KR20100131939A - Indolocarbazole derivatives and organoelectroluminescent device using the same - Google Patents

Indolocarbazole derivatives and organoelectroluminescent device using the same Download PDF

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KR20100131939A
KR20100131939A KR1020100053392A KR20100053392A KR20100131939A KR 20100131939 A KR20100131939 A KR 20100131939A KR 1020100053392 A KR1020100053392 A KR 1020100053392A KR 20100053392 A KR20100053392 A KR 20100053392A KR 20100131939 A KR20100131939 A KR 20100131939A
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제종태
권현중
강리경
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에스에프씨 주식회사
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

Abstract

PURPOSE: An indolocarbazole derivative is provided to obtain an organoelectroluminescent device with low driving voltage and excellent luminous efficiency when applied to the organoelectroluminescent device. CONSTITUTION: An indolocarbazole derivative is represented by chemical formula 1. In chemical formula 1, n is an integer of 1-5; when n is 1, A is substituted or unsubstituted C3-40 heteroaryl group containing one or more of nitrogen; when n is 2, A which is respectively the same or different is selected from hydrogen atom, heavy hydrogen atom, halogen atom, substituted or unsubstituted heteroarylamino group, substituted or unsubstituted C6-40 aryl group, and substituted or unsubstituted C3-40 heteroaryl group.

Description

인돌로카바졸 유도체 및 이를 이용한 유기전계발광소자{Indolocarbazole derivatives and organoelectroluminescent device using the same}Indolocarbazole derivatives and organoelectroluminescent device using the same

본 발명은 방향족 화합물 및 이를 이용한 유기전계발광소자에 관한 것으로서, 보다 구체적으로 인돌로카바졸 유도체 및 이를 이용한 구동전압이 낮고 발광효율이 우수한 유기전계발광소자에 관한 것이다.The present invention relates to an aromatic compound and an organic light emitting device using the same, and more particularly to an indolocarbazole derivative and an organic light emitting device having a low driving voltage and excellent luminous efficiency using the same.

유기전계발광소자는 다양한 전자 제품의 디스플레이 및 조명분야로 그 적용 분야를 점차 확대해 가고 있지만, 효율 및 수명 특성이 응용분야 확대를 제약하고 있는 상황이며, 효율 및 수명 특성 개선을 위해서 소자뿐만 아니라 재료 측면에서 많은 연구가 진행되고 있다. 재료 측면에서 발광효율 극대화를 위한 방법으로 주로 호스트- 도펀트 시스템을 채용하고, 발광물질인 도펀트는 인광 재료를, 그리고 도펀트의 발광특성을 극대화할 수 있는 호스트로는 CBP(4, 4′-N, N′-dicarbazolbipheny) 및 카바졸에 다양한 치환기가 도입된 물질들이 (일본 특허공개 2008-0214244, 일본 특허공개 2003-0133075) 알려져 있지만, 효율 및 수명 특성 측면에서 추가적인 개선이 요구되고 있는 상황이다.The organic light emitting device is gradually expanding its application field to the display and lighting field of various electronic products, but the efficiency and lifespan characteristics are restricting the expansion of the application field. There is a lot of research going on. In terms of materials, the host-dopant system is mainly adopted as a method for maximizing luminous efficiency, and the dopant as a luminescent material is phosphorescent material, and CBP (4, 4′-N, N'-dicarbazolbipheny) and substances in which various substituents are introduced into carbazole (Japanese Patent Laid-Open No. 2008-0214244, Japanese Patent Laid-Open No. 2003-0133075) are known, but further improvement is required in terms of efficiency and lifespan characteristics.

본 발명이 달성하고자 하는 첫 번째 과제는 유기전계발광소자의 구동전압이 낮고 발광효율이 높은 특성을 갖는 신규 인돌로카바졸 유도체를 제공하는 것이다.The first object of the present invention is to provide a novel indolocarbazole derivative having characteristics of low driving voltage and high luminous efficiency of an organic light emitting display device.

또한, 본 발명이 해결하고자 하는 두 번째 기술적 과제는 상기 인돌로카바졸 유도체를 채용하여 특성이 개선된 유기전계발광소자를 제공하는 것이다.In addition, the second technical problem to be solved by the present invention is to provide an organic electroluminescent device having improved properties by employing the indolocarbazole derivative.

상기 첫 번째 과제를 달성하기 위하여 본 발명은 하기 [화학식 1]의 인돌로카바졸 유도체를 제공한다.In order to achieve the first problem, the present invention provides an indolocarbazole derivative of the following [Formula 1].

[화학식 1][Formula 1]

Figure pat00001
Figure pat00001

상기 [화학식 1]에서, n은 1부터 5까지의 정수이며,In [Formula 1], n is an integer from 1 to 5,

n이 1인 경우, A는 1개 이상의 질소를 포함하는 치환 또는 비치환의 탄소수 3 - 40의 헤테로아릴기이고,when n is 1, A is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing one or more nitrogen,

n이 2 이상인 경우, A는 각각 독립적으로 동일 또는 상이할 수 있으며, 수소원자, 중수소원자, 할로겐원자, 치환 또는 비치환의 헤테로아릴아미노기, 치환 또는 비치환의 탄소수 6 - 40의 아릴기, 치환 또는 비치환의 탄소수 3 - 40의 헤테로아릴기로부터 선택되고, 이때, 1개 이상의 질소를 포함하는 헤테로아릴기가 적어도 1개 이상 반드시 포함하며,When n is 2 or more, A may be the same or different from each other independently, and a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted Selected from a heteroaryl group having 3 to 40 carbon atoms in the ring, wherein at least one heteroaryl group including one or more nitrogens is necessarily included;

상기 A의 치환기는 수소원자, 중수소 원자, 시아노기, 할로겐원자, 히드록시기, 니트로기, 탄소수 1 - 40의 알킬기, 탄소수 1 - 40의 알콕시기, 탄소수 1 - 40의 알킬아미노기, 탄소수 6 - 40의 아릴아미노기, 탄소수 3 - 40의 헤테로아릴아미노기, 탄소수 1 - 40의 알킬실릴기, 탄소수 6 - 40의 아릴실릴기, 탄소수 6 - 40의 아릴기, 탄소수 3 - 40의 아릴옥시기, 탄소수 3 - 40의 헤테로아릴기로 이루어진 군으로부터 선택된 어느 하나이다.The substituent of A is a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, a group having 6 to 40 carbon atoms Arylamino group, C3-C40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3- Any one selected from the group consisting of 40 heteroaryl groups.

본 발명의 일 실시예에 의하면, n이 2 이상인 경우 상기 A는 각각 결합하여 포화 또는 불포화 고리 또는 헤테로 원자를 갖는 고리를 형성할 수 있다. 또한 상기 A의 치환기는 서로 결합하여 포화 혹은 불포화 고리를 형성하거나, 펜던트 방법으로 함께 부착 또는 융합(fused)될 수 있다. According to an embodiment of the present invention, when n is 2 or more, A may combine to form a ring having a saturated or unsaturated ring or a hetero atom, respectively. In addition, the substituents of A may be bonded to each other to form a saturated or unsaturated ring, or may be attached or fused together by a pendant method.

