KR20200076383A - 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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- KR20200076383A KR20200076383A KR1020180165434A KR20180165434A KR20200076383A KR 20200076383 A KR20200076383 A KR 20200076383A KR 1020180165434 A KR1020180165434 A KR 1020180165434A KR 20180165434 A KR20180165434 A KR 20180165434A KR 20200076383 A KR20200076383 A KR 20200076383A
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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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.
유기 전계 발광(electroluminescent, EL) 소자는, 전계를 인가함으로써 양극으로부터 주입된 정공과 음극으로부터 주입된 전자의 재결합 에너지에 의해 형광성 물질이 발광하는 원리를 이용한 자발광 소자이다.An organic electroluminescent (EL) device is a self-luminous device using a principle in which a fluorescent material emits light by recombination energy between holes injected from an anode and electrons injected from a cathode by applying an electric field.
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.With the observation of organic thin film emission of Bernasose in the 1950s as a starting point, research on organic electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals continued in 1965, followed by Tang in 1987. ), an organic electroluminescent device having a stacked structure divided into a functional layer of a hole layer and a light emitting layer was proposed. Since then, in order to make a high-efficiency, high-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 specialized materials used therein.
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 the 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 the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground state, light is emitted. At this time, 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 its 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 luminescent material may be divided into blue, green, and red luminescent materials, and yellow and orange luminescent materials for realizing a better natural color according to the luminous color. In addition, a host/dopant system may be used as a light emitting material to increase color purity and increase light emission efficiency through energy transfer.
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 that of the fluorescence, research on phosphorescent host materials as well as phosphorescent dopants has been conducted.
현재까지 정공 주입층, 정공 수송층, 전자 수송 보조층, 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.To date, NPB, BCP, Alq 3 and the like are widely known as the hole injection layer, the hole transport layer, the electron transport auxiliary layer, and the electron transport layer material, and anthracene derivatives have been reported as the light emitting layer material. In particular, metal complex compounds containing Ir, such as Firpic, Ir(ppy) 3 , (acac)Ir(btp) 2, etc., 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 layers have an advantage in terms of luminescence properties, but are not satisfactory in terms of lifespan of an organic electroluminescent device because the glass transition temperature is low and thermal stability is very poor. Therefore, development of an organic material layer material having excellent performance is required.
본 발명은 열안정성 및 발광능이 우수한 인광 발광 재료를 유기 전계 발광 소자에 적용하여, 저전압 구동은 물론 장수명의 전자 주입 및 수송능 등이 우수한 신규 유기 화합물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a novel organic compound which is excellent in thermal stability and luminescence ability by applying a phosphorescence emitting material to an organic electroluminescent device, and is excellent in low voltage driving and long life electron injection and transport ability.
상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1 또는 화학식 2로 표시되는 화합물을 제공한다.In order to achieve the above object, the present invention provides a compound represented by the following formula 1 or formula 2.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 또는 화학식 2에서,In Formula 1 or Formula 2,
R1 내지 R12는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며, 인접한 기는 서로 결합하여 지방족 또는 방향족 고리를 형성하고,R 1 to R 12 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, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 ~ C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkyl silyl 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 Arylphosphine group, C 6 ~ C 60 Mono or diarylphosphinyl group and C 6 ~ C 60 arylamine group is selected from the group consisting of, adjacent groups combine with each other to form an aliphatic or aromatic ring,
Ar은 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며,Ar is a C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 Aryl group of ~C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 ~C 40 , aryloxy group of C 6 ~C 60 , alkylsilyl group of C 3 ~C 40 , C 6 ~ C aryl silyl group of 60, group alkylboronic of C 1 ~ C 40, C 6 ~ C group 60 arylboronic of, C 6 ~ mono or diaryl phosphine of C 60 aryl phosphine group, C 6 ~ C 60 of the blood It is selected from the group consisting of an arylamine group and a C 6 ~ C 60 ,
L은 단일결합 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며,L is selected from the group consisting of a single bond or an arylene group of C 6 ~ C 18 and a heteroarylene group having 5 to 18 nuclear atoms,
상기 L의 아릴렌기, 헤테로아릴렌기 및 R1 내지 R12, Ar 의 알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 시클로알킬기, 헤테로시클로알킬기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 모노 또는 디아릴포스피닐기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.The arylene group of L, heteroarylene group and R 1 to R 12 , Ar alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine Group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group, a mono or diarylphosphinyl group, and an arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 60 aryl group, a nuclear number of 5 to 60 heteroaryl group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 1 ~ C 40 alkylsilyl group, C 1 C ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 arylphosphine group, C 6 ~ C 60 mono or diarylphosphinyl group and C 6 ~ C 60 arylsilyl When substituted with one or more substituents selected from the group consisting of groups or unsubstituted, and substituted with a plurality of substituents, they may be the same or different from each other.
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 one or more organic material layers interposed between the anode and the cathode, wherein at least one of the organic material layers of the one or more layers 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 straight or branched saturated hydrocarbon having 1 to 40 carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, 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 (alkenyl)" in the present invention is a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms, having at least one carbon-carbon double bond, examples of which are vinyl (vinyl), Allyl, isopropenyl, 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 chain unsaturated hydrocarbon having 2 to 40 carbon atoms, having one or more carbon-carbon triple bonds, and examples thereof include 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, which is a single ring or a combination of two or more rings. In addition, two or more rings are condensed with each other, and contain only carbon as a ring forming atom (for example, the number of carbon atoms may be 8 to 60), and the entire molecule is monovalent with non-aromacity. Substituents may also be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, anthryl, and fluorenyl, but are not limited thereto.
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. At this time, 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 to or condensed with each other, and as ring-forming atoms, hetero atoms selected from among N, O, P, S, and Se other than carbon are included, and the whole molecule is non-aromatic (non-aromatic). It is interpreted as including a monovalent group having aromacity). Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl; Polysaises such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl Click rings; 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
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 phenyloxy, naphthyloxy, diphenyloxy, and the like, but are not limited thereto.
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 alkyls, and a linear, branched or cyclic structure It is 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 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, It is substituted with a hetero atom such as S or Se. Examples of such heterocycloalkyl include morpholine, piperazine, and the like, but are not limited thereto.
본 발명에서의 "알킬실릴"은 탄소수 1 내지 40개의 알킬로 치환된 실릴이고, "아릴실릴"은 탄소수 5 내지 60개의 아릴로 치환된 실릴을 의미한다."Alkylsilyl" in the present invention is silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means 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 is excellent in thermal stability, carrier transport ability, luminescence ability, and the like, 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, 열적 안정성 등의 측면이 크게 향상되어 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다.In addition, the organic electroluminescent device including the compound of the present invention in an organic material layer has significantly improved aspects such as light emission performance, driving voltage, life, efficiency, and thermal stability, and thus can be effectively applied to a full color display panel.
도 1은 본 발명의 일 실시예에 따른 유기 전계 발광 소자의 단면도를 나타낸 것이다.
도 2는 본 발명의 일 실시예에 따른 유기 전계 발광 소자의 단면도를 나타낸 것이다. 1 is a sectional view showing an organic electroluminescent device according to an embodiment of the present invention.
2 is a sectional view showing an organic electroluminescent device according to an embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. 신규 유기 화합물1. New organic compounds
본 발명의 신규 화합물은 하기 화학식 1 또는 화학식 2로 표시될 수 있다:The novel compounds of the present invention may be represented by the following Formula 1 or Formula 2:
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 또는 화학식 2에서,In Formula 1 or Formula 2,
R1 내지 R12는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며, 인접한 기는 서로 결합하여 지방족 또는 방향족 고리를 형성하고,R 1 to R 12 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, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 ~ C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkyl silyl 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 Arylphosphine group, C 6 ~ C 60 Mono or diarylphosphinyl group and C 6 ~ C 60 arylamine group is selected from the group consisting of, adjacent groups combine with each other to form an aliphatic or aromatic ring,
Ar은 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며,Ar is a C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 Aryl group of ~C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 ~C 40 , aryloxy group of C 6 ~C 60 , alkylsilyl group of C 3 ~C 40 , C 6 ~ C aryl silyl group of 60, group alkylboronic of C 1 ~ C 40, C 6 ~ C group 60 arylboronic of, C 6 ~ mono or diaryl phosphine of C 60 aryl phosphine group, C 6 ~ C 60 of the blood It is selected from the group consisting of an arylamine group and a C 6 ~ C 60 ,
L은 단일결합 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며,L is selected from the group consisting of a single bond or an arylene group of C 6 ~ C 18 and a heteroarylene group having 5 to 18 nuclear atoms,
상기 L의 아릴렌기, 헤테로아릴렌기 및 R1 내지 R12, Ar 의 알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 시클로알킬기, 헤테로시클로알킬기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 모노 또는 디아릴포스피닐기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.The arylene group of L, heteroarylene group and R 1 to R 12 , Ar alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine Group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group, a mono or diarylphosphinyl group, and an arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 60 aryl group, a nuclear number of 5 to 60 heteroaryl group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 1 ~ C 40 alkylsilyl group, C 1 C ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 arylphosphine group, C 6 ~ C 60 mono or diarylphosphinyl group and C 6 ~ C 60 arylsilyl When substituted with one or more substituents selected from the group consisting of groups or unsubstituted, and substituted with a plurality of substituents, they may be the same or different from each other.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화학식 1은 하기 화학식 3 또는 화학식 4로 표시될 수 있다.According to one preferred embodiment of the present invention, Formula 1 may be represented by Formula 3 or Formula 4 below.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
상기 화학식 3 내지 4에서, L과 Ar은 상기 화학식 1에서 정의된 바와 같다.In Chemical Formulas 3 to 4, L and Ar are as defined in Chemical Formula 1.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화학식 2는 하기 화학식 5 또는 화학식 6으로 표시될 수 있다.According to a preferred embodiment of the present invention, Formula 2 may be represented by Formula 5 or Formula 6 below.
[화학식 5][Formula 5]
[화학식 6][Formula 6]
상기 화학식 5 내지 6에서, L과 Ar은 상기 화학식 2에서 정의된 바와 같다.In Chemical Formulas 5 to 6, L and Ar are as defined in Chemical Formula 2.
본 발명의 바람직한 한 구현 예에 따르면, 상기 Ar은 하기 하기 A-1 내지 A-4 중에서 선택되는 치환기일 수 있다.According to a preferred embodiment of the present invention, Ar may be a substituent selected from the following A-1 to A-4.
상기 A-1 내지 A-4에서, *는 결합이 이루어지는 부분이고, In A-1 to A-4, * is a portion where a bond is made,
X1과 X2 중 어느 하나는 N이고 나머지는 C1이고, 상기 C1은 Ar1과 결합하며, X3 내지 X5은 N 또는 C(R13)이나, 적어도 둘 이상은 N이고, Z는 O 또는 S이며, Ar1 내지 Ar3은 각각 독립적으로 치환 또는 비치환된 아릴기이거나, 치환 또는 비치환된 헤테로아릴기이고, R13은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된다. One of X 1 and X 2 is N and the other is C 1 , C 1 is bonded to Ar 1 , X 3 to X 5 are N or C(R 13 ), or at least two or more are N, Z Is O or S, Ar 1 to Ar 3 are each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R 13 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, a number of nuclear atoms of 3 to 40 hetero cycloalkyl group, C 6 ~ C 60 Aryl group of, a heteroaryl group having 5 to 60 nuclear atoms, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkyl silyl 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 arylphosphine group, C 6 ~ C 60 mono or diarylphosphinyl group and C 6 ~ C 60 It is selected from the group consisting of arylamine groups.
본 발명의 바람직한 한 구현 예에 따르면, 상기 A-1 내지 A-3의 Ar1은 하기 B-1 내지 B-3 중에서 선택될 수 있다.According to a preferred embodiment of the present invention, Ar 1 of A-1 to A-3 may be selected from the following B-1 to B-3.
상기 B-1 내지 B-3에서, *는 결합이 이루어지는 부분이다.In B-1 to B-3, * is a portion where a bond is formed.
본 발명의 바람직한 한 구현 예에 따르면, 상기 A-4의 Ar2 또는 Ar3은 하기 C-1 내지 C-4 중에서 선택되는 치환기일 수 있다.According to a preferred embodiment of the present invention, Ar 2 or Ar 3 of A-4 may be a substituent selected from the following C-1 to C-4.
상기 C-1 내지 C-4에서, *는 결합이 이루어지는 부분이다.In C-1 to C-4, * is a portion where a bond is formed.
본 발명의 바람직한 한 구현 예에 따르면, 상기 L은 단일결합 또는 페닐렌일 수 있다.According to a preferred embodiment of the present invention, L may be a single bond or phenylene.
본 발명의 바람직한 한 구현 예에 따르면, 상기 화합물은 아래의 화합물로 이루어진 군에서 선택될 수 있다.According to one preferred embodiment of the present invention, the compound may be selected from the group consisting of the following compounds.
화학식 1 또는 화학식 2로 대표되는 본 발명의 화합물은 일반적인 합성방법에 따라 합성될 수 있다(Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95: 2457 (1995) 등 참조). 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다.The compound of the present invention represented by Formula 1 or Formula 2 may be synthesized according to general synthetic methods ( Chem. Rev. , 60 :313 (1960); J. Chem. SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995), etc.). The detailed synthesis process for the compounds of the present invention will be described in detail in the synthesis examples described later.
2. 유기 전계 발광 소자2. Organic electroluminescent device
한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1 또는 화학식 2로 대표되는 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 Chemical Formula 1 or Chemical Formula 2 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 It includes a compound represented by the formula (1). At this time, the compound may be used alone or in combination of two or more.
