#: 1803004-25-2CAS#: 1803004-25-2

III. Sub 3의 합성III. Synthesis of Sub 3

1. Sub3-1 합성예1. Sub3-1 Synthesis Example

Figure 112021084385904-pat00167
Figure 112021084385904-pat00167

둥근바닥플라스크에 1-Iodo-4-(trifluoromethyl)benzene (5.0 g, 18.4 mmol)을 넣고, Bis(pinacolato)diboron (4.9 g, 19.3 mmol), Pd2(dba)3 (0.51 g, 0.55 mmol), x-phos (0.53 g, 1.10 mmol), KOAc (3.6 g, 36.8 mmol) 및 Toluene (61 mL)을 넣고 120℃에서 환류하였다. 반응이 완료되면 반응용액을 농축한 후 실리카겔 칼럼을 통해 분리하여 생성물 3.9 g (수율: 79%)을 얻었다.Put 1-Iodo-4-(trifluoromethyl)benzene (5.0 g, 18.4 mmol) in a round-bottom flask, Bis(pinacolato)diboron (4.9 g, 19.3 mmol), Pd 2 (dba) 3 (0.51 g, 0.55 mmol) , x-phos (0.53 g, 1.10 mmol), KOAc (3.6 g, 36.8 mmol) and Toluene (61 mL) were added and refluxed at 120 °C. After the reaction was completed, the reaction solution was concentrated and separated through a silica gel column to obtain 3.9 g (yield: 79%) of the product.

2. Sub3-2 합성예2. Sub3-2 Synthesis Example

Figure 112021084385904-pat00168
Figure 112021084385904-pat00168

Figure 112021084385904-pat00169
Figure 112021084385904-pat00169

(1) Sub3-2-a 합성예시(1) Sub3-2-a synthesis example

둥근플라스크에 상기에서 합성된 1-bromo-4-chlorobenzene (30.0 g, 157 mmol), Cu (39.8 g, 627 mmol) 및 DMSO (313 mL)을 넣고 70℃에서 녹인 후 30분 동안 교반하였다. 그 후 Sub2-1 (76.9 g, 172 mmol)을 1시간 동안 천천히 적가한 뒤 120℃에서 24시간 동안 교반하였다. 반응이 완료되면 증류수를 넣은 후 생성된 고체를 감압여과하였다. 그 후 여과액은 Ethyl acetate를 이용하여 추출한 후 유기층을 MgSO4로 건조하고 농축한 뒤 생성된 화합물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 50.7 g (수율: 75%)을 얻었다.In a round flask, 1-bromo-4-chlorobenzene (30.0 g, 157 mmol), Cu (39.8 g, 627 mmol) and DMSO (313 mL) synthesized above were added and dissolved at 70° C., followed by stirring for 30 minutes. Then, Sub2-1 (76.9 g, 172 mmol) was slowly added dropwise for 1 hour, followed by stirring at 120° C. for 24 hours. When the reaction was completed, distilled water was added and the resulting solid was filtered under reduced pressure. After that, the filtrate was extracted using ethyl acetate, and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 50.7 g (yield: 75%) of the product.

(2) Sub3-2 합성예시(2) Sub3-2 synthesis example

상기에서 합성된 Sub3-2-a (50.7 g, 118 mmol), Bis(pinacolato)diboron (31.4 g, 124 mmol), Pd2(dba)3 (3.24 g, 3.54 mmol), x-phos (3.37 g, 7.07 mmol), KOAc (23.1 g, 236 mmol) 및 Toluene (393 mL)을 상기 Sub3-1의 합성법을 이용하여 생성물 49.9 g (수율: 81%)을 얻었다.Sub3-2-a synthesized above (50.7 g, 118 mmol), Bis(pinacolato)diboron (31.4 g, 124 mmol), Pd 2 (dba) 3 (3.24 g, 3.54 mmol), x-phos (3.37 g) , 7.07 mmol), KOAc (23.1 g, 236 mmol) and Toluene (393 mL) were used for the synthesis of Sub3-1 above to obtain 49.9 g (yield: 81%) of the product.

3. Sub3-7 합성예3. Sub3-7 Synthesis Example

Figure 112021084385904-pat00170
Figure 112021084385904-pat00170

Figure 112021084385904-pat00171
Figure 112021084385904-pat00171

(1) Sub3-7-a 합성예시(1) Sub3-7-a synthesis example

3-bromo-3'-chloro-1,1'-biphenyl (10.0 g, 37.4 mmol), Cu (9.5 g, 145 mmol), DMSO (75 mL) 및 Sub2-1 (18.3 g, 41.1 mmol)을 상기 Sub3-2-a의 합성법을 이용하여 생성물 14.6 g (수율: 77%)을 얻었다.3-bromo-3'-chloro-1,1'-biphenyl (10.0 g, 37.4 mmol), Cu (9.5 g, 145 mmol), DMSO (75 mL) and Sub2-1 (18.3 g, 41.1 mmol) were prepared above 14.6 g (yield: 77%) of the product was obtained by using the synthesis method of Sub3-2-a.

(2) Sub3-7 합성예시(2) Sub3-7 synthesis example

상기에서 합성된 Sub3-7-a (14.6 g, 28.9 mmol), Bis(pinacolato)diboron (7.7 g, 30.3 mmol), Pd2(dba)3 (0.79 g, 0.87 mmol), x-phos (0.83 g, 1.73 mmol), KOAc (5.7 g, 57.7 mmol) 및 Toluene (96 mL)을 상기 Sub3-1의 합성법을 이용하여 생성물 13.8 g (수율: 80%)을 얻었다.Sub3-7-a (14.6 g, 28.9 mmol), Bis(pinacolato)diboron (7.7 g, 30.3 mmol), Pd 2 (dba) 3 (0.79 g, 0.87 mmol), x-phos (0.83 g) synthesized above , 1.73 mmol), KOAc (5.7 g, 57.7 mmol) and Toluene (96 mL) were used for the synthesis of Sub3-1 above to obtain 13.8 g (yield: 80%) of the product.

4. Sub3-15 합성예4. Sub3-15 Synthesis Example

Figure 112021084385904-pat00172
Figure 112021084385904-pat00172

Figure 112021084385904-pat00173
Figure 112021084385904-pat00173

(1) Sub3-15-a 합성예시(1) Sub3-15-a synthesis example

둥근바닥플라스크에 (3-chlorophenyl)boronic acid (8.0 g, 51.2 mmol), 1,1,1,1,1,1,1,1,1,1,1,1,1-tridecafluoro-8-iodo-1λ16-octa-1,3,5-triyne (26.7 g, 56.3 mmol)을 넣고, DME(ethylene glycol dimethyl ether) (256 mL), 1N NaHCO3 수용액 (128 mL)로 녹인 후 Pd(PPh3)4 (3.55 g, 3.07 mmol)를 넣은 후 5시간 동안 환류하면서 교반시킨다. 반응이 종료되면 상온으로 식힌 뒤 Diethyl ether와 Brine으로 추출한 뒤 얻어낸 유기층을 MgSO4로 남은 수분을 제거한다. 이후 얻어낸 유기층을 감압여과하여 실리카겔 칼럼을 통해 생성물 17.7 g (수율: 76%)를 얻었다.(3-chlorophenyl)boronic acid (8.0 g, 51.2 mmol), 1,1,1,1,1,1,1,1,1,1,1,1,1-tridecafluoro-8-iodo in a round bottom flask -1λ 16 -octa-1,3,5-triyne (26.7 g, 56.3 mmol) was added and dissolved in DME (ethylene glycol dimethyl ether) (256 mL) and 1N NaHCO 3 aqueous solution (128 mL), and then Pd (PPh 3 ) 4 (3.55 g, 3.07 mmol) was added and stirred under reflux for 5 hours. After completion of the reaction, after cooling to room temperature, the organic layer obtained after extraction with diethyl ether and brine is removed with MgSO 4 to remove the remaining moisture. Then, the obtained organic layer was filtered under reduced pressure to obtain 17.7 g of a product (yield: 76%) through a silica gel column.

(2) Sub3-15 합성예시(2) Sub3-15 synthesis example

상기에서 합성된 Sub3-15-a (17.7 g, 38.7 mmol), Bis(pinacolato)diboron (10.3 g, 40.6 mmol), Pd2(dba)3 (1.06 g, 1.16 mmol), x-phos (1.11 g, 2.32 mmol), KOAc (7.6 g, 77.3 mmol) 및 Toluene (129 mL)을 상기 Sub3-1의 합성법을 이용하여 생성물 16.9 g (수율: 79%)을 얻었다.Sub3-15-a (17.7 g, 38.7 mmol), Bis(pinacolato)diboron (10.3 g, 40.6 mmol), Pd 2 (dba) 3 (1.06 g, 1.16 mmol), x-phos (1.11 g) synthesized above , 2.32 mmol), KOAc (7.6 g, 77.3 mmol) and Toluene (129 mL) were used for the synthesis of Sub3-1 above to obtain 16.9 g (yield: 79%) of the product.

5. Sub3-23 합성예5. Sub3-23 Synthesis Example

Figure 112021084385904-pat00174
Figure 112021084385904-pat00174

Figure 112021084385904-pat00175
Figure 112021084385904-pat00175

(1) Sub3-23-a 합성예시(1) Sub3-23-a synthesis example

1,3-dibromo-5-chlorobenzene (30.0 g, 111 mmol), Cu (56.4 g, 888 mmol), DMSO (222 mL) 및 Sub2-4 (158 g, 244 mmol)를 상기 Sub3-2-a의 합성법을 이용하여 생성물 99.8 g (수율: 78%)을 얻었다.1,3-dibromo-5-chlorobenzene (30.0 g, 111 mmol), Cu (56.4 g, 888 mmol), DMSO (222 mL) and Sub2-4 (158 g, 244 mmol) of Sub3-2-a 99.8 g (yield: 78%) of the product was obtained by using the synthetic method.

(2) Sub3-23 합성예시(2) Sub3-23 synthesis example

상기에서 합성된 Sub3-23-a (99.8 g, 86.9 mmol), Bis(pinacolato)diboron (23.2 g, 91.2 mmol), Pd2(dba)3 (2.39 g, 2.61 mmol), x-phos (2.49 g, 5.21 mmol), KOAc (17.1 g, 174 mmol) 및 Toluene (290 mL)을 상기 Sub3-1의 합성법을 이용하여 생성물 84.5 g (수율: 78%)을 얻었다.Sub3-23-a (99.8 g, 86.9 mmol), Bis(pinacolato)diboron (23.2 g, 91.2 mmol), Pd 2 (dba) 3 (2.39 g, 2.61 mmol), x-phos (2.49 g) synthesized above , 5.21 mmol), KOAc (17.1 g, 174 mmol) and Toluene (290 mL) were used for the synthesis of Sub3-1 above to obtain 84.5 g (yield: 78%) of the product.

한편, Sub3에 속하는 화합물은 하기와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 하기 표 3은 하기 화합물의 FD-MS 값을 나타낸 것이다.On the other hand, the compound belonging to Sub3 may be a compound as follows, but is not limited thereto, and Table 3 shows FD-MS values of the following compounds.

Figure 112021084385904-pat00176
Figure 112021084385904-pat00176

Figure 112021084385904-pat00177
Figure 112021084385904-pat00177

Figure 112021084385904-pat00178
Figure 112021084385904-pat00178

Figure 112021084385904-pat00179
Figure 112021084385904-pat00179

Figure 112021084385904-pat00180
Figure 112021084385904-pat00180

Figure 112021084385904-pat00181
Figure 112021084385904-pat00181

Figure 112021084385904-pat00182
Figure 112021084385904-pat00182

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS Sub3-1Sub3-1 m/z=272.12(C13H16BF3O2=272.07)m/z=272.12 (C 13 H 16 BF 3 O 2 =272.07) Sub3-2Sub3-2 m/z=522.1(C18H16BF13O2=522.11)m/z=522.1 (C 18 H 16 BF 13 O 2 =522.11) Sub3-3Sub3-3 m/z=622.1(C20H16BF17O2=622.13)m/z=622.1 (C 20 H 16 BF 17 O 2 =622.13) Sub3-4Sub3-4 m/z=522.1(C18H16BF13O2=522.11)m/z=522.1 (C 18 H 16 BF 13 O 2 =522.11) Sub3-5Sub3-5 m/z=722.09(C22H16BF21O2=722.14)m/z=722.09 (C 22 H 16 BF 21 O 2 =722.14) Sub3-6Sub3-6 m/z=722.09(C22H16BF21O2=722.14)m/z=722.09 (C 22 H 16 BF 21 O 2 =722.14) Sub3-7Sub3-7 m/z=598.13(C24H20BF13O2=598.21)m/z=598.13 (C 24 H 20 BF 13 O 2 =598.21) Sub3-8Sub3-8 m/z=572.12(C22H18BF13O2=572.17)m/z=572.12 (C 22 H 18 BF 13 O 2 =572.17) Sub3-9Sub3-9 m/z=372.11(C15H16BF7O2=372.09)m/z=372.11 (C 15 H 16 BF 7 O 2 =372.09) Sub3-10Sub3-10 m/z=422.11(C16H16BF9O2=422.1)m/z=422.11 (C 16 H 16 BF 9 O 2 =422.1) Sub3-11Sub3-11 m/z=572.1(C19H16BF15O2=572.12)m/z=572.1 (C 19 H 16 BF 15 O 2 =572.12) Sub3-12Sub3-12 m/z=794.05(C22H12BF25O2=794.11)m/z=794.05 (C 22 H 12 BF 25 O 2 =794.11) Sub3-13Sub3-13 m/z=536.12(C19H18BF13O2=536.14)m/z=536.12 (C 19 H 18 BF 13 O 2 =536.14) Sub3-14Sub3-14 m/z=550.13(C20H20BF13O2=550.17)m/z=550.13 (C 20 H 20 BF 13 O 2 =550.17) Sub3-15Sub3-15 m/z=550.13(C20H20BF13O2=550.17)m/z=550.13 (C 20 H 20 BF 13 O 2 =550.17) Sub3-16Sub3-16 m/z=566.13(C20H20BF13O3=566.17)m/z=566.13 (C 20 H 20 BF 13 O 3 =566.17) Sub3-17Sub3-17 m/z=438.1(C16H16BF9O3=438.1)m/z=438.1 (C 16 H 16 BF 9 O 3 =438.1) Sub3-18Sub3-18 m/z=404.1(C15H16BF7O4=404.09)m/z=404.1 (C 15 H 16 BF 7 O 4 =404.09) Sub3-19Sub3-19 m/z=898.12(C30H20BF25O2=898.26)m/z=898.12 (C 30 H 20 BF 25 O 2 =898.26) Sub3-20Sub3-20 m/z=840.07(C24H15BF26O2=840.15)m/z=840.07 (C 24 H 15 BF 26 O 2 =840.15) Sub3-21Sub3-21 m/z=940.07(C26H15BF30O2=940.17)m/z=940.07 (C 26 H 15 BF 30 O 2 =940.17) Sub3-22Sub3-22 m/z=1040.06(C28H15BF34O2=1040.18)m/z=1040.06 (C 28 H 15 BF 34 O 2 =1040.18) Sub3-23Sub3-23 m/z=1240.05(C32H15BF42O2=1240.21)m/z=1240.05 (C 32 H 15 BF 42 O 2 =1240.21) Sub3-24Sub3-24 m/z=916.11(C30H19BF26O2=916.25)m/z=916.11 (C 30 H 19 BF 26 O 2 =916.25) Sub3-25Sub3-25 m/z=992.14(C36H23BF26O2=992.35)m/z=992.14 (C 36 H 23 BF 26 O 2 =992.35) Sub3-26Sub3-26 m/z=896.14(C28H23BF26O2=896.26)m/z=896.14 (C 28 H 23 BF 26 O 2 =896.26) Sub3-27Sub3-27 m/z=1068.09(C30H19BF34O2=1068.24)m/z=1068.09 (C 30 H 19 BF 34 O 2 =1068.24) Sub3-28Sub3-28 m/z=1268.08(C34H19BF42O2=1268.27)m/z=1268.08 (C 34 H 19 BF 42 O 2 =1268.27) Sub3-29Sub3-29 m/z=1372.03(C34H15BF46O4=1372.23)m/z=1372.03 (C 34 H 15 BF 46 O 4 =1372.23) Sub3-30Sub3-30 m/z=1200.08(C32H19BF38O4=1200.25)m/z=1200.08 (C 32 H 19 BF 38 O 4 =1200.25) Sub3-31Sub3-31 m/z=692.16(C30H23BF14O2=692.3)m/z=692.16 (C 30 H 23 BF 14 O 2 =692.3) Sub3-32Sub3-32 m/z= 543.99(C15H6ClF17=544.64)m/z = 543.99 (C 15 H 6 ClF 17 =544.64)