본 발명의 다른 일 실시 예에 의하면, 상기 인돌로카바졸 유도체는 예를 들어, 하기 화학식 [SPH01] 내지 화학식 [SPH99]로 표시되는 군으로부터 선택된 어느 하나의 화합물일 수 있으나, 이들 예시 화합물에 한정되는 것은 아니다.According to another embodiment of the present invention, the indolocarbazole derivative may be, for example, any one compound selected from the group represented by the following formula [SPH01] to [SPH99], but is limited to these exemplary compounds. It doesn't happen.

Figure pat00002
Figure pat00002

[SPH01] [SPH02] [SPH03][SPH01] [SPH02] [SPH03]

Figure pat00003
Figure pat00003

[SPH04] [SPH05] [SPH06][SPH04] [SPH05] [SPH06]

Figure pat00004
Figure pat00004

[SPH07] [SPH08] [SPH09][SPH07] [SPH08] [SPH09]

Figure pat00005
Figure pat00005

[SPH10] [SPH11] [SPH12][SPH10] [SPH11] [SPH12]

Figure pat00006
Figure pat00006

[SPH13] [SPH14] [SPH15][SPH13] [SPH14] [SPH15]

Figure pat00007
Figure pat00007

[SPH16] [SPH17] [SPH18][SPH16] [SPH17] [SPH18]

Figure pat00008
Figure pat00008

[SPH19] [SPH20] [SPH21][SPH19] [SPH20] [SPH21]

Figure pat00009
Figure pat00009

[SPH22] [SPH23] [SPH24][SPH22] [SPH23] [SPH24]

Figure pat00010
Figure pat00010

[SPH25] [SPH26] [SPH27][SPH25] [SPH26] [SPH27]

Figure pat00011
Figure pat00011

[SPH28] [SPH29] [SPH30][SPH28] [SPH29] [SPH30]

Figure pat00012
Figure pat00012

[SPH31] [SPH32] [SPH33][SPH31] [SPH32] [SPH33]

Figure pat00013
Figure pat00013

[SPH34] [SPH35] [SPH36][SPH34] [SPH35] [SPH36]

Figure pat00014
Figure pat00014

[SPH37] [SPH38] [SPH39][SPH37] [SPH38] [SPH39]

Figure pat00015
Figure pat00015

[SPH40] [SPH41] [SPH42][SPH40] [SPH41] [SPH42]

Figure pat00016
Figure pat00016

[SPH43] [SPH44] [SPH45][SPH43] [SPH44] [SPH45]

Figure pat00017
Figure pat00017

[SPH46] [SPH47] [SPH48][SPH46] [SPH47] [SPH48]

Figure pat00018
Figure pat00018

[SPH49] [SPH50] [SPH51][SPH49] [SPH50] [SPH51]

Figure pat00019
Figure pat00019

[SPH52] [SPH53] [SPH54][SPH52] [SPH53] [SPH54]

Figure pat00020
Figure pat00020

[SPH55] [SPH56] [SPH57][SPH55] [SPH56] [SPH57]

Figure pat00021
Figure pat00021

[SPH58] [SPH59] [SPH60][SPH58] [SPH59] [SPH60]

Figure pat00022
Figure pat00022

[SPH61] [SPH62] [SPH63][SPH61] [SPH62] [SPH63]

Figure pat00023
Figure pat00023

[SPH64] [SPH65] [SPH66][SPH64] [SPH65] [SPH66]

Figure pat00024
Figure pat00024

[SPH67] [SPH68] [SPH69][SPH67] [SPH68] [SPH69]

Figure pat00025
Figure pat00025

[SPH70] [SPH71] [SPH72][SPH70] [SPH71] [SPH72]

Figure pat00026
Figure pat00026

[SPH73] [SPH74] [SPH75][SPH73] [SPH74] [SPH75]

Figure pat00027
Figure pat00027

[SPH76] [SPH77] [SPH78][SPH76] [SPH77] [SPH78]

Figure pat00028
Figure pat00028

[SPH79] [SPH80] [SPH81][SPH79] [SPH80] [SPH81]

Figure pat00029
Figure pat00029

[SPH82] [SPH83] [SPH84][SPH82] [SPH83] [SPH84]

Figure pat00030
Figure pat00030

[SPH85] [SPH86] [SPH87][SPH85] [SPH86] [SPH87]

Figure pat00031
Figure pat00031

[SPH88] [SPH89] [SPH90][SPH88] [SPH89] [SPH90]

Figure pat00032
Figure pat00032

[SPH91] [SPH92] [SPH93][SPH91] [SPH92] [SPH93]

Figure pat00033
Figure pat00033

[SPH94] [SPH95] [SPH96][SPH94] [SPH95] [SPH96]

Figure pat00034
Figure pat00034

[SPH97] [SPH98] [SPH99][SPH97] [SPH98] [SPH99]

본 발명은 상기 두 번째 기술적 과제를 달성하기 위해서, 애노드; 캐소드; 및 상기 애노드 및 캐소드 사이에 개재된 상기 [화학식 1]로 표시되는 인돌로카바졸 유도체를 포함하는 층을 구비한 유기전계발광소자를 제공한다.The present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an indolocarbazole derivative represented by the above [Formula 1] interposed between the anode and the cathode.

본 발명의 일 실시예에 따르면, 상기 애노드 및 캐소드 사이에 정공주입층, 정공수송층, 정공저지층, 발광층, 전자저지층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택된 하나 이상의 층을 더 포함할 수 있으며, 상기 인돌로카바졸 유도체는 상기 애노드 및 캐소드 사이의 발광층 중에 포함되는 것이 바람직하고, 상기 발광층의 두께는 50 내지 2,000 Å 이 바람직하다.According to an embodiment of the present invention, the anode and the cathode further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer The indolocarbazole derivative may be included in the light emitting layer between the anode and the cathode, and the thickness of the light emitting layer is preferably 50 to 2,000 Pa.

본 발명에 따른 인돌로카바졸 유도체를 사용하면, 구동전압이 낮고, 발광효율이 우수한 유기전계발광소자를 제공할 수 있다.By using the indolocarbazole derivative according to the present invention, it is possible to provide an organic light emitting device having a low driving voltage and excellent luminous efficiency.

도 1a 내지 1f는 본 발명의 바람직한 실시예에 따른 유기전계발광소자들의 적층구조를 나타낸 단면도들이다. 1A to 1F are cross-sectional views illustrating a laminated structure of organic light emitting diodes according to an exemplary embodiment of the present invention.