상기 1층 이상의 유기물층은 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 수송 보조층 및 전자 주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층이 상기 화학식 1 내지 2로 표시되는 화합물을 포함할 수 있으며, 보다 바람직하게는 상기 유기물층에서 전자 수송층, 전자 수송 보조층 및 전자 주입층 중 어느 하나 이상이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, wherein at least one organic material layer is a compound represented by Chemical Formulas 1 to 2 It may include, more preferably, any one or more of the electron transport layer, the electron transport auxiliary layer and the electron injection layer in the organic material layer may include a compound represented by the formula (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 Figure 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, 상기 전자 수송층 (34)과 발광층(32) 사이에 전자 수송 보조층(35)을 더 포함할 수 있다. 상기 발광층(32)으로 유기 발광 소자 내에서 이온화 포텐셜 레벨을 타고 이동하는 정공이 전자 수송 보조층(35)의 의 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, an electron transport
본 발명에서 상기 화학식 1 또는 2로 대표되는 화합물은 나프탈렌(Naphthalene)을 기준으로 인덴(Inden)과 인돌(Indole)이 축합되어 6환 내지 다환의 기본 골격을 이룬다. 기본 골격의 나프탈렌은 기존의 페닐 축합 골격에 비해 depo.와 구동전압을 낮추는 특성을 보이며, 특히 인덴에 축합된 싸이클로헥실(Cyclohexyl)로 인해 dialkyl 혹은 diarly 일때 보다 열적으로 안정성을 가지며, 그로 인해 효율의 증가와 장수명의 특성을 보이게 된다.In the present invention, the compound represented by Formula 1 or 2 is condensed with Inden and Indole based on Naphthalene to form a basic skeleton of 6 to polycyclic rings. The naphthalene of the basic skeleton shows lower depo. and driving voltage compared to the existing phenyl condensation skeleton, and is more thermally stable when dialkyl or diarly due to cyclohexyl condensed in inden. It shows the characteristics of increase and long life.
이러한 구조의 화학식 1 또는 2로 표시되는 전기화학적으로 안정하고, 전자 이동성이 우수할 뿐만 아니라 높은 유리 전이온도 및 열적 안정이 우수하며, 전자주입 및 전자 수송층에 더욱 적합한 물리화학적 성질을 가진다.The electrochemically stable structure represented by Chemical Formula 1 or 2, excellent in electron mobility, as well as high glass transition temperature and thermal stability, has more suitable physicochemical properties for electron injection and electron transport layers.
따라서, 본 발명의 화학식 1 또는 2 구조의 화합물들은 유기 전계 발광 소자에 사용할 경우, 우수한 열적 안정성 및 캐리어 수송능(특히, 전자 수송능 및 발광능)을 기대할 수 있을 뿐만 아니라 소자의 구동전압, 효율, 수명 등이 향상될 수 있다.Therefore, when the compounds of Formula 1 or 2 structure of the present invention are used in an organic electroluminescent device, excellent thermal stability and carrier transport capacity (especially electron transport capacity and luminous capacity) can be expected, as well as driving voltage and efficiency of the device. , Lifespan, etc. can be improved.
본 발명의 화학식 1 또는 2로 대표되는 화합물은 유기 전계 발광 소자의 유기물층(30) 재료, 바람직하게는 발광층(32) 재료(청색의 인광 호스트 재료), 전자 수송층(34), 전자 주입층(36) 재료, 정공 수송 보조층(33) 재료, 전자 수송 보조층(35) 재료, 더욱 바람직하게는 발광층(32) 재료, 전자 수송층(34) 재료, 전자 수송 보조층(35) 재료로 사용될 수 있다. 또한, 상기 화학식 1 또는 2의 화합물을 포함하는 유기 전계 발광 소자는 성능 및 수명 특성이 크게 향상될 수 있고, 이러한 유기 전계 발광 소자가 적용된 풀 칼라 유기 발광 패널도 성능이 극대화될 수 있다.The compound represented by the formula (1) or (2) of the present invention is an
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 include an anode, one or more organic material layers, and a cathode sequentially stacked as described above, and may further include an insulating layer or an adhesive layer at the interface between the electrode and the organic material layer.
본 발명의 유기 전계 발광 소자는 상기 유기물층 중 적어도 하나 이상(예컨대, 전자 수송 보조층)이 상기 화학식 1 또는 2로 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 is a material known in the art, except that at least one (eg, electron transport auxiliary layer) of the organic material layer is formed to contain the compound represented by Formula 1 or 2, and It can be produced by forming another organic material layer and an electrode using a method.
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 spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer, but are not limited thereto.
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 a silicon wafer, quartz, glass plate, metal plate, plastic film and sheet 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 positive electrode material may be made of a conductor having a high work function to facilitate hole injection, for example, a metal such as vanadium, chromium, copper, zinc, or gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide 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.Further, the negative electrode material may be made of a conductor having a low work function to facilitate electron injection, for example, 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 only to illustrate the present invention, the present invention is not limited by the following examples.
[준비예][Preparation example]
[준비예 1] 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] 의 합성[Preparation Example 1] Synthesis of 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane]
라운드 플라스크에 5-bromo-7H-benzo[c]fluorine (100.0 g, 338.8 mmol)을 넣고 THF 1L에 녹인다. 0℃ 저온에서 Potassium tert-Butoxide (112.2 g, 846.9 mmol) (이하 KOtBu)를 15분간 천천히 나누어 넣어 준다. 이후 10분간 교반 시켜 준다. 1,5-dibromopentane (77.9 g, 338.8 mmol)을 5분간 적가 한다. 상온으로 반응 온도를 올려 12시간 동안 교반 하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (82.8 g, 수율 67 %)을 얻었다.Put 5-bromo-7H-benzo[c]fluorine (100.0 g, 338.8 mmol) in a round flask and dissolve in 1 L of THF. Potassium tert-Butoxide (112.2 g, 846.9 mmol) (hereinafter referred to as KOtBu) is slowly divided into 15 minutes at 0°C. Then, stir for 10 minutes. 1,5-dibromopentane (77.9 g, 338.8 mmol) was added dropwise over 5 minutes. The reaction temperature was raised to room temperature and stirred for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (82.8 g, yield 67%) was obtained using column chromatography.
1H-NMR: δ 1.46-2.15(m, 10H), 7.36-7.38(m, 3H), 7.57(d, 1H), 7.73(s, 1H), 7.74(d, 1H), 8.16(d, 1H), 8.24(d, 1H), 8.84(d, 1H) 1 H-NMR: δ 1.46-2.15 (m, 10H), 7.36-7.38 (m, 3H), 7.57 (d, 1H), 7.73 (s, 1H), 7.74 (d, 1H), 8.16 (d, 1H) ), 8.24(d, 1H), 8.84(d, 1H)
[LCMS] : 362 [LCMS]: 362
[준비예 2] 4,4,5,5-tetramethyl-2-(spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-yl)-1,3,2-dioxaborolane 의 합성[Preparation Example 2] Synthesis of 4,4,5,5-tetramethyl-2-(spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-yl)-1,3,2-dioxaborolane
5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (80.0g, 220.2 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (67.1 g, 264.24 mmol)및 Pd(dppf)2 (5.4 g, 6.6 mmol), KOAc (43.2 g, 440.4 mmol)을 Toluene 1000ml, EtOH 200ml, H2O 200ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 4,4,5,5-tetramethyl-2-(spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-yl)-1,3,2-dioxaborolane (74.1 g, 수율 82 %)을 얻었다.5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (80.0g, 220.2 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2 '-bi(1,3,2-dioxaborolane) (67.1 g, 264.24 mmol) and Pd(dppf) 2 (5.4 g, 6.6 mmol), KOAc (43.2 g, 440.4 mmol) Toluene 1000ml, EtOH 200ml, H 2 O was added to 200 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound is 4,4,5,5-tetramethyl-2-(spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-yl) using column chromatography. -1,3,2-dioxaborolane (74.1 g, yield 82%) was obtained.
1H-NMR: δ 1.20(s, 12H), 1.46-2.15(m, 10H), 7.36-7.40(m, 3H), 7.57(d, 1H), 7.69(s, 1H), 7.74(d, 1H), 8.05(d, 1H), 8.24(d, 1H), 8.85(d, 1H) 1 H-NMR: δ 1.20 (s, 12H), 1.46-2.15 (m, 10H), 7.36-7.40 (m, 3H), 7.57 (d, 1H), 7.69 (s, 1H), 7.74 (d, 1H) ), 8.05(d, 1H), 8.24(d, 1H), 8.85(d, 1H)
[LCMS] : 410 [LCMS]: 410
[준비예 3] 5-(2-nitrophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexane]의 합성[Preparation Example 3] Synthesis of 5-(2-nitrophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexane]
준비예 2 의 목적 화합물 (50.0g, 121.8 mmol), 1-bromo-2-nitrobenzene (24.6 g, 121.8 mmol) 및 Pd(PPh3)4 (7.0 g, 6.1 mmol), K2CO3 (50.5 g, 365.5 mmol)을 Toluene 500ml, EtOH 100ml, H2O 100ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 5-(2-nitrophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (36.1 g, 수율 73 %)을 얻었다.The desired compound of Preparation Example 2 (50.0 g, 121.8 mmol), 1-bromo-2-nitrobenzene (24.6 g, 121.8 mmol) and Pd(PPh 3 ) 4 (7.0 g, 6.1 mmol), K 2 CO 3 (50.5 g , 365.5 mmol) was added to 500 ml of Toluene, 100 ml of EtOH, and 100 ml of H 2 O and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, 5-(2-nitrophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (36.1 g, yield 73%) was obtained using column chromatography.
1H-NMR: δ 1.46-2.15(m, 10H), 7.27-7.29(m, 2H), 7.38(m, 1H), 7.57(d, 1H), 7.68(s, 1H), 7.72-7.74(m, 2H), 7.89(m, 1H), 8.00-8.03(m, 2H), 8.24(d, 1H), 8.88-8.90(d, 2H) 1 H-NMR: δ 1.46-2.15 (m, 10H), 7.27-7.29 (m, 2H), 7.38 (m, 1H), 7.57 (d, 1H), 7.68 (s, 1H), 7.72-7.74 (m , 2H), 7.89(m, 1H), 8.00-8.03(m, 2H), 8.24(d, 1H), 8.88-8.90(d, 2H)
[LCMS] : 405 [LCMS]: 405
[준비예 4] 13H-spiro[benzo[c]indeno[2,1-a]carbazole-14,1'-cyclohexane]의 합성[Preparation Example 4] Synthesis of 13H-spiro[benzo[c]indeno[2,1-a]carbazole-14,1'-cyclohexane]
준비예 3 의 목적 화합물 (30.0g, 74.0 mmol)과 Triphenylphosphine (이하 PPh3) (48.5 g, 184.9 mmol) o-DCB 300ml에 넣고 18시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 13H-spiro[benzo[c]indeno[2,1-a]carbazole-14,1'-cyclohexane] (21.5 g, 수율 78 %)을 얻었다.The target compound of Preparation Example 3 (30.0 g, 74.0 mmol) and Triphenylphosphine (hereinafter PPh3) (48.5 g, 184.9 mmol) were placed in 300 ml of o-DCB and heated to reflux for 18 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, using column chromatography, the target compound, 13H-spiro[benzo[c]indeno[2,1-a]carbazole-14,1'-cyclohexane] (21.5 g, yield 78%) Got
1H-NMR: δ 1.43-2.15(m, 10H), 7.20(m, 1H), 7.38(m, 1H), 7.50-7.63(m, 5H), 7.74(d, 1H), 8.19-8.24(m, 2H), 8.97(m, 2H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.20 (m, 1H), 7.38 (m, 1H), 7.50-7.63 (m, 5H), 7.74 (d, 1H), 8.19-8.24 (m , 2H), 8.97(m, 2H), 11.70(s, 1H)
[LCMS] : 373 [LCMS]: 373
[준비예 5] 5-(2-nitronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane]의 합성[Preparation Example 5] Synthesis of 5-(2-nitronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane]
준비예 2 의 목적 화합물 (50.0g, 121.8 mmol), 1-bromo-2-nitronaphthalene (30.7 g, 121.8 mmol) 및 Pd(PPh3)4 (7.0 g, 6.1 mmol), K2CO3 (50.5 g, 365.5 mmol)을 Toluene 500ml, EtOH 100ml, H2O 100ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 5-(2-nitronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (34.4 g, 수율 62 %)을 얻었다.The desired compound of Preparation Example 2 (50.0 g, 121.8 mmol), 1-bromo-2-nitronaphthalene (30.7 g, 121.8 mmol) and Pd(PPh 3 ) 4 (7.0 g, 6.1 mmol), K 2 CO 3 (50.5 g , 365.5 mmol) was added to 500 ml of Toluene, 100 ml of EtOH, and 100 ml of H 2 O and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, using column chromatography, the target compound, 5-(2-nitronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (34.4 g, yield 62% ).
1H-NMR: δ 1.43-2.15(m, 10H), 7.27-7.44(m, 4H), 7.57(m, 1H), 7.68(s, 1H), 7.71-7.74(m, 2H), 8.08(d, 1H), 8.24-8.25(m, 2H), 8.76(d, 1H), 8.88-8.90(d, 2H), 9.10(d, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.27-7.44 (m, 4H), 7.57 (m, 1H), 7.68 (s, 1H), 7.71-7.74 (m, 2H), 8.08 (d , 1H), 8.24-8.25(m, 2H), 8.76(d, 1H), 8.88-8.90(d, 2H), 9.10(d, 1H)
[LCMS] : 455 [LCMS]: 455
[준비예 6] 11'H-spiro[cyclohexane-1,12'-dibenzo[c,g]indeno[2,1-a]carbazole]의 합성[Preparation Example 6] Synthesis of 11'H-spiro[cyclohexane-1,12'-dibenzo[c,g]indeno[2,1-a]carbazole]
준비예 5 의 목적 화합물 (30.0g, 65.8 mmol)과 PPh3 (43.2 g, 164.6 mmol) o-DCB 300ml에 넣고 18시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 11'H-spiro[cyclohexane-1,12'-dibenzo[c,g]indeno[2,1-a]carbazole] (19.2 g, 수율 69 %)을 얻었다.The target compound of Preparation Example 5 (30.0 g, 65.8 mmol) and PPh 3 (43.2 g, 164.6 mmol) were placed in 300 ml of o-DCB and heated to reflux for 18 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound 11'H-spiro[cyclohexane-1,12'-dibenzo[c,g]indeno[2,1-a]carbazole] (19.2 g, using column chromatography) Yield 69%).
