KR20210082318A - Organic compounds and organic electro luminescence device comprising the same - Google Patents
Organic compounds and organic electro luminescence device comprising the same Download PDFInfo
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- KR20210082318A KR20210082318A KR1020190174423A KR20190174423A KR20210082318A KR 20210082318 A KR20210082318 A KR 20210082318A KR 1020190174423 A KR1020190174423 A KR 1020190174423A KR 20190174423 A KR20190174423 A KR 20190174423A KR 20210082318 A KR20210082318 A KR 20210082318A
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- 150000002894 organic compounds Chemical class 0.000 title description 6
- 238000005401 electroluminescence Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 239000011368 organic material Substances 0.000 claims abstract description 25
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- 238000000034 method Methods 0.000 claims description 11
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
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- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000005104 aryl silyl group Chemical group 0.000 claims description 5
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Abstract
Description
본 발명은 유기 전계 발광 소자용 재료로서 사용될 수 있는 신규 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescent device and an organic electroluminescent device comprising the same.
1950년대 베르나소스(Bernanose)의 유기 박막 발광 관측을 시점으로 하여, 1965년 안트라센 단결정을 이용한 청색 전기발광으로 이어진 유기 전계 발광(electroluminescent, EL) 소자에 대한 연구가 이어져 오다가, 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층 구조의 유기 전계 발광 소자가 제시되었다. 이후, 고효율, 고수명의 유기 전계 발광 소자를 만들기 위하여, 소자 내 각각의 특징적인 유기물층을 도입하는 형태로 발전하여 왔으며, 이에 사용되는 특화된 물질의 개발로 이어졌다.Starting with the observation of organic thin film emission by Bernanose in the 1950s, research on organic electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals continued in 1965. ) presented an organic electroluminescent device having a stacked structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high-efficiency, long-life organic electroluminescent device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of a specialized material used for this.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 이때, 유기물층으로 사용되는 물질은 그 기능에 따라, 발광 물질, 정공 주입 물질, 정공 수송 물질, 전자 수송 물질, 전자 주입 물질 등으로 분류될 수 있다.In an organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.
발광 물질은 발광색에 따라 청색, 녹색, 적색 발광 물질과, 보다 나은 천연색을 구현하기 위한 노란색 및 주황색 발광 물질로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도펀트 계를 사용할 수 있다.The light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials for realizing a better natural color according to the emission color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material.
도펀트 물질은 유기 물질을 사용하는 형광 도펀트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도펀트로 나눌 수 있다. 이때, 인광 재료의 개발은 이론적으로 형광에 비해 4배까지 발광 효율을 향상시킬 수 있기 때문에, 인광 도펀트 뿐만 아니라 인광 호스트 재료들에 대한 연구도 많이 진행되고 있다.The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times compared to the fluorescence, research on phosphorescent host materials as well as the phosphorescent dopant is in progress.
현재까지 정공 주입층, 정공 수송층, 정공 차단층, 전자 수송층 재료로는 NPB, BCP, Alq3 등이 널리 알려져 있으며, 발광층 재료로는 안트라센 유도체들이 보고되고 있다. 특히, 발광층 재료 중 효율 향상 측면에서 장점을 가지고 있는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등과 같은 Ir을 포함하는 금속 착체 화합물이 청색(blue), 녹색(green), 적색(red)의 인광 도판트 재료로 사용되고 있으며, 4,4-디카바졸리비페닐(4,4-dicarbazolybiphenyl, CBP)은 인광 호스트 재료로 사용되고 있다. Until now, NPB, BCP, Alq 3 and the like have been widely known as materials for the hole injection layer, hole transport layer, hole blocking layer, and electron transport layer, and anthracene derivatives have been reported as materials for the emission layer. In particular, metal complex compounds containing Ir, such as Firpic, Ir(ppy) 3 , (acac)Ir(btp) 2 , which have advantages in terms of efficiency improvement among light emitting layer materials, are blue, green, and red. (red) is used as a phosphorescent dopant material, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.
그러나 종래의 유기물층 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮아 열적 안정성이 매우 좋지 않기 때문에, 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다. 따라서, 성능이 뛰어난 유기물층 재료의 개발이 요구되고 있다.However, conventional organic material layer materials have an advantage in terms of light emitting properties, but because the glass transition temperature is low and thermal stability is not very good, they are not at a satisfactory level in terms of the lifespan of the organic electroluminescent device. Accordingly, there is a demand for the development of an organic layer material having excellent performance.
본 발명은 유기 전계 발광 소자에 적용할 수 있으며, 정공, 전자 주입 및 수송능, 발광능 등이 모두 우수한 신규 유기 화합물을 제공하는 것을 목적으로 한다. The present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel organic compound having excellent hole, electron injection and transport ability, light emitting ability, and the like.
또한, 본 발명은 상기 신규 유기 화합물을 포함하여 낮은 구동 전압과 높은 발광 효율을 나타내며 수명이 향상되는 유기 전계 발광 소자를 제공하는 것을 또 다른 목적으로 한다.In addition, it is another object of the present invention to provide an organic electroluminescent device that includes the novel organic compound and exhibits a low driving voltage and high luminous efficiency and has an improved lifespan.
상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다. In order to achieve the above object, the present invention provides a compound represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
X1 내지 X3은 서로 동일하거나 또는 상이하며, 각각 독립적으로 C(R) 또는 N이나 적어도 하나 이상은 N이고, X2가 C(R)인 경우 인접한 Ar2와 서로 결합하여 축합 고리를 형성할 수 있고;X 1 to X 3 are the same as or different from each other, and each independently C(R) or N, but at least one is N, and when X 2 is C(R), they combine with adjacent Ar2 to form a condensed ring. can;
A는 하기 화학식 2로 표시되는 치환체이며;A is a substituent represented by the following formula (2);
[화학식 2][Formula 2]
상기 화학식 2에서,In Formula 2,
*는 결합이 이루어지는 부분을 의미하고;* means the part where the bond is made;
Y는 N(R1), C(R2)(R3), O, S이며;Y is N(R 1 ), C(R 2 )(R 3 ), O, S;
Z는 직접결합이거나, N(R1), C(R2)(R3), O, S이며;Z is a direct bond or N(R 1 ), C(R 2 )(R 3 ), O, S;
R1, R2 및 R3은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 치환기 간에는 서로 결합하여 축합 고리를 형성할 수 있고;R 1 , R 2 and R 3 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 Aryloxy group, C 3 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group, and adjacent substituents are bonded to each other to form a condensed ring, ;
X4 내지 X9는 서로 동일하거나 또는 상이하며, 각각 독립적으로 C(R) 또는 N이고, 인접한 C(R)간에 서로 결합하여 축합 고리를 형성할 수 있으며;X 4 to X 9 are the same as or different from each other, and each independently represents C(R) or N, and may be bonded to each other between adjacent C(R) to form a condensed ring;
R은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며;R is hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nucleus A heterocycloalkyl group having 3 to 40 atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyloxy group, a C 6 to C 60 aryloxy group, C 3 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 An aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group;
L은 직접결합, 치환되거나 비치환된 C6~C60의 아릴렌기, 및 치환되거나 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고;L is selected from the group consisting of a direct bond, a substituted or unsubstituted C 6 ~ C 60 arylene group, and a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms;
n은 0 내지 5 이며;n is 0 to 5;
Ar1 과 Ar2는 각각 독립적으로 C6~C60의 아릴기 또는 핵원자수 5 내지 60개의 헤테로아릴기이고;Ar 1 and Ar 2 are each independently a C 6 ~ C 60 aryl group or a heteroaryl group having 5 to 60 nuclear atoms;
a, b는 각각 0 또는 1이고, a + b ≥ 1 이다.a and b are 0 or 1, respectively, and a + b ≥ 1.
본 발명은 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중에서 적어도 하나는 상기 화학식 1의 화합물을 포함하는 유기 전계 발광 소자를 제공한다.The present invention provides an organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode, wherein at least one of the at least one organic material layer comprises the compound of Formula 1 .
본 발명에서의 "알킬"은 탄소수 1 내지 40개의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있는데, 이에 한정되지 않는다."Alkyl" in the present invention is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, and hexyl. and the like, but is not limited thereto.
