KR101577112B1 - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Organic compounds and organic electro luminescence device comprising the same Download PDF

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KR101577112B1
KR101577112B1 KR1020130105474A KR20130105474A KR101577112B1 KR 101577112 B1 KR101577112 B1 KR 101577112B1 KR 1020130105474 A KR1020130105474 A KR 1020130105474A KR 20130105474 A KR20130105474 A KR 20130105474A KR 101577112 B1 KR101577112 B1 KR 101577112B1
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심재의
손효석
이재훈
박호철
이창준
신진용
백영미
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H—ELECTRICITY
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract

본 발명은 신규 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것으로서, 디하이드로티에노퀴놀린 코어(Dihydrothienoquinoline Core)를 포함하는 화합물이 유기 전계 발광 소자용 재료, 바람직하게는 발광층의 호스트 재료로 도입됨으로써, 유기 전계 발광 소자의 발광효율, 구동 전압 및 수명 등의 전반적인 특성을 향상시킨 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device including the organic compound, wherein a compound containing dihydrothienoquinoline core is introduced into a material for an organic electroluminescence device, preferably a host material of a light emitting layer , The light emitting efficiency of the organic electroluminescent device, the driving voltage, and the lifetime.

Description

유기 화합물 및 이를 포함하는 유기 전계 발광 소자{ORGANIC COMPOUNDS AND ORGANIC ELECTRO LUMINESCENCE DEVICE COMPRISING THE SAME}TECHNICAL FIELD [0001] The present invention relates to an organic compound and an organic electroluminescent device including the organic compound.

본 발명은 신규 유기 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic compound and an organic electroluminescent device including the same.

유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 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 layer in the anode, and electrons are injected into the organic layer in the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. At this time, the material used as the organic material layer can be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material and the like depending on its function.

상기 발광 물질은 발광색에 따라 청색, 녹색, 적색 발광 물질과, 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 물질로 구분될 수 있다. 또한, 색순도의 증가와 에너지 전이를 통해 발광 효율을 증가시키기 위하여, 발광 물질로서 호스트/도판트 계를 사용할 수 있다.The luminescent material may be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials necessary to realize better natural colors. Further, a host / dopant system can be used as a light emitting material in order to increase the luminous efficiency through increase of color purity and energy transfer.

도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 이때, 인광 도판트는 이론적으로 형광 도판트에 비해 최대 4배의 발광 효율을 향상시킬 수 있기 때문에, 인광 도판트 뿐만 아니라 인광 호스트에 대한 연구가 많이 진행되고 있다.The dopant material can 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. Since the phosphorescent dopant can theoretically improve the luminous efficiency up to 4 times as compared with the fluorescent dopant, studies on the phosphorescent dopant as well as the phosphorescent host have been conducted.

발광층에 사용되는 형광 도판트/호스트 물질로는 안트라센 유도체들이 알려져 있다. 또한 발광층에 사용되는 인광 도판트 물질로는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등의 Ir을 포함하는 금속 착체 화합물이 알려져 있고, 인광 호스트 물질로는 4,4-dicarbazolybiphenyl(CBP)가 알려져 있다.An anthracene derivative is known as a fluorescent dopant / host material used in a light emitting layer. As phosphorescent dopant materials used for the light emitting layer, metal complex compounds including Ir such as Firpic, Ir (ppy) 3 , (acac) Ir (btp) 2 and the like are known. As phosphorescent host materials, 4,4-dicarbazolybiphenyl (CBP) is known.

그러나 기존의 재료들은 발광 특성 측면에서는 유리한 면이 있으나, 유리전이온도가 낮아 열적 안정성이 떨어지기 때문에 유기 전계 발광 소자의 수명 측면에서 만족할 만한 수준이 되지 못하고 있다.However, existing materials have advantages in terms of luminescent properties, but their thermal stability is poor due to their low glass transition temperature, which is not satisfactory in terms of lifetime of an organic electroluminescent device.

상기한 문제점을 해결하기 위해 본 발명은 삼중항 에너지가 높고, 정공과 전자의 결합력이 향상된 신규 유기 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, it is an object of the present invention to provide a novel organic compound having a high triplet energy and improved bonding strength between holes and electrons.

또, 본 발명은 상기 신규 유기 화합물을 포함하는 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.It is another object of the present invention to provide an organic electroluminescent device comprising the novel organic compound.

상기한 목적을 달성하기 위해 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.In order to accomplish the above object, the present invention provides a compound represented by the following general formula (1).

[화학식 1][Chemical Formula 1]

Figure 112013080502441-pat00001
Figure 112013080502441-pat00001

상기 화학식 1에서,In Formula 1,

X1 및 X2는 각각 독립적으로 O, S, N(Ar2) 및 C(Ar3)(Ar4)로 이루어진 군에서 선택되고, 이때, X1 및 X2가 모두 N(Ar2)일 경우 복수개의 N(Ar2)은 서로 동일하거나 상이며, X1 및 X2가 모두 C(Ar3)(Ar4)일 경우 복수개의 C(Ar3)(Ar4)는 서로 동일하거나 상이하며,X 1 and X 2 are each independently selected from the group consisting of O, S, N (Ar 2 ) and C (Ar 3 ) (Ar 4 ), wherein X 1 and X 2 are both N (Ar 2 ) a plurality of N (Ar 2) if the same or a phase with each other, X 1 and X 2 are both C (Ar 3) (Ar 4 ) a plurality of C (Ar 3) when the (Ar 4) are the same or different, and ,

R1 내지 R8은 각각 독립적으로 수소, 중수소, 할로겐기, 시아노기, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되거나, 인접한 기와 결합하여 축합 고리를 형성할 수 있으며,R 1 to R 8 are each independently hydrogen, deuterium, halogen group, cyano group, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group of the, C 6 ~ heteroaryl of C 60 aryl group, the nuclear atoms of 5 to 60 aryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 aryloxy group, C 3 ~ C 40 alkylsilyl group, a C 6 ~ group C 60 aryl silyl group, C 1 ~ alkyl boron C 40 of, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C of An arylamine group having 6 to 60 carbon atoms, or may be bonded to an adjacent group to form a condensed ring,

Ar1 내지 Ar4는 각각 독립적으로 C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,Ar 1 to Ar 4 each independently represent a C 1 to C 40 alkyl group, a C 3 to C 40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C 6 to C 60 aryl group, of to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 60 of the aryloxy group, C 3 ~ C 40 alkylsilyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ of group of the C 40 alkyl boron, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ the group consisting of an aryl amine of the C 60 Lt; / RTI >

상기 R1 내지 R8 및 Ar1 내지 Ar4의 알킬기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로, C1~C40의 알킬기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C3~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다. 이때, 복수개의 치환기로 치환될 경우 이들은 서로 동일하거나 상이할 수 있다.Alkyl group of the R 1 to R 8 and Ar 1 to Ar 4, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an arylamine group, each independently, C 1 ~ C 40 alkyl group, C 3 ~ C 40 cycloalkyl group, nuclear atoms, 3 to 40 heterocycloalkyl group of the, C 6 ~ C 60 aryl group, nuclear atoms aryl of from 5 to 60 heteroaryl group, a C 1 ~ C 40 alkyloxy group of, C 6 ~ aryloxy C 60, C 3 ~ C 40 alkyl silyl group, C 6 ~ C 60 aryl silyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C group 60 arylboronic of, C 6 ~ C 60 aryl phosphine group, C 6 ~ aryl phosphine oxide of a C 60 group, and An arylamine group having 6 to 60 carbon atoms, and an arylamine group having 6 to 60 carbon atoms. When substituted with a plurality of substituents, they may be the same or different.

또한, 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.Also, the present invention provides an organic electroluminescent device including a cathode, a cathode, and at least one organic layer interposed between the anode and the cathode, to provide.

여기서, 상기 화학식 1의 화합물을 포함하는 유기물층은 인광 발광층일 수 있다.Here, the organic compound layer containing the compound of Formula 1 may be a phosphorescent light-emitting layer.