1H-NMR: δ 1.43-2.15(m, 10H), 7.38(m, 1H), 7.53-7.74(m, 8H), 7.99(d, 1H), 8.24(d, 1H), 8.54(d, 1H), 8.97(m, 2H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.38 (m, 1H), 7.53-7.74 (m, 8H), 7.99 (d, 1H), 8.24 (d, 1H), 8.54 (d, 1H) ), 8.97 (m, 2H), 11.70 (s, 1H)
[LCMS] : 423 [LCMS]: 423
[준비예 7] 5-(1-nitronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane]의 합성[Preparation Example 7] Synthesis of 5-(1-nitronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane]
준비예 2 의 목적 화합물 (50.0g, 121.8 mmol), 2-bromo-1-nitronaphthalene (30.7 g, 121.8 mmol) 및 Pd(PPh3)4 (7.0 g, 6.1 mmol), K2CO3 (50.5 g, 365.5 mmol)을 Toluene 500ml, EtOH 100ml, H2O 100ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 5-(1-nitronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (36.1 g, 수율 65 %)을 얻었다.The desired compound of Preparation Example 2 (50.0 g, 121.8 mmol), 2-bromo-1-nitronaphthalene (30.7 g, 121.8 mmol) and Pd(PPh 3 ) 4 (7.0 g, 6.1 mmol), K 2 CO 3 (50.5 g) , 365.5 mmol) was added to 500 ml of Toluene, 100 ml of EtOH, and 100 ml of H 2 O and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound was 5-(1-nitronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexane] (36.1 g, yield 65%) using column chromatography. ).
1H-NMR: δ 1.43-2.15(m, 10H), 7.27-7.38(m, 3H), 7.57(m, 2H), 7.68(s, 1H), 7.74-7.81(m, 3H), 8.24-8.29(m, 2H), 8.61(d, 1H), 8.88-8.90(m, 3H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.27-7.38 (m, 3H), 7.57 (m, 2H), 7.68 (s, 1H), 7.74-7.81 (m, 3H), 8.24-8.29 (m, 2H), 8.61 (d, 1H), 8.88-8.90 (m, 3H)
[LCMS] : 455 [LCMS]: 455
[준비예 8] 16'H-spiro[cyclohexane-1,15'-dibenzo[c,i]indeno[2,1-a]carbazole]의 합성[Preparation Example 8] Synthesis of 16'H-spiro[cyclohexane-1,15'-dibenzo[c,i]indeno[2,1-a]carbazole]
준비예 7 의 목적 화합물 (30.0 g, 65.8 mmol)과 PPh3 (43.2 g, 164.6 mmol) o-DCB 300ml에 넣고 18시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 16'H-spiro[cyclohexane-1,15'-dibenzo[c,i]indeno[2,1-a]carbazole] (17.3 g, 수율 62 %)을 얻었다.The target compound of Preparation Example 7 (30.0 g, 65.8 mmol) and PPh 3 (43.2 g, 164.6 mmol) were placed in 300 ml of o-DCB and heated to reflux for 18 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, using column chromatography, the target compound, 16'H-spiro[cyclohexane-1,15'-dibenzo[c,i]indeno[2,1-a]carbazole] (17.3 g, Yield 62%).
1H-NMR: δ 1.43-2.15(m, 10H), 7.38(m, 1H), 7.57-7.74(m, 7H), 8.11-8.12(m, 2H), 8.24(d, 1H), 8.51(d, 1H), 8.97(d, 2H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.38 (m, 1H), 7.57-7.74 (m, 7H), 8.11-8.12 (m, 2H), 8.24 (d, 1H), 8.51 (d , 1H), 8.97(d, 2H), 11.70(s, 1H)
[LCMS] : 423 [LCMS]: 423
[준비예 9] N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine의 합성[Preparation Example 9] Synthesis of N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine
질소 기류 하에서 준비예 1의 목적화합물 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 2-chloroaniline (21.1 g, 165.1 mmol), Pd2(dba)3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs2CO3 (112.1 g, 344.1 mmol), xylene (500 ml)를 혼합하고 120℃에서 8시간 동안 교반하였다.The target compound of Preparation Example 1 under a stream of nitrogen 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 2-chloroaniline (21.1 g, 165.1 mmol), Pd 2 (dba) 3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs 2 CO 3 (112.1 g, 344.1 mmol), xylene (500 ml) were mixed and stirred at 120° C. for 8 hours.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 5:1 (v/v))로 정제하여 목적 화합물인 N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (37.8 g, 수율 67%)을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 5:1 (v/v)), the target compound N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'- Cyclohexan]-5-amine (37.8 g, yield 67%) was obtained.
1H-NMR: δ 1.43-2.15(m, 10H), 7.22(s, 1H), 7.27-7.38(m, 4H), 7.57(m, 3H), 7.73-7.74(d, 2H), 8.15(d, 1H), 8.24(d, 1H), 8.85(d, 1H), 10.48(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.22 (s, 1H), 7.27-7.38 (m, 4H), 7.57 (m, 3H), 7.73-7.74 (d, 2H), 8.15 (d , 1H), 8.24(d, 1H), 8.85(d, 1H), 10.48(s, 1H)
[LCMS] : 409 [LCMS]: 409
[준비예 10] 5H-spiro[benzo[a]indeno[1,2-c]carbazole-14,1'-cyclohexane]의 합성[Preparation Example 10] Synthesis of 5H-spiro[benzo[a]indeno[1,2-c]carbazole-14,1'-cyclohexane]
질소 기류 하에서 N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 73.2 mmol), Pd(OAc)2 (1.6 g, 7.3 mmol), TCy 3 HBF 4 (5.4 g, 14.6 mmol), K2CO3 (20.2 g, 146.4 mmol), DMA (300 ml)를 혼합하고 170℃에서 3시간 동안 교반하였다.N-(2-chlorophenyl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 73.2 mmol), Pd(OAc) 2 (1.6 g, 7.3 mmol) under nitrogen stream, TCy 3 HBF 4 (5.4 g, 14.6 mmol), K 2 CO 3 (20.2 g, 146.4 mmol), DMA (300 ml) were mixed and stirred at 170° C. for 3 hours.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 4:1 (v/v))로 정제하여 목적 화합물인 5H-spiro[benzo[a]indeno[1,2-c]carbazole-14,1'-cyclohexane] (19.1 g, 수율 70 %) 을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 4:1 (v/v)), the target compound 5H-spiro[benzo[a]indeno[1,2-c]carbazole-14, 1'-cyclohexane] (19.1 g, yield 70%).
1H-NMR: δ 1.43-2.15(m, 10H), 7.20(m, 1H), 7.38(m, 1H), 7.50-7.63(m, 5H), 7.74(d, 1H), 8.12-8.24(m, 3H), 8.97(d, 1H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.20 (m, 1H), 7.38 (m, 1H), 7.50-7.63 (m, 5H), 7.74 (d, 1H), 8.12-8.24 (m , 3H), 8.97(d, 1H), 11.70(s, 1H)
[LCMS] : 373 [LCMS]: 373
[준비예 11] N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine의 합성[Preparation Example 11] Synthesis of N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine
질소 기류 하에서 준비예 1의 목적화합물 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 2-chloronaphthalen-1-amine (29.3 g, 165.1 mmol), Pd2(dba)3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs2CO3 (112.1 g, 344.1 mmol), xylene (500 ml)를 혼합하고 120℃에서 8시간 동안 교반하였다.The target compound of Preparation Example 1 under a stream of nitrogen 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 2-chloronaphthalen-1-amine (29.3 g, 165.1 mmol), Pd 2 (dba) 3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs 2 CO 3 (112.1 g, 344.1 mmol), xylene (500 ml) and mixed at 120° C. for 8 hours It was stirred.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 5:1 (v/v))로 정제하여 목적 화합물인 N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (41.1 g, 수율 65%)을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 5:1 (v/v)), the target compound N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7 ,1'-cyclohexan]-5-amine (41.1 g, yield 65%).
1H-NMR: δ 1.43-2.15(m, 10H), 7.22(s, 1H), 7.27-7.57(m, 7H), 7.70-7.74(m, 2H), 8.05(m, 1H), 8.15-8.24(m, 3H), 8.85(d, 1H), 10.48(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.22 (s, 1H), 7.27-7.57 (m, 7H), 7.70-7.74 (m, 2H), 8.05 (m, 1H), 8.15-8.24 (m, 3H), 8.85 (d, 1H), 10.48 (s, 1H)
[LCMS] : 459 [LCMS]: 459
[준비예 12] 5'H-spiro[cyclohexane-1,14'-dibenzo[a,i]indeno[1,2-c]carbazole]의 합성[Preparation Example 12] Synthesis of 5'H-spiro[cyclohexane-1,14'-dibenzo[a,i]indeno[1,2-c]carbazole]
질소 기류 하에서 N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 65.2 mmol), Pd(OAc)2 (1.5 g, 6.5 mmol), TCy 3 HBF 4 (4.8 g, 13.0 mmol), K2CO3 (18.0 g, 130.4 mmol), DMA (300 ml)를 혼합하고 170℃에서 3시간 동안 교반하였다.N-(2-chloronaphthalen-1-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 65.2 mmol), Pd(OAc) 2 (1.5 g, under nitrogen stream) 6.5 mmol), TCy 3 HBF 4 (4.8 g, 13.0 mmol), K 2 CO 3 (18.0 g, 130.4 mmol), DMA (300 ml) were mixed and stirred at 170° C. for 3 hours.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 4:1 (v/v))로 정제하여 목적 화합물인 5'H-spiro[cyclohexane-1,14'-dibenzo[a,i]indeno[1,2-c]carbazole] (16.8 g, 수율 61 %) 을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 4:1 (v/v)) to obtain the target compound 5'H-spiro[cyclohexane-1,14'-dibenzo[a,i]indeno [1,2-c]carbazole] (16.8 g, yield 61%) was obtained.
1H-NMR: δ 1.43-2.15(m, 10H), 7.38(m, 1H), 7.57-7.74(m, 7H), 8.11-8.12(m, 3H), 8.24(d, 1H), 8.51(d, 1H), 8.97(d, 1H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.38 (m, 1H), 7.57-7.74 (m, 7H), 8.11-8.12 (m, 3H), 8.24 (d, 1H), 8.51 (d , 1H), 8.97(d, 1H), 11.70(s, 1H)
[LCMS] : 423 [LCMS]: 423
[준비예 13] N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine의 합성[Preparation Example 13] Synthesis of N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine
질소 기류 하에서 준비예 1의 목적화합물 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 1-chloronaphthalen-2-amine (29.3 g, 165.1 mmol), Pd2(dba)3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs2CO3 (112.1 g, 344.1 mmol), xylene (500 ml)를 혼합하고 120℃에서 8시간 동안 교반하였다.The target compound of Preparation Example 1 under a stream of nitrogen 5-bromospiro[benzo[c]fluorene-7,1'-cyclohexane] (50.0 g, 137.6 mmol), 1-chloronaphthalen-2-amine (29.3 g, 165.1 mmol), Pd 2 (dba) 3 (6.3 g, 6.9 mmol), X-Phos (6.6 g, 13.8 mmol), Cs 2 CO 3 (112.1 g, 344.1 mmol), xylene (500 ml) and mixed at 120° C. for 8 hours It was stirred.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 5:1 (v/v))로 정제하여 목적 화합물인 N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (43.7 g, 수율 69%)을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 5:1 (v/v)) to obtain the target compound, N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7 ,1'-cyclohexan]-5-amine (43.7 g, yield 69%).
1H-NMR: δ 1.43-2.15(m, 10H), 7.22(s, 1H), 7.27-7.38(m, 5H), 7.57-7.74(m, 4H), 7.83(d, 1H), 8.11-8.15(m, 2H), 8.24(d, 1H), 8.85(d, 1H), 10.48(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.22 (s, 1H), 7.27-7.38 (m, 5H), 7.57-7.74 (m, 4H), 7.83 (d, 1H), 8.11-8.15 (m, 2H), 8.24(d, 1H), 8.85(d, 1H), 10.48(s, 1H)
[LCMS] : 459 [LCMS]: 459
[준비예 14] 7'H-spiro[cyclohexane-1,16'-dibenzo[a,g]indeno[1,2-c]carbazole]의 합성[Preparation Example 14] Synthesis of 7'H-spiro[cyclohexane-1,16'-dibenzo[a,g]indeno[1,2-c]carbazole]
질소 기류 하에서 N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 65.2 mmol), Pd(OAc)2 (1.5 g, 6.5 mmol), TCy 3 HBF 4 (4.8 g, 13.0 mmol), K2CO3 (18.0 g, 130.4 mmol), DMA (300 ml)를 혼합하고 170℃에서 3시간 동안 교반하였다.N-(1-chloronaphthalen-2-yl)spiro[benzo[c]fluorene-7,1'-cyclohexan]-5-amine (30.0 g, 65.2 mmol), Pd(OAc) 2 (1.5 g, under nitrogen stream) 6.5 mmol), TCy 3 HBF 4 (4.8 g, 13.0 mmol), K 2 CO 3 (18.0 g, 130.4 mmol), DMA (300 ml) were mixed and stirred at 170° C. for 3 hours.
반응이 종결된 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 여과하였다. 얻어진 유기층에서 용매를 제거한 후 컬럼 크로마토그래피 (Hexane:EA = 4:1 (v/v))로 정제하여 목적 화합물인 7'H-spiro[cyclohexane-1,16'-dibenzo[a,g]indeno[1,2-c]carbazole] (12.4 g, 수율 45 %) 을 얻었다.After the reaction was completed, it was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent from the obtained organic layer, purified by column chromatography (Hexane:EA = 4:1 (v/v)) to obtain the target compound 7'H-spiro[cyclohexane-1,16'-dibenzo[a,g]indeno [1,2-c]carbazole] (12.4 g, yield 45%) was obtained.
1H-NMR: δ 1.43-2.15(m, 10H), 7.38(m, 1H), 7.53-7.74(m, 8H), 7.99(d, 1H), 8.12(d, 1H), 8.24(d, 1H), 8.54(d, 1H), 8.97(d, 1H), 11.70(s, 1H) 1 H-NMR: δ 1.43-2.15 (m, 10H), 7.38 (m, 1H), 7.53-7.74 (m, 8H), 7.99 (d, 1H), 8.12 (d, 1H), 8.24 (d, 1H) ), 8.54(d, 1H), 8.97(d, 1H), 11.70(s, 1H)
[LCMS] : 423 [LCMS]: 423
[합성예][Synthesis example]
[합성예 1] 화합물 A-01의 합성[Synthesis Example 1] Synthesis of Compound A-01
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylquinazoline (2.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-01 (4.2 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylquinazoline (2.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound A-01 (4.2 g, yield 91%) was obtained using column chromatography.
