KR102460493B1 - Dibenzo five-membered ring compounds and organic electroluminescent device including the same - Google Patents
Dibenzo five-membered ring compounds and organic electroluminescent device including the same Download PDFInfo
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Abstract
유기 전계 발광 소자의 실질적인 광 효율과 시야각 향상에 기여하는 디벤조 5원고리 화합물를 제공한다.
본 발명에 따른 유기 전계 발광 소자는, 제1 전극; 제2 전극; 상기 제1 전극과 제2 전극 사이에 배치된 1층 이상의 유기물층; 및 캡핑층을 포함하고, 상기 유기물층 또는 캡핑층은 하기 화학식 1로 표시되는 디벤조 5원고리 화합물를 포함한다.
[화학식 1]
(상기 화학식 1에서 각 치환기들은 발명의 상세한 설명에서 정의한 바와 같다.)Provided is a dibenzo 5-membered ring compound that contributes to the improvement of practical light efficiency and viewing angle of an organic electroluminescent device.
An organic electroluminescent device according to the present invention, a first electrode; a second electrode; one or more organic material layers disposed between the first electrode and the second electrode; and a capping layer, wherein the organic material layer or the capping layer includes a dibenzo 5-membered ring compound represented by the following formula (1).
[Formula 1]
(Each substituent in Formula 1 is as defined in the detailed description of the invention.)
Description
본 발명은 디벤조 5원고리 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로, 디벤조 5원고리 화합물에 의해 캡핑층을 포함한 유기 전계 발광 소자가 저굴절률 특성을 갖도록 하는 것이다. The present invention relates to a dibenzo 5-membered ring compound and an organic electroluminescent device comprising the same, and to have a low refractive index characteristic of an organic electroluminescent device including a capping layer by the dibenzo 5-membered ring compound.
디스플레이 산업에서 자기 발광 현상을 이용한 디스플레이로서 OLED(유기발광다이오드, Organic Light Emitting Diodes)가 주목받고 있다. OLED (Organic Light Emitting Diodes) is attracting attention as a display using self-luminescence in the display industry.
OLED에 있어, 1963년 Pope 등에 의하여 안트라센(Anthracene) 방향족 탄화수소의 단결정을 이용한 캐리어 주입형 전계발광(Electroluminescence; EL)의 연구가 최초로 시도되었다. 이러한 연구로부터 유기물에서 전하주입, 재결합, 여기자 생성, 발광 등의 기초적 메커니즘과 전기발광 특성이 이해되고 연구되어왔다.In OLED, a study of carrier injection electroluminescence (EL) using a single crystal of an anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, basic mechanisms such as charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescence properties have been understood and studied.
특히 발광 효율을 높이기 위해 소자의 구조 변화 및 물질 개발 등 다양한 접근이 이루어지고 있다[Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364]. In particular, in order to increase the luminous efficiency, various approaches are being made, such as changing the structure of the device and developing materials [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].
OLED 디스플레이의 기본적 구조는 일반적으로 양극(Anode), 정공주입층(Hole Injection Layer, HIL), 정공수송층(Hole Transporting Layer, HTL), 발광층 (Emission Layer, EML), 전자수송층(Electron Transporting Layer, ETL), 그리고 음극(Cathode)의 다층 구조로 구성되며, 전자 유기 다층막이 두 전극 사이에 형성된 샌드위치 구조로 되어 있다. The basic structure of an OLED display is generally an anode, a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), and an electron transport layer (ETL). ), and a multilayer structure of a cathode, and has a sandwich structure in which an electron organic multilayer film is formed between two electrodes.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이들 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등을 포함할 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층으로 주입되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이러한 유기 발광 소자는 자발광, 고휘도, 고효율, 낮은 구동전압, 넓은 시야각, 높은 콘트라스트, 고속 응답성 등의 특성을 갖는 것으로 알려져 있다.In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. It lights up when it falls into a state. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.
유기 발광 소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하 수송 재료, 예컨대 정공 주입 재료, 정공 수송 재료, 전자 수송 재료, 전자 주입 재료 등으로 분류될 수 있다. A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, for example, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, and the like, according to functions.
발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료가 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도판트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도판트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도판트로 수송되어 효율이 높게 빛을 내는 것이다. 이 때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials required to realize a better natural color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and excellent luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used.
전술한 유기 발광 소자가 갖는 우수한 특징들을 충분히 발현하기 위해, 소자 내 유기물층을 이루는 물질, 예컨대 정공 주입 물질, 정공 수송 물질, 발광 물질, 전자 수송 물질, 전자 주입 물질 등이 개발되었고, 이로 인해 상용화된 제품들에 의해 유기 발광 소자의 성능을 인정받고 있다. In order to sufficiently express the excellent characteristics of the above-described organic light emitting device, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. The performance of the organic light emitting device is recognized by the products.
그러나 유기 발광 소자의 상용화가 이루어지고 시간이 지남에 따라 유기 발광 소자 자체의 발광 특성 이외에 다른 특성들의 필요성이 대두되고 있다. However, as the commercialization of the organic light emitting device is made and time passes, the need for other characteristics in addition to the light emitting characteristic of the organic light emitting device itself is emerging.
유기 발광 소자는 외부 광원에 노출되는 시간이 많은 경우가 대부분이므로 고에너지를 갖는 자외선에 노출되는 환경에 있게 된다. 이에 따라 유기 발광 소자를 구성하는 유기물이 지속적인 영향을 받게 되는 문제가 있다. 이러한 고에너지 광원에 노출을 막기 위해 자외선 흡수특성을 갖는 캡핑층을 유기 발광 소자에 적용함으로써 문제를 해결할 수 있다.Since the organic light emitting device is exposed to an external light source for a large amount of time, it is in an environment exposed to ultraviolet rays having high energy. Accordingly, there is a problem that the organic material constituting the organic light emitting device is continuously affected. In order to prevent exposure to such a high energy light source, the problem can be solved by applying a capping layer having ultraviolet absorption characteristics to the organic light emitting diode.
일반적으로 유기 발광 소자의 시야각 특성은 넓다고 알려져 있지만 광원 스펙트럼 관점에서는 시야각에 따라 상당한 편차가 발생하게 되며 이는 유기 발광 소자를 이루는 유리 기판, 유기물, 전극재료 등의 전체 굴절률과 유기 발광 소자의 발광파장에 따른 적절한 굴절률 사이에서 편차가 발생하는 것에 기인한다.In general, it is known that the viewing angle characteristics of an organic light emitting device are wide, but a significant deviation occurs depending on the viewing angle from the viewpoint of the light source spectrum. This is due to the occurrence of a deviation between the appropriate refractive indices.
일반적으로 청색의 필요한 굴절률 값이 크고 파장이 길어질수록 필요 굴절률의 값은 작아진다. 이에 따라 상기 언급된 자외선 흡수특성과 적정 굴절률을 동시에 만족하는 캡핑층을 이루는 재료의 개발이 필요하다.In general, the larger the required refractive index value of blue and the longer the wavelength, the smaller the required refractive index value. Accordingly, it is necessary to develop a material for forming a capping layer that simultaneously satisfies the above-mentioned ultraviolet absorption characteristics and an appropriate refractive index.
유기 발광 소자의 효율은 일반적으로 내부 발광 효율 (internal luminescent efficiency)과 외부 발광 효율로 나눌 수 있다. 내부 발광 효율은 광변환이 이루어지기 위해 유기층에서 엑시톤의 형성의 효율성에 관련된다. The efficiency of an organic light emitting diode can be generally divided into internal luminescent efficiency and external luminescent efficiency. The internal luminous efficiency is related to the efficiency of the formation of excitons in the organic layer for light conversion to take place.
외부 발광 효율은 유기층에서 생성된 광이 유기 발광 소자 외부로 방출되는 효율을 말한다.The external luminous efficiency refers to the efficiency at which light generated in the organic layer is emitted to the outside of the organic light emitting device.
전체적으로 효율을 제고하기 위해서는 내부 발광 효율뿐만 아니라 외부 발광 효율을 높여야 한다. 외부 발광 효율을 높이는 능력이 우수한 캡핑층(CPL, 광효율 개선층) 물질 개발이 요구되고 있다.In order to improve the overall efficiency, it is necessary to increase the external luminous efficiency as well as the internal luminous efficiency. There is a demand for the development of a capping layer (CPL, light efficiency improving layer) material having an excellent ability to increase external luminous efficiency.
한편, 공진 구조의 전면(Top) 소자 구조는 비공진 구조의 배면(Bottom) 소자 구조와 비교해보면 형성된 빛이 반사막인 애노드에 반사되어 캐소드쪽으로 나오므로 SPP(Surface Plasmon Polariton)에 의한 광학 에너지 손실이 크다. On the other hand, the top device structure of the resonant structure is compared with the bottom device structure of the non-resonant structure, the formed light is reflected by the anode, which is a reflective film, and comes out toward the cathode, so optical energy loss due to SPP (Surface Plasmon Polariton) is reduced. Big.
따라서, EL Spectrum의 모양과 효율향상을 위한 중요한 방법 중의 하나는 탑 캐소드(Top cathode)에 광효율 개선층(캡핑층)을 사용하는 방법이 있다. Therefore, one of the important methods for improving the shape and efficiency of the EL spectrum is a method of using a light efficiency improving layer (capping layer) for the top cathode.
일반적으로 SPP는 전자방출은 Al, Pt, Ag, Au의 4종의 금속이 주로 사용되며 금속 전극 표면에서 표면 프라즈몬이 발생한다. 예를 들어 음극을 Ag로 사용할 경우 방출되는 빛이 SPP에 의해 Quenching(Ag로 인한 빛에너지 손실)되어 효율이 감소된다.In general, in SPP, four types of metals are mainly used for electron emission: Al, Pt, Ag, and Au, and surface plasmons are generated on the surface of the metal electrode. For example, when the cathode is used as Ag, the emitted light is quenched by SPP (light energy loss due to Ag) and the efficiency is reduced.
반면, 캡핑층(광효율 개선층)을 사용할 경우에는 MgAg 전극과 유기재료 경계면에서 SPP가 발생하는데, 이때 상기 유기재료가 고굴절의 경우에(예를 들면 n>1.69 @620), 그 중 TE(Transverse electric) 편광된 빛은 소산파(evanescent wave)에 의해 수직 방향으로 캡핑층면(광효율 개선층면)에서 소멸되며, 음극과 캡핑층을 따라 이동하는 TM(Transverse magnetic) 편광된 빛은 표면 프라즈마 공진(Surface plasma resonance)에 의해 파장의 증폭현상이 일어나며, 이로 인해 피크(peak)의 세기(Intensity)가 증가하여 높은 효율과 효과적인 색순도 조절이 가능하게 된다. On the other hand, when the capping layer (light efficiency improvement layer) is used, SPP occurs at the interface between the MgAg electrode and the organic material. electric) Polarized light is dissipated on the capping layer surface (light efficiency improving layer surface) in the vertical direction by an evanescent wave, and TM (Transverse magnetic) polarized light moving along the cathode and the capping layer is a surface plasma resonance (Surface) The amplification of the wavelength occurs due to plasma resonance, which increases the intensity of the peak, enabling high efficiency and effective color purity control.
그러나 여전히 유기 발광 소자에서 효율과 색순도의 향상과 더불어 균형이 있게 다양한 특성의 향상에 필요한 재료와 구조의 개발이 요구되고 있다. However, it is still required to develop materials and structures necessary for improving various properties in a balanced manner along with improvement of efficiency and color purity in organic light emitting devices.
본 발명의 목적은, 발광 효율과 수명을 개선할 수 있고 동시에 시야각 특성을 개선할 수 있는, 유기 발광 소자용 캡핑층 재료를 제공하는 것이다.SUMMARY OF THE INVENTION It is an object of the present invention to provide a capping layer material for an organic light emitting device, which can improve luminous efficiency and lifespan and can improve viewing angle characteristics at the same time.
본 발명의 목적은 특히 유기 전계 발광 소자의 광 추출율을 개선하기 위하여 굴절률이 조절된 캡핑층을 포함하는 고효율 및 장수명의 유기 전계 발광 소자를 제공하는 것에 있다. It is an object of the present invention to provide an organic electroluminescent device with high efficiency and long life, including a capping layer having a controlled refractive index, in particular to improve light extraction rate of the organic electroluminescent device.
본 발명은 제1 전극; 상기 제1 전극 상에 배치된 유기물층; 상기 유기물층 상에 배치된 제2전극; 및 상기 제2 전극 상에 배치된 캡핑층을 포함하며, 상기 유기물층 또는 캡핑층은 하기 화학식 1로 표시되는 디벤조 5원고리 화합물를 포함하는 유기 전계 발광 소자를 제공한다.The present invention is a first electrode; an organic material layer disposed on the first electrode; a second electrode disposed on the organic material layer; and a capping layer disposed on the second electrode, wherein the organic material layer or the capping layer provides an organic electroluminescent device comprising a dibenzo 5-membered ring compound represented by the following Chemical Formula 1.
[화학식 1][Formula 1]
상기 화학식 1에 있어서, In Formula 1,
Z1는 O, S, CRR' 및 NR'' 중 어느 하나이고(단, R 및 R'는 각각 독립적으로 메틸기, 페닐기 또는 스파이로플루오렌이며, R''은 페닐기임),Z 1 is any one of O, S, CRR' and NR'' (provided that R and R' are each independently a methyl group, a phenyl group, or spirofluorene, and R'' is a phenyl group),
L1 및 L2는 각각 독립적으로 페닐렌기 또는 피리딜렌기이며,L 1 and L 2 are each independently a phenylene group or a pyridylene group,
m 및 n은 각각 독립적으로 0 내지 3의 정수이고,m and n are each independently an integer of 0 to 3,
Ar1 및 Ar2는 각각 독립적으로 페닐기; F, CF3, 또는 Si(CH3)3로 치환된 페닐기; 피리딜기; 나프틸기; 퀴놀린기; 이소퀴놀린기; 벤조옥사졸기; 벤조티아졸기; 및 벤조이미다졸기; 중에서 선택되는 어느 하나이다.Ar 1 and Ar 2 are each independently a phenyl group; F, CF 3 , or a phenyl group substituted with Si(CH 3 ) 3 ; pyridyl group; naphthyl group; quinoline group; isoquinoline group; benzoxazole group; benzothiazole group; and a benzimidazole group; any one selected from
본 명세서에 기재된 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있다. The compound described herein may be used as a material for an organic material layer of an organic light emitting device.
본 명세서에 기재된 화합물을 저굴절 캡핑층(광효율 개선층)으로 이용한 유기 발광 소자에서 발광효율 향상, 발광 스펙트럼 반치폭 감소에 따른 색순도를 현저히 개선시킬 수 있다. In an organic light emitting device using the compound described in the present specification as a low refractive index capping layer (light efficiency improving layer), it is possible to significantly improve luminous efficiency and color purity according to a reduction in emission spectrum half width.
본 발명에 따른 유기 전계 발광 소자는 MgAg 전극 상에 고굴절의 유기재료 박막과 저굴절의 박막을 연속해서 도입함으로써 도파로 공진 현상으로 인해 공기 중으로 추출되는 빛의 시야각과 광효율 향상이 이루어질 수 있다.The organic electroluminescent device according to the present invention continuously introduces a thin film of a high refractive organic material and a thin film of low refractive index on an MgAg electrode, thereby improving the viewing angle and optical efficiency of light extracted into the air due to the waveguide resonance phenomenon.
도 1은 본 발명의 일 실시예에 따른 기판(100) 위에 제1 전극(110), 정공주입층(210), 정공수송층(215), 발광층(220), 전자수송층(230), 전자주입층(235), 제2 전극(120) 및 캡핑층(300)이 순차적으로 적층된 유기 발광 소자의 예를 도시한 것이다.
도 2는 본 발명의 일 실시예에 따른 디벤조 5원고리 화합물를 이용할 경우에 나타나는 빛의 굴절과 흡수 특성의 그래프이다.1 illustrates a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, and an electron injection layer on a substrate 100 according to an embodiment of the present invention. An example of an organic light emitting device in which 235 , the second electrode 120 , and the capping layer 300 are sequentially stacked is shown.
Figure 2 is a graph of the refraction and absorption characteristics of light appearing when using a dibenzo five-membered ring compound according to an embodiment of the present invention.
이하 본 발명에 대하여 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 본문에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.
각 도면을 설명하면서 유사한 참조부호를 유사한 구성요소에 대해 사용하였다. 첨부된 도면에 있어서, 구조물들의 치수는 본 발명의 명확성을 위하여 실제보다 확대하여 도시한 것이다. 제1, 제2 등의 용어는 다양한 구성요소들을 설명하는데 사용될 수 있지만, 상기 구성요소들은 상기 용어들에 의해 한정되어서는 안 된다. 상기 용어들은 하나의 구성요소를 다른 구성요소로부터 구별하는 목적으로만 사용된다. 예를 들어, 본 발명의 권리 범위를 벗어나지 않으면서 제1 구성요소는 제2 구성요소로 명명될 수 있고, 유사하게 제2 구성요소도 제1 구성요소로 명명될 수 있다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.
본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 또한, 층, 막, 영역, 판 등의 부분이 다른 부분 "상에" 있다고 할 경우, 이는 다른 부분 "바로 위에" 있는 경우뿐 만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case where the other part is “directly on” but also the case where there is another part in between.
본 명세서에서, “치환 또는 비치환된”은 중수소 원자, 할로겐 원자, 시아노기, 니트로기, 아미노기, 히드록시기, 실릴기, 붕소기, 포스핀 옥사이드기, 포스핀 설파이드기, 알킬기, 알콕시기, 알케닐기, 아릴기, 헤테로 아릴기 및 헤테로 고리기로 이루어진 군에서 선택되는 1개 이상의 치환기로 치환 또는 비치환된 것을 의미할 수 있다. 또한, 상기 예시된 치환기 각각은 치환 또는 비치환된 것일 수 있다. 예를 들어, 바이페닐기는 아릴기로 해석될 수도 있고, 페닐기로 치환된 페닐기로 해석될 수도 있다.As used herein, "substituted or unsubstituted" is a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxy group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, an alke group It may mean unsubstituted or substituted with one or more substituents selected from the group consisting of a nyl group, an aryl group, a heteroaryl group, and a heterocyclic group. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or a phenyl group substituted with a phenyl group.
본 명세서에서, 할로겐 원자의 예로는 불소 원자, 염소 원자, 브롬 원자 또는 요오드 원자가 있다.In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
본 명세서에서, 알킬기는 직쇄, 분지쇄 또는 고리형일 수 있다. 알킬기의 탄소수는 1 이상 50 이하, 1 이상 30 이하, 1 이상 20 이하, 1 이상 10 이하 또는 1 이상 6 이하이다. 알킬기의 예로는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, s-부틸기, t-부틸기, i-부틸기, 2- 에틸부틸기, 3, 3-디메틸부틸기, n-펜틸기, i-펜틸기, 네오펜틸기, t-펜틸기, 시클로펜틸기, 1-메틸펜틸기, 3-메틸펜틸기, 2-에틸펜틸기, 4-메틸-2-펜틸기, n-헥실기, 1-메틸헥실기, 2-에틸헥실기, 2-부틸헥실기, 시클로헥실기, 4-메틸시클로헥실기, 4-t-부틸시클로헥실기, n-헵틸기, 1-메틸헵틸기, 2,2-디메틸헵틸기, 2-에틸헵틸기, 2-부틸헵틸기, n-옥틸기, t-옥틸기, 2-에틸옥틸기, 2-부틸옥틸기, 2-헥실옥틸기, 3,7-디메틸옥틸기, 시클로옥틸기, n-노닐기, n-데실기, 아다만틸기, 2-에틸데실기, 2-부틸데실기, 2-헥실데실기, 2-옥틸데실기, n-운데실기, n-도데실기, 2-에틸도데실기, 2-부틸도데실기, 2-헥실도데실기, 2-옥틸도데실기, n-트리데실기, n-테트라데실기, n-펜타데실기, n-헥사데실기, 2-에틸헥사데실기, 2-부틸헥사데실기, 2-헥실헥사데실기, 2-옥틸헥사데실기, n-헵타데실기, n-옥타데실기, n-노나데실기, n-이코실기, 2-에틸이코실기, 2-부틸이코실기, 2-헥실이코실기, 2-옥틸이코실기, n-헨이코실기, n-도코실기, n-트리코실기, n-테트라코실기, n-펜타코실기, n-헥사코실기, n-헵타코실기, n-옥타코실기, n-노나코실기, 및 n-트리아콘틸기 등을 들 수 있지만, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear, branched or cyclic. Carbon number of an alkyl group is 1 or more and 50 or less, 1 or more and 30 or less, 1 or more and 20 or less, 1 or more and 10 or less, or 1 or more and 6 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3, 3-dimethylbutyl group , n-pentyl group, i-pentyl group, neopentyl group, t-pentyl group, cyclopentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group , n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, n-heptyl group, 1 -Methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyl group Siloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-ox Tyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group , n-nonadecyl group, n-icosyl group, 2-ethyl icosyl group, 2-butyl icosyl group, 2-hexyl icosyl group, 2-octyl icosyl group, n-henicosyl group, n-docosyl group, n-tricho Sil group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, etc. are mentioned, It is not limited to these.
본 명세서에서, 탄화수소 고리기는 지방족 탄화수소 고리로부터 유도된 임의의 작용기 또는 치환기를 의미한다. 탄화수소 고리기는 고리 형성 탄소수 5 이상 20 이하의 포화 탄화수소 고리기일 수 있다.As used herein, the hydrocarbon ring group means any functional group or substituent derived from an aliphatic hydrocarbon ring. The hydrocarbon ring group may be a saturated hydrocarbon ring group having 5 to 20 ring carbon atoms.
본 명세서에서, 아릴기는 방향족 탄화수소 고리로부터 유도된 임의의 작용기 또는 치환기를 의미한다. 아릴기는 단환식 아릴기 또는 다환식 아릴기일 수 있다. 아릴기의 고리 형성 탄소수는 6 이상 30 이하, 6 이상 20 이하, 또는 6 이상 15 이하일 수 있다. 아릴기의 예로는 페닐기, 나프틸기, 플루오레닐기, 안트라세닐기, 페난트릴기, 바이페닐기, 터페닐기, 쿼터페닐기, 퀸크페닐기, 섹시페닐기, 트리페닐에닐기, 피레닐기, 페릴렌일기, 나프타세닐기, 파이레닐기, 벤조 플루오란테닐기, 크리세닐기 등을 예시할 수 있지만, 이들에 한정되지 않는다.As used herein, the aryl group means any functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of ring carbon atoms of the aryl group may be 6 or more and 30 or less, 6 or more and 20 or less, or 6 or more and 15 or less. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a quinkphenyl group, a sexyphenyl group, a triphenylenyl group, a pyrenyl group, a peryleneyl group, a naphtha group Although a cenyl group, a pyrenyl group, a benzo fluoranthenyl group, a chrysenyl group, etc. can be illustrated, it is not limited to these.
본 명세서에서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수도 있다. In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
본 명세서에서, 헤테로아릴기는 이종 원소로 O, N, P, Si 및 S 중 1개 이상을 포함하는 헤테로아릴기일 수 있다. N 및 S 원자는 경우에 따라 산화될 수 있고, N 원자(들)은 경우에 따라 4차화될 수 있다. 헤테로아릴기의 고리 형성 탄소수는 2 이상 30 이하 또는 2 이상 20 이하이다. 헤테로아릴기는 단환식 헤테로아릴기 또는 다환식 헤테로아릴기일 수 있다. 다환식 헤테로아릴기는 예를 들어, 2환 또는 3환 구조를 갖는 것일 수 있다. In the present specification, the heteroaryl group may be a heteroaryl group including at least one of O, N, P, Si and S as a heterogeneous element. The N and S atoms may optionally be oxidized and the N atom(s) may optionally be quaternized. The number of ring carbon atoms in the heteroaryl group is 2 or more and 30 or less, or 2 or more and 20 or less. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group may have, for example, a bicyclic or tricyclic structure.
헤테로아릴기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 피라졸릴기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딘기, 비피리딘기, 피리미딘기, 트리아진기, 테트라진기, 트리아졸기, 테트라졸기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀린기, 퀴나졸린기, 퀴녹살린기, 페녹사진기, 프탈라진기, 피리도 피리미딘기, 피리도 피라지노 피라진기, 이소퀴놀린기, 신놀리기, 인돌기, 이소인돌기, 인다졸기, 카바졸기, N-아릴카바졸기, N-헤테로아릴카바졸기, N-알킬카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 벤조티오펜기, 벤조이소티아졸릴, 벤조이속사졸릴, 디벤조티오펜기, 티에노티오펜기, 벤조퓨란기, 페난트롤린기, 페난트리딘기, 티아졸기, 이소옥사졸기, 옥사디아졸기, 티아디아졸기, 이소티아졸기, 이속사졸기, 페노티아진기, 벤조디옥솔기, 디벤조실롤기 및 디벤조퓨란기, 이소벤조퓨란기 등이 있으나, 이들에 한정되지 않는다. 또한, 상기 단환식 헤테로 아릴기 또는 다환식 헤테로 아릴기에 상응하는 N-옥사이드 아릴기, 예를 들어, 피리딜 N-옥사이드기, 퀴놀릴 N-옥사이드기 등의 4차 염 등이 있으나, 이들에 한정되지 않는다. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a pyrazolyl group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group , tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyridopyrimidine group, pyridopyrazino group Pyrazine group, isoquinoline group, cinnol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzoxazole group, benzoimidazole group , benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl, benzoisoxazolyl, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , a thiazole group, an isoxazole group, an oxadiazole group, a thiadiazole group, an isothiazole group, an isoxazole group, a phenothiazine group, a benzodioxol group, a dibenzosilol group and a dibenzofuran group, an isobenzofuran group, etc. It is not limited to these. In addition, there are N-oxide aryl groups corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, for example, quaternary salts such as pyridyl N-oxide group, quinolyl N-oxide group, etc., but these not limited
본 명세서에서, 실릴기는 알킬 실릴기 및 아릴 실릴기를 포함한다. 실릴기의 예로는 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나, 이들에 한정되지 않는다.In the present specification, the silyl group includes an alkyl silyl group and an aryl silyl group. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. not limited
본 명세서에서, 붕소기는 알킬 붕소기 및 아릴 붕소기를 포함한다. 붕소기의 예로는 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 디페닐붕소기, 페닐붕소기 등이 있으나, 이들에 한정되지 않는다.In the present specification, the boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group include, but are not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a diphenylboron group, and a phenylboron group.
본 명세서에서, 알케닐기는 직쇄 또는 분지쇄일 수 있다. 탄소수는 특별히 한정되지 않으나, 2 이상 30 이하, 2 이상 20 이하 또는 2 이상 10 이하이다. 알케닐기의 예로는 비닐기, 1-부테닐기, 1-펜테닐기, 1,3-부타디에닐 아릴기, 스티레닐기, 스티릴비닐기 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched. Although carbon number is not specifically limited, 2 or more and 30 or less, 2 or more and 20 or less, or 2 or more and 10 or less. Examples of the alkenyl group include, but are not limited to, a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, a styryl vinyl group, and the like.
본 명세서에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기, 또는 단환식아릴기와 다환식 아릴기를 동시에 포함할 수 있다. In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, and may include a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.
아릴 아민기의 구체적인 예로는 페닐아민기, 나프틸아민기, 비페닐아민기, 안트라세닐아민기, 3-메틸-페닐아민기, 4-메틸-나프틸아민기, 2-메틸-비페닐아민기, 9-메틸-안트라세닐아민기, 디페닐 아민기, 페닐 나프틸아민기, 디톨릴 아민기, 페닐 톨릴 아민기, 카바졸 및 트리페닐 아민기 등이 있으나, 이에 한정되는 것은 아니다.Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenylamine group. group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, but is not limited thereto.
본 명세서에 있어서, 헤테로알릴아민기의 예로는 치환 또는 비치환된 모노헤테로아릴아민기, 치환 또는 비치환된 디헤테로아릴아민기, 또는 치환 또는 비치환된 트리헤테로아릴아민기가 있다. 상기 헤테로아릴아민기 중의 헤테로아릴기는 단환식 헤테로 고리기일 수 있고, 다환식 헤테로 고리기일 수 있다. 상기 2이상의 헤테로 고리기를 포함하는 헤테로아릴아민기는 단환식 헤테로 고리기, 다환식 헤테로 고리기, 또는 단환식 헤테로 고리기와 다환식 헤테로 고리기를 동시에 포함할 수 있다. In the present specification, examples of the heteroallylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group including two or more heterocyclic groups may include a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.
본 명세서에 있어서, 아릴헤테로아릴아민기는 아릴기 및 헤테로 고리기로 치환된 아민기를 의미한다.In the present specification, the aryl heteroarylamine group refers to an amine group substituted with an aryl group and a heterocyclic group.
본 명세서에서, “인접하는 기”는 해당 치환기가 치환된 원자와 직접 연결된 원자에 치환된 치환기, 해당 치환기가 치환된 원자에 치환된 다른 치환기 또는 해당 치환기와 입체구조적으로 가장 인접한 치환기를 의미할 수 있다. 예컨대, 1,2-디메틸벤젠(1,2-dimethylbenzene)에서 2개의 메틸기는 서로 “인접하는 기”로 해석될 수 있고, 1,1-디에틸시클로펜테인(1,1-diethylcyclopentene)에서 2개의 에틸기는 서로 “인접하는 기”로 해석될 수 있다.As used herein, "adjacent group" may mean a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, another substituent substituted on the atom in which the substituent is substituted, or a substituent most sterically adjacent to the substituent. have. For example, in 1,2-dimethylbenzene, two methyl groups can be interpreted as “adjacent groups” to each other, and in 1,1-diethylcyclopentene, 2 The two ethyl groups can be interpreted as “adjacent groups” to each other.
이하에서는 상기 유기물층 및/또는 캡핑층에 사용되는 디벤조 5원고리 화합물에 대해 설명한다. Hereinafter, the dibenzo 5-membered ring compound used in the organic material layer and/or the capping layer will be described.
본 발명의 일 실시예에 따른 디벤조 5원고리 화합물은 하기 화학식 1로 표시된다.The dibenzo 5-membered ring compound according to an embodiment of the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에 있어서, In Formula 1,
Z1는 O, S, CRR' 및 NR'' 중 어느 하나이고(단, R 및 R'는 각각 독립적으로 메틸기, 페닐기 또는 스파이로플루오렌이며, R''은 페닐기임),Z 1 is any one of O, S, CRR' and NR'' (provided that R and R' are each independently a methyl group, a phenyl group, or spirofluorene, and R'' is a phenyl group),
L1 및 L2는 각각 독립적으로 페닐렌기 또는 피리딜렌기이며,L 1 and L 2 are each independently a phenylene group or a pyridylene group,
m 및 n은 각각 독립적으로 0 내지 3의 정수이고,m and n are each independently an integer of 0 to 3,
Ar1 및 Ar2는 각각 독립적으로 페닐기; F, CF3, 또는 Si(CH3)3로 치환된 페닐기; 피리딜기; 나프틸기; 퀴놀린기; 이소퀴놀린기; 벤조옥사졸기; 벤조티아졸기; 및 벤조이미다졸기 중에서 선택되는 어느 하나이다. Ar 1 and Ar 2 are each independently a phenyl group; F, CF 3 , or a phenyl group substituted with Si(CH 3 ) 3 ; pyridyl group; naphthyl group; quinoline group; isoquinoline group; benzoxazole group; benzothiazole group; and any one selected from a benzimidazole group.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
[화학식 9][Formula 9]
[화학식 10][Formula 10]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[화학식 17][Formula 17]
[화학식 18][Formula 18]
상기 화학식 2 내지 화학식 18에 있어서,In Formulas 2 to 18,
R1 내지 R5는 각각 독립적으로 H; F; CF3 또는 Si(CH3)3 이고,R 1 to R 5 are each independently H; F; CF 3 or Si(CH 3 ) 3 and
Z1, L1, L2, m, n 및 Ar1은 화학식 1에서 정의된 것과 같다.Z 1 , L 1 , L 2 , m, n, and Ar 1 are as defined in Formula 1.