본 발명은 상기 [화학식 1]로 표시되는 인돌로카바졸을 기본 골격을 가지는 유도체로 유기전계소자의 모든 층에서 효과적으로 사용될 수 있지만, 특히 발광층 호스트로 채용시, 정공 및 전자 이동이 용이하여, 정공과 전자의 균형을 유지할 수 있기 때문에 발광층에서 엑시톤 형성을 극대화 시킬 수 있다.The present invention is a derivative having the basic skeleton of the indolocarbazole represented by the above [Formula 1] can be effectively used in all layers of the organic field device, especially when employed as a light emitting layer host, holes and electrons are easy to move, Since the electron balance can be maintained, exciton formation can be maximized in the emission layer.

본 발명에서 사용되는 치환기인 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, tert-부틸, 펜틸, iso-아밀, 헥실 등을 들 수 있고, 상기 알킬기 중 하나 이상의 수소 원자는 할로겐 원자, 히드록시기, 니트로기, 시아노기, 실릴기 (이 경우 "알킬실릴기"라 함), 치환 또는 비치환된 아미노기 (-NH2,-NH(R),-N(R')(R''),R'과 R"은 서로 독립적으로 탄소수 1 내지 10의 알킬기이며, 이 경우 "알킬아미노기"라 함), 히드라진기, 히드라존기, 카르복실기, 술폰산기, 인산기, 탄소수 1 내지 20의 알킬기, 탄소수 1 내지 20의 할로겐화된 알킬기, 탄소수 1 내지 20의 알케닐기, 탄소수 1 내지 20의 알키닐기, 탄소수 1 내지 20의 헤테로알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 6 내지 20의 아르알킬기, 탄소수 6 내지 20의 헤테로아릴기 또는 탄소수 6 내지 20의 헤테로아르알킬기로 치환될 수 있다.Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. Halogen atom, hydroxy group, nitro group, cyano group, silyl group (in this case referred to as "alkylsilyl group"), substituted or unsubstituted amino group (-NH 2 , -NH (R),-N (R ') (R ''), R 'and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, in this case called an" alkylamino group "), a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 20 carbon atoms A halogenated alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, C6-C20 heteroaryl group or C6-C20 heteroa It may be substituted with a lealkyl group.

본 발명의 화합물에서 사용되는 치환기인 알콕시기의 구체적인 예로는 메톡시, 에톡시, 프로폭시, 이소부틸옥시, sec-부틸옥시, 펜틸옥시, iso-아밀옥시, 헥실옥시 등을 들 수 있고, 상기 알콕시기 중 하나 이상의 수소 원자는 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다.Specific examples of the alkoxy group which is a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group may be substituted with the same substituent as in the alkyl group.

상기 본 발명의 화합물에서 사용되는 아릴기는 하나 이상의 고리를 포함하는 방향족 시스템을 의미하며, 상기 고리들은 펜던트 방법으로 함께 부착되거나 또는 융합(fused)될 수 있다. 또한 상기 아릴기는 비축합방향족기를 포함한다. 아릴기의 구체적인 예로는 페닐, 나프틸, 안트라세닐, 페난트릴, 피레닐, 크리세닐 및 플루오란테닐 등과 같은 방향족 그룹을 들 수 있고, 비축합방향족기의 일예로는 비페닐기, 터페닐기 등이 해당한다.The aryl group used in the compound of the present invention means an aromatic system including one or more rings, and the rings may be attached or fused together by a pendant method. The aryl group also includes non-condensed aromatic groups. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, chrysenyl, and fluoranthenyl, and examples of the non-condensed aromatic group include biphenyl group, terphenyl group, and the like. Corresponding.

상기 아릴기 중 하나 이상의 수소 원자는 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다 (예를 들어, 아미노기로 치환되는 경우는 "아릴아미노기", 실릴기로 치환되는 경우는 "아릴실릴기", 옥시기로 치환되는 경우는 "아릴옥시기"라 함).At least one hydrogen atom of the aryl group may be substituted with the same substituent as in the alkyl group (for example, "arylamino group" when substituted with an amino group, "arylsilyl group" when substituted with a silyl group, oxy When substituted with a group, referred to as an "aryloxy group".

본 발명의 화합물에서 사용되는 치환기인 헤테로아릴기는 N, O 또는 S 중에서 선택된 1, 2 또는 3개의 헤테로 원자를 포함하고, 나머지 고리 원자가 탄소인 탄소수 3 내지 30의 고리 방향족 시스템을 의미하며, 상기 고리가 펜던트 방법으로 함께 부착될 수 있다. 상기 헤테로아릴기가 아릴기 또는 다른 헤테로아릴기와 융합된(fused) 경우 이를 축합방향족 헤테로환이라 한다.The heteroaryl group which is a substituent used in the compound of the present invention means a ring aromatic system having 3 to 30 carbon atoms containing 1, 2 or 3 hetero atoms selected from N, O or S, and the remaining ring atoms are carbon. Can be attached together in a pendant manner. When the heteroaryl group is fused with an aryl group or another heteroaryl group, this is called a condensed aromatic heterocycle.

헤테로아릴기의 구체적인 예로는 피롤기, 퓨란기, 티오펜기, 비티오펜기, 터티오펜기, 피라졸기, 이미다졸기, 트리아졸기, 이소옥사졸기, 옥사졸기, 옥사디아졸기, 피리딘기, 디피리딜기, 터피리딘기, 피리다진기, 피리미딘기, 피라진기, 트리아진기 등이 있다.Specific examples of the heteroaryl group include pyrrole group, furan group, thiophene group, bithiophene group, terthiophene group, pyrazole group, imidazole group, triazole group, isoxazole group, oxazole group, oxadiazole group, pyridine group, di Pyridyl groups, terpyridine groups, pyridazine groups, pyrimidine groups, pyrazine groups, triazine groups and the like.

축합방향족 헤테로환기의 구체적인 예로는 인돌기, 카바졸기, 디벤조아제핀기, 아자안돌기, 인돌로카바졸기, 벤조퓨란기, 디벤조퓨란기, 티아나프텐기 (thianaphthene), 디벤조티오펜기, 인다졸기, 벤즈이미다졸기, 이미다조피리딘기, 벤조트리아졸기, 벤조티아졸기, 벤조티아디아졸기, 트리아졸로피리미딘기, 퓨린기, 퀴놀린기, 벤조퀴놀린기, 아크리딘기, 이소퀴놀린기, 페난트롤린기, 프탈라진기, 퀴나졸린기, 페녹살린기, 페나진기, 페난트롤린기, 페녹사진기 등이 있다.Specific examples of the condensed aromatic heterocyclic group include an indole group, a carbazole group, a dibenzoazine group, an azaandrodol group, an indolocarbazole group, a benzofuran group, a dibenzofuran group, a thianaphthene group, a dibenzothiophene group, Indazole group, benzimidazole group, imidazopyridine group, benzotriazole group, benzothiazole group, benzothiadiazole group, triazolopyrimidine group, purine group, quinoline group, benzoquinoline group, acridine group, isoquinoline group, Phenanthroline groups, phthalazine groups, quinazoline groups, phenoxaline groups, phenazine groups, phenanthroline groups, phenoxazine groups and the like.