본 발명에서 '알킬'은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, 'alkyl' means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.

본 발명에서 '알케닐(alkenyl)'은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkenyl" means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

본 발명에서 '알키닐(alkynyl)'은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소에서 유래되는 1가의 치환기를 의미한다. 이의 예로는 에티닐(ethynyl), 2-프로파닐(2-propynyl) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "alkynyl" means a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

본 발명에서 '아릴'은 단독 고리 또는 2 이상의 고리가 조합된 탄소수 6 내지 40의 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 또한, 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있다. 이러한 아릴의 예로는 페닐, 나프틸, 페난트릴, 안트릴 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. Also, a form in which two or more rings are pendant or condensed with each other may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

본 발명에서 '헤테로아릴'은 핵원자수 5 내지 40의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이때, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S 또는 Se와 같은 헤테로원자로 치환된다. 또한 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태도 포함될 수 있고, 나아가 아릴기와의 축합된 형태도 포함될 수 있다. 이러한 헤테로아릴의 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6-원 모노사이클릭 고리, 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, 'heteroaryl' means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. Wherein at least one of the carbons, preferably one to three carbons, is replaced by a heteroatom such as N, O, S or Se. It is also possible to include a form in which two or more rings are pendant or condensed with each other, and further, a condensed form with an aryl group may be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl indolyl), purinyl, quinolyl, benzothiazole, carbazolyl, and heterocyclic rings such as 2-furanyl, N-imidazolyl, 2- , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

본 발명에서 '아릴옥시'는 RO-로 표시되는 1가의 치환기로, 상기 R은 탄소수 5 내지 40의 아릴을 의미한다. 이러한 아릴옥시의 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, 'aryloxy' is a monovalent substituent represented by RO-, and R is aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

본 발명에서 '알킬옥시'는 R'O-로 표시되는 1가의 치환기로, 상기 R'는 탄소수 1 내지 40의 알킬을 의미하며, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 알킬옥시의 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, 'alkyloxy' means a monovalent substituent group represented by R'O-, wherein R 'represents alkyl having 1 to 40 carbon atoms, and may be a linear, branched or cyclic structure . ≪ / RTI > Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy and pentoxy.

본 발명에서 '아릴아민'은 탄소수 6 내지 40의 아릴로 치환된 아민을 의미한다.In the present invention, 'arylamine' means an amine substituted with aryl having 6 to 40 carbon atoms.

본 발명에서 '시클로알킬'은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소로부터 유래된 1가의 치환기를 의미한다. 이러한 사이클로알킬의 예로는 사이클로프로필, 사이클로펜틸, 사이클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine) 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

본 발명에서 '헤테로시클로알킬'은 핵원자수 3 내지 40의 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 등을 들 수 있으나, 이에 한정되지는 않는다.In the present invention, 'heterocycloalkyl' means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon atom, preferably 1 to 3 carbons, of the ring is N, O, S Or < RTI ID = 0.0 > Se. ≪ / RTI > Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

본 발명에서 '알킬실릴'은 탄소수 1 내지 40의 알킬로 치환된 실릴이고, '아릴실릴'은 탄소수 5 내지 40의 아릴로 치환된 실릴을 의미한다.In the present invention, 'alkylsilyl' is silyl substituted with alkyl having 1 to 40 carbon atoms, and 'arylsilyl' means silyl substituted with aryl having 5 to 40 carbon atoms.

본 발명에서 '축합 고리'는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.In the present invention, the term "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

본 발명의 화학식 1로 표시되는 화합물은 열적 안정성 및 인광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물층의 재료로 사용될 수 있다. 특히, 본 발명의 화학식 1로 표시되는 화합물을 인광 호스트 재료로 사용할 경우, 종래의 호스트 재료에 비해 우수한 발광 성능, 낮은 구동전압, 높은 효율 및 장수명을 갖는 유기 전계 발광 소자를 제조할 수 있고, 나아가 성능 및 수명이 향상된 풀 칼라 디스플레이 패널도 제조할 수 있다.The compound represented by the formula (1) of the present invention is excellent in thermal stability and phosphorescence properties and can be used as a material for an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, it is possible to produce an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency, and long life time, A full color display panel having improved performance and lifetime can be manufactured.

이하, 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.

1. 신규 유기 화합물1. New organic compounds

본 발명에 따른 신규 유기 화합물은 황(S) 또는 질소(N)로 치환된 디하이드로티에노퀴놀린 코어(Dihydrothienoquinoline Core)를 포함하는 것으로, 상기 화학식 1로 표시된다.The novel organic compound according to the present invention includes a dihydrothienoquinoline core substituted with sulfur (S) or nitrogen (N), and is represented by the above formula (1).

이러한 화학식 1로 표시되는 화합물은 삼중항 에너지가 높고 분자 전체가 바이폴라(bipolar) 특성을 가져 정공과 전자의 결합력이 높다. 또한 다양한 치환체로 치환됨으로써 분자량이 유의적으로 증대되어 유리전이온도가 높다.The compound represented by the formula (1) has high triplet energy and the bipolar characteristic of the whole molecule, so that the binding force between the hole and the electron is high. Also, the substitution of various substituents significantly increases the molecular weight and the glass transition temperature is high.

따라서 본 발명의 화학식 1로 표시되는 화합물을 유기 전계 발광 소자의 유기물층 재료로 사용할 경우 소자의 인광 특성뿐만 아니라 정공 주입 능력 및 정공 수송 능력도 높일 수 있다. 특히 본 발명의 화학식 1로 표시되는 화합물을 유기 전계 발광 소자의 유기물층 중 발광층의 재료로 사용할 경우 종래의 재료(예를 들어, CBP(4,4-dicarbazolybiphenyl))에 비해 높은 열적 안정성을 나타낼 수 있다.Therefore, when the compound represented by Formula 1 of the present invention is used as an organic material layer material of an organic electroluminescent device, not only the phosphorescence characteristics of the device, but also the hole injecting ability and the hole transporting ability can be increased. In particular, when the compound represented by Formula 1 of the present invention is used as a material of the light emitting layer in the organic material layer of the organic electroluminescent device, it can exhibit higher thermal stability than conventional materials (for example, CBP (4,4-dicarbazolylbiphenyl) .

또한 본 발명의 화학식 1로 표시되는 화합물은 다양한 치환체에 의해 유기물층의 결정화를 억제할 수 있기 때문에 유기 전계 발광 소자의 내구성 및 수명도 향상시킬 수 있다. 이와 같은 유기 전계 발광 소자의 수명 향상은 풀 칼라 디스플레이 패널의 성능을 향상시키는 결과를 얻을 수 있다.In addition, since the compound represented by Formula 1 of the present invention can inhibit the crystallization of the organic material layer by various substituents, the durability and lifetime of the organic electroluminescent device can be improved. The lifetime of the organic electroluminescent device can be improved by improving the performance of the full color display panel.

이러한 본 발명의 화학식 1로 표시되는 화합물은 유기 전계 발광 소자의 특성을 고려할 때, 상기 화학식 1에서, X1는 S 또는 O인 것이 바람직하며, S인 것이 더욱 바람직하다. 또 화학식 1에서, X2는 S 또는 N(Ar2)인 것이 바람직하다.In the compound represented by the formula (1) of the present invention, X 1 is preferably S or O, and more preferably S, in the formula (1), considering the characteristics of the organic electroluminescent device. In Formula (1), X 2 is preferably S or N (Ar 2 ).

또한 본 발명의 화학식 1로 표시되는 화합물은 유기 전계 발광 소자의 특성을 고려할 때, 화학식 1에서, R1 내지 R8은 모두 수소이고, Ar1 및 Ar2는 각각 독립적으로 C6~C60의 아릴기 또는 핵원자수 5 내지 60의 헤테로아릴기인 것이 바람직하다.In the formula 1, R 1 to R 8 are all hydrogen, Ar 1 and Ar 2 are each independently a C 6 to C 60 An aryl group or a heteroaryl group having 5 to 60 nuclear atoms.