본 발명의 일 실시예에 있어서, 상기 화학식 1로 표시되는 디벤조 5원고리 화합물는 하기 화학식 19 내지 화학식 30으로 표시된 화합물들 중에서 선택된 어느 하나일 수 있고, 하기 화합물들은 추가로 치환될 수 있다. In an embodiment of the present invention, the dibenzo 5-membered ring compound represented by Formula 1 may be any one selected from compounds represented by Formulas 19 to 30, and the following compounds may be further substituted.
[화학식 19][Formula 19]
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
[화학식 23][Formula 23]
[화학식 24][Formula 24]
[화학식 25][Formula 25]
[화학식 26][Formula 26]
[화학식 27][Formula 27]
[화학식 28][Formula 28]
[화학식 29][Formula 29]
[화학식 30][Formula 30]
이하 도 1 및 2를 참조하여 본 발명의 실시예를 설명한다.Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 and 2 .
도 1은 본 발명의 일 실시예에 따른 유기 발광 소자를 개략적으로 나타낸 단면도이다. 도 1을 참조하면, 일 실시예에 따른 유기 발광 소자는 기판(100)위에 순차적으로 적층된 제1 전극(110), 정공주입층(210), 정공수송층(215), 발광층(220), 전자수송층(230), 전자주입층(235), 제2 전극(120), 캡핑층(300)을 포함할 수 있다.1 is a cross-sectional view schematically illustrating an organic light emitting diode according to an embodiment of the present invention. Referring to FIG. 1 , in an organic light emitting diode according to an exemplary embodiment, a first electrode 110 , a hole injection layer 210 , a hole transport layer 215 , a light emitting layer 220 , and electrons are sequentially stacked on a substrate 100 . It may include a transport layer 230 , an electron injection layer 235 , a second electrode 120 , and a capping layer 300 .
제1 전극(110)과 제2 전극(120)은 서로 마주하고 배치되며, 제1 전극(110)과 제2 전극(120) 사이에는 유기물층(200)이 배치될 수 있다. 유기물층(200)은 정공주입층(210), 정공수송층(215), 발광층(220), 전자수송층(230), 전자주입층(235)를 포함할 수 있다.The first electrode 110 and the second electrode 120 are disposed to face each other, and the organic material layer 200 may be disposed between the first electrode 110 and the second electrode 120 . The organic material layer 200 may include a hole injection layer 210 , a hole transport layer 215 , a light emitting layer 220 , an electron transport layer 230 , and an electron injection layer 235 .
한편, 본 발명에서 제시되는 캡핑층(300)은 제2 전극(120) 위에 증착되는 기능층으로서, 본 발명의 화학식 1에 따른 유기물을 포함한다.Meanwhile, the capping layer 300 presented in the present invention is a functional layer deposited on the second electrode 120 and includes an organic material according to Chemical Formula 1 of the present invention.
도 1에 도시된 일 실시예의 유기 발광 소자에서 제1 전극(110)은 도전성을 갖는다. 제1 전극(110)은 금속 합금 또는 도전성 화합물로 형성될 수 있다. 제1 전극(110)은 일반적으로 양극(anode)이지만 전극으로의 기능은 제한하지 않는다.In the organic light emitting diode of the exemplary embodiment shown in FIG. 1 , the first electrode 110 has conductivity. The first electrode 110 may be formed of a metal alloy or a conductive compound. The first electrode 110 is generally an anode, but the function as an electrode is not limited.
제1 전극(110)은 기판(100) 상부에 전극 물질을 증착법, 전자빔 증발 또는 스퍼터링법 등을 이용하여 형성할 수 있다. 제1 전극(110)의 재료는 유기 발광 소자 내부로 정공의 주입이 용이하도록 높은 일함수를 갖는 물질 중에서 선택될 수 있다. The first electrode 110 may be formed by depositing an electrode material on the substrate 100 using a deposition method, electron beam evaporation, or sputtering. The material of the first electrode 110 may be selected from materials having a high work function to facilitate injection of holes into the organic light emitting device.
본 발명에서 제안되는 캡핑층(300)은 유기 발광 소자의 발광방향이 전면발광일 경우에 적용되며 따라서 제1 전극(110)은 반사형 전극을 사용한다. 이들의 재료로는 산화물이 아닌 Mg(마그네슘), Al(알루미늄), Al-Li(알루미늄-리튬), Ca(칼슘), Mg-In(마그네슘-인듐), Mg-Ag(마그네슘-은)과 같은 금속을 사용하여 제작할 수도 있다. 최근에 와서는 CNT(탄소나노튜브), Graphene(그래핀) 등 탄소기판 유연 전극 재료가 사용될 수도 있다. The capping layer 300 proposed in the present invention is applied when the emission direction of the organic light emitting device is top emission, and therefore, the first electrode 110 uses a reflective electrode. These materials include Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), Mg-Ag (magnesium-silver) and It can also be manufactured using the same metal. In recent years, carbon substrate flexible electrode materials such as CNT (carbon nanotube) and graphene (graphene) may be used.
상기 유기물층(200)은 복수의 층으로 형성될 수 있다. 상기 유기물층(200)이 복수의 층인 경우, 유기물층(200)은 제1 전극(110) 상에 배치된 정공수송영역(210~215), 상기 정공 수송영역 상에 배치된 발광층(220), 상기 발광층(220) 상에 배치된 전자 수송 영역(230~235)를 포함할 수 있다.The organic material layer 200 may be formed of a plurality of layers. When the organic material layer 200 is a plurality of layers, the organic material layer 200 includes the hole transport regions 210 to 215 disposed on the first electrode 110 , the light emitting layer 220 disposed on the hole transport region, and the light emitting layer. It may include electron transport regions 230 to 235 disposed on 220 .
일 실시예의 상기 캡핑층(300)은 후술하는 화학식 1로 표시되는 유기화합물을 포함한다. The capping layer 300 of an embodiment includes an organic compound represented by Chemical Formula 1, which will be described later.
정공 수송 영역(210~215)은 제1 전극(110) 상에 제공된다. 정공 수송 영역(210~215)은 정공 주입층(210), 정공 수송층(215), 정공 버퍼층 및 전자 저지층(EBL) 중 적어도 하나를 포함할 수 있고, 유기 발광 소자 내로 원활한 정공 주입과 수송의 역할을 맡고 있으며 일반적으로 정공이동도가 전자이동도 보다 빠르기 때문에 전자 수송영역보다 두꺼운 두께를 갖는다.The hole transport regions 210 to 215 are provided on the first electrode 110 . The hole transport regions 210 to 215 may include at least one of a hole injection layer 210 , a hole transport layer 215 , a hole buffer layer, and an electron blocking layer (EBL). In general, since hole mobility is faster than electron mobility, it has a thicker thickness than the electron transport region.
정공 수송 영역(210~215)은 단일 물질로 이루어진 단일층, 복수의 서로 다른 물질로 이루어진 단일층 또는 복수의 서로 다른 물질로 이루어진 복수의 층을 갖는 다층 구조를 가질 수 있다. The hole transport regions 210 to 215 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.
예를 들어, 정공 수송 영역(210~215)은 정공 주입층(210) 또는 정공 수송층(215)의 단일층의 구조를 가질 수도 있고, 정공 주입 물질과 정공 수송 물질로 이루어진 단일층 구조를 가질 수도 있다. 또한, 정공 수송 영역(210~215)은, 복수의 서로 다른 물질로 이루어진 단일층의 구조를 갖거나, 제1 전극(110)으로부터 차례로 적층된 정공 주입층(210)/정공 수송층(215), 정공 주입층(210)/정공 수송층(215)/정공 버퍼층, 정공 주입층(210)/정공 버퍼층, 정공 수송층(215)/정공 버퍼층, 또는 정공 주입층(210)/정공 수송층(215)/전자 저지층(EBL)의 구조를 가질 수 있으나, 실시예가 이에 한정되는 것은 아니다. For example, the hole transport regions 210 to 215 may have a single-layer structure of the hole injection layer 210 or the hole transport layer 215 , or may have a single-layer structure including a hole injection material and a hole transport material. have. In addition, the hole transport regions 210 to 215 have a single layer structure made of a plurality of different materials, or a hole injection layer 210/hole transport layer 215 stacked sequentially from the first electrode 110 , Hole injection layer 210 / hole transport layer 215 / hole buffer layer, hole injection layer 210 / hole buffer layer, hole transport layer 215 / hole buffer layer, or hole injection layer 210 / hole transport layer 215 / electron It may have a structure of the blocking layer EBL, but the embodiment is not limited thereto.
상기 정공 수송 영역(210~215) 중 정공 주입층(210)은 양극 위로 진공증착법, 스핀코팅법, 캐스트법, LB법 등 다양한 방법으로 형성될 수 있다. 진공 증착법에 의하여 정공 주입층(210)을 형성하는 경우, 그 증착 조건은 정공주입층(210) 재료로 사용하는 화합물, 목적으로 하는 정공주입층(210)의 구조 및 열적 특성 등에 따라 100 내지 500℃에서 증착 속도를 1Å/s 전 후로 하여 자유롭게 조절할 수 있으며, 특정한 조건에 한정되는 것은 아니다. 스핀 코팅법에 의하여 정공주입층(210)을 형성하는 경우 코팅 조건은 정공주입층(210) 재료로 사용하는 화합물과 계면으로 형성되는 층들 간의 특성에 따라 상이 하지만 고른 막형성을 위해 코팅속도, 코팅 후 용매 제거를 위한 열처리 등이 필요하다.The hole injection layer 210 of the hole transport regions 210 to 215 may be formed on the anode by various methods, such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. When the hole injection layer 210 is formed by vacuum deposition, the deposition conditions are 100 to 500 depending on the compound used as the material for the hole injection layer 210, the structure and thermal characteristics of the hole injection layer 210, etc. The deposition rate at ℃ can be freely controlled by before and after 1 Å/s, and is not limited to specific conditions. In the case of forming the hole injection layer 210 by the spin coating method, the coating conditions are different depending on the characteristics between the compound used as the hole injection layer 210 material and the layers formed as the interface, but for an even film formation, the coating speed, coating After that, heat treatment to remove the solvent is required.
상기 정공 수송 영역(210~215)은, 예를 들면, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA(4,4',4"-트리스(N-카바졸일)트리페닐아민(4,4',4"-tris(Ncarbazolyl) triphenylamine)), Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid:폴리아닐린/도데실벤젠술폰산), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene) /Poly(4-styrene sulfonate):폴리(3,4-에틸렌디옥시티오펜) /폴리(4-스티렌술포네이트)), Pani/CSA (Polyaniline/Camphor sulfonicacid : 폴리아닐린/캠퍼술폰산), PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate):폴리아닐린)/폴리(4-스티렌술포네이트)) 등을 포함 할 수 있다.The hole transport regions 210 to 215 are, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA. (4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4"-tris(Ncarbazolyl)triphenylamine)), Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: polyaniline/dodecylbenzene sulfonic acid), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene) /Poly(4-styrene sulfonate):poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)), Pani/CSA ( Polyaniline/Camphor sulfonicacid: polyaniline/camphor sulfonic acid), PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate):polyaniline)/poly(4-styrenesulfonate)), and the like.
상기 정공 수송 영역(210~215)의 두께는 약 100 내지 약 10,000Å으로 형성될 수 있으며, 각 정공 수송영역(210~215)의 해당 유기물 층들은 같은 두께로 한정되는 것은 아니다. 예를 들면, 정공 주입층(210)의 두께가 50Å이면 정공 수송층(215)의 두께는 1000Å, 전자 저지층의 두께는 500Å을 형성할 수 있다. 정공 수송영역(210~215)의 두께 조건은 유기 발광 소자의 구동전압 상승이 커지지 않는 범위 내에서 효율과 수명을 만족하는 정도로 정할 수 있다. 상기 유기막(200)은 정공주입층(210), 정공수송층(215), 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층, 버퍼층, 전자저지층, 발광층(220), 정공저지층, 전자수송층(230), 전자주입층(235), 및 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 1층 이상을 포함할 수 있다.The thickness of the hole transport regions 210 to 215 may be about 100 to about 10,000 Å, and the corresponding organic material layers in each of the hole transport regions 210 to 215 are not limited to the same thickness. For example, if the hole injection layer 210 has a thickness of 50 Å, the hole transport layer 215 may have a thickness of 1000 Å and the electron blocking layer may have a thickness of 500 Å. The thickness condition of the hole transport regions 210 to 215 may be determined to a degree that satisfies the efficiency and lifespan within a range in which an increase in the driving voltage of the organic light emitting diode does not increase. The organic layer 200 includes a hole injection layer 210, a hole transport layer 215, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer 220, a hole blocking layer, an electron transport layer. 230 , the electron injection layer 235 , and one or more layers selected from the group consisting of a functional layer having an electron transport function and an electron injection function at the same time.
정공 수송 영역(210~215)은 발광층(220)과 마찬가지로 특성 향상을 위해 도핑을 사용할 수 있으며 이러한 정공 수송 영역(210~215) 내로 전하-생성 물질의 도핑은 유기 발광 소자의 전기적 특성을 향상시킬 수 있다.The hole transport regions 210 to 215 may use doping to improve properties like the light emitting layer 220 , and doping of a charge-generating material into the hole transport regions 210 to 215 may improve the electrical properties of the organic light emitting device. can
전하-생성 물질은 일반적으로 HOMO와 LUMO가 굉장히 낮은 물질로 이루어지며 예를 들어, 전하-생성 물질의 LUMO는 정공수송층(215) 물질의 HOMO와 유사한 값을 갖는다. 이러한 낮은 LUMO로 인하여 LUMO의 전자가 비어있는 특성을 이용하여 인접한 정공수송층(215)에 쉽게 정공을 전달하여 전기적 특성을 향상시킨다.The charge-generating material is generally made of a material having a very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a value similar to the HOMO of the hole transport layer 215 material. Due to the low LUMO, holes are easily transferred to the adjacent hole transport layer 215 by using the electron vacancy characteristic of the LUMO, thereby improving electrical properties.
상기 전하-생성 물질은 예를 들면, p-도펀트일 수 있다. 상기 p-도펀트는 퀴논 유도체, 금속 산화물 및 시아노기-함유 화합물 중 하나일 수 있으나, 이에 한정되는 것은 아니다. 예를 들어, 상기 p-도펀트의 비제한적인 예로는, 테트라사이아노퀴논다이메테인(TCNQ) 및 2,3,5,6-테트라플루오로-테트라사이아노-1,4-벤조퀴논다이메테인(F4-TCNQ) 등과 같은 퀴논 유도체; 텅스텐 산화물 및 몰리브덴 산화물 등과 같은 금속 산화물; 및 시아노기-함유 화합물 등을 들 수 있으나, 이에 한정되는 것은 아니다.The charge-generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of the p-dopant include tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane quinone derivatives such as phosphorus (F4-TCNQ) and the like; metal oxides such as tungsten oxide and molybdenum oxide; and a cyano group-containing compound, but is not limited thereto.
정공 수송 영역(210~215)은 앞서 언급한 물질 외에, 도전성 향상을 위하여 전하 생성 물질을 더 포함할 수 있다. 전하 생성 물질은 정공 수송 영역(210~215) 내에 균일하게 또는 불균일하게 분산되어 있을 수 있다. 전하 생성 물질은 예를 들어, p-도펀트(dopant)일 수 있다. p-도펀트는 퀴논(quinone) 유도체, 금속 산화물 및 시아노(cyano)기 함유 화합물 중 하나일 수 있으나, 이에 한정되는 것은 아니다. 예를 들어, p-도펀트의 비제한적인 예로는, TCNQ(Tetracyanoquinodimethane) 및 F4-TCNQ(2,3,5,6-tetrafluoro-tetracyanoquinodimethane) 등과 같은 퀴논 유도체, 텅스텐 산화물 및 몰리브덴 산화물 등과 같은 금속 산화물 등을 들 수 있으나, 이에 한정되는 것은 아니다.In addition to the aforementioned materials, the hole transport regions 210 to 215 may further include a charge generating material to improve conductivity. The charge generating material may be uniformly or non-uniformly dispersed in the hole transport regions 210 to 215 . The charge generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of p-dopants include quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyanoquinodimethane (TCNQ), and metal oxides such as tungsten oxide and molybdenum oxide. may be mentioned, but is not limited thereto.
전술한 바와 같이, 정공 수송 영역(210~215)은 정공 주입층(210) 및 정공 수송층(215) 외에, 정공 버퍼층 및 전자 저지층 중 적어도 하나를 더 포함할 수 있다. 정공 버퍼층은 발광층(220)에서 방출되는 광의 파장에 따른 공진 거리를 보상하여 광 방출 효율을 증가시킬 수 있다. 정공 버퍼층에 포함되는 물질로는 정공 수송 영역(210~215)에 포함될 수 있는 물질을 사용할 수 있다. As described above, the hole transport regions 210 to 215 may further include at least one of a hole buffer layer and an electron blocking layer in addition to the hole injection layer 210 and the hole transport layer 215 . The hole buffer layer may increase light emission efficiency by compensating for a resonance distance according to a wavelength of light emitted from the emission layer 220 . As a material included in the hole buffer layer, a material capable of being included in the hole transport regions 210 to 215 may be used.
전자 저지층은 전자 수송 영역(230~235)으로부터 정공 수송 영역(210~215)으로의 전자 주입을 방지하는 역할을 하는 층이다. 전자 저지층은 정공 수송영역으로 이동하는 전자를 저지할 뿐 아니라 발광층(220)에서 형성된 엑시톤이 정공수송영역(210~215)으로 확산되지 않도록 높은 T1 값을 갖는 재료를 사용할 수 있다. 예를 들면 일반적으로 높은 T1값을 갖는 발광층(220)의 호스트 등을 전자저지층 재료로 사용할 수 있다.The electron blocking layer is a layer serving to prevent electron injection from the electron transport region 230 to 235 to the hole transport region 210 to 215 . The electron blocking layer may use a material having a high T1 value so that excitons formed in the emission layer 220 do not diffuse into the hole transport regions 210 to 215 as well as to block electrons moving to the hole transport region. For example, a host of the light emitting layer 220 having a generally high T 1 value may be used as the electron blocking layer material.
발광층(220)은 정공 수송 영역(210~215) 상에 제공된다. 발광층(220)은 예를 들어 약 100Å 내지 약 1000Å 또는, 약 100Å 내지 약 300Å의 두께를 갖는 것일 수 있다. 발광층(220)은 단일 물질로 이루어진 단일층, 복수의 서로 다른 물질로 이루어진 단일층 또는 복수의 서로 다른 물질로 이루어진 복수의 층을 갖는 다층 구조를 가질 수 있다. The emission layer 220 is provided on the hole transport regions 210 to 215 . The light emitting layer 220 may have a thickness of, for example, about 100 Å to about 1000 Å, or about 100 Å to about 300 Å. The emission layer 220 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.
발광층(220)은 정공과 전자가 만나 엑시톤을 형성하는 영역으로 발광층(220)을 이루는 재료는 높은 발광 특성 및 원하는 발광색을 나타내도록 적절한 에너지밴드갭을 가져야 하며 일반적으로 호스트와 도판트 두가지 역할을 가지는 두 재료로 이루어지나, 이에 한정된 것은 아니다.The light emitting layer 220 is a region where holes and electrons meet to form excitons. The material constituting the light emitting layer 220 should have an appropriate energy band gap to exhibit high light emitting characteristics and a desired light emitting color, and generally serve as both a host and a dopant. It is made of two materials, but is not limited thereto.
상기 호스트는 하기 TPBi, TBADN, ADN("DNA"라고도 함), CBP, CDBP, TCP, mCP, 중 적어도 하나를 포함할 수 있고, 특성이 적절하다면 재료는 이에 한정된 것은 아니다.The host may include at least one of the following TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, and mCP, and if the properties are appropriate, the material is not limited thereto.
일 실시예의 발광층(220)의 도판트는 유기 금속 착물일 수 있다. 일반적인 도판트의 함량은 0.01 내지 20%로 선택될 수 있으며, 경우에 따라 이에 한정되는 것은 아니다.The dopant of the light emitting layer 220 according to an embodiment may be an organometallic complex. The content of the general dopant may be selected from 0.01 to 20%, but is not limited thereto in some cases.
전자 수송 영역(230~235)은 발광층(220) 상에 제공된다. 전자 수송 영역(230~235)은, 정공 저지층, 전자 수송층(230) 및 전자 주입층(235) 중 적어도 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.The electron transport regions 230 to 235 are provided on the emission layer 220 . The electron transport regions 230 to 235 may include at least one of a hole blocking layer, an electron transport layer 230 , and an electron injection layer 235 , but are not limited thereto.
전자 수송 영역(230~235)은 단일 물질로 이루어진 단일층, 복수의 서로 다른 물질로 이루어진 단일층 또는 복수의 서로 다른 물질로 이루어진 복수의 층을 갖는 다층 구조를 가질 수 있다. The electron transport regions 230 to 235 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.
예를 들어, 전자 수송 영역(230~235)은 전자 주입층(235) 또는 전자 수송층(230)의 단일층의 구조를 가질 수도 있고, 전자 주입 물질과 전자 수송 물질로 이루어진 단일층 구조를 가질 수도 있다. 또한, 전자 수송 영역(230~235)은, 복수의 서로 다른 물질로 이루어진 단일층의 구조를 갖거나, 발광층(220)으로부터 차례로 적층된 전자 수송층(230)/전자 주입층(235), 정공 저지층/전자 수송층(230)/전자 주입층(235) 구조를 가질 수 있으나, 이에 한정되는 것은 아니다. 전자 수송 영역(230~235)의 두께는 예를 들어, 약 1000Å 내지 약 1500Å인 것일 수 있다.For example, the electron transport regions 230 to 235 may have a single-layer structure of the electron injection layer 235 or the electron transport layer 230 , or may have a single-layer structure including an electron injection material and an electron transport material. have. In addition, the electron transport regions 230 to 235 have a single-layer structure made of a plurality of different materials, or the electron transport layer 230/electron injection layer 235 and the hole blocking layer 230 are sequentially stacked from the emission layer 220 . It may have a layer/electron transport layer 230/electron injection layer 235 structure, but is not limited thereto. The thickness of the electron transport regions 230 to 235 may be, for example, about 1000 Å to about 1500 Å.
전자 수송 영역(230~235)은, 진공 증착법, 스핀 코팅법, 캐스트법, LB법(Langmuir-Blodgett), 잉크젯 프린팅법, 레이저 프린팅법, 레이저 열전사법(Laser Induced Thermal Imaging, LITI) 등과 같은 다양한 방법을 이용하여 형성될 수 있다.The electron transport regions 230 to 235 may include a vacuum deposition method, a spin coating method, a casting method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and a laser induced thermal imaging (LITI) method. method can be used.
전자 수송 영역(230~235)이 전자 수송층(230)을 포함할 경우, 전자 수송 영역(230)은 안트라센계 화합물을 포함하는 것일 수 있다. 다만, 이에 한정되는 것은 아니며, 전자 수송 영역은 예를 들어, Alq3(Tris(8-hydroxyquinolinato)aluminum),1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene,2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine,2-(4-(N-phenylbenzoimidazolyl-1-ylphenyl)-9,10-dinaphthylanthracene,TPBi(1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl),BCP(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline),Bphen(4,7-Diphenyl-1,10-phenanthroline),TAZ(3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole),NTAZ(4-(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole),tBu-PBD(2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole),BAlq(Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum),Bebq2(berylliumbis(benzoquinolin-10-olate),ADN(9,10-di(naphthalene-2-yl)anthracene)및 이들의 혼합물을 포함하는 것일 수 있다. When the electron transport regions 230 to 235 include the electron transport layer 230 , the electron transport region 230 may include an anthracene-based compound. However, the present invention is not limited thereto, and the electron transport region is, for example, Alq3(Tris(8-hydroxyquinolinato)aluminum),1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene,2 ,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine,2-(4-(N-phenylbenzoimidazolyl-1-ylphenyl)-9,10 -dinaphthylanthracene,TPBi(1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl),BCP(2,9-Dimethyl-4,7-diphenyl-1,10- phenanthroline), Bphen(4,7-Diphenyl-1,10-phenanthroline),TAZ(3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole),NTAZ(4 -(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole),tBu-PBD(2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1, 3,4-oxadiazole), BAlq(Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum), Bebq2(berylliumbis(benzoquinolin-10-olate), ADN (9,10-di(naphthalene-2-yl)anthracene) and mixtures thereof may be included.
전자 수송층(230)은 유기 발광 소자 구조에 따라 빠른 전자이동도 혹은 느린 전자이동도의 재료로 선택되므로 다양한 재료의 선택이 필요하며, 경우에 따라서 하기 Liq나 Li이 도핑되기도 한다.Since the electron transport layer 230 is selected as a material having a fast electron mobility or a slow electron mobility according to the structure of the organic light emitting device, various materials need to be selected, and in some cases, Liq or Li may be doped.
전자 수송층(230)들의 두께는 약 100Å 내지 약 1000Å, 예를 들어 약 150Å 내지 약 500Å일 수 있다. 전자 수송층(230)들의 두께가 전술한 바와 같은 범위를 만족할 경우, 실질적인 구동 전압 상승없이 만족스러운 정도의 전자 수송 특성을 얻을 수 있다.The electron transport layers 230 may have a thickness of about 100 Å to about 1000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layers 230 satisfies the above-described range, a satisfactory electron transport characteristic may be obtained without a substantial increase in driving voltage.
전자 수송 영역(230~235)이 전자 주입층(235)을 포함할 경우, 전자 수송 영역(230~235)은 전자의 주입을 용이하게 하는 금속재료를 선택하며, LiF, LiQ(Lithium quinolate), Li2O, BaO, NaCl, CsF, Yb와 같은 란타넘족 금속, 또는 RbCl, RbI와 같은 할로겐화 금속 등이 사용될 수 있으나 이에 한정되는 것은 아니다. When the electron transport regions 230 to 235 include the electron injection layer 235 , the electron transport regions 230 to 235 select a metal material that facilitates electron injection, LiF, Lithium quinolate (LiQ), Li 2 O, BaO, NaCl, CsF, a lanthanide metal such as Yb, or a metal halide such as RbCl or RbI may be used, but is not limited thereto.
전자 주입층(235)은 또한 전자 수송 물질과 절연성의 유기 금속염(organo metal salt)이 혼합된 물질로 이루어질 수 있다. 유기 금속염은 에너지 밴드 갭(energy band gap)이 대략 4eV 이상의 물질이 될 수 있다. 구체적으로 예를 들어, 유기 금속염은 금속 아세테이트(metal acetate), 금속 벤조에이트(metal benzoate), 금속 아세토아세테이트(metal acetoacetate), 금속 아세틸아세토네이트(metal acetylacetonate) 또는 금속 스테아레이트(stearate)를 포함할 수 있다. 전자 주입층(235)들의 두께는 약 1Å 내지 약 100Å, 약 3Å 내지 약 90Å일 수 있다. 전자 주입층(235)들의 두께가 전술한 바와 같은 범위를 만족할 경우, 실질적인 구동 전압 상승 없이 만족스러운 정도의 전자 주입 특성을 얻을 수 있다.The electron injection layer 235 may also be made of a material in which an electron transport material and an insulating organo metal salt are mixed. The organometallic salt may be a material having an energy band gap of about 4 eV or more. Specifically, for example, the organometallic salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate or metal stearate. can The electron injection layers 235 may have a thickness of about 1 Å to about 100 Å, or about 3 Å to about 90 Å. When the thickness of the electron injection layers 235 satisfies the above-described range, a satisfactory electron injection characteristic may be obtained without a substantial increase in driving voltage.
전자 수송 영역(230~235)은 앞서 언급한 바와 같이, 정공 저지층을 포함할 수 있다. 정공 저지층은 예를 들어, BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-diphenyl-1,10-phenanthroline) 및 Balq 중 적어도 하나를 포함할 수 있으나, 이에 한정되는 것은 아니다.As described above, the electron transport regions 230 to 235 may include a hole blocking layer. The hole blocking layer includes, for example, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), and Balq. can, but is not limited thereto.
제2 전극(120)은 전자 수송 영역(230~235) 상에 제공된다. 제2 전극(120)은 공통 전극 또는 음극일 수 있다. 제2 전극(120)은 투과형 전극 또는 반투과형 전극 전극일 수 있다. 제2 전극(120)은 제1 전극(110)과 다르게 상대적으로 낮은 일함수를 갖는 금속, 전기전도성 화합물, 합금 등을 조합하여 사용할 수 있다.The second electrode 120 is provided on the electron transport regions 230 to 235 . The second electrode 120 may be a common electrode or a cathode. The second electrode 120 may be a transmissive electrode or a transflective electrode. Unlike the first electrode 110 , the second electrode 120 may use a combination of a metal, an electrically conductive compound, an alloy, etc. having a relatively low work function.
제2 전극(120)은 반투과형 전극 또는 반사형 전극이다. 제2 전극(120)은 Li(리튬), Mg(마그네슘), Al(알루미늄), Al-Li(알루미늄-리튬), Ca(칼슘), Mg-In(마그네슘-인듐), Mg-Ag(마그네슘-은) 또는 이들을 포함하는 화합물이나 혼합물(예를 들어, Ag와 Mg의 혼합물)을 포함할 수 있다. 또는 상기 물질로 형성된 반사막이나 반투과막 및 ITO(indium tin oxide), IZO(indium zinc oxide), ZnO(zinc oxide), ITZO(indium tin zinc oxide) 등으로 형성된 투명 도전막을 포함하는 복수의 층 구조일 수 있다.The second electrode 120 is a transflective electrode or a reflective electrode. The second electrode 120 includes Li (lithium), Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), and Mg-Ag (magnesium). -silver) or a compound or mixture containing them (eg, a mixture of Ag and Mg). Alternatively, a plurality of layer structures including a reflective or semi-transmissive film formed of the above material and a transparent conductive film formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium tin zinc oxide (ITZO), etc. can be
도시하지는 않았으나, 제2 전극(120)은 보조 전극과 연결될 수 있다. 제2 전극(120)가 보조 전극과 연결되면, 제2 전극(120)의 저항을 감소시킬 수 있다.Although not shown, the second electrode 120 may be connected to the auxiliary electrode. When the second electrode 120 is connected to the auxiliary electrode, the resistance of the second electrode 120 may be reduced.
도시된 기판(100) 상에 전극 및 유기물층을 형성하며, 이 때 기판(100) 재료는 경성 또는 연성 재료를 사용할 수 있으며, 예를 들어 경성 재료로는 소다라임 글래스, 무알칼리 글래스, 알루미노 실리케이트 글래스 등을 사용할 수 있으며, 연성 재료로는 PC(폴리카보네이트), PES(폴리에테르술폰), COC(싸이클릭올리펜코폴리머), PET(폴리에틸렌테레프탈레이트), PEN(폴리에틸렌나프탈레이트) 등을 사용할 수 있다.An electrode and an organic material layer are formed on the illustrated substrate 100. In this case, the substrate 100 may use a rigid or flexible material, for example, soda lime glass, alkali-free glass, aluminosilicate as the rigid material. Glass, etc. can be used, and as soft materials, PC (polycarbonate), PES (polyethersulfone), COC (cyclic oliphene copolymer), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), etc. can be used. have.
유기 발광 소자에서, 제1 전극(110)과 제2 전극(120)에 각각 전압이 인가됨에 따라 제1 전극(110)으로부터 주입된 정공(hole)은 정공 수송 영역(210~215)을 거쳐 발광층(220)으로 이동되고, 제2 전극(120)로부터 주입된 전자가 전자 수송 영역(230~235)을 거쳐 발광층(220)으로 이동된다. 전자와 정공은 발광층(220)에서 재결합하여 여기자(exciton)를 생성하며, 여기자가 여기 상태에서 바닥 상태로 떨어지면서 발광하게 된다.In the organic light emitting device, as a voltage is applied to each of the first electrode 110 and the second electrode 120 , holes injected from the first electrode 110 pass through the hole transport regions 210 to 215 into the emission layer The electrons are moved to 220 , and electrons injected from the second electrode 120 are moved to the emission layer 220 through the electron transport regions 230 to 235 . Electrons and holes recombine in the emission layer 220 to generate excitons, and the excitons emit light as they fall from the excited state to the ground state.