본 발명에서의 "알케닐(alkenyl)"은 탄소-탄소 이중 결합을 1개 이상 가진, 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있는데, 이에 한정되지 않는다."Alkenyl" in the present invention is a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds, and examples thereof include vinyl, Allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl) and the like, but is not limited thereto.
본 발명에서의 "알키닐(alkynyl)"은 탄소-탄소 삼중 결합을 1개 이상 가진, 탄소수 2 내지 40개의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기이며, 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등이 있는데, 이에 한정되지 않는다."Alkynyl" in the present invention is a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond, an example of which is ethynyl) , 2-propynyl, and the like, but is not limited thereto.
본 발명에서의 "아릴"은 단독 고리 또는 2 이상의 고리가 조합된, 탄소수 6 내지 60개의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 축합되어 있고, 고리 형성 원자로서 탄소만을 포함(예를 들어, 탄소수는 8 내지 60개일 수 있음)하고, 분자 전체가 비-방향족성(non-aromacity)를 갖는 1가 치환기도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴, 플루오레닐 등이 있는데, 이에 한정되지 않는다."Aryl" in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, in which a single ring or two or more rings are combined. In addition, two or more rings are condensed with each other, contain only carbon as a ring-forming atom (eg, the number of carbon atoms may be 8 to 60), and the whole molecule is monovalent having non-aromaticity. Substituents may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, and the like.
본 발명에서의 "헤테로아릴"은 핵원자수 5 내지 60개의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, P, S 및 Se 중에서 선택된 헤테로원자로 치환된다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합되어 있고, 고리 형성 원자로서 탄소 외에 N, O, P, S 및 Se 중에서 선택된 헤테로 원자를 포함하고, 분자 전체가 비-방향족성(non-aromacity)를 갖는 1가 그룹도 포함하는 것으로 해석된다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리; 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(벤조thiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리; 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등이 있는데, 이에 한정되지 않는다."Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. In this case, at least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom selected from N, O, P, S and Se. In addition, two or more rings are simply attached or condensed to each other, and contain a hetero atom selected from N, O, P, S and Se in addition to carbon as a ring forming atom, and the entire molecule is non-aromatic (non-aromatic). It is interpreted to include a monovalent group having aromacity). Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycylates such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl click ring; 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.
본 발명에서의 "아릴옥시"는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 5 내지 60개의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있는데, 이에 한정되지 않는다."Aryloxy" in the present invention is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.
본 발명에서의 "알킬옥시"는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 1 내지 40개의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함하는 것으로 해석한다. 이러한 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등이 있는데, 이에 한정되지 않는다."Alkyloxy" in the present invention is a monovalent substituent represented by R'O-, wherein R' means 1 to 40 alkyl, and has a linear, branched or cyclic structure. interpreted as including Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.
본 발명에서의 "아릴아민"은 탄소수 6 내지 60개의 아릴로 치환된 아민을 의미한다."Arylamine" in the present invention means an amine substituted with an aryl having 6 to 60 carbon atoms.
본 발명에서의 "시클로알킬"은 탄소수 3 내지 40개의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 놀보닐(norbornyl), 아다만틴(adamantine) 등이 있는데, 이에 한정되지 않는다."Cycloalkyl" in the present invention means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.
본 발명에서의 "헤테로시클로알킬"은 핵원자수 3 내지 40개의 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로 원자로 치환된다. 이러한 헤테로시클로알킬의 예로는 모르폴린, 피페라진 등이 있는데, 이에 한정되지 않는다."Heterocycloalkyl" in the present invention means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, substituted with a hetero atom such as S or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.
본 발명에서의 "알킬실릴"은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 5 내지 60개의 아릴로 치환된 실릴을 의미한다.In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" refers to silyl substituted with aryl having 5 to 60 carbon atoms.
본 발명에서의 "축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다."Condensed ring" in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
본 발명의 화합물은 열적 안정성, 캐리어 수송능, 발광능 등이 우수하기 때문에 유기 전계 발광 소자의 유기물층 재료로 유용하게 적용될 수 있다.Since the compound of the present invention has excellent thermal stability, carrier transport ability, light emitting ability, etc., it can be usefully applied as an organic material layer material of an organic electroluminescent device.
또한, 본 발명의 화합물을 유기물층에 포함하는 유기 전계 발광 소자는 발광성능, 구동전압, 수명, 효율 등의 측면이 크게 향상되어 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.In addition, the organic electroluminescent device comprising the compound of the present invention in an organic material layer has greatly improved aspects such as light emitting performance, driving voltage, lifespan, and efficiency, and thus can be effectively applied to a full color display panel.
도 1은 본 발명의 일 실시예에 따른 유기 전계 발광 소자의 구조를 나타내는 단면도이다.
도 2는 본 발명의 다른 일 실시예에 따른 유기 전계 발광 소자의 구조를 나타내는 단면도이다.1 is a cross-sectional view showing the structure of an organic electroluminescent device according to an embodiment of the present invention.
2 is a cross-sectional view showing the structure of an organic electroluminescent device according to another embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. 신규 유기 화합물1. Novel Organic Compounds
본 발명에 따른 신규 유기 화합물은 6원 방향족 고리 또는 6원 방향족헤테로에 EWG가 결합되는 것으로, 상기 화학식 1로 표시된다.The novel organic compound according to the present invention has EWG bonded to a 6-membered aromatic ring or a 6-membered aromatic hetero, and is represented by Formula 1 above.
구체적으로, 상기 6원 방향족 고리 또는 6원 방향족헤테로 계열 코어 구조들은 전기화학적 안정성이 우수하고, 캐리어 수송 능력이 우수하다. 특히 전자 및 정공 수송 이동성이 매우 우수하여, 발광층 내에서의 캐리어들의 밸런스가 매우 우수한 특성들을 나타낸다. 그러나 유리전이온도가 다소 낮아 열적 안정성이 향상이 요구되고 있으며, 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다.Specifically, the 6-membered aromatic ring or 6-membered aromatic hetero-based core structures have excellent electrochemical stability and excellent carrier transport ability. In particular, the electron and hole transport mobility is very excellent, and thus the balance of carriers in the light emitting layer is very excellent. However, the glass transition temperature is somewhat low, and thermal stability is required to be improved, and it is not at a satisfactory level in terms of the lifetime of the organic electroluminescent device.
상기 화학식 1로 대표되는 재료들은 6원 방향족 고리 또는 6원 방향족헤테로계 핵심 코어와 적어도 하나의 전자끄는기(EWG, electron-withdrawing group)가 결합을 가지며 아다만탄이 결합하는 구조적 특징을 갖는데, 이러한 구조는 전공 이동성이 우수하며 특히 높은 유리 전이온도 및 열적 안정성 성능을 지닌다. The materials represented by Formula 1 have structural features in which a 6-membered aromatic ring or 6-membered aromatic hetero-based core core and at least one electron-withdrawing group (EWG) have a bond and adamantane is bonded, This structure has excellent pneumatic mobility and particularly high glass transition temperature and thermal stability performance.
실제로, 본 발명의 화학식 1로 표시되는 화합물은 대부분 증착 온도가 개선되어 열적 안전성을 지니며 수명이 개선되는 물리적 특징들을 나타낸다. 일례로, 하기 표 1에 예시된 일반적인 플루오렌(화합물 A)의 경우In fact, most of the compounds represented by Formula 1 of the present invention exhibit thermal stability due to improved deposition temperature and physical characteristics of improved lifespan. As an example, in the case of the general fluorene (Compound A) illustrated in Table 1 below
증착 온도가 (Ts)가 241°C 이며, 이에 비해, 본 발명의 화학식 1로 표시되는 화합물(화합물 R1)은 증착 온도가 (Ts)가 262로 21°C 개선되었으며 증착 시 증착 온도가 다른 재료들 보다 상대적으로 낮은 온도에서 증착이 가능하므로 공정성이 좋고 열안정성이 향상될 수 있다. 이를 통해 수명이 개선되는 물리적 특징들을 나타낸다. The deposition temperature (Ts) is 241 °C, in comparison, the compound (compound R1) represented by formula 1 of the present invention has a deposition temperature (Ts) of 262, which is 21°C improved, and a material having a different deposition temperature during deposition Since deposition is possible at a relatively lower temperature than these, processability is good and thermal stability can be improved. This shows the physical characteristics that improve the lifespan.