[LCMS] : 577[LCMS]: 577
[합성예 2] 화합물 A-02의 합성[Synthesis Example 2] Synthesis of Compound A-02
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-02 (4.6 g, 수율 92 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-02 (4.6 g, yield 92%) as a target compound was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 3] 화합물 A-03의 합성[Synthesis Example 3] Synthesis of Compound A-03
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-03 (4.5 g, 수율 90 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-03 (4.5 g, yield 90%) as a target compound was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 4] 화합물 A-04의 합성[Synthesis Example 4] Synthesis of Compound A-04
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-04 (4.7 g, 수율 89 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-04 (4.7 g, yield 89%) as a target compound was obtained using column chromatography.
[LCMS] : 653[LCMS]: 653
[합성예 5] 화합물 A-05의 합성[Synthesis Example 5] Synthesis of Compound A-05
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-05 (4.6 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t -Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-05 (4.6 g, yield 91%) as a target compound was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 6] 화합물 A-06의 합성[Synthesis Example 6] Synthesis of Compound A-06
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-06 (4.4 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-06 (4.4 g, yield 87%) as a target compound was obtained using column chromatography.
[LCMS] : 633[LCMS]: 633
[합성예 7] 화합물 A-07의 합성[Synthesis Example 7] Synthesis of Compound A-07
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-07 (4.8 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-07 (4.8 g, yield 87%) as a target compound was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 8] 화합물 A-08의 합성[Synthesis Example 8] Synthesis of Compound A-08
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-08 (4.7 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-08 (4.7 g, yield 85%) as a target compound was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 9] 화합물 A-09의 합성[Synthesis Example 9] Synthesis of Compound A-09
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-09 (4.9 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-09 (4.9 g, yield 87%) as a target compound was obtained using column chromatography.
[LCMS] : 709[LCMS]: 709
[합성예 10] 화합물 A-10의 합성[Synthesis Example 10] Synthesis of Compound A-10
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-10 (4.2 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol) , P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were placed in 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound A-10 (4.2 g, yield 85%) was obtained using column chromatography.
[LCMS] : 617[LCMS]: 617
[합성예 11] 화합물 A-11의 합성[Synthesis Example 11] Synthesis of Compound A-11
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-11 (4.6 g, 수율 86 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-11 (4.6 g, yield 86%) as a target compound was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 12] 화합물 A-12의 합성[Synthesis Example 12] Synthesis of Compound A-12
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-12 (4.4 g, 수율 82 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound A-12 (4.4 g, yield 82%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 13] 화합물 A-13의 합성[Synthesis Example 13] Synthesis of Compound A-13
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-09 (4.6 g, 수율 82 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-09 (4.6 g, yield 82%) as a target compound was obtained using column chromatography.
[LCMS] : 693[LCMS]: 693
[합성예 14] 화합물 A-14의 합성[Synthesis Example 14] Synthesis of Compound A-14
준비예 4의 목적 화합물 (5.0 g, 13.4 mmol)와 2,3-dichloroquinoxaline (3.5 g, 17.4 mmol) 및 Pd(PPh3)4 (0.8 g, 0.7 mmol), K2CO3 (5.6 g, 40.2 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 A-14p (5.0 g, 수율 70 %)을 얻었다.The desired compound of Preparation Example 4 (5.0 g, 13.4 mmol) and 2,3-dichloroquinoxaline (3.5 g, 17.4 mmol) and Pd(PPh 3 ) 4 (0.8 g, 0.7 mmol), K 2 CO 3 (5.6 g, 40.2 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, A-14p (5.0 g, yield 70%) as a target compound was obtained using column chromatography.
[LCMS] : 536[LCMS]: 536
위에서 얻은 A-14p의 화합물 (5.0 g, 9.3 mmol)와 phenylboronic acid (1.5 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 A-14 (4.3 g, 수율 80 %)을 얻었다.A-14p compound obtained above (5.0 g, 9.3 mmol) and phenylboronic acid (1.5 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g, 28.0 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound A-14 (4.3 g, yield 80%) was obtained using column chromatography.
[LCMS] : 577[LCMS]: 577
[합성예 15] 화합물 A-15의 합성[Synthesis Example 15] Synthesis of Compound A-15
위에서 얻은 A-14p의 화합물 (5.0 g, 9.3 mmol)와 naphthalen-1-ylboronic acid (2.1 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 A-15 (4.6 g, 수율 79 %)을 얻었다.A-14p compound obtained above (5.0 g, 9.3 mmol) and naphthalen-1-ylboronic acid (2.1 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g , 28.0 mmol) in 50 ml of THF and 20 ml of H 2 O, and refluxed for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, a final target compound A-15 (4.6 g, yield 79%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 16] 화합물 A-16의 합성[Synthesis Example 16] Synthesis of Compound A-16
위에서 얻은 A-14p의 화합물 (5.0 g, 9.3 mmol)와 naphthalen-2-ylboronic acid (2.1 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 A-16 (4.8 g, 수율 82 %)을 얻었다.A-14p compound obtained above (5.0 g, 9.3 mmol) and naphthalen-2-ylboronic acid (2.1 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g , 28.0 mmol) in 50 ml of THF and 20 ml of H 2 O, and refluxed for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound A-16 (4.8 g, yield 82%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 17] 화합물 A-17의 합성[Synthesis Example 17] Synthesis of Compound A-17
위에서 얻은 A-14p의 화합물 (5.0 g, 9.3 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (2.4 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 A-17 (5.0 g, 수율 82 %)을 얻었다.A-14p compound obtained above (5.0 g, 9.3 mmol) and [1,1'-biphenyl]-3-ylboronic acid (2.4 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g, 28.0 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound A-17 (5.0 g, yield 82%) was obtained using column chromatography.
[LCMS] : 653[LCMS]: 653
[합성예 18] 화합물 A-18의 합성[Synthesis Example 18] Synthesis of Compound A-18
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.2 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-18 (3.6 g, 수율 75%)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.2 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) under a nitrogen stream. ,
[LCMS] : 604[LCMS]: 604
[합성예 19] 화합물 A-19의 합성[Synthesis Example 19] Synthesis of Compound A-19
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 4-chloro-2,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-19 (3.5 g, 수율 72%)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 4-chloro-2,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol),
[LCMS] : 603[LCMS]: 603
[합성예 20] 화합물 A-20의 합성[Synthesis Example 20] Synthesis of Compound A-20
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 A-20 (3.6 g, 수율 74%)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), and
[LCMS] : 603[LCMS]: 603
[합성예 21] 화합물 B-01의 합성[Synthesis Example 21] Synthesis of Compound B-01
준비예 6의 목적 화합물 (3.0 g, 7.1 mmol)와 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-01 (3.6 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 7.1 mmol) and 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-01 (3.6 g, yield 91%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 22] 화합물 B-02의 합성[Synthesis Example 22] Synthesis of Compound B-02
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-02 (3.6 g, 수율 75 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-02 (3.6 g, yield 75%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 23] 화합물 B-03의 합성[Synthesis Example 23] Synthesis of Compound B-03
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-03 (3.4 g, 수율 70 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-03 (3.4 g, yield 70%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 24] 화합물 B-04의 합성[Synthesis Example 24] Synthesis of Compound B-04
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-04 (4.1 g, 수율 83 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-04 (4.1 g, yield 83%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 25] 화합물 B-05의 합성[Synthesis Example 25] Synthesis of Compound B-05
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-05 (4.2 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t -Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-05 (4.2 g, yield 87%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 26] 화합물 B-06의 합성[Synthesis Example 26] Synthesis of Compound B-06
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-06 (4.2 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-06 (4.2 g, yield 87%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 27] 화합물 B-07의 합성[Synthesis Example 27] Synthesis of Compound B-07
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-07 (4.7 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-07 (4.7 g, yield 91%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 28] 화합물 B-08의 합성[Synthesis Example 28] Synthesis of Compound B-08
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-08 (4.6 g, 수율 88 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-08 (4.6 g, yield 88%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 29] 화합물 B-09의 합성[Synthesis Example 29] Synthesis of Compound B-09
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-09 (4.4 g, 수율 82 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-09 (4.4 g, yield 82%) was obtained using column chromatography.
[LCMS] : 759[LCMS]: 759
[합성예 30] 화합물 B-10의 합성[Synthesis Example 30] Synthesis of Compound B-10
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-10 (3.4 g, 수율 73 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol) , P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-10 (3.4 g, yield 73%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 31] 화합물 B-11의 합성[Synthesis Example 31] Synthesis of Compound B-11
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-11 (3.6 g, 수율 72 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-11 (3.6 g, yield 72%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 32] 화합물 B-12의 합성[Synthesis Example 32] Synthesis of Compound B-12
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-12 (3.6 g, 수율 72 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-12 (3.6 g, yield 72%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 33] 화합물 B-13의 합성[Synthesis Example 33] Synthesis of Compound B-13
준비예 6의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-13 (4.4 g, 수율 83 %)을 얻었다.The desired compound of Preparation Example 6 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-13 (4.4 g, yield 83%) was obtained using column chromatography.
[LCMS] : 743[LCMS]: 743
[합성예 34] 화합물 B-14의 합성[Synthesis Example 34] Synthesis of Compound B-14
준비예 6의 목적 화합물 (5.0 g, 11.8 mmol)와 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) 및 Pd(PPh3)4 (0.7 g, 0.6 mmol), K2CO3 (4.9 g, 35.4 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 B-14p (6.3 g, 수율 82 %)을 얻었다.The desired compound of Preparation Example 6 (5.0 g, 11.8 mmol) and 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) and Pd(PPh 3 ) 4 (0.7 g, 0.6 mmol), K 2 CO 3 (4.9 g, 35.4 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound B-14p (6.3 g, yield 82%) was obtained using column chromatography.
[LCMS] : 586[LCMS]: 586
위에서 얻은 B-14p의 화합물 (5.0 g, 8.5 mmol)와 phenylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 B-14 (4.6 g, 수율 82 %)을 얻었다.The compound of B-14p obtained above (5.0 g, 8.5 mmol) and phenylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound B-14 (4.6 g, yield 82%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 35] 화합물 B-15의 합성[Synthesis Example 35] Synthesis of Compound B-15
위에서 얻은 B-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 B-15 (3.8 g, 수율 65 %)을 얻었다.The compound of B-14p obtained above (5.0 g, 8.5 mmol) and naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound B-15 (3.8 g, yield 65%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 36] 화합물 B-16의 합성[Synthesis Example 36] Synthesis of Compound B-16
위에서 얻은 B-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 B-16 (4.1 g, 수율 71 %)을 얻었다.The compound of B-14p obtained above (5.0 g, 8.5 mmol) and naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound B-16 (4.1 g, yield 71%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 37] 화합물 B-17의 합성[Synthesis Example 37] Synthesis of Compound B-17
위에서 얻은 B-14p의 화합물 (5.0 g, 8.5 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 B-17 (4.6 g, 수율 82 %)을 얻었다.Compound (5.0 g, 8.5 mmol) of B-14p obtained above and [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound B-17 (4.6 g, yield 82%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 38] 화합물 B-18의 합성[Synthesis Example 38] Synthesis of Compound B-18
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 B-18 (3.4 g, 수율 74%)을 얻었다.The target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) under nitrogen stream ,
[LCMS] : 654[LCMS]: 654
[합성예 39] 화합물 B-19의 합성[Synthesis Example 39] Synthesis of Compound B-19
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 B-19 (3.2 g, 수율 70%)을 얻었다.The target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), and
[LCMS] : 653[LCMS]: 653
[합성예 40] 화합물 B-20의 합성[Synthesis Example 40] Synthesis of Compound B-20
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 B-20 (3.1 g, 수율 68%)을 얻었다.Under nitrogen stream, 30 ml of the target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) and DMF were mixed at room temperature. It was stirred for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound B-20 (3.1 g, yield 68%).
[LCMS] : 653[LCMS]: 653
[합성예 41] 화합물 C-01의 합성[Synthesis Example 41] Synthesis of Compound C-01
준비예 8의 목적 화합물 (3.0 g, 7.1 mmol)와 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-01 (3.5 g, 수율 88 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 7.1 mmol) and 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-01 (3.5 g, yield 88%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 42] 화합물 C-02의 합성[Synthesis Example 42] Synthesis of Compound C-02
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-02 (3.3 g, 수율 70 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-02 (3.3 g, yield 70%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 43] 화합물 C-03의 합성[Synthesis Example 43] Synthesis of Compound C-03
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-03 (3.9 g, 수율 80 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-03 (3.9 g, yield 80%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 34] 화합물 C-04의 합성[Synthesis Example 34] Synthesis of Compound C-04
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-04 (4.1 g, 수율 83 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-04 (4.1 g, yield 83%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 45] 화합물 C-05의 합성[Synthesis Example 45] Synthesis of Compound C-05
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-05 (4.1 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t -Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-05 (4.1 g, yield 85%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 46] 화합물 C-06의 합성[Synthesis Example 46] Synthesis of Compound C-06
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-06 (3.9 g, 수율 80 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-06 (3.9 g, yield 80%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 47] 화합물 C-07의 합성[Synthesis Example 47] Synthesis of Compound C-07
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-07 (4.4 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-07 (4.4 g, yield 85%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 48] 화합물 C-08의 합성[Synthesis Example 48] Synthesis of Compound C-08
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-08 (4.4 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-08 (4.4 g, yield 85%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 49] 화합물 C-09의 합성[Synthesis Example 49] Synthesis of Compound C-09
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-09 (3.9 g, 수율 75 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-09 (3.9 g, yield 75%) was obtained using column chromatography.
[LCMS] : 759[LCMS]: 759
[합성예 50] 화합물 C-10의 합성[Synthesis Example 50] Synthesis of Compound C-10
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-10 (3.7 g, 수율 80 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol) , P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-10 (3.7 g, yield 80%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 51] 화합물 C-11의 합성[Synthesis Example 51] Synthesis of Compound C-11
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-11 (3.8 g, 수율 75 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-11 (3.8 g, yield 75%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 52] 화합물 C-12의 합성[Synthesis Example 52] Synthesis of Compound C-12
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-12 (4.0 g, 수율 80 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-12 (4.0 g, yield 80%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 53] 화합물 C-13의 합성[Synthesis Example 53] Synthesis of Compound C-13
준비예 8의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-13 (4.3 g, 수율 81 %)을 얻었다.The desired compound of Preparation Example 8 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-13 (4.3 g, yield 81%) was obtained using column chromatography.