발광층(220)에서 발생된 광경로는 유기 발광 소자를 구성하는 유무기물들의 굴절률에 따라 매우 다른 경향을 나타낼 수 있다. 제2 전극(120)을 통과하는 빛은 제2 전극(120)의 임계각보다 작은 각도로 투과되는 빛들만 통과할 수 있다. 그 외 임계각보다 크게 제2 전극(120)에 접촉하는 빛들은 전반사 또는 반사되어 유기 발광 소자 외부로 방출되지 못한다.The optical path generated in the light emitting layer 220 may exhibit a very different tendency according to the refractive index of the organic/inorganic materials constituting the organic light emitting device. Light passing through the second electrode 120 may pass only light transmitted at an angle smaller than the critical angle of the second electrode 120 . Lights contacting the second electrode 120 larger than the other critical angles are totally reflected or reflected, so that they are not emitted to the outside of the organic light emitting diode.
캡핑층(300)의 굴절률이 높으면 이러한 전반사 또는 반사 현상을 줄여서 발광효율 향상에 기여하고 또한 적절한 두께를 갖게 되면 미소공동현상(Micro-cavity)현상의 극대화로 높은 효율 향상과 색순도 향상에도 기여하게 된다.When the refractive index of the capping layer 300 is high, it contributes to the improvement of luminous efficiency by reducing such total reflection or reflection, and also, when it has an appropriate thickness, it contributes to high efficiency improvement and color purity by maximizing the micro-cavity phenomenon. .
캡핑층(300)은 유기 발광 소자의 가장 바깥에 위치하게 되며, 소자의 구동에 전혀 영향을 주지 않으면서 소자특성에는 지대한 영향을 미친다. 따라서 캡핑층(300)은 유기 발광 소자의 내부 보호역할과 동시에 소자특성 향상 두가지 관점에서 모두 중요하다. 유기물질들은 특정파장영역의 광에너지를 흡수하며 이는 에너지밴드갭에 의존한다. 이 에너지밴드갭을 유기 발광 소자내부의 유기물질들에 영향을 줄 수 있는 UV영역의 흡수를 목적으로 조정하면 캡핑층(300)이 광학특성 개선을 포함하여 유기 발광 소자 보호의 목적으로도 사용될 수 있다.The capping layer 300 is located at the outermost part of the organic light emitting device, and has a great influence on device characteristics without affecting the driving of the device. Accordingly, the capping layer 300 is important both in terms of both an internal protection role of the organic light emitting device and improvement of device characteristics. Organic materials absorb light energy in a specific wavelength region, which depends on the energy band gap. If this energy bandgap is adjusted for the purpose of absorbing the UV region that can affect the organic materials inside the organic light emitting device, the capping layer 300 can be used for the purpose of protecting the organic light emitting device including improving optical properties. have.
본 명세서에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present specification may be a top emission type, a back emission type, or a double side emission type depending on the material used.
이하 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나 본 명세서에 따른 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 출원의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 출원의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.
[제조예][Production Example]
중간체 intermediate 합성예Synthesis example 1: 중간체(2)의 합성 1: Synthesis of intermediate (2)
(중간체(1)의 합성)(Synthesis of Intermediate (1))
1구 2 L 플라스크에서 2-4-브로모페닐벤조옥사졸(2-(4-bromophenyl)benzo[d]oxazole) 50.0 g(182.4 mmol), 피나콜디보론(Bis(pinacolato)diboron) 69.5 g(273.6 mmol), Pd(dppf)Cl2-CH2Cl2 7.5 g(9.1 mmol), KOAc 54.0 g(547.2 mmol) 및 1,4-다이옥산 730 mL를 혼합한 다음, 100℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(1)) 52.5 g(수율: 89.6%)을 얻었다. 50.0 g (182.4 mmol) of 2-4-bromophenylbenzoxazole (2-(4-bromophenyl)benzo[d]oxazole) in a 1-neck 2L flask, 69.5 g of pinacol diboron (Bis(pinacolato)diboron) (273.6 mmol), Pd(dppf)Cl 2 -CH 2 Cl 2 7.5 g (9.1 mmol), KOAc 54.0 g (547.2 mmol) and 1,4-dioxane 730 mL were mixed, and then stirred at 100° C. for 12 hours. did. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solvent (DCM/EtOH) to obtain 52.5 g (yield: 89.6%) of the compound (intermediate (1)) as a white solid.
(중간체(2)의 합성)(Synthesis of Intermediate (2))
1구 500 mL 플라스크에서 2,8-다이브로모벤조퓨란(2,8-dibromodibenzo[b,d]furan) 10.0 g(30.7 mmol), 중간체(1) 9.9 g(30.7 mmol), Pd(PPh3)4 1.8 g(1.5 mmol), 2M K2CO3 40.0 mL(76.7 mmol) 톨루엔 120 mL 및 에탄올 30 mL를 혼합한 다음 3 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(2)) 5.3 g(수율: 39.4%)을 얻었다.In a 1-neck 500 mL flask, 2,8-dibromobenzofuran (2,8-dibromodibenzo[b,d]furan) 10.0 g (30.7 mmol), Intermediate (1) 9.9 g (30.7 mmol), Pd (PPh 3 ) 4 1.8 g (1.5 mmol), 2M K 2 CO 3 40.0 mL (76.7 mmol) 120 mL of toluene and 30 mL of ethanol were mixed and stirred under reflux for 3 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was purified by column chromatography (Hex:CHCl 3 ) and solidified with a mixed solvent (DCM/EtOH) to obtain 5.3 g (yield: 39.4%) of the compound as a white solid (intermediate (2)).
중간체 intermediate 합성예Synthesis example 2: 중간체(4)의 합성 2: Synthesis of intermediate (4)
(중간체(3)의 합성)(Synthesis of Intermediate (3))
2-(4-브로모페닐)벤조[d]티아졸(2-(4-bromophenyl)benzo[d]thiazole) 30.0 g(103.4 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 31.5 g(124.0 mmol), Pd(dppf)Cl2 3.4 g(4.1 mmol), 아세트산 칼륨 20.3 g(206.8 mol), 1,4-디옥산 300 mL의 혼합물을 90℃에서 12시간 동안 교반하였다. 반응 혼합물을 감압 농축한 후 디클로로메탄 600 mL을 가하여 30분간 교반하였다. 불용성 침전을 celite 패드로 여과하여 제거하고 감압 농축하였다. 농축 잔류물에 메탄올 200 mL를 가하고 1시간 동안 교반하였다. 생성된 침전을 여과하고 메탄올로 세척, 진공 건조하여 옅은 노란색 고체의 화합물(중간체(3)) 25.0 g(수율: 72.1%)을 얻었다.2-(4-bromophenyl)benzo[d]thiazole (2-(4-bromophenyl)benzo[d]thiazole) 30.0 g (103.4 mmol), bis(pinacolato)diboron (bis(pinacolato)diboron) ) 31.5 g (124.0 mmol), Pd(dppf)Cl 2 3.4 g (4.1 mmol), potassium acetate 20.3 g (206.8 mol), and 1,4-dioxane 300 mL. A mixture of 300 mL was stirred at 90° C. for 12 hours. After the reaction mixture was concentrated under reduced pressure, 600 mL of dichloromethane was added and stirred for 30 minutes. The insoluble precipitate was removed by filtration through a pad of celite and concentrated under reduced pressure. To the concentrated residue, 200 mL of methanol was added and stirred for 1 hour. The resulting precipitate was filtered, washed with methanol, and dried under vacuum to obtain 25.0 g (yield: 72.1%) of the compound (intermediate (3)) as a pale yellow solid.
(중간체(4)의 합성)(Synthesis of Intermediate (4))
2구 500 mL 플라스크에서 2,8-디브로모디벤조퓨란(2,8-dibromodibenzofuran) 7.5 g(23.1 mmol), 중간체(3) 6.0 g(17.8 mmol), Pd(PPh3)4 1.0 g(0.9 mmol), K2CO3 4.9 g(35.6 mmol) 및 톨루엔 72 mL, 정제수 30 mL 및 에탄올 25 mL를 혼합한 다음 80℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 뜨거운 모노클로로벤젠에 용해시켜 실리카겔 패드를 통하여 여과하고 메탄올로 고체화하여, 흰색 고체의 화합물(중간체(4)) 3.5 g(수율: 43.1%)을 얻었다.In a 2-neck 500 mL flask, 2,8-dibromodibenzofuran (2,8-dibromodibenzofuran) 7.5 g (23.1 mmol), Intermediate (3) 6.0 g (17.8 mmol), Pd (PPh 3 ) 4 1.0 g (0.9 mmol), K 2 CO 3 4.9 g (35.6 mmol), 72 mL of toluene, 30 mL of purified water, and 25 mL of ethanol were mixed and stirred at 80° C. for one day. After completion of the reaction, the mixture was cooled to room temperature and the resulting solid was filtered. The obtained reaction mixture was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified with methanol to obtain 3.5 g (yield: 43.1%) of the compound as a white solid (intermediate (4)).
중간체 intermediate 합성예Synthesis example 3: 중간체(5)의 합성 3: Synthesis of intermediate (5)
2구 500 mL 플라스크에서 2,8-디브로모디벤조퓨란(2,8-dibromodibenzofuran) 10.0 g(30.7 mmol), (4-(나프탈렌-2-일)페닐)보론산((4-(naphthalen-2-yl)phenyl)boronic acid) 7.6 g(30.7 mmol), Pd(PPh3)4 1.8 g(1.5 mmol), K2CO3 8.5 g(61.4 mmol), THF 200 mL 및 정제수 60 mL를 혼합한 다음 80℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 디클로로메탄에 용해시켜 실리카겔에 필터하고 디클로로메탄/아세톤으로 고체화하여, 흰색 고체의 화합물(중간체(5)) 5.1 g(수율: 37.3%)을 얻었다.2,8-dibromodibenzofuran (2,8-dibromodibenzofuran) 10.0 g (30.7 mmol), (4- (naphthalen-2-yl) phenyl) boronic acid ((4- (naphthalen- 2-yl)phenyl)boronic acid) 7.6 g (30.7 mmol), Pd(PPh 3 ) 4 1.8 g (1.5 mmol), K 2 CO 3 8.5 g (61.4 mmol), THF 200 mL and purified water 60 mL were mixed It was then stirred at 80° C. for one day. After completion of the reaction, the mixture was cooled to room temperature and the resulting solid was filtered. The obtained reaction mixture was dissolved in dichloromethane, filtered through silica gel, and solidified with dichloromethane/acetone to obtain 5.1 g (yield: 37.3%) of the compound as a white solid (intermediate (5)).
중간체 intermediate 합성예Synthesis example 4: 중간체(7)의 합성 4: Synthesis of intermediate (7)
(중간체(6)의 합성)(Synthesis of Intermediate (6))
1구 1 L 플라스크에서 2-브로모퀴놀린(2-bromoquinoline) 15.0 g(72.1 mmol), 4-클로로페닐 보론산((4-chlorophenyl)boronic acid) 11.3 g(72.1 mmol), Pd(PPh3)4 4.2 g(3.6 mmol), 2M K2CO3 90.0 mL(180.2 mmol), 톨루엔 200 mL 및 에탄올 90 mL를 혼합한 다음 4 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 에틸아세테이트로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물(중간체(6)) 12.0 g(수율: 69.4%)을 얻었다.In a 1-neck 1 L flask, 15.0 g (72.1 mmol) of 2-bromoquinoline, 11.3 g (72.1 mmol) of 4-chlorophenyl boronic acid, Pd (PPh 3 ) 4 4.2 g (3.6 mmol), 2M K 2 CO 3 90.0 mL (180.2 mmol), toluene 200 mL, and ethanol 90 mL were mixed and stirred under reflux for 4 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with ethyl acetate. The reaction mixture was purified by column chromatography (CHCl 3 ) and solidified with a mixed solvent (DCM/MeOH) to obtain 12.0 g (yield: 69.4%) of the compound (intermediate (6)) as a white solid.
(중간체(7)의 합성)(Synthesis of Intermediate (7))
1구 500 mL 플라스크에서 중간체(6) 8.0 g(33.4 mmol), 피나콜디보론(Bis(pinacolato)diboron) 12.7 g(50.1 mmol), Pd(dba)2 1.9 g(3.3 mmol), X-phos 3.2 g(6.7 mmol), KOAc 9.8 g(100.1 mmol) 및 톨루엔 130 mL를 혼합한 다음, 110℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 에탄올로 고체화하여, 흰색 고체의 화합물(중간체(7)) 7.3 g (수율: 66.0%)얻었다. In a one-necked 500 mL flask, 8.0 g (33.4 mmol) of intermediate (6), 12.7 g (50.1 mmol) of pinacol diboron (Bis(pinacolato)diboron), 1.9 g (3.3 mmol) of Pd(dba) 2 , X-phos 3.2 g (6.7 mmol), 9.8 g (100.1 mmol) of KOAc, and 130 mL of toluene were mixed, followed by stirring at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with ethanol to obtain 7.3 g (yield: 66.0%) of the compound (intermediate (7)) as a white solid.
중간체 intermediate 합성예Synthesis example 5: 중간체(8)의 합성 5: Synthesis of intermediate (8)
1구 250 mL 플라스크에서 2,8-다이브로모벤조퓨란(2,8-dibromodibenzo[b,d]furan) 6.0 g(18.4 mmol), 중간체(7) 6.1 g(18.4 mmol), Pd(PPh3)4 1.1 g(920.3 μmol), 2M K2CO3 23.0 mL(46.0 mmol), 톨루엔 60 mL 및 에탄올 20 mL을 혼합한 다음 2시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(Hex:CHCl3) 정제하고 디클로로메탄으로 고체화하여, 흰색 고체의 화합물(중간체(8)) 1.7 g(수율: 20.6%)을 얻었다.In a 1-neck 250 mL flask, 2,8-dibromobenzofuran (2,8-dibromodibenzo[b,d]furan) 6.0 g (18.4 mmol), Intermediate (7) 6.1 g (18.4 mmol), Pd (PPh 3 ) 4 1.1 g (920.3 μmol), 2M K 2 CO 3 23.0 mL (46.0 mmol), toluene 60 mL, and ethanol 20 mL were mixed and stirred under reflux for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with chloroform. The reaction mixture was purified by column chromatography (Hex:CHCl 3 ) and solidified with dichloromethane to obtain 1.7 g (yield: 20.6%) of the compound as a white solid (intermediate (8)).
중간체 intermediate 합성예Synthesis example 6: 중간체(10)의 합성 6: Synthesis of intermediate (10)
(중간체(9)의 합성)(Synthesis of Intermediate (9))
1구 1 L 플라스크에서 3-브로모퀴놀린(3-bromoquinoline) 30.0 g(144.2 mmol), 4-클로로페닐 보론산((4-chlorophenyl)boronic acid) 22.6 g(144.2 mmol), Pd(PPh3)4 5.0 g(4.3 mmol), K2CO3 49.8 g(360.5 mmol), 톨루엔 400 mL, 에탄올 150 mL 및 물 150 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 에틸아세테이트로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(EA)로 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(9)) 25.6 g(수율: 74.1%)을 얻었다.In a 1-neck 1 L flask, 3-bromoquinoline 30.0 g (144.2 mmol), 4-chlorophenyl boronic acid 22.6 g (144.2 mmol), Pd (PPh 3 ) 4 5.0 g (4.3 mmol), K 2 CO 3 49.8 g (360.5 mmol), toluene 400 mL, ethanol 150 mL, and water 150 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with ethyl acetate. The reaction mixture was purified by column chromatography (EA) and solidified with a mixed solvent (DCM/EtOH) to obtain 25.6 g (yield: 74.1%) of the compound (intermediate (9)) as a white solid.
(중간체(10)의 합성)(Synthesis of Intermediate (10))
1구 1 L 플라스크에서 중간체(9) 25.6 g(106.8 mmol), 피나콜디보론(Bis(pinacolato)diboron) 40.7 g(160.2 mmol), Pd(dba)2 6.1 g(10.7 mmol), X-phos 10.1 g(21.4 mmol), KOAc 26.2 g(267.0 mmol) 및 톨루엔 360 mL를 혼합한 다음, 110℃에서 12시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시켜 에틸아세테이드(EA)로 세척한 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3:EA)로 정제하고 에탄올로 고체화하여, 노란색 고체의 화합물(중간체(10)) 12.3 g(수율: 34.8%)을 얻었다. Intermediate (9) 25.6 g (106.8 mmol), pinacol diboron (Bis(pinacolato)diboron) 40.7 g (160.2 mmol), Pd(dba) 2 6.1 g (10.7 mmol), X-phos in a 1-neck 1 L flask 10.1 g (21.4 mmol), 26.2 g (267.0 mmol) of KOAc and 360 mL of toluene were mixed and stirred at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad, washed with ethyl acetate (EA), and then concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 :EA) and solidified with ethanol to obtain 12.3 g (yield: 34.8%) of the compound (intermediate (10)) as a yellow solid.
중간체 intermediate 합성예Synthesis example 7: 중간체(11)의 합성 7: Synthesis of intermediate (11)
1구 250 mL 플라스크에서 2,8-다이브로모벤조퓨란(2,8-dibromodibenzo[b,d]furan) 10.0 g(30.7 mmol), 중간체(10) 10.1 g(30.7 mmol), Pd(PPh3)4 1.7 g(1.5 mmol), 2M K2CO3 40.0 mL(76.7 mmol), 톨루엔 90 mL 및 에탄올 30 mL을 혼합한 다음 2 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(Hex:CHCl3) 정제하고 디클로로메탄으로 고체화하여, 노란색 고체의 화합물(중간체(11) 6.1g(수율: 44.2%)을 얻었다.In a 1-neck 250 mL flask, 10.0 g (30.7 mmol) of 2,8-dibromobenzofuran (2,8-dibromodibenzo [b, d] furan), 10.1 g (30.7 mmol) of intermediate (10), Pd (PPh 3 ) 4 1.7 g (1.5 mmol), 2M K 2 CO 3 40.0 mL (76.7 mmol), toluene 90 mL, and ethanol 30 mL were mixed and stirred under reflux for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with chloroform. The reaction mixture was purified by column chromatography (Hex:CHCl 3 ) and solidified with dichloromethane, the compound as a yellow solid (Intermediate (11)) 6.1 g (yield: 44.2%) was obtained.
중간체 intermediate 합성예Synthesis example 8: 중간체(13)의 합성 8: Synthesis of intermediate (13)
(중간체(12)의 합성)(Synthesis of Intermediate (12))
1구 2 L 플라스크에서 2-브로모피리딘(2-bromopyridine) 30.0 g(190.0 mmol), 4-클로로페닐 보론산((4-chlorophenyl)boronic acid) 29.7 g(190.0 mmol), Pd(PPh3)4 6.6 g(5.7 mmol), K2CO3 65.6 g(474.7 mmol), 톨루엔 500 mL, 에탄올 150 mL 및 물 150 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 에틸아세테이트로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(Hex:EA) 정제하여, 흰색 고체의 화합물(중간체(12)) 27.6 g(수율: 76.7%)을 얻었다.In a 1-neck 2 L flask, 2-bromopyridine 30.0 g (190.0 mmol), 4-chlorophenyl boronic acid 29.7 g (190.0 mmol), Pd (PPh 3 ) 4 6.6 g (5.7 mmol), K 2 CO 3 65.6 g (474.7 mmol), toluene 500 mL, ethanol 150 mL, and water 150 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with ethyl acetate. The reaction mixture was purified by column chromatography (Hex:EA) to obtain 27.6 g (yield: 76.7%) of the compound (intermediate (12)) as a white solid.
(중간체(13)의 합성)(Synthesis of Intermediate (13))
1구 2 L 플라스크에서 중간체(12) 27.6 g(145.5 mmol), 피나콜디보론(Bis(pinacolato)diboron) 55.4 g(218.3 mmol), Pd(dba)2 8.4 g(14.6 mmol), X-phos 13.9 g(29.1 mmol), KOAc 42.9 g(436.6 mmol) 및 톨루엔 580 mL를 혼합한 다음, 110℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 노란색 고체의 화합물(중간체(13)) 32.8 g(수율: 80.2%)얻었다. Intermediate (12) 27.6 g (145.5 mmol), pinacol diboron (Bis(pinacolato)diboron) 55.4 g (218.3 mmol), Pd(dba) 2 8.4 g (14.6 mmol), X-phos in a 1-neck 2 L flask 13.9 g (29.1 mmol), 42.9 g (436.6 mmol) of KOAc and 580 mL of toluene were mixed, followed by stirring at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 32.8 g (yield: 80.2%) of the compound as a yellow solid (intermediate (13)).
중간체 intermediate 합성예Synthesis example 9: 중간체(14)의 합성 9: Synthesis of intermediate (14)
1구 500 mL 플라스크에서 2,8-다이브로모벤조퓨란(2,8-dibromodibenzo[b,d]furan) 10.0 g(30.7 mmol), 중간체(13) 8.6 g(30.7 mmol), Pd(PPh3)4 1.8 g(1.5 mmol), 2M K2CO3 38.0 mL(76.7 mmol), 톨루엔 100 mL 및 에탄올 20 mL을 혼합한 다음 2 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피로(CHCl3) 정제하고 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물(중간체(14)) 1.4 g(수율: 11.7%)을 얻었다.2,8-dibromobenzofuran (2,8-dibromodibenzo[b,d]furan) 10.0 g (30.7 mmol), Intermediate (13) 8.6 g (30.7 mmol), Pd (PPh 3 ) in a 1-neck 500 mL flask 4 1.8 g (1.5 mmol), 2M K 2 CO 3 38.0 mL (76.7 mmol), toluene 100 mL, and ethanol 20 mL were mixed and stirred under reflux for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with chloroform. The reaction mixture was purified by column chromatography (CHCl 3 ) and solidified with dichloromethane to obtain 1.4 g (yield: 11.7%) of the compound as a white solid (intermediate (14)).
중간체 intermediate 합성예Synthesis example 10: 중간체(15)의 합성 10: Synthesis of intermediate (15)
2구 500 mL 플라스크에서 7-브로모-2-클로로디벤조퓨란(7-bromo-2-chlorodibenzofuran) 15.0 g(53.3 mmol), 페닐 보론산(phenylboronic acid) 13.0 g(106.6 mmol), Pd(PPh3)4 3.1 g(2.7 mmol), K2CO3 18.5 g(133.2 mmol), 톨루엔 180 mL, 정제수 75 mL 및 에탄올 60 mL를 혼합한 다음 90℃에서 2시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 에틸아세테이트로 추출하여 유기층을 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하여 흰색 고체의 화합물(중간체(15)) 13.4 g(수율: 90.7%)을 얻었다.In a 2-neck 500 mL flask, 7-bromo-2-chlorodibenzofuran 15.0 g (53.3 mmol), phenylboronic acid 13.0 g (106.6 mmol), Pd (PPh) 3 ) 4 3.1 g (2.7 mmol), K 2 CO 3 18.5 g (133.2 mmol), toluene 180 mL, purified water 75 mL, and ethanol 60 mL were mixed and stirred at 90° C. for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) to obtain 13.4 g (yield: 90.7%) of the compound (intermediate (15)) as a white solid.
중간체 intermediate 합성예Synthesis example 11: 중간체(19)의 합성 11: Synthesis of intermediate (19)
(중간체(16)의 합성)(Synthesis of Intermediate (16))
1구 1 L 플라스크에서 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 30.0 g(99.7 mol), 3,5-비스트리플루오로메틸페닐 보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 28.3 g(109.7 mmol), Pd(PPh3)4 5.8 g(5.0 mmol), 2M K2CO3 125.0 mL(249.3 mmol), 톨루엔 300 mL 및 에탄올 100 mL을 혼합한 다음 5 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여 무색 액체의 화합물(중간체(16)) 17.7 g(수율: 45.9%)을 얻었다.In a 1-neck 1 L flask, 1-bromo-2-fluoro-4-iodobenzene (1-bromo-2-fluoro-4-iodobenzene) 30.0 g (99.7 mol), 3,5-bistrifluoromethylphenyl Boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 28.3 g (109.7 mmol), Pd(PPh 3 ) 4 5.8 g (5.0 mmol), 2M K 2 CO 3 125.0 mL (249.3 mmol), toluene 300 mL and 100 mL of ethanol were mixed and stirred under reflux for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex) to obtain 17.7 g (yield: 45.9%) of the compound (intermediate (16)) as a colorless liquid.
(중간체(17)의 합성)(Synthesis of intermediate (17))
1구 500 mL 플라스크에서 중간체(16) 17.7 g(46.2 mmol), 피나콜디보론(Bis(pinacolato)diboron) 17.6 g(69.4 mmol), Pd(dppf)Cl2-CH2Cl2 1.9 g(2.3 mmol), KOAc 13.6 g(138.7 mmol) 및 1,4-디옥산 180 mL를 혼합한 다음, 100℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 노란색 액체의 화합물(중간체(17)) 19.0 g(수율: 100%)을 얻었다.In a one-necked 500 mL flask, 17.7 g (46.2 mmol) of intermediate (16), 17.6 g (69.4 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl 2 -CH 2 Cl 2 1.9 g (2.3 mmol), 13.6 g (138.7 mmol) of KOAc and 180 mL of 1,4-dioxane were mixed, and then stirred at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 19.0 g (yield: 100%) of the compound (intermediate (17)) as a yellow liquid.
(중간체(18)의 합성)(Synthesis of Intermediate (18))
1구 500 mL 플라스크에서 중간체(17) 19.0 g(43.7 mmol), 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 9.0 g(43.7 mmol), Pd(PPh3)4 2.5 g(2.2 mmol), 2M K2CO3 65.0 mL(131.3 mmol), 톨루엔 150 mL 및 에탄올 50 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:DCM)로 정제하여, 흰색 고체의 화합물(중간체(18)) 7.5 g(수율: 39.2%)을 얻었다.In a 1-neck 500 mL flask, 19.0 g (43.7 mmol) of the intermediate (17), 9.0 g (43.7 mmol) of 2-bromo-4-chlorophenol, 2.5 g of Pd (PPh 3 ) 4 (2.2 mmol), 2M K 2 CO 3 65.0 mL (131.3 mmol), 150 mL of toluene and 50 mL of ethanol were mixed and stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:DCM) to obtain 7.5 g (yield: 39.2%) of the compound (intermediate (18)) as a white solid.
(중간체(19)의 합성)(Synthesis of Intermediate (19))
1구 500 mL 플라스크에서 중간체(19) 7.5 g(17.2 mmol), K2CO3 5.9 g(42.9 mmol) 및 DMF 90 mL를 혼합한 후 100 ℃에서 12시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣어 교반하였다. 이때 생성된 고체를 여과한 후 물로 씻어서 건조하여 노란색 고체의 화합물(중간체(19)) 6.3 g(수율: 88.5%)을 얻었다.7.5 g (17.2 mmol) of intermediate (19), K 2 CO 3 in a one-necked 500 mL flask After mixing 5.9 g (42.9 mmol) and 90 mL of DMF, the mixture was stirred at 100 °C for 12 hours. After the reaction was completed, it was cooled to room temperature, and water was added and stirred. At this time, the resulting solid was filtered, washed with water and dried to obtain 6.3 g (yield: 88.5%) of a yellow solid compound (intermediate (19)).
중간체 intermediate 합성예Synthesis example 12: 중간체(23)의 합성 12: Synthesis of intermediate (23)
(중간체(20)의 합성)(Synthesis of Intermediate (20))
2구 2000 mL 플라스크에서 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 35.0 g(116.3 mmol), (4-플루오로페닐) 보론산((4-fluorophenyl)boronic acid) 16.6 g(116.3 mmol), Pd(PPh3)4 6.7 g(5.8 mmol), K2CO3 40.2 g(290.8 mmol), THF 420 mL 및 정제수 175 mL를 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 에틸아세테이트로 추출하여 유기층을 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하여 무색 액체의 화합물(중간체(20)) 19.1 g(수율: 46.0%)을 얻었다.In a 2-neck 2000 mL flask, 1-bromo-2-fluoro-4-iodobenzene (1-bromo-2-fluoro-4-iodobenzene) 35.0 g (116.3 mmol), (4-fluorophenyl) boronic acid ((4-fluorophenyl)boronic acid) 16.6 g (116.3 mmol), Pd(PPh 3 ) 4 6.7 g (5.8 mmol), K 2 CO 3 40.2 g (290.8 mmol), THF 420 mL and purified water 175 mL It was then stirred at 90° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) to obtain 19.1 g (yield: 46.0%) of the compound (intermediate (20)) as a colorless liquid.
(중간체(21)의 합성)(Synthesis of Intermediate (21))
2구 500 mL 플라스크에서 중간체(20) 19.0 g(70.6 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 26.9 g(105.9 mmol), Pd(PPh3)4 8.2 g(7.1 mmol), KOAc 20.8 g(211.8 mmol) 및 1,4-디옥센 230 mL를 혼합한 다음 107℃에서 29시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 후 생성된 고체를 여과하였다. 여액을 에틸아세테이트로 추출하여 유기층을 감압 농축하였다. 얻어진 고체와 농축된 여액을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여 흰색 고체의 화합물(중간체(21)) 20.1 g(수율: 90.1%)을 얻었다.In a 2-neck 500 mL flask, 19.0 g (70.6 mmol) of Intermediate (20), 26.9 g (105.9 mmol) of bis(pinacolato)diboron, 8.2 g (7.1 mmol) of Pd(PPh 3 ) 4 ), 20.8 g (211.8 mmol) of KOAc and 230 mL of 1,4-dioxene were mixed and stirred at 107°C for 29 hours. After the reaction was completed, the resulting solid was filtered after cooling to room temperature. The filtrate was extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained solid and the concentrated filtrate were purified by silica gel column chromatography (Hex:EA) to obtain 20.1 g (yield: 90.1%) of the compound as a white solid (intermediate (21)).
(중간체(22)의 합성)(Synthesis of Intermediate (22))
2구 1000 mL 플라스크에서 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 17.3 g(83.5 mmol), 중간체(21) 22.0 g(69.6 mmol), Pd(PPh3)4 4.0 g(3.5 mmol), K2CO3 24.0 g(174.0 mmol), 톨루엔 220 mL, 정제수 110 mL 및 에탄올 90 mL를 혼합한 다음, 90℃에서 하루 동안 반응하였다. 반응이 종결된 후 셀라이트에 여과한 다음 에틸아세테이트로 추출하여 유기층을 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(EA:CH2Cl2)로 정제하여 무색 액체의 화합물(중간체(22)) 21.3 g(수율: 96.6%)을 얻었다.In a 2-neck 1000 mL flask, 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol) 17.3 g (83.5 mmol), Intermediate (21) 22.0 g (69.6 mmol), Pd (PPh 3 ) 4 4.0 g (3.5 mmol), K 2 CO 3 24.0 g (174.0 mmol), toluene 220 mL, purified water 110 mL, and ethanol 90 mL were mixed, and then reacted at 90° C. for one day. After the reaction was completed, the mixture was filtered through celite, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (EA:CH 2 Cl 2 ) to obtain 21.3 g (yield: 96.6%) of the compound (intermediate (22)) as a colorless liquid.
(중간체(23)의 합성)(Synthesis of intermediate (23))
1구 1000 mL 플라스크에서 중간체(22) 21.3 g(67.2 mmol), K2CO3 27.9 g(201.7 mmol) 및 DMF 250 mL를 혼합한 다음, 105℃에서 하루 동안 반응하였다. 반응이 종결된 후 상온으로 냉각한 다음 정제수를 첨가하여 생성된 고체를 여과하였다. 반응 혼합물에 메탄올을 넣고 상온에서 1시간 동안 교반하였다. 이 침전물을 여과하여, 흰색 고체의 화합물(중간체(23)) 6.2 g(수율: 31.0%)을 얻었다.21.3 g (67.2 mmol) of intermediate (22) in a 1-necked 1000 mL flask, K 2 CO 3 27.9 g (201.7 mmol) and 250 mL of DMF were mixed, and then reacted at 105° C. for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, and the resulting solid was filtered. Methanol was added to the reaction mixture and stirred at room temperature for 1 hour. The precipitate was filtered to obtain 6.2 g (yield: 31.0%) of a white solid compound (intermediate (23)).