본 발명에 따라 화학식 1로 표시되는 화합물은 6원 방향족 고리 또는 6원 방향족헤테로계 구조에, 단환 또는 다환 모이어티(예컨대, 페닐 고리, 나프릴 고리 등)가 결합된 구조를 기본 골격으로 한다.According to the present invention, the compound represented by Formula 1 has a structure in which a monocyclic or polycyclic moiety (eg, a phenyl ring, a napryl ring, etc.) is bonded to a 6-membered aromatic ring or a 6-membered aromatic hetero-based structure as a basic skeleton.
본 발명의 화학식 1로 표시되는 화합물은 하기 화합물로 나타낼 수 있으나 이에 한정되는 것은 아니다.The compound represented by Formula 1 of the present invention may be represented by the following compound, but is not limited thereto.
2. 유기 전계 발광 소자2. Organic electroluminescent device
한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(유기 EL 소자)에 관한 것이다.Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by Formula 1 according to the present invention.
구체적으로, 본 발명은 양극(anode), 음극(cathode), 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 이때, 상기 화합물은 단독 또는 2 이상 혼합되어 사용될 수 있다.Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is and a compound represented by Formula 1 above. In this case, the compounds may be used alone or in mixture of two or more.
상기 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광층, 발광 보조층, 수명 개선층, 전자 수송층, 전자 수송 보조층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. The at least one organic material layer may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a light emitting auxiliary layer, a life improvement layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, of which at least one organic material layer is the above formula It may include a compound represented by 1.
전술한 본 발명에 따른 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 일 예시로 도 1을 참고하면, 예컨대 서로 마주하는 양극(10)과 음극(20), 그리고 상기 양극(10)과 음극(20) 사이에 위치하는 유기층(30)을 포함한다. 여기서, 상기 유기층(30)은 정공 수송층(31), 발광층(32) 및 전자 수송층(34)을 포함할 수 있다. 또한, 상기 정공 수송층(31)과 발광층(32) 사이에는 정공 수송 보조층(33)을 포함할 수 있으며, 상기 전자 수송층(34)과 발광층(32) 사이에는 전자 수송 보조층(35)을 포함할 수 있다. The structure of the organic electroluminescent device according to the present invention is not particularly limited, but referring to FIG. 1 as an example, for example, the
본 발명의 다른 예시로 도 2를 참고하면, 상기 유기층(30)은 정공 수송층(31)과 양극(10)사이에 정공 주입층(37)을 더 포함할 수 있으며, 전자 수송층(34)과 음극(20)사이에는 전자 주입층(36)을 추가로 더 포함할 수 있다. Referring to FIG. 2 as another example of the present invention, the
본 발명에서 상기 정공 수송층(31)과 양극(10) 사이에 적층되는 정공 주입층(37)은 양극으로 사용되는 ITO와, 정공 수송층(31)으로 사용되는 유기물질 사이의 계면 특성을 개선할 뿐만 아니라 그 표면이 평탄하지 않은 ITO의 상부에 도포되어 ITO의 표면을 부드럽게 만들어주는 기능을 하는 층으로, 당 기술분야에서 통상적으로 사용되는 것이면 특별한 제한없이 사용할 수 있으며, 예컨대, 아민 화합물을 사용할 수 있으나 이에 한정되는 것은 아니다.In the present invention, the
또한, 상기 전자 주입층(36)은 전자 수송층의 상부에 적층되어 음극으로부터의 전자 주입을 용이하게 해주어 궁극적으로 전력효율을 개선시키는 기능을 수행하는 층으로, 당 기술분야에서 통상적으로 사용되는 것이면 특별한 제한없이 사용할 수 있으며, 예컨대, LiF, Liq, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다. In addition, the
또한, 본 발명에서 도면에는 도시하지 않았으나, 상기 정공 수송 보조층(33)과 발광층(32) 사이에 발광 보조층을 더 포함할 수 있다. 상기 발광 보조층은 발광층(32)에 정공을 수송하는 역할을 하면서 유기층(30)의 두께를 조정하는 역할을 할 수 있다. 상기 발광 보조층은 정공 수송 물질을 포함할 수 있고, 정공 수송층(31)과 동일한 물질로 만들어질 수 있다.In addition, although not shown in the drawings in the present invention, a light emitting auxiliary layer may be further included between the hole transport
또한, 본 발명에서 도면에는 도시하지 않았으나, 상기 전자 수송 보조층 (35)과 발광층(32) 사이에 수명 개선층을 더 포함할 수 있다. 상기 발광층(32)으로 유기 발광 소자 내에서 이온화 포텐셜 레벨을 타고 이동하는 정공이 수명개선층의 높은 에너지 장벽에 막혀 전자 수송층으로 확산, 또는 이동하지 못해, 결과적으로 정공을 발광층에 제한시키는 기능을 한다. 이렇게 정공을 발광층에 제한시키는 기능은 환원에 의해 전자를 이동시키는 전자 수송층으로 정공이 확산되는 것을 막아, 산화에 의한 비가역적 분해반응을 통한 수명저하 현상을 억제하여, 유기 발광 소자의 수명 개선에 기여할 수 있다.In addition, although not shown in the drawings in the present invention, a lifespan improving layer may be further included between the electron transport
본 발명에서 상기 화학식 1로 표시되는 화합물은 인돌, 인다졸 인덴, 벤죠푸란, 벤죠싸이오펜, 트리아졸로등과 같은 5원 방향족 고리 또는 5원 방향족헤테로에 EWG가 결합되는 것으로, 이때 카바졸과 유사한 에너지 준위를 갖기 때문에 도펀트의 에너지 준위에 비해 높게 조절될 수 있어 호스트 물질로 적용 가능하다. 특히, 벤죠퓨란 및 벤죠사이오펜의 모이어티는 전자가 풍부하여 유기 전계 발광 소자의 전자 수송층 재료로 사용 시 이동성이 빨라지므로 발광 효율의 상승과 구동 전압의 감소를 기대할 수 있다. 또한, 본 발명의 상기 5원 방향족 고리 또는 5원 방향족헤테로 고리는 분자량이 기존 화합물 보다 적기 때문에 증착 시 증착 온도가 다른 재료들 보다 상대적으로 낮은 온도에서 증착이 가능하므로 공정성이 좋고 열안정성이 향상될 수 있다.In the present invention, the compound represented by Formula 1 is a compound in which EWG is bonded to a 5-membered aromatic ring or 5-membered aromatic heterocycle such as indole, indazole indene, benzofuran, benzothiophene, triazolo, etc. Since it has an energy level, it can be adjusted higher than the energy level of the dopant, so it can be applied as a host material. In particular, since the moieties of benzofuran and benzothiophene are rich in electrons, their mobility increases when used as an electron transport layer material of an organic electroluminescent device, so that an increase in luminous efficiency and a decrease in driving voltage can be expected. In addition, since the 5-membered aromatic ring or 5-membered aromatic heterocyclic ring of the present invention has a lower molecular weight than conventional compounds, deposition is possible at a relatively lower temperature than other materials, so the processability is good and thermal stability is improved. can
따라서, 본 발명의 화학식 1로 표시되는 화합물은 유기 전계 발광 소자의 유기물층인 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나의 재료로 사용될 수 있지만, 바람직하게는 발광층, 전자 수송층 및 전자 수송층에 추가로 적층되는 전자 수송 보조층 중 어느 하나의 재료, 보다 바람직하게는 전자 수송층, 또는 전자수송 보조층의 재료로 사용될 수 있다.Therefore, the compound represented by Formula 1 of the present invention may be used as any one material of the organic material layer of the organic electroluminescent device such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but preferably a light emitting layer, an electron It may be used as a material of any one of the transport layer and the electron transport auxiliary layer that is further laminated on the electron transport layer, more preferably, the electron transport layer or the electron transport auxiliary layer.
또한, 본 발명에 따른 화합물을 발광층 재료로 사용하는 경우, 구체적으로는 상기 화학식 1로 표시되는 화합물을 발광층의 인광 호스트, 형광 호스트 또는 도펀트 재료로 사용할 수 있으며, 바람직하게는 인광 호스트(청색, 녹색 및/또는 적색의 인광 호스트 재료)로 사용할 수 있다.In addition, when the compound according to the present invention is used as a material for the light emitting layer, specifically, the compound represented by Formula 1 may be used as a phosphorescent host, a fluorescent host or a dopant material of the light emitting layer, preferably a phosphorescent host (blue, green and/or a red phosphorescent host material).