IV. Final product의 합성IV. Synthesis of final product

1. P1-1 합성예1. P1-1 Synthesis Example

Figure 112021084385904-pat00183
Figure 112021084385904-pat00183

둥근플라스크에 Sub1-52 (3.0 g, 7.77 mmol), Cu (4.0 g, 62.2 mmol) 및 DMSO (16 mL)을 넣고 70℃에서 녹인 후 30분 동안 교반하였다. 그 후 Sub2-3 (9.3 g, 17.1 mmol)을 1시간 동안 천천히 적가한 뒤 120℃에서 24시간 동안 교반하였다. 반응이 완료되면 증류수를 넣은 후 생성된 고체를 감압여과하였다. 그 후 여과액은 Ethyl acetate를 이용하여 추출한 후 유기층을 MgSO4로 건조하고 농축한 뒤 생성된 화합물을 실리카겔 칼럼으로 분리 후 재결정하여 생성물 6.6 g (수율: 80%)을 얻었다.Sub1-52 (3.0 g, 7.77 mmol), Cu (4.0 g, 62.2 mmol) and DMSO (16 mL) were placed in a round flask and dissolved at 70°C, followed by stirring for 30 minutes. Then, Sub2-3 (9.3 g, 17.1 mmol) was slowly added dropwise over 1 hour, followed by stirring at 120° C. for 24 hours. When the reaction was completed, distilled water was added, and the resulting solid was filtered under reduced pressure. After that, the filtrate was extracted using ethyl acetate, and the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was separated by a silica gel column and recrystallized to obtain 6.6 g (yield: 80%) of the product.

2. P1-22 합성예2. Synthesis example of P1-22

Figure 112021084385904-pat00184
Figure 112021084385904-pat00184

Figure 112021084385904-pat00185
Figure 112021084385904-pat00185

(1) Inter1-22 합성예시(1) Inter1-22 synthesis example

둥근플라스크에 Sub1-1 (1.0 g, 5.22 mmol)을 Toluene (17 mL)에 녹인 후, Sub3-20 (4.39 g, 5.22 mmol), K2CO3 (2.17 g, 15.7 mmol) 및 Pd(PPh3)4 (0.12 g, 0.10 mmol)을 첨가하고 120℃에서 교반하였다. 반응이 완료되면 실리카겔 칼럼으로 분리 후 재결정하여 생성물 3.53 g (수율: 82%)을 얻었다.After dissolving Sub1-1 (1.0 g, 5.22 mmol) in Toluene (17 mL) in a round flask, Sub3-20 (4.39 g, 5.22 mmol), K 2 CO 3 (2.17 g, 15.7 mmol) and Pd (PPh 3 ) ) 4 (0.12 g, 0.10 mmol) was added and stirred at 120°C. When the reaction was completed, the product was separated by silica gel column and recrystallized to obtain 3.53 g (yield: 82%) of the product.

(2) P1-22 합성예시(2) P1-22 synthesis example

둥근플라스크에 상기에서 합성된 Inter1-22 (3.0 g, 3.64 mmol)을 Toluene (12 mL)에 녹인 후, Sub3-2 (1.9 g, 3.64 mmol), K2CO3 (1.5 g, 10.9 mmol) 및 Pd(PPh3)4 (0.08 g, 0.07 mmol)을 첨가하고 120℃에서 교반하였다. 반응이 완료되면 실리카겔 칼럼으로 분리 후 재결정하여 생성물 3.41 g (수율: 79%)을 얻었다.After dissolving Inter1-22 (3.0 g, 3.64 mmol) synthesized above in Toluene (12 mL) in a round flask, Sub3-2 (1.9 g, 3.64 mmol), K 2 CO 3 (1.5 g, 10.9 mmol) and Pd(PPh 3 ) 4 (0.08 g, 0.07 mmol) was added and stirred at 120° C. When the reaction was completed, the product was separated by silica gel column and recrystallized to obtain 3.41 g (yield: 79%) of the product.

3. P1-23 합성예3. P1-23 Synthesis Example

Figure 112021084385904-pat00186
Figure 112021084385904-pat00186

Figure 112021084385904-pat00187
Figure 112021084385904-pat00187

(1) Inter1-23 합성예시(1) Inter1-23 synthesis example

Sub1-1 (1.0 g, 5.22 mmol), Sub3-23 (7.1 g, 5.75 mmol), K2CO3 (2.2 g, 15.7 mmol), Pd(PPh3)4 (0.12 g, 0.10 mmol), Toluene (17.4 mL)을 상기 Inter1-22의 합성법을 통해 생성물 4.4 g (수율: 69%)을 얻었다.Sub1-1 (1.0 g, 5.22 mmol), Sub3-23 (7.1 g, 5.75 mmol), K 2 CO 3 (2.2 g, 15.7 mmol), Pd(PPh 3 ) 4 (0.12 g, 0.10 mmol), Toluene ( 17.4 mL) of the product was obtained through the synthesis of Inter1-22, 4.4 g (yield: 69%).

(2) P1-23 합성예시(2) P1-23 synthesis example

상기에서 합성된 Inter1-23 (4.4 g, 3.60 mmol), Sub3-5 (2.86 g, 3.96 mmol), K2CO3 (1.49 g, 10.8 mmol), Pd(PPh3)4 (0.08 g, 0.07 mmol), Toluene (12 mL)을 상기 P1-22의 합성법을 통해 생성물 4.9 g (수율: 76%)을 얻었다.Inter1-23 synthesized above (4.4 g, 3.60 mmol), Sub3-5 (2.86 g, 3.96 mmol), K 2 CO 3 (1.49 g, 10.8 mmol), Pd(PPh 3 ) 4 (0.08 g, 0.07 mmol) ), toluene (12 mL) was synthesized by the above P1-22 to obtain 4.9 g (yield: 76%) of the product.

4. P1-34 합성예4. Synthesis example of P1-34

Figure 112021084385904-pat00188
Figure 112021084385904-pat00188

Sub1-2 (1.0 g, 4.24 mmol), Sub3-20 (7.8 g, 9.33 mmol), K2CO3 (1.76 g, 12.72 mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 5.0 g (수율: 78%)을 얻었다.Sub1-2 (1.0 g, 4.24 mmol), Sub3-20 (7.8 g, 9.33 mmol), K 2 CO 3 (1.76 g, 12.72 mmol), Pd(PPh 3 ) 4 (0.10 g, 0.08 mmol), Toluene ( 14 mL) to obtain 5.0 g (yield: 78%) of the product through the synthesis of P1-22.

5. P1-44 합성예5. P1-44 Synthesis Example

Figure 112021084385904-pat00189
Figure 112021084385904-pat00189

Figure 112021084385904-pat00190
Figure 112021084385904-pat00190

(1) Inter1-44 합성예시(1) Inter1-44 synthesis example

Sub1-22 (1.0 g, 3.74 mmol), Sub3-23 (5.1 g, 4.11 mmol), K2CO3 (1.6 g, 11.21 mmol), Pd(PPh3)4 (0.09 g, 0.07 mmol), Toluene (13 mL)을 상기 Inter1-22의 합성법을 통해 생성물 3.3 g (수율: 67%)을 얻었다.Sub1-22 (1.0 g, 3.74 mmol), Sub3-23 (5.1 g, 4.11 mmol), K 2 CO 3 (1.6 g, 11.21 mmol), Pd(PPh 3 ) 4 (0.09 g, 0.07 mmol), Toluene ( 13 mL) was obtained through the synthesis of Inter1-22, 3.3 g (yield: 67%) of the product.

(2) P1-44 합성예시(2) P1-44 synthesis example

상기에서 합성된 Inter1-44 (3.3 g, 2.51 mmol), Sub3-5 (2.0 g, 2.76 mmol), K2CO3 (1.0 g, 7.52 mmol), Pd(PPh3)4 (0.06 g, 0.05 mmol), Toluene (8.4 mL)을 상기 P1-22의 합성법을 통해 생성물 3.6 g (수율: 77%)을 얻었다.Inter1-44 (3.3 g, 2.51 mmol), Sub3-5 (2.0 g, 2.76 mmol), K 2 CO 3 (1.0 g, 7.52 mmol), Pd(PPh 3 ) 4 (0.06 g, 0.05 mmol) synthesized above ), toluene (8.4 mL) was synthesized by the above P1-22 to obtain 3.6 g (yield: 77%) of the product.

6. P1-46 합성예6. P1-46 Synthesis Example

Figure 112021084385904-pat00191
Figure 112021084385904-pat00191

Sub1-23 (1.0 g, 3.21 mmol), Sub3-20 (5.9 g, 7.05 mmol), K2CO3 (1.3 g, 9.62 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (11 mL)을 상기 P1-22의 합성법을 통해 생성물 4.6 g (수율: 79%)을 얻었다.Sub1-23 (1.0 g, 3.21 mmol), Sub3-20 (5.9 g, 7.05 mmol), K 2 CO 3 (1.3 g, 9.62 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 11 mL) to obtain 4.6 g (yield: 79%) of the product through the synthesis of P1-22.

7. P1-50 합성예7. P1-50 Synthesis Example

Figure 112021084385904-pat00192
Figure 112021084385904-pat00192

Sub1-24 (1.0 g, 3.21 mmol), Sub3-23 (8.8 g, 7.05 mmol), K2CO3 (1.3 g, 9.62 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (11 mL)을 상기 P1-22의 합성법을 통해 생성물 5.3 g (수율: 70%)을 얻었다.Sub1-24 (1.0 g, 3.21 mmol), Sub3-23 (8.8 g, 7.05 mmol), K 2 CO 3 (1.3 g, 9.62 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 11 mL) to obtain 5.3 g (yield: 70%) of the product through the synthesis of P1-22.

8. P1-52 합성예8. P1-52 Synthesis Example

Figure 112021084385904-pat00193
Figure 112021084385904-pat00193

Sub1-36 (1.0 g, 2.58 mmol), Sub3-20 (4.8 g, 5.67 mmol), K2CO3 (1.1 g, 7.73 mmol), Pd(PPh3)4 (0.06 g, 0.05 mmol), Toluene (8.6 mL)을 상기 P1-22의 합성법을 통해 생성물 3.1 g (수율: 73%)을 얻었다.Sub1-36 (1.0 g, 2.58 mmol), Sub3-20 (4.8 g, 5.67 mmol), K 2 CO 3 (1.1 g, 7.73 mmol), Pd(PPh 3 ) 4 (0.06 g, 0.05 mmol), Toluene ( 8.6 mL) of the product 3.1 g (yield: 73%) was obtained through the synthesis of P1-22.

9. P1-55 합성예9. Synthesis example of P1-55

Figure 112021084385904-pat00194
Figure 112021084385904-pat00194

Sub1-26 (1.0 g, 3.21 mmol), Sub3-23 (8.8 g, 7.05 mmol), K2CO3 (1.3 g, 9.62 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (11 mL)을 상기 P1-22의 합성법을 통해 생성물 5.5 g (수율: 72%)을 얻었다.Sub1-26 (1.0 g, 3.21 mmol), Sub3-23 (8.8 g, 7.05 mmol), K 2 CO 3 (1.3 g, 9.62 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 11 mL) to obtain 5.5 g (yield: 72%) of the product through the synthesis of P1-22.

10. P1-61 합성예10. P1-61 Synthesis Example

Figure 112021084385904-pat00195
Figure 112021084385904-pat00195

Sub1-38 (2.0 g, 3.66 mmol), Sub3-2 (8.4 g, 16.1 mmol), K2CO3 (3.0 g, 22.0 mmol), Pd(PPh3)4 (0.08 g, 0.07 mmol), Toluene (12 mL)을 상기 P1-22의 합성법을 통해 생성물 3.8 g (수율: 58%)을 얻었다.Sub1-38 (2.0 g, 3.66 mmol), Sub3-2 (8.4 g, 16.1 mmol), K 2 CO 3 (3.0 g, 22.0 mmol), Pd(PPh 3 ) 4 (0.08 g, 0.07 mmol), Toluene ( 12 mL) to obtain 3.8 g (yield: 58%) of the product through the synthesis of P1-22.

11. P1-63 합성예11. Synthesis example of P1-63

Figure 112021084385904-pat00196
Figure 112021084385904-pat00196

Sub1-41 (2.0 g, 6.99 mmol), Sub3-2 (8.0 g, 15.4 mmol), K2CO3 (2.90 g, 21.0 mmol), Pd(PPh3)4 (0.16 g, 0.14 mmol), Toluene (23 mL)을 상기 P1-22의 합성법을 통해 생성물 4.8 g (수율: 75%)을 얻었다.Sub1-41 (2.0 g, 6.99 mmol), Sub3-2 (8.0 g, 15.4 mmol), K 2 CO 3 (2.90 g, 21.0 mmol), Pd(PPh 3 ) 4 (0.16 g, 0.14 mmol), Toluene ( 23 mL) to obtain 4.8 g (yield: 75%) of the product through the synthesis of P1-22.

12. P1-65 합성예12. P1-65 Synthesis Example

Figure 112021084385904-pat00197
Figure 112021084385904-pat00197

Sub1-44 (1.0 g, 3.50 mmol), Sub3-20 (6.5 g, 7.69 mmol), K2CO3 (1.45 g, 10.5 mmol), Pd(PPh3)4 (0.08 g, 0.07 mmol), Toluene (12 mL)을 상기 P1-22의 합성법을 통해 생성물 4.1 g (수율: 76%)을 얻었다.Sub1-44 (1.0 g, 3.50 mmol), Sub3-20 (6.5 g, 7.69 mmol), K 2 CO 3 (1.45 g, 10.5 mmol), Pd(PPh 3 ) 4 (0.08 g, 0.07 mmol), Toluene ( 12 mL) to obtain 4.1 g (yield: 76%) of the product through the synthesis of P1-22.

13. P1-67 합성예13. P1-67 Synthesis Example

Figure 112021084385904-pat00198
Figure 112021084385904-pat00198

Sub1-47 (2.0 g, 5.95 mmol), Sub3-2 (6.8 g, 13.1 mmol), K2CO3 (2.5 g, 17.9 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol), Toluene (20 mL)을 상기 P1-22의 합성법을 통해 생성물 4.4 g (수율: 77%)을 얻었다.Sub1-47 (2.0 g, 5.95 mmol), Sub3-2 (6.8 g, 13.1 mmol), K 2 CO 3 (2.5 g, 17.9 mmol), Pd(PPh 3 ) 4 (0.14 g, 0.12 mmol), Toluene ( 20 mL) to obtain 4.4 g (yield: 77%) of the product through the synthesis of P1-22.