중간체 intermediate 합성예Synthesis example 13: 중간체(27)의 합성 13: Synthesis of intermediate (27)
(중간체(24)의 합성)(Synthesis of Intermediate (24))
2구 2 L 플라스크에서 (3-(트리메틸실리)페닐) 보론산((3-(trimethylsilyl)phenyl)boronic acid) 30.0 g(154.6 mmol), 1-브로모-2-플루오로-4-아이오도밴젠(1-bromo-2-fluoro-4-iodobenzene) 46.5 g(154.6 mmol), Pd(PPh3)4 5.4 g(4.6 mmol), K2CO3 64.1 g(463.7 mmol), 톨루엔 750 mL, 에탄올 190 mL 및 증류수 190 mL을 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 헥산으로 추출하여 무수황산마그네슘으로 건조, 여과, 감압 증류하였다. 얻어진 고체를 헥산에 녹여 실리카 패드 여과한 후 혼합용액(MeOH/DCM)으로 고체화하여, 흰색 고체의 화합물(중간체(24)) 33.8 g(수율: 67.6%)을 얻었다.In a 2-neck 2 L flask, (3- (trimethylsilyl) phenyl) boronic acid ((3- (trimethylsilyl) phenyl) boronic acid) 30.0 g (154.6 mmol), 1-bromo-2-fluoro-4-iodo Benzene (1-bromo-2-fluoro-4-iodobenzene) 46.5 g (154.6 mmol), Pd (PPh 3 ) 4 5.4 g (4.6 mmol), K 2 CO 3 64.1 g (463.7 mmol), toluene 750 mL, ethanol After mixing 190 mL and 190 mL of distilled water, the mixture was stirred at 90° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with hexane, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid was dissolved in hexane, filtered through a silica pad, and solidified with a mixed solution (MeOH/DCM) to obtain 33.8 g (yield: 67.6%) of a white solid compound (Intermediate (24)).
(중간체(25)의 합성)(Synthesis of Intermediate (25))
2구 1 L 플라스크에서 중간체(24) 33.8 g(104.6 mmol), 피나콜디보론(Bis(pinacolato)diboron) 39.8 g(156.8 mmol), Pd(dppf)Cl2-CH2Cl2 8.5 g(10.5 mmol), KOAc 30.8 g(313.7 mmol) 및 1,4-다이옥산 500 mL를 혼합한 다음, 110℃에서 하루 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고, 셀라이트 패드 여과, 헥산으로 씻어 주었다. 여액을 농축하여 얻어진 고체를 실리카 패드 여과(Hex:EA)를 하였다. 얻어진 화합물을 메탄올을 이용하여 고체화하여, 백색 고체의 화합물(중간체(25)) 38.5 g(수율: 99.4%)을 얻었다.In a 2-neck 1 L flask, 33.8 g (104.6 mmol) of intermediate (24), 39.8 g (156.8 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl 2 -CH 2 Cl 2 8.5 g (10.5) mmol), 30.8 g (313.7 mmol) of KOAc and 500 mL of 1,4-dioxane were mixed, followed by stirring at 110° C. for one day. After the reaction was completed, it was cooled to room temperature, filtered through a Celite pad, and washed with hexane. The solid obtained by concentrating the filtrate was subjected to silica pad filtration (Hex:EA). The obtained compound was solidified using methanol to obtain 38.5 g (yield: 99.4%) of a white solid compound (intermediate (25)).
(중간체(26)의 합성)(Synthesis of Intermediate (26))
2구 2 L 플라스크에서 중간체(25) 38.5g g(104.0 mmol), 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 25.9 g(124.8 mmol), Pd(PPh3)4 3.6 g(3.1 mmol), K2CO3 43.1 g(311.9 mmol), 톨루엔 500 mL, 에탄올 125 mL 및 증류수 125 mL을 혼합한 다음 100℃에서 이틀 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트로 추출하여 무수황산마그네슘으로 건조하였다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 흰색 고체의 화합물(중간체(26)) 33.0 g(수율: 85.6%)을 얻었다.Intermediate (25) 38.5gg (104.0 mmol), 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol) 25.9 g (124.8 mmol), Pd (PPh 3 ) 4 3.6 g in a 2-neck 2 L flask (3.1 mmol), K 2 CO 3 43.1 g (311.9 mmol), 500 mL of toluene, 125 mL of ethanol and 125 mL of distilled water were mixed and stirred at 100° C. for two days. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The obtained mixture was purified by silica gel column chromatography (Hex:EA) to obtain 33.0 g (yield: 85.6%) of the compound as a white solid (intermediate (26)).
(중간체(27)의 합성)(Synthesis of intermediate (27))
1구 1 L 플라스크에서 중간체(26) 33.0 g(89.0 mmol)을 DMF 500 mL에 녹이고 K2CO3 61.5 g(444.8 mmol)을 첨가 후 140℃에서 이틀 동안 반응시켰다. 반응 종료 후 상온으로 냉각한 다음 증류수에 천천이 적가하면서 교반하였다. 고체를 여과한 후 물로 세척하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여, 흰색 고체의 화합물(중간체(27)) 9.0 g(수율: 28.8%)을 얻었다.In a 1-neck 1 L flask, 33.0 g (89.0 mmol) of the intermediate (26) was dissolved in 500 mL of DMF, and 61.5 g (444.8 mmol) of K 2 CO 3 was added thereto, followed by reaction at 140° C. for two days. After completion of the reaction, the mixture was cooled to room temperature and stirred while being added dropwise to distilled water. The solid was filtered and washed with water. The obtained reaction mixture was purified by silica gel column chromatography (Hex) to obtain 9.0 g (yield: 28.8%) of the compound as a white solid (intermediate (27)).
중간체 intermediate 합성예Synthesis example 14: 중간체(31)의 합성 14: Synthesis of intermediate (31)
(중간체(28)의 합성)(Synthesis of Intermediate (28))
2구 2 L 플라스크에서 (4-(트리메틸실리)페닐)보로닉에시드((4-(trimethylsilyl)phenyl)boronic acid) 30.0 g(154.6 mmol), 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 46.5 g(154.6 mmol), Pd(PPh3)4 5.4 g(4.6 mmol), K2CO3 64.1 g(463.7 mmol), 톨루엔 750 mL, 에탄올 190 mL 및 증류수 190 mL을 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 헥산으로 추출하여 무수황산마그네슘으로 건조, 여과, 감압 증류하였다. 얻어진 고체를 헥산에 녹여 실리카 패드 여과한 후 혼합용액(MeOH/DCM)으로 고체화하여, 흰색 고체의 화합물(중간체(28)) 45.6 g(수율: 91.8%)을 얻었다.(4- (trimethylsilyl) phenyl) boronic acid ((4- (trimethylsilyl) phenyl) boronic acid) 30.0 g (154.6 mmol), 1-bromo-2-fluoro-4-io in a 2-neck 2 L flask dobenzene (1-bromo-2-fluoro-4-iodobenzene) 46.5 g (154.6 mmol), Pd (PPh 3 ) 4 5.4 g (4.6 mmol), K 2 CO 3 64.1 g (463.7 mmol), toluene 750 mL, After mixing 190 mL of ethanol and 190 mL of distilled water, the mixture was stirred at 90°C for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with hexane, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid was dissolved in hexane, filtered through a silica pad, and solidified with a mixed solution (MeOH/DCM) to obtain 45.6 g (yield: 91.8%) of a white solid compound (intermediate (28)).
(중간체(29)의 합성)(Synthesis of Intermediate (29))
2구 1 L 플라스크에서 중간체(28) 45.6 g(141.1 mmol), 피나콜디보론(Bis(pinacolato)diboron) 53.7 g(211.6 mmol), Pd(dppf)Cl2-CH2Cl2 11.5 g(14.1 mmol), KOAc 41.5 g(423.2 mmol) 및 1,4-다이옥산 700 mL를 혼합한 다음, 110℃에서 하루 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고, 셀라이트 패드 여과, 클로로포름으로 씻어 주었다. 여액을 농축하여 얻어진 고체를 실리카 패드 여과(Hex:EA)를 하였다. 얻어진 화합물을 메탄올을 이용하여 고체화하여, 백색 고체의 화합물(중간체(29)) 36.0 g(수율: 68.9%)을 얻었다.In a 2-neck 1 L flask, 45.6 g (141.1 mmol) of intermediate (28), 53.7 g (211.6 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl 2 -CH 2 Cl 2 11.5 g (14.1) mmol), 41.5 g (423.2 mmol) of KOAc and 700 mL of 1,4-dioxane were mixed, followed by stirring at 110° C. for one day. After the reaction was completed, it was cooled to room temperature, filtered through a Celite pad, and washed with chloroform. The solid obtained by concentrating the filtrate was subjected to silica pad filtration (Hex:EA). The obtained compound was solidified using methanol to obtain 36.0 g (yield: 68.9%) of a white solid compound (intermediate (29)).
(중간체(30)의 합성)(Synthesis of intermediate (30))
2구 2 L 플라스크에서 중간체(29) 36.0 g(97.2 mmol), 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 24.2 g(116.6 mmol), Pd(PPh3)4 3.4 g(2.9 mmol), K2CO3 40.3 g(291.6 mmol), 톨루엔 500 mL, 에탄올 125 mL 및 증류수 125 mL을 혼합한 다음 100℃에서 이틀 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트로 추출하여 무수황산마그네슘으로 건조하였다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 흰색 고체의 화합물(중간체(30)) 35.0 g(수율: 97.1%)을 얻었다.Intermediate (29) 36.0 g (97.2 mmol), 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol) 24.2 g (116.6 mmol), Pd (PPh 3 ) 4 3.4 g in a 2-neck 2 L flask (2.9 mmol), K 2 CO 3 40.3 g (291.6 mmol), 500 mL of toluene, 125 mL of ethanol and 125 mL of distilled water were mixed and stirred at 100° C. for two days. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The obtained mixture was purified by silica gel column chromatography (Hex:EA) to obtain 35.0 g (yield: 97.1%) of the compound (intermediate (30)) as a white solid.
(중간체(31)의 합성)(Synthesis of intermediate (31))
1구 1 L 플라스크에서 중간체(30) 35.0 g(94.4 mmol)을 DMF 500 mL에 녹이고 K2CO3 39.1 g(283.1 mmol)을 첨가 후 140℃에서 이틀 동안 반응시켰다. 반응 종료 후 상온으로 식히고 증류수 500 mL에 넣어 교반하였다. 고체를 여과한 후 물로 세척하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여, 흰색 고체의 화합물(중간체(31)) 12.0 g(수율: 36.2%)을 얻었다.In a 1-neck 1 L flask, 35.0 g (94.4 mmol) of the intermediate (30) was dissolved in 500 mL of DMF, and 39.1 g (283.1 mmol) of K 2 CO 3 was added thereto, followed by reaction at 140° C. for two days. After completion of the reaction, the mixture was cooled to room temperature, and stirred into 500 mL of distilled water. The solid was filtered and washed with water. The obtained reaction mixture was purified by silica gel column chromatography (Hex) to obtain 12.0 g (yield: 36.2%) of the compound as a white solid (intermediate (31)).
중간체 intermediate 합성예Synthesis example 15: 중간체(35)의 합성 15: Synthesis of intermediate (35)
(중간체(32)의 합성)(Synthesis of Intermediate (32))
2구 2 L 플라스크에서 (4-(트리플루오로메틸)페닐)보론산((4-(trifluoromethyl)phenyl)boronic acid) 18.9 g(99.7 mmol), 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 30.0 g(99.7 mmol), Pd(PPh3)4 5.8 g(5.0 mmol), K2CO3 27.6 g(199.4 mmol), 톨루엔 750 mL, 에탄올 190 mL 및 증류수 190 mL을 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 헥산으로 추출하여 무수황산마그네슘으로 건조, 여과, 감압 증류하였다. 얻어진 고체를 헥산에 녹여 실리카 패드 여과한 후 혼합용액(MeOH/DCM)으로 고체화하여, 흰색 고체의 화합물(중간체(32)) 27.3 g(수율: 85.8%)을 얻었다.In a 2-neck 2 L flask, (4- (trifluoromethyl) phenyl) boronic acid ((4- (trifluoromethyl) phenyl) boronic acid) 18.9 g (99.7 mmol), 1-bromo-2-fluoro-4- Iodobenzene (1-bromo-2-fluoro-4-iodobenzene) 30.0 g (99.7 mmol), Pd (PPh 3 ) 4 5.8 g (5.0 mmol), K 2 CO 3 27.6 g (199.4 mmol), toluene 750 mL , 190 mL of ethanol and 190 mL of distilled water were mixed, and then stirred at 90 °C for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with hexane, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid was dissolved in hexane, filtered through a silica pad, and solidified with a mixed solution (MeOH/DCM) to obtain 27.3 g (yield: 85.8%) of a white solid compound (intermediate (32)).
(중간체(33)의 합성)(Synthesis of Intermediate (33))
2구 1 L 플라스크에서 중간체(32) 27.3 g(85.6 mmol), 피나콜디보론(Bis(pinacolato)diboron) 26.1 g(102.7 mmol), Pd(dppf)Cl2-CH2Cl2 3.5 g(4.3 mmol), KOAc 16.8 g(171.1 mmol) 및 1,4-다이옥산 420 mL를 혼합한 다음, 110℃에서 하루 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고, 셀라이트 패드 여과, 클로로포름으로 씻어 주었다. 여액을 농축하여 얻어진 고체를 실리카 패드 여과(Hex:EA)를 하였다. 얻어진 화합물을 메탄올을 이용하여 고체화하여, 백색 고체의 화합물(중간체(33)) 25.3 g(수율: 80.8%)을 얻었다.In a 2-neck 1 L flask, 27.3 g (85.6 mmol) of intermediate (32), 26.1 g (102.7 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl 2 -CH 2 Cl 2 3.5 g (4.3 mmol), KOAc 16.8 g (171.1 mmol) and 1,4-dioxane 420 mL were mixed, followed by stirring at 110° C. for one day. After the reaction was completed, it was cooled to room temperature, filtered through a Celite pad, and washed with chloroform. The solid obtained by concentrating the filtrate was subjected to silica pad filtration (Hex:EA). The obtained compound was solidified using methanol to obtain 25.3 g (yield: 80.8%) of a white solid compound (intermediate (33)).
(중간체(34)의 합성)(Synthesis of Intermediate (34))
2구 2 L 플라스크에서 중간체(33) 25.3 g(69.1 mmol), 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 14.3 g(69.1 mmol), Pd(PPh3)4 4.0 g(3.5 mmol), K2CO3 19.1 g(138.2 mmol), 톨루엔 500 mL, 에탄올 125 mL 및 증류수 125 mL을 혼합한 다음 100℃에서 이틀 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트로 추출하여 무수황산마그네슘으로 건조하였다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 흰색 고체의 화합물(중간체(34)) 20.2 g(수율: 79.7%)을 얻었다.In a 2-neck 2 L flask, 25.3 g (69.1 mmol) of intermediate (33), 14.3 g (69.1 mmol) of 2-bromo-4-chlorophenol, 4.0 g of Pd (PPh 3 ) 4 (3.5 mmol), K 2 CO 3 19.1 g (138.2 mmol), toluene 500 mL, ethanol 125 mL, and distilled water 125 mL were mixed and stirred at 100° C. for two days. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The obtained mixture was purified by silica gel column chromatography (Hex:EA) to obtain 20.2 g (yield: 79.7%) of the compound as a white solid (intermediate (34)).
(중간체(35)의 합성)(Synthesis of intermediate (35))
1구 500 mL 플라스크에 중간체(34) 20.2 g(55.1 mmol)을 DMF 275 mL에 녹이고 K2CO3 22.8 g(165.2 mmol)을 첨가 후 140℃에서 이틀 동안 반응시켰다. 반응 종료 후 상온으로 식히고 증류수 300 mL에 넣어 교반하였다. 고체를 여과한 후 물로 세척하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여, 흰색 고체의 화합물(중간체(35)) 8.2 g(수율: 42.9%)을 얻었다.In a 1-neck 500 mL flask, 20.2 g (55.1 mmol) of the intermediate (34) was dissolved in 275 mL of DMF, and 22.8 g (165.2 mmol) of K 2 CO 3 was added thereto, followed by reaction at 140° C. for two days. After completion of the reaction, the mixture was cooled to room temperature and stirred in 300 mL of distilled water. The solid was filtered and washed with water. The obtained reaction mixture was purified by silica gel column chromatography (Hex) to obtain 8.2 g (yield: 42.9%) of the compound as a white solid (intermediate (35)).
중간체 intermediate 합성예Synthesis example 16: 중간체(36)의 합성 16: Synthesis of intermediate (36)
2구 1 L 플라스크에서 2-(4-브로모페닐)피리딘(2-(4-bromophenyl)pyridine) 30.0 g(128.2 mmol), 피나콜디보론(Bis(pinacolato)diboron) 48.8 g(192.2 mmol), Pd(dppf)Cl2-CH2Cl2 5.2 g(6.4 mmol), KOAc 37.7 g(98.14 mmol) 및 1,4-다이옥산 640 mL를 혼합한 다음, 110℃에서 하루 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고, 셀라이트 패드 여과를 하고, 클로로포름으로 씻어주었다. 혼합액을 감압 농축하여 실리카겔 패드 여과(Hex:EA)를 두번 진행하였다. 얻어진 노란 오일 형태의 혼합물을 헥산을 이용하여 0℃에서 고체화하여, 백색 고체의 화합물(중간체(36)) 28.0 g(수율: 72.2%)을 얻었다.In a 2-neck 1 L flask, 2- (4-bromophenyl) pyridine (2- (4-bromophenyl) pyridine) 30.0 g (128.2 mmol), pinacol diboron (Bis (pinacolato) diboron) 48.8 g (192.2 mmol) , Pd(dppf)Cl 2 -CH 2 Cl 2 5.2 g (6.4 mmol), KOAc 37.7 g (98.14 mmol) and 1,4-dioxane 640 mL were mixed, followed by stirring at 110° C. for one day. After the reaction was completed, it was cooled to room temperature, filtered through a celite pad, and washed with chloroform. The mixture was concentrated under reduced pressure, and silica gel pad filtration (Hex:EA) was performed twice. The obtained mixture in the form of yellow oil was solidified at 0° C. using hexane to obtain 28.0 g (yield: 72.2%) of the compound (intermediate (36)) as a white solid.
중간체 intermediate 합성예Synthesis example 16-1: 중간체(38)의 합성 16-1: Synthesis of intermediate (38)
(중간체(37)의 합성)(Synthesis of intermediate (37))
1구 2 L 플라스크에서 1-브로모-4-클로로벤젠 (1-bromo-4-chlorobenzene) 30.0 g(156.7 mmol), 3,5-비스트리플루오로메틸페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 40.4 g(156.7 mmol), Pd(PPh3)4 5.4 g(4.7 mmol), K2CO3 65.0 g(470.1 mmol), 톨루엔 500 mL, 에탄올 150 mL 및 물 150 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 에틸아세테이트로 추출한 후 반응액을 농축하였다. 반응 혼합물을 컬럼 크로마토그래피(Hex)로 정제하여, 흰색 액체의 화합물(중간체(37)) 50.8 g(수율: 99.9%)을 얻었다.In a 1-neck 2 L flask, 1-bromo-4-chlorobenzene (1-bromo-4-chlorobenzene) 30.0 g (156.7 mmol), 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis ( trifluoromethyl)phenyl)boronic acid) 40.4 g (156.7 mmol), Pd(PPh 3 ) 4 5.4 g (4.7 mmol), K 2 CO 3 65.0 g (470.1 mmol), toluene 500 mL, ethanol 150 mL, and water 150 mL After mixing, the mixture was stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with ethyl acetate. The reaction mixture was purified by column chromatography (Hex) to obtain 50.8 g (yield: 99.9%) of the compound (intermediate (37)) as a white liquid.
(중간체(38)의 합성)(Synthesis of Intermediate (38))
1구 2 L 플라스크에서 중간체(37) 50.8 g(156.5 mmol), 피나콜디보론(Bis(pinacolato)diboron) 51.6 g(203.4 mmol), Pd(dba)2 14.3 g(15.7 mmol), X-phos 14.9 g(31.3 mmol), KOAc 46.1 g(436.6 mmol) 및 톨루엔 650 mL를 혼합한 다음, 110℃에서 12시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 노란색 고체의 화합물(중간체(38)) 54.6 g(수율: 83.8%)을 얻었다. In a 1-neck 2 L flask, intermediate (37) 50.8 g (156.5 mmol), pinacol diboron (Bis(pinacolato)diboron) 51.6 g (203.4 mmol), Pd(dba) 2 14.3 g (15.7 mmol), X-phos 14.9 g (31.3 mmol), 46.1 g (436.6 mmol) of KOAc and 650 mL of toluene were mixed and stirred at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 54.6 g (yield: 83.8%) of the compound (intermediate (38)) as a yellow solid.
중간체 intermediate 합성예Synthesis example 17: 중간체(40)의 합성 17: Synthesis of intermediate (40)
(중간체(39)의 합성)(Synthesis of Intermediate (39))
2구 500 mL 플라스크에서 7-브로모-2-클로로벤조[b,d]퓨란(7-bromo-2-chlorodibenzo[b,d]furan) 10.0 g(35.5 mmol), 중간체(1) 13.7 g(42.6 mmol), Pd(PPh3)4 1.2 g(1.1 mmol), K2CO3 14.7 g(106.6 mmol), 톨루엔 180 mL, 에탄올 45 mL 및 증류수 45 mL을 혼합한 다음 90℃에서 6시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 증류수를 넣은 후 여과, 증류수, 메탄올, 헥산, 에틸아세테이트로 씻어주었다. 얻어진 고체 화합물을 뜨거운 모노클로로벤젠에 녹여 실리카겔 패드 여과를 하고, 얻어진 화합물을 모노클로로벤젠으로 고체화하여, 흰색 고체의 화합물(중간체(39)) 12.5 g(수율: 88.9%)을 얻었다.In a two-necked 500 mL flask, 10.0 g (35.5 mmol) of 7-bromo-2-chlorobenzo [b, d] furan, 13.7 g of the intermediate (1) ( 42.6 mmol), Pd(PPh 3 ) 4 1.2 g (1.1 mmol), K 2 CO 3 14.7 g (106.6 mmol), toluene 180 mL, ethanol 45 mL, and distilled water 45 mL were mixed and stirred at 90° C. for 6 hours. did. After the reaction was completed, it was cooled to room temperature, distilled water was added, and then filtered, washed with distilled water, methanol, hexane, and ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and the obtained compound was solidified with monochlorobenzene to obtain 12.5 g (yield: 88.9%) of the compound as a white solid (intermediate (39)).
(중간체(40)의 합성)(Synthesis of intermediate (40))
2구 250 mL 플라스크에서 중간체(39) 11.5 g(29.1 mmol), 피나콜디보론(Bis(pinacolato)diboron) 15.4 g(43.6 mmol), Pd2(dba)3 1.7 g(2.9 mmol), KOAc 8.6 g(87.2 mmol), X-Phos 2.8 g(5.8 mmol) 및 톨루엔 145 mL를 혼합한 다음, 120℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후 여과하고, 증류수, 메탄올, 헥세인으로 씻어주었다. 얻어진 혼합물을 톨루엔에 녹여 실리카 패드 여과하여, 백색 고체의 화합물(중간체(40)) 10.1 g(수율: 98.7%)을 얻었다.In a 2-neck 250 mL flask, 11.5 g (29.1 mmol) of intermediate (39), 15.4 g (43.6 mmol) of pinacol diboron (Bis(pinacolato)diboron), 1.7 g (2.9 mmol) of Pd 2 (dba) 3 , KOAc 8.6 g (87.2 mmol), 2.8 g (5.8 mmol) of X-Phos and 145 mL of toluene were mixed, and then reacted at 120° C. for one day. Upon completion of the reaction, the mixture was cooled to room temperature, filtered, and washed with distilled water, methanol, and hexane. The obtained mixture was dissolved in toluene and filtered through a silica pad to obtain 10.1 g (yield: 98.7%) of the compound (intermediate (40)) as a white solid.
중간체 intermediate 합성예Synthesis example 18: 중간체(41)의 합성 18: Synthesis of intermediate (41)
1구 250 mL 플라스크에서 7-브로모-2-클로로다이벤조퓨란(7-bromo-2-chlorodibenzo[b,d]furan) 4.5 g(16.0 mmol), 중간체(7) 5.3 g(16.0 mmol), Pd(PPh3)4 923.0 mg(799.2 μmol), K2CO3 5.5 g(40.0 mmol), 톨루엔 50 mL, 에탄올 15 mL 및 물 15 mL을 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올, 에틸아세테이트로 씻어서 건조하여, 회색 고체의 화합물(중간체(41)) 5.1 g(수율: 78.9%)을 얻었다.In a 1-neck 250 mL flask, 7-bromo-2-chlorodibenzofuran (7-bromo-2-chlorodibenzo[b,d]furan) 4.5 g (16.0 mmol), intermediate (7) 5.3 g (16.0 mmol), Pd(PPh 3 ) 4 923.0 mg (799.2 μmol), K 2 CO 3 5.5 g (40.0 mmol), toluene 50 mL, ethanol 15 mL, and water 15 mL were mixed and stirred under reflux for 12 hours. After completion of the reaction, the reaction was cooled to room temperature, the solid was filtered, washed with water, methanol, and ethyl acetate, and dried, as a gray solid compound (Intermediate (41)) 5.1 g (yield: 78.9%) was obtained.
중간체 intermediate 합성예Synthesis example 19: 중간체(45)의 합성 19: Synthesis of intermediate (45)
(중간체(42)의 합성)(Synthesis of Intermediate (42))
2구 500 mL 플라스크에서 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 13.2 g(43.9 mmol), 중간체(7) 16.0 g(48.3 mmol), Pd(PPh3)4 2.5 g(2.2 mmol), K2CO3 21.6 g(153.8 mmol), 톨루엔 130 mL, 정제수 60 mL 및 에탄올 50 mL를 혼합한 다음, 90℃에서 3시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하여 생성된 고체를 여과하였다. 반응 혼합물을 디클로로메탄/메탄올로 고체화하여, 미색 고체의 화합물(중간체(42)) 8.8 g(수율: 53.1%)을 얻었다.In a 2-neck 500 mL flask, 13.2 g (43.9 mmol) of 1-bromo-2-fluoro-4-iodobenzene (1-bromo-2-fluoro-4-iodobenzene), 16.0 g (48.3 mmol) of the intermediate (7) ), Pd(PPh 3 ) 4 2.5 g (2.2 mmol), K 2 CO 3 21.6 g (153.8 mmol), 130 mL of toluene, 60 mL of purified water and 50 mL of ethanol were mixed, and then reacted at 90° C. for 3 hours. After the reaction was completed, it was cooled to room temperature and the resulting solid was filtered. The reaction mixture was solidified with dichloromethane/methanol to obtain 8.8 g (yield: 53.1%) of the compound (intermediate (42)) as an off-white solid.
(중간체(43)의 합성)(Synthesis of intermediate (43))
2구 250 mL 플라스크에서 중간체(42) 8.8 g(26.8 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 10.2 g(40.2 mmol), Pd(dppf)Cl2 1.0 g(1.3 mmol), KOAc 6.6 g(67.0 mmol) 및 1,4-디옥산 100 mL를 혼합한 다음 105℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 후 셀라이트 여과 후 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물(중간체(43)) 6.3 g(수율: 55.7%)을 얻었다.In a 2-neck 250 mL flask, 8.8 g (26.8 mmol) of intermediate (42), 10.2 g (40.2 mmol) of bis(pinacolato)diboron, 1.0 g (1.3 mmol) of Pd(dppf)Cl 2 ), 6.6 g (67.0 mmol) of KOAc and 100 mL of 1,4-dioxane were mixed and stirred at 105° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite, and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with methanol to obtain 6.3 g (yield: 55.7%) of the compound as a white solid (intermediate (43)).
(중간체(44)의 합성)(Synthesis of Intermediate 44)
2구 250 mL 플라스크에서 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 3.2 g(15.7 mmol), 중간체(43) 6.3 g(15.0 mmol), Pd(PPh3)4 0.9 g(0.7 mmol), K2CO3 5.2 g(37.4 mmol), 톨루엔 40 mL, 정제수 20 mL 및 에탄올 15 mL를 혼합한 다음, 90℃에서 3시간 동안 반응하였다. 반응이 종결된 후 생성된 고체를 여과하였다. 반응 혼합물을 헥산으로 고체화하여, 미색 고체의 화합물(중간체(44)) 5.8 g(수율: 91.0%)을 얻었다.In a 2-neck 250 mL flask, 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol) 3.2 g (15.7 mmol), Intermediate (43) 6.3 g (15.0 mmol), Pd (PPh 3 ) 4 0.9 g (0.7 mmol), K 2 CO 3 5.2 g (37.4 mmol), 40 mL of toluene, 20 mL of purified water and 15 mL of ethanol were mixed, and then reacted at 90° C. for 3 hours. After the reaction was completed, the resulting solid was filtered. The reaction mixture was solidified with hexane to obtain 5.8 g (yield: 91.0%) of the compound (intermediate (44)) as an off-white solid.
(중간체(45)의 합성)(Synthesis of Intermediate (45))
1구 250 mL 플라스크에서 중간체(44) 5.8 g(13.6 mmol), K2CO3 4.7 g(34.0 mmol) 및 DMF 70 mL를 혼합한 다음, 100℃에서 하루 동안 반응하였다. 반응이 종결된 후 상온으로 냉각시킨 후 정제수를 첨가하여 생성된 고체를 여과하였다. 반응 혼합물을 뜨거운 MCB에 용해시킨 후 실리카겔에 여과한 후 디클로로메탄/메탄올로 고체화하여, 옅은 갈색 고체의 화합물(중간체(45)) 2.9 g(수율: 53.6%)을 얻었다.5.8 g (13.6 mmol) of intermediate (44), K 2 CO 3 in a one-necked 250 mL flask 4.7 g (34.0 mmol) and 70 mL of DMF were mixed, and then reacted at 100° C. for one day. After completion of the reaction, after cooling to room temperature, purified water was added and the resulting solid was filtered. The reaction mixture was dissolved in hot MCB, filtered through silica gel, and then solidified with dichloromethane/methanol to obtain 2.9 g (yield: 53.6%) of the compound (intermediate (45)) as a pale brown solid.
중간체 intermediate 합성예Synthesis example 20: 중간체(49)의 합성 20: Synthesis of intermediate (49)
(중간체(46)의 합성)(Synthesis of Intermediate (46))
1구 1 L 플라스크에서 1-브로모-2-플루오로-4-아이오도벤젠(1-bromo-2-fluoro-4-iodobenzene) 38.0 g(126.3 mol), 중간체(36) 35.7 g(126.3 mmol), Pd(PPh3)4 4.4 g(6.3 mmol), 2M K2CO3 158.0 mL(315.7 mmol), 톨루엔 400 mL 및 에탄올 100 mL을 혼합한 다음 8 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:DCM)로 정제하여 고체화하여, 흰색 고체의 화합물(중간체(46)) 21.9 g(수율: 52.8%)을 얻었다.In a 1-neck 1 L flask, 1-bromo-2-fluoro-4-iodobenzene (1-bromo-2-fluoro-4-iodobenzene) 38.0 g (126.3 mol), Intermediate (36) 35.7 g (126.3 mmol) ), Pd(PPh 3 ) 4 4.4 g (6.3 mmol), 2M K 2 CO 3 158.0 mL (315.7 mmol), toluene 400 mL, and ethanol 100 mL were mixed and stirred under reflux for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:DCM) and solidified to obtain 21.9 g (yield: 52.8%) of the compound (intermediate (46)) as a white solid.
(중간체(47)의 합성)(Synthesis of intermediate (47))
1구 1 L 플라스크에서 중간체(46) 21.9 g(66.7 mmol), 피나콜디보론(Bis(pinacolato)diboron) 20.3 g(80.1 mmol), Pd(dppf)Cl2-CH2Cl2 2.7 g(3.3 mmol), KOAc 19.7 g(200.2 mmol) 및 1,4-디옥산 300 mL를 혼합한 다음, 100℃에서 12시간 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드에 통과시킨 후 감압 농축하였다. 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3:EA)로 정제하여, 노란색 액체의 화합물(중간체(47)) 23.0 g(91.9%)을 얻었다.In a 1-neck 1 L flask, 21.9 g (66.7 mmol) of intermediate (46), 20.3 g (80.1 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl 2 -CH 2 Cl 2 2.7 g (3.3 mmol), KOAc 19.7 g (200.2 mmol) and 1,4-dioxane 300 mL were mixed, and then stirred at 100° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 :EA) to obtain 23.0 g (91.9%) of the compound (intermediate (47)) as a yellow liquid.