이러한 본 발명의 화학식 1로 표시되는 화합물은 구체적으로, 하기 1 내지 142로 표시될 수 있으나, 이에 한정되지는 않는다.The compounds represented by formula (1) of the present invention may be represented by the following formulas (1) to (142), but are not limited thereto.

Figure 112013080502441-pat00002
Figure 112013080502441-pat00002

Figure 112013080502441-pat00003
Figure 112013080502441-pat00003

Figure 112013080502441-pat00004
Figure 112013080502441-pat00004

Figure 112013080502441-pat00005
Figure 112013080502441-pat00005

Figure 112013080502441-pat00006
Figure 112013080502441-pat00006

Figure 112013080502441-pat00007
Figure 112013080502441-pat00007

Figure 112013080502441-pat00008
Figure 112013080502441-pat00008

Figure 112013080502441-pat00009
Figure 112013080502441-pat00009

본 발명의 화학식 1로 표시되는 화합물을 합성하는 방법은 특별히 한정되지 않으나, 하기 반응식 1 또는 2에 따라 합성할 수 있다.
The method for synthesizing the compound represented by the formula (1) of the present invention is not particularly limited, but it can be synthesized according to the following Reaction Scheme 1 or 2.

[반응식 1] [Reaction Scheme 1] DihydrothienoquinolineDihydrothienoquinoline CoreCore I I

Figure 112013080502441-pat00010
Figure 112013080502441-pat00010

[반응식 2] [Reaction Scheme 2] DihydrothienoquinolineDihydrothienoquinoline CoreCore IIII

Figure 112013080502441-pat00011
Figure 112013080502441-pat00011

이러한 본 발명의 화학식 1로 표시되는 화합물의 합성 과정은 하기 합성예에서 구체적으로 설명하도록 한다.
The process for synthesizing the compound represented by the formula (1) of the present invention will be described in detail in the following Synthesis Examples.

2. 유기 2. Organic 전계Field 발광 소자 Light emitting element

본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.The present invention provides an organic electroluminescent device comprising a compound represented by the above formula (1).

구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode), 음극(cathode) 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함한다. 이때, 상기 화합물은 단독으로 사용되거나, 또는 2 이상이 혼합되어 사용될 수 있다.Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and at least one organic layer sandwiched between the anode and the cathode, wherein at least one of the one or more organic layers includes Include compounds represented by the above formula (1). At this time, the compounds may be used alone or in combination of two or more.

상기 1층 이상의 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있고, 이 중에서 적어도 하나의 유기물층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 구체적으로 상기 화학식 1의 화합물을 포함하는 유기물층은 발광층인 것이 바람직하다.The one or more organic layers may be at least one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer, and at least one of the organic layers may include a compound represented by Formula 1. [ Specifically, the organic material layer containing the compound of Formula 1 is preferably a light emitting layer.

본 발명의 유기 전계 발광 소자의 발광층은 호스트 재료를 포함할 수 있는데, 이때 호스트 재료로서 상기 화학식 1의 화합물을 포함할 수 있다. 이와 같이, 상기 화학식 1의 화합물을 유기 전계 발광 소자의 발광층 재료, 바람직하게는 청색, 녹색, 적색의 인광 호스트 재료로 포함할 경우, 발광층에서 정공과 전자의 결합력이 높아지기 때문에, 유기 전계 발광 소자의 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등을 향상시킬 수 있다.The light emitting layer of the organic electroluminescent device of the present invention may include a host material, and may include the compound of Formula 1 as a host material. When the compound of Formula 1 is included in the light emitting layer material of the organic electroluminescent device, preferably blue, green, and red phosphorescent host materials, the bonding strength between holes and electrons in the light emitting layer increases, Efficiency (luminous efficiency and power efficiency), lifetime, luminance, driving voltage, and the like can be improved.

이러한 본 발명의 유기 전계 발광 소자의 구조는 특별히 한정되지 않으나, 기판, 양극, 정공주입층, 정공수송층, 발광층, 전자수송층 및 음극이 순차적으로 적층된 구조일 수 있다. 이때, 상기 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 하나 이상은 상기 화학식 1로 표시되는 화합물을 포함할 수 있고, 바람직하게는 발광층이 상기 화학식 1로 표시되는 화합물을 포함할 수 있다. 구체적으로, 상기 화학식 1의 화합물은 발광층의 인광 호스트 재료로 이용될 수 있다. 한편 상기 전자수송층 위에는 전자주입층이 추가로 적층될 수 있다.The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode are sequentially laminated. At least one of the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer may include a compound represented by Formula 1, and preferably, the emitting layer includes a compound represented by Formula 1 . Specifically, the compound of Formula 1 may be used as a phosphorescent host material of the light emitting layer. On the other hand, an electron injection layer may be further stacked on the electron transport layer.

본 발명의 유기 전계 발광 소자의 구조는 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조일 수 있다.The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted into the interface between the electrode and the organic layer.

본 발명의 유기 전계 발광 소자는 상기 유기물층 중 1층 이상(바람직하게는 발광층)이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당업계에 공지된 재료 및 방법으로 유기물층 및 전극을 형성하여 제조할 수 있다.The organic electroluminescent device of the present invention may be formed by forming an organic material layer and an electrode by materials and methods known in the art, except that at least one layer (preferably a light emitting layer) of the organic material layer contains the compound represented by the above formula Can be manufactured.

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 한정되지는 않는다.The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

본 발명의 유기 전계 발광 소자 제조 시 사용되는 기판은 특별히 한정되지 않으나, 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등을 사용할 수 있다.The substrate used in the fabrication of the organic electroluminescent device of the present invention is not particularly limited, but silicon wafer, quartz, glass plate, metal plate, plastic film and sheet can be used.

또, 양극 물질로는 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 등을 들 수 있으나, 이에 한정되지는 않는다.Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO 2: a combination of a metal and an oxide such as 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 are not limited thereto.

또, 음극 물질로는 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 등을 들 수 있으나, 이에 한정되지는 않는다.The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or an alloy thereof; And multi-layer structure materials such as LiF / Al or LiO 2 / Al, but are not limited thereto.

또한, 정공 주입층, 정공 수송층, 전자 주입층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질을 사용할 수 있다.
The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and ordinary materials known in the art can be used.

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 with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[[ 준비예Preparation Example 1] 6,12- 1] 6,12- dihydrobenzodihydrobenzo [4,5][4,5] thienothieno [2,3-b][2,3-b] benzobenzo [4,5][4,5] thienothieno [2,3-e]pyridine의 합성[2,3-e] pyridine

<단계 1> 3-&Lt; Step 1 > 3- BromobenzoBromobenzo [b]thiophene의 합성Synthesis of [b] thiophene

Figure 112013080502441-pat00012
Figure 112013080502441-pat00012

Benzo[b]thiophene 30 g (0.224 mol)에 CHCl3 225 mL와 AcOH 225 mL를 상온에서 가하였다. N-Bromosuccinimide 43.8g (0.246 mol)을 반응액에 첨가하고, 3시간 동안 가열환류하였다. 0℃로 냉각하고 포화 NaHCO3 수용액으로 중화하여 반응을 종결하였다. CH3Cl 500 mL로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 45.3 g (수율 95%)을 얻었다.225 mL of CHCl 3 and 225 mL of AcOH were added to 30 g (0.224 mol) of Benzo [b] thiophene at room temperature. N- Bromosuccinimide (43.8 g, 0.246 mol) was added to the reaction solution, and the mixture was refluxed for 3 hours. The reaction mixture was cooled to 0 ° C and neutralized with a saturated aqueous solution of NaHCO 3 to terminate the reaction. The organic layer was separated with 500 mL of CH 3 Cl and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (45.3 g, yield 95%).