14. P1-69 합성예14. P1-69 Synthesis Example

Figure 112021084385904-pat00199
Figure 112021084385904-pat00199

Sub1-45 (1.0 g, 2.76 mmol), Sub3-23 (7.6 g, 6.08 mmol), K2CO3 (1.2 g, 8.29 mmol), Pd(PPh3)4 (0.06 g, 0.06 mmol), Toluene (9.2 mL)을 상기 P1-22의 합성법을 통해 생성물 4.8 g (수율: 71%)을 얻었다.Sub1-45 (1.0 g, 2.76 mmol), Sub3-23 (7.6 g, 6.08 mmol), K 2 CO 3 (1.2 g, 8.29 mmol), Pd(PPh 3 ) 4 (0.06 g, 0.06 mmol), Toluene ( 9.2 mL) to obtain 4.8 g (yield: 71%) of the product through the synthesis of P1-22.

15. P1-71 합성예15. Synthesis example of P1-71

Figure 112021084385904-pat00200
Figure 112021084385904-pat00200

Sub1-42 (2.0 g, 6.99 mmol), Sub3-2 (8.0 g, 15.4 mmol), K2CO3 (2.9 g, 21.0 mmol), Pd(PPh3)4 (0.16 g, 0.14 mmol), Toluene (23 mL)을 상기 P1-22의 합성법을 통해 생성물 4.7 g (수율: 74%)을 얻었다.Sub1-42 (2.0 g, 6.99 mmol), Sub3-2 (8.0 g, 15.4 mmol), K 2 CO 3 (2.9 g, 21.0 mmol), Pd(PPh 3 ) 4 (0.16 g, 0.14 mmol), Toluene ( 23 mL) to obtain 4.7 g (yield: 74%) of the product through the synthesis of P1-22.

16. P1-73 합성예16. Synthesis example of P1-73

Figure 112021084385904-pat00201
Figure 112021084385904-pat00201

Sub1-52 (0.8 g, 2.07 mmol), Sub3-23 (5.7 g, 4.56 mmol), K2CO3 (0.86 g, 6.22 mmol), Pd(PPh3)4 (0.05 g, 0.04 mmol), Toluene (6.9 mL)을 상기 P1-22의 합성법을 통해 생성물 3.9 g (수율: 76%)을 얻었다.Sub1-52 (0.8 g, 2.07 mmol), Sub3-23 (5.7 g, 4.56 mmol), K 2 CO 3 (0.86 g, 6.22 mmol), Pd(PPh 3 ) 4 (0.05 g, 0.04 mmol), Toluene ( 6.9 mL) to obtain 3.9 g (yield: 76%) of the product through the synthesis of P1-22.

17. P2-1 합성예17. P2-1 Synthesis Example

Figure 112021084385904-pat00202
Figure 112021084385904-pat00202

Sub1-54 (2.0 g, 6.33 mmol), Sub3-2 (10.9 g, 20.9 mmol), K2CO3 (5.3 g, 38.0 mmol), Pd(PPh3)4 (0.15 g, 0.13 mmol), Toluene (21 mL)을 상기 P1-22의 합성법을 통해 생성물 4.9 g (수율: 61%)을 얻었다.Sub1-54 (2.0 g, 6.33 mmol), Sub3-2 (10.9 g, 20.9 mmol), K 2 CO 3 (5.3 g, 38.0 mmol), Pd(PPh 3 ) 4 (0.15 g, 0.13 mmol), Toluene ( 21 mL) to obtain 4.9 g (yield: 61%) of the product through the synthesis of P1-22.

18. P2-2 합성예18. P2-2 Synthesis Example

Figure 112021084385904-pat00203
Figure 112021084385904-pat00203

Sub1-55 (1.0 g, 3.15 mmol), Sub3-2 (5.42 g, 10.4 mmol), K2CO3 (1.3 g, 9.44 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (11 mL)을 상기 P1-22의 합성법을 통해 생성물 3.1 g (수율: 78%)을 얻었다.Sub1-55 (1.0 g, 3.15 mmol), Sub3-2 (5.42 g, 10.4 mmol), K 2 CO 3 (1.3 g, 9.44 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 11 mL) to obtain 3.1 g of the product (yield: 78%) through the synthesis of P1-22.

19. P3-2 합성예19. P3-2 Synthesis Example

Figure 112021084385904-pat00204
Figure 112021084385904-pat00204

Sub1-56 (2.0 g, 4.15 mmol), Sub3-2 (7.2 g, 13.7 mmol), K2CO3 (3.4 g, 24.9 mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 3.6 g (수율: 61%)을 얻었다.Sub1-56 (2.0 g, 4.15 mmol), Sub3-2 (7.2 g, 13.7 mmol), K 2 CO 3 (3.4 g, 24.9 mmol), Pd(PPh 3 ) 4 (0.10 g, 0.08 mmol), Toluene ( 14 mL) to obtain 3.6 g (yield: 61%) of the product through the synthesis of P1-22.

20. P3-4 합성예20. P3-4 Synthesis Example

Figure 112021084385904-pat00205
Figure 112021084385904-pat00205

상기에서 합성된 Sub1-58 (1.5 g, 3.58 mmol), Cu (1.8 g, 28.6 mmol), Sub2-4 (5.1 g, 7.88 mmol), DMSO (7 mL)을 상기 P1-1의 합성법을 통해 생성물 3.8 g (수율: 76%)을 얻었다.Sub1-58 (1.5 g, 3.58 mmol), Cu (1.8 g, 28.6 mmol), Sub2-4 (5.1 g, 7.88 mmol), DMSO (7 mL) synthesized above was obtained through the synthesis of P1-1 as a product 3.8 g (yield: 76%) was obtained.

21. P3-5 합성예21. P3-5 Synthesis Example

Figure 112021084385904-pat00206
Figure 112021084385904-pat00206

Sub1-59 (2.0 g, 3.23 mmol), Sub3-20 (6.0 g, 7.10 mmol), K2CO3 (1.34 g, 9.69 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (11 mL)을 상기 P1-22의 합성법을 통해 생성물 4.1 g (수율: 68%)을 얻었다.Sub1-59 (2.0 g, 3.23 mmol), Sub3-20 (6.0 g, 7.10 mmol), K 2 CO 3 (1.34 g, 9.69 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 11 mL) to obtain 4.1 g (yield: 68%) of the product through the synthesis of P1-22.

22. P4-2 합성예22. P4-2 Synthesis Example

Figure 112021084385904-pat00207
Figure 112021084385904-pat00207

상기에서 합성된 Sub1-63 (1.5 g, 3.97 mmol), Cu (2.0 g, 31.7 mmol), Sub2-4 (5.6 g, 8.73 mmol), DMSO (8 mL)을 상기 P1-1의 합성법을 통해 생성물 3.6 g (수율: 72%)을 얻었다.Sub1-63 (1.5 g, 3.97 mmol), Cu (2.0 g, 31.7 mmol), Sub2-4 (5.6 g, 8.73 mmol), DMSO (8 mL) synthesized above was obtained through the synthesis of P1-1 as a product 3.6 g (yield: 72%) was obtained.

23. P4-4 합성예23. P4-4 Synthesis Example

Figure 112021084385904-pat00208
Figure 112021084385904-pat00208

Sub1-62 (2.0 g, 6.10 mmol), Sub3-3 (8.4 g, 13.4 mmol), K2CO3 (2.5 g, 18.3 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol), Toluene (20 mL)을 상기 P1-22의 합성법을 통해 생성물 5.2 g (수율: 73%)을 얻었다.Sub1-62 (2.0 g, 6.10 mmol), Sub3-3 (8.4 g, 13.4 mmol), K 2 CO 3 (2.5 g, 18.3 mmol), Pd(PPh 3 ) 4 (0.14 g, 0.12 mmol), Toluene ( 20 mL) to obtain 5.2 g (yield: 73%) of the product through the synthesis of P1-22.

24. P5-3 합성예24. P5-3 Synthesis Example

Figure 112021084385904-pat00209
Figure 112021084385904-pat00209

Sub1-67 (2.0 g, 5.81 mmol), Sub3-2 (6.7 g, 12.8 mmol), K2CO3 (2.4 g, 17.4 mmol), Pd(PPh3)4 (0.13 g, 0.12 mmol), Toluene (19 mL)을 상기 P1-22의 합성법을 통해 생성물 4.5 g (수율: 79%)을 얻었다.Sub1-67 (2.0 g, 5.81 mmol), Sub3-2 (6.7 g, 12.8 mmol), K 2 CO 3 (2.4 g, 17.4 mmol), Pd(PPh 3 ) 4 (0.13 g, 0.12 mmol), Toluene ( 19 mL) to obtain 4.5 g (yield: 79%) of the product through the synthesis of P1-22.

25. P5-6 합성예25. P5-6 Synthesis Example

Figure 112021084385904-pat00210
Figure 112021084385904-pat00210

Sub1-69 (2.0 g, 6.04 mmol), Sub3-2 (6.9 g, 13.3 mmol), K2CO3 (2.5 g, 18.1 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol), Toluene (20 mL)을 상기 P1-22의 합성법을 통해 생성물 4.8 g (수율: 75%)을 얻었다.Sub1-69 (2.0 g, 6.04 mmol), Sub3-2 (6.9 g, 13.3 mmol), K 2 CO 3 (2.5 g, 18.1 mmol), Pd(PPh 3 ) 4 (0.14 g, 0.12 mmol), Toluene ( 20 mL) to obtain 4.8 g (yield: 75%) of the product through the synthesis of P1-22.

26. P6-1 합성예26. Synthesis example of P6-1

Figure 112021084385904-pat00211
Figure 112021084385904-pat00211

Sub1-70 (3.0 g, 6.27 mmol), Cu (3.2 g, 50.2 mmol), Sub2-1 (6.2 g, 13.8 mmol), DMSO (13 mL)을 상기 P1-1의 합성법을 통해 생성물 4.9 g (수율: 81%)을 얻었다.Sub1-70 (3.0 g, 6.27 mmol), Cu (3.2 g, 50.2 mmol), Sub2-1 (6.2 g, 13.8 mmol), DMSO (13 mL) was synthesized by the above P1-1 synthesis method to 4.9 g of the product (yield) : 81%) was obtained.

27. P6-4 합성예27. P6-4 Synthesis Example

Figure 112021084385904-pat00212
Figure 112021084385904-pat00212

Sub1-70 (2.0 g, 4.18 mmol), Sub3-2 (4.8 g, 9.20 mmol), K2CO3 (1.7 g, 12.6 mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 3.3 g (수율: 72%)을 얻었다.Sub1-70 (2.0 g, 4.18 mmol), Sub3-2 (4.8 g, 9.20 mmol), K 2 CO 3 (1.7 g, 12.6 mmol), Pd(PPh 3 ) 4 (0.10 g, 0.08 mmol), Toluene ( 14 mL) to obtain 3.3 g (yield: 72%) of the product through the synthesis of P1-22.

28. P7-1 합성예28. P7-1 Synthesis Example

Figure 112021084385904-pat00213
Figure 112021084385904-pat00213

Sub1-73 (3.0 g, 6.07 mmol), Cu (3.1 g, 48.6 mmol), Sub2-1 (6.0 g, 13.4 mmol), DMSO (12 mL)을 상기 P1-1의 합성법을 통해 생성물 4.4 g (수율: 75%)을 얻었다.Sub1-73 (3.0 g, 6.07 mmol), Cu (3.1 g, 48.6 mmol), Sub2-1 (6.0 g, 13.4 mmol), DMSO (12 mL) was synthesized by the above P1-1 synthesis method to 4.4 g of the product (yield) : 75%) was obtained.

29. P7-4 합성예29. P7-4 Synthesis Example

Figure 112021084385904-pat00214
Figure 112021084385904-pat00214

Sub1-73 (2.0 g, 4.05 mmol), Sub3-2 (4.7 g, 8.90 mmol), K2CO3 (1.68 g, 12.1 mmol), Pd(PPh3)4 (0.09 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 3.5 g (수율: 76%)을 얻었다.Sub1-73 (2.0 g, 4.05 mmol), Sub3-2 (4.7 g, 8.90 mmol), K 2 CO 3 (1.68 g, 12.1 mmol), Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol), Toluene ( 14 mL) to obtain 3.5 g (yield: 76%) of the product through the synthesis of P1-22.

30. P8-2 합성예30. P8-2 Synthesis Example

Figure 112021084385904-pat00215
Figure 112021084385904-pat00215

Sub1-77 (3.0 g, 3.75 mmol), Cu (2.9 g, 45.0 mmol), Sub2-1 (7.4 g, 16.5 mmol), DMSO (7 mL)을 상기 P1-1의 합성법을 통해 생성물 3.4 g (수율: 52%)을 얻었다.Sub1-77 (3.0 g, 3.75 mmol), Cu (2.9 g, 45.0 mmol), Sub2-1 (7.4 g, 16.5 mmol), DMSO (7 mL) was synthesized by the above P1-1 synthesis method to 3.4 g of the product (yield) : 52%) was obtained.

31. P8-3 합성예31. P8-3 Synthesis Example

Figure 112021084385904-pat00216
Figure 112021084385904-pat00216

상기에서 합성된 Sub1-78 (2.0 g, 3.53 mmol), Cu (1.8 g, 28.2 mmol), Sub2-4 (5.0 g, 7.76 mmol), DMSO (7 mL)을 상기 P1-1의 합성법을 통해 생성물 3.9 g (수율: 77%)을 얻었다.Sub1-78 (2.0 g, 3.53 mmol), Cu (1.8 g, 28.2 mmol), Sub2-4 (5.0 g, 7.76 mmol), DMSO (7 mL) synthesized above was obtained through the synthesis of P1-1 as a product 3.9 g (yield: 77%) was obtained.

32. P9-3 합성예32. P9-3 Synthesis Example

Figure 112021084385904-pat00217
Figure 112021084385904-pat00217

Sub1-81 (2.0 g, 6.14 mmol), Sub3-2 (7.1 g, 13.5 mmol), K2CO3 (2.5 g, 18.4 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol), Toluene (21 mL)을 상기 P1-22의 합성법을 통해 생성물 4.3 g (수율: 73%)을 얻었다.Sub1-81 (2.0 g, 6.14 mmol), Sub3-2 (7.1 g, 13.5 mmol), K 2 CO 3 (2.5 g, 18.4 mmol), Pd(PPh 3 ) 4 (0.14 g, 0.12 mmol), Toluene ( 21 mL) to obtain 4.3 g (yield: 73%) of the product through the synthesis of P1-22.

33. P9-4 합성예33. P9-4 Synthesis Example

Figure 112021084385904-pat00218
Figure 112021084385904-pat00218

상기에서 합성된 Sub1-83 (3.0 g, 5.03 mmol), Cu (2.6 g, 40.2 mmol), Sub2-1 (2.3 g, 5.03 mmol), DMSO (10 mL)을 상기 P1-1의 합성법을 통해 생성물 3.6 g (수율: 82%)을 얻었다.Sub1-83 (3.0 g, 5.03 mmol), Cu (2.6 g, 40.2 mmol), Sub2-1 (2.3 g, 5.03 mmol), DMSO (10 mL) synthesized above was obtained through the synthesis of P1-1 as a product 3.6 g (yield: 82%) was obtained.