(중간체(48)의 합성)(Synthesis of Intermediate (48))
1구 1 L 플라스크에서 중간체(47) 23.0 g(61.3 mmol), 2-브로모-4-클로로페놀(2-bromo-4-chlorophenol) 12.7 g(61.3 mmol), Pd(PPh3)4 5.5 g(3.1 mmol), 2M K2CO3 92.0 mL(183.9 mmol), 톨루엔 250 mL 및 에탄올 50 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(48)) 5.7 g(수율: 24.7%)을 얻었다.Intermediate (47) 23.0 g (61.3 mmol), 2-bromo-4-chlorophenol (2-bromo-4-chlorophenol) 12.7 g (61.3 mmol), Pd (PPh 3 ) 4 5.5 g in a 1-neck 1 L flask (3.1 mmol), 2M K 2 CO 3 92.0 mL (183.9 mmol), toluene 250 mL, and ethanol 50 mL were mixed and stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 5.7 g (yield: 24.7%) of the compound (intermediate (48)) as a white solid.
(중간체(49)의 합성)(Synthesis of Intermediate (49))
1구 500 mL 플라스크에서 중간체(48) 5.7 g(15.1 mmol), K2CO3 5.2 g(37.9 mmol)과 DMF 70 mL를 혼합한 후 100 ℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣어 교반하였다. 이때 얻어진 고체를 여과한 후 물로 씻어서 건조하여 노란색 고체의 화합물(중간체(49)) 3.0 g(수율: 55.7%)을 얻었다.5.7 g (15.1 mmol) of intermediate (48) in a one-necked 500 mL flask, K 2 CO 3 After mixing 5.2 g (37.9 mmol) and 70 mL of DMF, the mixture was reacted at 100 °C for 12 hours. After the reaction was completed, it was cooled to room temperature, and water was added and stirred. At this time, the obtained solid was filtered, washed with water and dried to obtain 3.0 g (yield: 55.7%) of a yellow solid compound (intermediate (49)).
중간체 intermediate 합성예Synthesis example 21: 중간체(50)의 합성 21: Synthesis of intermediate (50)
1구 500 mL 플라스크에서 7-브로모-2-클로로벤조퓨란(7-bromo-2-chlorodibenzo[b,d]furan) 5.0 g(17.8 mmol), 바이페닐보론산([1,1'-biphenyl]-4-ylboronic acid) 3.5 g(17.8 mmol), Pd(PPh3)4 1.0 g(888.0 μmol), K2CO3 6.1 g(44.4 mmol), 톨루엔 60 mL, 에탄올 15 mL 및 물 15 mL를 혼합한 다음 5 시간 동안 환류 교반하였다. 반응이 종결된 후 고체를 여과하고 물과 메탄올로 씻어서 건조하여, 회색 고체의 화합물(중간체(50)) 4.7 g(수율: 75.1%)을 얻었다.In a 1-neck 500 mL flask, 5.0 g (17.8 mmol) of 7-bromo-2-chlorodibenzo[b,d]furan, biphenylboronic acid ([1,1'-biphenyl) ]-4-ylboronic acid) 3.5 g (17.8 mmol), Pd(PPh 3 ) 4 1.0 g (888.0 μmol), K 2 CO 3 6.1 g (44.4 mmol), toluene 60 mL, ethanol 15 mL, and water 15 mL After mixing, the mixture was stirred under reflux for 5 hours. After the reaction was completed, the solid was filtered, washed with water and methanol, and dried to obtain 4.7 g (yield: 75.1%) of the compound as a gray solid (intermediate (50)).
중간체 intermediate 합성예Synthesis example 22: 중간체(51)의 합성 22: Synthesis of intermediate (51)
2구 250 mL 플라스크에서 1-브로모-4-요오드디벤조퓨란(1-bromo-4-iododibenzo[b,d]furan) 8.7 g(23.2 mmol), 중간체(7) 7.0 g(21.1 mmol), Pd(PPh3)4 2.4 g(2.1 mmol), K3PO4 13.5 g(63.4 mmol), 톨루엔 84 mL, 정제수 35 mL 및 에탄올 28 mL를 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 생성된 고체를 여과하고 정제수와 메탄올로 세척하여, 흰색 고체의 화합물(51) 6.7 g(수율: 70.8%)을 얻었다.In a 2-neck 250 mL flask, 1-bromo-4-iododibenzofuran (1-bromo-4-iododibenzo[b,d]furan) 8.7 g (23.2 mmol), intermediate (7) 7.0 g (21.1 mmol), Pd(PPh 3 ) 4 2.4 g (2.1 mmol), K 3 PO 4 13.5 g (63.4 mmol), toluene 84 mL, purified water 35 mL, and ethanol 28 mL were mixed and stirred at 90° C. for one day. After the reaction was completed, the resulting solid was filtered and washed with purified water and methanol to obtain 6.7 g (yield: 70.8%) of compound (51) as a white solid.
중간체 intermediate 합성예Synthesis example 23: 중간체(52)의 합성 23: Synthesis of intermediate (52)
1-브로모-4-요오드디벤조퓨란(1-bromo-4-iododibenzo[b,d]furan) 10g(26.8 mmol), 중간체(36) 7.5 g(26.8 mmol), Pd(PPh3)4 0.9 g(0.8 mmol), K2CO3 9.3 g(67.0 mmol), Dioxane 80 mL 및 증류수 20 mL을 혼합한 다음 40 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 CHCl3와 물로 씻었다. 얻어진 혼합물을 실리카겔 컬럼크로마토 그래피(CHCl3)로 정제하여 흰색 고체의 화합물(중간체(52)) 6.0 g(수율: 55.5%)을 얻었다.1-bromo-4-iododibenzofuran (1-bromo-4-iododibenzo[b,d]furan) 10g (26.8 mmol), intermediate (36) 7.5 g (26.8 mmol), Pd (PPh 3 ) 4 0.9 g (0.8 mmol), K 2 CO 3 9.3 g (67.0 mmol), 80 mL of Dioxane and 20 mL of distilled water were mixed and stirred under reflux for 40 hours. After the reaction was completed, it was cooled to room temperature and washed with CHCl 3 and water. The obtained mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 6.0 g (yield: 55.5%) of the compound as a white solid (intermediate (52)).
중간체 intermediate 합성예Synthesis example 24: 중간체(55)의 합성 24: Synthesis of intermediate (55)
(중간체(53)의 합성)(Synthesis of intermediate (53))
브로모-3-플루오로-2-아이오도벤젠(1-bromo-3-fluoro-2-iodobenzene) 60.0 g(321.9 mmol), 4-클로로-2-메톡시페닐보론산((4-chloro-2-methoxyphenyl)boronic acid) 116.0 g(386.3 mmol), Pd(PPh3)4 11.2 g(9.7 mmol), 2M K2CO3 400.0 mL(804.7 mmol), 톨루엔 600 mL 및 에탄올 200 mL을 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 에틸아세테이트로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여, 투명한 액체의 화합물(중간체(53)) 46.9 g(수율: 46.2%)을 얻었다.Bromo-3-fluoro-2-iodobenzene (1-bromo-3-fluoro-2-iodobenzene) 60.0 g (321.9 mmol), 4-chloro-2-methoxyphenyl boronic acid ((4-chloro- 2-methoxyphenyl)boronic acid) 116.0 g (386.3 mmol), Pd(PPh 3 ) 4 11.2 g (9.7 mmol), 2M K 2 CO 3 400.0 mL (804.7 mmol), toluene 600 mL, and ethanol 200 mL were mixed. The mixture was stirred at reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) to obtain 46.9 g (yield: 46.2%) of the compound (intermediate (53)) as a clear liquid.
(중간체(54)의 합성)(Synthesis of intermediate 54)
1구 3 L 플라스크에서 중간체(53) 90.9 g(288.1 mmol)과 디클로로메탄 900 mL를 혼합한 다음 0℃로 온도를 낮추고, BBr3 30 mL(316.9 mmol)를 디클로로메탄 60 mL에 희석시킨 후 천천히 적가하였다. 서서히 상온으로 온도를 올린 후 12 시간 동안 교반하였다. 0℃로 온도를 낮추고 물로 천천히 중화시키고 3시간 동안 교반하였다. 유기층을 분리한 후, 물과 포화 Na2CO3 수용액으로 한번씩 더 씻어준 후 감압 농축하였다. 반응 혼합물을 실리카 패드(DCM)에 통과시킨 후, 노란색 액체의 화합물(중간체(54)) 86.8 g(수율: 99.9%)을 얻었다.In a 1-neck 3 L flask, 90.9 g (288.1 mmol) of the intermediate (53) and 900 mL of dichloromethane were mixed, the temperature was lowered to 0 °C, and 30 mL (316.9 mmol) of BBr 3 was diluted in 60 mL of dichloromethane, and then slowly was added dropwise. After slowly raising the temperature to room temperature, the mixture was stirred for 12 hours. The temperature was lowered to 0°C, neutralized slowly with water, and stirred for 3 hours. After separating the organic layer, it was washed once more with water and saturated Na 2 CO 3 aqueous solution, and then concentrated under reduced pressure. After passing the reaction mixture through a pad of silica (DCM), 86.8 g (yield: 99.9%) of the compound (intermediate (54)) as a yellow liquid was obtained.
(중간체(55)의 합성)(Synthesis of intermediate (55))
1구 2 L 플라스크에서 중간체(54) 86.8 g(287.9 mmol), K2CO3 119.0 g(863.6 mmol) 및 DMF 1.0 L를 혼합한 다음 2 시간 동안 100 ℃에서 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 교반하였다. 형성된 고체를 여과한 다음 물과 에탄올로 씻어서 건조하여, 흰색 고체의 화합물(중간체(55)) 71.9 g(수율: 88.7%)을 얻었다.86.8 g (287.9 mmol) of intermediate (54), 119.0 g (863.6 mmol) of K 2 CO 3 and 1.0 L of DMF were mixed in a 1-neck 2 L flask, followed by reaction at 100° C. for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the mixture was stirred. The formed solid was filtered, washed with water and ethanol, and dried to obtain 71.9 g (yield: 88.7%) of a white solid compound (intermediate (55)).
중간체 intermediate 합성예Synthesis example 25: 중간체(57)의 합성 25: Synthesis of intermediate (57)
(중간체(56)의 합성)(Synthesis of Intermediate (56))
1구 2 L 플라스크에서 중간체(55) 20.0 g(71.0 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 18.7 g(72.5 mmol), Pd(PPh3)4 4.1 g(3.55 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(56)) 26.3 g(수율: 88.9%)을 얻었다.20.0 g (71.0 mmol) of intermediate (55), 18.7 g (72.5 mmol) of 3,5-bis(trifluoromethyl)phenyl)boronic acid) in a 1-neck 2 L flask, Pd (PPh 3 ) 4 4.1 g (3.55 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL, and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 26.3 g (yield: 88.9%) of the compound as a white solid (intermediate (56)).
(중간체(57)의 합성)(Synthesis of intermediate (57))
중간체(56) 20.0 g(48.2 mmol), 피나콜디보론(Bis(pinacolato)diboron) 18.4 g(72.3 mmol), Pd2(dba)3 4.4 g(4.8 mmol), X-Phos 4.6 g(9.6 mmol), KOAc 14.2 g(144.7 mmol) 및 톨루엔 240 mL를 혼합한 다음, 3시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 반응물을 셀라이트 패드(CHCl3)에 통과시킨 후 감압 농축하였다. 반응 혼합물을 혼합용액(DCM/MeOH)로 고체화하여 흰색 고체의 화합물(중간체(57)) 19.4 g(수율: 79.5%)을 얻었다.Intermediate (56) 20.0 g (48.2 mmol), pinacol diboron (Bis(pinacolato)diboron) 18.4 g (72.3 mmol), Pd 2 (dba) 3 4.4 g (4.8 mmol), X-Phos 4.6 g (9.6 mmol) ), KOAc 14.2 g (144.7 mmol) and 240 mL of toluene were mixed, and then stirred under reflux for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad (CHCl 3 ) and concentrated under reduced pressure. The reaction mixture was solidified with a mixed solution (DCM/MeOH) to obtain 19.4 g (yield: 79.5%) of the compound (intermediate (57)) as a white solid.
중간체 intermediate 합성예Synthesis example 26: 중간체(58)의 합성 26: Synthesis of intermediate (58)
2,8-다이브로모다이벤조[b,d]티오펜(2,8-dibromodibenzo[b,d]thiophene) 10.0 g(29.2 mmol), (3,5-비스(트리플루오로메틸)페닐보론산((3,5-bis (trifluoromethyl)phenyl)boronic acid) 7.9 g(30.7 mmol), Pd(PPh3)4 1.0 g(877.1 μmol), K2CO3 12.1 g(87.7 mmol), 톨루엔 150 mL, 에탄올 37 mL 및 증류수 37 mL을 혼합한 다음 90℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트로 추출하여 유기층을 무수 황산마그네슘을 이용하여 건조, 여과, 감압 증류하였다. 얻어진 고체 혼합물을 실리카겔 컬럼(Hex)으로 정제하여, 흰색 고체의 화합물(중간체(58)) 4.9 g(수율: 35.3%)을 얻었다.2,8-dibromodibenzo[b, d ]thiophene (2,8-dibromodibenzo[b,d]thiophene) 10.0 g (29.2 mmol), (3,5-bis(trifluoromethyl)phenylboronic acid ((3,5-bis (trifluoromethyl)phenyl)boronic acid) 7.9 g (30.7 mmol), Pd(PPh 3 ) 4 1.0 g (877.1 μmol), K 2 CO 3 12.1 g (87.7 mmol), toluene 150 mL, After mixing 37 mL of ethanol and 37 mL of distilled water, the mixture was stirred for one day at 90° C. After completion of the reaction, the reaction was cooled to room temperature, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid mixture was purified by a silica gel column (Hex) to obtain 4.9 g (yield: 35.3%) of the compound as a white solid (intermediate (58)).
중간체 intermediate 합성예Synthesis example 27: 중간체(59)의 합성 27: Synthesis of intermediate (59)
2구 500 mL 플라스크에서 2,8-디브로모다이벤조[b,d]티오펜(2,8-dibromodibenzo[b,d]thiophene) 10.0 g(29.2 mmol), 중간체(36) 8.2 g(29.2 mmol), Pd(PPh3)4 1.0 g(877.1 μmol), K2CO3 12.1 g(87.7 mmol), 톨루엔 150 mL, 에탄올 37 mL 및 물 37 mL을 혼합한 다음 90℃에서 하루 동안 교반 하였다. 반응이 종결된 후 상온으로 냉각하고, 에틸아세테이트로 추출하여 유기층을 무수 황산마그네슘을 이용하여 건조, 여과, 감압 증류하였다. 얻어진 고체 혼합물을 실리카겔 컬럼(Tol:EA)으로 정제하여, 흰색 고체의 화합물(중간체(59)) 3.3 g(수율: 27.1%)을 얻었다.2,8-dibromodibenzo[b, d ]thiophene (2,8-dibromodibenzo[b,d]thiophene) 10.0 g (29.2 mmol) in a 2-neck 500 mL flask, 8.2 g (29.2 mmol) of the intermediate (36) ), Pd(PPh 3 ) 4 1.0 g (877.1 μmol), K 2 CO 3 12.1 g (87.7 mmol), toluene 150 mL, ethanol 37 mL, and water 37 mL were mixed and stirred at 90° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid mixture was purified by silica gel column (Tol:EA) to obtain 3.3 g (yield: 27.1%) of the compound as a white solid (intermediate (59)).
중간체 intermediate 합성예Synthesis example 28: 중간체(61)의 합성 28: Synthesis of intermediate (61)
(중간체(60)의 합성)(Synthesis of Intermediate (60))
1구 2 L 플라스크에서 3-브로모-9-페닐-9H-카바졸(3-bromo-9-phenyl-9H-carbazole) 20.0 g(62.1 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 19.3 g(74.5 mmol), Pd(PPh3)4 3.6 g(3.1 mmol), K2CO3 21.5 g(155.2 mmol), 톨루엔 150 mL, 에탄올 50 mL 및 물 50 mL를 혼합한 다음 하루 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 클로로포름으로 추출하여 용매를 감압 농축하였다. 반응 혼합물을 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 혼합용액(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물(중간체(60)) 18.4 g(수율: 65.1%)을 얻었다.3-bromo-9-phenyl-9H-carbazole 20.0 g (62.1 mmol), 3,5-bistrifluoromethylphenylboronic acid in a 1-neck 2 L flask (3,5-bis(trifluoromethyl)phenyl)boronic acid) 19.3 g (74.5 mmol), Pd(PPh 3 ) 4 3.6 g (3.1 mmol), K 2 CO 3 21.5 g (155.2 mmol), toluene 150 mL, ethanol 50 mL and 50 mL of water were mixed and then stirred at reflux for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with chloroform, and the solvent was concentrated under reduced pressure. The reaction mixture was purified by column chromatography (Hex:CHCl 3 ) and solidified with a mixed solution (DCM/EtOH) to obtain 18.4 g (yield: 65.1%) of the compound as a white solid (intermediate (60)).
(중간체(61)의 합성)(Synthesis of Intermediate (61))
1구 1 L 플라스크에서 중간체(60) 18.4 g(40.4 mmol)을 DMF 200 mL에 녹인다. NBS 7.2 g(40.4 mmol)을 천천히 넣어준 후, 상온에서 12시간 반응하였다. 반응이 종료되면 물을 반응물에 넣고 교반하여 얻은 고체를 여과한 후 물과 헥산으로 씻어서 건조하여, 핑크색 고체의 화합물(중간체(61)) 20.4 g(수율: 94.5%)을 얻었다.Dissolve 18.4 g (40.4 mmol) of Intermediate (60) in 200 mL of DMF in a 1-neck 1 L flask. After slowly adding 7.2 g (40.4 mmol) of NBS, the reaction was conducted at room temperature for 12 hours. When the reaction was completed, water was added to the reaction mixture, and the solid obtained by stirring was filtered, washed with water and hexane, and dried to obtain 20.4 g (yield: 94.5%) of a pink solid compound (intermediate (61)).
중간체 intermediate 합성예Synthesis example 29: 중간체(64)의 합성 29: Synthesis of intermediate (64)
(중간체(62)의 합성)(Synthesis of Intermediate 62)
4구 3000 mL 플라스크에서 4-브로모-2-플루오로-1-아이오도벤젠(4-bromo-2-fluoro-1-iodobenzene) 180.0 g(598.2 mmol), (4-클로로-2-메톡시페닐)보론산((4-chloro-2-methoxyphenyl)boronic acid) 111.5 g(598.2 mmol), Pd(PPh3)4 34.5 g(29.9 mmol), K2CO3 206.7 g(1495.6 mmol), 톨루엔 1000 mL, 정제수 600 mL 및 에탄올 300 mL를 혼합한 다음 80℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 에틸아세테이트로 추출하여 유기층을 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex)로 정제하여 투명한 액체의 화합물(중간체(62)) 198.3 g(수율: 105.0%)을 얻었다.In a 4-necked 3000 mL flask, 180.0 g (598.2 mmol) of 4-bromo-2-fluoro-1-iodobenzene (4-bromo-2-fluoro-1-iodobenzene), (4-chloro-2-methoxy Phenyl) boronic acid ((4-chloro-2-methoxyphenyl) boronic acid) 111.5 g (598.2 mmol), Pd(PPh 3 ) 4 34.5 g (29.9 mmol), K 2 CO 3 206.7 g (1495.6 mmol), toluene 1000 mL, 600 mL of purified water, and 300 mL of ethanol were mixed and stirred at 80° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex) to obtain 198.3 g (yield: 105.0%) of the compound (intermediate (62)) as a clear liquid.
(중간체(63)의 합성)(Synthesis of intermediate (63))
2구 3000 mL 플라스크에서 중간체(62) 180.0 g(570.4 mmol)과 피리딘 염화수소(pyridine hydrochloride) 675.0 g(5703.9 mmol)를 혼합한 다음 190℃에서 7시간 동안 교반하였다. 반응이 종결된 후 60℃로 냉각시킨 다음 정제수와 디클로로메탄을 넣고 교반하였다. 유기층을 추출하여 감압 농축 후 디클로로메탄에 용해시켜 실리카에 여과하였다. 얻어진 반응 혼합물을 헥산을 넣고 상온에서 1시간 교반 후 여과하여, 옅은 붉은색 고체의 화합물(중간체(63)) 85.7 g(수율: 49.8%)을 얻었다.180.0 g (570.4 mmol) of the intermediate (62) and 675.0 g (5703.9 mmol) of pyridine hydrochloride were mixed in a two-necked 3000 mL flask, followed by stirring at 190° C. for 7 hours. After completion of the reaction, the mixture was cooled to 60° C., purified water and dichloromethane were added thereto, and the mixture was stirred. The organic layer was extracted, concentrated under reduced pressure, dissolved in dichloromethane, and filtered over silica. Hexane was added to the obtained reaction mixture, stirred at room temperature for 1 hour, and then filtered to obtain 85.7 g (yield: 49.8%) of a pale red solid compound (intermediate (63)).
(중간체(64)의 합성)(Synthesis of Intermediate (64))
4구 3000 mL 플라스크에서 중간체(63) 85.7 g(284.2 mmol), K2CO3 117.8 g(852.6 mmol) 및 DMF 800 mL를 혼합한 다음, 105℃에서 하루 동안 반응하였다. 반응이 종결된 후 상온으로 냉각시킨 다음 정제수를 넣고 석출된 고체를 여과하였다. 얻어진 반응 혼합물을 메탄올/헥산을 넣고 실온에서 1시간 교반 후 여과하여 흰색의 고체 화합물(중간체(64)) 69.1 g(수율: 86.4%)을 얻었다.85.7 g (284.2 mmol) of intermediate (63) in a 4-necked 3000 mL flask, K 2 CO 3 117.8 g (852.6 mmol) and 800 mL of DMF were mixed, and then reacted at 105° C. for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, and the precipitated solid was filtered. Methanol/hexane was added to the obtained reaction mixture, stirred at room temperature for 1 hour, and then filtered to obtain 69.1 g (yield: 86.4%) of a white solid compound (intermediate (64)).
중간체 intermediate 합성예Synthesis example 30: 중간체(65)의 합성 30: synthesis of intermediate (65)
1구 1 L 플라스크에서 중간체(64) 20.0 g(71.0 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 18.7 g(72.5 mmol), Pd(PPh3)4 4.1 g(3.6 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(65)) 26.3 g(수율: 88.9%)을 얻었다.In a 1-neck 1 L flask, 20.0 g (71.0 mmol) of the intermediate (64), 18.7 g (72.5 mmol) of 3,5-bis(trifluoromethyl)phenyl)boronic acid, Pd (PPh 3 ) 4 4.1 g (3.6 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL, and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 26.3 g (yield: 88.9%) of the compound as a white solid (intermediate (65)).
중간체 intermediate 합성예Synthesis example 31: 중간체(67)의 합성 31: Synthesis of intermediate (67)
(중간체(66)의 합성)(Synthesis of Intermediate (66))
1구 1 L 플라스크에서 2,6-디브로모페놀(2,6-Dibromophenol) 20.0 g(79.4 mmol), 4-클로로-2-플루오로페닐 보론산((4-Chloro-2-fluorophenyl)boronic acid) 13.8 g(79.4 mmol), Pd(PPh3)4 4.6 g(4.0 mmol), 2M K2CO3 80.0 mL(22.0 mmol), 톨루엔 320 mL 및 에탄올 80 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(66)) 11.2 g(수율: 46.8%)을 얻었다.In a 1-neck 1 L flask, 20.0 g (79.4 mmol) of 2,6-dibromophenol (2,6-Dibromophenol), 4-chloro-2-fluorophenyl boronic acid ((4-Chloro-2-fluorophenyl) boronic acid) 13.8 g (79.4 mmol), Pd(PPh 3 ) 4 4.6 g (4.0 mmol), 2M K 2 CO 3 80.0 mL (22.0 mmol), toluene 320 mL and ethanol 80 mL were mixed and stirred under reflux for 12 hours. did. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 11.2 g (yield: 46.8%) of the compound (intermediate (66)) as a white solid.
(중간체(67)의 합성)(Synthesis of Intermediate (67))
1구 1 L 플라스크에서 중간체(66) 11.2 g(37.1 mmol), K2CO3 15.4 g(111.4 mmol) 및 DMF 185 mL를 혼합한 다음 2 시간 동안 100 ℃에서 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물를 넣고 교반하였다. 형성된 고체를 여과한 다음 물과 에탄올로 씻어서 건조하여, 흰색 고체의 화합물(중간체(67)) 8.1 g(수율: 77.5%)을 얻었다.In a 1-neck 1 L flask, 11.2 g (37.1 mmol) of the intermediate (66), 15.4 g (111.4 mmol) of K 2 CO 3 and 185 mL of DMF were mixed and then reacted at 100° C. for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the mixture was stirred. The formed solid was filtered, washed with water and ethanol, and dried to obtain 8.1 g (yield: 77.5%) of the compound as a white solid (intermediate (67)).
중간체 intermediate 합성예Synthesis example 32: 중간체(68)의 합성 32: synthesis of intermediate (68)
1구 1 L 플라스크에서 중간체(67) 8.1 g(28.8 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.4 g(28.8 mmol), Pd(PPh3)4 1.7 g(1.4 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(68)) 7.5 g(수율: 62.8%)을 얻었다.Intermediate (67) 8.1 g (28.8 mmol), 3,5-bistrifluoromethylphenylboronic acid (3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.4 g (28.8 mmol), Pd in a 1-neck 1 L flask (PPh 3 ) 4 1.7 g (1.4 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 7.5 g (yield: 62.8%) of the compound as a white solid (intermediate (68)).
중간체 intermediate 합성예Synthesis example 33: 중간체(70)의 합성 33: Synthesis of intermediate (70)
(중간체(69)의 합성)(Synthesis of Intermediate (69))
1구 1 L 플라스크에서 2,6-디브로모페놀(2,6-Dibromophenol) 20.0 g(79.4 mmol), 5-클로로-2-플루오로페닐 보론산((5-Chloro-2-fluorophenyl)boronic acid) 13.8 g(79.4 mmol), Pd(PPh3)4 4.6 g(4.0 mmol), 2M K2CO3 80.0 mL(22.0 mmol), 톨루엔 320 mL 및 에탄올 80 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(69)) 11.2 g(수율: 46.8%)을 얻었다.2,6-dibromophenol (2,6-Dibromophenol) 20.0 g (79.4 mmol), 5-chloro-2-fluorophenyl boronic acid ((5-Chloro-2-fluorophenyl) boronic in a 1-neck 1 L flask acid) 13.8 g (79.4 mmol), Pd(PPh 3 ) 4 4.6 g (4.0 mmol), 2M K 2 CO 3 80.0 mL (22.0 mmol), toluene 320 mL and ethanol 80 mL were mixed and stirred under reflux for 12 hours. did. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 11.2 g (yield: 46.8%) of the compound (intermediate (69)) as a white solid.
(중간체(70)의 합성)(Synthesis of Intermediate 70)
1구 1 L 플라스크에서 중간체(69) 11.2 g(37.1 mmol), K2CO3 15.4 g(111.4 mmol) 및 DMF 185 mL를 혼합한 다음 2 시간 동안 100 ℃에서 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물를 넣고 교반하였다. 형성된 고체를 여과한 다음 물과 에탄올로 씻어서 건조하여, 흰색 고체의 화합물(중간체(70)) 8.1 g(수율: 77.5%)을 얻었다.In a 1-neck 1 L flask, 11.2 g (37.1 mmol) of the intermediate (69), 15.4 g (111.4 mmol) of K 2 CO 3 and 185 mL of DMF were mixed and reacted at 100° C. for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the mixture was stirred. The formed solid was filtered, washed with water and ethanol, and dried to obtain 8.1 g (yield: 77.5%) of the compound as a white solid (intermediate (70)).
중간체 intermediate 합성예Synthesis example 34: 중간체(71)의 합성 34: Synthesis of intermediate (71)
1구 1 L 플라스크에서 중간체(70) 8.1 g(28.8 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.4 g(28.8 mmol), Pd(PPh3)4 1.7 g(1.4 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(71)) 7.5 g(수율: 62.8%)을 얻었다.In a 1-neck 1 L flask, 8.1 g (28.8 mmol) of the intermediate (70), 7.4 g (28.8 mmol) of 3,5-bistrifluoromethylphenylboronic acid (3,5-bis(trifluoromethyl)phenyl)boronic acid), Pd (PPh 3 ) 4 1.7 g (1.4 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 7.5 g (yield: 62.8%) of the compound as a white solid (intermediate (71)).
중간체 intermediate 합성예Synthesis example 35: 중간체(75)의 합성 35: synthesis of intermediate (75)
(중간체(72)의 합성)(Synthesis of Intermediate 72)
2구 250 mL 플라스크에서 1-브로모-3-클로로-2-메톡시벤젠(1-Bromo-3-chloro-2-methoxybenzene) 50.0 g(225.8 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 68.8 g(270.9 mmol), Pd(dppf)Cl2 5.5 g(6.8 mmol), KOAc 44.3 g(451.5 mmol) 및 1,4-디옥산 1.1 L를 혼합한 다음 105℃에서 하루 동안 교반하였다. 반응이 종결된 후 상온으로 냉각시킨 후 셀라이트 여과 후 감압 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 헥산으로 고체화하여, 흰색 고체의 화합물(중간체(72)) 35.0 g(수율: 57.7%)을 얻었다.In a 2-neck 250 mL flask, 50.0 g (225.8 mmol) of 1-bromo-3-chloro-2-methoxybenzene, bis (pinacolato) diboron (bis (pinacolato)diboron) 68.8 g (270.9 mmol), Pd(dppf)Cl 2 5.5 g (6.8 mmol), KOAc 44.3 g (451.5 mmol) and 1,4-dioxane 1.1 L were mixed and then stirred at 105° C. for one day. stirred. After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite, and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with hexane to obtain 35.0 g (yield: 57.7%) of the compound as a white solid (intermediate (72)).
(중간체(73)의 합성)(Synthesis of Intermediate (73))
1구 2 L 플라스크에서 중간체(72) 35.0 g(130.3 mmol), 1-브로모-3-플루오로-2-요오드벤젠(1-Bromo-3-fluoro-2-iodobenzene) 39.2g(130.3 mmol), Pd(PPh3)4 7.5 g(6.5 mmol), 2M K2CO3 130 mL(260.7 mmol), 톨루엔 520 mL 및 에탄올 130 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(73)) 23.5 g(수율: 57.1%)을 얻었다.Intermediate (72) 35.0 g (130.3 mmol), 1-bromo-3-fluoro-2-iodobenzene (1-Bromo-3-fluoro-2-iodobenzene) 39.2 g (130.3 mmol) in a 1-neck 2 L flask , Pd(PPh 3 ) 4 7.5 g (6.5 mmol), 2M K 2 CO 3 130 mL (260.7 mmol), toluene 520 mL, and ethanol 130 mL were mixed and stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 23.5 g (yield: 57.1%) of the compound (intermediate (73)) as a white solid.