[LCMS] : 743[LCMS]: 743
[합성예 54] 화합물 C-14의 합성[Synthesis Example 54] Synthesis of Compound C-14
준비예 8의 목적 화합물 (5.0 g, 11.8 mmol)와 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) 및 Pd(PPh3)4 (0.7 g, 0.6 mmol), K2CO3 (4.9 g, 35.4 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 C-14p (5.8 g, 수율 75 %)을 얻었다.The desired compound of Preparation Example 8 (5.0 g, 11.8 mmol) and 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) and Pd(PPh 3 ) 4 (0.7 g, 0.6 mmol), K 2 CO 3 (4.9 g, 35.4 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound C-14p (5.8 g, yield 75%) was obtained using column chromatography.
[LCMS] : 586[LCMS]: 586
위에서 얻은 C-14p의 화합물 (5.0 g, 8.5 mmol)와 phenylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 C-14 (4.0 g, 수율 71 %)을 얻었다.C-14p compound obtained above (5.0 g, 8.5 mmol) and phenylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound C-14 (4.0 g, yield 71%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 55] 화합물 C-15의 합성[Synthesis Example 55] Synthesis of Compound C-15
위에서 얻은 C-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 C-15 (3.6 g, 수율 61 %)을 얻었다.C-14p compound obtained above (5.0 g, 8.5 mmol) and naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound C-15 (3.6 g, yield 61%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 56] 화합물 C-16의 합성[Synthesis Example 56] Synthesis of Compound C-16
위에서 얻은 C-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 C-16 (4.3 g, 수율 75 %)을 얻었다.C-14p compound obtained above (5.0 g, 8.5 mmol) and naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound C-16 (4.3 g, yield 75%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 57] 화합물 C-17의 합성[Synthesis Example 57] Synthesis of Compound C-17
위에서 얻은 C-14p의 화합물 (5.0 g, 8.5 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 C-17 (4.2 g, 수율 75 %)을 얻었다.C-14p compound obtained above (5.0 g, 8.5 mmol) and [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound C-17 (4.2 g, yield 75%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 58] 화합물 C-18의 합성[Synthesis Example 58] Synthesis of Compound C-18
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 C-18 (3.7 g, 수율 80%)을 얻었다.The target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) under nitrogen stream ,
[LCMS] : 654[LCMS]: 654
[합성예 59] 화합물 C-19의 합성[Synthesis Example 59] Synthesis of Compound C-19
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 C-19 (3.2 g, 수율 70%)을 얻었다.The target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), and
[LCMS] : 653[LCMS]: 653
[합성예 60] 화합물 C-20의 합성[Synthesis Example 60] Synthesis of Compound C-20
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 C-20 (3.4g, 수율 75%)을 얻었다.Under nitrogen stream, 30 ml of the target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) and DMF were mixed at room temperature. It was stirred for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain C-20 (3.4 g, yield 75%) as a target compound.
[LCMS] : 653[LCMS]: 653
[합성예 61] 화합물 D-01의 합성[Synthesis Example 61] Synthesis of Compound D-01
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylquinazoline (2.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-01 (4.2 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylquinazoline (2.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-01 (4.2 g, yield 91%) was obtained using column chromatography.
[LCMS] : 577[LCMS]: 577
[합성예 62] 화합물 D-02의 합성[Synthesis Example 62] Synthesis of Compound D-02
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-02 (4.5 g, 수율 91 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-02 (4.5 g, yield 91%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 63] 화합물 D-03의 합성[Synthesis Example 63] Synthesis of Compound D-03
준비예 4의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-03 (4.4 g, 수율 89 %)을 얻었다.The desired compound of Preparation Example 4 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-03 (4.4 g, yield 89%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 64] 화합물 D-04의 합성[Synthesis Example 64] Synthesis of Compound D-04
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-04 (4.6 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, D-04 (4.6 g, yield 87%) as a target compound was obtained using column chromatography.
[LCMS] : 653[LCMS]: 653
[합성예 65] 화합물 D-05의 합성[Synthesis Example 65] Synthesis of Compound D-05
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-05 (4.5 g, 수율 90 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t -Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-05 (4.5 g, yield 90%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 66] 화합물 D-06의 합성[Synthesis Example 66] Synthesis of Compound D-06
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-06 (4.3 g, 수율 86 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-06 (4.3 g, yield 86%) was obtained using column chromatography.
[LCMS] : 633[LCMS]: 633
[합성예 67] 화합물 D-07의 합성[Synthesis Example 67] Synthesis of Compound D-07
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-07 (4.7 g, 수율 86 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-07 (4.7 g, yield 86%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 68] 화합물 D-08의 합성[Synthesis Example 68] Synthesis of Compound D-08
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-08 (4.6 g, 수율 84 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-08 (4.6 g, yield 84%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 69] 화합물 D-09의 합성[Synthesis Example 69] Synthesis of Compound D-09
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-09 (4.8 g, 수율 86 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-09 (4.8 g, yield 86%) was obtained using column chromatography.
[LCMS] : 709[LCMS]: 709
[합성예 70] 화합물 D-10의 합성[Synthesis Example 70] Synthesis of Compound D-10
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-10 (4.3 g, 수율 84 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol) , P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-10 (4.3 g, yield 84%) was obtained using column chromatography.
[LCMS] : 617[LCMS]: 617
[합성예 71] 화합물 D-11의 합성[Synthesis Example 71] Synthesis of Compound D-11
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-11 (4.5 g, 수율 85 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-11 (4.5 g, yield 85%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 72] 화합물 D-12의 합성[Synthesis Example 72] Synthesis of Compound D-12
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-12 (4.4 g, 수율 82 %)을 얻었다.The desired compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-12 (4.4 g, yield 82%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 73] 화합물 D-13의 합성[Synthesis Example 73] Synthesis of Compound D-13
준비예 10의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (3.1 g, 8.8 mmol) 및 Pd2(dba)3 (0.4 g, 0.2 mmol), P(t-Bu)3 (0.2 g, 0.8 mmol) 그리고 NaOtBu (1.5 g, 16.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-09 (4.6 g, 수율 82 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (3.1 g, 8.8 mmol) and Pd 2 (dba) 3 (0.4 g, 0.2 mmol), P(t-Bu) 3 (0.2 g, 0.8 mmol) and NaOtBu (1.5 g, 16.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-09 (4.6 g, yield 82%) was obtained using column chromatography.
[LCMS] : 693[LCMS]: 693
[합성예 74] 화합물 D-14의 합성[Synthesis Example 74] Synthesis of Compound D-14
준비예 10의 목적 화합물 (5.0 g, 13.4 mmol)와 2,3-dichloroquinoxaline (3.5 g, 17.4 mmol) 및 Pd(PPh3)4 (0.8 g, 0.7 mmol), K2CO3 (5.6 g, 40.2 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 D-14p (4.9 g, 수율 69 %)을 얻었다.The desired compound of Preparation Example 10 (5.0 g, 13.4 mmol) and 2,3-dichloroquinoxaline (3.5 g, 17.4 mmol) and Pd(PPh 3 ) 4 (0.8 g, 0.7 mmol), K 2 CO 3 (5.6 g, 40.2 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound D-14p (4.9 g, yield 69%) was obtained using column chromatography.
[LCMS] : 536[LCMS]: 536
위에서 얻은 D-14p의 화합물 (5.0 g, 9.3 mmol)와 phenylboronic acid (1.5 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 D-14 (4.2 g, 수율 79 %)을 얻었다.Compound of D-14p obtained above (5.0 g, 9.3 mmol) and phenylboronic acid (1.5 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g, 28.0 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound D-14 (4.2 g, yield 79%) was obtained using column chromatography.
[LCMS] : 577[LCMS]: 577
[합성예 75] 화합물 D-15의 합성[Synthesis Example 75] Synthesis of Compound D-15
위에서 얻은 D-14p의 화합물 (5.0 g, 9.3 mmol)와 naphthalen-1-ylboronic acid (2.1 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 D-15 (4.5 g, 수율 78 %)을 얻었다.The compound of D-14p obtained above (5.0 g, 9.3 mmol) and naphthalen-1-ylboronic acid (2.1 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g , 28.0 mmol) in 50 ml of THF and 20 ml of H 2 O, and refluxed for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound D-15 (4.5 g, yield 78%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 76] 화합물 D-16의 합성[Synthesis Example 76] Synthesis of Compound D-16
위에서 얻은 D-14p의 화합물 (5.0 g, 9.3 mmol)와 naphthalen-2-ylboronic acid (2.1 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 D-16 (4.7 g, 수율 81 %)을 얻었다.The compound of D-14p obtained above (5.0 g, 9.3 mmol) and naphthalen-2-ylboronic acid (2.1 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g , 28.0 mmol) in 50 ml of THF and 20 ml of H 2 O, and refluxed for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound D-16 (4.7 g, yield 81%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 77] 화합물 D-17의 합성[Synthesis Example 77] Synthesis of Compound D-17
위에서 얻은 D-14p의 화합물 (5.0 g, 9.3 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (2.4 g, 12.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.5 mmol), K2CO3 (3.9 g, 28.0 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 D-17 (4,9 g, 수율 81 %)을 얻었다.The compound of D-14p obtained above (5.0 g, 9.3 mmol) and [1,1'-biphenyl]-3-ylboronic acid (2.4 g, 12.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.5 mmol), K 2 CO 3 (3.9 g, 28.0 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound D-17 (4,9 g, yield 81%) was obtained using column chromatography.
[LCMS] : 653[LCMS]: 653
[합성예 78] 화합물 D-18의 합성[Synthesis Example 78] Synthesis of Compound D-18
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.2 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 D-18 (3.6 g, 수율 75%)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.2 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) under nitrogen stream ,
[LCMS] : 604[LCMS]: 604
[합성예 79] 화합물 D-19의 합성[Synthesis Example 79] Synthesis of Compound D-19
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 4-chloro-2,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 D-19 (3.3 g, 수율 70%)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 4-chloro-2,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol),
[LCMS] : 603[LCMS]: 603
[합성예 80] 화합물 D-20의 합성[Synthesis Example 80] Synthesis of Compound D-20
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 D-20 (3.5 g, 수율 70%)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-chloro-4,6-diphenylpyrimidine (2.1 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), and
[LCMS] : 603[LCMS]: 603
[합성예 81] 화합물 E-01의 합성[Synthesis Example 81] Synthesis of Compound E-01
준비예 12의 목적 화합물 (3.0 g, 7.1 mmol)와 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-01 (3.5 g, 수율 89 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 7.1 mmol) and 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-01 (3.5 g, yield 89%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 82] 화합물 E-02의 합성[Synthesis Example 82] Synthesis of Compound E-02
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-02 (3.5 g, 수율 73 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-02 (3.5 g, yield 73%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 83] 화합물 E-03의 합성[Synthesis Example 83] Synthesis of Compound E-03
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-03 (3.3 g, 수율 69 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-03 (3.3 g, yield 69%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 84] 화합물 E-04의 합성[Synthesis Example 84] Synthesis of Compound E-04
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-04 (4.0 g, 수율 81 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-04 (4.0 g, yield 81%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 85] 화합물 E-05의 합성[Synthesis Example 85] Synthesis of Compound E-05
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-05 (4.21 g, 수율 86 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t -Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-05 (4.21 g, yield 86%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 86] 화합물 E-06의 합성[Synthesis Example 86] Synthesis of Compound E-06
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-06 (4.0 g, 수율 84 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-06 (4.0 g, yield 84%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 87] 화합물 E-07의 합성[Synthesis Example 87] Synthesis of Compound E-07
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-07 (4.8 g, 수율 92 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-07 (4.8 g, yield 92%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 88] 화합물 E-08의 합성[Synthesis Example 88] Synthesis of Compound E-08
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-08 (4.5 g, 수율 87 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-08 (4.5 g, yield 87%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 89] 화합물 E-09의 합성[Synthesis Example 89] Synthesis of Compound E-09
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-09 (4.3 g, 수율 80 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-09 (4.3 g, yield 80%) was obtained using column chromatography.
[LCMS] : 759[LCMS]: 759
[합성예 90] 화합물 E-10의 합성[Synthesis Example 90] Synthesis of Compound E-10
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-10 (3.3 g, 수율 71 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol) , P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were placed in 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-10 (3.3 g, yield 71%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 91] 화합물 E-11의 합성[Synthesis Example 91] Synthesis of Compound E-11
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-11 (3.5 g, 수율 71 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-11 (3.5 g, yield 71%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 92] 화합물 E-12의 합성[Synthesis Example 92] Synthesis of Compound E-12
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-12 (3.65 g, 수율 70 %)을 얻었다.The desired compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-12 (3.65 g, yield 70%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 93] 화합물 E-13의 합성[Synthesis Example 93] Synthesis of Compound E-13
준비예 12의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-13 (4.5 g, 수율 84 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-13 (4.5 g, yield 84%) was obtained using column chromatography.
[LCMS] : 743[LCMS]: 743
[합성예 94] 화합물 E-14의 합성[Synthesis Example 94] Synthesis of Compound E-14
준비예 12의 목적 화합물 (5.0 g, 11.8 mmol)와 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) 및 Pd(PPh3)4 (0.7 g, 0.6 mmol), K2CO3 (4.9 g, 35.4 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 E-14p (6.3 g, 수율 82 %)을 얻었다.The target compound of Preparation Example 12 (5.0 g, 11.8 mmol) and 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) and Pd(PPh 3 ) 4 (0.7 g, 0.6 mmol), K 2 CO 3 (4.9 g, 35.4 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound E-14p (6.3 g, yield 82%) was obtained using column chromatography.
[LCMS] : 586[LCMS]: 586
위에서 얻은 E-14p의 화합물 (5.0 g, 8.5 mmol)와 phenylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 E-14 (4.5 g, 수율 81 %)을 얻었다.The compound of E-14p obtained above (5.0 g, 8.5 mmol) and phenylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound E-14 (4.5 g, yield 81%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 95] 화합물 E-15의 합성[Synthesis Example 95] Synthesis of Compound E-15
위에서 얻은 E-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 E-15 (3.9 g, 수율 66 %)을 얻었다.The compound of E-14p obtained above (5.0 g, 8.5 mmol) and naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound E-15 (3.9 g, yield 66%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 96] 화합물 E-16의 합성[Synthesis Example 96] Synthesis of Compound E-16
위에서 얻은 E-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 E-16 (4.1 g, 수율 71 %)을 얻었다.The compound of E-14p obtained above (5.0 g, 8.5 mmol) and naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound E-16 (4.1 g, yield 71%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 97] 화합물 E-17의 합성[Synthesis Example 97] Synthesis of Compound E-17
위에서 얻은 E-14p의 화합물 (5.0 g, 8.5 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 E-17 (4.5 g, 수율 81 %)을 얻었다.The compound of E-14p obtained above (5.0 g, 8.5 mmol) and [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound E-17 (4.5 g, yield 81%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 98] 화합물 E-18의 합성[Synthesis Example 98] Synthesis of Compound E-18
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 E-18 (3.3 g, 수율 72%)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) under nitrogen stream ,
[LCMS] : 654[LCMS]: 654
[합성예 99] 화합물 E-19의 합성[Synthesis Example 99] Synthesis of Compound E-19
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 E-19 (3.3 g, 수율 71%)을 얻었다.Under nitrogen stream, 30 ml of the target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) and DMF were mixed at room temperature. It was stirred for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound E-19 (3.3 g, yield 71%).