그리고 상기 헤테로아릴기 및 축합방향족 헤테로고리 중 하나 이상의 수소 원자는 상기 알킬기의 경우와 동일한 치환기로 치환가능하다.At least one hydrogen atom of the heteroaryl group and the condensed aromatic heterocycle may be substituted with the same substituent as in the alkyl group.

또한, 본 발명은 상기 두 번째 기술적 과제를 달성하기 위해서, 애노드; 캐소드; 및 상기 애노드 및 캐소드 사이에 개재된 상기 [화학식1]로 표시되는 인돌로카바졸 유도체를 포함하는 층을 구비한 유기전계발광소자를 제공한다.In addition, the present invention, in order to achieve the second technical problem, an anode; Cathode; And it provides an organic electroluminescent device having a layer comprising an indolocarbazole derivative represented by the above [Formula 1] interposed between the anode and the cathode.

본 발명에 따른 상기 유기전계발광소자를 보다 상세히 설명하면, 유기전계발광소자는 상기 애노드 및 캐소드 사이에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택된 하나 이상의 층을 더 포함할 수도 있는데, 상기 정공주입층, 정공수송층, 전자수송층 및 전자주입층은 정공 또는 전자들을 발광층으로 효율적으로 전달시켜 줌으로써 발광층 내에서 발광 결합의 확률을 높이는 역할을 한다.Referring to the organic light emitting device according to the present invention in more detail, the organic light emitting device comprises at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer between the anode and the cathode. The hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer may further increase the probability of light emitting coupling in the light emitting layer by efficiently transferring holes or electrons to the light emitting layer.

정공주입층 및 정공수송층은 애노드로부터 정공이 주입되고, 주입된 정공이 수송되는 것을 용이하게 하기 위해서 적층되는 것으로서, 이러한 정공수송층용 물질로는 이온화 포텐셜이 작은 전자공여성 분자들이 사용되는데, 주로 트리페닐아민을 기본골격으로 하는 디아민, 트리아민 또는 테트라아민 유도체가 많이 사용되고 있다.The hole injection layer and the hole transport layer are laminated to facilitate the injection of holes from the anode and the transport of the injected holes. As the material for the hole transport layer, electron donor molecules having small ionization potential are used. Diamine, triamine or tetraamine derivatives based on amines are frequently used.

본 발명에서도, 상기 정공수송층의 재료로서, 당업계에 통상적으로 사용되는 것인 한, 다양한 물질을 제한 없이 사용할 수 있으며, 예를 들어, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD) 또는 N,N'- 디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등을 사용할 수 있다.In the present invention, as the material of the hole transport layer, as long as it is commonly used in the art, various materials can be used without limitation, for example, N, N'-bis (3-methylphenyl) -N, N '-Diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD ) Can be used.

또한, 상기 정공수송층의 하부에는 정공주입층 (HIL: Hole Injecting Layer)을 추가적으로 더 적층할 수 있는데, 상기 정공주입층 재료 역시 당업계에서 통상적으로 사용되는 것인 한 특별히 제한되지 않고 사용할 수 있으며, 예를 들어 CuPc 또는 스타버스트(Starburst)형 아민류인 TCTA, m-MTDATA, IDE406 (이데미쯔사 재료) 등을 사용할 수 있다.In addition, a hole injection layer (HIL) may be further stacked below the hole transport layer, and the hole injection layer material may also be used without particular limitation as long as it is commonly used in the art. For example, CuPc or Starburst type amines such as TCTA, m-MTDATA, IDE406 (manufactured by Idemitsu Corp.) and the like can be used.

Figure pat00035
Figure pat00035

[CuPc] [TCTA]        [CuPc] [TCTA]

Figure pat00036
Figure pat00036

[m-MTDATA]       [m-MTDATA]

상기 정공수송층의 상부에 유기발광층이 적층되는데, 이러한 유기발광층은 단일물질로 이루어지거나 또는 호스트(host)/도판트(dopant)로 이루어질 수 있다. An organic light emitting layer is stacked on the hole transport layer, and the organic light emitting layer may be made of a single material or may be made of a host / dopant.

일반적으로, 단일 물질로 상기 화합물이 사용되는 경우, 분자 간 상호작용에 의해 장파장에서의 둔덕 피크가 생겨나 색순도가 떨어지고, 발광 감쇄 효과 등에 의하여 효율이 떨어지기 때문에, 호스트/도판트계 발광층이 바람직하며, 상기 인돌로카바졸 유도체는 호스트/도판트계 발광층에서 호스트 물질로 사용할 수 있다.In general, when the compound is used as a single material, a host / dopant-based light emitting layer is preferable, because an intermolecular interaction generates a mound peak at long wavelengths, resulting in poor color purity, and low efficiency due to a light emission decay effect. The indolocarbazole derivative may be used as a host material in the host / dopant light emitting layer.

상기 호스트/도판트계 발광층 중 호스트 물질은 일반적으로 CBP (4,4’-dicarbazolyl-1,1’-biphenyl)를 사용하며, 도판트 물질은 Ir(ppy)3를 많이 사용하나, 당업계에서 일반적으로 사용되는 한 특별히 제한되지 않는다.In the host / dopant light emitting layer, the host material generally uses CBP (4,4'-dicarbazolyl-1,1'-biphenyl), and the dopant material uses Ir (ppy) 3 a lot, but is generally used in the art. It is not particularly limited as long as it is used as.

전자 수송층은 캐소드로부터 공급된 전자를 발광층으로 원활히 수송하고 상기 발광층에서 결합하지 못한 정공의 이동을 억제함으로써 발광층 내에서 재결합할 수 있는 기회를 증가시키는 역할을 한다.The electron transport layer serves to increase the chance of recombination in the light emitting layer by smoothly transporting electrons supplied from the cathode to the light emitting layer and suppressing movement of holes that are not bonded in the light emitting layer.

이러한 전자수송층 재료로는 당업계에서 사용되는 물질인 한 특별히 제한되지 않으며, 예를 들어, Alq3(트리-8-히드록시퀴놀린 알루미늄), PBD(2-(4- 비페닐일)-5- (4-t-부틸페닐)-1,3,4-옥사디아졸), TNF(2,4,7-트리니트로 플루오 레논), BMD, BND 등을 사용할 수 있다.Such electron transport layer material is not particularly limited as long as it is a material used in the art, for example, Alq 3 (tri-8-hydroxyquinoline aluminum), PBD (2- (4-biphenylyl) -5- ( 4-t-butylphenyl) -1,3,4-oxadiazole), TNF (2,4,7-trinitrofluorenone), BMD, BND and the like can be used.

한편, 상기 전자 수송층의 상부에는 캐소드로부터의 전자 주입을 용이하게 해주어 궁극적으로 전력효율을 개선시키는 기능을 수행하는 전자주입층 (EIL: Electron Injecting Layer)을 더 적층시킬 수도 있는데, 상기 전자주입층 재료 역시 당업계에서 통상적으로 사용되는 것이면 특별한 제한 없이 사용될 수 있으며, 예를 들어, LiF, NaCl, CsF, Li2O, BaO 등의 물질을 이용할 수 있다.Meanwhile, an electron injection layer (EIL), which facilitates electron injection from the cathode and ultimately improves power efficiency, may be further stacked on the electron transport layer. Also commonly used in the art may be used without particular limitation, for example, it may be used a material such as LiF, NaCl, CsF, Li2O, BaO.