34. P9-6 합성예34. P9-6 Synthesis Example

Figure 112021084385904-pat00219
Figure 112021084385904-pat00219

Sub1-82 (1.0 g, 3.07 mmol), Sub3-24 (6.2 g, 6.75 mmol), K2CO3 (1.3 g, 9.20 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (10 mL)을 상기 P1-22의 합성법을 통해 생성물 3.8 g (수율: 71%)을 얻었다.Sub1-82 (1.0 g, 3.07 mmol), Sub3-24 (6.2 g, 6.75 mmol), K 2 CO 3 (1.3 g, 9.20 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 10 mL) to obtain 3.8 g (yield: 71%) of the product through the synthesis of P1-22.

35. P10-1 합성예35. P10-1 Synthesis Example

Figure 112021084385904-pat00220
Figure 112021084385904-pat00220

Sub1-81 (3.0 g, 8.77 mmol), Cu (4.5 g, 70.2 mmol), Sub2-4 (12.5 g, 19.3 mmol), DMSO (18 mL)을 상기 P1-1의 합성법을 통해 생성물 8.2 g (수율: 77%)을 얻었다.Sub1-81 (3.0 g, 8.77 mmol), Cu (4.5 g, 70.2 mmol), Sub2-4 (12.5 g, 19.3 mmol), DMSO (18 mL) was synthesized by the above P1-1 synthesis method to 8.2 g of the product (yield) : 77%) was obtained.

36. P10-5 합성예36. Synthesis example of P10-5

Figure 112021084385904-pat00221
Figure 112021084385904-pat00221

Sub1-85 (1.0 g, 2.92 mmol), Sub3-24 (5.9 g, 6.43 mmol), K2CO3 (1.2 g, 8.77 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (10 mL)을 상기 P1-22의 합성법을 통해 생성물 3.6 g (수율: 70%)을 얻었다.Sub1-85 (1.0 g, 2.92 mmol), Sub3-24 (5.9 g, 6.43 mmol), K 2 CO 3 (1.2 g, 8.77 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 10 mL) to obtain 3.6 g (yield: 70%) of the product through the synthesis of P1-22.

37. P11-2 합성예37. P11-2 Synthesis Example

Figure 112021084385904-pat00222
Figure 112021084385904-pat00222

Sub1-90 (1.0 g, 2.84 mmol), Sub3-20 (5.3 g, 6.25 mmol), K2CO3 (1.2 g, 8.52 mmol), Pd(PPh3)4 (0.07 g, 0.06 mmol), Toluene (10 mL)을 상기 P1-22의 합성법을 통해 생성물 3.4 g (수율: 73%)을 얻었다.Sub1-90 (1.0 g, 2.84 mmol), Sub3-20 (5.3 g, 6.25 mmol), K 2 CO 3 (1.2 g, 8.52 mmol), Pd(PPh 3 ) 4 (0.07 g, 0.06 mmol), Toluene ( 10 mL) to obtain 3.4 g (yield: 73%) of the product through the synthesis of P1-22.

38. P11-4 합성예38. P11-4 Synthesis Example

Figure 112021084385904-pat00223
Figure 112021084385904-pat00223

Sub1-91 (3.0 g, 6.30 mmol), Cu (3.2 g, 50.4 mmol), Sub2-1 (6.2 g, 13.9 mmol), DMSO (13 mL)을 상기 P1-1의 합성법을 통해 생성물 4.8 g (수율: 80%)을 얻었다.Sub1-91 (3.0 g, 6.30 mmol), Cu (3.2 g, 50.4 mmol), Sub2-1 (6.2 g, 13.9 mmol), DMSO (13 mL) was synthesized by the above P1-1 synthesis method to 4.8 g of the product (yield) : 80%) was obtained.

39. P11-6 합성예39. P11-6 Synthesis Example

Figure 112021084385904-pat00224
Figure 112021084385904-pat00224

Sub1-91 (2.0 g, 4.20 mmol), Sub3-20 (7.8 g, 9.24 mmol), K2CO3 (1.7 g, 12.6 mmol), Pd(PPh3)4 (0.10 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 5.2 g (수율: 71%)을 얻었다.Sub1-91 (2.0 g, 4.20 mmol), Sub3-20 (7.8 g, 9.24 mmol), K 2 CO 3 (1.7 g, 12.6 mmol), Pd(PPh 3 ) 4 (0.10 g, 0.08 mmol), Toluene ( 14 mL) to obtain 5.2 g (yield: 71%) of the product through the synthesis of P1-22.

40. P11-10 합성예40. P11-10 Synthesis Example

Figure 112021084385904-pat00225
Figure 112021084385904-pat00225

Sub1-95 (2.0 g, 4.08 mmol), Sub3-20 (7.5 g, 8.98 mmol), K2CO3 (1.7 g, 12.2 mmol), Pd(PPh3)4 (0.09 g, 0.08 mmol), Toluene (14 mL)을 상기 P1-22의 합성법을 통해 생성물 4.9 g (수율: 68%)을 얻었다.Sub1-95 (2.0 g, 4.08 mmol), Sub3-20 (7.5 g, 8.98 mmol), K 2 CO 3 (1.7 g, 12.2 mmol), Pd(PPh 3 ) 4 (0.09 g, 0.08 mmol), Toluene ( 14 mL) to obtain 4.9 g (yield: 68%) of the product through the synthesis of P1-22.

41. P12-1 합성예41. P12-1 Synthesis Example

Figure 112021084385904-pat00226
Figure 112021084385904-pat00226

Sub1-98 (2.0 g, 5.43 mmol), Sub3-2 (6.2 g, 12.0 mmol), K2CO3 (2.3 g, 16.3 mmol), Pd(PPh3)4 (0.13 g, 0.11 mmol), Toluene (18 mL)을 상기 P1-22의 합성법을 통해 생성물 4.0 g (수율: 73%)을 얻었다.Sub1-98 (2.0 g, 5.43 mmol), Sub3-2 (6.2 g, 12.0 mmol), K 2 CO 3 (2.3 g, 16.3 mmol), Pd(PPh 3 ) 4 (0.13 g, 0.11 mmol), Toluene ( 18 mL) to obtain 4.0 g (yield: 73%) of the product through the synthesis of P1-22.

42. P13-3 합성예42. P13-3 Synthesis Example

Figure 112021084385904-pat00227
Figure 112021084385904-pat00227

둥근바닥플라스크에 Sub1-103 (2.0 g, 6.5 mmol), Toluene (33 mL), Sub3-2-a (6.2 g, 14.4 mmol), Pd2(dba)3 (0.18 g, 0.20 mmol), P(t-Bu)3 (0.08 g, 0.39 mmol), NaOt-Bu (2.5 g, 26.1 mmol)을 첨가하고 120℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축하였다. 이후, 생성된 화합물을 실리카겔 칼럼을 적용한 후 재결정하여 생성물 5.1 g (수율: 72%)을 얻었다.Sub1-103 (2.0 g, 6.5 mmol), Toluene (33 mL), Sub3-2-a (6.2 g, 14.4 mmol), Pd 2 (dba) 3 (0.18 g, 0.20 mmol), P ( t-Bu) 3 (0.08 g, 0.39 mmol) and NaOt-Bu (2.5 g, 26.1 mmol) were added and stirred at 120°C. Upon completion of the reaction , the mixture was extracted with CH 2 Cl 2 and water, and the organic layer was dried over MgSO 4 and concentrated. Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 5.1 g (yield: 72%) of the product.

43. P14-4 합성예43. P14-4 Synthesis Example

Figure 112021084385904-pat00228
Figure 112021084385904-pat00228

Sub1-108 (2.0 g, 4.52 mmol), Sub3-20 (4.2 g, 4.97 mmol), K2CO3 (1.9 g, 13.6 mmol), Pd(PPh3)4 (0.10 g, 0.09 mmol), Toluene (15 mL)을 상기 P1-22의 합성법을 통해 생성물 4.0 g (수율: 79%)을 얻었다.Sub1-108 (2.0 g, 4.52 mmol), Sub3-20 (4.2 g, 4.97 mmol), K 2 CO 3 (1.9 g, 13.6 mmol), Pd(PPh 3 ) 4 (0.10 g, 0.09 mmol), Toluene ( 15 mL) to obtain 4.0 g (yield: 79%) of the product through the synthesis of P1-22.

44. P15-2 합성예44. P15-2 Synthesis Example

Figure 112021084385904-pat00229
Figure 112021084385904-pat00229

Sub1-110 (3.0 g, 9.41 mmol), Cu (4.8 g, 75.3 mmol), Sub2-4 (13.4 g, 20.7 mmol), DMSO (19 mL)을 상기 P1-1의 합성법을 통해 생성물 5.8 g (수율: 77%)을 얻었다.Sub1-110 (3.0 g, 9.41 mmol), Cu (4.8 g, 75.3 mmol), Sub2-4 (13.4 g, 20.7 mmol), DMSO (19 mL) was synthesized by the above P1-1 synthesis method to 5.8 g of the product (yield) : 77%) was obtained.

45. P16-2 합성예45. P16-2 Synthesis Example

Figure 112021084385904-pat00230
Figure 112021084385904-pat00230

Sub1-114 (3.0 g, 8.26 mmol), Cu (4.2 g, 66.1 mmol), Sub2-1 (11.7 g, 18.2 mmol), DMSO (17 mL)을 상기 P1-1의 합성법을 통해 생성물 3.7 g (수율: 75%)을 얻었다.Sub1-114 (3.0 g, 8.26 mmol), Cu (4.2 g, 66.1 mmol), Sub2-1 (11.7 g, 18.2 mmol), DMSO (17 mL) was synthesized by the above P1-1 synthesis method to 3.7 g of the product (yield) : 75%) was obtained.

46. P17-1 합성예46. P17-1 Synthesis Example

Figure 112021084385904-pat00231
Figure 112021084385904-pat00231

Sub1-117 (2.0 g, 7.80 mmol), Sub3-32 (9.3 g, 17.2 mmol), Pd2(dba)3 (0.21 g, 0.23 mmol), P(t-Bu)3 (0.09 g, 0.47 mmol), NaOt-Bu (3.0 g, 31.2 mmol), Toluene (39 mL)을 상기 P13-3의 합성법을 통해 생성물 7.3 g (수율: 74%)을 얻었다.Sub1-117 (2.0 g, 7.80 mmol), Sub3-32 (9.3 g, 17.2 mmol), Pd 2 (dba) 3 (0.21 g, 0.23 mmol), P(t-Bu) 3 (0.09 g, 0.47 mmol) , NaOt-Bu (3.0 g, 31.2 mmol), and Toluene (39 mL) were synthesized through the above P13-3 method to obtain 7.3 g (yield: 74%) of the product.

상기와 같은 합성예에 따라 제조된 본 발명의 화합물 P1-1 내지 P17-4의 FD-MS 값은 하기 표 4와 같다.FD-MS values of compounds P1-1 to P17-4 of the present invention prepared according to the above synthesis examples are shown in Table 4 below.