[LCMS] : 653[LCMS]: 653
[합성예 100] 화합물 E-20의 합성[Synthesis Example 100] Synthesis of Compound E-20
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 E-20 (3.2 g, 수율 69%)을 얻었다.Under nitrogen stream, 30 ml of the target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) and DMF were mixed and at room temperature. It was stirred for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound E-20 (3.2 g, yield 69%).
[LCMS] : 653[LCMS]: 653
[합성예 101] 화합물 F-01의 합성[Synthesis Example 101] Synthesis of Compound F-01
준비예 14의 목적 화합물 (3.0 g, 7.1 mmol)와 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-01 (3.4 g, 수율 87 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 7.1 mmol) and 2-chloro-4-phenylquinazoline (1.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-01 (3.4 g, yield 87%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 102] 화합물 F-02의 합성[Synthesis Example 102] Synthesis of Compound F-02
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-02 (3.3 g, 수율 70 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-02 (3.3 g, yield 70%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 103] 화합물 F-03의 합성[Synthesis Example 103] Synthesis of Compound F-03
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-03 (3.8 g, 수율 79 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-03 (3.8 g, yield 79%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 104] 화합물 F-04의 합성[Synthesis Example 104] Synthesis of Compound F-04
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-04 (4.0 g, 수율 81 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline (2.5 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-04 (4.0 g, yield 81%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 105] 화합물 F-05의 합성[Synthesis Example 105] Synthesis of Compound F-05
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-05 (4.0 g, 수율 83 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[h]quinazoline (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t -Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-05 (4.0 g, yield 83%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 106] 화합물 F-06의 합성[Synthesis Example 106] Synthesis of Compound F-06
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-06 (3.8 g, 수율 79 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2.3 g, 8.8 mmol) and Pd 2 (dba) 3 ( 0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-06 (3.8 g, yield 79%) was obtained using column chromatography.
[LCMS] : 683[LCMS]: 683
[합성예 107] 화합물 F-07의 합성[Synthesis Example 107] Synthesis of Compound F-07
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-07 (4.3 g, 수율 84 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-07 (4.3 g, yield 84%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 108] 화합물 F-08의 합성[Synthesis Example 108] Synthesis of Compound F-08
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-08 (4.4 g, 수율 85 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzo[4,5]thieno[3,2-d]pyrimidine (2.7 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-08 (4.4 g, yield 85%) was obtained using column chromatography.
[LCMS] : 733[LCMS]: 733
[합성예 109] 화합물 F-09의 합성[Synthesis Example 109] Synthesis of Compound F-09
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-09 (3.8 g, 수율 74 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.9 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) in 50 ml of Toluene for 12 hours It was heated to reflux for a while. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-09 (3.8 g, yield 74%) was obtained using column chromatography.
[LCMS] : 759[LCMS]: 759
[합성예 110] 화합물 F-10의 합성[Synthesis Example 110] Synthesis of Compound F-10
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-10 (3.6 g, 수율 79 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine (2.2 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol) , P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-10 (3.6 g, yield 79%) was obtained using column chromatography.
[LCMS] : 667[LCMS]: 667
[합성예 111] 화합물 F-11의 합성[Synthesis Example 111] Synthesis of Compound F-11
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-11 (3.9 g, 수율 76 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-1-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-11 (3.9 g, yield 76%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 112] 화합물 F-12의 합성[Synthesis Example 112] Synthesis of Compound F-12
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-12 (4.1 g, 수율 81 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 2-chloro-4-(naphthalen-2-yl)benzofuro[3,2-d]pyrimidine (2.6 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to Toluene 50 ml and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-12 (4.1 g, yield 81%) was obtained using column chromatography.
[LCMS] : 717[LCMS]: 717
[합성예 113] 화합물 F-13의 합성[Synthesis Example 113] Synthesis of Compound F-13
준비예 14의 목적 화합물 (3.0 g, 8.0 mmol)와 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) 및 Pd2(dba)3 (0.3 g, 0.4 mmol), P(t-Bu)3 (0.1 g, 0.7 mmol) 그리고 NaOtBu (1.4 g, 14.1 mmol)을 Toluene 50ml에 넣고 12시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-13 (4.2 g, 수율 80 %)을 얻었다.The desired compound of Preparation Example 14 (3.0 g, 8.0 mmol) and 4-([1,1'-biphenyl]-4-yl)-2-chlorobenzofuro[3,2-d]pyrimidine (2.8 g, 8.8 mmol) and Pd 2 (dba) 3 (0.3 g, 0.4 mmol), P(t-Bu) 3 (0.1 g, 0.7 mmol) and NaOtBu (1.4 g, 14.1 mmol) were added to 50 ml of Toluene and heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-13 (4.2 g, yield 80%) was obtained using column chromatography.
[LCMS] : 743[LCMS]: 743
[합성예 114] 화합물 F-14의 합성[Synthesis Example 114] Synthesis of Compound F-14
준비예 14의 목적 화합물 (5.0 g, 11.8 mmol)와 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) 및 Pd(PPh3)4 (0.7 g, 0.6 mmol), K2CO3 (4.9 g, 35.4 mmol)을 Toluene 50ml에 넣고 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 목적 화합물인 F-14p (5.7 g, 수율 74 %)을 얻었다.The desired compound of Preparation Example 14 (5.0 g, 11.8 mmol) and 2,3-dichloroquinoxaline (3.1 g, 15.4 mmol) and Pd(PPh 3 ) 4 (0.7 g, 0.6 mmol), K 2 CO 3 (4.9 g, 35.4 mmol) was put in 50 ml of Toluene and heated to reflux. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the target compound F-14p (5.7 g, yield 74%) was obtained using column chromatography.
[LCMS] : 586[LCMS]: 586
위에서 얻은 F-14p의 화합물 (5.0 g, 8.5 mmol)와 phenylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 F-14 (4.1 g, 수율 72 %)을 얻었다.F-14p compound obtained above (5.0 g, 8.5 mmol) and phenylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) Was added to 50 ml of THF and 20 ml of H 2 O, and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound F-14 (4.1 g, yield 72%) was obtained using column chromatography.
[LCMS] : 627[LCMS]: 627
[합성예 115] 화합물 F-15의 합성[Synthesis Example 115] Synthesis of Compound F-15
위에서 얻은 F-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 F-15 (3.5 g, 수율 60 %)을 얻었다.F-14p compound obtained above (5.0 g, 8.5 mmol) and naphthalen-1-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound F-15 (3.5 g, yield 60%) was obtained using column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 116] 화합물 F-16의 합성[Synthesis Example 116] Synthesis of Compound F-16
위에서 얻은 F-14p의 화합물 (5.0 g, 8.5 mmol)와 naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 F-16 (4.2 g, 수율 74 %)을 얻었다.The compound of F-14p obtained above (5.0 g, 8.5 mmol) and naphthalen-2-ylboronic acid (1.9 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g , 25.6 mmol) in a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, F-16 (4.2 g, yield 74%) was obtained as a final target compound by column chromatography.
[LCMS] : 677[LCMS]: 677
[합성예 117] 화합물 F-17의 합성[Synthesis Example 117] Synthesis of Compound F-17
위에서 얻은 F-14p의 화합물 (5.0 g, 8.5 mmol)와 [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) 및 Pd(PPh3)4 (0.5 g, 0.4 mmol), K2CO3 (3.5 g, 25.6 mmol)을 THF 50ml와 H2O 20ml 혼합 용매에 넣고 8시간동안 가열환류하였다. 반응 종결 후 메틸렌클로라이드로 추출하고 MgSO4를 넣고 필터하였다. 필터된 유기층의 용매를 제거한 후 컬럼크로마토그래피를 이용하여 최종 목적 화합물인 F-17 (4.2 g, 수율 75 %)을 얻었다.The compound of F-14p obtained above (5.0 g, 8.5 mmol) and [1,1'-biphenyl]-3-ylboronic acid (1.4 g, 11.1 mmol) and Pd(PPh 3 ) 4 (0.5 g, 0.4 mmol), K 2 CO 3 (3.5 g, 25.6 mmol) was added to a mixed solvent of 50 ml of THF and 20 ml of H 2 O and heated to reflux for 8 hours. After completion of the reaction, the mixture was extracted with methylene chloride, MgSO 4 was added and filtered. After removing the solvent of the filtered organic layer, the final target compound F-17 (4.2 g, yield 75%) was obtained using column chromatography.
[LCMS] : 703[LCMS]: 703
[합성예 118] 화합물 F-18의 합성[Synthesis Example 118] Synthesis of Compound F-18
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 F-18 (3.6 g, 수율 79 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol) under nitrogen stream ,
[LCMS] : 654[LCMS]: 654
[합성예 119] 화합물 F-19의 합성[Synthesis Example 119] Synthesis of Compound F-19
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 F-19 (3.3 g, 수율 72%)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 4-chloro-2,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), and 30 ml of DMF were mixed under nitrogen stream at room temperature. It was stirred for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the desired compound, F-19 (3.3 g, yield 72%).
[LCMS] : 653[LCMS]: 653
[합성예 120] 화합물 F-20의 합성[Synthesis Example 120] Synthesis of Compound F-20
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 F-20 (3.5g, 수율 76%)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-chloro-4,6-diphenylpyrimidine (1.9 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), and
[LCMS] : 653[LCMS]: 653
[합성예 121] 화합물 G-01의 합성[Synthesis Example 121] Synthesis of Compound G-01
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-01 (3.7 g, 수율 68 %)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g) under a nitrogen stream. , 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-01 (3.7 g, yield 68%).
[LCMS] : 680[LCMS]: 680
[합성예 122] 화합물 G-02의 합성[Synthesis Example 122] Synthesis of Compound G-02
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-02 (3.3 g, 수율 64 %)을 얻었다.The target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 123] 화합물 G-03의 합성[Synthesis Example 123] Synthesis of Compound G-03
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-03 (3.5 g, 수율 67 %)을 얻었다.Target compound of Preparation Example 8 under nitrogen stream (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 654[LCMS]: 654
[합성예 124] 화합물 G-04의 합성[Synthesis Example 124] Synthesis of Compound G-04
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-04 (3.5 g, 수율 65 %)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g) under a nitrogen stream. , 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-04 (3.5 g, yield 65%).
[LCMS] : 680[LCMS]: 680
[합성예 125] 화합물 G-05의 합성[Synthesis Example 125] Synthesis of Compound G-05
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 4-(3-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-05 (3.6 g, 수율 70%)을 얻었다.The target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 4-(3-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 126] 화합물 G-06의 합성[Synthesis Example 126] Synthesis of Compound G-06
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-06 (3.1 g, 수율 61 %)을 얻었다.Target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 127] 화합물 G-07의 합성[Synthesis Example 127] Synthesis of Compound G-07
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-07 (4.0 g, 수율 66 %)을 얻었다.The target compound of Preparation Example 4 under a stream of nitrogen (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3, 30 ml of 5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) and DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-07 (4.0 g, yield 66%).
[LCMS] : 756[LCMS]: 756
[합성예 128] 화합물 G-08의 합성[Synthesis Example 128] Synthesis of Compound G-08
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-08 (4.0 g, 수율 70%)을 얻었다.The target compound of Preparation Example 6 under a nitrogen stream (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-08 (4.0 g, yield 70%).
[LCMS] : 806[LCMS]: 806
[합성예 129] 화합물 G-09의 합성[Synthesis Example 129] Synthesis of Compound G-09
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-09 (3.5 g, 수율 61%)을 얻었다.The target compound of Preparation Example 8 under a stream of nitrogen (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-09 (3.5 g, yield 61%).
[LCMS] : 806[LCMS]: 806
[합성예 130] 화합물 G-10의 합성[Synthesis Example 130] Synthesis of Compound G-10
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-10 (4.0 g, 수율 66 %)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3, under a nitrogen stream. 30 ml of 5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) and DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-10 (4.0 g, yield 66%).
[LCMS] : 756[LCMS]: 756
[합성예 131] 화합물 G-11의 합성[Synthesis Example 131] Synthesis of Compound G-11
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-11 (3.1 g, 수율 55%)을 얻었다.The desired compound of Preparation Example 6 under a nitrogen stream (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-11 (3.1 g, yield 55%).
[LCMS] : 806[LCMS]: 806
[합성예 132] 화합물 G-12의 합성[Synthesis Example 132] Synthesis of Compound G-12
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-12 (2.5 g, 수율 44%)을 얻었다.The target compound of Preparation Example 8 under a nitrogen stream (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-12 (2.5 g, yield 44%).
[LCMS] : 806[LCMS]: 806
[합성예 133] 화합물 G-13의 합성[Synthesis Example 133] Synthesis of Compound G-13
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (3.5 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-13 (3.7 g, 수율 60 %)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5 under nitrogen stream -triazine (3.5 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-13 (3.7 g, yield 60%).
[LCMS] : 770[LCMS]: 770
[합성예 134] 화합물 G-14의 합성[Synthesis Example 134] Synthesis of Compound G-14
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]furan-4-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-14 (4.1 g, 수율 71 %)을 얻었다.The target compound of Preparation Example 6 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]furan-4-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol) under a nitrogen stream. ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-14 (4.1 g, yield 71%).
[LCMS] : 820[LCMS]: 820
[합성예 135] 화합물 G-15의 합성[Synthesis Example 135] Synthesis of Compound G-15
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-1-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-15 (3.8 g, 수율 65 %)을 얻었다.The target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-1-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol) under nitrogen stream ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-15 (3.8 g, yield 65%).