더 나아가, 본 발명에 따른 유기전계발광소자는 상기 언급한 정공주입층, 정공수송층, 전자수송층 및 전자주입층 이외에도, 정공저지층 또는 전자저지층 등과 같은 부가적 기능성 적층 구조들을 더 포함할 수도 있다. 이때, 정공저지층은 정공이 유기발광층을 통과하여 캐소드로 유입되는 경우에는 소자의 수명과 효율이 감소되기 때문에 HOMO 레벨이 매우 낮은 물질을 사용함으로써 이러한 문제를 방지하는 역할을 한다. 정공저지층을 이루는 물질은 특별히 제한되지는 않으나, 전자수송능력을 가지면서 발광 화합물보다 높은 이온화 포텐셜을 가져야 하며, 대표적으로 BAlq, BCP, TPBI 등을 사용할 수 있다.Furthermore, in addition to the above-described hole injection layer, hole transport layer, electron transport layer, and electron injection layer, the organic light emitting device according to the present invention may further include additional functional laminated structures such as a hole blocking layer or an electron blocking layer. . At this time, the hole blocking layer serves to prevent such a problem by using a material having a very low HOMO level because the life and efficiency of the device is reduced when holes are introduced into the cathode through the organic light emitting layer. The material constituting the hole blocking layer is not particularly limited, but must have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

보다 구체적으로, 하기 도 1a 내지 도 1f에는 다양한 형태의 적층 구조를 갖는 유기전계발광소자들을 도시하였으며, 이를 참조하면, 도 1a의 유기전계 발광소자는 애노드 / 정공주입층 / 발광층 / 캐소드로 이루어진 구조를 갖고, 도 1b의 유기전계발광소자는 애노드 / 정공주입층 / 발광층 / 전자주입층 / 캐소드로 이루어진 구조를 갖는다.More specifically, FIGS. 1A to 1F illustrate organic light emitting diodes having various stacked structures. Referring to this, the organic light emitting diode of FIG. 1A includes an anode, a hole injection layer, a light emitting layer, and a cathode. The organic electroluminescent device of FIG. 1B has a structure consisting of an anode / hole injection layer / light emitting layer / electron injection layer / cathode.

또한, 도 1c의 유기전계발광소자는 애노드 / 정공주입층 / 정공수송층 / 발광층 / 캐소드의 구조를 갖고, 도 1d에 도시된 유기전계발광소자는 애노드 / 정공주입층 / 정공수송층 / 발광층 / 전자주입층 / 캐소드의 구조를 갖고, 도 1e의 유기전계발광소자는 애노드 / 정공주입층 / 정공수송층 / 발광층 / 전자수송층 / 전자주입층 / 캐소드의 구조를 갖고 마지막으로 도 1f의 유기전계발광소자는 애노드 / 정공주입층 / 정공수송층 / 발광층 / 정공저지층 / 전자수송층 / 전자주입층 / 캐소드의 구조를 갖는다.In addition, the organic light emitting device of Figure 1c has the structure of anode / hole injection layer / hole transport layer / light emitting layer / cathode, the organic electroluminescent device shown in Figure 1d is anode / hole injection layer / hole transport layer / light emitting layer / electron injection It has a layer / cathode structure, the organic electroluminescent device of Figure 1e has the structure of anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode and finally the organic electroluminescent device of Figure 1f is an anode It has a structure of / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

본 발명에 따른 유기전계발광소자는 상기 인돌로카바졸 유도체를, 애노드 및 캐소드 사이에 개재되는 다양한 적층 구조 내에 포함할 수 있지만, 바람직하게는, 상기 인돌로카바졸 유도체는 애노드 및 캐소드 사이의 발광층에서 호스트물질로 사용될 수 있다.The organic electroluminescent device according to the present invention may include the indolocarbazole derivative in various laminated structures interposed between the anode and the cathode. Preferably, the indolocarbazole derivative is a light emitting layer between the anode and the cathode. Can be used as host material in

또한, 상기 인돌로카바졸 유도체를 포함하는 발광층의 두께는 50 내지 2,000 Å 일 수 있는데, 두께가 50 Å 미만인 경우에는 발광 효율이 저하되고, 2,000 Å을 초과하는 경우에는 구동 전압이 상승하기 때문에 비경제적이다.In addition, the thickness of the light emitting layer including the indolocarbazole derivative may be 50 to 2,000 kPa, but when the thickness is less than 50 kPa, the luminous efficiency is lowered. It is economical.

본 발명에 따른 유기전계발광소자를 제조하는 방법에 관하여 도 1a 내지 1f를 참조하여 설명한다.A method of manufacturing an organic light emitting display device according to the present invention will be described with reference to FIGS. 1A to 1F.

먼저, 기판 상부에 애노드용 물질을 코팅한다. 기판으로는 통상적인 발광 소자에서 사용되는 기판을 사용하는데, 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유리기판 또는 투명 플라스틱 기판이 바람직하다. 또한, 애노드 물질로는 투명하고 전도성이 우수한 산화인듐주석 (ITO), 산화인듐아연 (IZO), 산화주석 (SnO2) 또는 산화아연 (ZnO) 등의 당업계에서 통상적으로 사용되고 있는 물질들이 사용될 수 있다. 상기 애노드 상부로는 정공주입층이 적층되며, 그 다음으로 상기 정공주입층 상부에 정공수송층을 형성한다.First, an anode material is coated on the substrate. As the substrate, a substrate used in a conventional light emitting device is used. A glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, as the anode material, materials commonly used in the art, such as transparent and highly conductive indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), or zinc oxide (ZnO), may be used. . A hole injection layer is stacked on the anode, and then a hole transport layer is formed on the hole injection layer.

다음으로는, 상기 정공수송층 상부에 발광층을 적층한 후, 그 위에 선택적으로 정공저지층을 형성한다. 마지막으로, 이러한 정공저지층 위에 전자수송층을 적층한 후에 전자주입층을 선택적으로 형성하고, 상기 전자주입층 상부에 캐소드 형성용 금속을 진공 열증착함으로써 본 발명에 따른 유기전계발광소자를 제조할 수 있게 된다. 상기 유기층의 적층은 진공 열증착, 스핀코팅 또는 잉크젯 프린팅의 방법 중에서 선택된 하나 또는 그 이상의 방법에 의하여 수행된다.Next, after the light emitting layer is laminated on the hole transport layer, a hole blocking layer is selectively formed thereon. Finally, after the electron transport layer is laminated on the hole blocking layer, the electron injection layer may be selectively formed, and the organic light emitting diode according to the present invention may be manufactured by vacuum thermal depositing a metal for forming a cathode on the electron injection layer. Will be. Lamination of the organic layer is performed by one or more methods selected from the methods of vacuum thermal deposition, spin coating or inkjet printing.