1H-NMR(in CDCl3) : δ 7.85 (d, 2H), 7.46 (m, 3H) 1 H-NMR (in CDCl 3 ):? 7.85 (d, 2H), 7.46 (m, 3H)

<단계 2> 3-&Lt; Step 2 > 3- BromoBromo -2--2- nitrobenzonitrobenzo [b]thiophene의 합성Synthesis of [b] thiophene

Figure 112013080502441-pat00013
Figure 112013080502441-pat00013

3-Bromobenzo[b]thiophene 45 g (0.211 mol)에 CH2Cl2 350 mL를 가하였다. 온도를 0℃로 냉각하고 trifluoroacetic anhydride 64 mL를 첨가하고 10 분간 교반하였다. HNO3 16 mL를 동일온도에서 반응액에 천천히 적가하였다. 0℃에서 30분간 교반 후 반응액을 포화 NaHCO3 수용액으로 중화하여 반응을 종결하였다. CH2Cl2 500 mL로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 32.3 g (수율 60%)을 얻었다.To 45 g (0.211 mol) of 3-bromobenzo [b] thiophene was added 350 mL of CH 2 Cl 2 . The temperature was cooled to 0 ° C and 64 mL of trifluoroacetic anhydride was added and stirred for 10 min. 16 mL of HNO 3 was slowly added dropwise to the reaction solution at the same temperature. After stirring at 0 ° C for 30 minutes, the reaction solution was neutralized with a saturated aqueous solution of NaHCO 3 , and the reaction was terminated. The organic layer was separated with 500 mL of CH 2 Cl 2 and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (32.3 g, yield 60%).

1H-NMR : δ 8.04 (d, 1H), 7.81 (d, 1H), 7.64 (t, 1H), 7.57 (t, 1H) 1 H-NMR: δ 8.04 ( d, 1H), 7.81 (d, 1H), 7.64 (t, 1H), 7.57 (t, 1H)

<단계 3> 2-<Step 3> 2- NitroNitro -N--N- phenylbenzophenylbenzo [b]thiophen-3-[b] thiophen-3- amineamine 의 합성Synthesis of

Figure 112013080502441-pat00014
Figure 112013080502441-pat00014

3-Bromo-2-nitrobenzo[b]thiophene 32 g (0.124 mol)과 aniline 52 g (0.558 mol)에 dioxane 250 mL를 가하였다. Pd2(dba)3 5.7 g (0.006 mol), BINAP 3.9 g (0.006 mol), Cs2CO3 80.8 g (0.248 mol)을 첨가 후 120℃에서 8시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 30.8 g (수율 92%)을 얻었다.250 mL of dioxane was added to 32 g (0.124 mol) of 3-bromo-2-nitrobenzo [b] thiophene and 52 g (0.558 mol) of aniline. 5.7 g (0.006 mol) of Pd 2 (dba) 3 , 3.9 g (0.006 mol) of BINAP and 80.8 g (0.248 mol) of Cs 2 CO 3 were added and the mixture was refluxed at 120 ° C for 8 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA, and then washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the aimed compound (30.8 g, yield 92%).

1H-NMR : δ 10.25 (s, 1H), 7.66 (d, 1H), 7.50 (m, 3H), 7.37 (d, 1H), 7.30 (m, 2H), 7.07 (m, 2H) 1 H-NMR: δ 10.25 ( s, 1H), 7.66 (d, 1H), 7.50 (m, 3H), 7.37 (d, 1H), 7.30 (m, 2H), 7.07 (m, 2H)

<단계 4> <Step 4> terttert -- ButylButyl -2--2- nitrobenzonitrobenzo [b]thiophen-3-[b] thiophen-3- ylyl (( phenylphenyl )carbamate의 합성) Synthesis of carbamate

Figure 112013080502441-pat00015
Figure 112013080502441-pat00015

2-Nitro-N-phenylbenzo[b]thiophen-3-amine 30 g (0.111 mol)에 CH2Cl2 700 mL를 가하였다. 0℃로 냉각하고 dimethylaminopyridine 27.1g (0.222 mol)과 triethylamine 77.3 mL (0.555 mol)를 반응액에 첨가하였다. 동일온도에서 Di-tert-butyl dicarbonate 242 g (1.11 mol)을 CH2Cl2 250 mL에 용해시켜 적가하였다. 반응액을 12시간 동안 가열환류하고 반응을 종결하였다. 포화 NH4Cl 수용액으로 중화하고 혼합액을 CH2Cl2 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 20.6 g (수율 50%)을 얻었다.To 30 g (0.111 mol) of 2-nitro-N-phenylbenzo [b] thiophen-3-amine was added 700 mL of CH 2 Cl 2 . After cooling to 0 ° C, 27.1 g (0.222 mol) of dimethylaminopyridine and 77.3 mL (0.555 mol) of triethylamine were added to the reaction mixture. At the same temperature, 242 g (1.11 mol) of di-tert-butyl dicarbonate was dissolved in 250 mL of CH 2 Cl 2 and added dropwise. The reaction solution was heated to reflux for 12 hours, and the reaction was terminated. The reaction mixture was neutralized with saturated aqueous NH 4 Cl solution, and the mixture was extracted with 500 mL of CH 2 Cl 2 and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the aimed compound (20.6 g, yield 50%).

[HRMS] : 370[HRMS]: 370

<단계 5> <Step 5> BenzothienoBenzothieno [2,3-b]quinoxaline의 합성Synthesis of [2,3-b] quinoxaline

Figure 112013080502441-pat00016
Figure 112013080502441-pat00016

tert-Butyl-2-nitrobenzo[b]thiophen-3-yl(phenyl)carbamate 20 g (0.054 mol)에 1,2-dichlorobenzene 100 mL를 가하였다. Triphenylphosphine 35.4 g (0.135 mol)을 반응액에 첨가하였다. 반응액을 8시간 동안 가열환류하고 반응을 종결하였다. 반응액을 감압증류하여 DCB 용매를 제거하고 증류수 300 mL와 E.A 500 mL로 유기층을 분리하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 4.5 g (수율 35%)을 얻었다.100 mL of 1,2-dichlorobenzene was added to 20 g (0.054 mol) of tert-butyl-2-nitrobenzo [b] thiophen-3-yl (phenyl) carbamate. 35.4 g (0.135 mol) of triphenylphosphine was added to the reaction solution. The reaction solution was heated under reflux for 8 hours and the reaction was terminated. The reaction mixture was distilled under reduced pressure to remove the DCB solvent, and the organic layer was separated with 300 mL of distilled water and 500 mL of EA. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 4.5 g (yield 35%) of the desired compound.

1H-NMR(in DMSO) : δ 8.58 (d, 1H), 8.28 (m, 1H), 8.17 (m, 1H), 7.87 (d, 1H), 7.81 (m, 2H), 7.70 (t, 1H), 7.59 (t, 1H) 1 H-NMR (in DMSO) : δ 8.58 (d, 1H), 8.28 (m, 1H), 8.17 (m, 1H), 7.87 (d, 1H), 7.81 (m, 2H), 7.70 (t, 1H ), 7.59 (t, 1 H)

<단계 6> 6,12-&Lt; Step 6 > 6,12- dihydrobenzodihydrobenzo [4,5][4,5] thienothieno [2,3-b][2,3-b] benzobenzo [4,5][4,5] thienothieno [2,3-e]pyridine의 합성[2,3-e] pyridine

Figure 112013080502441-pat00017
Figure 112013080502441-pat00017

Benzothieno[2,3-b]quinoxaline 4.5 g (0.019 mol)에 tetrahydrofuran 100 mL를 가하였다. 반응액을 0℃로 냉각하고 phenyllithium 2.0M 19.0 mL (0.038 mol)를 천천히 적가하였다. 반응액을 상온에서 2시간 동안 교반하고 증류수 100 mL를 첨가하여 반응을 종결하였다. E.A 300 mL로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 4.2 g (수율 70%)을 얻었다.To benzothieno [2,3-b] quinoxaline 4.5 g (0.019 mol) was added 100 mL of tetrahydrofuran. The reaction solution was cooled to 0 ° C and 19.0 mL (0.038 mol) of phenyllithium 2.0M was slowly added dropwise. The reaction solution was stirred at room temperature for 2 hours and 100 mL of distilled water was added to terminate the reaction. The organic layer was separated with 300 mL of EA and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 4.2 g (yield 70%) of the target compound.