또한, 본 발명에서 상기 유기 전계 발광 소자는 상기한 바와 같이 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층될 뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층을 추가로 포함할 수 있다. In addition, in the present invention, the organic electroluminescent device may further include an insulating layer or an adhesive layer at the interface between the electrode and the organic material layer as well as the anode, one or more organic material layers and the cathode are sequentially stacked as described above.
본 발명의 유기 전계 발광 소자는 상기 유기물층 중 적어도 하나 이상(예컨대, 전자 수송 보조층)이 상기 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 다른 유기물층 및 전극을 형성하여 제조될 수 있다.The organic electroluminescent device of the present invention uses materials and methods known in the art, except that at least one of the organic material layers (eg, electron transport auxiliary layer) is formed to include the compound represented by Formula 1 above. It can be manufactured by forming another organic material layer and an electrode using it.
상기 유기물층은 진공 증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이에 한정되지 않는다.The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution application method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.
본 발명에서 사용 가능한 기판으로는 특별히 한정되지 않으며, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등이 사용될 수 있다.The substrate usable in the present invention is not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films and sheets may be used.
또, 양극 물질로는 예컨대 정공 주입이 원활하도록 일 함수가 높은 도전체로 만들어질 수 있으며, 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등이 있으나, 이에 한정되지는 않는다.In addition, the anode material may be made of, for example, a conductor having a high work function to facilitate hole injection, and may include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole or polyaniline; and carbon black, but is not limited thereto.
또, 음극 물질로는 예컨대 전자 주입이 원활하도록 일 함수가 낮은 도전체로 만들어질 수 있으며, 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이에 한정되지는 않는다.In addition, the negative electrode material may be made of, for example, a conductor having a low work function to facilitate electron injection, and may be formed of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead. the same metal or alloys thereof; and a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.
[준비예 1] A1의 합성[Preparation Example 1] Synthesis of A1
질소 기류 하에서 2-(3-bromophenyl)-9,9-dimethyl-9H-fluorene 8.5g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.2-(3-bromophenyl)-9,9-dimethyl-9H-fluorene 8.5g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4- Dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A1, (6.8g, 17.1 mmol, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A1, (6.8 g, 17.1 mmol, yield 70%).
GC-Mass (이론치: 396.3g/mol, 측정치: 396g/mol) GC-Mass (theoretical: 396.3 g/mol, measured: 396 g/mol)
1H-NMR: δ 1.25(s, 12H), 1.73(s, 6H), 7.21~7.39(m, 5H), 7.51~73(m, 6H)1H-NMR: δ 1.25 (s, 12H), 1.73 (s, 6H), 7.21 to 7.39 (m, 5H), 7.51 to 73 (m, 6H)
[준비예 2] A2의 합성[Preparation Example 2] Synthesis of A2
질소 기류 하에서 2-(4-bromophenyl)-9,9-dimethyl-9H-fluorene8.5g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.2-(4-bromophenyl)-9,9-dimethyl-9H-fluorene8.5g (24.4 mmol), 4,4,4',4',5,5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4- Dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A2, (6.8g, 17.1 mmol, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, then water was removed with MgSO 4 and purified by column chromatography to obtain the target compound A2, (6.8 g, 17.1 mmol, yield 70%).
GC-Mass (이론치: 396.3g/mol, 측정치: 396g/mol) GC-Mass (theoretical: 396.3 g/mol, measured: 396 g/mol)
1H-NMR: δ 1.25(s, 12H), 1.73(s, 6H), 7.21~7.41(m, 5H), 7.50~73(m, 6H)1H-NMR: δ 1.25 (s, 12H), 1.73 (s, 6H), 7.21 to 7.41 (m, 5H), 7.50 to 73 (m, 6H)
[준비예 3] A3의 합성[Preparation Example 3] Synthesis of A3
질소 기류 하에서 9-(3-bromophenyl)-7,7-dimethyl-7H-benzo[c]fluorene 9.7g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.9-(3-bromophenyl)-7,7-dimethyl-7H-benzo[c]fluorene 9.7g (24.4 mmol), 4,4,4',4',5,5,5',5' under nitrogen stream -octamethyl-2,2'-bi (1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd (dppf) Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A3, (8.2g, 18.3 mmol, 수율 75%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A3, (8.2 g, 18.3 mmol, yield 75%).
GC-Mass (이론치: 446.4g/mol, 측정치: 446g/mol) GC-Mass (theoretical: 446.4 g/mol, measured: 446 g/mol)
1H-NMR: δ 1.25(s, 12H), 1.73(s, 6H), 7.25~7.45(m, 4H), 7.51~73(m, 5H), 7.88~8.01(m. 4H)1H-NMR: δ 1.25 (s, 12H), 1.73 (s, 6H), 7.25 to 7.45 (m, 4H), 7.51 to 73 (m, 5H), 7.88 to 8.01 (m. 4H)
[준비예 4] A4의 합성[Preparation Example 4] Synthesis of A4
질소 기류 하에서 2-(3-bromophenyl)-9,9-diphenyl-9H-fluorene 11.5g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.2-(3-bromophenyl)-9,9-diphenyl-9H-fluorene 11.5 g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4- Dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A4, (9.1g, 17.5 mmol, 수율 72%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, then water was removed with MgSO 4 and purified by column chromatography to obtain the target compound A4, (9.1 g, 17.5 mmol, yield 72%).
GC-Mass (이론치: 520.5g/mol, 측정치: 521g/mol) GC-Mass (theoretical: 520.5 g/mol, measured: 521 g/mol)
1H-NMR: δ 1.24(s, 12H), 7.21~7.39(m, 9H), 7.49~71(m, 8H), 7.85~8.00(m. 4H)1H-NMR: δ 1.24 (s, 12H), 7.21 to 7.39 (m, 9H), 7.49 to 71 (m, 8H), 7.85 to 8.00 (m. 4H)
[준비예 5] A5의 합성[Preparation Example 5] Synthesis of A5
질소 기류 하에서 2-(3-bromophenyl)-9,9'-spirobi[fluorene] 11.5g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.2-(3-bromophenyl)-9,9'-spirobi[fluorene] 11.5g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4- Dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A5, (9.1g, 17.5 mmol, 수율 72%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A5, (9.1 g, 17.5 mmol, yield 72%).
GC-Mass (이론치: 520.5g/mol, 측정치: 521g/mol) GC-Mass (theoretical: 520.5 g/mol, measured: 521 g/mol)
1H-NMR: δ 1.24(s, 12H), 7.18~7.37(m, 8H), 7.49~71(m, 7H), 7.86~7.98(m. 4H)1H-NMR: δ 1.24 (s, 12H), 7.18 to 7.37 (m, 8H), 7.49 to 71 (m, 7H), 7.86 to 7.98 (m. 4H)
[준비예 6] A6의 합성[Preparation Example 6] Synthesis of A6
질소 기류 하에서 3-(3-bromophenyl)dibenzo[b,d]furan 7.9g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.3-(3-bromophenyl)dibenzo[b,d]furan 7.9g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2 under nitrogen stream '-Bi (1,3,2-dioxaborolane) 7.4 g ( 29.2 mmol), Pd (dppf) Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A6, (6.3g, 17.1 mmol, 수율 70%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A6, (6.3 g, 17.1 mmol, yield 70%).
GC-Mass (이론치: 370.3g/mol, 측정치: 370g/mol) GC-Mass (theoretical: 370.3 g/mol, measured: 370 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.31~7.43(m, 5H), 7.51~75(m, 6H)1H-NMR: δ 1.25 (s, 12H), 7.31 to 7.43 (m, 5H), 7.51 to 75 (m, 6H)
[준비예 7] A7의 합성[Preparation Example 7] Synthesis of A7
질소 기류 하에서 9-(3-bromophenyl)naphtho[2,1-b]benzofuran 9.1g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.9.1 g (24.4 mmol) of 9- (3-bromophenyl) naphtho [2,1-b] benzofuran under a nitrogen stream, 4,4,4',4',5,5,5',5'-octamethyl-2 ,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A7, (7.6g, 18.0 mmol, 수율 74%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, then water was removed with MgSO 4 and purified by column chromatography to obtain the target compound A7, (7.6 g, 18.0 mmol, yield 74%).