(중간체(74)의 합성)(Synthesis of Intermediate (74))
1구 1 L 플라스크에서 중간체(73) 23.5 g(74.5 mmol)과 디클로로메탄 300 mL를 혼합한 다음 0℃로 온도를 낮추고, BBr3 20.5 g(81.9 mmol)을 디클로로메탄 70 mL에 희석시킨 후 천천히 적가하였다. 서서히 상온으로 온도를 올린 후 12 시간 동안 교반하였다. 0℃로 온도를 낮추고 물로 천천히 중화시키고 3시간 동안 교반하였다. 유기층을 분리한 후, 물과 포화 Na2CO3 수용액으로 한번씩 더 씻어준 후 감압 농축하였다. 반응 혼합물을 실리카 패드(DCM)에 통과시킨 후, 노란색 액체의 화합물(중간체(74)) 20.1 g(수율: 89.5%)을 얻었다.In a 1-neck 1 L flask, 23.5 g (74.5 mmol) of the intermediate (73) and 300 mL of dichloromethane were mixed, the temperature was lowered to 0°C, and 20.5 g (81.9 mmol) of BBr 3 was diluted in 70 mL of dichloromethane, and then slowly was added dropwise. After slowly raising the temperature to room temperature, the mixture was stirred for 12 hours. The temperature was lowered to 0°C, neutralized slowly with water, and stirred for 3 hours. After separating the organic layer, it was washed once more with water and saturated Na 2 CO 3 aqueous solution, and then concentrated under reduced pressure. After passing the reaction mixture through a pad of silica (DCM), 20.1 g (yield: 89.5%) of the compound (intermediate (74)) as a yellow liquid was obtained.
(중간체(75)의 합성)(Synthesis of Intermediate (75))
1구 1 L 플라스크에서 중간체(74) 20.1 g(66.7 mmol), K2CO3 27.6 g(200.0 mmol) 및 DMF 330 mL를 혼합한 다음 2 시간 동안 100 ℃에서 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물를 넣고 교반하였다. 형성된 고체를 여과한 다음 물과 에탄올로 씻어서 건조하여, 흰색 고체의 화합물(중간체(75)) 15.3 g(수율: 81.5%)을 얻었다.In a 1-neck 1 L flask, 20.1 g (66.7 mmol) of the intermediate (74), 27.6 g (200.0 mmol) of K 2 CO 3 and 330 mL of DMF were mixed and then reacted at 100° C. for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the mixture was stirred. The formed solid was filtered, washed with water and ethanol, and dried to obtain 15.3 g (yield: 81.5%) of the compound as a white solid (intermediate (75)).
중간체 intermediate 합성예Synthesis example 36: 중간체(76)의 합성 36: synthesis of intermediate (76)
1구 1 L 플라스크에서 중간체(75) 8.1 g(28.8 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.4 g(28.8 mmol), Pd(PPh3)4 1.7 g(1.4 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(76)) 7.5 g(수율: 62.8%)을 얻었다.In a 1-neck 1 L flask, 8.1 g (28.8 mmol) of the intermediate (75), 7.4 g (28.8 mmol) of 3,5-bistrifluoromethylphenylboronic acid (3,5-bis(trifluoromethyl)phenyl)boronic acid, Pd (PPh 3 ) 4 1.7 g (1.4 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 7.5 g of a white solid compound (intermediate (76)) (yield: 62.8%).
중간체 intermediate 합성예Synthesis example 37: 중간체(78)의 합성 37: Synthesis of intermediate (78)
(중간체(77)의 합성)(Synthesis of Intermediate (77))
1구 1 L 플라스크에서 2,6-디브로모페놀(2,6-Dibromophenol) 20.0 g(79.4 mmol), 3-클로로-2-플루오로페닐 보론산((3-Chloro-2-fluorophenyl)boronic acid) 13.8 g(79.4 mmol), Pd(PPh3)4 4.6 g(4.0 mmol), 2M K2CO3 80.0 mL(22.0 mmol), 톨루엔 320 mL 및 에탄올 80 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하여, 흰색 고체의 화합물(중간체(77)) 11.2 g(수율: 46.8%)을 얻었다.2,6-dibromophenol (2,6-Dibromophenol) 20.0 g (79.4 mmol), 3-chloro-2-fluorophenyl boronic acid ((3-Chloro-2-fluorophenyl) boronic in a 1-neck 1 L flask acid) 13.8 g (79.4 mmol), Pd(PPh 3 ) 4 4.6 g (4.0 mmol), 2M K 2 CO 3 80.0 mL (22.0 mmol), toluene 320 mL and ethanol 80 mL were mixed and stirred under reflux for 12 hours. did. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) to obtain 11.2 g (yield: 46.8%) of the compound as a white solid (intermediate (77)).
(중간체(78)의 합성)(Synthesis of Intermediate (78))
1구 1 L 플라스크에서 중간체(77) 11.2 g(37.1 mmol), K2CO3 15.4 g(111.4 mmol) 및 DMF 185 mL를 혼합한 다음 2 시간 동안 100 ℃에서 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 교반하였다. 형성된 고체를 여과한 다음 물과 에탄올로 씻어서 건조하여, 흰색 고체의 화합물(중간체(78)) 8.1 g(수율: 77.5%)을 얻었다.In a 1-neck 1 L flask, 11.2 g (37.1 mmol) of the intermediate (77), 15.4 g (111.4 mmol) of K 2 CO 3 and 185 mL of DMF were mixed, followed by reaction at 100° C. for 2 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the mixture was stirred. The formed solid was filtered, washed with water and ethanol, and dried to obtain 8.1 g (yield: 77.5%) of the compound as a white solid (intermediate (78)).
중간체 intermediate 합성예Synthesis example 38: 중간체(79)의 합성 38: Synthesis of intermediate (79)
1구 1 L 플라스크에서 중간체(78) 20.0 g(71.0 mmol), 3,5-비스트리플루오로메틸페닐보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 18.7 g(72.5 mmol), Pd(PPh3)4 4.1 g(3.6 mmol), K2CO3 24.6 g(177.6 mmol), 톨루엔 300 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 5시간 동안 환류 교반하였다. 반응이 종결된 후, 물을 넣고 클로로포름으로 추출하고 감압 증류하였다. 반응 혼합물을 실리카 패드(CHCl3)에 통과시킨 후 감압 농축하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물(중간체(79)) 26.3 g(수율: 88.9%)을 얻었다.In a 1-neck 1 L flask, 20.0 g (71.0 mmol) of the intermediate (78), 18.7 g (72.5 mmol) of 3,5-bis(trifluoromethyl)phenyl)boronic acid, Pd (PPh 3 ) 4 4.1 g (3.6 mmol), K 2 CO 3 24.6 g (177.6 mmol), toluene 300 mL, ethanol 100 mL, and water 100 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, water was added, extracted with chloroform, and distilled under reduced pressure. The reaction mixture was passed through a silica pad (CHCl 3 ), concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH) to obtain 26.3 g (yield: 88.9%) of the compound as a white solid (intermediate (79)).
상기 합성된 중간체 화합물을 이용하여 이하와 같이 다양한 디벤조 5원고리 화합물를 합성하였다. Various dibenzo 5-membered ring compounds were synthesized as follows using the synthesized intermediate compound.
제조예production example 1: 화합물 19-24(LT20-30-463)의 합성 1: Synthesis of compound 19-24 (LT20-30-463)
1구 250 mL 플라스크에서 중간체(2) 2.2 g(5.0 mmol), 3,5-비스트리플루오로메틸페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 2.6 g(10.0 mmol), Pd2(dba)3 458.0 mg(499.7 μmol), X-Phos 476.0 mg(999.3 mmol), K3PO4 2.7 g(12.5 mmol) 및 자일렌 30 mL를 혼합한 다음, 24시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 증류수와 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 셀라이트 패드에 통과시킨 후 감압 농축하였다. 모노클로로벤젠를 넣고 끓여서 고체를 다 녹인 후, 상온까지 서서히 냉각하면서 고체화하여, 흰색 고체의 화합물 19-24(LT20-30-463) 1.3 g(수율: 44.3%)을 얻었다.In a 1-neck 250 mL flask, 2.2 g (5.0 mmol) of intermediate (2), 2.6 g (10.0 mmol) of 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid), Pd 2 (dba) 3 458.0 mg (499.7 μmol), 476.0 mg (999.3 mmol) of X-Phos, 2.7 g (12.5 mmol) of K 3 PO 4 and 30 mL of xylene were mixed and stirred under reflux for 24 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with distilled water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a celite pad, and concentrated under reduced pressure. After adding monochlorobenzene and boiling to dissolve the solid, it was solidified while slowly cooling to room temperature to obtain 1.3 g (yield: 44.3%) of compound 19-24 (LT20-30-463) as a white solid.
제조예production example 2: 화합물 19-30(LT20-30-489)의 합성 2: Synthesis of compound 19-30 (LT20-30-489)
2구 250 mL 플라스크에서 중간체(4) 3.5 g(7.7 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 3.9 g(15.3 mmol), Pd(PPh3)4 0.5 g(0.4 mmol), K2CO3 2.7 g(19.2 mmol), NMP 50 mL 및 정제수 25 mL를 혼합한 다음, 130℃에서 3시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 19-30(LT20-30-489) 2.6 g(수율: 57.3%)을 얻었다.In a 2-neck 250 mL flask, 3.5 g (7.7 mmol) of intermediate (4), (3,5-bis (trifluoromethyl) phenyl) boronic acid ((3,5-bis (trifluoromethyl) phenyl) boronic acid) 3.9 g (15.3 mmol), Pd(PPh 3 ) 4 0.5 g (0.4 mmol), K 2 CO 3 2.7 g (19.2 mmol), NMP 50 mL and purified water 25 mL were mixed, and then reacted at 130° C. for 3 hours. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with chloroform/methanol to obtain 2.6 g (yield: 57.3%) of compound 19-30 (LT20-30-489) as a white solid.
제조예production example 3: 화합물 19-79(LT20-30-487)의 합성 3: Synthesis of compound 19-79 (LT20-30-487)
2구 250 mL 플라스크에서 중간체(5) 5.1 g(11.4 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 4.4 g(17.2 mmol), Pd(PPh3)4 0.7 g(0.6 mmol), K2CO3 3.2 g(22.9 mmol), 톨루엔 60 mL, 정제수 25 mL 및 에탄올 20 mL를 혼합한 다음, 90℃에서 4시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 클로로포름/메탄올로 고체화하여, 흰색 고체의 화합물 19-79(LT20-30-487) 1.9 g(수율: 29.4%)을 얻었다.In a 2-neck 250 mL flask, 5.1 g (11.4 mmol) of intermediate (5), (3,5-bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 4.4 g (17.2 mmol), Pd(PPh 3 ) 4 0.7 g (0.6 mmol), K 2 CO 3 3.2 g (22.9 mmol), toluene 60 mL, purified water 25 mL, and ethanol 20 mL were mixed, and then at 90° C. for 4 hours. reacted while Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with chloroform/methanol to obtain 1.9 g (yield: 29.4%) of compound 19-79 (LT20-30-487) as a white solid.
제조예production example 4: 화합물 19-88(LT20-30-346)의 합성 4: Synthesis of compound 19-88 (LT20-30-346)
1구 100 mL 플라스크에서 중간체(8) 1.7 g(3.8 mmol), 3,5-비스트리플루오로메틸페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 1.5 g(5.7 mmol), Pd(PPh3)4 219.0 mg(189.9 μmol), K3PO4 2.0 g(9.5 mmol), 톨루엔 12 mL, 에탄올 3 mL 및 물 3 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피로(CHCl3) 정제하고 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 19-88(LT20-30-346) 1.8 g(수율: 79.0%)을 얻었다.In a 1-neck 100 mL flask, 1.7 g (3.8 mmol) of intermediate (8), 1.5 g (5.7 mmol) of 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid), Pd(PPh 3 ) 4 219.0 mg (189.9 μmol), K 3 PO 4 2.0 g (9.5 mmol), toluene 12 mL, ethanol 3 mL and water 3 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 ), and solidified with a mixed solvent (DCM/MeOH), 1.8 g of compound 19-88 (LT20-30-346) as a white solid (yield: 79.0%) got
제조예production example 5: 화합물 19-89(LT20-30-471)의 합성 5: Synthesis of compound 19-89 (LT20-30-471)
1구 250 mL 플라스크에서 중간체(11) 3.0 g(6.7 mmol), 3,5-비스트리플루오로메틸페닐 보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 2.6 g(10.0 mmol), Pd(PPh3)4 385.0 mg(333.1 μmol), K3PO4 3.5 g(16.7 mmol), 톨루엔 25 mL, 에탄올 5 mL 및 물 5 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피로(DCM)로 정제하고 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 19-89(LT20-30-471) 2.2 g(수율: 56.3%)을 얻었다.In a 1-neck 250 mL flask, 3.0 g (6.7 mmol) of the intermediate (11), 2.6 g (10.0 mmol) of 3,5-bistrifluoromethylphenyl boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid), Pd(PPh 3 ) 4 385.0 mg (333.1 μmol), K 3 PO 4 3.5 g (16.7 mmol), toluene 25 mL, ethanol 5 mL, and water 5 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was purified by column chromatography (DCM) and solidified with a mixed solvent (DCM/MeOH) to obtain 2.2 g (yield: 56.3%) of compound 19-89 (LT20-30-471) as a white solid.
제조예production example 6: 화합물 19-103(LT20-30-351)의 합성 6: Synthesis of compound 19-103 (LT20-30-351)
1구 100 mL 플라스크에서 중간체(14) 1.4 g(3.6 mmol), 3,5-비스트리플루오로메틸페닐 보론산(3,5-bis(trifluoromethyl)phenyl)boronic acid) 1.4 g(5.4 mmol), Pd(PPh3)4 208.0 mg(179.9 μmol), K3PO4 1.9 g(9.0 mmol), 톨루엔 12 mL, 에탄올 3 mL 및 물 3 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피로(CHCl3) 정제하고 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 19-103(LT20-30-351) 1.4 g(수율: 72.9%)을 얻었다.In a 1-neck 100 mL flask, 1.4 g (3.6 mmol) of intermediate (14), 1.4 g (5.4 mmol) of 3,5-bistrifluoromethylphenyl boronic acid (3,5-bis(trifluoromethyl)phenyl)boronic acid, Pd (PPh 3 ) 4 208.0 mg (179.9 μmol), K 3 PO 4 1.9 g (9.0 mmol), toluene 12 mL, ethanol 3 mL and water 3 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 ), and solidified with a mixed solvent (DCM/MeOH), 1.4 g of compound 19-103 (LT20-30-351) as a white solid (yield: 72.9%) got
제조예production example 7: 화합물 19-119(LT20-30-283)의 합성 7: Synthesis of compound 19-119 (LT20-30-283)
1구 250 mL 플라스크에서 2,8-다이브로모디벤조퓨란(2,8-dibromodibenzo[b,d]furan) 4.0 g(12.3 mmol), 3,5-비스트리플루오로메틸페닐 보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.9 g(30.7 mmol), Pd(PPh3)4 850.8 mg(736.2 μmol), K3PO4 13.0 g(61.4 mmol), 톨루엔 40 mL, 에탄올 10 mL 및 물 10 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피로(CHCl3) 정제하고 혼합용매(DCM/EtOH)로 고체화하여, 흰색 고체의 화합물 19-119(LT20-30-283) 4.9 g(수율: 67.6%)을 얻었다.In a 1-neck 250 mL flask, 2,8-dibromodibenzofuran (2,8-dibromodibenzo[b,d]furan) 4.0 g (12.3 mmol), 3,5-bistrifluoromethylphenyl boronic acid ((3, 5-bis(trifluoromethyl)phenyl)boronic acid) 7.9 g (30.7 mmol), Pd(PPh 3 ) 4 850.8 mg (736.2 μmol), K 3 PO 4 13.0 g (61.4 mmol), toluene 40 mL, ethanol 10 mL and After mixing 10 mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 ), and solidified with a mixed solvent (DCM/EtOH), 4.9 g of compound 19-119 (LT20-30-283) as a white solid (yield: 67.6%) got
제조예production example 8: 화합물 20-17(LT20-30-495)의 합성 8: Synthesis of compound 20-17 (LT20-30-495)
2구 250 mL 플라스크에서 중간체(15) 3.5 g(12.8 mmol), 중간체(1) 4.0 g(12.5 mmol), Pd(dba)2 0.4 g(0.6 mmol), X-Phos 0.6 g(1.3 mmol), K3PO4 6.7 g(31.4 mmol) 및 자일렌 42 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 20-17(LT20-30-495) 2.0 g(수율: 36.9%)을 얻었다.In a 2-neck 250 mL flask, 3.5 g (12.8 mmol) of Intermediate (15), 4.0 g (12.5 mmol) of Intermediate (1), 0.4 g (0.6 mmol) of Pd(dba) 2 , 0.6 g (1.3 mmol) of X-Phos, K 3 PO 4 6.7 g (31.4 mmol) and 42 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 2.0 g (yield: 36.9%) of Compound 20-17 (LT20-30-495) as a white solid.
제조예production example 9: 화합물 20-24(LT20-30-413)의 합성 9: Synthesis of compound 20-24 (LT20-30-413)
중간체(19) 4.0 g(9.6 mmol), 중간체(1) 3.4 g(10.6 mmol), Pd2(dba)3 883.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 셀라이트 패드에 통과시킨 후 감압 농축하였다. 모노클로로벤젠을 넣고 끓여서 고체를 다 녹인 후, 상온까지 천천히 냉각하여 흰색 고체의 화합물 20-24(LT20-30-413) 1.8 g(수율: 31.6%)을 얻었다.Intermediate (19) 4.0 g (9.6 mmol), Intermediate (1) 3.4 g (10.6 mmol), Pd 2 (dba) 3 883.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed and then stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a celite pad, and concentrated under reduced pressure. After adding monochlorobenzene and boiling to dissolve the solid, it was cooled slowly to room temperature to obtain 1.8 g (yield: 31.6%) of compound 20-24 (LT20-30-413) as a white solid.
제조예production example 10: 화합물 20-30(LT20-30-480)의 합성 10: Synthesis of compound 20-30 (LT20-30-480)
중간체(19) 4.0 g(9.6 mmol), 중간체(3) 3.3 g(9.6 mmol), Pd2(dba)3 883.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 컬럼 크로마토그래피로(CHCl3)로 정제하고 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 20-30(LT20-30-480) 2.6 g(수율: 46.3%)을 얻었다.Intermediate (19) 4.0 g (9.6 mmol), Intermediate (3) 3.3 g (9.6 mmol), Pd 2 (dba) 3 883.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed and then stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was purified by column chromatography (CHCl 3 ) and solidified with a mixed solvent (DCM/MeOH) to obtain 2.6 g (yield: 46.3%) of Compound 20-30 (LT20-30-480) as a white solid.
제조예production example 11: 화합물 20-79(LT20-30-501)의 합성 11: Synthesis of compound 20-79 (LT20-30-501)
중간체(19) 4.0 g(9.6 mmol), 4-나프탈렌-2-페닐 보론산(4-(naphthalen-2-yl)phenyl)boronic acid) 2.4 g(9.6 mmol), Pd2(dba)3 883.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 셀라이트 패드에 통과시킨 후 감압 농축하였다. 모노클로로벤젠을 넣고 끓여서 고체를 다 녹인 후, 상온으로 천천히 냉각하여 흰색 고체의 화합물 20-79(LT20-30-501) 1.6 g(수율: 28.7%)을 얻었다.Intermediate (19) 4.0 g (9.6 mmol), 4-naphthalen-2-phenyl boronic acid (4- (naphthalen-2-yl) phenyl) boronic acid) 2.4 g (9.6 mmol), Pd 2 (dba) 3 883.0 mg (964.5 μmol), 919.0 mg (1.9 mmol) of X-Phos, 6.1 g (28.9 mmol) of K 3 PO 4 and 50 mL of xylene were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a celite pad, and concentrated under reduced pressure. After adding monochlorobenzene and boiling to dissolve the solid, it was cooled slowly to room temperature to obtain 1.6 g (yield: 28.7%) of compound 20-79 (LT20-30-501) as a white solid.
제조예production example 12: 화합물 20-81(LT20-30-437)의 합성 12: Synthesis of compound 20-81 (LT20-30-437)
중간체(15) 3.3 g(11.8 mmol), 중간체(7) 5.9 g(17.8 mmol), Pd2(dba)3 0.5 g (0.6 mmol), S-phos 0.7 g (0.1 mmol), K3PO4 7.5 g(35.4 mmol) 및 자일렌(110 mL)을 혼합한 다음 20 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 건조하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토 그래피(CHCl3)로 정제한 후 헥산으로 고체화하여 흰색 고체의 화합물 20-81(LT20-30-437) 0.9 g(수율: 18.8%)을 얻었다.Intermediate (15) 3.3 g (11.8 mmol), Intermediate (7) 5.9 g (17.8 mmol), Pd 2 (dba) 3 0.5 g (0.6 mmol), S-phos 0.7 g (0.1 mmol), K 3 PO 4 7.5 g (35.4 mmol) and xylene (110 mL) were mixed and stirred under reflux for 20 hours. After the reaction was completed, it was cooled to room temperature, and the solid was filtered and dried. The obtained compound was purified by silica gel column chromatography (CHCl 3 ) and then solidified with hexane to form a white solid compound 20-81 (LT20-30-437) 0.9 g (yield: 18.8%) was obtained.
제조예production example 13: 화합물 20-82(LT20-30-475)의 합성 13: Synthesis of compound 20-82 (LT20-30-475)
2구 250 mL 플라스크에 중간체(23) 3.0 g(10.1 mmol), 중간체(7) 3.3 g(10.1 mmol), Pd(dba)2 0.6 g(1.0 mmol), S-Phos 0.8 g(2.0 mmol), K3PO4 6.5 g(30.3 mmol) 및 자일렌 36 mL를 혼합한 다음, 130℃에서 3시간 동안 반응하였다. 반응이 종료 확인 후 실온으로 냉각한 다음, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 뜨거운 모노클로로벤젠에 용해시켜 실리카겔에 여과하고 혼합용액(모노클로로벤젠/클로로포름)으로 고체화하여, 미색 고체의 화합물 20-82(LT20-30-475) 1.4 g(수율: 30.6%)을 얻었다.In a two-necked 250 mL flask, 3.0 g (10.1 mmol) of Intermediate (23), 3.3 g (10.1 mmol) of Intermediate (7), 0.6 g (1.0 mmol) of Pd(dba) 2 , 0.8 g (2.0 mmol) of S-Phos, K 3 PO 4 6.5 g (30.3 mmol) and 36 mL of xylene were mixed, and then reacted at 130° C. for 3 hours. After confirming the completion of the reaction, it was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was dissolved in hot monochlorobenzene, filtered through silica gel, and solidified with a mixed solution (monochlorobenzene/chloroform), 1.4 g of compound 20-82 (LT20-30-475) as an off-white solid (yield: 30.6%) got
제조예production example 14: 화합물 20-84(LT20-30-460)의 합성 14: Synthesis of compound 20-84 (LT20-30-460)
2구 250 mL 플라스크에서 중간체(27) 3.5 g(10.0 mmol), 중간체(7) 4.0 g(12.0 mmol), Pd2(dba)3 456.7 mg(498.7 μmol), X-Phos 1.0 g(2.0 mmol), K3PO4 6.4 g(29.9 mmol) 및 자일엔 50 mL를 혼합한 다음, 130℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 증류수를 여과, 증류수, 메탄올, 헥산으로 씻어주었다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(Hot toluene)로 정제하고, 얻어진 화합물을 에틸아세테이트로 고체화하여, 백색 고체의 화합물 20-84(LT20-30-460) 2.5 g(수율: 48.4%)을 얻었다.In a 2-neck 250 mL flask, intermediate (27) 3.5 g (10.0 mmol), intermediate (7) 4.0 g (12.0 mmol), Pd 2 (dba) 3 456.7 mg (498.7 μmol), X-Phos 1.0 g (2.0 mmol) , K 3 PO 4 6.4 g (29.9 mmol) and xylene 50 mL were mixed, and then reacted at 130° C. for one day. Upon completion of the reaction, the mixture was cooled to room temperature, filtered, and washed with distilled water, methanol, and hexane. The obtained mixture was purified by silica gel column chromatography (hot toluene), and the obtained compound was solidified with ethyl acetate to obtain 2.5 g (yield: 48.4%) of compound 20-84 (LT20-30-460) as a white solid.
제조예production example 15: 화합물 20-85(LT20-30-462)의 합성 15: Synthesis of compound 20-85 (LT20-30-462)
2구 250 mL 플라스크에서 중간체(31) 5.0 g(14.2 mmol), 중간체(7) 5.7 g(17.1 mmol), Pd2(dba)3 652.4 mg(712.4 μmol), X-Phos 1.4 g(2.8 mmol), K3PO4 9.1 g(42.7 mmol) 및 자일엔 100 mL를 혼합한 다음, 130℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 증류수를 여과, 증류수, 메탄올, 헥산으로 씻어주었다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(hot toluene)로 정제하고, 얻어진 화합물을 에틸아세테이트로 고체화하여, 백색 고체의 화합물 20-85(LT20-30-462) 3.0 g(수율: 40.5%)을 얻었다.In a two-necked 250 mL flask, 5.0 g (14.2 mmol) of intermediate (31), 5.7 g (17.1 mmol) of intermediate (7), 652.4 mg (712.4 μmol) of Pd 2 (dba) 3 , 1.4 g (2.8 mmol) of X-Phos , K 3 PO 4 9.1 g (42.7 mmol) and xylene 100 mL were mixed, and then reacted at 130° C. for one day. Upon completion of the reaction, the mixture was cooled to room temperature, filtered, and washed with distilled water, methanol, and hexane. The obtained mixture was purified by silica gel column chromatography (hot toluene), and the obtained compound was solidified with ethyl acetate to obtain 3.0 g (yield: 40.5%) of Compound 20-85 (LT20-30-462) as a white solid.
제조예production example 16: 화합물 20-86(LT20-30-474)의 합성 16: Synthesis of compound 20-86 (LT20-30-474)
2구 250 mL 플라스크에서 중간체(35) 3.5 g(10.1 mmol), 중간체(7) 3.3 g(10.1 mmol), Pd(dba)2 0.5 g(1.0 mmol), S-Phos 0.8 g(2.0 mmol), K3PO4 6.4 g(30.3 mmol) 및 자일렌 42 mL를 혼합한 다음, 140℃에서 3시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 뜨거운 MCB에 용해시켜 실리카겔에 여과한 후 MCB/클로로포름으로 고체화하여, 미색 고체의 화합물 20-86(LT20-30-474) 2.0 g(수율: 39.4%)을 얻었다.In a 2-neck 250 mL flask, intermediate (35) 3.5 g (10.1 mmol), intermediate (7) 3.3 g (10.1 mmol), Pd(dba) 2 0.5 g (1.0 mmol), S-Phos 0.8 g (2.0 mmol), K 3 PO 4 6.4 g (30.3 mmol) and 42 mL of xylene were mixed, and then reacted at 140° C. for 3 hours. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was dissolved in hot MCB, filtered through silica gel, and then solidified with MCB/chloroform to obtain 2.0 g (yield: 39.4%) of compound 20-86 (LT20-30-474) as an off-white solid.
제조예production example 17: 화합물 20-88(LT20-30-337)의 합성 17: Synthesis of compound 20-88 (LT20-30-337)
중간체(19) 4.0 g(9.6 mmol), 중간체(7) 3.5 g(10.6 mmol), Pd(dba)2 554.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 끓여서 녹인 후, 실리카겔 패드에 여과한 후 감압 농축하였고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 20-88(LT20-30-337) 2.0 g(수율: 34.8%)을 얻었다.Intermediate (19) 4.0 g (9.6 mmol), Intermediate (7) 3.5 g (10.6 mmol), Pd(dba) 2 554.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in chloroform, filtered through a silica gel pad, concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH), 2.0 g of compound 20-88 (LT20-30-337) as a white solid (yield: 34.8) %) was obtained.
제조예production example 18: 화합물 20-97(LT20-30-472)의 합성 18: Synthesis of compound 20-97 (LT20-30-472)
2구 250 mL 플라스크에서 중간체(23) 3.2 g(10.7 mmol), 중간체(36) 3.0 g(10.7 mmol), Pd(dba)2 0.6 g(1.0 mmol), S-Phos 0.9 g(2.1 mmol), K3PO4 6.8 g(32.3 mmol) 및 자일렌 38 mL를 혼합한 다음, 130℃에서 3시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 뜨거운 MCB에 용해시켜 실리카겔에 여과한 후 클로로포름으로 고체화하여, 미색 고체의 화합물 20-97(LT20-30-472) 1.4 g(수율: 31.0%)을 얻었다.In a two-necked 250 mL flask, 3.2 g (10.7 mmol) of intermediate (23), 3.0 g (10.7 mmol) of intermediate (36), 0.6 g (1.0 mmol) of Pd(dba) 2 , 0.9 g (2.1 mmol) of S-Phos, K 3 PO 4 6.8 g (32.3 mmol) and 38 mL of xylene were mixed, and then reacted at 130° C. for 3 hours. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was dissolved in hot MCB, filtered through silica gel, and then solidified with chloroform to obtain 1.4 g (yield: 31.0%) of compound 20-97 (LT20-30-472) as an off-white solid.
제조예production example 19: 화합물 20-99(LT20-30-455)의 합성 19: Synthesis of compound 20-99 (LT20-30-455)
2구 250 mL 플라스크에서 중간체(27) 4.6 g(13.1 mmol), 중간체(36) 4.4 g(15.7 mmol), Pd2(dba)3 600.2 mg(655.4 μmol), X-Phos 1.2 g(2.6 mmol), K3PO4 8.3 g(39.3 mmol) 및 자일엔 100 mL를 혼합한 다음, 130℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 증류수를 넣고 클로로포름으로 추출하여 무수황산마그네슘을 이용하여 건조, 여과, 농축하였다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 2회 정제하여, 흰색 고체의 화합물 20-99(LT20-30-455) 1.6 g(수율: 25.2%)을 얻었다.In a two-necked 250 mL flask, intermediate (27) 4.6 g (13.1 mmol), intermediate (36) 4.4 g (15.7 mmol), Pd 2 (dba) 3 600.2 mg (655.4 μmol), X-Phos 1.2 g (2.6 mmol) , K 3 PO 4 8.3 g (39.3 mmol) and xylene 100 mL were mixed, and then reacted at 130° C. for one day. After completion of the reaction, after cooling to room temperature, distilled water was added, extracted with chloroform, dried over anhydrous magnesium sulfate, filtered, and concentrated. The obtained mixture was purified twice by silica gel column chromatography (Hex:EA) to obtain 1.6 g (yield: 25.2%) of compound 20-99 (LT20-30-455) as a white solid.
제조예production example 20: 화합물 20-100(LT20-30-465)의 합성 20: Synthesis of compound 20-100 (LT20-30-465)
2구 250 mL 플라스크에서 중간체(31) 4.6 g(13.1 mmol), 중간체(36) 4.4 g(15.7 mmol), Pd2(dba)3 600.2 mg(655.4 μmol), X-Phos 1.2 g(2.6 mmol), K3PO4 8.3 g(39.3 mmol) 및 자일엔 100 mL를 혼합한 다음, 130℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 증류수를 넣고 에틸아세테이트로 추출하여 무수황산마그네슘을 이용하여 건조, 여과, 농축하였다. 얻어진 혼합물을 실리카겔 컬럼 크로마토그래피로 2회(toluene) 정제하고, 얻어진 화합물을 혼합용액(DCM/MeOH)으로 고체화하여, 백색 고체의 화합물 20-100(LT20-30-465) 1.3 g(수율: 12.1%)을 얻었다.Intermediate (31) 4.6 g (13.1 mmol), Intermediate (36) 4.4 g (15.7 mmol), Pd 2 (dba) 3 600.2 mg (655.4 μmol), X-Phos 1.2 g (2.6 mmol) in a 2-neck 250 mL flask , K 3 PO 4 8.3 g (39.3 mmol) and xylene 100 mL were mixed, and then reacted at 130° C. for one day. When the reaction was completed, after cooling to room temperature, distilled water was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and concentrated. The obtained mixture was purified twice by silica gel column chromatography (toluene), and the obtained compound was solidified with a mixed solution (DCM/MeOH), and 1.3 g of compound 20-100 (LT20-30-465) as a white solid (yield: 12.1) %) was obtained.