1H-NMR(in DMSO) : δ 8.10 (s, 1H), 7.59 (t, 2H), 7.50 (d, 2H), 7.31 (t, 1H), 7.24 (d, 1H), 7.18 (d, 2H), 7.11 (d, 1H), 7.00 (m, 3H), 6.66 (t, 1H)
 1 H-NMR (in DMSO) : δ 8.10 (s, 1H), 7.59 (t, 2H), 7.50 (d, 2H), 7.31 (t, 1H), 7.24 (d, 1H), 7.18 (d, 2H ), 7.11 (d, 1 H), 7.00 (m, 3 H), 6.66 (t,

[[ 준비예Preparation Example 2] 11H- 2] 11H- benzobenzo [b][b] benzobenzo [4,5][4,5] thienothieno [3,2-e][1,4][3,2-e] [1, 4] thiazinethiazine 의 합성Synthesis of

<단계 1> <Step 1> BenzoBenzo [b]thiophene-2-[b] thiophene-2- thiolthiol 의 합성Synthesis of

Figure 112013080502441-pat00018
Figure 112013080502441-pat00018

Benzothiophene 30 g (0.224 mol)에 THF 500 mL를 가하였다. -78℃로 냉각하고 n-BuLi 2.5M solution 98.3 mL (0.246 mol)를 천천히 적가하였다. 1시간 동안 교반한 후 sulfur 14.4 g (0.447 mol)을 반응액에 첨가하였다. 온도를 상온으로 서서히 올리고 12시간 동안 교반한 후 12N HCl 수용액 300 mL를 가하여 반응을 종결하였다. E.A 1 L로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 25.3 g (수율 68%)을 얻었다.To 30 g (0.224 mol) of benzothiophene was added 500 mL of THF. The solution was cooled to -78 ° C and 98.3 mL (0.246 mol) of n-BuLi 2.5M solution was slowly added dropwise. After stirring for 1 hour, 14.4 g (0.447 mol) of sulfur was added to the reaction solution. The temperature was gradually raised to room temperature, stirred for 12 hours, and then 300 mL of a 12N HCl aqueous solution was added to terminate the reaction. The organic layer was separated with 1 L of EA and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (25.3 g, yield 68%).

1H-NMR(in CDCl3) : δ 7.79 (d, 1H), 7.76 (d, 1H), 7.40 (s, 1H), 7.36 (m, 2H) 1 H-NMR (in CDCl 3 ): δ 7.79 (d, 1H), 7.76 (d, 1H), 7.40 (s, 1H), 7.36 (m, 2H)

<단계 2> 2-(<Step 2> 2- ( PhenylthioPhenylthio )) benzobenzo [b][b] thiophenethiophene 의 합성Synthesis of

Figure 112013080502441-pat00019
Figure 112013080502441-pat00019

Benzo[b]thiophene-2-thiol 25 g (0.15 mol)과 1-bromobenzene 26 g (0.165 mol)에 dimethylformamide 250 mL 가하였다. CuI 14.3 g (0.075 mol)과 KOH 16.9 g (0.30 mol)을 반응액에 첨가하였다. 120℃로 가온하여 5 시간 동안 교반하고 증류수 200 mL로 반응을 종결하였다. E.A 1 L로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 32.4 g (수율 75%)을 얻었다.250 mL of dimethylformamide was added to 25 g (0.15 mol) of Benzo [b] thiophene-2-thiol and 26 g (0.165 mol) of 1-bromobenzene. 14.3 g (0.075 mol) of CuI and 16.9 g (0.30 mol) of KOH were added to the reaction solution. The mixture was heated to 120 ° C, stirred for 5 hours, and the reaction was terminated with 200 mL of distilled water. The organic layer was separated with 1 L of EA and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (32.4 g, yield 75%).

1H-NMR(in CDCl3) : δ 7.75 (d, 2H), 7.49 (s, 1H), 7.35 (m, 4H), 7.30 (d, 2H), 7.23 (d, 1H) 1 H-NMR (in CDCl 3 ):? 7.75 (d, 2H), 7.49 (s,

<단계 3> 3-&Lt; Step 3 > 3- NitroNitro -2-(-2-( phenylthio메틸THIO )) benzobenzo [b][b] thiophenethiophene 의 합성Synthesis of

Figure 112013080502441-pat00020
Figure 112013080502441-pat00020

2-(Phenylthio)benzo[b]thiophene 32 g (0.132 mol)에 CH2Cl2 350 mL를 가하였다. 온도를 0℃로 냉각하고 trifluoroacetic anhydride 40 mL를 첨가하고 10분간 교반하였다. HNO3 10 mL를 동일온도에서 반응액에 천천히 적가하였다. 0℃에서 30분간 교반 후 반응액을 포화 NaHCO3 수용액으로 중화하여 반응을 종결하였다. CH2Cl2 500 mL로 유기층을 분리하고 증류수와 소금물로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 19.7 g (수율 52%)을 얻었다.To 32 g (0.132 mol) of 2- (Phenylthio) benzo [b] thiophene was added 350 mL of CH 2 Cl 2 . The temperature was cooled to 0 ° C and 40 mL of trifluoroacetic anhydride was added and stirred for 10 minutes. 10 mL of HNO 3 was slowly added dropwise to the reaction solution at the same temperature. After stirring at 0 ° C for 30 minutes, the reaction solution was neutralized with a saturated aqueous solution of NaHCO 3 , and the reaction was terminated. The organic layer was separated with 500 mL of CH 2 Cl 2 and washed with distilled water and brine. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 19.7 g (yield: 52%) of the title compound.

1H-NMR(in CDCl3) : δ 8.80 (d, 1H), 8.01 (d, 2H), 7.87 (d, 1H), 7.82 (d, 2H), 7.77 (m, 2H), 7.60 (t, 1H) 1 H-NMR (in CDCl 3 ): δ 8.80 (d, 1H), 8.01 (d, 2H), 7.87 (d, 1H), 7.82 (d, 2H), 7.77 (m, 2H), 7.60 (t, 1H)

<단계 4> 11H-&Lt; Step 4 > 11H- benzobenzo [b][b] benzobenzo [4,5][4,5] thienothieno [3,2-e][1,4][3,2-e] [1, 4] thiazinethiazine 의 합성Synthesis of

Figure 112013080502441-pat00021
Figure 112013080502441-pat00021

3-Nitro-2-(phenylthio)benzo[b]thiophene 19 g (0.066 mol)에 1,2-dichlorobenzene 200 mL를 가하였다. Triphenylphosphine 43 g (0.165 mol)을 반응액에 첨가하였다. 반응액을 12 시간 동안 가열환류하고 반응을 종결하였다. 반응액을 감압증류하여 DCB 용매를 제거하고 증류수 300 mL와 E.A 500 mL로 유기층을 분리하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 3.5 g (수율 21%)을 얻었다.200 mL of 1,2-dichlorobenzene was added to 19 g (0.066 mol) of 3-nitro-2- (phenylthio) benzo [b] thiophene. 43 g (0.165 mol) of triphenylphosphine was added to the reaction solution. The reaction solution was heated to reflux for 12 hours, and the reaction was terminated. The reaction mixture was distilled under reduced pressure to remove the DCB solvent, and the organic layer was separated with 300 mL of distilled water and 500 mL of EA. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (3.5 g, yield 21%).