GC-Mass (이론치: 420.3g/mol, 측정치: 420g/mol) GC-Mass (theoretical: 420.3 g/mol, measured: 420 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.30~7.51(m, 4H), 7.55~79(m, 5H), 7.95~8.11(m. 4H)1H-NMR: δ 1.25 (s, 12H), 7.30 to 7.51 (m, 4H), 7.55 to 79 (m, 5H), 7.95 to 8.11 (m. 4H)
[준비예 8] A8의 합성[Preparation Example 8] Synthesis of A8
질소 기류 하에서 3-(3-bromophenyl)dibenzo[b,d]thiophene 8.3g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.3-(3-bromophenyl)dibenzo[b,d]thiophene 8.3g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2 under nitrogen stream '-Bi (1,3,2-dioxaborolane) 7.4 g ( 29.2 mmol), Pd (dppf) Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A8, (7.1g, 18.3 mmol, 수율 75%)을 얻었다.After completion of the reaction, extraction was performed with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A8, (7.1 g, 18.3 mmol, yield 75%).
GC-Mass (이론치: 386.31g/mol, 측정치: 386g/mol) GC-Mass (Theory: 386.31 g/mol, Measured: 386 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.34~7.45(m, 5H), 7.52~77(m, 6H)1H-NMR: δ 1.25 (s, 12H), 7.34 to 7.45 (m, 5H), 7.52 to 77 (m, 6H)
[준비예 9] A9의 합성[Preparation Example 9] Synthesis of A9
질소 기류 하에서 2-(3-bromophenyl)-9-phenyl-9H-carbazole 9.7g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.2- (3-bromophenyl) -9-phenyl-9H-carbazole 9.7 g (24.4 mmol) under a nitrogen stream, 4,4,4',4',5,5,5',5'-octamethyl-2, 2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane ( 200 ml) and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A9, (7.8g, 17.5 mmol, 수율 72%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A9, (7.8 g, 17.5 mmol, yield 72%).
GC-Mass (이론치: 243.1g/mol, 측정치: 243g/mol) GC-Mass (theoretical: 243.1 g/mol, measured: 243 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.31~7.43(m, 3H), 7.51~75(m, 9H), 7.83~8.01(m, 4H)1H-NMR: δ 1.25 (s, 12H), 7.31 to 7.43 (m, 3H), 7.51 to 75 (m, 9H), 7.83 to 8.01 (m, 4H)
[준비예 10] A10의 합성[Preparation Example 10] Synthesis of A10
질소 기류 하에서 2-(3-bromophenyl)dibenzo[b,e][1,4]dioxine 11.5g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.11.5 g (24.4 mmol) of 2-(3-bromophenyl)dibenzo[b,e][1,4]dioxine, 4,4,4',4',5,5,5',5'-octa under a nitrogen stream Methyl-2,2'-bi(1,3,2-dioxaborolein) 7.4 g ( 29.2 mmol), Pd(dppf)Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1, 4-dioxane (200 ml) was mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A10, (6.8g, 17.5 mmol, 수율 72%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, then water was removed with MgSO 4 and purified by column chromatography to obtain the target compound A10, (6.8 g, 17.5 mmol, yield 72%).
GC-Mass (이론치: 386.3g/mol, 측정치: 386g/mol) GC-Mass (theoretical: 386.3 g/mol, measured: 386 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.21~7.35(m, 5H), 7.47~7.68(m, 6H)1H-NMR: δ 1.25 (s, 12H), 7.21 to 7.35 (m, 5H), 7.47 to 7.68 (m, 6H)
[준비예 11] A11의 합성[Preparation Example 11] Synthesis of A11
질소 기류 하에서 9-(4-(3-bromophenyl)-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazin-2-yl)-9H-carbazole 13.8g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.9-(4-(3-bromophenyl)-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazin-2-yl)-9H-carbazole 13.8 g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) 7.4 g (29.2 mmol) , Pd(dppf)Cl 2 0.6 g (0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) were mixed and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A11, (10.2g, 16.6 mmol, 수율 68%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A11, (10.2 g, 16.6 mmol, yield 68%).
GC-Mass (이론치: 614.5g/mol, 측정치: 615g/mol) GC-Mass (theoretical: 614.5 g/mol, measured: 615 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.36~7.45(m, 6H), 7.55~78(m, 8H), 7.86~8.02(m, 5H)1H-NMR: δ 1.25 (s, 12H), 7.36 to 7.45 (m, 6H), 7.55 to 78 (m, 8H), 7.86 to 8.02 (m, 5H)
[준비예 12] A12의 합성[Preparation Example 12] Synthesis of A12
질소 기류 하에서 3-(4-((3R,5R)-adamantan-1-yl)phenyl)-9-(4-(3-bromophenyl)-6-(dibenzo[b,d]furan-3-yl)-1,3,5-triazin-2-yl)-9H-carbazole 18.9g(24.4 mmol), 4,4,4',4',5,5,5',5'-옥타메틸-2,2'-바이(1,3,2-디옥사보로레인) 7.4 g( 29.2 mmol), Pd(dppf)Cl2 0.6 g( 0.7 mmol), KOAc 7.2 g( 73.1 mmol) 및 1,4-다이옥산 (200 ml)를 혼합하고 130℃에서 6시간 동안 교반하였다.3-(4-((3R,5R)-adamantan-1-yl)phenyl)-9-(4-(3-bromophenyl)-6-(dibenzo[b,d]furan-3-yl) under nitrogen stream -1,3,5-triazin-2-yl)-9H-carbazole 18.9g (24.4 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2 '-Bi (1,3,2-dioxaborolane) 7.4 g ( 29.2 mmol), Pd (dppf) Cl 2 0.6 g ( 0.7 mmol), KOAc 7.2 g ( 73.1 mmol) and 1,4-dioxane (200 ml) and stirred at 130° C. for 6 hours.
반응 종료 후, 에틸아세테이트로 추출한 다음 MgSO4로 수분을 제거하고 컬럼크로마토그래피로 정제하여 목적 화합물인 A12, (13.7g, 16.6 mmol, 수율 68%)을 얻었다.After completion of the reaction, the mixture was extracted with ethyl acetate, water was removed with MgSO 4 , and purified by column chromatography to obtain the target compound A12, (13.7 g, 16.6 mmol, yield 68%).
GC-Mass (이론치: 824.8g/mol, 측정치: 825g/mol) GC-Mass (theoretical: 824.8 g/mol, measured: 825 g/mol)
1H-NMR: δ 1.25(s, 12H), 7.25~7.41(m, 12H), 7.51~75(m, 16H), 7.86~8.09(m, 9H)1H-NMR: δ 1.25 (s, 12H), 7.25 to 7.41 (m, 12H), 7.51 to 75 (m, 16H), 7.86 to 8.09 (m, 9H)
[합성예 1] R1의 합성[Synthesis Example 1] Synthesis of R1
질소 기류 하에서 A1 6.8g(17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8 g (17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 9.8 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R1, (9.1g, 12.8 mmol, 수율 75%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R1, (9.1 g, 12.8 mmol, yield 75%).
GC-Mass (이론치 : 711.9g/mol, 측정치 : 712g/mol) GC-Mass (theoretical value: 711.9 g/mol, measured value: 712 g/mol)
[합성예 2] R2의 합성[Synthesis Example 2] Synthesis of R2
질소 기류 하에서 A1 6.8g(17.1 mmol), 4-(4-((3S,5S)-adamantan-1-yl)phenyl)-2-(3-bromophenyl)-6-phenylpyrimidine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8g (17.1 mmol), 4-(4-((3S,5S)-adamantan-1-yl)phenyl)-2-(3-bromophenyl)-6-phenylpyrimidine, 9.8g (18.8 mmol) under a nitrogen stream , 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added and stirred at 110° C. for 3 hours. .
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R2, (9.3g, 13.1 mmol, 수율 77%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R2, (9.3 g, 13.1 mmol, yield 77%).
