KR20230028648A - Tertiary amine derivatives and organic electroluminescent device including the same - Google Patents
Tertiary amine derivatives and organic electroluminescent device including the same Download PDFInfo
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- KR20230028648A KR20230028648A KR1020210109930A KR20210109930A KR20230028648A KR 20230028648 A KR20230028648 A KR 20230028648A KR 1020210109930 A KR1020210109930 A KR 1020210109930A KR 20210109930 A KR20210109930 A KR 20210109930A KR 20230028648 A KR20230028648 A KR 20230028648A
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- 150000003512 tertiary amines Chemical class 0.000 title description 2
- 239000010410 layer Substances 0.000 claims abstract description 200
- 239000012044 organic layer Substances 0.000 claims abstract description 34
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- 150000001875 compounds Chemical class 0.000 claims description 202
- 239000011368 organic material Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 150000004059 quinone derivatives Chemical class 0.000 description 4
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 3
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- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
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Abstract
Description
본 발명은 3차 아민 유도체 및 이를 포함하는 유기전계발광소자에 관한 것으로, 3차 아민 유도체에 의해 캡핑층을 포함한 유기전계발광소자가 고굴절률 특성과 자외선 흡수특성을 동시에 갖도록 하는 것이다.The present invention relates to a tertiary amine derivative and an organic electroluminescent device including the same, and provides an organic electroluminescent device including a capping layer by the tertiary amine derivative to have high refractive index characteristics and ultraviolet ray absorption characteristics at the same time.
디스플레이 산업에서 표시장치의 대형화에 따라 공간 점유가 작은 평면표시소자의 요구가 증대되고 있다. LCD(Liquid Crystal Display)는 시야각이 제한되고, 자체 발광형이 아니므로 별도의 광원이 필요하다는 단점을 가지고 있다. 이러한 이유로 자기 발광 현상을 이용한 디스플레이로서 OLED(유기발광다이오드, Organic Light Emitting Diodes)가 주목받고 있다.In the display industry, demand for a flat display device having a small space occupancy is increasing according to the size of the display device. A liquid crystal display (LCD) has a limited viewing angle and has disadvantages in that a separate light source is required because it is not self-luminous. For this reason, OLED (Organic Light Emitting Diodes) is attracting attention as a display using a self-luminous phenomenon.
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 특성 등에 대한 많은 이해와 연구가 시작되었다.In OLED, research on carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, a lot of understanding and research on the basic mechanisms of charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescent properties began.
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 such as structural changes and material development of devices have been made [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 transporting layer (HTL), an emission layer (EML), an electron transporting layer, It consists of a multi-layer structure of ETL) and a cathode, and has a sandwich structure in which an organic multi-layer 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. In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials 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.
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.When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls to the ground state, it emits light. 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. Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their 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.Light-emitting materials include blue, green, and red light-emitting materials according to light-emitting colors, and yellow and orange light-emitting materials required to realize better natural colors. In addition, in order to increase color purity and increase light emitting 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 higher luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated in 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 range of the dopant, light of a desired wavelength can be obtained according to the type of 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 fully express the excellent characteristics of the organic light emitting device described above, materials constituting the organic material layer in the device, such as hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. have been developed. The performance of organic light emitting devices is being recognized by products.
그러나 유기 발광 소자의 상용화가 이루어지고 시간이 지남에 따라 유기 발광 소자 자체의 발광 특성 이외에 다른 특성들의 필요성이 대두되고 있다. However, as organic light emitting diodes are commercialized and time passes, the need for other characteristics in addition to the light emitting properties of the organic light emitting diode itself has emerged.
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 element is exposed to an external light source for a long time, it is in an environment where it is exposed to high-energy ultraviolet light. Accordingly, there is a problem in that organic materials constituting the organic light emitting device are continuously affected. The problem can be solved by applying a capping layer having UV absorption characteristics to the organic light emitting device in order to prevent exposure to such a high energy light source.
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 organic light emitting diodes are wide, but from the viewpoint of the light source spectrum, considerable deviations occur depending on the viewing angles. This is due to the occurrence of deviations between appropriate refractive indices according to the
일반적으로 청색에 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, as the refractive index value required for blue is large and the wavelength becomes longer, the required refractive index value becomes smaller. Accordingly, it is necessary to develop a material constituting the capping layer that simultaneously satisfies the above-mentioned UV absorption characteristics and 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. Efficiency of an organic light emitting diode can generally be 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 light emitting efficiency refers to the efficiency with 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. The development of a capping layer (CPL, light efficiency improvement layer) material with excellent ability to increase the external luminous efficiency is required.
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, compared to the bottom element structure of the non-resonant structure, the top element structure of the resonance structure is reflected by the anode, which is a reflective film, and comes out toward the cathode. 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 to use a light efficiency improving layer (capping layer) on 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, Al, Pt, Ag, and Au, are mainly used for electron emission, and surface plasmons are generated on the surface of metal electrodes. For example, when Ag is used as the cathode, 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 a capping layer (light efficiency improvement layer) is used, SPP occurs at the interface between the MgAg electrode and the organic material. At this time, when the organic material has high refractive index (eg n>1.69 @ 620), TE (Transverse electric) polarized light is dissipated on the surface of the capping layer (light efficiency improvement layer) in the vertical direction by evanescent waves, and TM (Transverse magnetic) polarized light moving along the cathode and capping layer generates surface plasma resonance (Surface Plasma Resonance). Wavelength amplification occurs by 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, there is still a demand for development of materials and structures necessary for improvement of various characteristics 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.An object of the present invention is to provide a capping layer material for an organic light emitting device, which can improve luminous efficiency and lifetime and at the same time improve viewing angle characteristics.
본 발명의 목적은 특히 유기 전계 발광 소자의 광 추출율을 개선하기 위하여 굴절률과 내열성이 높은 캡핑층을 포함하는 고효율 및 장수명의 유기 전계 발광 소자를 제공하는 것에 있다.An object of the present invention is to provide a high-efficiency and long-life organic electroluminescent device including a capping layer having a high refractive index and high heat resistance in order to improve the light extraction rate of the organic electroluminescent device.
본 발명자들은 상기의 목적을 달성하기 위해서, 이하에 나타내는 바와 같이 일 예의 연구를 실시하였다.In order to achieve the above object, the present inventors conducted an example of research as shown below.
본 발명에 따른 화합물은 굴절률이 높은 특성을 갖는 벤조아졸 고리를 갖는 3차 아민 화합물로부터 시아노기를 도입하여 굴절률이 크게 향상된 재료를 선별하였다. 그리고, 이 재료를 캡핑층으로 이용한 유기 발광 소자를 제조하고, 소자의 특성 평가를 일 예로 실시하였다. The compound according to the present invention was selected as a material having a greatly improved refractive index by introducing a cyano group from a tertiary amine compound having a benzoazole ring having a high refractive index. Then, an organic light emitting device using this material as a capping layer was manufactured, and characteristics of the device were evaluated as an example.
본 발명은 제1 전극; 상기 제1 전극 상에 배치된 유기물층; 상기 유기물층 상에 배치된 제2전극; 및 제2 전극 상에 배치된 캡핑층을 포함하며, 상기 유기물층 또는 캡핑층은 하기 화학식 1로 표시되는 3차 아민 유도체를 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 layer; and a capping layer disposed on the second electrode, wherein the organic material layer or the capping layer includes a tertiary amine derivative represented by Chemical Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에 있어서,In Formula 1,
L1, L2 및 L3는 각각 독립적으로 치환 또는 비치환된 페닐렌기; 치환 비치환된 나프틸렌기; 및 치환 또는 비치환된 피리딜렌기; 중에서 선택되고,L 1 , L 2 and L 3 are each independently a substituted or unsubstituted phenylene group; A substituted unsubstituted naphthylene group; And a substituted or unsubstituted pyridylene group; is selected from
Ar1 및 Ar2는 각각 독립적으로 페닐기; 나프탈렌기; 디벤조퓨란기 및 디벤조티오펜기; 중에서 선택되고,Ar 1 and Ar 2 are each independently a phenyl group; naphthalene group; a dibenzofuran group and a dibenzothiophene group; is selected from
Z1 은 O 또는 S이고,Z 1 is O or S;
Q1 은 CH 또는 N이고,Q 1 is CH or N;
a, b 및 c는 0 내지 3의 정수이며,a, b and c are integers from 0 to 3;
x는 1 내지 4의 정수이며, x is an integer from 1 to 4;
y 및 z는 0 내지 4의 정수이다.y and z are integers from 0 to 4.
본 명세서에 기재된 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있다. The compounds described in this specification can be used as a material for an organic material layer of an organic light emitting device.
적어도 하나의 실시 상태에 따른 화합물은 자외선 흡수특성을 나타내어 외부 광원에 의한 유기 발광 소자 내 유기물 손상을 최소화할 수 있고, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. A compound according to at least one exemplary embodiment may exhibit ultraviolet ray absorption characteristics to minimize damage to organic materials in an organic light emitting device caused by an external light source, and improve efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting device. there is.
또한, 본 명세서에 기재된 화합물을 캡핑층으로 이용한 유기 발광 소자에서 발광효율 향상, 발광 스펙트럼 반치폭 감소에 따른 색순도를 현저히 개선시킬 수 있다. In addition, in an organic light emitting device using the compound described in this specification as a capping layer, it is possible to significantly improve color purity due to improvement in light emitting efficiency and decrease in half width of the emission spectrum.
본 발명에 따른 화합물은 종래의 화합물에 시아노기가 도입됨으로써 예상하지 못할 만큼의 높은 굴절률을 나타내고, 이로 인해 높은 굴절률을 갖는 시아노기가 치환된 3차 아민 화합물은 공기중으로 추출되는 빛의 시야각과 광효율을 향상시킬 수 있는 캡핑층(광효율 개선층)의 재료로 이용할 수 있다.The compound according to the present invention exhibits an unexpectedly high refractive index due to the introduction of a cyano group into a conventional compound. As a result, the tertiary amine compound substituted with a cyano group having a high refractive index has a viewing angle and light efficiency of light extracted into the air. It can be used as a material for a capping layer (light efficiency improvement layer) that can improve
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 3차 아민 유도체를 이용할 경우에 나타나는 빛의 굴절과 흡수 특성의 그래프이다.1 shows a
2 is a graph of light refraction and absorption characteristics when using a tertiary amine derivative 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 may have various changes and various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes 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.Like reference numerals have been used for like elements throughout the description of each figure. In the accompanying drawings, the dimensions of the structures are shown enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention. Singular expressions include plural expressions 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 this application, the terms "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part such as a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case where it is “directly on” the other part, but also the case where another part is present in the middle.
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.In this specification, “substituted or unsubstituted” means a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, an alkene It may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a yl 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 this 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 this specification, the alkyl group may be straight chain, branched chain or cyclic. The number of carbon atoms of the 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 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-tricot practical group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group; 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.In this specification, a 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.In this specification, an 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 in 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, anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a quinquephenyl group, a sexyphenyl group, a triphenylenyl group, a pyrenyl group, a peryleneyl group, and 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 containing one or more of O, N, P, Si, and S as heterogeneous elements. 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, and 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 Pyrazine group, isoquinoline group, synol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzooxazole group, benzoimidazole group , Benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl group, benzoisoxazolyl group, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , Thiazole group, isoxazole group, oxadiazole group, thiadiazole group, isothiazole group, isoxazole group, phenothiazine group, benzodioxol group, dibenzosilol group and dibenzofuran group, isobenzofuran group, etc. 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 and quinolyl N-oxide group, 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 this 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, and a phenylsilyl group. 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 this 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, trimethylboron, triethylboron, t-butyldimethylboron, triphenylboron, diphenylboron, and phenylboron.
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 this specification, an alkenyl group may be straight-chain or branched-chain. The carbon number is not particularly limited, but is 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, and a styrylvinyl group.
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, 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 aryl amine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine groups, but are 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 arylheteroarylamine 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.In the present specification, “adjacent group” may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, another substituent substituted on the atom on which the substituent is substituted, or a substituent sterically closest to the substituent. there is. For example, two methyl groups in 1,2-dimethylbenzene can be interpreted as “adjacent groups” to each other, and 2 methyl groups in 1,1-diethylcyclopentene Two ethyl groups can be interpreted as "adjacent groups".
이하에서는 상기 유기물층 및/또는 캡핑층에 사용되는 3차 아민 유도체 화합물에 대해 설명한다. Hereinafter, the tertiary amine derivative compound used for the organic material layer and/or the capping layer will be described.
본 발명의 일 실시예에 따른 3차 아민 유도체 화합물은 하기 화학식 1로 표시된다.A tertiary amine derivative compound according to an embodiment of the present invention is represented by Formula 1 below.
[화학식 1][Formula 1]
상기 화학식 1에 있어서,In Formula 1,
L1, L2 및 L3는 각각 독립적으로 치환 또는 비치환된 페닐렌기; 치환 비치환된 나프틸렌기; 및 치환 또는 비치환된 피리딜렌기; 중에서 선택되고,L 1 , L 2 and L 3 are each independently a substituted or unsubstituted phenylene group; A substituted unsubstituted naphthylene group; And a substituted or unsubstituted pyridylene group; is selected from
Ar1 및 Ar2는 각각 독립적으로 페닐기; 나프탈렌기; 디벤조퓨란기 및 디벤조티오펜기; 중에서 선택되고,Ar 1 and Ar 2 are each independently a phenyl group; naphthalene group; a dibenzofuran group and a dibenzothiophene group; is selected from
Z1 은 O 또는 S이고,Z 1 is O or S;
Q1 은 CH 또는 N이고,Q 1 is CH or N;
a, b 및 c는 0 내지 3의 정수이며,a, b and c are integers from 0 to 3;
x는 1 내지 4의 정수이며, x is an integer from 1 to 4;
y 및 z는 0 내지 4의 정수이다.y and z are integers from 0 to 4.
본 발명의 일 실시예에 있어서, 상기 화학식 1로 표시되는 3차 아민 유도체는 하기 화학식 2 또는 하기 화학식 3로 표시된 화합물들 중에서 선택된 어느 하나의 화합물일 수 있고, 하기 화합물들은 추가로 치환될 수 있다. In one embodiment of the present invention, the tertiary amine derivative represented by Formula 1 may be any one compound selected from compounds represented by Formula 2 or Formula 3 below, and the following compounds may be further substituted. .
[화학식 2][Formula 2]
[화학식 3][Formula 3]
이하 도 1 및 2를 참조하여 본 발명의 실시예를 설명한다.An embodiment of the present invention will be described with reference to FIGS. 1 and 2 below.
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 schematic cross-sectional view of an organic light emitting diode according to an exemplary embodiment of the present invention. Referring to FIG. 1 , an organic light emitting device according to an exemplary embodiment includes a
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
한편, 본 발명에서 제시되는 캡핑층(300)은 제2 전극(120) 위에 증착되는 기능층으로서, 본 발명의 화학식 1에 따른 유기물을 포함한다.Meanwhile, the
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 according to an embodiment shown in FIG. 1 , the
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
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
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 hole transport regions 210 to 215 disposed on the
일 실시예의 상기 캡핑층(300)은 후술하는 화학식 1로 표시되는 유기화합물을 포함한다. The
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.Hole transport regions 210 to 215 are provided on the
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 structure 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 composed of a hole injection material and a hole transport material. there is. In addition, the hole transport regions 210 to 215 have a single layer structure made of a plurality of different materials, or the hole injection layer 210 / hole transport layer 215 sequentially stacked from the
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 500Å에서 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.Among the hole transport regions 210 to 215 , the hole injection layer 210 may be formed on the anode by various methods such as a vacuum deposition method, a spin coating method, a cast method, or an LB method. When the hole injection layer 210 is formed by the vacuum deposition method, the deposition conditions are 100 to 500 Å 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 as a target, and the like. The deposition rate can be freely adjusted at around 1 Å/s, and is not limited to specific conditions. When the hole injection layer 210 is formed by the spin coating method, the coating conditions vary depending on the properties of the compound used as the material for the hole injection layer 210 and the layers formed as the interface, but the coating speed and coating for uniform film formation. After that, heat treatment for solvent removal 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/camphorsulfonic 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 유기물층(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 hole transport regions 210 to 215 may have a thickness of about 100 to about 10,000 Å, and corresponding organic layers of each hole transport region 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. Thickness conditions of the hole transport regions 210 to 215 may be determined to a degree that satisfies efficiency and lifetime within a range in which the increase in driving voltage of the organic light emitting device is not increased. 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
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 be doped to improve characteristics like the
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 비어 있는 특성을 이용하여 인접한 정공수송층(215)에 쉽게 정공을 전달하여 전기적 특성을 향상시킨다.The charge-generating material is generally made of a material having very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a similar value to the HOMO of the hole transport layer 215 material. Due to such a low LUMO, holes are easily transferred to the adjacent hole transport layer 215 by using the characteristic that electrons of the LUMO are empty, thereby improving electrical characteristics.
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 하기 화합물 2-22 등과 같은 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 tetracyanoquinondimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinondimethane quinone derivatives such as phosphorus (F4-TCNQ); metal oxides such as tungsten oxide and molybdenum oxide; and cyano group-containing compounds such as the following compound 2-22, etc., but are not limited thereto.
정공 수송 영역(210~215)은 앞서 언급한 물질 외에, 도전성 향상을 위하여 전하 생성 물질을 더 포함할 수 있다. In addition to the aforementioned materials, the hole transport regions 210 to 215 may further include a charge generating material to improve conductivity.