1H-NMR(in DMSO) : δ 8.65 (s, 1H), 7.89 (d, 1H), 7.80 (d, 1H), 7.37 (t, 1H), 7.27 (t, 1H), 7.01 (t, 1H), 6.89 (d, 1H), 6.84 (d, 1H), 6.76 (t, 1H)
 1 H-NMR (in DMSO) : δ 8.65 (s, 1H), 7.89 (d, 1H), 7.80 (d, 1H), 7.37 (t, 1H), 7.27 (t, 1H), 7.01 (t, 1H ), 6.89 (d, 1 H), 6.84 (d, 1 H), 6.76 (t,

[[ 준비예Preparation Example 3] 4-( 3] 4- ( BiphenylBiphenyl -4--4- ylyl )-2-(4-) -2- (4- bromophenylbromophenyl )) quinazolinequinazoline 의 합성Synthesis of

Figure 112013080502441-pat00022
Figure 112013080502441-pat00022

4-(biphenyl-4-yl)-2-chloroquinazoline 10.0 g (31.6 mmol)과 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 9.8 g (34.7 mmol)에 dioxane 200 mL와 증류수 50 mL를 가하였다. Pd(PPh3)4 1.8 g (1.6 mmol), K2CO3 13.1 g (94.7 mmol)을 첨가한 후 120℃에서 3시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 10.8 g (수율 78%)을 얻었다.9.8 g (34.7 mmol) of 2- (4-bromophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 10.0 g (31.6 mmol) of 4- (biphenyl- ) Were added 200 mL of dioxane and 50 mL of distilled water. Pd (PPh 3) 4 1.8 g (1.6 mmol), K 2 CO 3 13.1 g After the addition of (94.7 mmol) was heated to reflux at 120 ℃ for 3 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (10.8 g, yield 78%).

[HRMS]: 437
[HRMS]: 437

[[ 준비예Preparation Example 4] 2-(4- 4] 2- (4- bromophenylbromophenyl )-4,6-) -4,6- bisbis (4-((4-( naphthalennaphthalen -1--One- ylyl )) phenylphenyl )-1,3,5-triazine의 합성) -1,3,5-triazine

Figure 112013080502441-pat00023
Figure 112013080502441-pat00023

반응물로 4-(biphenyl-4-yl)-2-chloroquinazoline 대신 2-chloro-4,6-bis(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine을 사용한 것을 제외하고는 [준비예 3]과 동일한 과정을 수행하여 목적 화합물 8.7 g (수율 71%)을 얻었다.Except that 2-chloro-4,6-bis (4- (naphthalen-1-yl) phenyl) -1,3,5-triazine was used as the reactant instead of 4- (biphenyl-4-yl) Was subjected to the same procedure as in [Preparation Example 3] to obtain 8.7 g (yield 71%) of the desired compound.

[HRMS]: 640
[HRMS]: 640

[[ 준비예Preparation Example 5]  5] PhenylPhenyl linkerlinker 의 합성Synthesis of

Figure 112013080502441-pat00024
Figure 112013080502441-pat00024

반응물로 준비예 1의 6,12-dihydrobenzo[4,5]thieno[2,3-b]benzo[4,5]thieno[2,3-e]pyridine 5.0 g (15.9 mmol)과 1-bromo-4-iodobenzene 6.2 g (17.5 mmol)에 dioxane 150 mL를 가하였다. Pd2(dba)3 0.73 g (0.8 mmol), BINAP 0.5 g (0.8 mmol), Cs2CO3 10.4 g (31.8 mmol)을 첨가 후 120℃에서 12시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 7.5 g (수율 65%)을 얻었다.As a reaction product, A mixture of 5.0 g (15.9 mmol) of 6,12-dihydrobenzo [4,5] thieno [2,3-b] benzo [4,5] thieno [2,3-e] pyridine and 6.2 g of 1-bromo-4-iodobenzene 17.5 mmol) was added 150 mL of dioxane. 0.73 g (0.8 mmol) of Pd 2 (dba) 3 , 0.5 g (0.8 mmol) of BINAP and 10.4 g (31.8 mmol) of Cs 2 CO 3 were added and the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO4, distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (7.5 g, yield 65%).

[HRMS]: 469
[HRMS]: 469

[[ 준비예Preparation Example 6] 2-(3- 6] 2- (3- bromophenylbromophenyl )-4-()-4-( naphthalennaphthalen -2--2- ylyl )) quinazolinequinazoline 의 합성Synthesis of

Figure 112013080502441-pat00025
Figure 112013080502441-pat00025

반응물로 4-(biphenyl-4-yl)-2-chloroquinazoline 대신 2-chloro-4-(naphthalen-2-yl)quinazoline을, 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 대신 2-(3-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane을 사용한 것을 제외하고는 [준비예 3]과 동일한 과정을 수행하여 목적 화합물 6.5 g (수율 82%)을 얻었다.2-chloro-4- (naphthalen-2-yl) quinazoline was used instead of 4- (biphenyl-4-yl) -2-chloroquinazoline as a reactant, 2- (4-bromophenyl) -4,4,5,5- The procedure of Preparation Example 3 was repeated except that 2- (3-bromophenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 1,3,2-dioxaborolane 6.5 g (yield 82%) of the aimed compound was obtained.

[HRMS]: 411
[HRMS]: 411

[[ 합성예Synthetic example 1] 화합물 1의 합성 1] Synthesis of Compound 1

Figure 112013080502441-pat00026
Figure 112013080502441-pat00026

준비예 1의 6,12-dihydrobenzo[4,5]thieno[2,3-b]benzo[4,5]thieno[2,3-e]pyridine 4.0 g (12.7 mmol)과 2-chloro-4-phenylquinazoline 3.4 g (14 mmol)에 dioxane 150 mL를 가하였다. Pd(OAc)2 0.14 g (0.64 mmol), XPhos 0.61 g (1.3 mmol), K2CO3 5.3 g (38.2 mmol)을 첨가 후 120℃에서 12시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 300 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 2.8 g (수율 42%)을 얻었다.A mixture of 4.0 g (12.7 mmol) of 6,12-dihydrobenzo [4,5] thieno [2,3-b] benzo [4,5] thieno [ phenylquinazoline (3.4 g, 14 mmol) was added 150 mL of dioxane. 0.14 g (0.64 mmol) of Pd (OAc) 2 , 0.61 g (1.3 mmol) of XPhos and 5.3 g (38.2 mmol) of K 2 CO 3 were added and the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled to room temperature and 300 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 2.8 g (yield 42%) of the desired compound.

[HRMS]: 518
[HRMS]: 518

[[ 합성예Synthetic example 2] 화합물 9의 합성 2] Synthesis of Compound 9

Figure 112013080502441-pat00027
Figure 112013080502441-pat00027

준비예 1의 6,12-dihydrobenzo[4,5]thieno[2,3-b]benzo[4,5]thieno[2,3-e]pyridine 5.0 g (15.9 mmol)과 2-chloro-4-(9,9-dimethyl-9H-fluoren-3-yl)quinazoline 6.2 g (17.5 mmol)에 dioxane 150 mL를 가하였다. Pd2(dba)3 0.73 g (0.8 mmol), BINAP 0.5 g (0.8 mmol), Cs2CO3 10.4 g (31.8 mmol)을 첨가 후 120℃에서 12시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 4.8 g (수율 48%)을 얻었다.A mixture of 5.0 g (15.9 mmol) of 6,12-dihydrobenzo [4,5] thieno [2,3-b] benzo [4,5] thieno [ (9,9-dimethyl-9H-fluoren-3-yl) quinazoline (6.2 g, 17.5 mmol) was added 150 mL of dioxane. 0.73 g (0.8 mmol) of Pd 2 (dba) 3 , 0.5 g (0.8 mmol) of BINAP and 10.4 g (31.8 mmol) of Cs 2 CO 3 were added and the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 4.8 g (yield 48%) of the desired compound.