GC-Mass (이론치 : 711.0g/mol, 측정치 : 711g/mol) GC-Mass (theoretical value: 711.0 g/mol, measured value: 711 g/mol)
[합성예 3] R4의 합성[Synthesis Example 3] Synthesis of R4
질소 기류 하에서 A1 6.8g(17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(4-((3r,5r,7r)-adamantan-1-yl)phenyl)-6-(3-bromophenyl)-1,3,5-triazine, 12.3g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8 g (17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(4-((3r,5r,7r)-adamantan-1- yl)phenyl)-6-(3-bromophenyl)-1,3,5-triazine, 12.3 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g ( 51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R4, (10.1g, 11.9 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R4, (10.1 g, 11.9 mmol, yield 70%).
GC-Mass (이론치 : 846.2g/mol, 측정치 : 846g/mol) GC-Mass (theoretical value: 846.2 g/mol, measured value: 846 g/mol)
[합성예 4] R5의 합성[Synthesis Example 4] Synthesis of R5
질소 기류 하에서 A1 6.8g(17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine, 11.5g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8 g (17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-(dibenzo[b,d]furan under nitrogen stream -4-yl)-1,3,5-triazine, 11.5 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) with 80 ml/40 ml /40ml of toluene/H 2 O/ethanol was added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R5, (9.6g, 11.9 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R5, (9.6 g, 11.9 mmol, yield 70%).
GC-Mass (이론치 : 802.0g/mol, 측정치 : 802g/mol) GC-Mass (theoretical value: 802.0 g/mol, measured value: 802 g/mol)
[합성예 5] R7의 합성[Synthesis Example 5] Synthesis of R7
질소 기류 하에서 A1 6.8g(17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-(pyridin-4-yl)-1,3,5-triazine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8g (17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-(pyridin-4-yl)- under nitrogen stream 1,3,5-triazine, 9.8 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80 ml/40 ml/40 ml of toluene/H 2 O/ethanol was added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R7, (8.5g, 11.9 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R7, (8.5 g, 11.9 mmol, yield 70%).
GC-Mass (이론치 : 712.9g/mol, 측정치 : 713g/mol) GC-Mass (theoretical value: 712.9 g/mol, measured value: 713 g/mol)
[합성예 6] R10의 합성[Synthesis Example 6] Synthesis of R10
질소 기류 하에서 A1 6.8g(17.1 mmol), 2-(4-((3r,5r,7r)-adamantan-1-yl)phenyl)-4-(8-bromodibenzo[b,d]furan-2-yl)-6-phenyl-1,3,5-triazine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A1 6.8g (17.1 mmol), 2-(4-((3r,5r,7r)-adamantan-1-yl)phenyl)-4-(8-bromodibenzo[b,d]furan-2-yl under nitrogen stream )-6-phenyl-1,3,5-triazine, 9.8 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80 ml/40 ml /40ml of toluene/H 2 O/ethanol was added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R10, (8.7g, 11.9 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R10, (8.7 g, 11.9 mmol, yield 70%).
GC-Mass (이론치 : 725.9g/mol, 측정치 : 726g/mol) GC-Mass (theoretical value: 725.9 g/mol, measured value: 726 g/mol)
[합성예 7] R12의 합성[Synthesis Example 7] Synthesis of R12
질소 기류 하에서 A2 6.8g(17.1 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A2 6.8 g (17.1 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 9.8 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R12, (9.1g, 12.8 mmol, 수율 75%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R12, (9.1 g, 12.8 mmol, yield 75%).
GC-Mass (이론치 : 711.9g/mol, 측정치 : 712g/mol) GC-Mass (theoretical value: 711.9 g/mol, measured value: 712 g/mol)
[합성예 8] R19의 합성[Synthesis Example 8] Synthesis of R19
질소 기류 하에서 A3 8.2g(18.3 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 10.5g (20.1 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A3 8.2 g (18.3 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under a nitrogen stream triazine, 10.5 g (20.1 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R19, (9.7g, 12.8 mmol, 수율 75%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R19, (9.7 g, 12.8 mmol, yield 75%).
GC-Mass (이론치 : 762.0g/mol, 측정치 : 762g/mol) GC-Mass (theoretical value: 762.0 g/mol, measured value: 762 g/mol)
[합성예 9] R21의 합성[Synthesis Example 9] Synthesis of R21
질소 기류 하에서 A4 9.1g(17.5 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 10.1g (19.3 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A4 9.1 g (17.5 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 10.1 g (19.3 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R21, (10.7g, 12.8 mmol, 수율 73%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R21, (10.7 g, 12.8 mmol, yield 73%).
GC-Mass (이론치 : 836.1g/mol, 측정치 : 836g/mol) GC-Mass (theoretical value: 836.1 g/mol, measured value: 836 g/mol)
[합성예 10] R41의 합성[Synthesis Example 10] Synthesis of R41
질소 기류 하에서 A5 9.1g(17.5 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 10.1g (19.3 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A5 9.1g (17.5 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 10.1 g (19.3 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R41, (11.3g, 13.5 mmol, 수율 77%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R41, (11.3 g, 13.5 mmol, yield 77%).
GC-Mass (이론치 : 834.1g/mol, 측정치 : 834g/mol) GC-Mass (theoretical value: 834.1 g/mol, measured value: 834 g/mol)
[합성예 11] R61의 합성[Synthesis Example 11] Synthesis of R61
질소 기류 하에서 A6 6.3g(17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 9.8g (18.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A6 6.3 g (17.1 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under a nitrogen stream triazine, 9.8 g (18.8 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R61, (8.2g, 11.9 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R61, (8.2 g, 11.9 mmol, yield 70%).
GC-Mass (이론치 : 685.9g/mol, 측정치 : 686g/mol) GC-Mass (theoretical value: 685.9 g/mol, measured value: 686 g/mol)
[합성예 12] R76의 합성[Synthesis Example 12] Synthesis of R76
질소 기류 하에서 A7 7.6g(18.0 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5-triazine, 10.4g (19.8 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A7 7.6 g (18.0 mmol), 2-(4-((3S,5S)-adamantan-1-yl)phenyl)-4-(3-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 10.4g (19.8 mmol), 1.0g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R76, (7.6g, 12.6 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R76, (7.6 g, 12.6 mmol, yield 70%).
GC-Mass (이론치 : 601.7g/mol, 측정치 : 602g/mol) GC-Mass (theoretical value: 601.7 g/mol, measured value: 602 g/mol)
[합성예 13] R81의 합성[Synthesis Example 13] Synthesis of R81
질소 기류 하에서 A8 7.1g(18.3 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, 10.5g (20.1 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A8 7.1 g (18.3 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 10.5 g (20.1 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R81, (9.6g, 13.7 mmol, 수율 75%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R81, (9.6 g, 13.7 mmol, yield 75%).
GC-Mass (이론치 : 701.9g/mol, 측정치 : 702g/mol) GC-Mass (theoretical value: 701.9 g/mol, measured value: 702 g/mol)
[합성예 14] R101의 합성[Synthesis Example 14] Synthesis of R101
질소 기류 하에서 A9 7.8g(17.5 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, 10.1g (19.3 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A9 7.8 g (17.5 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5- under a nitrogen stream triazine, 10.1 g (19.3 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R101, (9.6g, 13.3 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R101, (9.6 g, 13.3 mmol, yield 70%).
GC-Mass (이론치 : 761.0g/mol, 측정치 : 761g/mol) GC-Mass (theoretical value: 761.0 g/mol, measured value: 761 g/mol)
[합성예 15] R126의 합성[Synthesis Example 15] Synthesis of R126
질소 기류 하에서 A10 6.8g(17.5 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, 10.1g (19.3 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A10 6.8g (17.5 mmol), 2-(4-((3R,5R)-adamantan-1-yl)phenyl)-4-(4-bromophenyl)-6-phenyl-1,3,5- under nitrogen stream triazine, 10.1 g (19.3 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added Stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R126, (9.0g, 12.8 mmol, 수율 73%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R126, (9.0 g, 12.8 mmol, yield 73%).