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.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 compound containing a cyano group, but is not limited thereto. For example, non-limiting examples of the p-dopant include quinone derivatives such as TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, and the like. It may include, 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
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 that serves to prevent injection of electrons from the
발광층(220)은 정공 수송 영역(210~215) 상에 제공된다. 발광층(220)은 예를 들어 약 100Å내지 약 1000Å또는, 약 100Å내지 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
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
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 the material is not limited thereto if the properties are appropriate.
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.A dopant of the
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.
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
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 1000Å내지 약 1500Å인 것일 수 있다.For example, the
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
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
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
전자 수송층(230)들의 두께는 약 100Å내지 약 1000Å, 예를 들어 약 150Å내지 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
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
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 1Å내지 약 100Å, 약 3Å내지 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 mixture of an electron transport material and an insulating organometal salt. 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 aforementioned range, satisfactory electron injection characteristics 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
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
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 is Li (lithium), Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), 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 film 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), or the like. 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 an auxiliary electrode. When the second electrode 120 is connected to the auxiliary electrode, 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
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 voltage is applied to the
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.An optical path generated in the
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.If the refractive index of the
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 유기 발광층(220)에서 발생된 빛이 효율적으로 외부를 향해 방출될 수 있도록 돕는 역할을 한다. 유기물질들은 특정 파장영역의 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. 그리고 이러한 3차 아민 화합물을 포함하는 캡핑층(300)은 1.9 이상의 큰 굴절률을 가진다. 예를 들어, 캡핑층은 1.9 내지 3.0 범위의 굴절률을 가질 수 있다. 캡핑층(300)의 굴절률이 큰 경우, 캡핑층(300)의 계면에서 빛의 반사가 이루어져 빛의 공진이 일어날 수 있다.The
본 명세서에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.An organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type depending on materials 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 지시을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, an example will be described in detail to describe the present specification in detail. However, embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of this application are provided to more completely explain the present disclosure to those of ordinary skill in the art.
[실시예][Example]
중간체 합성예 1: 중간체(6)의 합성Intermediate Synthesis Example 1: Synthesis of Intermediate (6)
(중간체(1)의 합성)(Synthesis of Intermediate (1))
5-브로모벤조[b]티오펜(5-bromobenzo[b]thiophene) 5.0 g(23.5 mmol), CuCN 2.5 g(28.2 mmol) 및 DMF 15 mL를 혼합하고 160℃에서 3시간동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉가하고 2N NaOH 수용액을 첨가하고 30분 동안 교반하였다. 혼합액을 에틸아세테이트로 추출하고 무수 황산마그네슘으로 건조 여과 및 농축하였다. 농축액을 컬럼 크로마토그래피(EA:HEX)를 통하여 정제하여 황색 고체의 화합물(중간체(1)) 2.3 g(수율: 62.1%)을 얻었다.5.0 g (23.5 mmol) of 5-bromobenzo[b]thiophene, 2.5 g (28.2 mmol) of CuCN, and 15 mL of DMF were mixed and stirred under reflux at 160°C for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, 2N NaOH aqueous solution was added, and the mixture was stirred for 30 minutes. The mixed solution was extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and concentrated. The concentrate was purified through column chromatography (EA:HEX) to obtain 2.3 g (yield: 62.1%) of the compound (intermediate (1)) as a yellow solid.
(중간체(2)의 합성)(Synthesis of Intermediate (2))
무수 THF 83 mL에 중간체(1) 2.3 g(14.5 mmol)가 녹아 있는 용액에 -78℃에서 n-BuLi 10.2 mL(17.3 mmol, 1.7 M in pentane)를 천천히 적가하고 15분 동안 교반하였다. 트리메틸보레이트(Trimethylborate) 43.0 mL(385.7 mmol)를 천천히 적가한 후 -78℃에서 15분 동안 교반한 다음 상온에서 2시간동안 교반하였다. 반응 종결 확인 후 1M HCl 수용액을 천천히 적가하고 농축하였다. 농축액에 증류수를 첨가하고 에틸아세테이트로 추출하였다. 분리한 유기층을 무수 황산나트륨으로 건조 여과 및 농축하였다. 농축액을 컬럼크로마토 그래피(MeOH/CHCl3)로 정제하여 미색 고체의 화합물(중간체(2)) 1.2 g(수율: 40.9%)을 얻었다.To a solution of 2.3 g (14.5 mmol) of intermediate (1) in 83 mL of anhydrous THF, 10.2 mL (17.3 mmol, 1.7 M in pentane) of n-BuLi was slowly added dropwise at -78°C and stirred for 15 minutes. After slowly adding 43.0 mL (385.7 mmol) of trimethylborate dropwise, the mixture was stirred at -78°C for 15 minutes and then stirred at room temperature for 2 hours. After confirming the completion of the reaction, 1M HCl aqueous solution was slowly added dropwise and concentrated. Distilled water was added to the concentrate and extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, filtered and concentrated. The concentrate was purified by column chromatography (MeOH/CHCl 3 ) to obtain 1.2 g (yield: 40.9%) of the compound (intermediate (2)) as an off-white solid.
(중간체(3)의 합성)(Synthesis of intermediate (3))
1-브로모-4-요오드벤젠(1-Bromo-4-iodobenzene) 2.0 g(7.1 mmol), 중간체(2) 1.2 g(5.7 mmol), Pd(PPh3)4 0.2 g(0.2 mmol) 2M K2CO3 수용액 7.1 mL(14.1 mmol), 톨루엔 14 mL 및 에탄올 7 mL를 혼합하여 2시간동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉각하여 유기층을 분리하였다. 분리한 유기층을 실리카 및 셀라이트 패드를 통하여 여과하고 톨루엔으로 세척하였다. 여액을 감압하에 농축하고 혼합용액(DCM/HEX)으로 슬러리하여 옅은 노랑색 고체의 화합물(중간체(3)) 1.1 g(수율: 49.5%)을 얻었다.1-Bromo-4-iodobenzene 2.0 g (7.1 mmol), intermediate (2) 1.2 g (5.7 mmol), Pd (PPh 3 ) 4 0.2 g (0.2 mmol) 2M K 2 CO 3 Aqueous solution of 7.1 mL (14.1 mmol), 14 mL of toluene and 7 mL of ethanol were mixed and stirred under reflux for 2 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature to separate an organic layer. The separated organic layer was filtered through a pad of silica and celite and washed with toluene. The filtrate was concentrated under reduced pressure and slurried with a mixed solution (DCM/HEX) to obtain 1.1 g (yield: 49.5%) of the compound (intermediate (3)) as a pale yellow solid.
(중간체(4)의 합성)(Synthesis of intermediate (4))
1구 1 L 플라스크에서 중간체(3) 10.0 g(31.8 mmol), PIN2B2 9.7 g(35.0 mmol), Pd(dppf)Cl2-DCM 1.3 g(1.6 mmol), KOAc 9.4 g(95.5 mmol) 및 1,4-디옥산 250 mL를 하루동안 환류 및 교반하였다. 상온에서 식힌 후 셀라이트 여과를 통해 불순물을 제거하였다. 용매를 완전히 제거한 후 실리카겔 컬럼 크로마토그래피(DCM:HEX)로 정제하였다. 얻어진 고체를 헥산으로 여과하여 노란색 고체의 화합물(중간체(4)) 7.5 g(수율: 65.2%)을 얻었다.In a one-necked 1 L flask, 10.0 g (31.8 mmol) of intermediate (3), 9.7 g (35.0 mmol) of PIN 2 B 2 , 1.3 g (1.6 mmol) of Pd( dppf )Cl 2 -DCM, 9.4 g (95.5 mmol) of KOAc were obtained. and 250 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 7.5 g (yield: 65.2%) of the compound (intermediate (4)) as a yellow solid.
(중간체(5)의 합성)(Synthesis of Intermediate (5))
1-브로모-4-니트로벤젠(1-Bromo-4-nirtrobenzene) 3.5 g(17.3 mmol), 중간체(4) 7.5 g(20.8 mmol), Pd(PPh3)4 0.6 g(0.5 mmol) 2M K2CO3 수용액 26.0 mL(51.9 mmol), 톨루엔 90mL 및 에탄올 45 mL를 혼합하여 4시간 동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 메탄올을 적가하였다. 형성된 침전물을 여과하였다. 고체를 클로로포름으로 용해시킨후 셀라이트 및 실리카패드를 통하여 여과하고 클로로포름으로 세척하였다. 여액을 감압하에 농축하고 메탄올로 슬러리하여 황색 고체의 화합물(중간체(5)) 4.1 g(수율: 66.5%)을 얻었다.1-Bromo-4-nitrobenzene 3.5 g (17.3 mmol), intermediate (4) 7.5 g (20.8 mmol), Pd (PPh 3 ) 4 0.6 g (0.5 mmol) 2M K 2 CO 3 Aqueous solution of 26.0 mL (51.9 mmol), 90 mL of toluene and 45 mL of ethanol were mixed and stirred under reflux for 4 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature and methanol was added dropwise. The precipitate formed was filtered off. After dissolving the solid in chloroform, it was filtered through celite and a silica pad and washed with chloroform. The filtrate was concentrated under reduced pressure and slurried with methanol to obtain 4.1 g (yield: 66.5%) of the compound (intermediate (5)) as a yellow solid.
(중간체(6)의 합성)(Synthesis of Intermediate (6))
에탄올 50 mL에 진한 염산(conc. HCl) 5 mL을 천천히 적가한 후 중간체(5) 4.1 g(11.5 mmol)과 철(Fe) 1.9 g(34.5 mmol)를 첨가하고 90℃에서 8시간동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 셀라이트 패드를 통하여 여과하고 디클로로메탄(DCM)으로 세척하였다. 여액을 농축하고 디클로로메탄으로 묽힌 후 포화탄산나트륨 용액으로 pH 10까지 조절한 후 유기층을 분리하였다. 유기층을 무수 황산마그네슘으로 건조, 여과 및 농축하였다. 농축액을 혼합용액(DCM/HEX)으로 재결정하여 아이보리색 고체의 화합물(중간체(6)) 1.8 g(수율: 47.9%)을 얻었다.After slowly adding 5 mL of concentrated hydrochloric acid (conc. HCl) dropwise to 50 mL of ethanol, 4.1 g (11.5 mmol) of intermediate (5) and 1.9 g (34.5 mmol) of iron (Fe) were added, followed by reflux stirring at 90 ° C for 8 hours. did After confirming the completion of the reaction, it was cooled to room temperature, filtered through a celite pad, and washed with dichloromethane (DCM). The filtrate was concentrated, diluted with dichloromethane, adjusted to pH 10 with saturated sodium carbonate solution, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The concentrate was recrystallized from a mixed solution (DCM/HEX) to obtain 1.8 g (yield: 47.9%) of the compound (intermediate (6)) as an ivory solid.
중간체 합성예 2: 중간체(8)의 합성Intermediate Synthesis Example 2: Synthesis of Intermediate (8)
(중간체(7)의 합성)(Synthesis of Intermediate (7))
1-브로모-4-니트로벤젠(1-Bromo-4-nirtrobenzene) 5.0 g(24.8 mmol), 중간체(2) 5.3 g(29.8 mmol), Pd(PPh3)4 0.8 g(0.7 mmol) 2M K2CO3 수용액 37.2 mL(74.4 mmol), 톨루엔 83 mL 및 에탄올 41 mL를 혼합하여 4시간 동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 메탄올을 적가하였다. 형성된 침전물을 여과하였다. 고체를 클로로포름으로 용해시킨후 셀라이트 및 실리카패드를 통하여 여과하고 클로로포름으로 세척하였다. 여액을 감압하에 농축하고 메탄올로 슬러리하여 황색 고체의 화합물(중간체(7)) 4.5 g(수율: 68.3%)을 얻었다.1-Bromo-4-nitrobenzene 5.0 g (24.8 mmol), intermediate (2) 5.3 g (29.8 mmol), Pd (PPh 3 ) 4 0.8 g (0.7 mmol) 2M K 2 CO 3 Aqueous solution of 37.2 mL (74.4 mmol), 83 mL of toluene and 41 mL of ethanol were mixed and stirred under reflux for 4 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature and methanol was added dropwise. The precipitate formed was filtered off. After dissolving the solid in chloroform, it was filtered through celite and a silica pad and washed with chloroform. The filtrate was concentrated under reduced pressure and slurried with methanol to obtain 4.5 g (yield: 68.3%) of the compound (intermediate (7)) as a yellow solid.
(중간체(8)의 합성)(Synthesis of Intermediate (8))
에탄올 50 mL에 진한 염산(conc. HCl) 5 mL을 천천히 적가한 후 중간체(7) 4.5 g(17.6 mmol)과 철(Fe) 2.9 g(52.8 mmol)를 첨가하고 90℃에서 8시간동안 환류 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 셀라이트 패드를 통하여 여과하고 디클로로메탄(DCM)으로 세척하였다. 여액을 농축하고 디클로로메탄으로 묽힌 후 포화탄산나트륨 용액으로 pH 10까지 조절한 후 유기층을 분리하였다. 유기층을 무수 황산마그네슘으로 건조, 여과 및 농축하였다. 농축액을 혼합용액(DCM/HEX)으로 재결정하여 아이보리색 고체의 화합물(중간체(8)) 1.7 g(수율: 42.5%)을 얻었다.After slowly adding 5 mL of concentrated hydrochloric acid (conc. HCl) dropwise to 50 mL of ethanol, 4.5 g (17.6 mmol) of intermediate (7) and 2.9 g (52.8 mmol) of iron (Fe) were added, followed by reflux stirring at 90 ° C for 8 hours. did After confirming the completion of the reaction, it was cooled to room temperature, filtered through a celite pad, and washed with dichloromethane (DCM). The filtrate was concentrated, diluted with dichloromethane, adjusted to pH 10 with saturated sodium carbonate solution, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated. The concentrate was recrystallized from a mixed solution (DCM/HEX) to obtain 1.7 g (yield: 42.5%) of the compound (intermediate (8)) as an ivory solid.
중간체 합성예 3: 중간체(10)의 합성Intermediate Synthesis Example 3: Synthesis of Intermediate (10)
(중간체(9)의 합성)(Synthesis of Intermediate (9))
4-시아노페놀(4-Cyanophenol) 10.0 g(84.0 mmol), 4-브로모스타이렌(4-Bromostyrene) 7.7 g(42.0 mmol), Pd(OAc)2 0.9 g(4.2 mmol), 1,10-phenanthroline 1.5 g(8.4 mmol), Cu(OAc)2 7.6 g(42.0 mmol), NaOAc 10.3 g(125.9 mmol), molecular sieves(4 Å) 10.0 g 및 DCE 330 mL를 혼합하여 110°C에서 24시간 동안 교반하였다. 반응 종결 확인 후 셀라이트 패드를 통하여 여과하고 에틸아세테이로 세척하였다. 유기층을 포화 염화나트륨 용액으로 세척하고 무수 황산나트륨으로 건조, 여과 및 농축하였다. 농축액을 컬럼 크로마토그래피(Petroleum-ether/EA)로 정제하여 백색 고체의 화합물(중간체(9) 10.5 g(수율: 42.0%)을 얻었다.4-Cyanophenol (4-Cyanophenol) 10.0 g (84.0 mmol), 4-Bromostyrene (4-Bromostyrene) 7.7 g (42.0 mmol), Pd (OAc) 2 0.9 g (4.2 mmol), 1,10 -Phenanthroline 1.5 g (8.4 mmol), Cu(OAc) 2 7.6 g (42.0 mmol), NaOAc 10.3 g (125.9 mmol), molecular sieves (4 Å) 10.0 g, and DCE 330 mL were mixed at 110 ° C for 24 hours. while stirring. After confirming the completion of the reaction, the mixture was filtered through a celite pad and washed with ethyl acetate. The organic layer was washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered and concentrated. The concentrate was purified by column chromatography (Petroleum-ether/EA) to obtain 10.5 g (yield: 42.0%) of the compound (Intermediate (9)) as a white solid.
(중간체(10)의 합성)(Synthesis of Intermediate (10))
중간체(9) 10.0 g(35.5 mmol), 벤조페논 이민(Benzophenone imine) 7.3 g(40.2 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 1.0 g(1.7 mmol), BINAP 2.1 g(3.4 mmol), Cs2CO3 21.9 g(67.1 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(10)) 6.8 g(수율: 86.5%)을 얻었다.After adding 10.0 g (35.5 mmol) of intermediate (9), 7.3 g (40.2 mmol) of benzophenone imine and 120 mL of toluene, 1.0 g (1.7 mmol) of Pd (dba) 2 and 2.1 g (3.4 mmol) of BINAP ), Cs 2 CO 3 21.9 g (67.1 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 6.8 g (yield: 86.5%) of the compound (intermediate (10)) as a yellow solid.
중간체 합성예 4: 중간체(13)의 합성Intermediate Synthesis Example 4: Synthesis of Intermediate (13)
(중간체(11)의 합성)(Synthesis of Intermediate (11))
중간체(9) 20.0 g(66.9 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 20.4 g(80.2 mmol), Pd(dppf)Cl2-DCM 1.6 g(2.0 mmol), 아세트산 칼륨 11.8 g(120.4 mmol), 1,4-디옥산 330 mL의 혼합물을 90℃에서 12시간 동안 교반하였다. 반응 혼합물을 감압 농축한 후 디클로로메탄을 가하여 30분간 교반하였다. 불용성 침전을 celite 패드로 여과하여 제거하고 감압 농축하였다. 농축 잔류물에 메탄올를 가하고 1시간 동안 교반하였다. 생성된 침전을 여과하고 메탄올로 세척, 진공 건조하여 옅은 노란색 고체 화합물(중간체(11)) 18.3 g(수율: 79.1%)을 얻었다.Intermediate (9) 20.0 g (66.9 mmol), bis (pinacolato) diboron 20.4 g (80.2 mmol), Pd (dppf) Cl 2 -DCM 1.6 g (2.0 mmol), potassium acetate A mixture of 11.8 g (120.4 mmol) and 330 mL of 1,4-dioxane was stirred at 90° C. for 12 hours. After concentrating the reaction mixture under reduced pressure, dichloromethane was added and stirred for 30 minutes. The insoluble precipitate was removed by filtration through a celite pad and concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred for 1 hour. The resulting precipitate was filtered, washed with methanol, and vacuum dried to obtain 18.3 g (yield: 79.1%) of a pale yellow solid compound (Intermediate (11)).