제조예production example 21: 화합물 20-101(LT20-30-469)의 합성 21: Synthesis of compound 20-101 (LT20-30-469)
2구 250 mL 플라스크에서 중간체(35) 4.0 g(11.5 mmol), 중간체(36) 3.2 g(11.5 mmol), Pd(dba)2 0.6 g(1.2 mmol), S-Phos 0.9 g(2.3 mmol), K3PO4 7.4 g(34.6 mmol) 및 자일렌 48 mL를 혼합한 다음, 140℃에서 4시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하여 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 클로로포름/메탄올로 고체화하여, 미색 고체의 화합물 20-101(LT20-30-469) 1.1 g(수율: 21.7%)을 얻었다.In a two-necked 250 mL flask, 4.0 g (11.5 mmol) of intermediate (35), 3.2 g (11.5 mmol) of intermediate (36), 0.6 g (1.2 mmol) of Pd(dba) 2 , 0.9 g (2.3 mmol) of S-Phos, K 3 PO 4 7.4 g (34.6 mmol) and 48 mL of xylene were mixed, and then reacted at 140° C. for 4 hours. Upon completion of the reaction, after cooling to room temperature, the resulting solid was filtered, and the resulting reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with chloroform/methanol, as an off-white solid compound 20-101 (LT20- 30-469), 1.1 g (yield: 21.7%) was obtained.
제조예production example 22: 화합물 20-103(LT20-30-332)의 합성 22: Synthesis of compound 20-103 (LT20-30-332)
중간체(19) 3.5 g(8.4 mmol), 중간체(36) 2.6 g(9.3 mmol), Pd(dba)2 485.0 mg(843.9 μmol), X-Phos 805.0 mg(1.7 mmol), K3PO4 5.4 g(25.3 mmol) 및 자일렌 45 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 흰색 고체의 화합물 20-103(LT20-30-332) 1.0 g(수율: 22.7%)을 얻었다.Intermediate (19) 3.5 g (8.4 mmol), Intermediate (36) 2.6 g (9.3 mmol), Pd(dba) 2 485.0 mg (843.9 μmol), X-Phos 805.0 mg (1.7 mmol), K 3 PO 4 5.4 g (25.3 mmol) and 45 mL of xylene were mixed, and then stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 1.0 g (yield: 22.7%) of compound 20-103 (LT20-30-332) as a white solid.
제조예production example 23: 화합물 20-104(LT20-30-436)의 합성 23: Synthesis of compound 20-104 (LT20-30-436)
1구 250 mL 플라스크에서 중간체(15) 4.1 g(14.5 mmol), 중간체(36) 6.1 g(21.8 mmol), Pd2(dba)3 0.7 g(0.7 mmol), S-phos 0.9 g (0.2 mmol), K3PO4 9.2 g(43.5 mmol) 및 크실렌 140 mL을 혼합한 다음 20 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 건조하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토 그래피(CHCl3)로 정제한 후 n-Hex로 고체화하여 흰색 고체의 화합물 20-104(LT20-30-436) 2.2 g(수율: 39.5%)을 얻었다.In a one-necked 250 mL flask, 4.1 g (14.5 mmol) of intermediate (15), 6.1 g (21.8 mmol) of intermediate (36), 0.7 g (0.7 mmol) of Pd 2 (dba) 3 , 0.9 g (0.2 mmol) of S-phos , K 3 PO 4 9.2 g (43.5 mmol) and xylene 140 mL were mixed and stirred under reflux for 20 hours. After the reaction was completed, it was cooled to room temperature, and the solid was filtered and dried. The obtained compound was purified by silica gel column chromatography (CHCl 3 ) and then solidified with n-Hex to obtain 2.2 g (yield: 39.5%) of compound 20-104 (LT20-30-436) as a white solid.
제조예production example 24: 화합물 20-119(LT20-30-334)의 합성 24: Synthesis of compound 20-119 (LT20-30-334)
중간체(19) 4.0 g(9.6 mmol), 3,5-비스트리플루오로메틸페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 3.7 g(14.5 mmol), Pd(dba)2 554.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 20-119(LT20-30-334) 2.5 g(수율: 44.5%)을 얻었다.Intermediate (19) 4.0 g (9.6 mmol), 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 3.7 g (14.5 mmol), Pd (dba) 2 554.0 mg (964.5 μmol), 919.0 mg (1.9 mmol) of X-Phos, 6.1 g (28.9 mmol) of K 3 PO 4 and 50 mL of xylene were mixed and stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The obtained reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solution (DCM/MeOH) to obtain 2.5 g of compound 20-119 (LT20-30-334) as a white solid (yield: 44.5%) got it
제조예production example 25: 화합물 20-127(LT20-30-479)의 합성 25: Synthesis of compound 20-127 (LT20-30-479)
중간체(19) 4.0 g(9.6 mmol), 바이페닐-4-보론산([1,1'-biphenyl]-4-ylboronic acid) 2.1 g(10.6 mmol), Pd2(dba)3 883.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 디클로로메탄으로 고체화하여, 흰색 고체의 화합물 20-127(LT20-30-479) 1.3 g(수율: 25.7%)을 얻었다. Intermediate (19) 4.0 g (9.6 mmol), biphenyl-4-boronic acid ([1,1'-biphenyl] -4-ylboronic acid) 2.1 g (10.6 mmol), Pd 2 (dba) 3 883.0 mg (964.5) μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and xylene 50 mL were mixed, and then stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with dichloromethane to obtain 1.3 g (yield: 25.7%) of compound 20-127 (LT20-30-479) as a white solid.
제조예production example 26: 화합물 20-134(LT20-30-502)의 합성 26: Synthesis of compound 20-134 (LT20-30-502)
중간체(19) 4.0 g(9.6 mmol), 중간체(38) 4.8 g(11.6 mmol), Pd2(dba)3 883.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 모노클로로벤젠으로 고체화하여, 흰색 고체의 화합물 20-134(LT20-30-502) 1.2 g(수율: 18.6%)을 얻었다Intermediate (19) 4.0 g (9.6 mmol), Intermediate (38) 4.8 g (11.6 mmol), Pd 2 (dba) 3 883.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed and then stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with monochlorobenzene to obtain 1.2 g (yield: 18.6%) of compound 20-134 (LT20-30-502) as a white solid.
제조예production example 27: 화합물 20-159(LT20-30-516)의 합성 27: Synthesis of compound 20-159 (LT20-30-516)
2구 250 mL 플라스크에서 중간체(40) 4.0 g(8.2 mmol), 1-브로모-3,5-비스(트리플루오로메틸)벤젠(1-bromo-3,5-bis(trifluoromethyl)benzene) 4.2 mL(24.6 mmol), Pd(PPh3)4 948.4 mg(820.8 μmol), K2CO3 3.4 g(24.6 mmol), 톨루엔 41 mL, 에탄올 10 mL 및 증류수 10 mL을 혼합한 다음 90℃에서 이틀 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 증류수를 넣은 후 여과, 증류수, 메탄올, 헥산, 에틸아세테이트로 씻어주었다. 얻어진 고체 화합물을 뜨거운 모노클로로벤젠에 녹여 실리카겔 패드 여과를 하고, 얻어진 화합물을 모노클로로벤젠으로 고체화하여, 흰색 고체의 화합물 20-159(LT20-30-516) 2.8 g(수율: 58.4%)을 얻었다.In a 2-neck 250 mL flask, 4.0 g (8.2 mmol) of intermediate (40), 1-bromo-3,5-bis(trifluoromethyl)benzene (1-bromo-3,5-bis(trifluoromethyl)benzene) 4.2 mL (24.6 mmol), Pd(PPh 3 ) 4 948.4 mg (820.8 μmol), K 2 CO 3 3.4 g (24.6 mmol), toluene 41 mL, ethanol 10 mL and distilled water 10 mL were mixed, and then at 90° C. for two days. stirred. After the reaction was completed, it was cooled to room temperature, distilled water was added, and then filtered, washed with distilled water, methanol, hexane, and ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and the obtained compound was solidified with monochlorobenzene to obtain 2.8 g (yield: 58.4%) of compound 20-159 (LT20-30-516) as a white solid. .
제조예production example 28: 화합물 20-216(LT20-30-490)의 합성 28: Synthesis of compound 20-216 (LT20-30-490)
중간체(41) 4.0 g(9.9 mmol), 페닐보론산(phenyl)boronic acid) 3.6 g(29.6 mmol), Pd2(dba)3 902.0 mg(985.5 μmol), X-Phos 939.0 mg(2.0 mmol), K3PO4 6.3 g(29.6 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 셀라이트 패드에 통과시킨 후 감압 농축하였다. 모노클로로벤젠을 넣고 끓여서 고체를 다 녹인 후, 90℃에서 고체화하여, 흰색 고체의 화합물 20-216(LT20-30-490) 3.3 g(수율: 74.6%)을 얻었다.Intermediate (41) 4.0 g (9.9 mmol), phenyl boronic acid) 3.6 g (29.6 mmol), Pd 2 (dba) 3 902.0 mg (985.5 μmol), X-Phos 939.0 mg (2.0 mmol), After mixing 6.3 g (29.6 mmol) of K 3 PO 4 and 50 mL of xylene, the mixture was stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a celite pad, and concentrated under reduced pressure. After adding monochlorobenzene and boiling to dissolve the solid, it was solidified at 90° C. to obtain 3.3 g (yield: 74.6%) of compound 20-216 (LT20-30-490) as a white solid.
제조예production example 29: 화합물 20-223(LT20-30-427)의 합성 29: Synthesis of compound 20-223 (LT20-30-427)
2구 250 mL 플라스크에서 중간체(45) 2.8 g(7.1 mmol), (3,5-비스(트리플루오로메틸)페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 2.8 g(10.6 mmol), Pd2(dba)3 0.3 g(0.4 mmol), S-Phos 0.4 g(1.1 mmol), K3PO4 4.5 g(21.2 mmol) 및 자일렌 40 mL를 혼합한 다음, 125℃에서 3시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하여 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CHCl3)로 정제하고 클로로포름/2-프로판올로 고체화하여, 흰색 고체의 화합물 20-223(LT20-30-427) 2.1 g(수율: 51.9%)을 얻었다.In a 2-neck 250 mL flask, 2.8 g (7.1 mmol) of the intermediate (45), 2.8 g (3,5-bis(trifluoromethyl)phenyl)boronic acid) 10.6 mmol), Pd 2 (dba) 3 0.3 g (0.4 mmol), S-Phos 0.4 g (1.1 mmol), K 3 PO 4 4.5 g (21.2 mmol) and 40 mL of xylene were mixed, and then reacted at 125° C. for 3 hours. Upon completion of the reaction, after cooling to room temperature, the resulting solid was filtered, and the resulting reaction mixture was purified by silica gel column chromatography (Hex:CHCl 3 ) and solidified with chloroform/2-propanol, as a white solid compound 20-223 ( LT20-30-427) 2.1 g (yield: 51.9%) was obtained.
제조예production example 30: 화합물 20-238(LT20-30-420)의 합성 30: Synthesis of compound 20-238 (LT20-30-420)
중간체(49) 2.9 g(8.2 mmol), 3,5-비스트리플루오로메틸페닐보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 3.2 g(12.2 mmol), Pd2(dba)3 746.0 mg(815.0 μmol), X-Phos 777.0 mg(1.6 mmol), K3PO4 5.2 g(24.5 mmol) 및 자일렌 40 mL를 혼합한 다음, 2일 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로벤젠에 끓여서 녹인 후 셀라이트 패드에 통과시킨 후 감압 농축하였다. 에틸아세테이트를 넣고 끓여서 고체화하여, 흰색 고체의 화합물 20-238(LT20-30-420) 1.9 g(수율: 43.0%)을 얻었다.Intermediate (49) 2.9 g (8.2 mmol), 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 3.2 g (12.2 mmol), Pd 2 (dba) 3 746.0 mg (815.0 μmol), 777.0 mg (1.6 mmol) of X-Phos, 5.2 g (24.5 mmol) of K 3 PO 4 and 40 mL of xylene were mixed and stirred under reflux for 2 days. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved by boiling in chlorobenzene, passed through a celite pad, and concentrated under reduced pressure. Ethyl acetate was added and solidified by boiling to obtain 1.9 g (yield: 43.0%) of compound 20-238 (LT20-30-420) as a white solid.
제조예production example 31: 화합물 20-263(LT20-30-496)의 합성 31: Synthesis of compound 20-263 (LT20-30-496)
2구 250 mL 플라스크에서 중간체(15) 4.3 g(15.5 mmol), [1,1'-비페닐]-4-일보론산([1,1'-biphenyl]-4-ylboronic acid) 3.0 g(15.1 mmol), Pd(dba)2 0.5 g(0.8 mmol), X-Phos 0.7 g(1.5 mmol), K3PO4 8.0 g(37.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 20-263(LT20-30-496) 3.3 g(수율: 55.3%)을 얻었다.In a 2-neck 250 mL flask, 4.3 g (15.5 mmol) of intermediate (15), 3.0 g (15.1) of [1,1'-biphenyl]-4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) mmol), Pd(dba) 2 0.5 g (0.8 mmol), X-Phos 0.7 g (1.5 mmol), K 3 PO 4 8.0 g (37.9 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 3.3 g (yield: 55.3%) of Compound 20-263 (LT20-30-496) as a white solid.
제조예production example 32: 화합물 20-264(LT20-30-504)의 합성 32: Synthesis of compound 20-264 (LT20-30-504)
1구 250 mL 플라스크에서 중간체(50) 4.7 g(13.3 mmol), 페닐보론산(Phenylboronic acid) 4.9 g(39.7 mmol), Pd2(dba)3 1.2 g(39.7 mmol), X-Phos 1.2 g(1.3 mmol), K3PO4 8.4 g(39.7 mmol) 및 자일렌 70 mL를 혼합한 다음, 24시간 동안 환류 교반하였다. 반응이 종결된 후 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 실리카겔 패드에 통과시킨 후 감압 농축하였다. 클로로포름를 넣고 끓인 후, 상온에서 고체화하여, 흰색 고체의 화합물 20-264(LT20-30-504) 3.4 g(수율: 65.5%)을 얻었다.In a 1-neck 250 mL flask, 4.7 g (13.3 mmol) of the intermediate (50), 4.9 g (39.7 mmol) of Phenylboronic acid, Pd 2 (dba) 3 1.2 g (39.7 mmol), 1.2 g (1.3 mmol) of X-Phos, 8.4 g (39.7 mmol) of K 3 PO 4 and 70 mL of xylene were mixed and stirred under reflux for 24 hours. After the reaction was completed, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a silica gel pad, and then concentrated under reduced pressure. After adding chloroform and boiling, the mixture was solidified at room temperature to obtain 3.4 g (yield: 65.5%) of compound 20-264 (LT20-30-504) as a white solid.
제조예production example 33: 화합물 21-24(LT20-35-867)의 합성 33: Synthesis of compound 21-24 (LT20-35-867)
2구 250 mL 플라스크에서 중간체(65) 3.0 g(7.2 mmol), 중간체(1) 2.3 g(7.2 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 21-24(LT20-35-867) 1.5 g(수율: 36.2%)을 얻었다.In a two-necked 250 mL flask, Intermediate (65) 3.0 g (7.2 mmol), Intermediate (1) 2.3 g (7.2 mmol), Pd(dba) 2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.5 g (yield: 36.2%) of compound 21-24 (LT20-35-867) as a white solid.
제조예production example 34: 화합물 21-103(LT20-35-865)의 합성 34: Synthesis of compound 21-103 (LT20-35-865)
2구 250 mL 플라스크에서 중간체(65) 3.0 g(7.2 mmol), 중간체(36) 2.0 g(7.2 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 21-103(LT20-35-865) 1.3 g(수율: 33.7%)을 얻었다.In a two-necked 250 mL flask, intermediate (65) 3.0 g (7.2 mmol), intermediate (36) 2.0 g (7.2 mmol), Pd(dba) 2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.3 g (yield: 33.7%) of compound 21-103 (LT20-35-865) as a white solid.
제조예production example 35: 화합물 22-119(LT20-30-373)의 합성 35: Synthesis of compound 22-119 (LT20-30-373)
1-브로모-4-요오드디벤조퓨란(1-bromo-4-iododibenzo[b,d]furan) 3.5 g(9.4 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 5.1 g(19.7 mmol), Pd(dba)2 0.5 g(0.9 mmol), X-phos 1.8 g (3.7 mmol), K3PO4 11.9 g(56.2 mmol) 및 자일렌 90 mL를 혼합한 다음 15 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 CHCl3와 물로 씻었다. 얻어진 혼합물을 실리카겔 컬럼크로마토 그래피(CHCl3:Hex)로 정제한 후 MeOH로 고체화하여 흰색 고체의 화합물 22-119(LT20-30-373) 1.4 g(수율: 25.9%)을 얻었다.1-bromo-4-iododibenzofuran (1-bromo-4-iododibenzo [b, d] furan) 3.5 g (9.4 mmol), (3,5-bis (trifluoromethyl) phenyl) boronic acid ( (3,5-bis(trifluoromethyl)phenyl)boronic acid) 5.1 g (19.7 mmol), Pd(dba) 2 0.5 g (0.9 mmol), X-phos 1.8 g (3.7 mmol), K 3 PO 4 11.9 g ( 56.2 mmol) and 90 mL of xylene were mixed and stirred under reflux for 15 hours. After the reaction was completed, it was cooled to room temperature and washed with CHCl 3 and water. The resulting mixture was purified by silica gel column chromatography (CHCl 3 :Hex) and then solidified with MeOH to obtain 1.4 g (yield: 25.9%) of compound 22-119 (LT20-30-373) as a white solid.
제조예production example 36: 화합물 22-222(LT20-30-365)의 합성 36: Synthesis of compound 22-222 (LT20-30-365)
2구 500 mL 플라스크에서 중간체(51) 5.2 g(13.3 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 5.2 g(20.0 mmol), Pd(PPh3)4 0.7 g(0.7 mmol), K2CO3 3.7 g(26.5 mmol), 톨루엔 72 mL, 정제수 30 mL 및 에탄올 24 mL를 혼합한 다음 90℃에서 2시간 동안 교반하였다. 반응이 종료되면 실온으로 냉각한 후, 에틸아세테이트로 추출하여 유기층을 농축하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 디클로로메탄/아이소프로판올로 고체화하여, 흰색 고체의 화합물 22-222(LT20-30-365) 2.7 g(수율: 34.6%)을 얻었다.In a two-necked 500 mL flask, 5.2 g (13.3 mmol) of intermediate (51), (3,5-bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 5.2 g (20.0 mmol), Pd(PPh 3 ) 4 0.7 g (0.7 mmol), K 2 CO 3 3.7 g (26.5 mmol), toluene 72 mL, purified water 30 mL, and ethanol 24 mL were mixed, and then at 90° C. for 2 hours. stirred. Upon completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was concentrated. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with dichloromethane/isopropanol, and 2.7 g of compound 22-222 (LT20-30-365) as a white solid (yield: 34.6%) got
제조예production example 37: 화합물 22-245(LT20-30-374)의 합성 37: Synthesis of compound 22-245 (LT20-30-374)
중간체(52) 5.3 g(13.2 mmol), 3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 5.1 g(19.8 mmol), Pd(PPh3)4 0.4 g(0.4 mmol), K3PO4 7.0 g(32.9 mmol), Toluene 70 mL, EtOH 35 mL 및 증류수 35 mL을 혼합한 다음 15 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 여과하여 CHCl3와 물로 씻었다. 얻어진 혼합물을 실리카겔 컬럼크로마토 그래피(DCM:Hex)로 정제한 후 메탄올로 고체화하여 흰색 고체의 화합물 22-245(LT20-30-374) 4.5 g(수율: 64.6%)을 얻었다.Intermediate (52) 5.3 g (13.2 mmol), 3,5-bis (trifluoromethyl) phenyl) boronic acid ((3,5-bis (trifluoromethyl) phenyl) boronic acid) 5.1 g (19.8 mmol), Pd ( PPh 3 ) 4 0.4 g (0.4 mmol), K 3 PO 4 7.0 g (32.9 mmol), Toluene 70 mL, EtOH 35 mL, and distilled water 35 mL were mixed and stirred under reflux for 15 hours. After the reaction was completed, it was cooled to room temperature, filtered, and washed with CHCl 3 and water. The resulting mixture was purified by silica gel column chromatography (DCM:Hex) and then solidified with methanol to obtain 4.5 g (yield: 64.6%) of compound 22-245 (LT20-30-374) as a white solid.
제조예production example 38: 화합물 23-159(LT20-35-873)의 합성 38: Synthesis of compound 23-159 (LT20-35-873)
2구 250 mL 플라스크에서 중간체(68) 3.0 g(7.2 mmol), 중간체(1) 2.8 g(8.7 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 23-159(LT20-35-873) 1.5 g(수율: 36.2%)을 얻었다.In a two-necked 250 mL flask, 3.0 g (7.2 mmol) of Intermediate (68), 2.8 g (8.7 mmol) of Intermediate (1), 0.2 g (0.4 mmol) of Pd(dba) 2 , 0.3 g (0.7 mmol) of X-Phos, K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.5 g (yield: 36.2%) of compound 23-159 (LT20-35-873) as a white solid.
제조예production example 39: 화합물 23-175(LT20-35-100)의 합성 39: Synthesis of compound 23-175 (LT20-35-100)
2구 250 mL 플라스크에서 중간체(68) 3.0 g(7.2 mmol), 2-나프틸보론산(2-Naphthylboronic acid) 1.5 g(8.7 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 23-175(LT20-35-100) 1.1 g(수율: 30.0%)을 얻었다.In a 2-neck 250 mL flask, 3.0 g (7.2 mmol) of intermediate (68), 1.5 g (8.7 mmol) of 2-Naphthylboronic acid, 0.2 g (0.4 mmol) of Pd (dba) 2 , X- Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.1 g (yield: 30.0%) of compound 23-175 (LT20-35-100) as a white solid.
제조예production example 40: 화합물 23-249(LT20-35-876)의 합성 40: Synthesis of compound 23-249 (LT20-35-876)
2구 250 mL 플라스크에서 중간체(68) 3.0 g(7.2 mmol), 중간체(38) 3.6 g(8.7 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 23-249(LT20-35-876) 1.7 g(수율: 35.2%)을 얻었다.In a two-necked 250 mL flask, intermediate (68) 3.0 g (7.2 mmol), intermediate (38) 3.6 g (8.7 mmol), Pd(dba) 2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.7 g (yield: 35.2%) of compound 23-249 (LT20-35-876) as a white solid.
제조예production example 41: 화합물 24-159(LT20-30-510)의 합성 41: Synthesis of compound 24-159 (LT20-30-510)
1구 250 mL 플라스크에서 2,4-브로모페닐벤조옥사졸(2-(4-bromophenyl)benzo[d]oxazole) 2.4 g(8.9 mmol), 중간체(57) 4.5 g(8.9 mmol), Pd(PPh3)4 514.0 mg(444.4 μmol), K2CO3 3.1 g(22.2 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 증류수 10 mL을 혼합한 다음 5 시간 동안 환류 교반하였다. 반응이 종결된 후, 고체를 여과한 다음 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 실리카 패드에 통과시킨 후 감압 농축하였다. 다이클로로메탄으로 고체화하여, 흰색 고체의 화합물 24-159(LT20-30-510) 2.0 g(수율: 39.2%)을 얻었다.In a 1-neck 250 mL flask, 2,4-bromophenylbenzoxazole (2-(4-bromophenyl)benzo[d]oxazole) 2.4 g (8.9 mmol), intermediate (57) 4.5 g (8.9 mmol), Pd ( PPh 3 ) 4 514.0 mg (444.4 μmol), K 2 CO 3 3.1 g (22.2 mmol), toluene 30 mL, ethanol 10 mL and distilled water 10 mL were mixed, and then stirred under reflux for 5 hours. After the reaction was completed, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a silica pad, and then concentrated under reduced pressure. It was solidified with dichloromethane to obtain 2.0 g (yield: 39.2%) of compound 24-159 (LT20-30-510) as a white solid.
제조예production example 42: 화합물 24-223(LT20-30-509)의 합성 42: Synthesis of compound 24-223 (LT20-30-509)
1구 250 mL 플라스크에서 2-(4-브로모페닐)퀴놀린(2-(4-bromophenyl)quinoline) 2.5 g(8.9 mmol), 중간체(57) 4.5 g(8.9 mmol), Pd(PPh3)4 514.0 mg(444.4 μmol), K2CO3 3.1 g(22.2 mmol) 톨루엔 30 mL, 에탄올 10 mL 및 증류수 10 mL을 혼합한 다음 5 시간 동안 환류 교반하였다. 반응이 종결된 후, 고체를 여과한 다음 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 실리카 패드에 통과시킨 후 감압 농축하였다. 디클로로메탄으로 고체화하여, 흰색 고체의 화합물 24-223(LT20-30-509) 1.6 g(수율: 31.6%)을 얻었다.2.5 g (8.9 mmol) of 2- (4-bromophenyl) quinoline (2- (4-bromophenyl) quinoline) in a 1-neck 250 mL flask, 4.5 g (8.9 mmol) of intermediate (57), Pd (PPh 3 ) 4 514.0 mg (444.4 μmol), K 2 CO 3 3.1 g (22.2 mmol) toluene 30 mL, ethanol 10 mL, and distilled water 10 mL were mixed and stirred under reflux for 5 hours. After the reaction was completed, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a silica pad, and then concentrated under reduced pressure. It was solidified with dichloromethane to obtain 1.6 g (yield: 31.6%) of compound 24-223 (LT20-30-509) as a white solid.
제조예production example 43: 화합물 24-238(LT20-30-506)의 합성 43: Synthesis of compound 24-238 (LT20-30-506)
1구 250 mL 플라스크에서 2-(4-브로모페닐)피리딘(2-(4-bromophenyl)pyridine) 2.1 g(8.9 mmol), 중간체(57) 4.5 g(8.9 mmol), Pd(PPh3)4 514.0 mg(444.4 μmol), K2CO3 3.1 g(22.2 mmol) 톨루엔 30 mL, 에탄올 10 mL 및 증류수 10 mL을 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후, 고체를 여과한 다음 물과 메탄올, 에틸아세테이트로 씻어서 건조하였다. 건조한 고체를 모노클로로벤젠에 끓여서 녹인 후 실리카 패드에 통과시킨 후 감압 농축하였다. 혼합용매(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 24-238(LT20-30-506) 1.7 g(수율: 36.7%)을 얻었다.2- (4-bromophenyl) pyridine (2- (4-bromophenyl) pyridine) 2.1 g (8.9 mmol), intermediate (57) 4.5 g (8.9 mmol), Pd (PPh 3 ) 4 in a 1-neck 250 mL flask 514.0 mg (444.4 μmol), K 2 CO 3 3.1 g (22.2 mmol) toluene 30 mL, ethanol 10 mL, and distilled water 10 mL were mixed and stirred under reflux for 12 hours. After the reaction was completed, the solid was filtered, washed with water, methanol, and ethyl acetate, and dried. The dried solid was dissolved by boiling in monochlorobenzene, passed through a silica pad, and then concentrated under reduced pressure. It was solidified with a mixed solvent (DCM/MeOH) to obtain 1.7 g (yield: 36.7%) of compound 24-238 (LT20-30-506) as a white solid.
제조예production example 44: 화합물 25-24(LT20-35-1044)의 합성 44: Synthesis of compound 25-24 (LT20-35-1044)
2구 250 mL 플라스크에서 중간체(71) 3.0 g(7.2 mmol), 중간체(1) 2.8 g(8.7 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 25-24(LT20-35-1044) 1.5 g(수율: 36.2%)을 얻었다.In a 2-neck 250 mL flask, Intermediate (71) 3.0 g (7.2 mmol), Intermediate (1) 2.8 g (8.7 mmol), Pd(dba) 2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.5 g of compound 25-24 (LT20-35-1044) as a white solid (yield: 36.2%).
제조예production example 45: 화합물 25-88(LT20-35-1043)의 합성 45: Synthesis of compound 25-88 (LT20-35-1043)
중간체(71) 4.0 g(9.6 mmol), 중간체(7) 3.5 g(10.6 mmol), Pd(dba)2 554.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 끓여서 녹인 후, 실리카겔 패드에 여과한 후 감압 농축하였고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 25-88(LT20-35-1043) 2.0 g(수율: 34.8%)을 얻었다.Intermediate (71) 4.0 g (9.6 mmol), Intermediate (7) 3.5 g (10.6 mmol), Pd(dba) 2 554.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in chloroform, filtered through a silica gel pad, concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH), 2.0 g of compound 25-88 (LT20-35-1043) as a white solid (yield: 34.8) %) was obtained.
제조예production example 46: 화합물 25-112(LT20-35-1042)의 합성 46: Synthesis of compound 25-112 (LT20-35-1042)
2구 250 mL 플라스크에서 중간체(71) 3.0 g(7.2 mmol), 중간체(36) 2.0 g(7.2 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 25-112(LT20-35-1042 1.3 g(수율: 33.7%)을 얻었다.In a two-necked 250 mL flask, 3.0 g (7.2 mmol) of intermediate (71), 2.0 g (7.2 mmol) of intermediate (36), Pd (dba)2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K3PO4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was subjected to silica gel column chromatography (Hex:CH2Cl2) and solidified with methanol to obtain compound 25-112 (LT20-35-1042, 1.3 g (yield: 33.7%) as a white solid).
제조예production example 47: 화합물 26-158(LT20-35-1047)의 합성 47: Synthesis of compound 26-158 (LT20-35-1047)
2구 250 mL 플라스크에서 중간체(76) 3.0 g(7.2 mmol), 중간체(1) 2.8 g(8.7 mmol), Pd(dba)2 0.2 g(0.4 mmol), X-Phos 0.3 g(0.7 mmol), K3PO4 3.8 g(18.1 mmol) 및 자일렌 50 mL를 혼합한 다음, 120℃에서 1시간 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:CH2Cl2)로 정제하고 메탄올로 고체화하여, 흰색 고체의 화합물 26-158(LT20-35-1047) 1.5 g(수율: 36.2%)을 얻었다.In a two-necked 250 mL flask, Intermediate (76) 3.0 g (7.2 mmol), Intermediate (1) 2.8 g (8.7 mmol), Pd(dba) 2 0.2 g (0.4 mmol), X-Phos 0.3 g (0.7 mmol), K 3 PO 4 3.8 g (18.1 mmol) and 50 mL of xylene were mixed, and then reacted at 120° C. for 1 hour. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH 2 Cl 2 ) and solidified with methanol to obtain 1.5 g (yield: 36.2%) of compound 26-158 (LT20-35-1047) as a white solid.
제조예production example 48: 화합물 26-222(LT20-35-1046)의 합성 48: Synthesis of compound 26-222 (LT20-35-1046)
중간체(76) 4.0 g(9.6 mmol), 중간체(7) 3.5 g(10.6 mmol), Pd(dba)2 554.0 mg(964.5 μmol), X-Phos 919.0 mg(1.9 mmol), K3PO4 6.1 g(28.9 mmol) 및 자일렌 50 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과하고 물과 메탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 끓여서 녹인 후, 실리카겔 패드에 여과한 후 감압 농축하였고, 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 26-222(LT20-35-1046) 2.0 g(수율: 34.8%)을 얻었다.Intermediate (76) 4.0 g (9.6 mmol), Intermediate (7) 3.5 g (10.6 mmol), Pd(dba) 2 554.0 mg (964.5 μmol), X-Phos 919.0 mg (1.9 mmol), K 3 PO 4 6.1 g (28.9 mmol) and 50 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in chloroform, filtered through a silica gel pad, concentrated under reduced pressure, and solidified with a mixed solution (DCM/MeOH), 2.0 g of compound 26-222 (LT20-35-1046) as a white solid (yield: 34.8) %) was obtained.
제조예production example 49: 화합물 27-112(LT20-35-1048)의 합성 49: Synthesis of compound 27-112 (LT20-35-1048)
중간체(79) 3.5 g(8.4 mmol), 중간체(36) 2.6 g(9.3 mmol), Pd(dba)2 485.0 mg(843.9 μmol), X-Phos 805.0 mg(1.7 mmol), K3PO4 5.4 g(25.3 mmol) 및 자일렌 45 mL를 혼합한 다음, 12시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하여, 흰색 고체의 화합물 27-112(LT20-35-1048) 1.0 g(수율: 22.7%)을 얻었다.Intermediate (79) 3.5 g (8.4 mmol), Intermediate (36) 2.6 g (9.3 mmol), Pd(dba) 2 485.0 mg (843.9 μmol), X-Phos 805.0 mg (1.7 mmol), K 3 PO 4 5.4 g (25.3 mmol) and 45 mL of xylene were mixed, and then stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 1.0 g (yield: 22.7%) of compound 27-112 (LT20-35-1048) as a white solid.