한편, 캐소드 형성용 금속으로는, 리튬 (Li), 마그네슘 (Mg), 알루미늄 (Al), 알루'-미늄-리튬 (Al-Li), 칼슘 (Ca), 마그네슘-인듐 (Mg-In), 마그네슘-은 (Mg-Ag) 등을 사용할 수 있으며, 전면발광소자를 얻기 위해서는 ITO, IZO를 사용한 투과형 캐소드를 사용할 수도 있다.On the other hand, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminium-lithium-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), Magnesium-silver (Mg-Ag) or the like may be used, and a transmissive cathode using ITO or IZO may be used to obtain a front light emitting device.

<실시예><Examples>

<합성예 1> [SPH10]로 표시되는 화합물의 합성Synthesis Example 1 Synthesis of Compound Represented by [SPH10]

(1) [화학식 1-a]로 표시되는 화합물의 합성(1) Synthesis of Compound Represented by [Formula 1-a]

하기 [반응식 1]에 의하여 [화학식 1-a]를 합성하였다.[Scheme 1-a] was synthesized by the following [Scheme 1].

[반응식 1]Scheme 1

Figure pat00037
Figure pat00037

[화학식 1-a]                                                       [Formula 1-a]

2 L 의 둥근 바닥 플라스크에 1,2-씨클로헥산디온 50 g (0.45 mol), 페닐 하이드라진-하이드로클로라이드 135 g (0.92 mol), 에틸알코올 1500 ml를 넣고, 30분간 교반 후에, 반응 용액에 진한 황산 5 ml를 가한다. 65℃에서 10시간 교반시킨다. 반응이 종결되면 상온으로 내리고, 여과하고 에틸알코올로 씻어준다.50 g (0.45 mol) of 1,2-cyclohexanedione, 135 g (0.92 mol) of phenyl hydrazine-hydrochloride, and 1500 ml of ethyl alcohol were added to a 2 L round bottom flask, and after stirring for 30 minutes, concentrated sulfuric acid was added to the reaction solution. 5 ml are added. Stir at 65 ° C. for 10 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, filtered, and washed with ethyl alcohol.

상온에서 감압으로 건조시키고, 정제없이 여과물을 2L 둥근 바닥 플라스크에 여과물, 아세트산 1200 ml, 트리플로오루아세트산 120 ml를 넣고 110℃에서 8시간 교반시킨다. 반응이 종결되면 상온으로 내리고, 여과하고 에틸알코올과 헥산순으로 씻어준다. 상온에서 감압건조하여 [화학식 1-a]로 표시되는 화합물 80 g 를 얻었다. (수율 76.8 %)After drying under reduced pressure at room temperature, the filtrate was poured into a 2L round bottom flask without purification, 1200 ml of acetic acid and 120 ml of trifluoroacetic acid were stirred at 110 ° C. for 8 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, filtered, and washed with ethyl alcohol and hexane in that order. It dried under reduced pressure at normal temperature, and obtained 80 g of the compound represented by [Formula 1-a]. (Yield 76.8%)

(2) [화학식 1-b]로 표시되는 화합물의 합성(2) Synthesis of Compound Represented by [Formula 1-b]

하기 [반응식 2]에 의하여 [화학식 1-b]를 합성하였다.[Scheme 1-b] was synthesized by the following [Scheme 2].

[반응식 2]Scheme 2

Figure pat00038
Figure pat00038

[화학식 1-a] [화학식 1-b]          [Formula 1-a] [Formula 1-b]

1 L 의 둥근 바닥 플라스크에 [화학식 1-a]로 표시되는 화합물 48.5 g (0.189 mol), 아이오도벤젠 42.5 g (0.208mol), 구리분말 19.4 g (0.378 mol), 18-크라운-6 15 g (0.057 mol), 탄산칼륨 104.5 g (0.756 mol)을 순서대로 넣고, 올쏘-디클로로벤젠 480 ml 를 가한 후, 180 ℃ 에서 2일간 환류시킨다.In a 1 L round bottom flask, 48.5 g (0.189 mol) of compound represented by [Formula 1-a], 42.5 g (0.208 mol) of iodobenzene, 19.4 g (0.378 mol) of copper powder, 15 g of 18-crown-6 (0.057 mol) and 104.5 g (0.756 mol) of potassium carbonate were added sequentially, and 480 ml of ols-dichlorobenzene was added thereto, and the mixture was refluxed at 180 ° C. for 2 days.

반응이 종료되면, 메틸렌 클로라이드 500 ml 와 증류수 400 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 헥산 단독으로 컬럼 크로마토 그래피에서 올쏘-디클로로벤젠을 제거한다. 용매가 제거된 후, 메틸렌 클로라이드를 과량 넣어 불순한 생성물을 얻고, 메틸렌클로라이드 : 헥산 = 1 : 10으로 컬럼크로마토그래피하여 [화학식 1-b]로 표시되는 화합물 17.9 g을 얻었다. (수율 28 %)After the reaction was completed, the mixture was extracted using 500 ml of methylene chloride and 400 ml of distilled water. Repeat twice. The organic layer was concentrated under reduced pressure to remove olso-dichlorobenzene from the column chromatography using hexane alone. After the solvent was removed, an excess of methylene chloride was added to obtain an impure product, and then column chromatography was performed with methylene chloride: hexane = 1: 10 to obtain 17.9 g of a compound represented by [Formula 1-b]. (Yield 28%)

(3) [화학식 1-c]로 표시되는 화합물의 합성(3) Synthesis of Compound Represented by [Formula 1-c]

하기 [반응식 3]에 의하여 [화학식 1-c]를 합성하였다.[Scheme 1-c] was synthesized by the following [Scheme 3].

[반응식 3]Scheme 3

Figure pat00039
Figure pat00039

[화학식 1-b] [화학식 1-c]             [Formula 1-b] [Formula 1-c]

1 L 의 둥근 바닥 플라스크에 [화학식1-c]로 표시되는 화합물 27.7 g (0.083 mol), 1,3-디브로모-5-아이오도벤젠 39.1 g (0.108mol), 구리분말 15.8 g (0.249 mol), 18-크라운-6 4.4 g (0.017 mol), 탄산칼륨 57.48 g (0.415 mol)을 순서대로 넣고, 올쏘-디클로로벤젠 270 ml 를 가한 후, 180 ℃ 에서 3일간 환류시킨다.27.7 g (0.083 mol) of the compound represented by [Formula 1-c], 39.1 g (0.108 mol) of 1,3-dibromo-5-iodobenzene, and 15.8 g of copper powder (0.249) in a 1 L round bottom flask mol), 18-crown-6 4.4 g (0.017 mol) and potassium carbonate 57.48 g (0.415 mol) are added in this order, 270 ml of ortho-dichlorobenzene is added, and it refluxed at 180 degreeC for 3 days.