(중간체(12)의 합성)(Synthesis of Intermediate (12))
중간체(11) 18.3 g(52.9 mmol), 1-브로모-4-요오드벤젠(1-Bromo-4-iodobenzene) 22.4 g(79.3 mmol), Pd(PPh3)4 3.1 g(2.6 mmol), 2M 탄산나트륨 수용액 53 mL(105.7 mmol), 톨루엔 110 mL 및 에탄올 50 mL의 혼합물을 12시간 동안 환류 교반하였다. 반응 혼합물을 상온으로 냉각한 후 용매를 제거하고 물을 첨가한 후 디클로로메탄를 넣어 유기층을 분리하여 무수 황산마그네슘으로 건조하고 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 노란색 고체 화합물(중간체(12)) 15.2 g(수율: 76.6%)을 얻었다.Intermediate (11) 18.3 g (52.9 mmol), 1-Bromo-4-iodobenzene 22.4 g (79.3 mmol), Pd (PPh 3 ) 4 3.1 g (2.6 mmol), 2M A mixture of 53 mL (105.7 mmol) of aqueous sodium carbonate solution, 110 mL of toluene and 50 mL of ethanol was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, the solvent was removed, water was added, dichloromethane was added, the organic layer was separated, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a yellow solid compound (intermediate (12)) 15.2 g (yield: 76.6%) was obtained.
(중간체(13)의 합성)(Synthesis of Intermediate (13))
중간체(12) 15.2 g(40.5 mmol), 벤조페논 이민(Benzophenone imine) 11.0 g(60.8 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 698.8 mg(1.2 mmol), BINAP 1.5 g(2.4 mmol), Cs2CO3 26.4 g(81.0 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(13)) 10.0 g(수율: 80.9%)을 얻었다.After adding 15.2 g (40.5 mmol) of intermediate (12), 11.0 g (60.8 mmol) of benzophenone imine and 120 mL of toluene, 698.8 mg (1.2 mmol) of Pd (dba) 2 and 1.5 g (2.4 mmol) of BINAP ), Cs 2 CO 3 26.4 g (81.0 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 10.0 g (yield: 80.9%) of the compound (intermediate (13)) as a yellow solid.
중간체 합성예 5: 중간체(15)의 합성Intermediate Synthesis Example 5: Synthesis of Intermediate (15)
(중간체(14)의 합성)(Synthesis of Intermediate (14))
중간체(2) 10.0 g(49.3 mmol), 1-브로모-3-요오드벤젠(1-Bromo-3-iodobenzene) 11.6 g(41.1 mmol), Pd(PPh3)4 2.4 g(2.1 mmol), K2CO3 11.4 g(82.1 mmol), 톨루엔 300 mL, 에탄올 150 mL 및 물 150 mL를 혼합한 다음 15 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 다이클로로메탄으로 추출한 후 감압 하에 용매를 제거하였다. 이렇게 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:DCM)로 정제하고 메탄올로 고체화하여, 옅은 노란색 고체의 화합물(중간체(14)) 7.4 g(수율: 57.4%)을 얻었다.Intermediate (2) 10.0 g (49.3 mmol), 1-Bromo-3-iodobenzene 11.6 g (41.1 mmol), Pd (PPh 3 ) 4 2.4 g (2.1 mmol), K 2 CO 3 11.4 g (82.1 mmol), 300 mL of toluene, 150 mL of ethanol, and 150 mL of water were mixed and stirred under reflux for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extraction was performed with dichloromethane, and the solvent was removed under reduced pressure. The reaction mixture thus obtained was purified by silica gel column chromatography (Hex:DCM) and solidified with methanol to obtain 7.4 g (yield: 57.4%) of the compound (Intermediate (14)) as a pale yellow solid.
(중간체(15)의 합성)(Synthesis of Intermediate (15))
중간체(14) 7.4 g(23.6 mmol), 벤조페논 이민(Benzophenone imine) 4.7 g(25.9 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 0.7 g(1.2 mmol), BINAP 1.5 g(2.4 mmol), Cs2CO3 15.4 g(47.1 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(15)) 2.7 g(수율: 45.8%)을 얻었다.After adding 7.4 g (23.6 mmol) of intermediate (14), 4.7 g (25.9 mmol) of benzophenone imine and 120 mL of toluene, 0.7 g (1.2 mmol) of Pd (dba) 2 and 1.5 g (2.4 mmol) of BINAP ), Cs 2 CO 3 15.4 g (47.1 mmol) was added and the mixture was stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 2.7 g (yield: 45.8%) of the compound (intermediate (15)) as a yellow solid.
중간체 합성예 6: 중간체(17)의 합성Intermediate Synthesis Example 6: Synthesis of Intermediate (17)
(중간체(16)의 합성)(Synthesis of Intermediate (16))
중간체(4) 10.0 g(27.7 mmol), 1-브로모-3-요오드벤젠(1-Bromo-3-iodobenzene) 6.5 g(23.1 mmol), Pd(PPh3)4 1.3 g(1.2 mmol), K2CO3 6.4 g(46.1 mmol), 톨루엔 200 mL, 에탄올 100 mL 및 물 100 mL를 혼합한 다음 15 시간 동안 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 다이클로로메탄으로 추출한 후 감압 하에 용매를 제거하였다. 이렇게 얻어진 반응 혼합물을 실리카겔 컬럼 크로마토그래피(Hex:DCM)로 정제하고 메탄올로 고체화하여, 옅은 노란색 고체의 화합물(중간체(16)) 6.7 g(수율: 74.4%)을 얻었다.Intermediate (4) 10.0 g (27.7 mmol), 1-Bromo-3-iodobenzene 6.5 g (23.1 mmol), Pd (PPh 3 ) 4 1.3 g (1.2 mmol), K 2 CO 3 6.4 g (46.1 mmol), 200 mL of toluene, 100 mL of ethanol, and 100 mL of water were mixed and stirred under reflux for 15 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extraction was performed with dichloromethane, and the solvent was removed under reduced pressure. The reaction mixture thus obtained was purified by silica gel column chromatography (Hex:DCM) and solidified with methanol to obtain 6.7 g (yield: 74.4%) of the compound (Intermediate (16)) as a pale yellow solid.
(중간체(17)의 합성)(Synthesis of Intermediate (17))
중간체(16) 6.7 g(17.2 mmol), 벤조페논 이민(Benzophenone imine) 3.4 g(18.9 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 0.5 g(0.9 mmol), BINAP 1.1 g(1.7 mmol), Cs2CO3 11.2 g(34.3 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(17)) 2.4 g(수율: 42.8%)을 얻었다.After adding 6.7 g (17.2 mmol) of intermediate (16), 3.4 g (18.9 mmol) of benzophenone imine and 120 mL of toluene, 0.5 g (0.9 mmol) of Pd (dba) 2 and 1.1 g (1.7 mmol) of BINAP ), Cs 2 CO 3 11.2 g (34.3 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 2.4 g (yield: 42.8%) of the compound (intermediate (17)) as a yellow solid.
중간체 합성예 7: 중간체(19)의 합성Intermediate Synthesis Example 7: Synthesis of Intermediate (19)
(중간체(18)의 합성)(Synthesis of Intermediate (18))
1구 500 mL 플라스크에 5-브로모이소프탈로니트릴(5-bromoisophthalonitrile) 10.0 g(48.3 mmol), 비스(피나콜레이토)디보론(bis(pinacolato)diboron) 14.7 g(58.0 mmol), Pd(dppf)Cl2 1.6 g (1.9 mmol), 포타슘아세테이트(potassium acetate, KOAc) 9.5 g (96.6 mmol) 및 다이옥산 300mL을 같이 넣고 질소하에서 100℃에서 하루종일 환류시켰다. 반응이 종결되면 용매를 날리고 물을 첨가 후 클로로포름으로 추출하고 분리된 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 흰색 고체의 화합물(중간체(18)) 7.6 g(수율: 62.1%)을 얻었다.In a one-
(중간체(19)의 합성)(Synthesis of Intermediate (19))
1구 500 mL 플라스크에 중간체(18) 7.6 g(30.0 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 8.5 g(30.0 mmol), Pd(PPh3)4 1.0 g(0.9 mmol), 톨루엔 150 mL와 같이 넣고 교반하다가 에탄올 80 mL, K2CO3 8.3 g(59.8 mmol) 및 증류수 80 mL를 첨가하고, 가열 환류하에 하루종일 교반하였다. 반응이 종결되면 상온으로 냉각하고 용매를 제거하고 증류수를 첨가한 후 디클로로메탄으로 추출하고 분리한 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(19)) 2.9 g(수율: 34.1%)을 얻었다.In a one-
중간체 합성예 8: 중간체(22)의 합성Intermediate Synthesis Example 8: Synthesis of Intermediate (22)
(중간체(20)의 합성)(Synthesis of Intermediate (20))
6-하이드록시-2-나프토나이트릴(6-hydroxy-2-naphthonitrile) 30.0 g(177.3 mmol)을 다이클로로메탄 700 mL에 녹이고 피리딘 42.9 mL(531.9 mmol)을 첨가한 후, 0℃로 온도를 낮췄다. Tf2O 35.7 mL(212.8 mmol)를 천천히 적가 한 후, 상온으로 승온하여 12시간 동안 반응하였다. 반응물을 증류수 500 mL로 세척한 후, 분리한 유기층을 무수 황산나트륨으로 건조 여과하고 농축한 후, 컬럼 크로마토그래피로(CHCl3) 정제하여 노란색 고체의 화합물(중간체(20)) 53.0 g(수율: 99.2%)을 얻었다. After dissolving 30.0 g (177.3 mmol) of 6-hydroxy-2-naphthonitrile in 700 mL of dichloromethane, adding 42.9 mL (531.9 mmol) of pyridine, the temperature was reduced to 0 ° C. lowered After slowly adding 35.7 mL (212.8 mmol) of Tf 2 O dropwise, the temperature was raised to room temperature and reacted for 12 hours. After washing the reactant with 500 mL of distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl 3 ) to obtain 53.0 g of the compound (intermediate (20)) as a yellow solid (yield: 99.2) %) was obtained.
(중간체(21)의 합성)(Synthesis of Intermediate (21))
1구 2 L 플라스크에 중간체(20) 53.0 g(175.9 mmol), 피나콜디보론(Bis(pinacolato)diboron) 67.0 g(263.9 mmol), Pd(dppf)Cl2-CH2Cl2 2.9 g(3.5 mmol), KOAc 51.8 g(527.8 mmol) 및 1,4-디옥산 800 mL를 혼합한 후, 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/MeOH)로 고체화하여 흰색 고체의 화합물(중간체(21)) 38.0 g(수율: 77.4%)얻었다In a one-necked 2 L flask, 53.0 g (175.9 mmol) of intermediate (20), 67.0 g (263.9 mmol) of pinacoldiboron (Bis (pinacolato) diboron), Pd (dppf) Cl 2 -CH 2 Cl 2 2.9 g (3.5 mmol), KOAc 51.8 g (527.8 mmol) and 1,4-dioxane 800 mL were mixed, and then stirred at 100°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, passed through a celite pad, and then concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl 3 ) and solidified with a mixed solvent (DCM/MeOH) to obtain 38.0 g (yield: 77.4%) of the compound (Intermediate (21)) as a white solid.
(중간체(22)의 합성)(Synthesis of Intermediate (22))
1구 250mL 플라스크에 중간체(21) 4.3 g(15.4 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 21.8 g(77.0 mmol), Pd(PPh3)4 0.5 g(0.5 mmol), 2M 수용액 K2CO3 15.4 mL(30.8 mmol), 톨루엔 102 mL 및 에탄올 51 mL과 혼합한 후, 80oC에서 3시간 동안 교반하였다. 반응이 종결 확인 후, 상온으로 냉각하고, 증류수를 적가하였다. 반응물을 디클로로메탄으로 추출하고 분리한 유기층을 무수 황산나트륨으로 건조시킨 후, 감압 하에 용매를 제거하였다. 얻어진 반응물을 실리카겔 컬럼크로마토 그래피(Hexanes/DCM)로 정제하여 흰색 고체의 화합물(중간체(22)) 3.4 g(수율: 72.3%)을 얻었다4.3 g (15.4 mmol) of intermediate (21), 21.8 g (77.0 mmol) of 1-bromo-4-iodobenzene, 0.5 g of Pd (PPh 3 ) 4 were placed in a 250 mL flask with one neck. (0.5 mmol), 2M aqueous solution of K 2 CO 3 15.4 mL (30.8 mmol), 102 mL of toluene and 51 mL of ethanol, and then stirred at 80 ° C for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and distilled water was added dropwise. After extracting the reactant with dichloromethane and drying the separated organic layer over anhydrous sodium sulfate, the solvent was removed under reduced pressure. The obtained reaction product was purified by silica gel column chromatography (Hexanes/DCM) to obtain 3.4 g (yield: 72.3%) of the compound (Intermediate (22)) as a white solid.
중간체 합성예 9: 중간체(24)의 합성Intermediate Synthesis Example 9: Synthesis of Intermediate (24)
(중간체(23)의 합성)(Synthesis of Intermediate (23))
1구 1 L 플라스크에서 4-브로모프탈로니트릴(4-Bromophthalonitrile) 15.0 g(72.5 mmol), PIN2B2 22.1 g(86.9 mmol), Pd(dppf)Cl2-DCM 5.9 g(7.2 mmol), KOAc 35.6 g(362 mmol) 및 1,4-디옥산 300 mL를 하루동안 환류 및 교반하였다. 상온에서 식힌 후 셀라이트 여과를 통해 불순물을 제거하였다. 용매를 완전히 제거한 후 실리카겔 컬럼 크로마토그래피(DCM:HEX)로 정제하였다. 얻어진 고체를 헥산으로 여과하여 흰색 고체의 화합물(중간체(23)) 13.7 g(수율: 74.6%)을 얻었다.In a one-necked 1 L flask, 15.0 g (72.5 mmol) of 4-Bromophthalonitrile, 22.1 g (86.9 mmol) of PIN 2 B 2 , 5.9 g (7.2 mmol) of Pd (dppf)Cl 2 - DCM, 35.6 g (362 mmol) of KOAc and 300 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 13.7 g (yield: 74.6%) of the compound (intermediate (23)) as a white solid.
(중간체(24)의 합성)(Synthesis of Intermediate (24))
1구 500 mL 플라스크에 중간체(23) 5.0 g(19.7 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 5.6 g(19.7 mmol), Pd(PPh3)4 0.7 g(0.6 mmol), 톨루엔 120 mL와 같이 넣고 교반하다가 에탄올 60 mL, K2CO3 5.4 g(39.4 mmol) 및 증류수 60 mL를 첨가하고, 가열 환류하에 하루종일 교반하였다. 반응이 종결되면 상온으로 냉각하고 용매를 제거하고 증류수를 첨가한 후 디클로로메탄으로 추출하고 분리한 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(24)) 2.5 g(수율: 44.9%)을 얻었다.In a one-necked 500 mL flask, 5.0 g (19.7 mmol) of intermediate (23), 5.6 g (19.7 mmol) of 1-bromo-4-iodobenzene, and Pd (PPh 3 ) 4 0.7 g (0.6 mmol) and 120 mL of toluene were added and stirred, then 60 mL of ethanol, 5.4 g (39.4 mmol) of K 2 CO 3 and 60 mL of distilled water were added, and the mixture was stirred under reflux heating throughout the day. After the reaction was completed, it was cooled to room temperature, the solvent was removed, distilled water was added, extracted with dichloromethane, and the separated organic layer was dried over anhydrous MgSO 4 , and purified by column chromatography (Hex:CHCl 3 ) to form a yellow solid compound ( Intermediate (24)) 2.5 g (yield: 44.9%) was obtained.