제조예production example 50: 화합물 28-88(LT20-30-353)의 합성 50: Synthesis of compound 28-88 (LT20-30-353)
2구 250 mL 플라스크에서 중간체(58) 4.5 g(9.5 mmol), 중간체(7) 3.8 g(11.4 mmol), Pd(PPh3)4 328.3 mg(284.1 μmol), K2CO3 3.9 g(28.4 mmol), 톨루엔 50 mL, 에탄올 12 mL 및 증류수 12 mL를 혼합한 다음, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 고체를 증류수, 메탄올, 헥산으로 씻어 주었다. 얻어진 고체 혼합물을 뜨거운 톨루엔에 녹여 실리카 패드 여과하고, 뜨거운 톨루엔에 용해시킨 후 50℃에서 고체화하여, 백색 고체의 화합물 28-88(LT20-30-353) 2.3 g(수율: 41.0%)을 얻었다.In a 2-neck 250 mL flask, intermediate (58) 4.5 g (9.5 mmol), intermediate (7) 3.8 g (11.4 mmol), Pd(PPh 3 ) 4 328.3 mg (284.1 μmol), K 2 CO 3 3.9 g (28.4 mmol) ), toluene 50 mL, ethanol 12 mL and distilled water 12 mL were mixed, and then reacted at 90° C. for one day. Upon completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, followed by filtration, and the solid was washed with distilled water, methanol, and hexane. The obtained solid mixture was dissolved in hot toluene, filtered through a silica pad, dissolved in hot toluene, and solidified at 50° C. to obtain 2.3 g (yield: 41.0%) of compound 28-88 (LT20-30-353) as a white solid.
제조예production example 51: 화합물 28-103(LT20-30-377)의 합성 51: Synthesis of compound 28-103 (LT20-30-377)
2구 100 mL 플라스크에서 중간체(59) 3.0 g(7.2 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 2.8 g(10.8 mmol), Pd(PPh3)4 249.8 mg(216.2 μmol), K2CO3 3.0 g(21.6 mmol), 톨루엔 40 mL, 에탄올 10 mL 및 증류수 10 mL를 혼합한 다음, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 고체를 증류수, 메탄올, 헥산으로 씻어 주었다. 얻어진 고체 혼합물을 뜨거운 톨루엔에 녹여 실리카 패드 여과를 하였다. 얻어진 고체 혼합물을 실리카겔 컬럼(EA:Hex)으로 정제하여, 백색 고체의 화합물 28-103(LT20-30-377) 1.1 g(수율: 28.5%)을 얻었다.In a two-necked 100 mL flask, 3.0 g (7.2 mmol) of intermediate (59), 2.8 g of (3,5-bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) (10.8 mmol), Pd(PPh 3 ) 4 249.8 mg (216.2 μmol), K 2 CO 3 3.0 g (21.6 mmol), toluene 40 mL, ethanol 10 mL and distilled water 10 mL were mixed, and then at 90° C. for one day. reacted. Upon completion of the reaction, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, followed by filtration, and the solid was washed with distilled water, methanol, and hexane. The obtained solid mixture was dissolved in hot toluene and filtered through a silica pad. The obtained solid mixture was purified by silica gel column (EA:Hex) to obtain 1.1 g (yield: 28.5%) of compound 28-103 (LT20-30-377) as a white solid.
제조예production example 52: 화합물 28-119(LT20-30-345)의 합성 52: Synthesis of compound 28-119 (LT20-30-345)
2구 250 mL 플라스크에서 2,8-다이브로모다이벤조[b,d]티오펜(2,8-dibromodibenzo[b,d]thiophene) 3.0 g(8.8 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 6.6 g(19.3 mmol), Pd(PPh3)4 506.8 mg(438.5 μmol), K2CO3 7.3 g(52.6 mmol), 톨루엔 44 mL, 에탄올 11 mL 및 증류수 11 mL를 혼합한 다음, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올로 씻어 주었다. 얻어진 고체 혼합물을 실리카 패드 여과(Hex:EA)를 하고, 혼합용액(Hex:EA)으로 고체화하여, 백색 고체의 화합물 28-119(LT20-30-345) 2.7 g(수율: 50.4%)을 얻었다.In a 2-neck 250 mL flask, 3.0 g (8.8 mmol) of 2,8-dibromodibenzo[ b , d ] thiophene , ( 3,5-bis(trifluoro Romethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 6.6 g (19.3 mmol), Pd(PPh 3 ) 4 506.8 mg (438.5 μmol), K 2 CO 3 7.3 g (52.6 mmol), toluene 44 mL, ethanol 11 mL, and distilled water 11 mL were mixed, and then reacted at 90° C. for one day. After the reaction was completed, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water and methanol. The obtained solid mixture was subjected to silica pad filtration (Hex:EA) and solidified with a mixed solution (Hex:EA) to obtain 2.7 g (yield: 50.4%) of compound 28-119 (LT20-30-345) as a white solid. .
제조예production example 53: 화합물 29-119(LT20-35-119)의 합성 53: Synthesis of compound 29-119 (LT20-35-119)
2구 250 mL 플라스크에서 3,7-다이브로모다이벤조[b,d]티오펜(3,7-dibromodibenzo[b,d]thiophene) 3.0 g(8.8 mmol), (3,5-비스(트리플루오로메틸)페닐)보론산((3,5-bis(trifluoromethyl)phenyl)boronic acid) 6.6 g(19.3 mmol), Pd(PPh3)4 506.8 mg(438.5 μmol), K2CO3 7.3 g(52.6 mmol), 톨루엔 44 mL, 에탄올 11 mL 및 증류수 11 mL를 혼합한 다음, 90℃에서 하루 동안 반응하였다. 반응이 종료되면 실온으로 냉각한 후, 반응물에 증류수 50 mL를 첨가한 후 여과하고, 증류수, 메탄올로 씻어 주었다. 얻어진 고체 혼합물을 실리카 패드 여과(Hex:EA)를 하고, 혼합용액(Hex:EA)으로 고체화하여, 백색 고체의 화합물 29-119(LT20-35-119) 2.7 g(수율: 50.4%)을 얻었다.3.0 g (8.8 mmol) of 3,7-dibromodibenzo[ b , d ] thiophene , ( 3,5-bis(trifluoro Romethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 6.6 g (19.3 mmol), Pd(PPh 3 ) 4 506.8 mg (438.5 μmol), K 2 CO 3 7.3 g (52.6 mmol), toluene 44 mL, ethanol 11 mL, and distilled water 11 mL were mixed, and then reacted at 90° C. for one day. After the reaction was completed, after cooling to room temperature, 50 mL of distilled water was added to the reaction product, filtered, and washed with distilled water and methanol. The obtained solid mixture was subjected to silica pad filtration (Hex:EA) and solidified with a mixed solution (Hex:EA) to obtain 2.7 g (yield: 50.4%) of compound 29-119 (LT20-35-119) as a white solid. .
제조예production example 54: 화합물 30-88(LT20-30-482)의 합성 54: Synthesis of compound 30-88 (LT20-30-482)
1구 250 mL 플라스크에서 중간체(61) 4.0 g(7.5 mmol), 중간체(7) 2.5 g(7.5 mmol), Pd(PPh3)4 423.0 mg(374.3 μmol), K2CO3 2.6 g(18.7 mmol) 톨루엔 30 mL, 에탄올 10 mL 및 증류수 10 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피로(CHCl3) 정제하고 혼합용액(DCM/MeOH)로 고체화하여, 흰색 고체의 화합물 30-88(LT20-30-482) 2.8 g(수율: 56.8%)을 얻었다.In a 1-neck 250 mL flask, Intermediate (61) 4.0 g (7.5 mmol), Intermediate (7) 2.5 g (7.5 mmol), Pd(PPh 3 ) 4 423.0 mg (374.3 μmol), K 2 CO 3 2.6 g (18.7 mmol) ) 30 mL of toluene, 10 mL of ethanol, and 10 mL of distilled water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 ), and solidified with a mixed solution (DCM/MeOH), 2.8 g of compound 30-88 (LT20-30-482) as a white solid (yield: 56.8%) got
제조예production example 55: 화합물 30-103(LT20-30-481)의 합성 55: Synthesis of compound 30-103 (LT20-30-481)
1구 250 mL 플라스크에서 중간체(61) 4.0 g(7.5 mmol), 중간체(36) 2.1 g(7.5 mmol), Pd(PPh3)4 423.0 mg(374.3 μmol), K2CO3 2.6 g(18.7 mmol), 톨루엔 30 mL, 에탄올 10 mL 및 증류수 10 mL를 혼합한 다음 12 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 고체를 여과한 후 물과 에탄올로 씻어서 건조하였다. 건조한 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용액(DCM/MeOH)으로 고체화하여, 흰색 고체의 화합물 30-103(LT20-30-481) 1.1 g(수율: 23.1%)을 얻었다.In a 1-neck 250 mL flask, intermediate (61) 4.0 g (7.5 mmol), intermediate (36) 2.1 g (7.5 mmol), Pd(PPh 3 ) 4 423.0 mg (374.3 μmol), K 2 CO 3 2.6 g (18.7 mmol) ), toluene 30 mL, ethanol 10 mL, and distilled water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography (CHCl 3 ), and solidified with a mixed solution (DCM/MeOH). Compound 30-103 (LT20-30-481) as a white solid 1.1 g (yield: 23.1%) got
<시험예><Test Example>
본 발명의 화합물에 대하여 J.A. WOOLLAM社 Ellipsometer 기기를 이용하여 광학 특성 평가용 단막의 n(refractive index)와 k(extinction coefficient)을 측정하였다.For the compounds of the present invention J.A. The n (refractive index) and k (extinction coefficient) of the single film for optical property evaluation were measured using WOOLLAM's Ellipsometer device.
광학 특성 평가용 단막 제작 : Fabrication of single film for evaluation of optical properties:
화합물의 광학 특성 측정을 위해, 유리기판(0.7T)을 Ethanol, DI Water, Acetone에 각각 10분씩 세척한 후, 2×10- 2Torr에서 125 W로 2분간 산소 플라즈마 처리하고, 9×10- 7Torr의 진공도에서 1Å/sec의 속도로 유리기판 위에 화합물을 800Å증착하여 단막을 제작한다. To measure the optical properties of the compound, the glass substrate (0.7T) was washed in Ethanol, DI Water, and Acetone for 10 minutes each, and then treated with oxygen plasma at 2×10 - 2 Torr at 125 W for 2 minutes, and 9×10 - A single film is fabricated by depositing 800 Å of the compound on a glass substrate at a rate of 1 Å/sec in a vacuum of 7 Torr.
상기 광학 특성 평가용 단막 제작에서 화합물로 Alq3와 REF01을 각각 사용하였다. Alq 3 and REF01 were used as compounds in the production of the single film for evaluation of optical properties, respectively.
< 시험예 1 내지 55 >< Test Examples 1 to 55 >
상기 광학 특성 평가용 단막 제작에서 화합물로 하기 표 1에 나타낸 각각의 화합물을 각각 사용하였다. Each compound shown in Table 1 below was used as a compound in the production of the single film for evaluation of optical properties.
상기 비교시험예 및 시험예 1 내지 55에 의한 화합물의 광학 특성을 표 1에 나타냈다.The optical properties of the compounds according to the Comparative Test Examples and Test Examples 1 to 55 are shown in Table 1.
광학 특성은 460nm 및 620nm 파장에서 굴절률 상수이다.The optical properties are refractive index constants at 460 nm and 620 nm wavelengths.
(LT20-30-463)19-24
(LT20-30-463)
(LT20-30-489)19-30
(LT20-30-489)
(LT20-30-487)19-79
(LT20-30-487)
(LT20-30-346)19-88
(LT20-30-346)
(LT20-30-471)19-89
(LT20-30-471)
(LT20-30-351)19-103
(LT20-30-351)
(LT20-30-283)19-119
(LT20-30-283)
(LT20-30-495)20-17
(LT20-30-495)
(LT20-30-413)20-24
(LT20-30-413)
(LT20-30-480)20-30
(LT20-30-480)
(LT20-30-501)20-79
(LT20-30-501)
(LT20-30-437)20-81
(LT20-30-437)
(LT20-30-475)20-82
(LT20-30-475)
(LT20-30-460)20-84
(LT20-30-460)
(LT20-30-462)20-85
(LT20-30-462)
(LT20-30-474)20-86
(LT20-30-474)
(LT20-30-337)20-88
(LT20-30-337)
(LT20-30-472)20-97
(LT20-30-472)
(Lt20-30-455)20-99
(LT20-30-455)
(LT20-30-465)20-100
(LT20-30-465)
(LT20-30-469)20-101
(LT20-30-469)
(LT20-30-332)20-103
(LT20-30-332)
(LT20-30-436)20-104
(LT20-30-436)
(LT20-30-334)20-119
(LT20-30-334)
(LT20-30-479)20-127
(LT20-30-479)
(LT20-30-502)20-134
(LT20-30-502)
(LT20-30-516)20-159
(LT20-30-516)
(LT20-30-490)20-216
(LT20-30-490)
(LT20-30-427)20-223
(LT20-30-427)
(LT20-30-420)20-238
(LT20-30-420)
(LT20-30-496)20-263
(LT20-30-496)
(LT20-30-504)20-264
(LT20-30-504)
(LT20-35-867)21-24
(LT20-35-867)
(LT20-35-865)21-103
(LT20-35-865)
(LT20-30-373)22-119
(LT20-30-373)
(LT20-30-365)22-222
(LT20-30-365)
(LT20-30-374)22-245
(LT20-30-374)
(LT20-35-873)23-159
(LT20-35-873)
(LT20-35-100)23-175
(LT20-35-100)
(LT20-35-876)23-249
(LT20-35-876)
(LT20-30-510)24-159
(LT20-30-510)
(LT20-30-509)24-223
(LT20-30-509)
(LT20-30-506)24-238
(LT20-30-506)
(LT20-35-1044)25-24
(LT20-35-1044)
(LT20-35-1043)25-88
(LT20-35-1043)
(LT20-35-1042)25-112
(LT20-35-1042)
(LT20-35-1047)26-158
(LT20-35-1047)
(LT20-35-1046)26-222
(LT20-35-1046)
(LT20-35-1048)27-112
(LT20-35-1048)
(LT20-30-353)28-88
(LT20-30-353)
(LT20-30-377)28-103
(LT20-30-377)
(LT20-30-345)28-119
(LT20-30-345)
(LT20-35-119)29-119
(LT20-35-119)
(LT20-30-482)30-88
(LT20-30-482)
(LT20-30-481)30-103
(LT20-30-481)
상기 표 1에서 알 수 있는 바와 같이, 비교시험예(Alq3)의 청색영역(460nm)과 적색영역(620nm)에서의 n값이 각각 1.808, 1.690이었고, 이에 반해 대부분의 본 발명에 따른 화합물들은 대체적으로 청색영역, 녹색영역 및 적색영역에서 비교시험예 화합물(Alq3) 보다 낮은 굴절률(n<1.69 @620nm)을 갖는 것으로 확인되었다. 이것은 청색영역에서의 높은 시야각을 확보하기 위해 필요한 낮은 굴절률 값에 만족한다. As can be seen from Table 1, the n values in the blue region (460 nm) and the red region (620 nm) of the comparative test example (Alq 3 ) were 1.808 and 1.690, respectively, whereas most of the compounds according to the present invention were In general, it was confirmed to have a lower refractive index (n<1.69 @620nm) than the comparative test example compound (Alq 3 ) in the blue region, the green region and the red region. This satisfies the low refractive index value required to secure a high viewing angle in the blue region.
<실시예><Example>
소자 제작device fabrication
소자 제작을 위해 투명 전극인 ITO는 양극 층으로 사용하였고, 2-TNATA는 정공 주입층, NPB는 정공 수송층, αβ-ADN은 발광층의 호스트, Pyrene-CN은 청색 형광 도판트, Alq3는 전자 수송층, Liq는 전자 주입층, Mg:Ag은 음극으로 사용하였다. 이 화합물들의 구조는 하기의 화학식과 같다.For device fabrication, ITO, a transparent electrode, was used as an anode layer, 2-TNATA is a hole injection layer, NPB is a hole transport layer, αβ-ADN is a host of the light emitting layer, Pyrene-CN is a blue fluorescent dopant, and Alq 3 is an electron transport layer. , Liq was used as the electron injection layer, and Mg:Ag was used as the cathode. The structures of these compounds are as follows.
비교실시예 1(캡핑층을 없음): ITO / 2-TNATA(60 nm) / NPB(20 nm) / αβ-ADN:10% Pyrene-CN(30 nm) / Alq3(30 nm) / Liq(2 nm) / Mg:Ag(1:9, 10 nm) Comparative Example 1 (without capping layer): ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq 3 (30 nm) / Liq ( 2 nm) / Mg:Ag (1:9, 10 nm)
비교실시예 2(캡핑층을 1층으로 구성): ITO / 2-TNATA(60 nm) / NPB(20 nm) / αβ-ADN:10% Pyrene-CN(30 nm) / Alq3(30 nm) / Liq(2 nm) / Mg:Ag(1:9, 10 nm) / Alq3(80nm) Comparative Example 2 (Capping layer consists of one layer): ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / Alq 3 (80 nm)
실시예 (캡핑층을 2층으로 구성): ITO / 2-TNATA(60 nm) / NPB(20 nm) / αβ-ADN:10% Pyrene-CN(30 nm) / Alq3(30 nm) / Liq(2 nm) / Mg:Ag(1:9, 10 nm) / 본 발명의 화합물(20nm, 저굴절 화합물) / REF01(60nm, 고굴절 화합물) Example (Capping layer consists of two layers): ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / Compound of the present invention (20 nm, low refractive compound) / REF01 (60 nm, high refractive compound)
청색 형광 유기발광소자는 ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN:Pyrene-CN 10% (30 nm) / Alq3 (30 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / 캡핑층 순으로 증착하여 소자를 제작하였다. Blue fluorescent organic light emitting device is ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN:Pyrene-CN 10% (30 nm) / Alq 3 (30 nm) / Liq (2 nm) / Mg :Ag (1:9, 10 nm) / capping layer was deposited in the order to fabricate a device.
유기물을 증착하기 전에 ITO 전극은 2 × 10- 2Torr에서 125W로 2분간 산소 플라즈마 처리를 하였다. 유기물은 9 × 10- 7Torr의 진공도에서 증착하였으며, Liq는 0.1 Å/sec, αβ-ADN은 0.18 Å/sec의 기준으로 Pyrene-CN는 0.02Å/sec으로 동시 증착하였고, 나머지 유기물들은 모두 1 Å/sec의 속도로 증착하였다. Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 2 × 10 - 2 Torr at 125 W for 2 minutes. Organic materials were deposited at a vacuum of 9 × 10 - 7 Torr, Liq was 0.1 Å/sec, αβ-ADN was 0.18 Å/sec, and Pyrene-CN was simultaneously deposited at 0.02 Å/sec, and all other organic materials were 1 Deposited at a rate of Å/sec.
소자 제작이 끝난 후 소자의 공기 및 수분의 접촉을 막기 위하여 질소 기체로 채워져 있는 글러브 박스 안에서 봉지를 하였다. 3M사의 접착용 테이프로 격벽을 형성 후 수분 등을 제거할 수 있는 흡습제인 바륨산화물(Barium Oxide)을 넣고 유리판을 붙였다.After the device was manufactured, it was encapsulated in a glove box filled with nitrogen gas to prevent the device from contacting air and moisture. After forming the barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.
< 실시예 1 내지 55 >< Examples 1 to 55 >
상기 실시예에서, 캡핑층으로서 저굴절 층(20nm) 위에 고굴절 층(60nm)이 형성된 복층을 구비하고, 고굴절 층에 REF01 화합물을 저굴절 층에 하기 표 2에 나타낸 각각의 화합물을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 소자를 제작하였다.In the above embodiment, a multilayer having a high refractive layer (60 nm) formed on a low refractive layer (20 nm) as a capping layer, REF01 compound in the high refractive layer, and each compound shown in Table 2 below in the low refractive layer was used except that fabricated the device in the same manner as in Example 1.
상기 비교실시예 1, 비교실시예 2 및 실시예 1 내지 55에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 표 2에 나타냈다.Table 2 shows the electroluminescence characteristics of the organic light emitting devices prepared in Comparative Example 1, Comparative Example 2, and Examples 1 to 55.
[V]drive voltage
[V]
[cd/A]efficiency
[cd/A]
(%)life span
(%)
(LT20-30-463)19-24
(LT20-30-463)
(LT20-30-489)19-30
(LT20-30-489)
(LT20-30-487)19-79
(LT20-30-487)
(LT20-30-346)19-88
(LT20-30-346)
(LT20-30-471)19-89
(LT20-30-471)
(LT20-30-351)19-103
(LT20-30-351)
(LT20-30-283)19-119
(LT20-30-283)
(LT20-30-495)20-17
(LT20-30-495)
(LT20-30-413)20-24
(LT20-30-413)
(LT20-30-480)20-30
(LT20-30-480)
(LT20-30-501)20-79
(LT20-30-501)
(LT20-30-437)20-81
(LT20-30-437)
(LT20-30-475)20-82
(LT20-30-475)
(LT20-30-460)20-84
(LT20-30-460)
(LT20-30-462)20-85
(LT20-30-462)
(LT20-30-474)20-86
(LT20-30-474)
(LT20-30-337)20-88
(LT20-30-337)
(LT20-30-472)20-97
(LT20-30-472)
(LT20-30-455)20-99
(LT20-30-455)
(LT20-30-465)20-100
(LT20-30-465)
(LT20-30-469)20-101
(LT20-30-469)
(LT20-30-332)20-103
(LT20-30-332)
(LT20-30-436)20-104
(LT20-30-436)
(LT20-30-334)20-119
(LT20-30-334)
(LT20-30-479)20-127
(LT20-30-479)
(LT20-30-502)20-134
(LT20-30-502)
(LT20-30-516)20-159
(LT20-30-516)
(LT20-30-490)20-216
(LT20-30-490)
(LT20-30-427)20-223
(LT20-30-427)
(LT20-30-420)20-238
(LT20-30-420)
(LT20-30-496)20-263
(LT20-30-496)
(LT20-30-504)20-264
(LT20-30-504)
(LT20-35-867)21-24
(LT20-35-867)
(LT20-35-865)21-103
(LT20-35-865)
(LT20-30-373)22-119
(LT20-30-373)
(LT20-30-365)22-222
(LT20-30-365)
(LT20-30-374)22-245
(LT20-30-374)
(LT20-35-873)23-159
(LT20-35-873)
(LT20-35-100)23-175
(LT20-35-100)
(Lt20-35-876)23-249
(LT20-35-876)
(LT20-30-510)24-159
(LT20-30-510)
(LT20-30-509)24-223
(LT20-30-509)
(LT20-30-506)24-238
(LT20-30-506)
(LT20-35-1044)25-24
(LT20-35-1044)
(LT20-35-1043)25-88
(LT20-35-1043)
(LT20-35-1042)25-112
(LT20-35-1042)
(LT20-35-1047)26-158
(LT20-35-1047)
(LT20-35-1046)26-222
(LT20-35-1046)
(LT20-35-1048)27-112
(LT20-35-1048)
(LT20-30-353)28-88
(LT20-30-353)
(LT20-30-377)28-103
(LT20-30-377)
(LT20-30-345)28-119
(LT20-30-345)
(LT20-35-119)29-119
(LT20-35-119)
(LT20-30-482)30-88
(LT20-30-482)
(LT20-30-481)30-103
(LT20-30-481)
상기 표 2의 결과로부터 알 수 있듯이, 캡핑층(Capping Layer, 광효율 개선층)이 있는 소자(비교실시예2)와 없는 소자(비교실시예1)의 결과를 보면 캡핑층(Capping Layer, 광효율 개선층)으로 효율을 상승시킬 수 있음을 확인할 수 있다.As can be seen from the results of Table 2, when looking at the results of the device (Comparative Example 2) and the device without (Comparative Example 1) with the capping layer (Capping Layer, light efficiency improvement layer), the capping layer (Capping Layer, light efficiency improvement) layer), it can be seen that the efficiency can be increased.
상기 표 2의 결과로부터, 본 발명에 따른 특정의 디벤조 5원고리 화합물은 유기 발광 소자를 비롯한 유기 전자 소자의 저굴절 캡핑층의 재료로서 사용될 수 있고, 이를 이용한 유기 발광 소자를 비롯한 유기 전자 소자는 효율, 구동전압, 안정성 등에서 우수한 특성을 나타냄을 알 수 있다. From the results of Table 2, a specific dibenzo 5-membered ring compound according to the present invention can be used as a material for a low refractive index capping layer of an organic electronic device including an organic light emitting device, and an organic electronic device including an organic light emitting device using the same It can be seen that shows excellent characteristics in efficiency, driving voltage, and stability.
캡핑층(Capping Layer, 광효율 개선층)으로 고굴절(n>1.69 @620nm) 화합물로 단일층만 사용하고 있는 소자와 고굴절(n>1.69 @620nm) 화합물과 저굴절(n<1.69 @620nm) 화합물로 복층으로 사용하고 있는 소자의 결과를 보면 복층으로 사용한 캡핑층(Capping Layer, 광효율 개선층)이 효율을 상승시킬 수 있음을 확인할 수 있으며, 캡핑층(Capping Layer, 광효율 개선층)으로 Alq3를 사용한 소자(비교실시예2) 보다 본 발명의 재료를 복층으로 사용하였을 경우에 효율이 개선됨을 알 수 있다.A device using only a single layer with a high refractive index (n> 1.69 @620nm) compound as a capping layer (Capping Layer), a high refractive index (n>1.69 @620nm) compound, and a low refractive index (n<1.69 @620nm) compound If you look at the results of the device using the multilayer, it can be confirmed that the capping layer (Capping Layer, light efficiency improving layer) used as the multilayer can increase the efficiency, and Alq 3 is used as the capping layer (Capping Layer, light efficiency improving layer). It can be seen that the efficiency is improved when the material of the present invention is used in multiple layers rather than the device (Comparative Example 2).
이는 굴절률로 설명할 수 있는데, 고굴절률을 가지는 REF01 단일층 보다 높은 굴절률(고굴절)과 낮은 굴절률(저굴절)을 가지는 본 발명의 화합물을 복층으로 사용한 유기 전기발광소자가 높은 효율을 가지는 것은 자명한 일이다.This can be explained by the refractive index, and it is obvious that an organic electroluminescent device using the compound of the present invention having a higher refractive index (high refractive index) and a lower refractive index (low refractive index) than a REF01 single layer having a high refractive index has high efficiency. it's a thing
따라서 화학식 1의 화합물은 OLED에서 저굴절 캡핑층으로 사용하기 위한 의외의 바람직한 특성을 가지고 있다. Therefore, the compound of Formula 1 has unexpectedly desirable properties for use as a low refractive index capping layer in an OLED.
본 발명의 화합물이 이러한 특성에 의해 산업용 유기 전자 소자 제품에 적용될 수 있다.The compound of the present invention can be applied to industrial organic electronic device products due to these properties.
다만, 전술한 합성예는 일 예시이며, 반응 조건은 필요에 따라 변경될 수 있다. 또한, 본 발명의 일 실시예에 따른 화합물은 당 기술분야에 알려진 방법 및 재료를 이용하여 다양한 치환기를 가지도록 합성될 수 있다. 화학식 1로 표시되는 코어 구조에 다양한 치환체를 도입함으로써 유기 전계 발광 소자에 사용되기에 적합한 특성을 가질 수 있다.However, the above-described synthesis example is an example, and the reaction conditions may be changed as needed. In addition, the compound according to an embodiment of the present invention may be synthesized to have various substituents using methods and materials known in the art. By introducing various substituents into the core structure represented by Formula 1, it may have properties suitable for use in an organic electroluminescent device.
100: 기판, 110: 제1 전극, 120: 제2 전극, 200: 유기물층, 210: 정공주입층, 215: 정공수송층, 220: 발광층, 230: 전자수송층, 235: 전자주입층, 300: 캡핑층100: substrate, 110: first electrode, 120: second electrode, 200: organic material layer, 210: hole injection layer, 215: hole transport layer, 220: light emitting layer, 230: electron transport layer, 235: electron injection layer, 300: capping layer
Claims (6)
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 5]
[화학식 6]
[화학식 7]
[화학식 8]
[화학식 9]
[화학식 10]
[화학식 11]
[화학식 12]
[화학식 13]
[화학식 14]
[화학식 15]
[화학식 16]
[화학식 17]
상기 화학식 2 내지 화학식 17에 있어서,
R1 내지 R5는 각각 독립적으로 H; F; CF3 또는 Si(CH3)3 이고,
Z1는 O 또는 S 중 어느 하나이고,
L1 및 L2는 각각 독립적으로 페닐렌기 또는 피리딜렌기이며,
m 및 n은 각각 독립적으로 0 내지 3의 정수이고,
Ar1은 페닐기; F, CF3, 또는 Si(CH3)3로 치환된 페닐기; 피리딜기; 나프틸기; 퀴놀린기; 이소퀴놀린기; 벤조옥사졸기; 벤조티아졸기; 및 벤조이미다졸기 중에서 선택되는 어느 하나이다.A dibenzo 5-membered ring compound represented by any one of the following Chemical Formulas 2 to 17, and having a low refractive index of less than 1.69 at a wavelength of 620 nm for a capping layer of an organic electroluminescent device.
[Formula 2]
[Formula 3]
[Formula 4]
[Formula 5]
[Formula 6]
[Formula 7]
[Formula 8]
[Formula 9]
[Formula 10]
[Formula 11]
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
[Formula 16]
[Formula 17]
In Formulas 2 to 17,
R 1 to R 5 are each independently H; F; CF 3 or Si(CH 3 ) 3 and
Z 1 is any one of O or S,
L 1 and L 2 are each independently a phenylene group or a pyridylene group,
m and n are each independently an integer of 0 to 3,
Ar 1 is a phenyl group; F, CF 3 , or a phenyl group substituted with Si(CH 3 ) 3 ; pyridyl group; naphthyl group; quinoline group; isoquinoline group; benzoxazole group; benzothiazole group; and any one selected from a benzimidazole group.
상기 화학식 2 내지 화학식 17의 화합물은 하기 화학식 19 내지 화학식 26, 화학식 28 및 화학식 29로 구성된 화합물로부터 선택되는 어느 하나의 유기전계발광 소자의 캡핑층용 디벤조 5원고리 화합물.
[화학식 19]
[화학식 20]
[화학식 21]
[화학식 22]
[화학식 23]
[화학식 24]
[화학식 25]
[화학식 26]
[화학식 28]
[화학식 29]
The compound of Formulas 2 to 17 is a dibenzo 5-membered ring compound for a capping layer of any one organic electroluminescent device selected from compounds consisting of Formulas 19 to 26, Formula 28 and Formula 29.
[Formula 19]
[Formula 20]
[Formula 21]
[Formula 22]
[Formula 23]
[Formula 24]
[Formula 25]
[Formula 26]
[Formula 28]
[Formula 29]
상기 제1 전극 상에 배치된, 복수의 유기물층으로 구성된 유기물층;
상기 유기물층 상에 배치된 제2 전극; 및
상기 제2 전극 상에 배치된 캡핑층;을 포함하고,
상기 캡핑층은 상기 제 1항 또는 제 3항의 디벤조 5원고리 화합물를 포함하는 유기전계발광소자.a first electrode;
an organic material layer formed of a plurality of organic material layers disposed on the first electrode;
a second electrode disposed on the organic material layer; and
a capping layer disposed on the second electrode; and
The capping layer is an organic electroluminescent device comprising the dibenzo 5-membered ring compound of claim 1 or 3.
상기 캡핑층은 상이한 굴절률을 가지는 복수개의 층을 포함하여 이루어진 것을 특징으로 하는 유기전계발광소자. 5. The method of claim 4,
The capping layer is an organic light emitting device, characterized in that it comprises a plurality of layers having different refractive indices.
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| WO2022119174A1 (en) | 2022-06-09 |
| CN116568683A (en) | 2023-08-08 |
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