화합물compound FD-MSFD-MS 화합물compound FD-MSFD-MS P1-1P1-1 m/z=1064.02(C34H10F34=1064.4)m/z=1064.02 (C 34 H 10 F 34 =1064.4) P1-2P1-2 m/z=1190(C32H8F42=1190.35)m/z=1190 (C 32 H 8 F 42 =1190.35) P1-3P1-3 m/z=1266.03(C38H12F42=1266.45)m/z=1266.03 (C 38 H 12 F 42 =126.45) P1-4P1-4 m/z=1785.98(C46H9F63N2=1786.49)m/z=1785.98 (C 46 H 9 F 63 N 2 =1786.49) P1-5P1-5 m/z=1707.95(C42H7F63=1708.42)m/z=1707.95 (C 42 H 7 F 63 =1708.42) P1-6P1-6 m/z=2225.91(C52H6F84=2226.49)m/z=2225.91 (C 52 H 6 F 84 =2226.49) P1-7P1-7 m/z=548.08(C24H13F13=548.35)m/z=548.08 (C 24 H 13 F 13 =548.35) P1-8P1-8 m/z=748.07(C28H13F21=748.38)m/z=748.07 (C 28 H 13 F 21 =748.38) P1-9P1-9 m/z=648.07(C26H13F17=648.36)m/z=648.07 (C 26 H 13 F 17 =648.36) P1-10P1-10 m/z=753.1(C28H8D5F21=753.41)m/z=753.1 (C 28 H 8 D 5 F 21 =753.41) P1-11P1-11 m/z=564.08(C24H13F13O=564.35)m/z=564.08 (C 24 H 13 F 13 O=564.35) P1-12P1-12 m/z=692.1(C28H17F17O=692.42)m/z=692.1 (C 28 H 17 F 17 O=692.42) P1-13P1-13 m/z=866.05(C30H12F26=866.38)m/z=866.05 (C 30 H 12 F 26 =866.38) P1-14P1-14 m/z=1266.03(C38H12F42=1266.45)m/z=1266.03 (C 38 H 12 F 42 =126.45) P1-15P1-15 m/z=796.07(C29H14F22O=796.39)m/z=796.07 (C 29 H 14 F 22 O=796.39) P1-16P1-16 m/z=938.11(C34H20F26O=938.49)m/z=938.11 (C 34 H 20 F 26 O=938.49) P1-17P1-17 m/z=966.05(C32H12F30=966.4)m/z=966.05 (C 32 H 12 F 30 =966.4) P1-18P1-18 m/z=1392.07(C48H18F42=1392.6)m/z=1392.07 (C 48 H 18 F 42 =1392.6) P1-19P1-19 m/z=1482.08(C54H20F42O=1482.69)m/z=1482.08 (C 54 H 20 F 42 O=1482.69) P1-20P1-20 m/z=978.18(C38H28F26=978.6)m/z=978.18 (C 38 H 28 F 26 =978.6) P1-21P1-21 m/z=1002.03(C32H10F32=1002.38)m/z=1002.03 (C 32 H 10 F 32 =1002.38) P1-22P1-22 m/z=1184.02(C36H11F39=1184.42)m/z=1184.02 (C 36 H 11 F 39 =1184.42) P1-23P1-23 m/z=1783.99(C48H11F63=1784.52)m/z=1783.99 (C 48 H 11 F 63 =1784.52) P1-24P1-24 m/z=1820.07(C50H7D8F63=1820.62)m/z=1820.07 (C 50 H 7 D 8 F 63 =1820.62) P1-25P1-25 m/z=1960.05(C62H19F63=1960.73)m/z=1960.05 (C 62 H 19 F 63 =1960.73) P1-26P1-26 m/z=2016.02(C64H19F63S=2016.82)m/z=2016.02 (C 64 H 19 F 63 S=2016.82) P1-27P1-27 m/z=1261.05(C41H14F39N=1261.51)m/z=1261.05 (C 41 H 14 F 39 N=1261.51) P1-28P1-28 m/z=909.98(C28H4F30=910.29)m/z=909.98 (C 28 H 4 F 30 =910.29) P1-29P1-29 m/z=938.01(C30H8F30=938.35)m/z=938.01 (C 30 H 8 F 30 =938.35) P1-30P1-30 m/z=1266.03(C38H12F42=1266.45)m/z=1266.03 (C 38 H 12 F 42 =126.45) P1-31P1-31 m/z=894.08(C32H16F26=894.44)m/z=894.08 (C 32 H 16 F 26 =894.44) P1-32P1-32 m/z=1358.05(C44H16F42O=1358.54)m/z=1358.05 (C 44 H 16 F 42 O=1358.54) P1-33P1-33 m/z=1783.99(C48H11F63=1784.52)m/z=1783.99 (C 48 H 11 F 63 =1784.52) P1-34P1-34 m/z=1502(C42H10F52=1502.46)m/z=1502 (C 42 H 10 F 52 =1502.46) P1-35P1-35 m/z=2301.94(C58H10F84=2302.58)m/z=2301.94 (C 58 H 10 F 84 =2302.58) P1-36P1-36 m/z=1574.05(C46H18F52O=1574.57)m/z=1574.05 (C 46 H 18 F 52 O=1574.57) P1-37P1-37 m/z=1573.96(C42H6F56=1574.42)m/z=1573.96 (C 42 H 6 F 56 =1574.42) P1-38P1-38 m/z=1634.09(C52H22F52=1634.66)m/z=1634.09 (C 52 H 22 F 52 =1634.66) P1-39P1-39 m/z=1734.03(C58H18F52S=1734.76)m/z=1734.03 (C 58 H 18 F 52 S=1734.76) P1-40P1-40 m/z=2055.03(C61H17F68N=2055.71)m/z=2055.03 (C 61 H 17 F 68 N=2055.71) P1-41P1-41 m/z=1142.07(C40H16F34=1142.51)m/z=1142.07 (C 40 H 16 F 34 =1142.51) P1-42P1-42 m/z=1010.07(C37H15F29=1010.48)m/z=1010.07 (C 37 H 15 F 29 =1010.48) P1-43P1-43 m/z=1110.06(C39H15F33=1110.5)m/z=1110.06 (C 39 H 15 F 33 =1110.5) P1-44P1-44 m/z=1860.02(C54H15F63=1860.61)m/z=1860.02 (C 54 H 15 F 63 =1860.61) P1-45P1-45 m/z=1977.04(C61H18F63NO=1977.72)m/z=1977.04 (C 61 H 18 F 63 NO=1977.72) P1-46P1-46 m/z=1578.03(C48H14F52=1578.56)m/z=1578.03 (C 48 H 14 F 52 =1578.56) P1-47P1-47 m/z=1778.01(C52H14F60=1778.59)m/z=1778.01 (C 52 H 14 F 60 =1778.59) P1-48P1-48 m/z=1690.15(C56H30F52=1690.77)m/z=1690.15 (C 56 H 30 F 52 =1690.77) P1-49P1-49 m/z=1819.12(C66H25F52N=1819.85)m/z=1819.12 (C 66 H 25 F 52 N=1819.85) P1-50P1-50 m/z=2377.98(C64H14F84=2378.68)m/z=2377.98 (C 64 H 14 F 84 =2378.68) P1-51P1-51 m/z=2377.98(C64H14F84=2378.68)m/z=2377.98 (C 64 H 14 F 84 =2378.68) P1-52P1-52 m/z=1654.06(C54H18F52=1654.65)m/z=1654.06 (C 54 H 18 F 52 =1654.65) P1-53P1-53 m/z=2110.09(C66H26F68=2110.83)m/z=2110.09 (C 66 H 26 F 68 =2110.83) P1-54P1-54 m/z=2454.01(C70H18F84=2454.78)m/z=2454.01 (C 70 H 18 F 84 =2454.78) P1-55P1-55 m/z=2377.98(C64H14F84=2378.68)m/z=2377.98 (C 64 H 14 F 84 =2378.68) P1-56P1-56 m/z=1668.04(C54H16F52O=1668.64)m/z=1668.04 (C 54 H 16 F 52 O=1668.64) P1-57P1-57 m/z=2036.04(C62H19F67=2036.73)m/z=2036.04 (C 62 H 19 F 67 =2036.73) P1-58P1-58 m/z=2088.11(C72H27F63=2088.91)m/z=2088.11 (C 72 H 27 F 63 =2088.91) P1-59P1-59 m/z=2088.11(C72H27F63=2088.91)m/z=2088.11 (C 72 H 27 F 63 =2088.91) P1-60P1-60 m/z=3641.99(C102H24F126=3643.11)m/z=3641.99 (C 102 H 24 F 126 =3643.11) P1-61P1-61 m/z=1806.12(C66H26F52=1806.85)m/z=1806.12 (C 66 H 26 F 52 =1806.85) P1-62P1-62 m/z=3382.13(C114H38F104=3383.39)m/z=3382.13 (C 114 H 38 F 104 =3383.39) P1-63P1-63 m/z=916.07(C34H14F26=916.44)m/z=916.07 (C 34 H 14 F 26 =916.44) P1-64P1-64 m/z=1316.04(C42H14F42=1316.51)m/z=1316.04 (C 42 H 14 F 42 =1316.51) P1-65P1-65 m/z=1552.01(C46H12F52=1552.52)m/z=1552.01 (C 46 H 12 F 52 =1552.52) P1-66P1-66 m/z=916.07(C34H14F26=916.44)m/z=916.07 (C 34 H 14 F 26 =916.44) P1-67P1-67 m/z=966.08(C38H16F26=966.5)m/z=966.08 (C 38 H 16 F 26 =966.5) P1-68P1-68 m/z=1584.04(C50H15F51=1584.59)m/z=1584.04 (C 50 H 15 F 51 =1584.59) P1-69P1-69 m/z=2427.99(C68H16F84=2428.74)m/z=2427.99 (C 68 H 16 F 84 =2428.74) P1-70P1-70 m/z=2427.99(C68H16F84=2428.74)m/z=2427.99 (C 68 H 16 F 84 =2428.74) P1-71P1-71 m/z=916.07(C34H14F26=916.44)m/z=916.07 (C 34 H 14 F 26 =916.44) P1-72P1-72 m/z=1316.04(C42H14F42=1316.51)m/z=1316.04 (C 42 H 14 F 42 =1316.51) P1-73P1-73 m/z=2451.99(C70H16F84=2452.76)m/z=2451.99 (C 70 H 16 F 84 =2452.76) P1-74P1-74 m/z=2478.01(C72H18F84=2478.8)m/z=2478.01 (C 72 H 18 F 84 =2478.8) P1-75P1-75 m/z=2665.94(C70H14F92O4=2666.73)m/z=2665.94 (C 70 H 14 F 92 O 4 =2666.73) P1-76P1-76 m/z=1584.04(C50H15F51=1584.59)m/z=1584.04 (C 50 H 15 F 51 =1584.59) P1-77P1-77 m/z=2322.03(C66H22F76O4=2322.78)m/z=2322.03 (C 66 H 22 F 76 O 4 =2322.78) P1-78P1-78 m/z=2458.04(C70H22F84=2458.81)m/z=2458.04 (C 70 H 22 F 84 =2458.81) P2-1P2-1 m/z=1261.05(C41H14F39N=1261.51)m/z=1261.05 (C 41 H 14 F 39 N=1261.51) P2-2P2-2 m/z=1263.04(C39H12F39N3=1263.48)m/z=1263.04 (C 39 H 12 F 39 N 3 =1263.48) P2-3P2-3 m/z=949.03(C30H11F28NO2=949.38)m/z=949.03 (C 30 H 11 F 28 NO 2 =949.38) 　 　 P3-1P3-1 m/z=1799(C48H12F63N=1799.53)m/z=1799 (C 48 H 12 F 63 N=1799.53) P3-2P3-2 m/z=1427.13(C54H24F39N=1427.73)m/z=1427.13 (C 54 H 24 F 39 N=1427.73) P3-3P3-3 m/z=1172.17(C52H26F26N2=1172.75)m/z=1172.17 (C 52 H 26 F 26 N 2 =1172.75) P3-4P3-4 m/z=1387.03(C44H15F42NS=1387.6)m/z=1387.03 (C 44 H 15 F 42 NS=1387.6) P3-5P3-5 m/z=1885.13(C70H27F52NO=1885.91)m/z=1885.13 (C 70 H 27 F 52 NO=1885.91) P3-6P3-6 m/z=2028.16(C69H32F60N2=2028.93)m/z=2028.16 (C 69 H 32 F 60 N 2 =2028.93) P3-7P3-7 m/z=1925.04(C58H18F63N=1925.69)m/z=1925.04 (C 58 H 18 F 63 N=1925.69) P3-8P3-8 m/z=1401.11(C52H22F39N=1401.69)m/z=1401.11 (C 52 H 22 F 39 N=1401.69) P4-1P4-1 m/z=1205.99(C32H8F42O=1206.35)m/z=1205.99 (C 32 H 8 F 42 O=1206.35) P4-2P4-2 m/z=1256.01(C36H10F42O=1256.41)m/z=1256.01 (C 36 H 10 F 42 O=1256.41) P4-3P4-3 m/z=1349.92(C32F50O=1350.27)m/z=1349.92 (C 32 F 50 O=1350.27) P4-4P4-4 m/z=1158.07(C40H16F34O=1158.51)m/z=1158.07 (C 40 H 16 F 34 O=1158.51) P4-5P4-5 m/z=1350.16(C55H28F34O=1350.77)m/z=1350.16 (C 55 H 28 F 34 O=1350.77) P4-6P4-6 m/z=2446.06(C66H26F84O2=2446.8)m/z=2446.06 (C 66 H 26 F 84 O 2 =2446.8) P5-1P5-1 m/z=1221.97(C32H8F42S=1222.41)m/z=1221.97 (C 32 H 8 F 42 S=1222.41) P5-2P5-2 m/z=1271.98(C36H10F42S=1272.47)m/z=1271.98 (C 36 H 10 F 42 S=1272.47) P5-3P5-3 m/z=974.06(C36H16F26S=974.54)m/z=974.06 (C 36 H 16 F 26 S=974.54) P5-4P5-4 m/z=1074.09(C44H20F26S=1074.66)m/z = 1074.09 (C 44 H 20 F 26 S = 1074.66) P5-5P5-5 m/z=1074.09(C44H20F26S=1074.66)m/z = 1074.09 (C 44 H 20 F 26 S = 1074.66) P5-6P5-6 m/z=1050.09(C42H20F26S=1050.64)m/z=1050.09 (C 42 H 20 F 26 S=1050.64) P6-1P6-1 m/z=956.1(C37H18F26=956.51)m/z=956.1 (C 37 H 18 F 26 =956.51) P6-2P6-2 m/z=866.22(C49H31F13=866.77)m/z=866.22 (C 49 H 31 F 13 =866.77) P6-3P6-3 m/z=1056.13(C45H22F26=1056.63)m/z=1056.13 (C 45 H 22 F 26 =1056.63) P6-4P6-4 m/z=1108.16(C49H26F26=1108.71)m/z=1108.16 (C 49 H 26 F 26 =1108.71) P6-5P6-5 m/z=945.24(C52H32F13N3=945.83)m/z=945.24 (C 52 H 32 F 13 N 3 =945.83) 　 　 P7-1P7-1 m/z=972.08(C36H18F26Si=972.58)m/z=972.08 (C 36 H 18 F 26 Si=972.58) P7-2P7-2 m/z=1124.14(C48H26F26Si=1124.78)m/z=1124.14 (C 48 H 26 F 26 Si=1124.78) P7-3P7-3 m/z=1124.14(C48H26F26Si=1124.78)m/z=1124.14 (C 48 H 26 F 26 Si=1124.78) P7-4P7-4 m/z=1124.14(C48H26F26Si=1124.78)m/z=1124.14 (C 48 H 26 F 26 Si=1124.78) P8-1P8-1 m/z=1279.02(C38H11F42N=1279.45)m/z=1279.02 (C 38 H 11 F 42 N=1279.45) P8-2P8-2 m/z=1756.08(C60H20F52N2=1756.75)m/z=1756.08 (C 60 H 20 F 52 N 2 =1756.75) P8-3P8-3 m/z=1445.01(C44H10F47N=1445.5)m/z=1445.01 (C 44 H 10 F 47 N=1445.5) P8-4P8-4 m/z=1211.02(C42H9F36N=1211.48)m/z=1211.02 (C 42 H 9 F 36 N=1211.48) P8-5P8-5 m/z=1543.21(C58H35F42N=1543.86)m/z=1543.21 (C 58 H 35 F 42 N=1543.86) 　 　 P9-1P9-1 m/z=1203.97(C32H6F42O=1204.33)m/z=1203.97 (C 32 H 6 F 42 O=1204.33) P9-2P9-2 m/z=956.06(C36H14F26O=956.47)m/z=956.06 (C 36 H 14 F 26 O=956.47) P9-3P9-3 m/z=956.06(C36H14F26O=956.47)m/z=956.06 (C 36 H 14 F 26 O=956.47) P9-4P9-4 m/z=880.03(C30H10F26O=880.37)m/z=880.03 (C 30 H 10 F 26 O=880.37) P9-5P9-5 m/z=1896.13(C72H28F52O=1896.93)m/z=1896.13 (C 72 H 28 F 52 O=1896.93) P9-6P9-6 m/z=1744.07(C60H20F52O=1744.74)m/z=1744.07 (C 60 H 20 F 52 O=1744.74) P9-7P9-7 m/z=1056.06(C38H14F30O=1056.48)m/z=1056.06 (C 38 H 14 F 30 O=1056.48) 　 　 P10-1P10-1 m/z=1219.95(C32H6F42S=1220.39)m/z=1219.95 (C 32 H 6 F 42 S=1220.39) P10-2P10-2 m/z=972.04(C36H14F26S=972.53)m/z=972.04 (C 36 H 14 F 26 S=972.53) P10-3P10-3 m/z=896.01(C30H10F26S=896.43)m/z=896.01 (C 30 H 10 F 26 S=896.43) P10-4P10-4 m/z=1912.11(C72H28F52S=1912.99)m/z=1912.11 (C 72 H 28 F 52 S=1912.99) P10-5P10-5 m/z=1760.05(C60H20F52S=1760.8)m/z=1760.05 (C 60 H 20 F 52 S=1760.8) P10-6P10-6 m/z=1198.12(C54H24F26S=1198.8)m/z=1198.12 (C 54 H 24 F 26 S=1198.8) P10-7P10-7 m/z=735.13(C36H14D5F13S=735.62)m/z=735.13 (C 36 H 14 D 5 F 13 S=735.62) 　 　 P11-1P11-1 m/z=982.11(C39H20F26=982.55)m/z=982.11 (C 39 H 20 F 26 =982.55) P11-2P11-2 m/z=1618.06(C51H18F52=1618.62)m/z=1618.06 (C 51 H 18 F 52 =1618.62) P11-3P11-3 m/z=2418.01(C67H18F84=2418.75)m/z=2418.01 (C 67 H 18 F 84 =2418.75) P11-4P11-4 m/z=954.08(C37H16F26=954.49)m/z=954.08 (C 37 H 16 F 26 =954.49) P11-5P11-5 m/z=1354.06(C45H16F42=1354.56)m/z=1354.06 (C 45 H 16 F 42 =1354.56) P11-6P11-6 m/z=1742.09(C61H22F52=1742.76)m/z=1742.09 (C 61 H 22 F 52 =1742.76) P11-7P11-7 m/z=1278.1(C48H21F35O=1278.64)m/z=1278.1 (C 48 H 21 F 35 O=1278.64) P11-8P11-8 m/z=952.07(C37H14F26=952.48)m/z=952.07 (C 37 H 14 F 26 =952.48) P11-9P11-9 m/z=954.08(C37H16F26=954.49)m/z=954.08 (C 37 H 16 F 26 =954.49) P11-10P11-10 m/z=1756.07(C61H20F52O=1756.75)m/z=1756.07 (C 61 H 20 F 52 O=1756.75) P11-11P11-11 m/z=1772.05(C61H20F52S=1772.81)m/z=1772.05 (C 61 H 20 F 52 S=1772.81) P11-12P11-12 m/z=1831.12(C67H25F52N=1831.86)m/z=1831.12 (C 67 H 25 F 52 N=1831.86) P12-1P12-1 m/z=998.09(C38H20F26Si=998.62)m/z=998.09 (C 38 H 20 F 26 Si=998.62) P12-2P12-2 m/z=998.09(C38H20F26Si=998.62)m/z=998.09 (C 38 H 20 F 26 Si=998.62) P12-3P12-3 m/z=1370.04(C44H16F42Si=1370.63)m/z=1370.04 (C 44 H 16 F 42 Si=1370.63) 　 　 P13-1P13-1 m/z=1213.13(C54H25F26NS=1213.82)m/z=1213.13 (C 54 H 25 F 26 NS=1213.82) P13-2P13-2 m/z=986.02(C36H12F26OS=986.51)m/z=986.02 (C 36 H 12 F 26 OS=986.51) P13-3P13-3 m/z=1094.12(C46H20F26N2=1094.64)m/z=1094.12 (C 46 H 20 F 26 N 2 =1094.64) P13-4P13-4 m/z=848.18(C45H26F14O=848.68)m/z=848.18 (C 45 H 26 F 14 O=848.68) P14-1P14-1 m/z=817.07(C36H13F18NO=817.48)m/z=817.07 (C 36 H 13 F 18 NO=817.48) P14-2P14-2 m/z=892.15(C49H25F13S=892.78)m/z=892.15 (C 49 H 25 F 13 S=892.78) P14-3P14-3 m/z=652.07(C30H13F13O2=652.41)m/z=652.07 (C 30 H 13 F 13 O 2 =652.41) P14-4P14-4 m/z=1120.13(C49H22F26O=1120.67)m/z=1120.13 (C 49 H 22 F 26 O=1120.67) P15-1P15-1 m/z=776.15(C40H21F13N2=776.60)m/z=776.15 (C 40 H 21 F 13 N 2 =776.60) P15-2P15-2 m/z=802.08(C31H15F21O=802.43)m/z=802.08 (C 31 H 15 F 21 O=802.43) P15-3P15-3 m/z=622.03(C25H11F13O2S=622.4)m/z=622.03 (C 25 H 11 F 13 O 2 S=622.4) P15-4P15-4 m/z=853.16(C41H24F17N=853.62)m/z=853.16 (C 41 H 24 F 17 N=853.62) P16-1P16-1 m/z=985.04(C36H13F26NS=985.53)m/z=985.04 (C 36 H 13 F 26 NS=985.53) P16-2P16-2 m/z=602.09(C27H15F13O=602.40)m/z=602.09 (C 27 H 15 F 13 O=602.40) P16-3P16-3 m/z=734.04(C34H15F13S2=734.59)m/z=734.04 (C 34 H 15 F 13 S 2 =734.59) P16-4P16-4 m/z=628.14(C30H21F13=628.48)m/z=628.14 (C 30 H 21 F 13 =628.48) P17-1P17-1 m/z=1272.12(C48H22F34N2=1272.66)m/z=1272.12 (C 48 H 22 F 34 N 2 =1272.66) P17-2P17-2 m/z=576.04(C24H9F13O2=576.31)m/z=576.04 (C 24 H 9 F 13 O 2 =576.31) P17-3P17-3 m/z=986.02(C36H12F26OS=986.51)m/z=986.02 (C 36 H 12 F 26 OS=986.51) P17-4P17-4 m/z=628.14(C30H21F13=628.48)m/z=628.14 (C 30 H 21 F 13 =628.48)