중간체 합성예 10: 중간체(27)의 합성Intermediate Synthesis Example 10: Synthesis of Intermediate (27)
(중간체(25)의 합성)(Synthesis of Intermediate (25))
1구 2000 mL 플라스크에 4-브로모-3-메톡시벤조니트릴(4-bromo-3-methoxybenzonitrile) 50.0 g(235.8 mmol), 4-클로로-2-플루오로페닐보론산(4-chloro-2-fluorophenylboronic acid) 45.2 g(259.4 mmol), Pd(PPh3)4 8.2 g(7.1 mmol), 톨루엔 800 mL를 혼합 교반한 후 에탄올 400 mL, K2CO3 65.2 g(471.6 mmol) 및 증류수 400mL를 첨가하고 가열 환류하에 하루종일 교반하였다. 반응이 종결 확인 후, 상온으로 냉각하고 용매를 제거하였다 에틸아세테이트와 증류수로 추출하여 분리한 유기층을 감압 증류하여 용매를 제거하였다. 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(25)) 43.2 g(수율: 70.0%)을 얻었다In a one-neck 2000 mL flask, 50.0 g (235.8 mmol) of 4-bromo-3-methoxybenzonitrile, 4-chloro-2-fluorophenylboronic acid (4-chloro-2 -fluorophenylboronic acid) 45.2 g (259.4 mmol), Pd (PPh 3 ) 4 8.2 g (7.1 mmol), and toluene 800 mL were mixed and stirred, followed by
(중간체(26)의 합성)(Synthesis of Intermediate (26))
1구 2000 mL 플라스크에 중간체(25) 43.2 g(165.1 mmol), 디클로로메탄 850 mL를 혼합 교반한 후, 0 ℃에서 붕소 트리 브로마이드(boron tribromide, BBr3) 23.9 mL(247.6 mmol)를 천천히 적가한 후, 상온으로 승온하고 5일동안 교반하였다. 반응이 종결 확인 후, 0 ℃에서 증류수을 천천히 적가한 후 디클로로메탄으로 추출하였다, 분리한 유기층을 MgSO4로 건조한 후, 컬럼 크로마토그래피(DCM)로 정제하여 붉은색 고체의 화합물(중간체(26)) 27.2 g(수율: 66.5%)을 얻었다43.2 g (165.1 mmol) of the intermediate (25) and 850 mL of dichloromethane were mixed and stirred in a 2000 mL one-necked flask, and then 23.9 mL (247.6 mmol) of boron tribromide (BBr 3 ) was slowly added dropwise at 0 ° C. Then, the temperature was raised to room temperature and stirred for 5 days. After confirming the completion of the reaction, distilled water was slowly added dropwise at 0 ° C, followed by extraction with dichloromethane. The separated organic layer was dried with MgSO 4 and purified by column chromatography (DCM) to obtain a red solid compound (intermediate (26)) 27.2 g (yield: 66.5%) was obtained
(중간체(27)의 합성)(Synthesis of Intermediate (27))
1구 500 mL 플라스크에 중간체(26) 27.2 g(109.8 mmol), K2CO3 45.5 g(329.5 mmol), N,N-디메틸포름아마이드(DMF) 300 mL를 혼합한 후, 105℃에서 하루 동안 교반하였다. 반응 종결 확인 후, 상온으로 냉각하고 증류수를 첨가한 후, 생성된 고체를 여과하였다. 얻어진 반응 혼합물을 메탄올과 헥산을 첨가하고 실온에서 1시간 교반하고 여과하여 붉은색 고체의 화합물(중간체(27)) 15.8 g(수율: 63.3%)을 얻었다27.2 g (109.8 mmol) of intermediate (26), 45.5 g (329.5 mmol) of K 2 CO 3 , and 300 mL of N,N-dimethylformamide (DMF) were mixed in a 500 mL one-necked flask, followed by mixing at 105 ° C for one day. Stir. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, and the resulting solid was filtered. The obtained reaction mixture was added with methanol and hexane, stirred at room temperature for 1 hour, and filtered to obtain 15.8 g (yield: 63.3%) of the compound as a red solid (Intermediate (27)).
중간체 합성예 11: 중간체(29)의 합성Intermediate Synthesis Example 11: Synthesis of Intermediate (29)
(중간체(28)의 합성)(Synthesis of Intermediate (28))
1구 1 L 플라스크에서 중간체(27) 10.0 g(43.9 mmol), PIN2B2 12.3 g(48.3 mmol), Pd(dppf)Cl2-DCM 1.8 g(2.2 mmol), KOAc 12.9 g(131.8 mmol) 및 1,4-디옥산 250 mL를 하루동안 환류 및 교반하였다. 상온에서 식힌 후 셀라이트 여과를 통해 불순물을 제거하였다. 용매를 완전히 제거한 후 실리카겔 컬럼 크로마토그래피(DCM:HEX)로 정제하였다. 얻어진 고체를 헥산으로 여과하여 노란색 고체의 화합물(중간체(28)) 8.9 g(수율: 63.5%)을 얻었다.In a one-necked 1 L flask, 10.0 g (43.9 mmol) of intermediate (27), 12.3 g (48.3 mmol) of PIN 2 B 2 , 1.8 g (2.2 mmol) of Pd(dppf)Cl 2 -DCM, 12.9 g (131.8 mmol) of KOAc and 250 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 8.9 g (yield: 63.5%) of the compound (intermediate (28)) as a yellow solid.
(중간체(29)의 합성)(Synthesis of Intermediate (29))
1구 500 mL 플라스크에 중간체(28) 5.0 g(15.7 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 4.4 g(15.7 mmol), Pd(PPh3)4 0.5 g(0.5 mmol), 톨루엔 120 mL와 같이 넣고 교반하다가 에탄올 60 mL, K2CO3 4.3 g(31.3 mmol) 및 증류수 60 mL를 첨가하고, 가열 환류하에 하루종일 교반하였다. 반응이 종결되면 상온으로 냉각하고 용매를 제거하고 증류수를 첨가한 후 디클로로메탄으로 추출하고 분리한 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(29)) 3.1 g(수율: 56.8%)을 얻었다.In a one-
중간체 합성예 12: 중간체(32)의 합성Intermediate Synthesis Example 12: Synthesis of Intermediate (32)
3,7-다이브로모다이벤조[b,d]티오펜(3,7-dibromodibenzo[b,d]thiophene) 14.3 g(40.6 mmol)과 시안화구리(CuCN) 3.64 g(40.6 mmol) 을 N,N-다이메틸포름아미드(DMF) 100 mL에 혼합한 후, 20시간 동안 교반 환류하였다. 반응이 종결된 후, 상온으로 온도를 낮추고, 반응혼합물을 산성화된 FeCl3 용액(acidified aqueous FeCl3 solution)(물 80 mL와 진한 염산 20 mL에 50.0 g의 FeCl3을 녹인 용액)에 천천히 붓고, 90에서 0.5시간 동안 교반하였다. 유기층을 분리하고, 물층을 클로로포름(CHCl3)으로 추출하였다. 무수황산마그네슘(MgSO4)으로 건조한 후 여과하였다. 여과액을 감압농축시키고 클로로포름/헥산으로 컬럼 크로마토그래피로 정제하여 흰색 고체 화합물(중간체(30)) 4.7 g(수율: 39.2%)을 얻었다.14.3 g (40.6 mmol) of 3,7-dibromodibenzo[b,d]thiophene and 3.64 g (40.6 mmol) of copper cyanide (CuCN) were mixed with N,N - After mixing in 100 mL of dimethylformamide (DMF), the mixture was stirred and refluxed for 20 hours. After the reaction was completed, the temperature was lowered to room temperature, and the reaction mixture was slowly poured into an acidified aqueous FeCl 3 solution (a solution of 50.0 g of FeCl 3 dissolved in 80 mL of water and 20 mL of concentrated hydrochloric acid). was stirred for 0.5 hour. The organic layer was separated, and the aqueous layer was extracted with chloroform (CHCl 3 ). After drying with anhydrous magnesium sulfate (MgSO 4 ), it was filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography using chloroform/hexane to obtain 4.7 g (yield: 39.2%) of a white solid compound (Intermediate (30)).
(중간체(31)의 합성)(Synthesis of Intermediate (31))
1구 1 L 플라스크에서 중간체(30) 10.0 g(34.7 mmol), PIN2B2 9.7 g(38.2 mmol), Pd(dppf)Cl2-DCM 1.4 g(1.7 mmol), KOAc 10.2 g(104.1 mmol) 및 1,4-디옥산 250 mL를 하루동안 환류 및 교반하였다. 상온에서 식힌 후 셀라이트 여과를 통해 불순물을 제거하였다. 용매를 완전히 제거한 후 실리카겔 컬럼 크로마토그래피(DCM:HEX)로 정제하였다. 얻어진 고체를 헥산으로 여과하여 흰색 고체의 화합물(중간체(31)) 6.7 g(수율: 57.6%)을 얻었다.In a one-necked 1 L flask, 10.0 g (34.7 mmol) of intermediate (30), 9.7 g (38.2 mmol) of PIN 2 B 2 , 1.4 g (1.7 mmol) of Pd(dppf)Cl 2 -DCM, 10.2 g (104.1 mmol) of KOAc and 250 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 6.7 g (yield: 57.6%) of the compound (intermediate (31)) as a white solid.
(중간체(32)의 합성)(Synthesis of Intermediate (32))
1구 500 mL 플라스크에 중간체(31) 5.0 g(15.0 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 4.2 g(15.0 mmol), Pd(PPh3)4 0.5 g(0.4 mmol), 톨루엔 120 mL와 같이 넣고 교반하다가 에탄올 60 mL, K2CO3 4.1 g(29.8 mmol) 및 증류수 60 mL를 첨가하고, 가열 환류하에 하루종일 교반하였다. 반응이 종결되면 상온으로 냉각하고 용매를 제거하고 증류수를 첨가한 후 디클로로메탄으로 추출하고 분리한 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(32)) 2.9 g(수율: 53.4%)을 얻었다.5.0 g (15.0 mmol) of intermediate (31), 4.2 g (15.0 mmol) of 1-bromo-4-iodobenzene, Pd (PPh 3 ) 4 0.5 g (0.4 mmol) and 120 mL of toluene were added and stirred, then 60 mL of ethanol, 4.1 g (29.8 mmol) of K 2 CO 3 and 60 mL of distilled water were added, and the mixture was stirred under reflux heating throughout the day. After the reaction was completed, it was cooled to room temperature, the solvent was removed, distilled water was added, extracted with dichloromethane, and the separated organic layer was dried over anhydrous MgSO 4 , and purified by column chromatography (Hex:CHCl 3 ) to form a yellow solid compound ( Intermediate (32)) 2.9 g (yield: 53.4%) was obtained.
중간체 합성예 13: 중간체(33)의 합성Intermediate Synthesis Example 13: Synthesis of Intermediate (33)
(중간체(33)의 합성)(Synthesis of Intermediate (33))
1 구 250 mL 플라스크에 중간체(8) 5.0 g(20.0 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 5.2 g(20.0 mmol), Pd(dba)2 0.3 g(0.6 mmol), S-Phos 0.5 g(1.2 mmol), NaOtBu 3.8 g(40.0 mmol), 자일렌(Xylene) 100 mL를 혼합한 후 130 ℃로 가열 및 40분 동안 교반하였다. 반응을 종결하고 상온으로 냉각시킨 후 석출된 고체화합물을 증류수와 톨루엔, 헥산으로 세척하면서 여과하였다. 고체화합물을 디클로로벤젠에 넣고 가열하여 용해시킨 후 셀라이트 여과한 후, 아세톤으로 세척하여 노란색 고체의 화합물(중간체(33)) 4.2 g(수율: 49.2%)을 얻었다.In a one-neck 250 mL flask, 5.0 g (20.0 mmol) of intermediate (8), 5.2 g (20.0 mmol) of 4-(4-Bromophenyl)benzonitrile, and Pd (dba) 2 After mixing 0.3 g (0.6 mmol), 0.5 g (1.2 mmol) of S-Phos, 3.8 g (40.0 mmol) of NaOtBu, and 100 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 4.2 g (yield: 49.2%) of the compound (Intermediate (33)) as a yellow solid.
중간체 합성예 14: 중간체(34)의 합성Intermediate Synthesis Example 14: Synthesis of Intermediate (34)
(중간체(34)의 합성)(Synthesis of Intermediate (34))
1 구 250 mL 플라스크에 중간체(10) 5.0 g(21.3 mmol), 중간체(22) 6.6 g(21.3 mmol), Pd(dba)2 0.4 g(0.6 mmol), S-Phos 0.5 g(1.3 mmol), NaOtBu 4.1 g(42.7 mmol), 자일렌(Xylene) 100 mL를 혼합한 후 130 ℃로 가열 및 40분 동안 교반하였다. 반응을 종결하고 상온으로 냉각시킨 후 석출된 고체화합물을 증류수와 톨루엔, 헥산으로 세척하면서 여과하였다. 고체화합물을 디클로로벤젠에 넣고 가열하여 용해시킨 후 셀라이트 여과한 후, 아세톤으로 세척하여 노란색 고체의 화합물(중간체(34)) 4.7 g(수율: 47.7%)을 얻었다.5.0 g (21.3 mmol) of intermediate (10), 6.6 g (21.3 mmol) of intermediate (22), 0.4 g (0.6 mmol) of Pd (dba) 2 , 0.5 g (1.3 mmol) of S-Phos, After mixing 4.1 g (42.7 mmol) of NaOtBu and 100 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 4.7 g (yield: 47.7%) of the compound (Intermediate (34)) as a yellow solid.
중간체 합성예 15: 중간체(35)의 합성Intermediate Synthesis Example 15: Synthesis of Intermediate (35)
(중간체(35)의 합성)(Synthesis of Intermediate (35))
1 구 250 mL 플라스크에 중간체(6) 5.0 g(15.3 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 4.0 g(15.3 mmol), Pd(dba)2 0.3 g(0.5 mmol), S-Phos 0.4 g(0.9 mmol), NaOtBu 2.9 g(30.6 mmol), 자일렌(Xylene) 100 mL를 혼합한 후 130 ℃로 가열 및 40분 동안 교반하였다. 반응을 종결하고 상온으로 냉각시킨 후 석출된 고체화합물을 증류수와 톨루엔, 헥산으로 세척하면서 여과하였다. 고체화합물을 디클로로벤젠에 넣고 가열하여 용해시킨 후 셀라이트 여과한 후, 아세톤으로 세척하여 노란색 고체의 화합물(중간체(35)) 3.8 g(수율: 49.3%)을 얻었다.In a one-neck 250 mL flask, 5.0 g (15.3 mmol) of intermediate (6), 4.0 g (15.3 mmol) of 4-(4-Bromophenyl)benzonitrile, and Pd (dba) 2 After mixing 0.3 g (0.5 mmol), 0.4 g (0.9 mmol) of S-Phos, 2.9 g (30.6 mmol) of NaOtBu, and 100 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 3.8 g (yield: 49.3%) of the compound (Intermediate (35)) as a yellow solid.
중간체 합성예 16: 중간체(36)의 합성Intermediate Synthesis Example 16: Synthesis of Intermediate (36)
(중간체(36)의 합성)(Synthesis of Intermediate (36))
1구 500 mL 플라스크에 (3-시아노페닐)보론산((3-cyanophenyl)boronic acid) 5.0 g(34.0 mmol), 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 9.6 g(34.0 mmol), Pd(PPh3)4 1.2 g(1.0 mmol), 톨루엔 200 mL와 같이 넣고 교반하다가 에탄올 80 mL, K2CO3 4.1 g(29.8 mmol) 및 증류수 80 mL를 첨가하고, 가열 환류하에 하루종일 교반하였다. 반응이 종결되면 상온으로 냉각하고 용매를 제거하고 증류수를 첨가한 후 디클로로메탄으로 추출하고 분리한 유기층을 무수 MgSO4로 건조하고, 컬럼 크로마토그래피(Hex:CHCl3)로 정제하여 노란색 고체의 화합물(중간체(36)) 4.4 g(수율: 50.1%)을 얻었다.In a one-
중간체 합성예 17: 중간체(44)의 합성Intermediate Synthesis Example 17: Synthesis of Intermediate (44)
(중간체(37)의 합성)(Synthesis of intermediate (37))
아닐린(Aniline) 30.0 g(322.1 mmol)을 아세토니트릴 300 mL에 녹인 용액을 0°C에서 NBS(N-Bromosuccinimide) 114.7 g(644.3 mmol)를 천천히 적가하였다. 반응 혼합물을 상온으로 승온한 후 4시간동안 교반하였다. 반응 종결 확인 후, 증류수를 투입하여 유기층을 분리하였다. 분리한 유기층을 무수 MgSO4로 건조, 여과 및 농축하였다. 이 농축액을 컬럼크로마토그래피(EA:HEX)를 통하여 정제하여 옅은 노란색 고체의 화합물(중간체(37) 52.3 g(수율: 64.7%)을 얻었다.To a solution of 30.0 g (322.1 mmol) of aniline dissolved in 300 mL of acetonitrile at 0 ° C, 114.7 g (644.3 mmol) of NBS (N-Bromosuccinimide) was slowly added dropwise. The reaction mixture was heated to room temperature and then stirred for 4 hours. After confirming the completion of the reaction, distilled water was added to separate the organic layer. The separated organic layer was dried over anhydrous MgSO 4 , filtered and concentrated. The concentrate was purified through column chromatography (EA:HEX) to obtain 52.3 g (yield: 64.7%) of the compound (Intermediate (37)) as a pale yellow solid.
(중간체(38)의 합성)(Synthesis of Intermediate (38))
중간체(37) 52.3 g(208.4 mmol)과 NMP(N-Methyl-2-pyrrolidone) 1000 mL를 넣고 교반하였다. 4-메톡시벤조일 클로라이드(4-Methoxybenzoyl chloride) 35.6 g(208.4 mmol)을 상온에서 천천히 적가한 후, 하루 종일 교반하였다 반응 종결 확인 후, 증류수를 넣고 교반하여 얻어진 고체를 여과하였다. 메탄올로 고체를 씻어 흰색 고체의 화합물(중간체(38)) 62.5 g(수율: 77.8%)을 얻었다.52.3 g (208.4 mmol) of the intermediate (37) and 1000 mL of NMP ( N -Methyl-2-pyrrolidone) were added and stirred. After slowly adding 35.6 g (208.4 mmol) of 4-methoxybenzoyl chloride dropwise at room temperature, the mixture was stirred throughout the day. After confirming the completion of the reaction, distilled water was added and stirred, and the obtained solid was filtered. The solid was washed with methanol to obtain 62.5 g (yield: 77.8%) of the compound (intermediate (38)) as a white solid.