반응이 종료되면, 메틸렌 클로라이드 200 ml 와 증류수 200 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 헥산 단독으로 컬럼 크로마토 그래피에서 올쏘-디클로로벤젠을 제거한다. 용매가 제거된 후, 메틸렌 클로라이드를 과량 넣어 불순한 생성물을 얻고, 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼 크로마토그래피하여 [화학식 1-c]로 표시되는 화합물 30 g 을 얻었다. (수율 64 %)After the reaction is completed, the mixture is extracted using 200 ml of methylene chloride and 200 ml of distilled water. Repeat twice. The organic layer was concentrated under reduced pressure to remove olso-dichlorobenzene from the column chromatography using hexane alone. After the solvent was removed, an excess of methylene chloride was added to obtain an impure product, and column chromatography was carried out with methylene chloride: hexane = 1: 20 to obtain 30 g of a compound represented by [Formula 1-c]. (Yield 64%)

(4) [화학식 1-d]로 표시되는 화합물의 합성(4) Synthesis of Compound Represented by [Formula 1-d]

하기 [반응식 4]에 의하여 [화학식 1-d]를 합성하였다.[Scheme 1-d] was synthesized by the following [Scheme 4].

[반응식 4]Scheme 4

Figure pat00040
Figure pat00040

[화학식 1-c] [화학식 1-d]           [Formula 1-c] [Formula 1-d]

1000 mL 의 둥근 바닥 플라스크에 [화학식 1-c]로 표시되는 화합물 29.4 g (0.052 mol), 비스(피나콜라토)디보론 32.4 g (0.126mol), PdCl2(dppf) 2.54 g (0.0032 mol), 칼륨아세테이트 23.6 g (0.312 mol), 디메틸설폭사이드 500 ml 를 가한 후, 110 ℃ 에서 1일간 환류시킨다.In a 1000 mL round bottom flask, 29.4 g (0.052 mol) of compound represented by [Formula 1-c], 32.4 g (0.126 mol) of bis (pinacolato) diboron, 2.54 g (0.0032 mol) of PdCl 2 (dppf), After adding 23.6 g (0.312 mol) of potassium acetate and 500 ml of dimethyl sulfoxide, the mixture was refluxed at 110 ° C for 1 day.

반응이 종료되면, 메틸렌 클로라이드 200 ml 와 증류수 200 ml 를 사용하여 추출한다. 3회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼크로마토그래피하여 [화학식 1-d]로 표시되는 화합물 26.7 g 을 얻었다. (수율 78 %)After the reaction is completed, the mixture is extracted using 200 ml of methylene chloride and 200 ml of distilled water. Repeat three times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with methylene chloride: hexane = 1: 20 to obtain 26.7 g of the compound represented by [Formula 1-d]. (Yield 78%)

(5) [SPH10]로 표시되는 화합물의 합성(5) Synthesis of Compound Represented by [SPH10]

하기 [반응식 5]에 의하여 [SPH10]을 합성하였다.[SPH10] was synthesized according to [Scheme 5].

[반응식 5]Scheme 5

Figure pat00041
Figure pat00041

[화학식 1-d] [SPH10]           [Formula 1-d] [SPH10]

250 mL 의 둥근 바닥 플라스크에 [화학식 1-d]로 표시되는 화합물 15.8 g (0.024 mol), 클로로디페닐아민 16 g (0.06 mol), Pd[PPh3]4 0.7 g (0.0006 mol), 탄산칼륨 8.2 g (0.0588 mol), 테트라하이드로퓨란 50 ml, 톨루엔 50 ml, 물 20 ml 를 가한 후, 80 ℃ 에서 5시간 환류시킨다.In a 250 mL round bottom flask, 15.8 g (0.024 mol) of compound represented by [Formula 1-d], 16 g (0.06 mol) of chlorodiphenylamine, 0.7 g (0.0006 mol) of Pd [PPh3] 4, potassium carbonate 8.2 g (0.0588 mol), 50 ml of tetrahydrofuran, 50 ml of toluene and 20 ml of water are added, and the mixture is refluxed at 80 DEG C for 5 hours.

반응이 종료되면, 에틸아세테이트 50 ml 와 증류수 100 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드과 헥산으로 재결정을 반복하여 [SPH10]로 표시되는 화합물 6.2 g을 얻었다. (수율 31 %)After the reaction was completed, 50 ml of ethyl acetate and 100 ml of distilled water were used for extraction. Repeat twice. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 6.2 g of the compound represented by [SPH10]. (Yield 31%)

MS(MALDI-TOF):m/z= 871.00 [M]+ MS (MALDI-TOF): m / z = 871.00 [M] +

EA(Elemental analysis) : 이론값 - C. 82.74 % ; H. 4.4 % ; N. 12.86 %Elemental analysis (EA): theoretical value-C. 82.74%; H. 4.4%; N. 12.86%

실제값 - C. 82.66 % ; H. 4.46 % ; N. 12.88 %;
Found-C. 82.66%; H. 4.46%; N. 12.88%;

<합성예 2> [SPH34]로 표시되는 화합물의 합성Synthesis Example 2 Synthesis of Compound Represented by [SPH34]

(1) [화학식 2-a]로 표시되는 화합물의 합성(1) Synthesis of Compound Represented by [Formula 2-a]

하기 [반응식 6]에 의하여 [화학식 2-a]를 합성하였다.[Scheme 2-a] was synthesized according to [Scheme 6].

[반응식 6]Scheme 6

Figure pat00042
Figure pat00042

[화학식 1-b] [화학식 2-a]          [Formula 1-b] [Formula 2-a]

1 L 의 둥근 바닥 플라스크에 상기 [화학식 1-b]로 표시되는 화합물 27.7 g (0.083 mol), 3-브로모아이오도벤젠 30.5 g (0.108mol), 구리분말 15.8 g (0.249 mol), 18-크라운-6 4.4 g (0.017 mol), 탄산칼륨 57.48 g (0.415 mol)을 순서대로 넣고, 올쏘-디클로로벤젠 270 ml 를 가한 후, 180 ℃ 에서 3일간 환류시킨다.27.7 g (0.083 mol) of the compound represented by the above [Formula 1-b], 30.5 g (0.108 mol) of 3-bromoiodobenzene, 15.8 g (0.249 mol) of copper powder, 18-crown in a 1 L round bottom flask -6 4.4 g (0.017 mol) and 57.48 g (0.415 mol) of potassium carbonate are added in this order, 270 ml of ols-dichlorobenzene is added, and it is refluxed at 180 degreeC for 3 days.