GC-Mass (이론치 : 701.9g/mol, 측정치 : 702g/mol) GC-Mass (theoretical value: 701.9 g/mol, measured value: 702 g/mol)
[합성예 16] R131의 합성[Synthesis Example 16] Synthesis of R131
질소 기류 하에서 A11 10.2g(16.6 mmol), (3R,5R)-1-(4-bromophenyl)adamantane, 5.3g (18.2 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.10.2 g (16.6 mmol) of A11, (3R,5R)-1-(4-bromophenyl)adamantane, 5.3 g (18.2 mmol), 1.0 g (5 mol%) of Pd(PPh 3 ) 4 , and carbonic acid under a nitrogen stream Potassium, 7.1g (51.2mmol) and 80ml/40ml/40ml of toluene/H 2 O/ethanol were added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R131, (8.9g, 12.8 mmol, 수율 77%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R131, (8.9 g, 12.8 mmol, yield 77%).
GC-Mass (이론치 : 698.9g/mol, 측정치 : 699g/mol) GC-Mass (theoretical value: 698.9 g/mol, measured value: 699 g/mol)
[합성예 17] R136의 합성[Synthesis Example 17] Synthesis of R136
질소 기류 하에서 A12 13.7g(16.6 mmol), bromobenzene, 2.9g (18.2 mmol), 1.0g (5 mol%)의 Pd(PPh3)4, 및 탄산칼륨, 7.1g (51.2 mmol)와 80ml/40ml/40ml의 톨루엔/H2O/에탄올을 넣고 110℃에서 3시간 동안 교반하였다.A12 13.7 g (16.6 mmol), bromobenzene, 2.9 g (18.2 mmol), 1.0 g (5 mol %) of Pd(PPh 3 ) 4 , and potassium carbonate, 7.1 g (51.2 mmol) and 80 ml/40 ml/ 40ml of toluene/H 2 O/ethanol was added and stirred at 110° C. for 3 hours.
반응 종료 후, 메틸렌클로라이드를 이용하여 유기층을 분리하고 MgSO4를 사용하여 물을 제거하였다. 유기층의 용매를 제거한 후 컬럼크로마토그래피로 정제하여 목적 화합물인 R136, (9.0 11.6 mmol, 수율 70%)을 얻었다.After completion of the reaction, the organic layer was separated using methylene chloride, and water was removed using MgSO 4 . After removing the solvent of the organic layer, it was purified by column chromatography to obtain the target compound R136, (9.0 11.6 mmol, yield 70%).
GC-Mass (이론치 : 775.0g/mol, 측정치 : 775g/mol) GC-Mass (theoretical value: 775.0 g/mol, measured value: 775 g/mol)
[실시예 1 ~ 2] 녹색 유기 전계 발광 소자의 제작 [Examples 1 to 2] Preparation of green organic electroluminescent device
합성예에서 합성한 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 전계 발광 소자를 제작하였다.After high-purity sublimation purification of the compound synthesized in Synthesis Example by a commonly known method, a green organic electroluminescent device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and vacuum evaporator The substrate was transferred to
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ R131, R136의 각각의 화합물 + 10 % Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다. Each compound of m-MTDATA (60 nm)/TCTA (80 nm)/ R131, R136 + 10% Ir(ppy) 3 (300 nm)/BCP (10 nm)/Alq 3 (30 nm) on the prepared ITO transparent electrode )/LiF (1 nm)/Al (200 nm) were stacked in the order to fabricate an organic electroluminescent device.
m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir(ppy) 3 , CBP and BCP are as follows.
[비교예 1] 녹색 유기 전계 발광 소자의 제작[Comparative Example 1] Preparation of green organic electroluminescent device
발광층 형성시 발광 호스트 물질로서 화합물 R131 대신 CBP를 사용하는 것을 제외하고는 실시예 1과 동일한 과정으로 녹색 유기 전계 발광 소자를 제작하였다.A green organic electroluminescent device was manufactured in the same manner as in Example 1, except that CBP was used instead of compound R131 as a light emitting host material when the light emitting layer was formed.
[평가예 1][Evaluation Example 1]
실시예 1 ~ 2 및 비교예 2에서 제작한 각각의 녹색 유기 전계 발광 소자에 대하여 전류밀도 (10) mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 2에 나타내었다.For each green organic EL device manufactured in Examples 1 to 2 and Comparative Example 2, the driving voltage, current efficiency, and emission peak at a current density of (10) mA/cm 2 were measured, and the results are shown in Table 2 below. indicated.
(V)drive voltage
(V)
(nm)EL peak
(nm)
(cd/A)current efficiency
(cd/A)
상기 표 2에 나타낸 바와 같이, 본 발명에 따른 화합물(R131, R136)을 녹색 유기 EL 소자의 발광층으로 사용하였을 경우(실시예 1 내지 2) 종래 CBP를 사용한 녹색 유기 EL 소자(비교예 1)와 비교해 볼 때 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 2, when the compounds (R131, R136) according to the present invention were used as a light emitting layer of a green organic EL device (Examples 1 and 2), a green organic EL device using conventional CBP (Comparative Example 1) and In comparison, it can be seen that the performance is better in terms of efficiency and driving voltage.
[실시예 3 내지 17] 청색 유기 전계 발광 소자의 제작[Examples 3 to 17] Fabrication of a blue organic electroluminescent device
합성예에서 합성한 화합물을 을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 청색 유기 전계 발광 소자를 제작하였다.After high-purity sublimation purification of the compound synthesized in Synthesis Example by a commonly known method, a blue organic electroluminescent device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음, UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. and transferred the substrate to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (㈜두산전자 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (㈜두산전자, 30nm)/ R1, R2, R4, R5, R7, R10, R12,R19, R21, R41, R61, R76, R81, R101, R126 (5 nm)/Alq3 (25 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제조하였다.On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics Co., Ltd. 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (Doosan Electronics Co., Ltd., 30 nm)/ R1, R2, R4, R5, R7 , R10, R12, R19, R21, R41, R61, R76, R81, R101, R126 (5 nm)/Alq 3 (25 nm)/LiF (1 nm)/Al (200 nm) stacked in the order of organic electroluminescence The device was fabricated.
[비교예 2] 청색 유기 전계 발광 소자의 제작[Comparative Example 2] Fabrication of a blue organic electroluminescent device
전자 수송 보조층 물질로서 R1를 사용하지 않고, 전자 수송층 물질인 Alq3를 25 nm 대신 30 nm로 증착하는 것을 제외하고는, 상기 실시예 3과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was manufactured in the same manner as in Example 3, except that R1 was not used as the electron transport auxiliary layer material, and Alq 3 , the electron transport layer material, was deposited at 30 nm instead of 25 nm.
상기 실시예 3 내지 17 및 비교예 2에서 사용된 NPB, AND 및 Alq3의 구조는 하기와 같다. The structures of NPB, AND, and Alq 3 used in Examples 3 to 17 and Comparative Example 2 are as follows.
[평가예 2] [Evaluation Example 2]
실시예 3 내지 17 및 비교예 2 에서 각각 제조된 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 발광파장, 전류효율을 측정하였고, 그 결과를 하기 표 3에 나타내었다.For the organic electroluminescent devices prepared in Examples 3 to 17 and Comparative Example 2, respectively, the driving voltage, the emission wavelength, and the current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 3 below.
(V)drive voltage
(V)
(nm)luminescence peak
(nm)
(cd/A)current efficiency
(cd/A)
상기 표 3에 나타낸 바와 같이, 본 발명의 화합물을 전자 수송 보조층에 사용한 청색 유기 전계 발광 소자(실시예 3 내지 17)는 전자 수송 보조층이 없는청색 유기 전계 발광 소자(비교예 2)에 비해 전류 효율, 발광 피크 및 구동전압 면에서 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 3, the blue organic electroluminescent device (Examples 3 to 17) using the compound of the present invention as the electron transport auxiliary layer was compared to the blue organic electroluminescent device without the electron transport auxiliary layer (Comparative Example 2). It was found that excellent performance was exhibited in terms of current efficiency, emission peak and driving voltage.
[실시예 18 내지 22] 청색 유기 전계 발광 소자의 제작[Examples 18 to 22] Fabrication of a blue organic electroluminescent device
합성예에서 합성한 화합물을 을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 전계 발광 소자를 제작하였다.The compound synthesized in Synthesis Example was subjected to high-purity sublimation purification by a commonly known method, and then a green organic electroluminescent device was manufactured according to the following procedure.