[LCMS] : 821[LCMS]: 821
[합성예 136] 화합물 G-16의 합성[Synthesis Example 136] Synthesis of Compound G-16
질소 기류 하에서 준비예 4의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine (3.6 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-16 (3.8 g, 수율 60 %)을 얻었다.The target compound of Preparation Example 4 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5 under nitrogen stream -triazine (3.6 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-16 (3.8 g, yield 60%).
[LCMS] : 787[LCMS]: 787
[합성예 137] 화합물 G-17의 합성[Synthesis Example 137] Synthesis of Compound G-17
질소 기류 하에서 준비예 6의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]thiophen-4-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-17 (4.0 g, 수율 67 %)을 얻었다.The desired compound of Preparation Example 6 under a nitrogen stream (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]thiophen-4-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol) ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-17 (4.0 g, yield 67%).
[LCMS] : 836[LCMS]: 836
[합성예 138] 화합물 G-18의 합성[Synthesis Example 138] Synthesis of Compound G-18
질소 기류 하에서 준비예 8의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-1-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 G-18 (3.9 g, 수율 66 %)을 얻었다.The target compound of Preparation Example 8 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-1-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol) under a stream of nitrogen. ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound G-18 (3.9 g, yield 66%).
[LCMS] : 837[LCMS]: 837
[합성예 139] 화합물 H-01의 합성[Synthesis Example 139] Synthesis of Compound H-01
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-01 (3.6 g, 수율 66 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g) under nitrogen stream , 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-01 (3.6 g, yield 66%).
[LCMS] : 680[LCMS]: 680
[합성예 140] 화합물 H-02의 합성[Synthesis Example 140] Synthesis of Compound H-02
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-02 (3.2 g, 수율 63 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 141] 화합물 H-03의 합성[Synthesis Example 141] Synthesis of Compound H-03
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-03 (3.5 g, 수율 67 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 654[LCMS]: 654
[합성예 142] 화합물 H-04의 합성[Synthesis Example 142] Synthesis of Compound H-04
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-04 (3.4 g, 수율 64 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (2.8 g, 8.0 mmol), NaH (0.4 g) under nitrogen stream , 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-04 (3.4 g, yield 64%).
[LCMS] : 680[LCMS]: 680
[합성예 143] 화합물 H-05의 합성[Synthesis Example 143] Synthesis of Compound H-05
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 4-(3-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-05 (3.5 g, 수율 69%)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 4-(3-chlorophenyl)-2,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 144] 화합물 H-06의 합성[Synthesis Example 144] Synthesis of Compound H-06
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-06 (3.0 g, 수율 59 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (2.4 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol),
[LCMS] : 729[LCMS]: 729
[합성예 145] 화합물 H-07의 합성[Synthesis Example 145] Synthesis of Compound H-07
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3,5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-07 (4.1 g, 수율 68 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(4-chlorophenyl)-6-phenyl-1,3, under a nitrogen stream. 30 ml of 5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) and DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-07 (4.1 g, yield 68%).
[LCMS] : 756[LCMS]: 756
[합성예 146] 화합물 H-08의 합성[Synthesis Example 146] Synthesis of Compound H-08
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-08 (3.9 g, 수율 68%)을 얻었다.The target compound of Preparation Example 12 under a stream of nitrogen (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-08 (3.9 g, yield 68%).
[LCMS] : 806[LCMS]: 806
[합성예 147] 화합물 H-09의 합성[Synthesis Example 147] Synthesis of Compound H-09
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-09 (3.4 g, 수율 60%)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(4-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1) under a nitrogen stream. mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-09 (3.4 g, yield 60%).
[LCMS] : 806[LCMS]: 806
[합성예 148] 화합물 H-10의 합성[Synthesis Example 148] Synthesis of Compound H-10
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-10 (4.1 g, 수율 68 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3, under a nitrogen stream. 30 ml of 5-triazine (3.4 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol) and DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-10 (4.1 g, yield 68%).
[LCMS] : 756[LCMS]: 756
[합성예 149] 화합물 H-11의 합성[Synthesis Example 149] Synthesis of Compound H-11
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-11 (3.0 g, 수율 53%)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 2-([1,1'-biphenyl]-3-yl)-4-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1) under a nitrogen stream. mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-11 (3.0 g, yield 53%).
[LCMS] : 806[LCMS]: 806
[합성예 150] 화합물 H-12의 합성[Synthesis Example 150] Synthesis of Compound H-12
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-12 (2.4 g, 수율 43%)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 4-([1,1'-biphenyl]-2-yl)-2-(3-chlorophenyl)-6-phenylpyrimidine (3.0 g, 7.1) under a nitrogen stream. mmol), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-12 (2.4 g, yield 43%).
[LCMS] : 806[LCMS]: 806
[합성예 151] 화합물 H-13의 합성[Synthesis Example 151] Synthesis of Compound H-13
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine (3.5 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-13 (3.7 g, 수율 60 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5 under nitrogen stream -triazine (3.5 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-13 (3.7 g, yield 60%).
[LCMS] : 770[LCMS]: 770
[합성예 152] 화합물 H-14의 합성[Synthesis Example 152] Synthesis of Compound H-14
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]furan-4-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-14 (4.0 g, 수율 70 %)을 얻었다.The target compound of Preparation Example 12 under a stream of nitrogen (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]furan-4-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol) ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-14 (4.0 g, yield 70%).
[LCMS] : 820[LCMS]: 820
[합성예 153] 화합물 H-15의 합성[Synthesis Example 153] Synthesis of Compound H-15
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-1-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-15 (3.8 g, 수율 65 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]furan-1-yl)-6-phenylpyrimidine (3.1 g, 7.1 mmol) under nitrogen stream ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-15 (3.8 g, yield 65%).
[LCMS] : 821[LCMS]: 821
[합성예 154] 화합물 H-16의 합성[Synthesis Example 154] Synthesis of Compound H-16
질소 기류 하에서 준비예 10의 목적 화합물 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5-triazine (3.6 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-16 (3.8 g, 수율 60 %)을 얻었다.The target compound of Preparation Example 10 (3.0 g, 8.0 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-3-yl)-6-phenyl-1,3,5 under nitrogen stream -triazine (3.6 g, 8.0 mmol), NaH (0.4 g, 8.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-16 (3.8 g, yield 60%).
[LCMS] : 787[LCMS]: 787
[합성예 155] 화합물 H-17의 합성[Synthesis Example 155] Synthesis of Compound H-17
질소 기류 하에서 준비예 12의 목적 화합물 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]thiophen-4-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-17 (4.1 g, 수율 68 %)을 얻었다.The target compound of Preparation Example 12 (3.0 g, 7.1 mmol), 4-(4-chlorophenyl)-2-(dibenzo[b,d]thiophen-4-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol) under nitrogen stream ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-17 (4.1 g, yield 68%).
[LCMS] : 836[LCMS]: 836
[합성예 156] 화합물 H-18의 합성[Synthesis Example 156] Synthesis of Compound H-18
질소 기류 하에서 준비예 14의 목적 화합물 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-1-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol), NaH (0.3 g, 7.8 mmol), DMF 30 ml를 혼합하고 상온에서 2시간 동안 교반하였다. 반응이 종결된 후 고체염을 filter한 후, 컬럼 크로마토그래피로 정제하여 목적 화합물인 H-18 (3.8 g, 수율 65 %)을 얻었다.The target compound of Preparation Example 14 (3.0 g, 7.1 mmol), 2-(4-chlorophenyl)-4-(dibenzo[b,d]thiophen-1-yl)-6-phenylpyrimidine (3.2 g, 7.1 mmol) under nitrogen stream ), NaH (0.3 g, 7.8 mmol), 30 ml of DMF were mixed and stirred at room temperature for 2 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the target compound H-18 (3.8 g, yield 65%).
[LCMS] : 837[LCMS]: 837
[소자예][Device Example]
상기 합성예 에서 합성한 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 EL 소자를 제작하였다.The compound synthesized in the above synthesis example was subjected to a high-purity sublimation purification in a conventionally known method, and then a green organic EL 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 a thin film of ITO (Indium tin oxide) at a thickness of 1500 Å was washed with distilled water. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone or methanol, dried and transferred to a UV ozone cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and then vacuum-deposited. The substrate was transferred to.
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 90% 하기 표 1의 호스트 화합물 + 10 % Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 EL 소자를 제작하였다. M-MTDATA (60 nm)/TCTA (80 nm)/ 90% on the ITO transparent electrode thus prepared, host compound of Table 1 below + 10% Ir(ppy) 3 (300 nm)/BCP (10 nm)/Alq 3 (30 nm)/LiF (1 nm)/Al (200 nm).
m-MTDATA, TCTA, M-1, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, M-1, Ir(ppy) 3 , CBP and BCP are as follows.
[비교예 1-1] 녹색 유기 EL 소자의 제작[Comparative Example 1-1] Fabrication of green organic EL device
발광층 형성시 발광 호스트 물질로서 화합물 A-05 대신 CBP를 사용하는 것을 제외하고는 실시예 1과 동일한 과정으로 녹색 유기 EL 소자를 제작하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound A-05 as a light emitting host material when forming the light emitting layer.
[비교예 1-2] 녹색 유기 EL 소자의 제작[Comparative Example 1-2] Fabrication of green organic EL device
발광층 형성시 발광 호스트 물질로서 화합물 A-05 대신 M-1을 사용하는 것을 제외하고는 실시예 1과 동일한 과정으로 녹색 유기 EL 소자를 제작하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that M-1 was used instead of Compound A-05 as a light emitting host material when forming the light emitting layer.
[평가예 1][Evaluation Example 1]
실시예 1 내지 36 및 비교예 1에서 제작한 각각의 녹색 유기 EL 소자에 대하여 전류밀도 10mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.For each green organic EL device produced in Examples 1 to 36 and Comparative Example 1, 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 1 below.
(V)Driving voltage
(V)
(nm)EL peak
(nm)
(cd/A)Current efficiency
(cd/A)
상기 표1에 나타낸 바와 같이, 본 발명에 따른 화합물을 녹색 유기 EL 소자의 발광층에 사용하였을 경우 (실시예 1 내지 36)가 종래 CBP를 녹색 유기 EL 소자(비교예1-1)에 사용한 경우보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다. 또 싸이클로헥실이 포함되지 않은 M-1을 녹색 유기 EL 소자(비교예 1-2)에 사용한 경우보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다.As shown in Table 1 above, when the compound according to the present invention was used for the light emitting layer of the green organic EL device (Examples 1 to 36) than when the conventional CBP was used for the green organic EL device (Comparative Example 1-1) It was confirmed that the efficiency and the driving voltage were excellent. In addition, it was confirmed that the efficiency and driving voltage were superior to that in the case where M-1 without cyclohexyl was used in the green organic EL device (Comparative Example 1-2).
[실시예 37 내지 72] 적색 유기 EL 소자의 제조[Examples 37 to 72] Preparation of red organic EL device
상기 에서 합성한 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 적색 유기 전계 발광 소자를 제작하였다.A red organic electroluminescent device was manufactured according to the following procedure after high-purity sublimation purification of the compound synthesized in the above by a conventionally known method.
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 a thin film of ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone or methanol, dried and transferred to a UV ozone cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and then vacuum-deposited. The substrate was transferred to.
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm) / 90% 하기 표 2 의 호스트 화합물 + 10 % (piq)2Ir(acac) (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제작하였다.M-MTDATA (60 nm)/TCTA (80 nm) / 90% on the ITO transparent electrode thus prepared, host compound of Table 2 below + 10% (piq) 2 Ir(acac) (300 nm)/BCP (10 nm)/Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) stacked in order to prepare an organic electroluminescent device.
[비교예 2-1][Comparative Example 2-1]
발광층 형성시 발광 호스트 물질로서 화합물 A-01 대신 CBP를 사용하는 것을 제외하고는 상기 실시예 36과 동일한 과정으로 적색 유기 전계 발광 소자를 제작하였다.A red organic electroluminescent device was manufactured in the same manner as in Example 36, except that CBP was used instead of Compound A-01 as a light emitting host material when forming the light emitting layer.
[비교예 2-2][Comparative Example 2-2]
발광층 형성시 발광 호스트 물질로서 화합물 A-01 대신 M-1을 사용하는 것을 제외하고는 상기 실시예 36과 동일한 과정으로 적색 유기 전계 발광 소자를 제작하였다.A red organic electroluminescent device was manufactured in the same manner as in Example 36, except that M-1 was used instead of Compound A-01 as a light emitting host material when the light emitting layer was formed.
상기 실시예 37 내지 72 및 비교예2에서 사용된 m-MTDATA, NPB, (piq)2Ir(acac), BCP, CBP 및 M-1의 구조는 하기와 같다.The structures of m-MTDATA, NPB, (piq) 2 Ir(acac), BCP, CBP and M-1 used in Examples 37 to 72 and Comparative Example 2 are as follows.
[평가예 2][Evaluation Example 2]
실시예 37 내지 72 및 비교예 2에서 제작한 각각의 유기 전계 발광 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압 및 전류효율을 측정하고, 그 결과를 하기 표 2에 나타내었다.For each of the organic electroluminescent devices prepared in Examples 37 to 72 and Comparative Example 2, the driving voltage and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 2 below.
(V)Driving voltage
(V)
(cd/A)Current efficiency
(cd/A)
상기 표2에 나타낸 바와 같이, 본 발명에 따른 화합물을 적색 유기 전계 발광 소자의 발광층에 사용한 경우(실시예 37 내지 72) 종래 CBP를 적색 유기 전계 발광 소자(비교예2-1)에 사용한 경우보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다. 또 싸이클로헥실이 포함되지 않은 M-1을 녹색 유기 EL 소자(비교예 2-2)에 사용한 경우보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다.As shown in Table 2 above, when the compound according to the present invention was used for the light emitting layer of the red organic electroluminescent device (Examples 37 to 72), the conventional CBP was used for the red organic electroluminescent device (Comparative Example 2-1). It was confirmed that the efficiency and the driving voltage were excellent. In addition, it was confirmed that M-1 without cyclohexyl was used in the green organic EL device (Comparative Example 2-2), and the efficiency and driving voltage were superior.
[실시예 73 내지 108] 청색 유기 EL 소자의 제조[Examples 73 to 108] Preparation of blue organic EL device
합성예에서 합성된 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기와 같이 청색 유기 전계 발광 소자를 제조하였다.After the high purity sublimation purification of the compound synthesized in the synthesis example by a conventionally known method, a blue organic electroluminescent device was manufactured as follows.