(중간체(39)의 합성)(Synthesis of Intermediate (39))
중간체(38) 62.5 g(162.3 mmol), Lawesson's reagent 78.8 g(194.8 mmoi) 및 Toluene 600 mL와 혼합한 다음, 110-120 ℃에서 7시간 동안 교반하였다. 반응 종결 확인 후 상온으로 냉각하고, 반응물을 감압 하에 용매를 제거하였다. 얻어진 화합물을 클로로포름에 용해하고 짧은 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하고 혼합용액(MeOH/EtOAc)으로 결정화하여 노란색 고체의 화합물(중간체(39)) 42.1 g(수율: 64.7%)을 얻었다.62.5 g (162.3 mmol) of intermediate (38), 78.8 g (194.8 mmoi) of Lawesson's reagent and 600 mL of Toluene were mixed, followed by stirring at 110-120 °C for 7 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the solvent was removed from the reactant under reduced pressure. The obtained compound was dissolved in chloroform, purified by short silica gel column chromatography (CHCl 3 ), and crystallized from a mixed solution (MeOH/EtOAc) to obtain 42.1 g (yield: 64.7%) of the compound (intermediate (39)) as a yellow solid.
(중간체(40)의 합성)(Synthesis of Intermediate (40))
중간체(39) 42.1 g(105.0 mmol), CuI 2.0 g(10.5 mmol), 1,10-phenanthroline 3.8 g(21.0 mmol), 세슘카보네이트(Cs2CO3) 119.7 g(367.4 mmol)과 디옥산(Dioxane) 420 mL을 같이 넣고, 100℃에서 3시간 환류 교반하였다. 반응 종결 확인 후 반응물을 감압 하에 용매를 제거하였다. 생성된 고체를 디클로로메탄(DCM)에 용해시킨 후 Celite 패드를 통하여 여과하고 디클로로메탄(DCM)으로 세척하였다. 감압하여 용매를 제거한 후 얻어진 화합물을 메탄올로 결정화하여 고체의 화합물(중간체(40)) 22.1 g(수율: 65.8%)을 얻었다. Intermediates (39) 42.1 g (105.0 mmol), CuI 2.0 g (10.5 mmol), 1,10-phenanthroline 3.8 g (21.0 mmol), cesium carbonate (Cs 2 CO 3 ) 119.7 g (367.4 mmol) and dioxane 420 mL together. Then, the mixture was stirred under reflux at 100°C for 3 hours. After confirming the completion of the reaction, the solvent was removed from the reactant under reduced pressure. The resulting solid was dissolved in dichloromethane (DCM), filtered through a Celite pad, and washed with dichloromethane (DCM). After removing the solvent under reduced pressure, the obtained compound was crystallized with methanol to obtain 22.1 g (yield: 65.8%) of a solid compound (intermediate (40)).
(중간체(41)의 합성)(Synthesis of Intermediate (41))
중간체(40) 22.1 g(69.0 mmol), CuCN 49.5 g(552.2 mmol) 및 1-메틸피리리디논(1-methylpyrilidinone) 220 mL 혼합하였다. 혼합요액을 200°C에서 18시간동안 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 증류수를 첨가하였다. 반응물을 EA로 추출하고 무수 MgSO4로 건조, 여과 및 농축하였다. 농축액을 컬럼크로마토 그래피(EA:HEX)로 정제하여 옅은 노랑색 고체의 화합물(중간체(41) 12.5 g(수율: 68.0%)을 얻었다.22.1 g (69.0 mmol) of the intermediate (40), 49.5 g (552.2 mmol) of CuCN, and 220 mL of 1-methylpyrilidinone were mixed. The mixed solution was stirred at 200°C for 18 hours. After confirming the completion of the reaction, it was cooled to room temperature and distilled water was added. The reaction was extracted with EA, dried over anhydrous MgSO 4 , filtered and concentrated. The concentrate was purified by column chromatography (EA:HEX) to obtain 12.5 g (yield: 68.0%) of the compound (Intermediate (41)) as a pale yellow solid.
(중간체(42)의 합성)(Synthesis of Intermediate (42))
중간체(41) 12.5 g(47.0 mmol) 및 Pyridine hydrochloride 108.5 g(938.7 mmol)를 200℃에서 5시간 동안 환류 및 교반하였다. 반응 종결 확인 후, 증류수를 천천히 첨가한 다음 NH4OH를 첨가하여 교반햐였다. 에틸 아세테이트로로 추출하여 수분 및 용매를 제거한 후, 실리카겔 컬럼 크로마토그래피(CHCl3)로 정제하였다. 메탄올을 이용해 고체화하여 흰색의 중간체(42) 8.1 g(수율: 68.4%)를 얻었다.12.5 g (47.0 mmol) of intermediate (41) and 108.5 g (938.7 mmol) of Pyridine hydrochloride were refluxed and stirred at 200° C. for 5 hours. After confirming the completion of the reaction, distilled water was slowly added and then NH 4 OH was added and stirred. After extracting with ethyl acetate to remove moisture and solvent, the mixture was purified by silica gel column chromatography (CHCl 3 ). It was solidified using methanol to obtain 8.1 g (yield: 68.4%) of a white intermediate (42).
(중간체(43)의 합성)(Synthesis of Intermediate (43))
중간체(42) 8.1 g(32.1 mmol)을 다이클로로메탄(DCM) 170 mL에 녹이고 피리딘(Pyridine) 7.6 g(96.3 mmol)을 적가한 후 0℃로 온도를 낮췄다. Tf2O 11.8 g(41.7 mmol)를 천천히 적가한 후 상온으로 온도를 올린 후 12시간 동안 반응시켰다. 반응물을 증류수에 세척한 후, 분리한 유기층을 무수 황산나트륨으로 건조, 여과하고 농축한 후 컬럼 크로마토그래피로(CHCl3) 정제하여 노란색 고체의 화합물(중간체(43)) 12.0 g(수율: 97.3%)을 얻었다.After dissolving 8.1 g (32.1 mmol) of intermediate (42) in 170 mL of dichloromethane (DCM) and adding 7.6 g (96.3 mmol) of pyridine dropwise, the temperature was lowered to 0°C. After slowly adding 11.8 g (41.7 mmol) of Tf 2 O dropwise, the mixture was heated to room temperature and reacted for 12 hours. After washing the reactant with distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl 3 ) to obtain 12.0 g of the compound (intermediate (43)) as a yellow solid (yield: 97.3%) got
(중간체(44)의 합성)(Synthesis of Intermediate (44))
중간체(43) 12.0 g(31.2 mmol), 벤조페논 이민(Benzophenone imine) 6.8 g(37.5 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 0.9 g(1.6 mmol), BINAP 1.9 g(3.1 mmol), Cs2CO3 30.5 g(93.7 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(44)) 6.9 g(수율: 87.9%)을 얻었다.After adding 12.0 g (31.2 mmol) of intermediate (43), 6.8 g (37.5 mmol) of benzophenone imine and 120 mL of toluene, 0.9 g (1.6 mmol) of Pd (dba) 2 and 1.9 g (3.1 mmol) of BINAP ), Cs 2 CO 3 30.5 g (93.7 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 6.9 g (yield: 87.9%) of the compound (Intermediate (44)) as a yellow solid.
중간체 합성예 18: 중간체(47)의 합성Intermediate Synthesis Example 18: Synthesis of Intermediate (47)
(중간체(45)의 합성)(Synthesis of Intermediate (45))
1구 1 L 플라스크에서 중간체(43) 12.0 g(31.2 mmol), PIN2B2 8.7 g(34.3 mmol), Pd(dppf)Cl2-DCM 1.3 g(1.6 mmol), KOAc 9.2 g(93.7 mmol) 및 1,4-디옥산 250 mL를 하루동안 환류 및 교반하였다. 상온에서 식힌 후 셀라이트 여과를 통해 불순물을 제거하였다. 용매를 완전히 제거한 후 실리카겔 컬럼 크로마토그래피(DCM:HEX)로 정제하였다. 얻어진 고체를 헥산으로 여과하여 흰색 고체의 화합물(중간체(45)) 7.5 g(수율: 66.3%)을 얻었다.In a one-necked 1 L flask, 12.0 g (31.2 mmol) of intermediate (43), 8.7 g (34.3 mmol) of PIN 2 B 2 , 1.3 g (1.6 mmol) of Pd(dppf)Cl 2 -DCM, 9.2 g (93.7 mmol) of KOAc and 250 mL of 1,4-dioxane were refluxed and stirred for one day. After cooling at room temperature, impurities were removed through celite filtration. After completely removing the solvent, it was purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 7.5 g (yield: 66.3%) of the compound (intermediate (45)) as a white solid.
(중간체(46)의 합성)(Synthesis of Intermediate (46))
중간체(45) 7.5 g(20.7 mmol), 1-브로모-4-요오드벤젠(1-Bromo-4-iodobenzene) 8.8 g(31.1 mmol), Pd(PPh3)4 1.2 g(1.0 mmol), 2M 탄산나트륨 수용액 21 mL(41.4 mmol), 톨루엔 100 mL 및 에탄올 50 mL의 혼합물을 12시간 동안 환류 교반하였다. 반응 혼합물을 상온으로 냉각한 후 용매를 제거하고 물을 첨가한 후 디클로로메탄를 넣어 유기층을 분리하여 무수 황산마그네슘으로 건조하고 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 노란색 고체 화합물(중간체(46)) 4.7 g(수율: 58.0%)을 얻었다.Intermediate (45) 7.5 g (20.7 mmol), 1-Bromo-4-iodobenzene 8.8 g (31.1 mmol), Pd (PPh 3 ) 4 1.2 g (1.0 mmol), 2M A mixture of 21 mL (41.4 mmol) of sodium carbonate aqueous solution, 100 mL of toluene and 50 mL of ethanol was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, the solvent was removed, water was added, dichloromethane was added, the organic layer was separated, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a yellow solid compound (Intermediate (46)) 4.7 g (yield: 58.0%) was obtained.
(중간체(47)의 합성)(Synthesis of Intermediate (47))
중간체(46) 4.7 g(12.0 mmol), 벤조페논 이민(Benzophenone imine) 2.4 g(13.2 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 0.3 g(0.6 mmol), BINAP 0.7 g(1.2 mmol), Cs2CO3 7.8 g(24.0 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(47)) 2.3 g(수율: 58.5%)을 얻었다.After adding 4.7 g (12.0 mmol) of intermediate (46), 2.4 g (13.2 mmol) of benzophenone imine and 120 mL of toluene, 0.3 g (0.6 mmol) of Pd (dba) 2 and 0.7 g (1.2 mmol) of BINAP ), Cs 2 CO 3 7.8 g (24.0 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 2.3 g (yield: 58.5%) of the compound (Intermediate (47)) as a yellow solid.
중간체 합성예 19: 중간체(50)의 합성Intermediate Synthesis Example 19: Synthesis of Intermediate (50)
(중간체(48)의 합성)(Synthesis of Intermediate (48))
4-아미노-3-브로모벤조니트릴(4-Amino-3-bromobenzonitrile) 50.0 g(253.8 mmol), 4-브로모벤조일 클로라이드(4-Bromobenzoyl chloride) 55.7 g(253.8 mmol) 및 피리딘(Pyridine) 500 mL를 넣고 12시간 이상 환류 교반하였다. 반응 종결 확인 후 용매를 감압 증류하였다. 디아이소프로필 에테르(IPE)로 고체화하여 미황색의 고체 화합물(중간체(48)) 75.6 g(수율: 78.3 %)을 얻었다.50.0 g (253.8 mmol) of 4-amino-3-bromobenzonitrile, 55.7 g (253.8 mmol) of 4-Bromobenzoyl chloride and 500 pyridine mL was added and stirred under reflux for 12 hours or more. After confirming the completion of the reaction, the solvent was distilled under reduced pressure. It was solidified with diisopropyl ether (IPE) to obtain 75.6 g (yield: 78.3%) of a pale yellow solid compound (Intermediate (48)).
(중간체(49)의 합성)(Synthesis of Intermediate (49))
1구 1 L 플라스크에 중간체(48) 75.6 g(251.1 mmol), CuI 2.39 g(12.6 mmol), 1,10-Phenanthroline 4.5 g(25.1 mmol), Cs2CO3 148.7 g(456.6 mmol) 및 니트로벤젠(Nitrobenzene) 800 mL를 하루 종일 환류 교반하였다. 반응이 종결된 후 DCM으로 셀라이트 패드에 통과시켰다. 용매 제거 후 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피(CHCl3)를 이용하여 정제하였다. 메탄올로 고체화하여 미황색의 고체 화합물(중간체(49)) 42.3 g(수율: 56.3%)을 얻었다.In a one-necked 1 L flask, 75.6 g (251.1 mmol) of intermediate (48), 2.39 g (12.6 mmol) of CuI, 4.5 g (25.1 mmol) of 1,10-Phenanthroline, 148.7 g (456.6 mmol) of Cs 2 CO 3 and nitrobenzene (Nitrobenzene) 800 mL was refluxed and stirred throughout the day. After the reaction was complete, DCM was passed through a celite pad. After solvent removal, the solid was dissolved in chloroform and purified using column chromatography (CHCl 3 ). It was solidified with methanol to obtain 42.3 g (yield: 56.3%) of a pale yellow solid compound (intermediate (49)).
(중간체(50)의 합성)(Synthesis of Intermediate (50))
1구 500 mL 플라스크에 중간체(49) 5.0 g(16.7 mmol), 벤조페논 이민(Benzophenone imine) 4.5 g(25.1 mmol), Pd(dba)2 961.0 mg(1.7 mmol), BINAP 2.1 g(3.3 mmol), NaOtBu 4.8 g(50.2 mmol) 및 톨루엔 80 mL를 혼합한 다음, 100 ℃에서 3시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 반응 혼합물을 셀라이트 패드에 여과한 후 감압 증류하였다. THF 50 mL와 6N HCl 수용액 50 mL를 넣고 하루 동안 교반하였다. 형성된 고체를 여과한 후 클로로포름으로 세척하였다. 이렇게 얻은 고체를 증류수로 묽힌 다음 Na2CO3 용액으로 중화시켜 클로로포름으로 추출하였다. 건조된 유기층을 농축한 후 DCM으로 완전히 용해시킨 다음 Hexane을 천천히 적가하면서 고체화하여 노란색 고체의 화합물(중간체(50)) 3.3 g(수율: 85.0%)을 얻었다.5.0 g (16.7 mmol) of intermediate (49), 4.5 g (25.1 mmol) of benzophenone imine, 961.0 mg (1.7 mmol) of Pd (dba) 2 , 2.1 g (3.3 mmol) of BINAP in a one-necked 500 mL flask , NaO t Bu 4.8 g (50.2 mmol) and toluene 80 mL were mixed, and then stirred at 100 °C for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was filtered through a celite pad and distilled under reduced pressure. 50 mL of THF and 50 mL of 6N HCl aqueous solution were added and stirred for one day. After filtering the formed solid, it was washed with chloroform. The solid thus obtained was diluted with distilled water, neutralized with Na 2 CO 3 solution, and extracted with chloroform. After concentrating the dried organic layer, the mixture was completely dissolved in DCM and solidified while slowly adding hexane dropwise to obtain 3.3 g (yield: 85.0%) of the compound (Intermediate (50)) as a yellow solid.
중간체 합성예 20: 중간체(53)의 합성Intermediate Synthesis Example 20: Synthesis of Intermediate (53)
(중간체(51)의 합성)(Synthesis of Intermediate (51))
중간체(49) 20.0 g(66.9 mmol), 비스(피나콜라토)디보론(bis(pinacolato)diboron) 20.4 g(80.2 mmol), Pd(dppf)Cl2-DCM 1.6 g(2.0 mmol), 아세트산 칼륨 11.8 g(120.4 mmol), 1,4-디옥산 330 mL의 혼합물을 90℃에서 12시간 동안 교반하였다. 반응 혼합물을 감압 농축한 후 디클로로메탄을 가하여 30분간 교반하였다. 불용성 침전을 celite 패드로 여과하여 제거하고 감압 농축하였다. 농축 잔류물에 메탄올를 가하고 1시간 동안 교반하였다. 생성된 침전을 여과하고 메탄올로 세척, 진공 건조하여 옅은 노란색 고체 화합물(중간체(51)) 18.3 g(수율: 79.1%)을 얻었다.Intermediate (49) 20.0 g (66.9 mmol), bis (pinacolato) diboron 20.4 g (80.2 mmol), Pd (dppf) Cl 2 -DCM 1.6 g (2.0 mmol), potassium acetate A mixture of 11.8 g (120.4 mmol) and 330 mL of 1,4-dioxane was stirred at 90° C. for 12 hours. After concentrating the reaction mixture under reduced pressure, dichloromethane was added and stirred for 30 minutes. The insoluble precipitate was removed by filtration through a celite pad and concentrated under reduced pressure. Methanol was added to the concentrated residue and stirred for 1 hour. The resulting precipitate was filtered, washed with methanol, and vacuum dried to obtain 18.3 g (yield: 79.1%) of a pale yellow solid compound (Intermediate (51)).