광 투과율 측정Light transmittance measurement

[실시예 1] : 금속패터닝층의 종류에 따른 광 투과율 비교[Example 1]: Comparison of light transmittance according to the type of metal patterning layer

먼저, 유리기판 위에 우선 유기층으로서 N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (이하, C-1으로 약기함) 막을 진공증착하여 100 nm 두께로 형성하였다. 유기층 위에 본 발명의 화합물 P1-22를 10 nm 두께로 진공증착하여 전극 패터닝층을 형성하였다. 이어서, 전극 패터닝층 위에 전자주입층으로 Yb를 진공증착한 후, Mg 및 Ag를 1:9 중량으로 음극을 증착하였다. 그 후 캡핑층으로 N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine (이하, D-1으로 약기함)을 70 nm 두께로 증착하여 광투과율에 측정에 필요한 샘플을 제작하였다.First, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl as an organic layer on a glass substrate )-9H-fluoren-2-amine (hereinafter, abbreviated as C-1) film was vacuum-deposited to form a thickness of 100 nm. On the organic layer, the compound P1-22 of the present invention was vacuum-deposited to a thickness of 10 nm to form an electrode patterning layer. Then, after vacuum deposition of Yb as an electron injection layer on the electrode patterning layer, a cathode was deposited with Mg and Ag in a weight of 1:9. Then, as a capping layer, N4,N4'-diphenyl-N4,N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]-4,4'-diamine (hereinafter, D-1) was deposited to a thickness of 70 nm to prepare a sample required for measurement of light transmittance.

[실시예 2] 내지 [실시예 8][Example 2] to [Example 8]

금속(전극) 패터닝층 물질로 본 발명의 화합물 P1-22 대신 하기 표 5에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 광 투과율 샘플을 제작하였다.A light transmittance sample was prepared in the same manner as in Example 1, except that the compound of the present invention described in Table 5 was used instead of the compound P1-22 of the present invention as the metal (electrode) patterning layer material.

[비교예 1][Comparative Example 1]

금속(전극) 패터닝층을 사용하지 않은 점을 제외하고는 상기 실시예 1과 동일한 방법으로 광 투과율 샘플을 제작하였다.A light transmittance sample was prepared in the same manner as in Example 1, except that the metal (electrode) patterning layer was not used.

[비교예 2][Comparative Example 2]

금속(전극) 패터닝층 물질로 본 발명의 화합물 P1-22 대신 하기 비교화합물 A를 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 광 투과율 샘플을 제작하였다.A light transmittance sample was prepared in the same manner as in Example 1, except that the following comparative compound A was used instead of the compound P1-22 of the present invention as the metal (electrode) patterning layer material.

[비교화합물 A][Comparative compound A]

Figure 112021084385904-pat00232
Figure 112021084385904-pat00232

이와 같이 제작된 실시예 및 비교예 광 투과율 샘플을 Perkinelmer사의 Lambda 365 UV/VIS Spectrometer 측정장비로 가시광선 영역인 550 nm에서의 광 투과율을 측정하였으며, 그 측정결과는 하기 표 5에 평가한 결과를 나타내었다. 또한, 금속(전극) 패터닝층 물질의 불소 함량을 하기 표 5에 나타내었다. 하기 표 5의 결과는 도 5의 광 투과율 측정 결과 그래프를 근거로 작성하였다.The light transmittance samples of Examples and Comparative Examples prepared as described above were measured for light transmittance in the visible ray region of 550 nm with Perkinelmer's Lambda 365 UV/VIS Spectrometer measuring equipment, and the measurement results are shown in Table 5 below. indicated. In addition, the fluorine content of the metal (electrode) patterning layer material is shown in Table 5 below. The results of Table 5 below were prepared based on the light transmittance measurement result graph of FIG. 5 .

구분division 화합물compound 불소 함량(%)Fluorine content (%) 광투과율(%)Light transmittance (%) T(%)T(%) 비교예1Comparative Example 1 -- 0.00%0.00% 69.13~72.3869.13~72.38 100%100% 비교예2Comparative Example 2 비교화합물AComparative compound A 13.16%13.16% 50.16 50.16 73%73% 실시예1Example 1 P1-22P1-22 45.35%45.35% 95.50 95.50 139%139% 실시예2Example 2 P1-34P1-34 50.00%50.00% 95.11 95.11 138%138% 실시예3Example 3 P1-46P1-46 45.61%45.61% 95.03 95.03 137%137% 실시예4Example 4 P1-63P1-63 35.14%35.14% 93.80 93.80 130%130% 실시예5Example 5 P1-65P1-65 47.27%47.27% 95.45 95.45 132%132% 실시예6Example 6 P1-71P1-71 35.14%35.14% 92.73 92.73 128%128% 실시예7Example 7 P1-73P1-73 49.41%49.41% 92.20 92.20 130%130% 실시예8Example 8 P7-1P7-1 32.10%32.10% 93.40 93.40 129%129%

상기 표 5의 결과를 살펴보면, 금속패터닝층을 사용하지 않은 비교예 1과 분자 내 불소 함량이 작은 화합물인 비교화합물 A를 사용했을 경우 광 투과율이 90% 미만으로 나오는 것을 확인할 수 있었으며, 분자 내 불소 함량이 30% 이상인 본 발명 화합물을 사용한 실시예 1 내지 실시예 8의 경우 광 투과율이 90% 이상 나오는 것을 확인할 수 있었다. 특히 비교예 1의 경우 비교예 2, 실시예 1 내지 실시예 8과 각각 비교 평가를 한 결과 각 lot별로 69.13% 내지 72.38%의 광 투과율을 나타내는 것을 확인할 수 있었다. 또한 분자 내 불소 함량이 13.16%으로 30% 미만인 비교화합물 A의 경우 분자 내 불소를 포함하는 재료가 없는 비교예 1보다 더 낮은 광 투과율을 갖는 것을 확인할 수 있었다.Looking at the results of Table 5, when Comparative Example 1 without using a metal patterning layer and Comparative Compound A, which is a compound having a small intramolecular fluorine content, were used, it was confirmed that the light transmittance was less than 90%, and intramolecular fluorine In the case of Examples 1 to 8 using the compound of the present invention having a content of 30% or more, it was confirmed that the light transmittance was 90% or more. In particular, in the case of Comparative Example 1, as a result of comparative evaluation with Comparative Example 2 and Examples 1 to 8, it was confirmed that the light transmittance was 69.13% to 72.38% for each lot. In addition, it was confirmed that Comparative Compound A having an intramolecular fluorine content of 13.16% and less than 30% had a lower light transmittance than Comparative Example 1 without a material containing intramolecular fluorine.

비교예 1의 각 lot별로 광 투과율이 약간의 차이를 나타내어 이를 보정하고자 T% (각 lot별로 비교예 1의 광 투과율을 100%로 산정한 후, 본 발명 화합물과의 광 투과율 차이를 나타냄)로 나타낸 결과 비교예 1보다 본 발명 화합물을 사용했을 때 광 투과율이 28% 내지 39% 증가하는 것을 알 수 있었다. In order to correct the light transmittance for each lot of Comparative Example 1, it was calculated as T% (after calculating the light transmittance of Comparative Example 1 as 100% for each lot, indicating the difference in light transmittance with the compound of the present invention) As a result, it was found that the light transmittance increased by 28% to 39% when the compound of the present invention was used compared to Comparative Example 1.

전극(전기 전도성 물질)의 코팅과 관련하여 어느 표면 위에 존재하는 전극 물질의 양을 알아보는데 사용되는 것이 광 투과율이다. 그 이유는 전극 물질은 금속을 포함하고 있으며, 금속과 같은 전기전도성 물질은 빛을 감쇠 및/또는 흡수하기 때문이다. 따라서 전자기 스펙트럼의 가시광선 영역에서 광 투과율이 90%를 초과할 경우의 표면은 전기 전도성 물질을 실질적으로 갖고 있지 않은 것으로 간주 될 수 있다.Light transmittance is used to determine the amount of electrode material present on a surface in relation to the coating of an electrode (electrically conductive material). The reason is that the electrode material contains a metal, and an electrically conductive material such as a metal attenuates and/or absorbs light. Therefore, when the light transmittance exceeds 90% in the visible region of the electromagnetic spectrum, the surface can be considered to be substantially free of an electrically conductive material.

따라서 본 발명에서 제작한 샘플의 광 투과율을 측정한 결과, 상기 표 5와 같이 분자 내 불소함량이 30% 이상인 본 발명 화합물을 사용할 경우, 전자주입층으로 사용된 금속인 Yb, 음극으로 사용된 Ag, Mg가 본 발명 화합물의 위에 증착되지 않았음을 알 수 있었다. Therefore, as a result of measuring the light transmittance of the sample prepared in the present invention, as shown in Table 5 above, when the compound of the present invention having an intramolecular fluorine content of 30% or more is used, Yb, the metal used as the electron injection layer, and Ag used as the cathode , it can be seen that Mg was not deposited on the compound of the present invention.

상기 내용을 확인하고자 금속 종류의 표면을 관찰할 수 있는 분석장비인 주사전자현미경(SEM : Scanning Electron Microscope)을 이용하여 비교예 1과 실시예 3 샘플의 단면을 확인한 결과 도 4와 같았다. (FE-SEM : JEOL사의 JMS6701F) In order to confirm the above contents, the cross-sections of the samples of Comparative Examples 1 and 3 were checked using a scanning electron microscope (SEM), which is an analysis equipment capable of observing the surface of a metal type, as shown in FIG. 4 . (FE-SEM: JMS6701F of JEOL)

도 4의 (a)에서 보이는 바와 같이 유기층(하단부)과 캡핑층(상단부) 사이에 흰색으로 얇은 박막이 형성된 것을 확인할 수 있으며, 도 4의 (b)에서 보이는 바와 같이 유기층 및 금속패터닝층(하단부)과 캡핑층(상단부) 사이에는 얇은 박막이 형성되지 않은 것을 확인할 수 있었다.As shown in (a) of FIG. 4, it can be seen that a thin white thin film is formed between the organic layer (lower part) and the capping layer (upper part), and as shown in FIG. ) and the capping layer (upper part), it was confirmed that a thin film was not formed.

[[ 실시예Example 9] 9] 전자주입층electron injection layer 금속 유무 및 전극의 금속 종류에 따른 광 투과율 비교 Comparison of light transmittance according to presence of metal and metal type of electrode

유리기판 위에 우선 유기층으로서 C-1 막을 진공증착하여 100 nm 두께로 형성하였다. 유기층 위에 본 발명의 화합물 P1-46을 10 nm 두께로 진공증착하여 금속패터닝층을 형성하였다. 이어서, 금속패터닝층 위에 전자주입층으로 Yb를 진공증착한 후, Mg 및 Ag를 1:9 중량으로 음극을 증착하였다. 그 후 캡핑층으로 D-1을 70 nm 두께로 증착하여 샘플을 제조하였다.First, a C-1 film was vacuum-deposited as an organic layer on a glass substrate to form a thickness of 100 nm. On the organic layer, the compound P1-46 of the present invention was vacuum-deposited to a thickness of 10 nm to form a metal patterning layer. Then, after vacuum deposition of Yb as an electron injection layer on the metal patterning layer, a cathode was deposited with Mg and Ag in a weight of 1:9. Thereafter, D-1 was deposited as a capping layer to a thickness of 70 nm to prepare a sample.

[비교예 3][Comparative Example 3]

금속패터닝층을 사용하지 않은 점을 제외하고는 상기 실시예 9와 동일한 방법으로 유기전기소자를 제조하였다.An organic electric device was manufactured in the same manner as in Example 9, except that the metal patterning layer was not used.

[실시예 10] 전자주입층 금속인 Yb 미사용 샘플[Example 10] Sample without Yb as electron injection layer metal

유리기판 위에 우선 유기층으로서 C-1 막을 진공증착하여 100 nm 두께로 형성하였다. 유기층 위에 본 발명의 화합물 P1-46을 10 nm 두께로 진공증착하여 금속패터닝층을 형성하였다. 이어서, 금속패터닝층 위에 음극으로 Mg 및 Ag를 1:9 중량으로 증착하였다. 그 후 캡핑층으로 D-1을 70 nm 두께로 증착하여 유기전기소자를 제조하였다.First, a C-1 film was vacuum-deposited as an organic layer on a glass substrate to form a thickness of 100 nm. On the organic layer, the compound P1-46 of the present invention was vacuum-deposited to a thickness of 10 nm to form a metal patterning layer. Then, Mg and Ag were deposited in a weight of 1:9 on the metal patterning layer as a cathode. Then, as a capping layer, D-1 was deposited to a thickness of 70 nm to manufacture an organic electric device.