ITO (Indium tin oxide)가 1500 
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (80 nm)/NPB (15 nm)/AND + 5 % DS-405 (30nm)/표 3의 화합물 (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 (80 nm)/NPB (15 nm)/AND + 5% DS-405 (30 nm)/compound of Table 3 (5 nm)/ Alq 3 (25 nm)/ An organic electroluminescent device was manufactured by stacking in order of LiF (1 nm)/Al (200 nm).
이때 사용된 NPB, ADN, Alq3 및 M-2의 구조는 다음과 같다.The structures of NPB, ADN, Alq 3 and M-2 used at this time are as follows.
[실시예 109 내지 118] - 청색 유기 EL 소자의 제조 [Examples 109 to 118]-Preparation of blue organic EL device
합성예에서 합성된 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후, 하기와 같이 청색 유기 전계 발광 소자를 제조하였다.After the high purity sublimation purification of the compound synthesized in the synthesis example by a conventionally known method, a blue organic electroluminescent device was manufactured as follows.
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.The glass substrate coated with ITO (Indium tin oxide) with a thickness of 1500Å was washed with distilled water ultrasonically. After washing with distilled water, ultrasonic cleaning is performed with a solvent such as isopropyl alcohol, acetone or methanol, dried, transferred to a UV ozone cleaner (Power sonic 405, Hwashin Tech), and then the substrate is used for 5 minutes using UV. The substrate was cleaned and transferred to a vacuum evaporator.
상기와 같이 준비된 ITO 투명 전극 위에, DS-205 (80 nm)/NPB (15 nm)/AND + 5 % DS-405 (30nm)/표 4의 화합물(30nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 유기 전계 발광 소자를 제조하였다.On the ITO transparent electrode prepared as above, DS-205 (80 nm)/NPB (15 nm)/AND + 5% DS-405 (30 nm)/compound of Table 4 (30 nm)/LiF (1 nm)/Al ( 200 nm) in order to prepare an organic electroluminescent device.
[비교예 3-1] - 청색 유기 전계 발광 소자의 제조[Comparative Example 3-1]-Preparation of blue organic electroluminescent device
전자 수송 보조층을 포함하지 않고, 전자 수송층 물질인 Alq3을 25 nm 대신 30nm로 증착하는 것을 제외하고는, 실시예 73과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다. A blue organic electroluminescent device was manufactured in the same manner as in Example 73, except that the electron transport layer material, Alq 3 , which is an electron transport layer material, was deposited at 30 nm instead of 25 nm.
[비교예 3-2] - 청색 유기 전계 발광 소자의 제조[Comparative Example 3-2]-Preparation of blue organic electroluminescent device
전자 수송 보조층 물질인 G-01 대신 BCP를 사용하는 것을 제외하고는, 실시예 73과 동일하게 수행하여 청색 유기 전계 발광 소자를 제작하였다. A blue organic electroluminescent device was manufactured in the same manner as in Example 73, except that BCP was used instead of the electron transport auxiliary layer material G-01.
[비교예 4-1] - 청색 유기 전계 발광 소자의 제조[Comparative Example 4-1]-Preparation of blue organic electroluminescent device
실시예 109에서 전자 수송층 물질로 화합물 G-14 대신 Alq3를 사용하는 것을 제외하고는, 실시예 109과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in Example 109, except that Alq 3 was used instead of the compound G-14 in Example 109 as the electron transport layer material.
[비교예 4-2] - 청색 유기 전계 발광 소자의 제조[Comparative Example 4-2]-Preparation of blue organic electroluminescent device
실시예 109에서 전자 수송층 물질로 화합물 G-14 대신 M-2를 사용하는 것을 제외하고는, 실시예 109과 동일하게 수행하여 유기 전계 발광 소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 109, except that in Example 109, M-2 was used instead of the compound G-14 as the electron transport layer material.
[평가예 3][Evaluation Example 3]
실시예 73 내지 118 및 비교예 3, 4에서 각각 제조된 유기 전계 발광 소자에 대하여, 전류밀도 10 mA/㎠에서의 구동전압, 전류효율, 발광파장 및 수명(T97)을 측정하였고, 그 결과를 하기 표 3 및 4에 나타내었다.For the organic electroluminescent devices manufactured in Examples 73 to 118 and Comparative Examples 3 and 4, respectively, the driving voltage, current efficiency, emission wavelength, and lifetime (T97) at a current density of 10 mA/cm 2 were measured, and the results were obtained. It is shown in Tables 3 and 4 below.
(V)Driving voltage
(V)
(cd/A)Current efficiency
(cd/A)
(nm)EL peak
(nm)
(hr, T97)life span
(hr, T 97 )
(V)Driving voltage
(V)
(cd/A)Current efficiency
(cd/A)
(nm)Luminous peak
(nm)
표 3에서 알 수 있는 바와 같이, 화합물 G-01 내지 H-18을 전자 수송 보조층 물질로 사용한 실시예 73 내지 108의 청색 유기 EL 소자의 경우, 전자 수송 보조층을 사용하지 않는 비교예 3-1 의 청색 유기 EL 소자와 구동 전압이 유사하거나 약간 우수하나, 전류 효율 및 수명이 크게 향상되었다.As can be seen in Table 3, in the case of the blue organic EL devices of Examples 73 to 108 using the compounds G-01 to H-18 as the electron transport auxiliary layer material, Comparative Example 3- without using the electron transport auxiliary layer Although the driving voltage is similar or slightly superior to that of the blue organic EL device 1, the current efficiency and lifespan are greatly improved.
또한, 실시예 73 내지 108의 청색 유기 EL 소자는 전자 수송 보조층으로 종래 BCP를 사용한 비교예 3-2 의 청색 유기 EL 소자에 비해 구동 전압 및 전류 효율이 우수할 뿐만 아니라, 수명은 현저하게 향상되었다.In addition, the blue organic EL devices of Examples 73 to 108 are not only excellent in driving voltage and current efficiency, but also have significantly improved lifespan compared to the blue organic EL device of Comparative Example 3-2 using a conventional BCP as an electron transport auxiliary layer. Became.
나아가, 화합물 G-14 내지 H-18을 전자 수송층 물질로 사용한 실시예 109 내지 118의 청색 유기 EL 소자의 경우, 전자 수송층으로 종래 Alq3를 사용한 비교예 4-1의 청색 유기 EL 소자 및 싸이클로헥실이 포함되지 않은 M-2를 사용한 비교예 4-2의 청색 유기 EL 소자에 비해 구동 전압 및 전류 효율이 더 향상되었다.Furthermore, in the case of the blue organic EL devices of Examples 109 to 118 using compounds G-14 to H-18 as the electron transport layer material, the blue organic EL device and cyclohexyl of Comparative Example 4-1 using conventional Alq 3 as the electron transport layer The driving voltage and current efficiency were further improved compared to the blue organic EL device of Comparative Example 4-2 using M-2 which did not include this.
이와 같이, 본 발명에 따른 화합물을 전자 수송 보조층 물질이나 전자 수송층 물질로 사용한 경우, 구동전압 및 전류 효율이 향상되고, 나아가 수명 특성이 크게 향상될 수 있다는 것을 확인할 수 있었다.As described above, when the compound according to the present invention is used as an electron transport auxiliary layer material or an electron transport layer material, it was confirmed that driving voltage and current efficiency are improved, and further, life characteristics can be greatly improved.
10: 양극
20: 음극
30: 유기물층
31: 정공 수송층
32: 발광층
33: 정공 수송 보조층
34: 전자 수송층
35: 전자 수송 보조층
36: 전자 주입층
37: 정공 주입층10: anode 20: cathode
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 (11)
[화학식 1]
[화학식 2]
상기 화학식 1 또는 화학식 2에서,
R1 내지 R12는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며, 인접한 기는 서로 결합하여 지방족 또는 방향족 고리를 형성하고,
Ar은 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되며,
L은 단일결합 또는 C6~C18의 아릴렌기 및 핵원자수 5 내지 18개의 헤테로아릴렌기로 이루어진 군에서 선택되며,
상기 L의 아릴렌기, 헤테로아릴렌기 및 R1 내지 R12, Ar 의 알킬기, 알케닐기, 알키닐기, 아릴기, 헤테로아릴기, 아릴옥시기, 알킬옥시기, 시클로알킬기, 헤테로시클로알킬기, 아릴아민기, 알킬실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 모노 또는 디아릴포스피닐기 및 아릴실릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C6~C60의 아릴옥시기, C1~C40의 알킬옥시기, C6~C60의 아릴아민기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C1~C40의 알킬실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴실릴기로 이루어진 군에서 선택된 1종 이상의 치환기로 치환되거나 비치환되고, 복수 개의 치환기로 치환되는 경우, 이들은 서로 동일하거나 상이할 수 있다.Compound represented by the following formula 1 or formula 2:
[Formula 1]
[Formula 2]
In Formula 1 or Formula 2,
R 1 to R 12 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, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 ~ C 60 aryl group, 5 to 60 nuclear atoms heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkyl silyl 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 Arylphosphine group, C 6 ~ C 60 Mono or diarylphosphinyl group and C 6 ~ C 60 arylamine group is selected from the group consisting of, adjacent groups combine with each other to form an aliphatic or aromatic ring,
Ar is a C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 6 Aryl group of ~C 60 , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C 1 ~C 40 , aryloxy group of C 6 ~C 60 , alkylsilyl group of C 3 ~C 40 , C 6 ~ C aryl silyl group of 60, group alkylboronic of C 1 ~ C 40, C 6 ~ C group 60 arylboronic of, C 6 ~ mono or diaryl phosphine of C 60 aryl phosphine group, C 6 ~ C 60 of the blood It is selected from the group consisting of an arylamine group and a C 6 ~ C 60 ,
L is selected from the group consisting of a single bond or an arylene group of C 6 ~ C 18 and a heteroarylene group having 5 to 18 nuclear atoms,
The arylene group of L, heteroarylene group and R 1 to R 12 , Ar alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine Group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an arylphosphine group, a mono or diarylphosphinyl group, and an arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C 1 to C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 60 aryl group, a nuclear number of 5 to 60 heteroaryl group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 arylamine group, C 3 ~ C 40 cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C 1 ~ C 40 alkylsilyl group, C 1 C ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 arylphosphine group, C 6 ~ C 60 mono or diarylphosphinyl group and C 6 ~ C 60 arylsilyl When substituted with one or more substituents selected from the group consisting of groups or unsubstituted, and substituted with a plurality of substituents, they may be the same or different from each other.
상기 화학식 1은 하기 화학식 3 또는 화학식 4로 표시되는 것을 특징으로 하는 화합물:
[화학식 3]
[화학식 4]
상기 화학식 3 내지 4에서,
L과 Ar은 상기 화학식 1에서 정의된 바와 같다.According to claim 1,
Formula 1 is a compound characterized in that represented by the following formula (3) or formula (4):
[Formula 3]
[Formula 4]
In Chemical Formulas 3 to 4,
L and Ar are as defined in Formula 1 above.
상기 화학식 2는 하기 화학식 5 또는 화학식 6으로 표시되는 것을 특징으로 하는 화합물:
[화학식 5]
[화학식 6]
상기 화학식 5 내지 6에서,
L과 Ar은 상기 화학식 2에서 정의된 바와 같다.According to claim 1,
Formula 2 is a compound characterized in that represented by the following Formula 5 or Formula 6:
[Formula 5]
[Formula 6]
In Chemical Formulas 5 to 6,
L and Ar are as defined in Formula 2 above.
상기 Ar은 하기 하기 A-1 내지 A-4 중에서 선택되는 치환기인 것을 특징으로 하는 화합물:
상기 A-1 내지 A-4에서,
*는 결합이 이루어지는 부분이고,
X1과 X2 중 어느 하나는 N이고 나머지는 C1이고, 상기 C1은 Ar1과 결합하며,
X3 내지 X5은 N 또는 C(R13)이나, 적어도 둘 이상은 N이고,
Z는 O 또는 S이며,
Ar1 내지 Ar3은 각각 독립적으로 치환 또는 비치환된 아릴기이거나, 치환 또는 비치환된 헤테로아릴기이고,
R13은 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40개의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60개의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 모노 또는 디아릴포스피닐기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된다.According to claim 1,
The Ar is a compound, characterized in that a substituent selected from the following A-1 to A-4:
In A-1 to A-4,
* Is the part where the bond is made,
One of X 1 and X 2 is N and the other is C 1 , and C 1 is bonded to Ar 1 ,
X 3 to X 5 is N or C(R 13 ), but at least two or more are N,
Z is O or S,
Ar 1 to Ar 3 are each independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
R 13 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, Heterocycloalkyl group having 3 to 40 nuclear atoms, aryl group of C 6 to C 60 , heteroaryl group having 5 to 60 nuclear atoms, alkyloxy group of C 1 to C 40 , aryloxy group of C 6 to C 60 , 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 arylphosphine group , C 6 ~ C 60 mono or diarylphosphinyl group and C 6 ~ C 60 arylamine group.
Ar1은 하기 B-1 내지 B-3 중에서 선택되는 치환기인 것을 특징으로 하는 화합물:
상기 B-1 내지 B-3에서, *는 결합이 이루어지는 부분이다.According to claim 4,
Ar 1 is a compound characterized in that it is a substituent selected from B-1 to B-3:
In B-1 to B-3, * is a portion where a bond is formed.
Ar2 또는 Ar3은 하기 C-1 내지 C-4 중에서 선택되는 치환기인 것을 특징으로 하는 화합물:
상기 C-1 내지 C-4에서, *는 결합이 이루어지는 부분이다.According to claim 4,
Ar 2 or Ar 3 is a compound, characterized in that a substituent selected from the following C-1 to C-4:
In C-1 to C-4, * is a portion where a bond is formed.
상기 L은 단일결합 또는 페닐렌인 것을 특징으로 하는 화합물.According to claim 1,
The L is a compound characterized in that the single bond or phenylene.
상기 화합물은 아래의 화합물로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.
The compound is a compound characterized in that it is 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 organic material layer of the one or more layers comprises 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.The method of claim 9,
The organic material layer includes 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.
상기 유기물층은 발광층, 전자 수송층 및 전자 수송 보조층으로 이루어진 군에서 선택되는 하나 이상의 층을 포함하는, 유기 전계 발광 소자.The method of claim 9,
The organic material layer comprises at least one layer selected from the group consisting of a light emitting layer, an electron transport layer and an electron transport auxiliary layer, an organic electroluminescent device.
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