(중간체(52)의 합성)(Synthesis of Intermediate (52))
중간체(51) 18.3 g(52.9 mmol), 1-브로모-4-요오드벤젠(1-Bromo-4-iodobenzene) 22.4 g(79.3 mmol), Pd(PPh3)4 3.1 g(2.6 mmol), 2M 탄산나트륨 수용액 53 mL(105.7 mmol), 톨루엔 110 mL 및 에탄올 50 mL의 혼합물을 12시간 동안 환류 교반하였다. 반응 혼합물을 상온으로 냉각한 후 용매를 제거하고 물을 첨가한 후 디클로로메탄를 넣어 유기층을 분리하여 무수 황산마그네슘으로 건조하고 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 노란색 고체 화합물(중간체(52)) 15.2 g(수율: 76.6%)을 얻었다.Intermediate (51) 18.3 g (52.9 mmol), 1-Bromo-4-iodobenzene 22.4 g (79.3 mmol), Pd (PPh 3 ) 4 3.1 g (2.6 mmol), 2M A mixture of 53 mL (105.7 mmol) of aqueous sodium carbonate solution, 110 mL of toluene and 50 mL of ethanol was stirred under reflux for 12 hours. After cooling the reaction mixture to room temperature, the solvent was removed, water was added, dichloromethane was added, the organic layer was separated, dried over anhydrous magnesium sulfate, and the obtained compound was purified by silica gel column chromatography to obtain a yellow solid compound (Intermediate (52)) 15.2 g (yield: 76.6%) was obtained.
(중간체(53)의 합성)(Synthesis of Intermediate (53))
중간체(52) 15.2 g(40.5 mmol), 벤조페논 이민(Benzophenone imine) 11.0 g(60.8 mmol) 및 톨루엔 120 mL를 첨가한 후 Pd(dba)2 698.8 mg(1.2 mmol), BINAP 1.5 g(2.4 mmol), Cs2CO3 26.4 g(81.0 mmol)을 넣고 110 ℃에서 하루 종일 교반하였다. 반응 종결 확인 상온으로 냉각하고 반응물을 감압하에 클로로포름을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물을 THF 100 mL에 희석한 후 진한 염산 10 mL를 천천히 첨가하여 산성화(pH<2)하여 상온에서 하루 종일 교반하였다. 석출된 고체를 여과한 후 클로로포름으로 세척하였다. 여과한 고체는 Na2CO3 포화용액을 이용하여 염기성화(pH>8)시킨 후 클로로포름으로 추출하여 MgSO4로 수분을 제거한 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물(중간체(53)) 10.0 g(수율: 80.9%)을 얻었다.After adding 15.2 g (40.5 mmol) of intermediate (52), 11.0 g (60.8 mmol) of benzophenone imine and 120 mL of toluene, 698.8 mg (1.2 mmol) of Pd (dba) 2 and 1.5 g (2.4 mmol) of BINAP ), Cs 2 CO 3 26.4 g (81.0 mmol) was added and stirred at 110 °C all day. Confirmation of completion of the reaction After cooling to room temperature, the reactant was passed through a celite pad using chloroform under reduced pressure, and the solvent was removed by distillation under reduced pressure. After diluting the obtained compound in 100 mL of THF, 10 mL of concentrated hydrochloric acid was slowly added to acidify (pH<2), and the mixture was stirred at room temperature all day. After filtering the precipitated solid, it was washed with chloroform. The filtered solid was basicized (pH>8) using a saturated Na 2 CO 3 solution, extracted with chloroform, dried with MgSO 4 , and distilled under reduced pressure to remove the solvent. The obtained compound was slurried with DCM and Hexane to obtain 10.0 g (yield: 80.9%) of the compound (intermediate (53)) as a yellow solid.
중간체 합성예 21: 중간체(56)의 합성Intermediate Synthesis Example 21: Synthesis of Intermediate (56)
(중간체(54)의 합성)(Synthesis of Intermediate (54))
4-아미노-3-브로모벤조니트릴(4-Amino-3-bromobenzonitrile) 50.0 g(253.8 mmol), 3-브로모벤조일 클로라이드(3-Bromobenzoyl chloride) 55.7 g(253.8 mmol) 및 피리딘(Pyridine) 500 mL를 넣고 12시간 이상 환류 교반하였다. 반응 종결 확인 후 용매를 감압 증류하였다. 디아이소프로필 에테르(IPE)로 고체화하여 미황색의 고체 화합물(중간체(54)) 75.6 g(수율: 78.3 %)을 얻었다.50.0 g (253.8 mmol) of 4-Amino-3-bromobenzonitrile, 55.7 g (253.8 mmol) of 3-Bromobenzoyl chloride and 500 Pyridine mL was added and stirred under reflux for 12 hours or more. After confirming the completion of the reaction, the solvent was distilled under reduced pressure. It was solidified with diisopropyl ether (IPE) to obtain 75.6 g (yield: 78.3%) of a pale yellow solid compound (Intermediate (54)).
(중간체(55)의 합성)(Synthesis of Intermediate (55))
중간체(54) 75.6 g(251.1 mmol), CuI 2.39 g(12.6 mmol), 1,10-Phenanthroline 4.5 g(25.1 mmol), Cs2CO3 148.7 g(456.6 mmol) 및 니트로벤젠(Nitrobenzene) 800 mL를 하루 종일 환류 교반하였다. 반응이 종결된 후 DCM으로 셀라이트 패드에 통과시켰다. 용매 제거 후 고체를 클로로포름에 녹인 후 컬럼 크로마토그래피(CHCl3)를 이용하여 정제하였다. 메탄올로 고체화하여 미황색의 고체 화합물(중간체(55)) 42.3 g(수율: 56.3%)을 얻었다.Intermediate (54) 75.6 g (251.1 mmol), CuI 2.39 g (12.6 mmol), 1,10-Phenanthroline 4.5 g (25.1 mmol), Cs 2 CO 3 148.7 g (456.6 mmol) and nitrobenzene 800 mL It was stirred at reflux throughout the day. After the reaction was complete, DCM was passed through a celite pad. After solvent removal, the solid was dissolved in chloroform and purified using column chromatography (CHCl 3 ). It was solidified with methanol to obtain 42.3 g (yield: 56.3%) of a pale yellow solid compound (intermediate (55)).
(중간체(56)의 합성)(Synthesis of Intermediate (56))
중간체(55) 5.0 g(16.7 mmol), 벤조페논 이민(Benzophenone imine) 4.5 g(25.1 mmol), Pd(dba)2 961.0 mg(1.7 mmol), BINAP 2.1 g(3.3 mmol), NaOtBu 4.8 g(50.2 mmol) 및 톨루엔 80 mL를 혼합한 다음, 100 ℃에서 3시간 동안 교반하였다. 반응이 종결된 후 상온으로 냉각하고, 반응 혼합물을 셀라이트 패드에 여과한 후 감압 증류하였다. THF 50 mL와 6N HCl 수용액 50 mL를 넣고 하루 동안 교반하였다. 형성된 고체를 여과한 후 클로로포름으로 세척하였다. 이렇게 얻은 고체를 증류수로 묽힌 다음 Na2CO3 용액으로 중화시켜 클로로포름으로 추출하였다. 건조된 유기층을 농축한 후 DCM으로 완전히 용해시킨 다음 Hexane을 천천히 적가하면서 고체화하여 노란색 고체의 화합물(중간체(56)) 3.3 g(수율: 85.0%)을 얻었다.Intermediate (55) 5.0 g (16.7 mmol), Benzophenone imine 4.5 g (25.1 mmol), Pd (dba) 2 961.0 mg (1.7 mmol), BINAP 2.1 g (3.3 mmol), NaO t Bu 4.8 g (50.2 mmol) and 80 mL of toluene were mixed, and stirred at 100 °C for 3 hours. After the reaction was completed, it was cooled to room temperature, and the reaction mixture was filtered through a celite pad and distilled under reduced pressure. 50 mL of THF and 50 mL of 6N HCl aqueous solution were added and stirred for one day. After filtering the formed solid, it was washed with chloroform. The solid thus obtained was diluted with distilled water, neutralized with Na 2 CO 3 solution, and extracted with chloroform. After concentrating the dried organic layer, it was completely dissolved in DCM, and solidified while slowly adding hexane dropwise to obtain 3.3 g (yield: 85.0%) of the compound (Intermediate (56)) as a yellow solid.
중간체 합성예 22: 중간체(57)의 합성Intermediate Synthesis Example 22: Synthesis of Intermediate (57)
(중간체(57)의 합성)(Synthesis of Intermediate (57))
1 구 250 mL 플라스크에 중간체(44) 5.0 g(19.9 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 5.1 g(19.9 mmol), Pd(dba)2 0.3 g(0.6 mmol), S-Phos 0.5 g(1.2 mmol), NaOtBu 3.8 g(39.8 mmol), 자일렌(Xylene) 100 mL를 혼합한 후 130 ℃로 가열 및 40분 동안 교반하였다. 반응을 종결하고 상온으로 냉각시킨 후 석출된 고체화합물을 증류수와 톨루엔, 헥산으로 세척하면서 여과하였다. 고체화합물을 디클로로벤젠에 넣고 가열하여 용해시킨 후 셀라이트 여과한 후, 아세톤으로 세척하여 노란색 고체의 화합물(중간체(57)) 3.8 g(수율: 49.3%)을 얻었다.In a one-neck 250 mL flask, 5.0 g (19.9 mmol) of intermediate (44), 5.1 g (19.9 mmol) of 4-(4-Bromophenyl)benzonitrile, and Pd (dba) 2 After mixing 0.3 g (0.6 mmol), 0.5 g (1.2 mmol) of S-Phos, 3.8 g (39.8 mmol) of NaOtBu, and 100 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 3.8 g (yield: 49.3%) of the compound (Intermediate (57)) as a yellow solid.
중간체 합성예 23: 중간체(58)의 합성Intermediate Synthesis Example 23: Synthesis of Intermediate (58)
(중간체(58)의 합성)(Synthesis of Intermediate (58))
1 구 250 mL 플라스크에 중간체(50) 5.0 g(21.3 mmol), 중간체(22) 6.6 g(21.3 mmol), Pd(dba)2 0.4 g(0.6 mmol), S-Phos 0.5 g(1.3 mmol), NaOtBu 4.1 g(42.5 mmol), 자일렌(Xylene) 100 mL를 혼합한 후 130 ℃로 가열 및 40분 동안 교반하였다. 반응을 종결하고 상온으로 냉각시킨 후 석출된 고체화합물을 증류수와 톨루엔, 헥산으로 세척하면서 여과하였다. 고체화합물을 디클로로벤젠에 넣고 가열하여 용해시킨 후 셀라이트 여과한 후, 아세톤으로 세척하여 노란색 고체의 화합물(중간체(58)) 3.8 g(수율: 46.8%)을 얻었다.5.0 g (21.3 mmol) of intermediate (50), 6.6 g (21.3 mmol) of intermediate (22), 0.4 g (0.6 mmol) of Pd (dba) 2 , 0.5 g (1.3 mmol) of S-Phos, After mixing 4.1 g (42.5 mmol) of NaOtBu and 100 mL of xylene, the mixture was heated to 130 °C and stirred for 40 minutes. After the reaction was terminated and cooled to room temperature, the precipitated solid compound was filtered while washing with distilled water, toluene, and hexane. The solid compound was dissolved by heating in dichlorobenzene, filtered through Celite, and washed with acetone to obtain 3.8 g (yield: 46.8%) of the compound (Intermediate (58)) as a yellow solid.
상기 합성된 중간체 화합물을 이용하여 이하와 같이 다양한 3차 아민 유도체를 합성하였다. Using the synthesized intermediate compound, various tertiary amine derivatives were synthesized as follows.
실시예 1: 화합물 2-2(LT21-35-450)의 합성Example 1: Synthesis of Compound 2-2 (LT21-35-450)
1구 250 mL 플라스크에 중간체(8) 2.0 g(8.0 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 4.1 g(16.0 mmol) 및 Xylene 100 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 0.2 g(0.4 mmol), NaOt-Bu 3.1 g(32.0 mmol) 및 P(t-Bu)3 0.3 g(0.8 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-2(LT21-35-450) 2.5 g(수율: 51.7%)을 얻었다.Add 2.0 g (8.0 mmol) of intermediate (8), 4.1 g (16.0 mmol) of 4-(4-Bromophenyl)benzonitrile, and 100 mL of Xylene to a 250 mL one-necked flask. After stirring at 50 ℃, Pd (dba)2 0.2 g (0.4 mmol), NaOt-3.1 g of Bu (32.0 mmol) and P(t-Bu)3 After adding 0.3 g (0.8 mmol, 50 wt% in toluene), the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, it was cooled to room temperature and the reactant was CHCl under reduced pressure.3After passing through a celite pad using , the solvent was removed using reduced pressure distillation. After solidifying the obtained compound with hexane to obtain a yellow solid, CHCl3by After melting by heating, charcoal was added and stirred for 30 minutes. Mixed solution (Hot CHCl3:EA) using Celite and SiO2 After passing through a pad, the solvent was removed by distillation under reduced pressure. The obtained compound is SiO2 Column chromatography (EA:CHCl3:HEX). Slurry with DCM and Hexane to obtain 2.5 g (yield: 51.7%) of Compound 2-2 (LT21-35-450) as a yellow solid.
실시예 2: 화합물 2-5(LT21-35-452)의 합성Example 2: Synthesis of compound 2-5 (LT21-35-452)
1구 250 mL 플라스크에 중간체(8) 2.0 g(8.0 mmol), 중간체(19) 4.5 g(16.0 mmol), Pd(dba)2 229.7 mg(0.4 mmol), NaOtBu 3.1 g(32.0 mmol), 50% t-Bu3P 323.3 mg(0.8 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 2-5(LT21-35-452) 2.8 g(수율: 53.5%)을 얻었다In a one-neck 250 mL flask, 2.0 g (8.0 mmol) of intermediate (8), 4.5 g (16.0 mmol) of intermediate (19), 229.7 mg (0.4 mmol) of Pd (dba) 2 , 3.1 g (32.0 mmol) of NaO t Bu, After mixing 323.3 mg (0.8 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.8 g (yield: 53.5%) of Compound 2-5 (LT21-35-452) as a yellow solid. got
실시예 3: 화합물 2-7(LT21-35-462)의 합성Example 3: Synthesis of Compound 2-7 (LT21-35-462)
1구 250 mL 플라스크에 중간체(8) 2.0 g(8.0 mmol), 2-(4-브로모페닐)나프탈렌(2-(4-bromophenyl)naphthalene) 4.5 g(16.0 mmol), Pd(dba)2 229.7 mg(0.4 mmol), NaOtBu 3.1 g(32.0 mmol), 50% t-Bu3P 323.3 mg(0.8 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 2-7(LT21-35-462) 2.6 g(수율: 49.7%)을 얻었다In a one-necked 250 mL flask, 2.0 g (8.0 mmol) of intermediate (8), 4.5 g (16.0 mmol) of 2- (4-bromophenyl) naphthalene, and Pd (dba) 2 229.7 mg (0.4 mmol), 3.1 g (32.0 mmol) of NaO t Bu, 323.3 mg (0.8 mmol) of 50% t -Bu 3 P, and 80 mL of Xylene were mixed and reacted at 120 °C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.6 g (yield: 49.7%) of Compound 2-7 (LT21-35-462) as a yellow solid. got
실시예 4: 화합물 2-8(LT21-35-455)의 합성Example 4: Synthesis of Compound 2-8 (LT21-35-455)
1구 250 mL 플라스크에 중간체(8) 2.0 g(8.0 mmol), 중간체(22) 4.9 g(16.0 mmol) 및 Xylene 100 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 229.7 mg(0.4 mmol), NaOt-Bu 3.1 g(32.0 mmol) 및 P(t-Bu)3 323.3 mg(0.8 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-8(LT21-35-455) 3.1 g(수율: 55.1%)을 얻었다.After adding 2.0 g (8.0 mmol) of intermediate (8), 4.9 g (16.0 mmol) of intermediate (22) and 100 mL of Xylene to a 250 mL one-necked flask, stir at 50 ° C, and then 229.7 mg (0.4 mg of Pd (dba) 2 ) mmol), 3.1 g (32.0 mmol) of NaO t- Bu and 323.3 mg (0.8 mmol, 50 wt% in toluene) of P( t- Bu) 3 were added, followed by stirring at 125-130 °C throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and hexane to obtain 3.1 g (yield: 55.1%) of Compound 2-8 (LT21-35-455) as a yellow solid.
실시예 5: 화합물 2-42(LT21-35-494)의 합성Example 5: Synthesis of Compound 2-42 (LT21-35-494)
1구 250 mL 플라스크에 중간체(10) 2.0 g(8.5 mmol), 중간체(24) 4.8 g(17.1 mmol), Pd(dba)2 245.5 mg(0.4 mmol), NaOtBu 3.3 g(34.2 mmol), 50% t-Bu3P 345.5 mg(0.9 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 2-42(LT21-35-494) 2.8 g(수율: 51.4%)을 얻었다In a one-necked 250 mL flask, 2.0 g (8.5 mmol) of intermediate (10), 4.8 g (17.1 mmol) of intermediate (24), 245.5 mg (0.4 mmol) of Pd (dba) 2 , 3.3 g (34.2 mmol) of NaO t Bu, After mixing 345.5 mg (0.9 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.8 g (yield: 51.4%) of Compound 2-42 (LT21-35-494) as a yellow solid. got
실시예 6: 화합물 2-48(LT21-35-472)의 합성Example 6: Synthesis of compound 2-48 (LT21-35-472)
1구 250 mL 플라스크에 중간체(10) 2.0 g(8.5 mmol), 중간체(29) 6.0 g(17.1 mmol), Pd(dba)2 245.5 mg(0.4 mmol), NaOtBu 3.3 g(34.2 mmol), 50% t-Bu3P 345.5 mg(0.9 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 2-48(LT21-35-472) 3.2 g(수율: 48.8%)을 얻었다 In a one-necked 250 mL flask, 2.0 g (8.5 mmol) of intermediate (10), 6.0 g (17.1 mmol) of intermediate (29), 245.5 mg (0.4 mmol) of Pd (dba) 2 , 3.3 g (34.2 mmol) of NaO t Bu, After mixing 345.5 mg (0.9 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 3.2 g (yield: 48.8%) of Compound 2-48 (LT21-35-472) as a yellow solid. got
실시예 7: 화합물 2-74(LT21-35-465)의 합성Example 7: Synthesis of Compound 2-74 (LT21-35-465)
1구 250 mL 플라스크에 중간체(6) 2.0 g(6.1 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 3.2 g(12.3 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 176.2 mg(0.3 mmol), NaOt-Bu 2.4 g(24.5 mmol) 및 P(t-Bu)3 247.9 mg(0.6 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-74(LT21-35-465) 2.2 g(수율: 52.7%)을 얻었다.2.0 g (6.1 mmol) of intermediate (6), 3.2 g (12.3 mmol) of 4-(4-Bromophenyl)benzonitrile, and 100 mL of Xylene were added to a 250 mL one-necked flask. After stirring at 50 ℃, Pd (dba) 2 176.2 mg (0.3 mmol), NaO t- Bu 2.4 g (24.5 mmol) and P ( t- Bu) 3 247.9 mg (0.6 mmol, 50 wt% in toluene) After addition, it was stirred all day at 125-130 °C. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.2 g (yield: 52.7%) of Compound 2-74 (LT21-35-465) as a yellow solid.