[HRMS]: 634
[HRMS]: 634

[[ 합성예Synthetic example 3] 화합물 20의 합성 3] Synthesis of Compound 20

Figure 112013080502441-pat00028
Figure 112013080502441-pat00028

준비예 1의 6,12-dihydrobenzo[4,5]thieno[2,3-b]benzo[4,5]thieno[2,3-e]pyridine 3.2 g (10.2 mmol)과 준비예 3의 4-(Biphenyl-4-yl)-2-(4-bromophenyl)quinazoline 5.3 g (12.2 mmol)에 toluene 150 mL를 가하였다. Pd(OAc)2 0.11 g (0.5 mmol), S-Phos 0.42 g (1.0 mmol), Cs2CO3 6.6 g (20.4 mmol)을 첨가한 후 120℃에서 12시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 3.6 g (수율 52%)을 얻었다.3.2 g (10.2 mmol) of the 6,12-dihydrobenzo [4,5] thieno [2,3-b] benzo [4,5] thieno [2,3- (Biphenyl-4-yl) -2- (4-bromophenyl) quinazoline (5.3 g, 12.2 mmol) was added 150 mL of toluene. After adding 0.11 g (0.5 mmol) of Pd (OAc) 2 , 0.42 g (1.0 mmol) of S-Phos and 6.6 g (20.4 mmol) of Cs 2 CO 3 , the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain the desired compound (3.6 g, yield 52%).

[HRMS]: 670
[HRMS]: 670

[[ 합성예Synthetic example 4] 화합물 47의 합성 4] Synthesis of Compound 47

Figure 112013080502441-pat00029
Figure 112013080502441-pat00029

2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine 5.5 g (15.0 mmol)과 준비예 1의 6,12-dihydrobenzo[4,5]thieno[2,3-b]benzo[4,5]thieno[2,3-e]pyridine 4.3 g (13.7 mmol)에 toluene 150 mL를 가하였다. Pd(OAc)2 0.15 g (0.68 mmol), P(t-Bu)3 0.14 g (0.68 mmol), NaOt-Bu 3.9 g (41 mmol)을 첨가한 후 120℃에서 12시간 동안 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL를 투입하여 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출하고 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류한 후 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 3.9 g (수율 44%)을 얻었다. 5.5 g (15.0 mmol) of 2-chloro-4,6-di (naphthalen-1-yl) -1,3,5-triazine and 6,12- dihydrobenzo [4,5] thieno [2,3 -b] benzo [4,5] thieno [2,3-e] pyridine was added 150 mL of toluene. 0.14 g (0.68 mmol) of Pd (OAc) 2, 0.14 g (0.68 mmol) of P (t-Bu) 3 and 3.9 g (41 mmol) of NaOt-Bu were added and the mixture was refluxed at 120 ° C for 12 hours. The reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure, and then purified by silica gel column chromatography to obtain 3.9 g (yield: 44%) of the target compound.

[HRMS]: 645
[HRMS]: 645

[[ 합성예Synthetic example 5] 화합물 59의 합성 5] Synthesis of Compound 59

Figure 112013080502441-pat00030
Figure 112013080502441-pat00030

반응물로 2-chloro-4-(9,9-dimethyl-9H-fluoren-3-yl)quinazoline 대신 준비예 4의 2-(4-bromophenyl)-4,6-bis(4-(naphthalen-1-yl)phenyl)-1,3,5-triazine를 사용한 것을 제외하고는 [합성예 2]과 동일한 과정을 수행하여 목적 화합물 3.7 g (수율 33%)을 얻었다.(4-bromophenyl) -4,6-bis (4- (naphthalen-1-yl) quinazoline was used in place of 2-chloro-4- (9,9- yl) phenyl) -1,3,5-triazine was used in place of the compound [Synthesis Example 2], 3.7 g (yield 33%) of the target compound was obtained.

[HRMS]: 874
[HRMS]: 874

[[ 합성예Synthetic example 6] 화합물 80의 합성 6] Synthesis of Compound 80

Figure 112013080502441-pat00031
Figure 112013080502441-pat00031

반응물로 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole과 준비예 5의 Phenyl linker를 사용한 것을 제외하고는 [준비예 4]와 동일한 과정을 수행하여 목적 화합물 3.0 g (수율 55%)을 얻었다.Except that 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole and the phenyl linker of Preparation Example 5 were used as the reactant Example 4] to obtain 3.0 g of the objective compound (yield: 55%).

[HRMS]: 631
[HRMS]: 631

[[ 합성예Synthetic example 7] 화합물 87의 합성 7] Synthesis of Compound 87

Figure 112013080502441-pat00032
Figure 112013080502441-pat00032

반응물로 2-chloro-4-phenylquinazoline 대신 2-bromotriphenylene를 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 3.5 g (수율 41%)을 얻었다.The procedure of Synthesis Example 1 was repeated except that 2-bromotriphenylene was used instead of 2-chloro-4-phenylquinazoline as a reactant to obtain 3.5 g (yield 41%) of the desired compound.

[HRMS]: 540
[HRMS]: 540

[[ 합성예Synthetic example 8] 화합물 102의 합성 8] Synthesis of Compound 102

Figure 112013080502441-pat00033
Figure 112013080502441-pat00033

반응물로 2-chloro-4-(4-phenylnaphthalen-1-yl)quinazoline과 준비예 2의 11H-benzo[b]benzo[4,5]thieno[3,2-e][1,4]thiazine를 사용한 것을 제외하고는 [합성예 3]과 동일한 과정을 수행하여 목적 화합물 4.5 g (수율 33%)을 얻었다.Benzo [b] benzo [4,5] thieno [3,2-e] [1,4] thiazine of Preparation Example 2 was reacted with 2-chloro-4- (4-phenylnaphthalen- The same procedure as in [Synthesis Example 3] was repeated to obtain the desired compound (4.5 g, yield 33%).

[HRMS]: 833
[HRMS]: 833

[[ 합성예Synthetic example 9] 화합물 123의 합성 9] Synthesis of Compound 123

Figure 112013080502441-pat00034
Figure 112013080502441-pat00034

반응물로 준비예 2의 11H-benzo[b]benzo[4,5]thieno[3,2-e][1,4]thiazine 와 준비예 6의 2-(3-bromophenyl)-4-(naphthalen-2-yl)quinazoline를 사용한 것을 제외하고는 [합성예 4]과 동일한 과정을 수행하여 목적 화합물 2.2 g (수율 42%)을 얻었다.Benzo [4,5] thieno [3,2-e] [1,4] thiazine of Preparation Example 2 and 2- (3-bromophenyl) -4- (naphthalen- 2-yl) quinazoline, the procedure of Synthesis Example 4 was repeated to obtain 2.2 g of the desired compound (yield 42%).

[HRMS]: 585
[HRMS]: 585

[[ 합성예Synthetic example 10] 화합물 131의 합성 10] Synthesis of Compound 131

Figure 112013080502441-pat00035
Figure 112013080502441-pat00035

반응물로 2,4-di(biphenyl-4-yl)-6-chloro-1,3,5-triazine과 준비예 2의 11H-benzo[b]benzo[4,5]thieno[3,2-e][1,4]thiazine를 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 8.5 g (수율 41%)을 얻었다.Benzo [b] benzo [4,5] thieno [3,2-e (4-methylphenyl) ] [1,4] thiazine, the procedure of Synthesis Example 2 was repeated to obtain the desired compound (8.5 g, yield 41%).

[HRMS]: 638
[HRMS]: 638

[[ 합성예Synthetic example 11] 화합물 140의 합성 11] Synthesis of Compound 140

Figure 112013080502441-pat00036
Figure 112013080502441-pat00036

반응물로 2-bromotriphenylene과 준비예 2의 11H-benzo[b]benzo[4,5]thieno[3,2-e][1,4]thiazine을 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 5.2 g (수율 50%)을 얻었다.Benzo [b] benzo [4,5] thieno [3,2-e] [1,4] thiazine of Preparation Example 2 was used instead of 2-bromotriphenylene as a reaction product in the same manner as in [Synthesis Example 1] To obtain 5.2 g of the desired compound (yield: 50%).

[HRMS]: 481
[HRMS]: 481

[[ 실시예Example 1 내지 7] 녹색 유기  1 to 7] green organic 전계Field 발광 소자의 제조 Manufacturing of light emitting device

상기 합성예에서 합성한 화합물을 통상적인 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 녹색 유기 전계 발광 소자를 제조하였다.The compound synthesized in Synthesis Example was subjected to high purity sublimation purification by a conventional method, and then a green organic electroluminescent device was manufactured according to the following procedure.