[비교예 4] 전자주입층 금속인 Yb 미사용 샘플[Comparative Example 4] Sample without using Yb as the electron injection layer metal

금속패터닝층을 사용하지 않은 점을 제외하고는 상기 실시예 10과 동일한 방법으로 유기전기소자를 제조하였다.An organic electric device was manufactured in the same manner as in Example 10, except that the metal patterning layer was not used.

[실시예 11] 전극(음극)을 Ag로만 사용한 샘플[Example 11] Sample using only Ag electrode (cathode)

유리기판 위에 우선 유기층으로서 C-1 막을 진공증착하여 100 nm 두께로 형성하였다. 유기층 위에 본 발명의 화합물 P1-46을 10 nm 두께로 진공증착하여 금속패터닝층을 형성하였다. 이어서, 금속패터닝층 위에 전자주입층으로 Yb를 진공증착한 후, 음극으로 Ag를 증착하였다. 그 후 캡핑층으로 D-1을 70 nm 두께로 증착하여 유기전기소자를 제조하였다.First, a C-1 film was vacuum-deposited as an organic layer on a glass substrate to form a thickness of 100 nm. On the organic layer, the compound P1-46 of the present invention was vacuum-deposited to a thickness of 10 nm to form a metal patterning layer. Then, after vacuum deposition of Yb as an electron injection layer on the metal patterning layer, Ag was deposited as a cathode. Then, as a capping layer, D-1 was deposited to a thickness of 70 nm to manufacture an organic electric device.

[비교예 5] 전극(음극)을 Ag로만 사용한 샘플[Comparative Example 5] Sample using only Ag electrode (cathode)

금속패터닝층을 사용하지 않은 점을 제외하고는 상기 실시예 11과 동일한 방법으로 유기전기소자를 제조하였다.An organic electric device was manufactured in the same manner as in Example 11, except that the metal patterning layer was not used.

이와 같이 제조된 실시예 및 비교예 광 투과율 샘플을 Perkinelmer사의 Lambda 365 UV/VIS Spectrometer 측정장비로 가시광선 영역인 550 nm에서의 광 투과율을 측정하였으며, 그 측정결과는 하기 표 6에 평가한 결과를 나타내었다.The light transmittance samples of Examples and Comparative Examples prepared as described above were measured for light transmittance in the visible ray region of 550 nm with Perkinelmer's Lambda 365 UV/VIS Spectrometer measuring equipment, and the measurement results are shown in Table 6 below. indicated.

구분division 화합물compound 전자주입층electron injection layer 음극cathode 광투과율light transmittance T(%)T(%) 비교예3Comparative Example 3 -- YbYb Mg:AgMg: Ag 73.73 73.73 100%100% 실시예9Example 9 P1-46P1-46 YbYb Mg:AgMg: Ag 95.63 95.63 130%130% 비교예4Comparative Example 4 -- -- Mg:AgMg: Ag 66.17 66.17 100%100% 실시예10Example 10 P1-46P1-46 -- Mg:AgMg: Ag 96.68 96.68 146%146% 비교예5Comparative Example 5 -- YbYb AgAg 72.01 72.01 100%100% 실시예11Example 11 P1-46P1-46 YbYb AgAg 97.23 97.23 135%135%

상기 표 6의 결과는 도 6의 광 투과율 측정 결과 그래프를 근거로 작성하였다. 상기 표 6은 금속패터닝층을 사용하지 않은 비교예 3, 비교예 4, 비교예 5와 분자 내 불소 함량이 30% 이상인 본 발명 발명화합물 P1-46을 사용한 실시예 9, 실시예 10, 실시예 11의 광 투과율을 비교하여 전자주입층 금속의 유무에 따른 전극 패터닝 가능 여부와 음극의 금속 종류에 따른 전극 패터닝 변화를 알아보았다. 비교예 3 및 실시예 9는 전자주입층 금속인 Yb 및 음극 전극 금속인 Mg를 사용하지 않았을 경우에 대한 비교군(reference)으로 평가되었으며, 분자 내 불소 함량이 30% 이상인 본 발명 화합물 P1-46을 금속패터닝층에 사용했을 경우 95.63%의 광 투과율을 나타내는 것을 확인할 수 있었다.The results of Table 6 were prepared based on the light transmittance measurement result graph of FIG. 6 . Table 6 shows Comparative Examples 3, 4, and 5 without using a metal patterning layer, and Examples 9, 10, and Examples using the inventive compound P1-46 having an intramolecular fluorine content of 30% or more. By comparing the light transmittance of Fig. 11, the possibility of electrode patterning according to the presence or absence of the electron injection layer metal and the electrode patterning change according to the metal type of the cathode were investigated. Comparative Examples 3 and 9 were evaluated as a reference for the case where the electron injection layer metal, Yb, and the cathode electrode metal, Mg, were not used, and the compound P1-46 of the present invention had an intramolecular fluorine content of 30% or more. When used for the metal patterning layer, it was confirmed that the light transmittance of 95.63% was exhibited.

전자주입층으로 사용된 금속인 Yb를 제외하여 음극의 금속에 대한 패터닝 성능을 확인하고자 비교예 4, 실시예 10을 실시한 결과, 전자주입층 금속인 Yb가 없을 경우 본 발명 화합물을 사용한 실시예 10의 광 투과율은 96.68% (T% : 146%)로 전자주입층이 있을 경우인 실시예 9보다 더 높은 광 투과율(T%로 16% 증가)을 보이는 것을 확인할 수 있었다.As a result of performing Comparative Examples 4 and 10 to confirm the patterning performance of the metal of the cathode except for Yb, which is the metal used as the electron injection layer, Example 10 using the compound of the present invention in the absence of Yb as the electron injection layer metal The light transmittance of 96.68% (T%: 146%) was confirmed to show a higher light transmittance (16% increase in T%) than Example 9 when the electron injection layer was present.

또한 음극의 금속 종류에 따른 패터닝 성능을 알아보고자 음극에 Ag만을 사용한 비교예 5, 실시예 11과 비교군인 비교예 3과 실시예 9를 비교한 결과, 음극에 Ag만을 사용했을 경우 본 발명화합물을 금속패터닝층에 사용했을 경우 135% (T%)로 실시예 9에 비해 5% 광 투과율이 증가한 것을 확인할 수 있었다.In addition, in order to investigate the patterning performance according to the type of metal of the anode, Comparative Examples 5 and 11 using only Ag for the anode and Comparative Examples 3 and 9, which are comparative groups, were compared. When used for the metal patterning layer, it was confirmed that the light transmittance was increased by 5% compared to Example 9 to 135% (T%).

[실시예 12][Example 12]

유리기판 위에 우선 유기층으로서 C-1 막을 진공증착하여 100 nm 두께로 형성하였다. 유기층 위에 본 발명의 화합물 P1-22를 3 nm 두께로 진공증착하여 금속패터닝층을 형성하였다. 이어서, 금속패터닝층 위에 전자주입층으로 Yb를 진공증착한 후, Mg 및 Ag를 1:9 중량으로 음극을 증착하였다. 그 후 캡핑층으로 D-1을 70 nm 두께로 증착하여 샘플을 제작하였다.First, a C-1 film was vacuum-deposited as an organic layer on a glass substrate to form a thickness of 100 nm. On the organic layer, the compound P1-22 of the present invention was vacuum-deposited to a thickness of 3 nm to form a metal patterning layer. Then, after vacuum deposition of Yb as an electron injection layer on the metal patterning layer, a cathode was deposited with Mg and Ag in a weight of 1:9. Then, as a capping layer, D-1 was deposited to a thickness of 70 nm to prepare a sample.

[실시예 13] 내지 [실시예 23][Example 13] to [Example 23]

금속패터닝층 물질로 본 발명의 화합물 P1-22 대신 하기 표 7에 기재된 본 발명의 화합물 및 하기 표7에 기재된 두께를 사용한 점을 제외하고는 상기 실시예 12와 동일한 방법으로 샘플을 제작하였다.A sample was prepared in the same manner as in Example 12, except that the compound of the present invention described in Table 7 and the thickness described in Table 7 were used instead of the compound P1-22 of the present invention as the metal patterning layer material.

[비교예 6][Comparative Example 6]

금속패터닝층을 사용하지 않은 점을 제외하고는 상기 실시예 12와 동일한 방법으로 샘플을 제작하였다.A sample was prepared in the same manner as in Example 12, except that the metal patterning layer was not used.

이와 같이 제조된 실시예 및 비교예 광 투과율 샘플을 Perkinelmer사의 Lambda 365 UV/VIS Spectrometer 측정장비로 가시광선 영역인 550 nm에서의 광 투과율을 측정하였으며, 그 측정결과는 하기 표 7에 평가한 결과를 나타내었다.The light transmittance samples of Examples and Comparative Examples prepared as described above were measured for light transmittance in the visible ray region of 550 nm with Perkinelmer's Lambda 365 UV/VIS Spectrometer measuring equipment, and the measurement results are shown in Table 7 below. indicated.

구분division 화합물compound 금속패터닝층의 두께Thickness of metal patterning layer 광투과율light transmittance T(%)T(%) 비교예6Comparative Example 6 -- -　- 69.13~72.3869.13~72.38 100%100% 실시예12Example 12 P1-22P1-22 3 nm3 nm 95.01 95.01 139%139% 실시예13Example 13 5 nm5 nm 96.14 96.14 140%140% 실시예14Example 14 10 nm10 nm 95.50 95.50 139%139% 실시예15Example 15 P1-34P1-34 3 nm3 nm 96.37 96.37 139%139% 실시예16Example 16 5 nm5 nm 95.93 95.93 139%139% 실시예17Example 17 10 nm10 nm 95.11 95.11 138%138% 실시예18Example 18 P1-46P1-46 3 nm3 nm 96.31 96.31 139%139% 실시예19Example 19 5 nm5 nm 96.00 96.00 139%139% 실시예20Example 20 10 nm10 nm 95.03 95.03 137%137% 실시예21Example 21 P1-65P1-65 3 nm3 nm 96.60 96.60 133%133% 실시예22Example 22 5 nm5 nm 96.47 96.47 133%133% 실시예23Example 23 10 nm10 nm 95.45 95.45 132%132%

상기 표 7의 결과는 도 7의 광 투과율 측정 결과 그래프를 근거로 작성하였다. 상기 표 7은 본 발명 화합물을 사용하는 금속패터닝층의 두께에 따른 광 투과율의 변화를 확인하고자 진행되었다. 비교예 6의 경우 실시예 12 내지 실시예 23에 기재된 각 재료별 평가 진행 시 사용된 비교예의 각 Lot별 광 투과율 결과를 범위(69.13%~72.38%)로 기재하였으며, 각 lot별로 측정된 광 투과율을 100%(T%)로 산정하여 그에 대한 실시예의 광 투과율을 T%로 기재하였다.The results of Table 7 were prepared based on the light transmittance measurement result graph of FIG. 7 . Table 7 was carried out to confirm the change in light transmittance according to the thickness of the metal patterning layer using the compound of the present invention. In the case of Comparative Example 6, the light transmittance results for each lot of Comparative Examples used in the evaluation of each material described in Examples 12 to 23 were described in the range (69.13% to 72.38%), and the light transmittance measured for each lot was calculated as 100% (T%), and the light transmittance of the Example was described as T%.

실시예 12 내지 실시예 23에서 본 발명 화합물을 각각 3 nm, 5 nm, 10 nm 두께를 갖는 금속패터닝층으로 사용할 경우 광 투과율은 95.01%~96.47% (T% 132%~140%) 큰 차이가 없는 것을 확인할 수 있었다. 이는 본 발명 화합물을 금속패터닝용 재료로 사용할 경우 증착공정에서 발생할 수 있는 증착 두께의 편차에 따른 성능 저하 등의 문제를 미연에 방지할 수 있을 것이다.In Examples 12 to 23, when the compound of the present invention is used as a metal patterning layer having a thickness of 3 nm, 5 nm, and 10 nm, respectively, the light transmittance is 95.01% to 96.47% (T% 132% to 140%) There is a large difference could confirm that there was no This will prevent problems such as performance degradation due to variations in deposition thickness that may occur in the deposition process when the compound of the present invention is used as a material for metal patterning.

[실시예 24] [Example 24]

접촉각을 측정하기 위해서, 유리기판 위에 본 발명 화합물 P1-34를 50 nm 두께로 진공증착하여 샘플을 제작하였다.In order to measure the contact angle, a sample was prepared by vacuum-depositing the compound P1-34 of the present invention to a thickness of 50 nm on a glass substrate.

[실시예 25] 내지 [실시예 30][Example 25] to [Example 30]

유리기판 위에 본 발명의 화합물 P1-34 대신 하기 표 8에 기재된 본 발명의 화합물을 사용한 점을 제외하고는 상기 실시예 24와 동일한 방법으로 샘플을 제작하였다.A sample was prepared in the same manner as in Example 24, except that the compound of the present invention described in Table 8 was used instead of the compound P1-34 of the present invention on a glass substrate.

[비교예 7] [Comparative Example 7]

상기 실시예 24와 동일한 방법으로 진행하되, 본 발명 화합물 P1-34 대신에 C-1을 사용하였다.It proceeded in the same manner as in Example 24, except that C-1 was used instead of compound P1-34 of the present invention.

이와 같이 제작된 비교예 7, 실시예 24 내지 실시예 30 샘플의 접촉각을 KRUSS사의 DSA25 접촉각 측정장비로 측정하였으며, 그 측정결과는 하기 표 8에 평가한 결과를 나타내었다.The contact angles of the samples of Comparative Example 7 and Examples 24 to 30 prepared in this way were measured with a DSA25 contact angle measuring device manufactured by KRUSS, and the measurement results are shown in Table 8 below.

구분division 화합물compound 접촉각 (o)contact angle ( o ) 비교예 7Comparative Example 7 C-1C-1 83.283.2 실시예24Example 24 P1-34P1-34 103.6 103.6 실시예25Example 25 P1-46P1-46 116.4 116.4 실시예26Example 26 P1-63P1-63 109.6 109.6 실시예27Example 27 P1-65P1-65 116.1 116.1 실시예28Example 28 P1-71P1-71 117.0 117.0 실시예29Example 29 P1-73P1-73 118.2 118.2 실시예30Example 30 P7-1P7-1 111.1 111.1

상기 표 8을 보면, 불소를 포함하지 않고 광 투과율이 낮은 C-1 물질의 접촉각은 83.2˚를 나타내는 것을 확인할 수 있으며, 반면에 광 투과율이 90% 이상인 본 발명 화합물의 접촉각은 모두 100˚ 이상(103.6~118.2) 갖는 것을 확인할 수 있었다. 상기 표 8의 결과는 높은 광 투과율 (90% 이상)을 갖는 본 발명 화합물의 금속패터닝에 적합한 이유를 보여주고 있다고 판단된다.Looking at Table 8, it can be seen that the contact angle of the C-1 material, which does not contain fluorine and has low light transmittance, is 83.2˚, whereas the contact angle of the compound of the present invention having a light transmittance of 90% or more is 100˚ or more ( 103.6~118.2) could be confirmed. The results of Table 8 are judged to show the reason why the compound of the present invention having high light transmittance (90% or more) is suitable for metal patterning.