실시예 8: 화합물 2-119(LT21-35-496)의 합성Example 8: Synthesis of Compound 2-119 (LT21-35-496)
1구 250 mL 플라스크에 중간체(13) 2.0 g(6.4 mmol), 중간체(30) 3.7 g(12.9 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 185.3 mg(0.3 mmol), NaOt-Bu 2.5 g(25.8 mmol) 및 P(t-Bu)3 260.8 mg(0.6 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-119(LT21-35-496) 2.2 g(수율: 52.7%)을 얻었다.2.0 g (6.4 mmol) of intermediate (13), 3.7 g (12.9 mmol) of intermediate (30), and 100 mL of Xylene were added to a 250 mL one-necked flask, stirred at 50 ° C, and 185.3 mg (0.3 mmol) of Pd (dba) 2 ), 2.5 g (25.8 mmol) of NaO t- Bu and 260.8 mg (0.6 mmol, 50 wt% in toluene) of P( t- Bu) 3 were added, followed by stirring at 125-130 ° C. throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.2 g (yield: 52.7%) of Compound 2-119 (LT21-35-496) as a yellow solid.
실시예 9: 화합물 2-150(LT21-35-451)의 합성Example 9: Synthesis of Compound 2-150 (LT21-35-451)
중간체(33) 3.0 g(7.0 mmol), 중간체(22) 2.2 g(7.0 mmol) 및 Xylene 50 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 80.7 mg(0.1 mmol), NaOt-Bu 1.4 g(14.0 mmol) 및 P(t-Bu)3 142.0 mg(0.4 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 아세톤으로 고체화하여 노란색의 고체을 수득한 후 모노클로로벤젠으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 뜨거운 모노클로로벤젠을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 혼합용액(모노클로로벤젠/아세톤)으로 재결정하여 노란색 고체의 화합물 2-150(LT21-35-451) 2.1 g(수율: 45.7%)을 얻었다.After adding 3.0 g (7.0 mmol) of intermediate (33), 2.2 g (7.0 mmol) of intermediate (22) and 50 mL of Xylene, stirring at 50 ° C., 80.7 mg (0.1 mmol) of Pd (dba) 2 and NaO t- After adding 1.4 g (14.0 mmol) of Bu and 142.0 mg (0.4 mmol, 50 wt% in toluene) of P( t- Bu) 3, the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with acetone to obtain a yellow solid and then treated with monochlorobenzene. After melting by heating, charcoal was added and stirred for 30 minutes. Hot monochlorobenzene was passed through a pad of celite and SiO 2 and the solvent was removed by distillation under reduced pressure. It was recrystallized from a mixed solution (monochlorobenzene/acetone) to obtain 2.1 g (yield: 45.7%) of Compound 2-150 (LT21-35-451) as a yellow solid.
실시예 10: 화합물 2-202(LT21-35-461)의 합성Example 10: Synthesis of Compound 2-202 (LT21-35-461)
중간체(34) 3.0 g(6.5 mmol), 중간체(30) 1.9 g(6.5 mmol) 및 Xylene 50 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 74.8 mg(0.1 mmol), NaOt-Bu 1.3 g(13.0 mmol) 및 P(t-Bu)3 131.5 mg(0.3 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 아세톤으로 고체화하여 노란색의 고체을 수득한 후 모노클로로벤젠으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 뜨거운 모노클로로벤젠을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 혼합용액(모노클로로벤젠/아세톤)으로 재결정하여 노란색 고체의 화합물 2-202(LT21-35-461) 1.9 g(수율: 43.7%)을 얻었다.After adding 3.0 g (6.5 mmol) of intermediate (34), 1.9 g (6.5 mmol) of intermediate (30) and 50 mL of Xylene, stirring at 50 ° C., 74.8 mg (0.1 mmol) of Pd (dba) 2 and NaO t- After adding 1.3 g (13.0 mmol) of Bu and 131.5 mg (0.3 mmol, 50 wt% in toluene) of P( t- Bu) 3 , the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with acetone to obtain a yellow solid and then treated with monochlorobenzene. After melting by heating, charcoal was added and stirred for 30 minutes. Hot monochlorobenzene was passed through a pad of celite and SiO 2 and the solvent was removed by distillation under reduced pressure. It was recrystallized from a mixed solution (monochlorobenzene/acetone) to obtain 1.9 g (yield: 43.7%) of Compound 2-202 (LT21-35-461) as a yellow solid.
실시예 11: 화합물 2-244(LT21-35-460)의 합성Example 11: Synthesis of Compound 2-244 (LT21-35-460)
중간체(35) 3.0 g(6.0 mmol), 중간체(20) 1.8 g(6.0 mmol) 및 Xylene 50 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 68.5 mg(0.1 mmol), NaOt-Bu 1.1 g(12.0 mmol) 및 P(t-Bu)3 120.5 mg(0.3 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 아세톤으로 고체화하여 노란색의 고체을 수득한 후 모노클로로벤젠으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 뜨거운 모노클로로벤젠을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 혼합용액(모노클로로벤젠/아세톤)으로 재결정하여 노란색 고체의 화합물 2-244(LT21-35-460) 1.7 g(수율: 43.6%)을 얻었다.After adding 3.0 g (6.0 mmol) of intermediate (35), 1.8 g (6.0 mmol) of intermediate (20) and 50 mL of Xylene, stirring at 50 ° C., 68.5 mg (0.1 mmol) of Pd (dba) 2 and NaO t- After adding 1.1 g (12.0 mmol) of Bu and 120.5 mg (0.3 mmol, 50 wt% in toluene) of P( t- Bu) 3, the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with acetone to obtain a yellow solid and then treated with monochlorobenzene. After melting by heating, charcoal was added and stirred for 30 minutes. Hot monochlorobenzene was passed through a pad of celite and SiO 2 and the solvent was removed by distillation under reduced pressure. It was recrystallized from a mixed solution (monochlorobenzene/acetone) to obtain 1.7 g (yield: 43.6%) of Compound 2-244 (LT21-35-460) as a yellow solid.
실시예 12: 화합물 2-299(LT21-35-478)의 합성Example 12: Synthesis of Compound 2-299 (LT21-35-478)
1구 250 mL 플라스크에 중간체(15) 2.0 g(8.0 mmol), 중간체(22) 4.9 g(16.0 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 229.7 mg(0.4 mmol), NaOt-Bu 3.1 g(32.0 mmol) 및 P(t-Bu)3 323.3 mg(0.8 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-299(LT21-35-478) 2.5 g(수율: 44.4%)을 얻었다.2.0 g (8.0 mmol) of intermediate (15), 4.9 g (16.0 mmol) of intermediate (22), and 100 mL of Xylene were added to a 250 mL one-necked flask, stirred at 50 ° C, and 229.7 mg (0.4 mmol) of Pd (dba) 2 ), NaO t- Bu 3.1 g (32.0 mmol) and P( t- Bu) 3 323.3 mg (0.8 mmol, 50 wt% in toluene) were added, and the mixture was stirred at 125-130 ° C. throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.5 g (yield: 44.4%) of Compound 2-299 (LT21-35-478) as a yellow solid.
실시예 13: 화합물 2-313(LT21-35-482)의 합성Example 13: Synthesis of Compound 2-313 (LT21-35-482)
1구 250 mL 플라스크에 중간체(17) 2.0 g(6.1 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 3.2 g(12.3 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 176.2 mg(0.3 mmol), NaOt-Bu 2.4 g(24.5 mmol) 및 P(t-Bu)3 247.9 mg(0.6 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 2-313(LT21-35-482) 2.0 g(수율: 47.9%)을 얻었다.2.0 g (6.1 mmol) of intermediate (17), 3.2 g (12.3 mmol) of 4-(4-Bromophenyl)benzonitrile, and 100 mL of Xylene were added to a 250 mL one-necked flask. After stirring at 50 ℃, Pd (dba) 2 176.2 mg (0.3 mmol), NaO t- Bu 2.4 g (24.5 mmol) and P ( t- Bu) 3 247.9 mg (0.6 mmol, 50 wt% in toluene) After addition, it was stirred all day at 125-130 °C. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.0 g (yield: 47.9%) of Compound 2-313 (LT21-35-482) as a yellow solid.
실시예 14: 화합물 3-14(LT21-35-473)의 합성Example 14: Synthesis of compound 3-14 (LT21-35-473)
1구 250 mL 플라스크에 중간체(44) 2.0 g(8.0 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 4.1 g(15.9 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 228.8 mg(0.4 mmol), NaOt-Bu 3.1 g(31.8 mmol) 및 P(t-Bu)3 322.0 mg(0.8 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 3-14(LT21-35-473) 2.4 g(수율: 49.8%)을 얻었다.2.0 g (8.0 mmol) of the intermediate (44), 4.1 g (15.9 mmol) of 4-(4-Bromophenyl)benzonitrile, and 100 mL of Xylene were added to a 250 mL one-necked flask. After stirring at 50 ℃, Pd (dba) 2 228.8 mg (0.4 mmol), NaO t- Bu 3.1 g (31.8 mmol) and P ( t- Bu) 3 322.0 mg (0.8 mmol, 50 wt% in toluene) After addition, it was stirred all day at 125-130 °C. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.4 g (yield: 49.8%) of Compound 3-14 (LT21-35-473) as a yellow solid.
실시예 15: 화합물 3-17(LT21-35-485)의 합성Example 15: Synthesis of compound 3-17 (LT21-35-485)
1구 250 mL 플라스크에 중간체(44) 2.0 g(8.0 mmol), 중간체(19) 4.5 g(15.9 mmol), Pd(dba)2 228.8 mg(0.4 mmol), NaOtBu 3.1 g(31.8 mmol), 50% t-Bu3P 322.0 mg(0.8 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 3-17(LT21-35-485) 2.8 g(수율: 53.7%)을 얻었다.In a one-necked 250 mL flask, 2.0 g (8.0 mmol) of intermediate (44), 4.5 g (15.9 mmol) of intermediate (19), 228.8 mg (0.4 mmol) of Pd (dba) 2 , 3.1 g (31.8 mmol) of NaO t Bu, After mixing 322.0 mg (0.8 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.8 g (yield: 53.7%) of Compound 3-17 (LT21-35-485) as a yellow solid. got it
실시예 16: 화합물 3-20(LT21-35-483)의 합성Example 16: Synthesis of Compound 3-20 (LT21-35-483)
1구 250 mL 플라스크에 중간체(44) 2.0 g(8.0 mmol), 중간체(22) 4.9 g(15.9 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 228.8 mg(0.4 mmol), NaOt-Bu 3.1 g(31.8 mmol) 및 P(t-Bu)3 322.0 mg(0.8 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 3-20(LT21-35-483) 3.1 g(수율: 55.2%)을 얻었다.After adding 2.0 g (8.0 mmol) of intermediate (44), 4.9 g (15.9 mmol) of intermediate (22) and 100 mL of Xylene to a 250 mL one-necked flask, stirring at 50 ° C, 228.8 mg (0.4 mmol) of Pd (dba) 2 ), 3.1 g (31.8 mmol) of NaO t- Bu and 322.0 mg (0.8 mmol, 50 wt% in toluene) of P( t- Bu) 3 were added, followed by stirring at 125-130 ° C. throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 3.1 g (yield: 55.2%) of Compound 3-20 (LT21-35-483) as a yellow solid.
실시예 17: 화합물 3-24(LT21-35-470)의 합성Example 17: Synthesis of compound 3-24 (LT21-35-470)
1구 250 mL 플라스크에 중간체(44) 2.0 g(8.0 mmol), 중간체(32) 5.8 g(15.9 mmol), Pd(dba)2 228.8 mg(0.4 mmol), NaOtBu 3.1 g(31.8 mmol), 50% t-Bu3P 322.0 mg(0.8 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 3-24(LT21-35-470) 3.3 g(수율: 50.7%)을 얻었다In a one-necked 250 mL flask, 2.0 g (8.0 mmol) of intermediate (44), 5.8 g (15.9 mmol) of intermediate (32), 228.8 mg (0.4 mmol) of Pd (dba) 2 , 3.1 g (31.8 mmol) of NaO t Bu, After mixing 322.0 mg (0.8 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 3.3 g (yield: 50.7%) of Compound 3-24 (LT21-35-470) as a yellow solid. got
실시예 18: 화합물 3-43(LT21-35-491)의 합성Example 18: Synthesis of compound 3-43 (LT21-35-491)
1구 250 mL 플라스크에 중간체(50) 2.0 g(8.5 mmol), 중간체(36) 4.4 g(17.0 mmol), Pd(dba)2 244.4 mg(0.4 mmol), NaOtBu 3.3 g(34.0 mmol), 50% t-Bu3P 344.0 mg(0.9 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 3-43(LT21-35-491) 2.1 g(수율: 41.9%)을 얻었다In a one-necked 250 mL flask, 2.0 g (8.5 mmol) of intermediate (50), 4.4 g (17.0 mmol) of intermediate (36), 244.4 mg (0.4 mmol) of Pd (dba) 2 , 3.3 g (34.0 mmol) of NaO t Bu, After mixing 344.0 mg (0.9 mmol) of 50% t -Bu 3 P and 80 mL of Xylene, the mixture was reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.1 g (yield: 41.9%) of Compound 3-43 (LT21-35-491) as a yellow solid. got
실시예 19: 화합물 3-70(LT21-35-458)의 합성Example 19: Synthesis of Compound 3-70 (LT21-35-458)
1구 250 mL 플라스크에 중간체(47) 2.0 g(6.1 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 3.2 g(12.2 mmol), Pd(dba)2 175.6 mg(0.3 mmol), NaOtBu 2.4 g(24.4 mmol), 50% t-Bu3P 247.2 mg(0.6 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 3-70(LT21-35-458) 2.0 g(수율: 48.0%)을 얻었다In a one-necked 250 mL flask, 2.0 g (6.1 mmol) of intermediate (47), 3.2 g (12.2 mmol) of 4-(4-Bromophenyl)benzonitrile, and Pd (dba) 2 175.6 mg (0.3 mmol), NaO t Bu 2.4 g (24.4 mmol), 50% t -Bu 3 P 247.2 mg (0.6 mmol) and 80 mL of Xylene were mixed and reacted at 120 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.0 g (yield: 48.0%) of Compound 3-70 (LT21-35-458) as a yellow solid. got
실시예 20: 화합물 3-107(LT21-35-490)의 합성Example 20: Synthesis of Compound 3-107 (LT21-35-490)
1구 250 mL 플라스크에 중간체(53) 2.0 g(6.4 mmol), 중간체(30) 3.7 g(12.9 mmol) 및 Xylene 100 mL를 첨가하고 50 ℃에서 교반한 후 Pd(dba)2 184.7 mg(0.3 mmol), NaOt-Bu 2.5 g(25.7 mmol) 및 P(t-Bu)3 259.9 mg(0.6 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 Hexane으로 고체화하여 노란색의 고체을 수득한 후 CHCl3으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 혼합용액(Hot CHCl3:EA)을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 얻어진 화합물은 SiO2 컬럼 크로마토그래피(EA:CHCl3:HEX)로 정제하였다. DCM과 Hexane으로 슬러리하여 노란색 고체의 화합물 3-107(LT21-35-490) 2.5 g(수율: 53.6%)을 얻었다.After adding 2.0 g (6.4 mmol) of the intermediate (53), 3.7 g (12.9 mmol) of the intermediate (30) and 100 mL of Xylene to a 250 mL one-necked flask, stirring at 50 ° C, 184.7 mg (0.3 mmol) of Pd (dba) 2 ), NaO t- Bu 2.5 g (25.7 mmol) and P( t- Bu) 3 259.9 mg (0.6 mmol, 50 wt% in toluene) were added, and the mixture was stirred at 125-130 ° C. throughout the day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with hexane to obtain a yellow solid, and then with CHCl 3 After melting by heating, charcoal was added and stirred for 30 minutes. After passing the mixed solution (Hot CHCl 3 :EA) through Celite and SiO 2 pad, the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO 2 column chromatography (EA:CHCl 3 :HEX). Slurry with DCM and Hexane to obtain 2.5 g (yield: 53.6%) of Compound 3-107 (LT21-35-490) as a yellow solid.