먼저. ITO (Indium tin oxide)가 1500 Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면, 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후, UV OZONE 세정기(Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.first. A glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc. The substrate was transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (㈜두산전자, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (㈜두산전자, 30nm)/ R2, R7, R12, R76, R101 각각의 화합물 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.On the ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80 nm)/NPB (15 nm)/ADN + 5 % DS-405 (Doosan Electronics, 30 nm)/ R2, R7, R12, R76, Each compound of R101 (30 nm)/LiF (1 nm)/Al (200 nm) was laminated in the order to fabricate an organic electroluminescent device.
[비교예 4] 청색 유기 전계 발광 소자의 제작[Comparative Example 4] Fabrication of a blue organic electroluminescent device
전자 수송층 물질로서 R2 대신 Alq3을 사용하는 것을 제외하고는, 상기 실시예 29와 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was manufactured in the same manner as in Example 29, except that Alq 3 was used instead of R2 as the electron transport layer material.
[비교예 5] 청색 유기 전계 발광 소자의 제작[Comparative Example 5] Fabrication of a blue organic electroluminescent device
전자 수송층 물질로서 R1을 사용하지 않은 것을 제외하고는, 상기 실시예 18과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다.A blue organic electroluminescent device was manufactured in the same manner as in Example 18, except that R1 was not used as the electron transport layer material.
[평가예 3][Evaluation Example 3]
실시예 18 내지 22 및 비교예 2, 3 에서 각각 제작한 청색 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율, 발광파장을 측정하였고, 그 결과를 하기 표 4에 나타내었다.For the blue organic electroluminescent devices prepared in Examples 18 to 22 and Comparative Examples 2 and 3, respectively, the driving voltage, current efficiency, and emission wavelength at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 4 below. indicated.
(V)drive voltage
(V)
(nm)luminescence peak
(nm)
(cd/A)current efficiency
(cd/A)
상기 표 4에 나타낸 바와 같이, 본 발명의 화합물을 전자 수송층에 사용한 청색 유기 전계 발광 소자(실시예 18 내지 22)는 종래의 Alq3를 전자 수송층에 사용한 청색 유기 전계 발광 소자(비교예 4) 및 전자 수송층이 없는 청색 유기 전계 발광 소자(비교예 5)에 비해 구동전압, 발광피크 및 전류효율 면에서 우수한 성능을 나타내는 것을 알 수 있었다.As shown in Table 4, the blue organic electroluminescent device (Examples 18 to 22) using the compound of the present invention for the electron transport layer is a blue organic electroluminescent device using the conventional Alq 3 for the electron transport layer (Comparative Example 4) and It was found that the blue organic EL device without an electron transport layer (Comparative Example 5) exhibited superior performance in terms of driving voltage, emission peak and current efficiency.
10: 양극
20: 음극
30: 유기층
31: 정공 수송층
32: 발광층
33: 정공 수송 보조층
34: 전자 수송층
35: 전자 수송 보조층
36: 전자 주입층
37: 정공 주입층10: positive electrode 20: negative electrode
30: organic layer 31: hole transport layer
32: light emitting layer 33: hole transport auxiliary layer
34: electron transport layer 35: electron transport auxiliary layer
36: electron injection layer 37: hole injection layer
Claims (7)
[화학식 1]
상기 화학식 1에서,
X1 내지 X3은 서로 동일하거나 또는 상이하며, 각각 독립적으로 C(R) 또는 N이나 적어도 하나 이상은 N이고, X2가 C(R)인 경우 인접한 Ar2와 서로 결합하여 축합 고리를 형성할 수 있고;
A는 하기 화학식 2로 표시되는 치환체이며;
[화학식 2]
상기 화학식 2에서,
*는 결합이 이루어지는 부분을 의미하고;
Y는 N(R1), C(R2)(R3), O, S이며;
Z는 직접결합이거나, N(R1), C(R2)(R3), O, S이며;
R1, R2 및 R3은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 치환기 간에는 서로 결합하여 축합 고리를 형성할 수 있고;
X4 내지 X9는 서로 동일하거나 또는 상이하며, 각각 독립적으로 C(R) 또는 N이고, 인접한 C(R)간에 서로 결합하여 축합 고리를 형성할 수 있으며;
R은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며;
L은 직접결합, 치환되거나 비치환된 C6~C60의 아릴렌기, 및 치환되거나 비치환된 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되고;
n은 0 내지 5 이며;
Ar1 과 Ar2는 각각 독립적으로 C6~C60의 아릴기 또는 핵원자수 5 내지 60개의 헤테로아릴기이고;
a, b는 각각 0 또는 1이고, a + b ≥ 1 이다.A compound represented by the following formula (1):
[Formula 1]
In Formula 1,
X 1 to X 3 are the same as or different from each other, and each independently C(R) or N, but at least one is N, and when X 2 is C(R), they combine with adjacent Ar2 to form a condensed ring. can;
A is a substituent represented by the following formula (2);
[Formula 2]
In Formula 2,
* means the part where the bond is made;
Y is N(R 1 ), C(R 2 )(R 3 ), O, S;
Z is a direct bond or N(R 1 ), C(R 2 )(R 3 ), O, S;
R 1 , R 2 and R 3 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C 6 ~ C 60 aryl group, heteroaryl group of 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 Aryloxy group, C 3 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 Aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group, and adjacent substituents are bonded to each other to form a condensed ring, ;
X 4 to X 9 are the same as or different from each other, and each independently represents C(R) or N, and may be bonded to each other between adjacent C(R) to form a condensed ring;
R is hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nucleus A heterocycloalkyl group having 3 to 40 atoms, a C 6 to C 60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C 1 to C 40 alkyloxy group, a C 6 to C 60 aryloxy group, C 3 ~ C 40 Alkylsilyl group, C 6 ~ C 60 Arylsilyl group, C 1 ~ C 40 Alkyl boron group, C 6 ~ C 60 Aryl boron group, C 6 ~ C 60 Aryl phosphine group, C 6 ~ C 60 An aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group;
L is selected from the group consisting of a direct bond, a substituted or unsubstituted C 6 ~ C 60 arylene group, and a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms;
n is 0 to 5;
Ar 1 and Ar 2 are each independently a C 6 ~ C 60 aryl group or a heteroaryl group having 5 to 60 nuclear atoms;
a and b are 0 or 1, respectively, and a + b ≥ 1.
상기 A는 하기 A-1 내지 A-18로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물:
A-1 내지 A-18에서,
*는 결합이 이루어지는 부분을 의미하고,
X4 내지 X9는 화학식 2에서 정의한 바와 같다.According to claim 1,
Wherein A is a compound, characterized in that selected from the group consisting of A-1 to A-18:
In A-1 to A-18,
* means the part where the bond is made,
X 4 to X 9 are as defined in Formula 2.
상기 Ar1 또는 Ar2는 아릴기, 디벤조퓨란기, 피리딜기 및 카바졸기로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물. According to claim 1,
The Ar 1 or Ar 2 is a compound, characterized in that selected from the group consisting of an aryl group, a dibenzofuran group, a pyridyl group and a carbazole group.
상기 L은 직접결합, 페닐렌기, 비페닐기, 피리디닐렌기, 디벤조퓨란닐렌기 또는 카바졸릴렌기인 것을 특징으로 하는 화합물.According to claim 1,
wherein L is a direct bond, a phenylene group, a biphenyl group, a pyridinylene group, a dibenzofurannylene group, or a carbazolylene group.
상기 화합물은 아래의 화합물로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.
The compound is a compound, characterized in that selected from the group consisting of the following compounds.
상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항의 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is an organic electroluminescent device comprising a compound represented by the formula (1) of claim 1.
상기 유기물층은 정공 주입층, 정공 수송층, 정공 수송 보조층, 전자 수송층, 전자 수송 보조층 및 발광층으로 이루어진 군에서 선택되는 하나 이상의 층을 포함하는, 유기 전계 발광 소자.7. The method of claim 6,
The organic material layer is an organic electroluminescent device comprising one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron transport layer, an electron transport auxiliary layer and a light emitting layer.
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| WO2024203493A1 (en) * | 2023-03-30 | 2024-10-03 | 日鉄ケミカル＆マテリアル株式会社 | Organic electroluminescent element |
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