일반적으로 접촉각(Wetting Angle or Contact Angle)과 젖음성(Wettability)을 통한 고체 표면에너지로 접착성은 설명이 된다. 일반적으로 접촉각이 클수록 젖음성(wettability)이 작아지고 이로 인해 접착성(Adhesiveness)이 작아지게 되면, 낮은 고체 표면에너지를 갖는다. 이는 액체의 표면장력이 크면 자기들끼리 잡아당기는 힘이 크게 되어 고체 표면에 퍼지기가 어렵게 되기 때문이다.In general, adhesion is explained by the solid surface energy through the Wetting Angle or Contact Angle and Wettability. In general, the larger the contact angle, the smaller the wettability and thus the smaller the adhesiveness, the lower the solid surface energy. This is because if the surface tension of the liquid is large, the force that attracts them to each other becomes large, making it difficult to spread on the surface of the solid.

상기 내용은 하기 Young's Equation 통해서도 확인할 수 있다.The above can also be confirmed through the following Young's Equation.

계면장력과 접촉각 사이에 다음과 같은 관계가 성립된다.The following relationship is established between the interfacial tension and the contact angle.

gLVcosθ = gSV-gSL (식 1)gLVcosθ = gSV-gSL (Equation 1)

gSL : 고체와 액체 사이의 계면장력, gSV 고체면과 액체 증기 사이의 계면 장력, gLV 액체와 액체 증기 사이의 계면 장력 gSL: interfacial tension between solid and liquid, gSV interfacial tension between solid surface and liquid vapor, gLV interfacial tension between liquid and liquid vapor

상기 식(1)을 Dupre에 의해 제시된 접착의 일(work of adhesion) Wa에 대한 식은 다음과 같이 표현된다.Equation (1) for the work of adhesion Wa presented by Dupre is expressed as follows.

Wa = gS + gLV-gSL = gS + gLV + (gLVcosθ-gSV) = (gS - gSV) + gLV(1+cosθ) (식 2)Wa = gS + gLV-gSL = gS + gLV + (gLVcosθ-gSV) = (gS - gSV) + gLV(1+cosθ) (Equation 2)

상기 식 (2)의 gS는 고체 자체의 표면장력이며, 일반적으로 작은 저 표면 에너지에서 gS와 gSV를 같다고 볼 수 있기 때문에 상기 식 2는 다음과 같이 정리된다.gS in Equation (2) is the surface tension of the solid itself, and since gS and gSV are generally considered to be the same at a small low surface energy, Equation 2 is summarized as follows.

Wa = gLV(1+cosθ) (식 3)Wa = gLV(1+cosθ) (Equation 3)

상기 식 3으로부터 접촉각이 0˚이면 cos0˚=1이므로 완전히 젖고, 반면에 접촉각이 180˚이면 cos180˚=-1이 되므로 전혀 젖지 않는다고 할 수 있다.From Equation 3 above, if the contact angle is 0˚, it is completely wet because cos0˚=1, whereas if the contact angle is 180˚, it is not wet at all because cos180˚=-1.

따라서 접촉각이 90˚에서 0˚로 갈수록 cosθ = 1에 가까워지게 되며 이로 인해 젖음성 및 접착성이 증가하게 되고, 반면에 90˚에서 180˚로 갈수록 cosθ = -1에 가까워지게 되면 이로 인해 젖음성 및 접착성이 감소하게 된다.Therefore, as the contact angle increases from 90˚ to 0˚, cosθ = 1 approaches, which increases the wettability and adhesion. sex will decrease.

본 발명 화합물을 금속패터닝 재료로 사용할 경우, 본 발명 화합물이 가지는 낮은 표면 에너지로 인해 금속(전극)의 접착성이 감소되며, 광 투과율이 높게 나오는 것으로 판단된다.When the compound of the present invention is used as a metal patterning material, it is determined that the adhesion of the metal (electrode) is reduced due to the low surface energy of the compound of the present invention, and the light transmittance is high.

이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명에 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100, 200, 300 : 유기전기소자 110 : 제1 전극
120 : 정공주입층 130 : 정공수송층
140 : 발광층 150 : 전자수송층
170 : 제2 전극 180 : 광효율 개선층
190 : 금속패터닝100, 200, 300: organic electric device 110: first electrode
120: hole injection layer 130: hole transport layer
140: light emitting layer 150: electron transport layer
170: second electrode 180: light efficiency improvement layer
190: metal patterning

Claims (12)

하기 화학식 (2-11)로 표시되는 금속(음극) 패터닝 소재용 재료로서, 분자 내 불소 함량이 30% 이상인 불소화 화합물
화학식 (2-11)
Figure 112021110737196-pat00233

{상기 화학식 2-11에서,
1) b는 0 내지 10의 정수이며,
2) x는 5 내지 15의 정수이고, y+z는 2x+1의 정수이며,
3) A'은 C6~C30의 아릴렌기;이고,
4) R4는 C6~C30의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C30의 헤테로고리기; C1~C20의 알킬기; 및 C1~C20의 알콕실기; 로 이루어진 군에서 선택되며, 또는 이웃한 기끼리 서로 결합하여 고리를 형성할 수 있고,
5) 여기서, 상기 아릴기, 아릴렌기, 헤테로고리기, 플루오렌일기, 알킬기, 알콕실기는 각각 중수소; 할로겐; C1~C20의 알킬기; C2~C20의 알켄일기; C6~C20의 아릴기; 중수소로 치환된 C6~C20의 아릴기; 및 C2~C20의 헤테로고리기; 로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있다.}
A material for a metal (cathode) patterning material represented by the following formula (2-11), a fluorinated compound having an intramolecular fluorine content of 30% or more
Formula (2-11)
Figure 112021110737196-pat00233

{In Formula 2-11,
1) b is an integer from 0 to 10,
2) x is an integer of 5 to 15, y+z is an integer of 2x+1,
3) A' is a C 6 ~ C 30 arylene group;
4) R 4 is a C 6 ~ C 30 aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C 2 ~ C 30 A heterocyclic group; C 1 ~ C 20 Alkyl group; And C 1 ~ C 20 An alkoxyl group; is selected from the group consisting of, or adjacent groups may combine with each other to form a ring,
5) wherein the aryl group, the arylene group, the heterocyclic group, the fluorenyl group, the alkyl group, and the alkoxyl group are each deuterium; halogen; C 1 ~ C 20 Alkyl group; C 2 ~ C 20 Alkenyl group; C 6 ~ C 20 Aryl group; C 6 ~ C 20 Aryl group substituted with deuterium; And C 2 ~ C 20 A heterocyclic group; It may be further substituted with one or more substituents selected from the group consisting of.}
 제1항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물은 하기 화합물 중 어느 하나인 것을 특징으로 하는 불소화 화합물
Figure 112021084385904-pat00234

Figure 112021084385904-pat00235

Figure 112021084385904-pat00236

Figure 112021084385904-pat00237

Figure 112021084385904-pat00238

Figure 112021084385904-pat00239

Figure 112021084385904-pat00240

Figure 112021084385904-pat00241

The fluorinated compound according to claim 1, wherein the compound represented by Formula (2-11) is any one of the following compounds.
Figure 112021084385904-pat00234

Figure 112021084385904-pat00235

Figure 112021084385904-pat00236

Figure 112021084385904-pat00237

Figure 112021084385904-pat00238

Figure 112021084385904-pat00239

Figure 112021084385904-pat00240

Figure 112021084385904-pat00241

 제1항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물의 불소 함량이 30% 내지 80%인 것을 특징으로 하는 불소화 화합물
The fluorinated compound according to claim 1, wherein the fluorine content of the compound represented by the formula (2-11) is 30% to 80%.
 제1항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물의 접촉각이 90° 내지 180°인 것을 특징으로 하는 불소화 화합물
The fluorinated compound according to claim 1, wherein the contact angle of the compound represented by the formula (2-11) is 90° to 180°.
 제1항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물의 접촉각이 90° 내지 150°인 것을 특징으로 하는 불소화 화합물
The fluorinated compound according to claim 1, wherein the contact angle of the compound represented by the formula (2-11) is 90° to 150°.
 양극, 양극 위에 적어도 1층 이상의 유기물층 및 상기 유기물층 위에 금속패터닝층을 포함하는 비-발광 영역과 상기 유기물층 위에 금속; 금속 전극; 또는 금속 및 금속 전극;을 포함하는 발광 영역을 갖는 유기전기소자에 있어서, 상기 금속패터닝층이 제1항에 따른 화학식 (2-11)로 표시되며 분자 내 불소 함량이 30% 이상인 불소 화합물인 것을 특징으로 하는 유기전기소자
a non-light emitting region comprising an anode, at least one organic material layer on the anode, and a metal patterning layer on the organic material layer, and a metal on the organic material layer; metal electrode; or a metal and a metal electrode; in an organic electric device having a light emitting region comprising: the metal patterning layer is a fluorine compound represented by Formula (2-11) according to claim 1 and having an intramolecular fluorine content of 30% or more Organic electric device characterized by
 제6항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물을 이용한 금속패터닝 시, 상기 금속이 Ag를 포함하는 것을 특징으로 하는 유기전기소자
The organic electric device according to claim 6, wherein the metal includes Ag when metal is patterned using the compound represented by Formula (2-11).
 제6항에 있어서, 상기 화학식 (2-11)로 표시되는 화합물을 이용한 금속패터닝 시, 상기 금속이 Ag 또는 Mg를 포함하는 것을 특징으로 하는 유기전기소자
The organic electric device according to claim 6, wherein the metal includes Ag or Mg when metal is patterned using the compound represented by Formula (2-11).
 제6항에 있어서, 상기 화학식 (2-11)로 표시되는 서로 상이한 화합물 2종 이상의 혼합물을 사용하는 유기전기소자
The organic electric device according to claim 6, wherein a mixture of two or more different compounds represented by the formula (2-11) is used.
 제6항의 유기전기소자를 포함하는 디스플레이 장치; 및 상기 디스플레이 장치를 구동하는 제어부;를 포함하는 전자장치
A display device comprising the organic electric device of claim 6; and a controller for driving the display device;
 제10항에 있어서, 상기 유기전기소자는 유기전기발광소자, 유기트랜지스터, 단색 조명용 소자 및 퀀텀닷 디스플레이용 소자로 이루어진 군에서 선택되는 것을 특징으로 하는 전자장치
11. The electronic device of claim 10, wherein the organic electric device is selected from the group consisting of an organic electroluminescent device, an organic transistor, a monochromatic lighting device, and a quantum dot display device.
 제1항의 상기 화학식 (2-11)에 따른 불소화 화합물 중 어느 하나 또는 구조가 서로 상이한 둘 이상의 화합물을 포함하는 금속패터닝용 조성물
A composition for metal patterning comprising any one of the fluorinated compounds according to Formula (2-11) of claim 1 or two or more compounds having different structures from each other
KR1020210095913A 2021-07-05 2021-07-21 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof KR102324529B1 (en)

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KR1020210095913A KR102324529B1 (en) 2021-07-05 2021-07-21 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
EP23157255.3A EP4234524A3 (en) 2021-07-05 2022-06-24 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
EP23157287.6A EP4219436A3 (en) 2021-07-05 2022-06-24 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
PCT/KR2022/009054 WO2023282511A1 (en) 2021-07-05 2022-06-24 Compound for organic electric element, organic electric element using same, and electronic device thereof
EP22773092.6A EP4137474A1 (en) 2021-07-05 2022-06-24 Compound for organic electric element, organic electric element using same, and electronic device thereof
JP2022559772A JP2023537800A (en) 2021-07-05 2022-06-24 COMPOUND FOR ORGANIC ELECTRONIC DEVICE, ORGANIC ELECTRONIC DEVICE AND ELECTRONIC DEVICE USING THE SAME
CN202310097924.7A CN116082119A (en) 2021-07-05 2022-06-24 Compound for organic electronic element, organic electronic element using the same, and electronic device using the same
CN202310139903.7A CN116162015B (en) 2021-07-05 2022-06-24 Compound for organic electronic element, organic electronic element using the same, and electronic device using the same
CN202280003311.6A CN115776979A (en) 2021-07-05 2022-06-24 Compound for organic electronic element, organic electronic element using the same, and electronic device thereof
JP2023019426A JP2023119583A (en) 2021-07-05 2023-02-10 Compound for organic electronic element, organic electronic element using the same, and electronic device therefor
JP2023019427A JP2023123379A (en) 2021-07-05 2023-02-10 Compound for organic electronic element, organic electronic element using the same, and electronic device thereof
US18/169,524 US11856841B2 (en) 2021-07-05 2023-02-15 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
US18/169,541 US11877508B2 (en) 2021-07-05 2023-02-15 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022203222A1 (en) * 2021-03-26 2022-09-29 주식회사 랩토 Material for forming nucleation-inhibition, and organic electroluminescent element comprising same
WO2023013697A1 (en) * 2021-08-03 2023-02-09 東ソー株式会社 Material for metal patterning, fluoro compound, thin film for metal patterning, organic electroluminescence device, electronic device, and method for forming metal pattern
WO2023153482A1 (en) * 2022-02-09 2023-08-17 東ソー株式会社 Material for metal patterning, heterocyclic compound, thin film for metal patterning, organic electroluminescent device, electronic device, and method for forming metal pattern
KR102577530B1 (en) 2022-11-17 2023-09-12 덕산네오룩스 주식회사 Organic electric element comprising a metal patterning layer and device therof
KR102608034B1 (en) 2022-07-06 2023-12-01 덕산네오룩스 주식회사 Organic electric element comprising a metal patterning layer and device therof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020103385A1 (en) * 2001-01-26 2002-08-01 Kwangju Institute Of Science And Technology 3,6-di(3',5'-bis(fluoroalkyl) phenyl) pyromellitic dianhydride and method for the preparation thereof
US20200062778A1 (en) * 2017-12-13 2020-02-27 Beijing Summer Sprout Technology Co., Ltd. Organic electroluminescent materials and devices
CN111377977A (en) * 2020-04-23 2020-07-07 安徽工业大学 4, 7-diaryl thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020103385A1 (en) * 2001-01-26 2002-08-01 Kwangju Institute Of Science And Technology 3,6-di(3',5'-bis(fluoroalkyl) phenyl) pyromellitic dianhydride and method for the preparation thereof
US20200062778A1 (en) * 2017-12-13 2020-02-27 Beijing Summer Sprout Technology Co., Ltd. Organic electroluminescent materials and devices
CN111377977A (en) * 2020-04-23 2020-07-07 安徽工业大学 4, 7-diaryl thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022203222A1 (en) * 2021-03-26 2022-09-29 주식회사 랩토 Material for forming nucleation-inhibition, and organic electroluminescent element comprising same
WO2023013697A1 (en) * 2021-08-03 2023-02-09 東ソー株式会社 Material for metal patterning, fluoro compound, thin film for metal patterning, organic electroluminescence device, electronic device, and method for forming metal pattern
WO2023153482A1 (en) * 2022-02-09 2023-08-17 東ソー株式会社 Material for metal patterning, heterocyclic compound, thin film for metal patterning, organic electroluminescent device, electronic device, and method for forming metal pattern
KR102608034B1 (en) 2022-07-06 2023-12-01 덕산네오룩스 주식회사 Organic electric element comprising a metal patterning layer and device therof
KR102577530B1 (en) 2022-11-17 2023-09-12 덕산네오룩스 주식회사 Organic electric element comprising a metal patterning layer and device therof

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