실시예 21: 화합물 3-118(LT21-35-469)의 합성Example 21: Synthesis of Compound 3-118 (LT21-35-469)
중간체(57) 3.0 g(7.0 mmol), 중간체(22) 2.2 g(7.0 mmol) 및 Xylene 50 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 80.5 mg(0.1 mmol), NaOt-Bu 1.4 g(14.0 mmol) 및 P(t-Bu)3 141.6 mg(0.4 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 아세톤으로 고체화하여 노란색의 고체을 수득한 후 모노클로로벤젠으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 뜨거운 모노클로로벤젠을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 혼합용액(모노클로로벤젠/아세톤)으로 재결정하여 노란색 고체의 화합물 3-118(LT21-35-469) 2.4 g(수율: 52.3%)을 얻었다.After adding 3.0 g (7.0 mmol) of intermediate (57), 2.2 g (7.0 mmol) of intermediate (22) and 50 mL of Xylene, stirring at 50 ° C., 80.5 mg (0.1 mmol) of Pd (dba) 2 and NaO t- After adding 1.4 g (14.0 mmol) of Bu and 141.6 mg (0.4 mmol, 50 wt% in toluene) of P( t- Bu) 3, the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with acetone to obtain a yellow solid and then treated with monochlorobenzene. After melting by heating, charcoal was added and stirred for 30 minutes. Hot monochlorobenzene was passed through a pad of celite and SiO 2 and the solvent was removed by distillation under reduced pressure. It was recrystallized from a mixed solution (monochlorobenzene/acetone) to obtain 2.4 g (yield: 52.3%) of compound 3-118 (LT21-35-469) as a yellow solid.
실시예 22: 화합물 3-166(LT21-35-477)의 합성Example 22: Synthesis of Compound 3-166 (LT21-35-477)
중간체(58) 3.0 g(6.5 mmol), 중간체(30) 1.9 g(6.5 mmol) 및 Xylene 50 mL를 첨가한 후 50 ℃에서 교반한 후 Pd(dba)2 74.6 mg(0.1 mmol), NaOt-Bu 1.3 g(13.0 mmol) 및 P(t-Bu)3 131.2 mg(0.3 mmol, 50 wt% in toluene)을 첨가한 후 125~130 ℃에서 하루 종일 교반하였다. 반응 종결 확인 후 상온으로 냉각하고 반응물을 감압하에 CHCl3을 사용하여 셀라이트 패드에 통과시킨 후 감압 증류를 이용해 용매를 제거하였다. 얻어진 화합물을 아세톤으로 고체화하여 노란색의 고체을 수득한 후 모노클로로벤젠으로 가열하여 녹인 후 charcoal을 첨가하여 30분간 교반하였다. 뜨거운 모노클로로벤젠을 사용하여 셀라이트와 SiO2 패드에 통과시킨 후 감압 증류하여 용매를 제거하였다. 혼합용액(모노클로로벤젠/아세톤)으로 재결정하여 노란색 고체의 화합물 3-166(LT21-35-477) 2.2 g(수율: 50.6%)을 얻었다.After adding 3.0 g (6.5 mmol) of intermediate (58), 1.9 g (6.5 mmol) of intermediate (30) and 50 mL of Xylene, stirring at 50 ° C., 74.6 mg (0.1 mmol) of Pd (dba) 2 and NaO t- After adding 1.3 g (13.0 mmol) of Bu and 131.2 mg (0.3 mmol, 50 wt% in toluene) of P( t- Bu) 3 , the mixture was stirred at 125-130 °C all day. After confirming the completion of the reaction, the mixture was cooled to room temperature, and the reactant was passed through a celite pad using CHCl 3 under reduced pressure, and then the solvent was removed by distillation under reduced pressure. The obtained compound was solidified with acetone to obtain a yellow solid and then treated with monochlorobenzene. After melting by heating, charcoal was added and stirred for 30 minutes. Hot monochlorobenzene was passed through a pad of celite and SiO 2 and the solvent was removed by distillation under reduced pressure. It was recrystallized from a mixed solution (monochlorobenzene/acetone) to obtain 2.2 g (yield: 50.6%) of compound 3-166 (LT21-35-477) as a yellow solid.
실시예 23: 화합물 3-257(LT21-35-464)의 합성Example 23: Synthesis of Compound 3-257 (LT21-35-464)
1구 250 mL 플라스크에 중간체(56) 2.0 g(8.5 mmol), 4-(4-브로모페닐)벤조니트릴(4-(4-Bromophenyl)benzonitrile) 4.4 g(17.0 mmol), Pd(dba)2 244.4 mg(0.4 mmol), NaOtBu 3.3 g(34.0 mmol), 50% t-Bu3P 344.0 mg(0.9 mmol) 및 Xylene 80 mL를 혼합한 다음, 120℃에서 12시간 동안 반응하였다. 반응이 종결된 후 상온으로 냉각하고, 물을 넣고 클로로포름으로 추출한 후 감압 하에 용매를 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피(Hex:EA)로 정제하고 아세톤에 녹인 후 메탄올을 천천히 적가하면서 고체화하여, 노란색 고체의 화합물 3-257(LT21-35-464) 2.3 g(수율: 45.9%)을 얻었다In a one-necked 250 mL flask, 2.0 g (8.5 mmol) of intermediate (56), 4.4 g (17.0 mmol) of 4-(4-bromophenyl)benzonitrile, and Pd (dba) 2 244.4 mg (0.4 mmol), 3.3 g (34.0 mmol) of NaO t Bu, 344.0 mg (0.9 mmol) of 50% t -Bu 3 P, and 80 mL of Xylene were mixed and reacted at 120° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, water was added, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and solidified while slowly adding methanol dropwise to obtain 2.3 g (yield: 45.9%) of compound 3-257 (LT21-35-464) as a yellow solid. got
<시험예><Test Example>
본 발명의 화합물에 대하여 J.A. WOOLLAM社 Ellipsometer 기기를 이용하여 n(refractive index)와 k(extinction coefficient)을 측정한다.For the compounds of the present invention, J.A. Measure n (refractive index) and k (extinction coefficient) using WOOLLAM's Ellipsometer.
시험예를 위한 단막 제작 : Fabrication of single film for test example:
화합물의 광학 특성 측정을 위해, 유리기판(0.7T)을 Ethanol, DI Water, Acetone에 각각 10분씩 세척한 후, 유리기판 위에 화합물을 800Å증착하여 단막을 제작한다. To measure the optical properties of the compound, a glass substrate (0.7T) was washed with Ethanol, DI Water, and Acetone for 10 minutes each, and then the compound was deposited on the glass substrate to a thickness of 800 Å to form a single film.
비교시험예를 위한 단막 제작(Glass/REF01(80 nm)) : Fabrication of single film for comparative test example (Glass/REF01 (80 nm)):
광학 특성 소자는 Glass상에 REF01(80nm)을 증착하여 소자를 제작하였다. 화합물을 증착하기 전에 Glass는 2×10-2Torr에서 125 W로 2분간 산소 플라즈마 처리를 하였다. 화합물을 9×10-7Torr의 진공도에서 1Å/sec의 속도로 증착하여 단막을 제작한다. The optical characteristic element was fabricated by depositing REF01 (80nm) on Glass. Before depositing the compound, Glass was treated with oxygen plasma for 2 minutes at 2×10 -2 Torr at 125 W. The compound is deposited at a rate of 1 Å/sec in a vacuum of 9×10 -7 Torr to form a single film.
<시험예 1 내지 6><Test Examples 1 to 6>
상기 비교시험예에서, REF01을 이용하는 대신에 하기 표 1에 나타낸 각각의 화합물을 사용한 것을 제외하고는 상기 비교 시험예와 동일한 방법으로 단막을 제작하였다.In the Comparative Test Example, a single film was prepared in the same manner as in the Comparative Test Example, except that each compound shown in Table 1 was used instead of REF01.
상기 비교시험예 및 시험예 1 내지 6에 대한 화합물의 광학 특성을 표 1에 나타냈다.Optical properties of the compounds for the Comparative Test Example and Test Examples 1 to 6 are shown in Table 1.
광학 특성은 450nm 및 620nm 파장에서 굴절률(n) 상수이다.The optical properties are the refractive index (n) constants at 450 nm and 620 nm wavelengths.
상기 표 1에서 알 수 있는 바와 같이, 비교시험예 1(REF01)와 시험예 1(화합물(2-2))를 비교한 결과는 화학적 구조는 유사하지만, 시아노기의 도입 유·무에 따라 굴절률(2.182 대비 2.287)이 높아짐을 확인할 수 있었다. As can be seen from Table 1, the results of comparing Comparative Test Example 1 (REF01) and Test Example 1 (Compound (2-2)) show similar chemical structures, but the refractive index depending on whether or not a cyano group is introduced. (2.287 compared to 2.182) was confirmed to be higher.
굴절률이 높아짐에 따라 전극 내부에서 발광되는 빛을 외부로 추출하는 효과가 증가될 것으로 판단할 수 있다.It can be determined that as the refractive index increases, the effect of extracting light emitted from inside the electrode to the outside increases.
비교시험예 1(REF01)의 450nm에서의 n값은 2.182 이었고, 이에 반해 대부분의 실시예 화합물들은 대체적으로 2.250 보다 높은 굴절률을 갖는 것으로 확인되었다. 이것은 청색영역에서의 높은 시야각을 확보하기 위해 필요한 높은 굴절률 값에 만족한다. The n value at 450 nm of Comparative Test Example 1 (REF01) was 2.182, whereas most of the Example compounds were found to have refractive indices generally higher than 2.250. This satisfies the high 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, HT01은 정공 주입층, NPB는 정공 수송층, αβ-ADN은 발광층의 호스트, Pyene-CN은 청색 형광 도판트, 전자 수송층은 ET201, Liq는 전자 주입층, Mg:Ag은 음극으로 사용하였다. 이 화합물들의 구조는 하기의 화학식과 같다.For device fabrication, ITO, a transparent electrode, was used as the anode layer, HT01 was the hole injection layer, NPB was the hole transport layer, αβ-ADN was the host of the light emitting layer, Pyene-CN was the blue fluorescent dopant, ET201 was the electron transport layer, and Liq was An electron injection layer, Mg:Ag, was used as a cathode. The structures of these compounds are as follows.
비교실시예: ITO / HT01(90 nm) / NPB(25 nm) / αβ-ADN:5% Pyrene-CN(200 nm) / ET201:Liq(=1:1, 40nm) / Liq(2 nm) / Mg:Ag(1:9, 10 nm)/REF01(60nm)Comparative Example: ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN: 5% Pyrene-CN (200 nm) / ET201: Liq (=1: 1, 40 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm)/REF01 (60 nm)
청색 형광 유기발광소자는 ITO / HT01(90 nm) / NPB(25 nm) / αβ-ADN:5% Pyrene-CN(200 nm) / ET201:Liq(=1:1, 40nm) / Liq(2 nm) / Mg:Ag(1:9, 10 nm)/REF01(60nm) 순으로 증착하여 소자를 제작하였다. 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 0.02 Å/sec으로 동시 증착하였고, 나머지 유기물들은Å 모두 1 Å/sec의 속도로 증착하였다. 실험에 사용된 캡핌층 물질은 REF01로 선택하였다. 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.Blue fluorescence organic light emitting device is ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN:5% Pyrene-CN (200 nm) / ET201:Liq (=1:1, 40 nm) / Liq (2 nm) ) / Mg: Ag (1:9, 10 nm) / REF01 (60 nm) were deposited in the order to fabricate a device. Before depositing the organic material, the ITO electrode was treated with oxygen plasma for 2 minutes at 125 W at 2 × 10 -2 Torr. Organic materials were deposited at a vacuum of 9 × 10 -7 Torr, Liq was deposited at 0.1 Å/sec, αβ-ADN was 0.18 Å/sec, Pyrene-CN was deposited at 0.02 Å/sec, and the rest of the organic materials were deposited at 0.18 Å/sec. It was deposited at a rate of 1 Å/sec. The capping layer material used in the experiment was selected as REF01. After the device fabrication was completed, the device was sealed in a glove box filled with nitrogen gas to prevent contact with air and moisture. After forming a barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.
비교시험예 1(REF01) 비교시험예 2(REF02)Comparative test example 1 (REF01) Comparative test example 2 (REF02)
<실시예 1 내지 23><Examples 1 to 23>
상기 비교실시예에서, REF01을 이용하는 대신에 하기 표 2에 나타낸 각각의 화합물을 사용한 것을 제외하고는 상기 비교실시예와 동일한 방법으로 소자를 제작하였다.In the Comparative Example, a device was fabricated in the same manner as in the Comparative Example, except that each compound shown in Table 2 was used instead of REF01.
상기 비교실시예 및 실시예 1 내지 23에서 제조된 유기 발광 소자에 대한 전기적 발광특성을 표 2에 나타냈다.Table 2 shows the electrical emission characteristics of the organic light emitting devices prepared in Comparative Example and Examples 1 to 23.
상기 표 2의 결과로부터, 본 발명에 따른 3차 아민 유도체 화합물은 유기 발광 소자를 비롯한 유기 전자 소자의 캡핑층의 재료로서 사용될 수 있고, 이를 이용한 유기 발광 소자를 비롯한 유기 전자 소자는 효율, 구동전압, 안정성 등에서 우수한 특성을 나타냄을 알 수 있다. 특히, 본 발명에 따른 화합물은 미소공동현상(Micro-cavity)현상의 능력이 우수하여 높은 효율 특성을 나타냈다.From the results of Table 2, the tertiary amine derivative compound according to the present invention can be used as a material for a 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 has efficiency, driving voltage , it can be seen that excellent properties such as stability are exhibited. In particular, the compound according to the present invention exhibited high efficiency characteristics due to its excellent ability of micro-cavity phenomenon.
화학식 1의 화합물은 OLED에서 캡핑층으로 사용하기 위한 의외의 바람직한 특성을 가지고 있다. The compound of Formula 1 has unexpectedly desirable properties for use as a capping layer in OLEDs.
본 발명의 화합물이 이러한 특성에 의해 산업용 유기 전자 소자 제품에 적용될 수 있다.The compounds 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 synthesis example described above is an example, and reaction conditions may be changed as needed. In addition, the compound according to one embodiment of the present invention can 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 can have properties suitable for use in organic electroluminescent devices.
100: 기판, 110: 제1 전극, 120: 제2 전극, 200: 유기물층, 210: 정공주입층, 215: 정공수송층, 220: 발광층, 230: 전자수송층, 235: 전자주입층, 300: 캡핑층Reference Numerals 100: 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 (3)
[화학식 1]
상기 화학식 1에 있어서,
L1, L2 및 L3는 각각 독립적으로 치환 또는 비치환된 페닐렌기; 치환 비치환된 나프틸렌기; 및 치환 또는 비치환된 피리딜렌기; 중에서 선택되고,
Ar1 및 Ar2는 각각 독립적으로 페닐기; 나프탈렌기; 디벤조퓨란기 및 디벤조티오펜기; 중에서 선택되고,
Z1 은 O 또는 S이고,
Q1 은 CH 또는 N이고,
a, b 및 c는 0 내지 3의 정수이며,
x는 1 내지 4의 정수이며,
y 및 z는 0 내지 4의 정수이다.A high refractive index (n>1.7) tertiary amine derivative for an organic light emitting device, represented by Formula 1 below.
[Formula 1]
In Formula 1,
L 1 , L 2 and L 3 are each independently a substituted or unsubstituted phenylene group; A substituted unsubstituted naphthylene group; And a substituted or unsubstituted pyridylene group; is selected from
Ar 1 and Ar 2 are each independently a phenyl group; naphthalene group; a dibenzofuran group and a dibenzothiophene group; is selected from
Z 1 is O or S;
Q 1 is CH or N;
a, b and c are integers from 0 to 3;
x is an integer from 1 to 4;
y and z are integers from 0 to 4.
상기 화학식 1의 화합물은 하기 화학식 2 또는 화학식 3로 표시된 화합물들 중에서 선택된 어느 하나의 화합물인 3차 아민 유도체.
[화학식 2]
[화학식 3]
According to claim 1,
The compound of Formula 1 is a tertiary amine derivative which is any one compound selected from compounds represented by Formula 2 or Formula 3 below.
[Formula 2]
[Formula 3]
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 유기물층 또는 캡핑층은 상기 제 1항에 따른 3차 아민 유도체를 포함하는 유기전계발광소자.a first electrode;
an organic material layer composed of a plurality of organic material layers disposed on the first electrode;
a second electrode disposed on the organic layer; and
A capping layer disposed on the second electrode; includes,
The organic electroluminescent device or the capping layer includes the tertiary amine derivative according to claim 1.
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KR20160062307A (en) | 2014-11-24 | 2016-06-02 | 삼성디스플레이 주식회사 | Organic light emitting diode display compring capping layer having high refractive index |
KR20170030427A (en) | 2015-09-09 | 2017-03-17 | 주식회사 엘지화학 | Organoluminescent device |
KR20210052311A (en) | 2019-10-31 | 2021-05-10 | 주식회사 동진쎄미켐 | New organic compound for capping layer and Organic light emitting diode comprising to the same |
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KR20160062307A (en) | 2014-11-24 | 2016-06-02 | 삼성디스플레이 주식회사 | Organic light emitting diode display compring capping layer having high refractive index |
KR20170030427A (en) | 2015-09-09 | 2017-03-17 | 주식회사 엘지화학 | Organoluminescent device |
KR20210052311A (en) | 2019-10-31 | 2021-05-10 | 주식회사 동진쎄미켐 | New organic compound for capping layer and Organic light emitting diode comprising to the same |
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