먼저, ITO (Indium tin oxide)가 1500Å두께로 박막 코팅된 유리 기판을 증류수로 초음파 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 ITO (Indium Tin Oxide) with a thickness of 1500 Å was ultrasonically washed with distilled water. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

이렇게 준비된 ITO 투명 기판(전극) 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 90% 합성예 1 내지 7 각각의 화합물 + 10% Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 소자를 제조하였다.
(60 nm) / TCTA (80 nm) / 90% Each compound of each of Synthetic Examples 1 to 7 + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) was formed on the ITO transparent substrate / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) in this order.

[[ 비교예Comparative Example 1] 녹색 유기  1] Green organic 전계Field 발광 소자의 제작 Fabrication of light emitting device

발광층 형성시 발광 호스트 물질로서 합성예 1의 화합물 대신 CBP를 사용하는 것을 제외하고는 실시예 1과 동일한 과정으로 소자를 제조하였다.
A device was prepared in the same manner as in Example 1, except that CBP was used instead of the compound of Synthesis Example 1 as a luminescent host material in forming the light emitting layer.

상기 실시예 1 내지 7 및 비교예 1에서 사용된 m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP and BCP used in Examples 1 to 7 and Comparative Example 1 are as follows.

Figure 112013080502441-pat00037
Figure 112013080502441-pat00037

Figure 112013080502441-pat00038

Figure 112013080502441-pat00038

[[ 평가예Evaluation example ]]

실시예 1 내지 7 및 비교예 1에서 제조한 각각의 녹색 유기 전계 발광 소자에 대하여 전류밀도 10mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.
The driving voltage, current efficiency and emission peak at the current density of 10 mA / cm 2 were measured for each of the green organic electroluminescent devices prepared in Examples 1 to 7 and Comparative Example 1, and the results are shown in Table 1 below.

샘플Sample 호스트Host 구동 전압(V)The driving voltage (V) EL 피크(nm)EL peak (nm) 전류효율(cd/A)Current efficiency (cd / A) 실시예 1Example 1 1One 6.35 6.35 517517 42.342.3 실시예 2Example 2 99 6.55 6.55 517517 41.241.2 실시예 3Example 3 2020 6.426.42 518518 43.043.0 실시예 4Example 4 4747 6.446.44 518518 41.641.6 실시예 5Example 5 5959 6.566.56 510510 40.840.8 실시예 6Example 6 8080 6.626.62 517517 42.642.6 실시예 7Example 7 8787 6.44 6.44 519519 42.542.5 비교예 1Comparative Example 1 CBPCBP 6.936.93 516516 38.238.2

상기 표1을 참조하면, 본 발명에 따른 화합물을 소자의 발광층으로 사용한 실시예 1 내지 7이 종래의 CBP를 소자의 발광층으로 사용한 비교예 1보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다.
Referring to Table 1, it was confirmed that Examples 1 to 7 using the compound according to the present invention as a light emitting layer of the device were superior in efficiency and driving voltage to Comparative Example 1 in which the conventional CBP was used as the light emitting layer of the device.

[[ 실시예Example 8 내지 11] 적색 유기  8 to 11] Red organic 전계Field 발광 소자의 제조 Manufacturing of light emitting device

상기 합성예에서 합성한 화합물을 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 적색 유기 전계 발광 소자를 제조하였다.The compound synthesized in the Synthesis Example was subjected to high purity sublimation purification by a conventionally known method, and then a red organic electroluminescent device was manufactured according to the following procedure.

먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수로 초음파 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 ITO (Indium Tin Oxide) with a thickness of 1500 Å was ultrasonically washed with distilled water. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

이렇게 준비된 ITO 투명 기판(전극) 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 90% 합성예 8 내지 11 각각의 화합물 + 10% (piq)2Ir(acac) (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 소자를 제조하였다
(60 nm) / TCTA (80 nm) / 90% compound of each of Synthetic Examples 8 to 11 + 10% (piq) 2 Ir (acac) (300 nm) / BCP 10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm)

[[ 비교예Comparative Example 2] 적색 유기  2] Red organic 전계Field 발광 소자의 제조  Manufacturing of light emitting device

발광층 형성시 발광 호스트 물질로서 합성예 8의 화합물 대신 CBP를 사용하는 것을 제외하고는 상기 실시예 8과 동일한 과정으로 소자를 제조하였다.
A device was fabricated in the same manner as in Example 8 except that CBP was used instead of the compound of Synthesis Example 8 as a luminescent host material in forming the light emitting layer.

상기 실시예 8 내지 11 및 비교예 2에서 사용된 m-MTDATA, (piq)2Ir(acac), NPB 및 CBP의 구조는 하기와 같다.The structures of m-MTDATA, (piq) 2 Ir (acac), NPB and CBP used in Examples 8 to 11 and Comparative Example 2 are as follows.

Figure 112013080502441-pat00039

Figure 112013080502441-pat00039

[[ 평가예Evaluation example ]]

실시예 8 내지 11 및 비교예 2에서 제조한 각각의 유기 전계 발광 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압 및 전류효율을 측정하고, 그 결과를 하기 표 2에 나타내었다.
The driving voltage and the current efficiency at a current density of 10 mA / cm 2 were measured for each of the organic electroluminescent devices manufactured in Examples 8 to 11 and Comparative Example 2, and the results are shown in Table 2 below.

샘플Sample 호스트Host 구동 전압(V)The driving voltage (V) 전류효율(cd/A)Current efficiency (cd / A) 실시예 8Example 8 102102 4.514.51 14.014.0 실시예 9Example 9 123123 4.624.62 13.413.4 실시예 10Example 10 131131 4.554.55 13.713.7 실시예 11Example 11 140140 4.694.69 14.214.2 비교예 2Comparative Example 2 CBPCBP 5.255.25 8.28.2

상기 표1을 참조하면, 본 발명에 따른 화합물을 소자의 발광층으로 사용한 실시예 8 내지 11이 종래의 CBP를 소자의 발광층으로 사용한 비교예2 보다 효율 및 구동전압이 우수한 것을 확인할 수 있었다.Referring to Table 1, it was confirmed that Examples 8 to 11, in which the compound according to the present invention was used as a light emitting layer of the device, were superior in efficiency and driving voltage to Comparative Example 2 in which the conventional CBP was used as the light emitting layer of the device.

Claims (6)

하기 화학식 1로 표시되는 화합물:
[화학식 1]
Figure 112015041851414-pat00040

상기 화학식 1에서,
X1 및 X2는 모두 S이고,
R1 내지 R8은 모두 수소이고,
Ar1은 C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되고,
상기 Ar1의 아릴기 및 헤테로아릴기는 각각 독립적으로, C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있다.A compound represented by the following formula (1):
[Chemical Formula 1]
Figure 112015041851414-pat00040

In Formula 1,
X 1 and X 2 are all S,
R 1 to R 8 are all hydrogen,
Ar 1 is selected from the group consisting of a C 6 to C 60 aryl group and a heteroaryl group having 5 to 60 nuclear atoms,
Aryl and heteroaryl groups of the Ar 1 each independently may be substituted with at least one member selected from the group consisting of C 6 ~ C 60 aryl group and a heteroaryl group of nuclear atoms of 5 to 60. 삭제delete 삭제delete 삭제delete 양극, 음극 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며,
상기 1층 이상의 유기물층 중 적어도 하나는 제1항에 기재된 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.A cathode, and at least one organic layer interposed between the anode and the cathode,
Wherein at least one of the one or more organic compound layers comprises the compound according to claim 1. 제5항에 있어서,
상기 화합물을 포함하는 유기물층은 인광 발광층인 것을 특징으로 하는 유기 전계 발광 소자.6. The method of claim 5,
Wherein the organic compound layer containing the compound is a phosphorescent light-emitting layer.
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