반응이 종료되면, 메틸렌 클로라이드 200 ml 와 증류수 200 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 헥산 단독으로 컬럼 크로마토 그래피에서 올쏘-디클로로벤젠을 제거한다. 용매가 제거된 후, 메틸렌 클로라이드를 과량 넣어 불순한 생성물을 얻고, 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼 크로마토그래피하여 [화학식 2-a]로 표시되는 화합물 25 g 을 얻었다. (수율 64 %)After the reaction is completed, the mixture is extracted using 200 ml of methylene chloride and 200 ml of distilled water. Repeat twice. The organic layer was concentrated under reduced pressure to remove olso-dichlorobenzene from the column chromatography using hexane alone. After the solvent was removed, an excess of methylene chloride was added to obtain an impure product, and column chromatography was carried out with methylene chloride: hexane = 1: 20 to obtain 25 g of a compound represented by [Formula 2-a]. (Yield 64%)

(2) [화학식 2-b]로 표시되는 화합물의 합성(2) Synthesis of Compound Represented by [Formula 2-b]

하기 [반응식 7]에 의하여 [화학식 2-b]를 합성하였다.[Scheme 2-b] was synthesized according to [Scheme 7].

[반응식 7]Scheme 7

Figure pat00043
Figure pat00043

[화학식 2-a] [화학식 2-b]            [Formula 2-a] [Formula 2-b]

500 mL 의 둥근 바닥 플라스크에 [화학식 2-a]로 표시되는 화합물 25.3 g (0.052 mol), 비스(피나콜라토)디보론 16.2 g (0.063mol), PdCl2(dppf) 1.27 g (0.0016 mol), 칼륨아세테이트 11.8 g (0.156 mol), 디메틸설폭사이드 250 ml 를 가한 후, 110 ℃ 에서 1일간 환류시킨다.In a 500 mL round bottom flask, 25.3 g (0.052 mol) of compound represented by [Formula 2-a], 16.2 g (0.063 mol) of bis (pinacolato) diboron, 1.27 g (0.0016 mol) of PdCl 2 (dppf), 11.8 g (0.156 mol) of potassium acetate and 250 ml of dimethyl sulfoxide were added, and the mixture was refluxed at 110 ° C for 1 day.

반응이 종료되면, 메틸렌 클로라이드 100 ml 와 증류수 500 ml 를 사용하여 추출한다. 3회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼 크로마토그래피하여 생성물 21.6 g (78 %)을 얻는다.After the reaction was completed, 100 ml of methylene chloride and 500 ml of distilled water were used for extraction. Repeat three times. The organic layer was concentrated under reduced pressure, and the organic layer solution was column chromatographed with methylene chloride: hexane = 1: 20 to obtain 21.6 g (78%) of a product.

(3) [SPH34]로 표시되는 화합물의 합성(3) Synthesis of Compound Represented by [SPH34]

하기 [반응식 8]에 의하여 [SPH34]를 합성하였다.[SPH34] was synthesized according to [Scheme 8].

[반응식 8]Scheme 8

Figure pat00044
Figure pat00044

[화학식 2-b] [SPH34]           [Formula 2-b] [SPH34]

250 mL 의 둥근 바닥 플라스크에 [화학식 2-b]로 표시되는 화합물 6.3 g (0.024 mol), 클로로디페닐벤젠 5.1 g (0.019 mol), Pd[PPh3]4 0.7 g (0.0006 mol), 탄산칼륨 8.2 g (0.0588 mol), 테트라하이드로퓨란 50 ml, 톨루엔 50 ml, 물 20 ml 를 가한 후, 80 ℃ 에서 5시간 환류시킨다.In a 250 mL round bottom flask, 6.3 g (0.024 mol) of compound represented by [Formula 2-b], 5.1 g (0.019 mol) of chlorodiphenylbenzene, 0.7 g (0.0006 mol) of Pd [PPh3] 4, potassium carbonate 8.2 g (0.0588 mol), 50 ml of tetrahydrofuran, 50 ml of toluene and 20 ml of water are added, and the mixture is refluxed at 80 DEG C for 5 hours.

반응이 종료되면, 에틸아세테이트 50 ml 와 증류수 100 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드과 헥산으로 재결정을 반복하여 SPH10 3.8 g (29 %)을 얻는다.After the reaction was completed, 50 ml of ethyl acetate and 100 ml of distilled water were used for extraction. Repeat twice. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 3.8 g (29%) of SPH10.

MS(MALDI-TOF):m/z= 639.24 [M]+ MS (MALDI-TOF): m / z = 639.24 [M] +

EA(Elemental analysis) : 이론값 - C. 84.48 % ; H. 4.57 % ; N. 10.95 %Elemental analysis (EA): theoretical value-C. 84.48%; H. 4.57%; N. 10.95%

실제값 - C. 84.26 % ; H. 4.47 % ; N. 10.83 %;
Found-C. 84.26%; H. 4.47%; N. 10.83%;

<합성예 3> [SPH35]로 표시되는 화합물의 합성Synthesis Example 3 Synthesis of Compound Represented by [SPH35]

상기 <합성예 2>의 [반응식 8]에서 사용된 클로로디페닐벤젠 대신 2- 클로로-4,6-디페닐피리미딘을 사용한 것을 제외하고는, 상기 <합성예 2>와 동일한 합성방법으로 [SPH35]로 표시되는 화합물을 합성하였다.In the same manner as in <Synthesis Example 2>, except that 2-chloro-4,6-diphenylpyrimidine was used instead of the chlorodiphenylbenzene used in [Scheme 8] of <Synthesis Example 2> SPH35] was synthesized.

MS(MALDI-TOF):m/z= 638.25 [M]+ MS (MALDI-TOF): m / z = 638.25 [M] +

EA(Elemental analysis) : 이론값 - C. 84.49 % ; H. 4.73 % ; N. 8.77 %Elemental analysis (EA): theoretical value-C. 84.49%; H. 4.73%; N. 8.77%

실제값 - C. 84.26 % ; H. 4.93 % ; N. 8.74 %;
Found-C. 84.26%; H. 4.93%; N. 8.74%;

<합성예 4> [SPH39]로 표시되는 화합물의 합성Synthesis Example 4 Synthesis of Compound Represented by [SPH39]

(1) [화학식 4-a]로 표시되는 화합물의 합성(1) Synthesis of Compound Represented by [Formula 4-a]

하기 [반응식 9]에 의하여 [화학식 4-a]를 합성하였다.[Scheme 4-a] was synthesized by the following [Scheme 9].

[반응식 9]Scheme 9

Figure pat00045
Figure pat00045

[화학식 4-a]                                                     [Formula 4-a]

5 L 의 둥근 바닥 플라스크에 질소 기류하에서 N-페닐-3-브로모 카바졸 265 g (0.82 mol), 테트라하이드로퓨란 2500 ml를 넣는다. -73 ℃로 내리고, 노르말-부틸리튬 670 ml 를 적가하고, 적가가 완료되면 저온에서 1시간 교반시키다가 상온으로 올려서 2시간 교반시킨다. 다시 -73 ℃로 내리고, 트리메틸 보레이트 182.5 ml를 적가시킨다. 상온으로 서서히 올리고, 2M 염산수용액 500 ml를 적가시킨다. 에틸아세테이트와 물로 추출하고 유기층을 감압농축하고 헥산에서 재결정하여 [화학식 4-a]로 표시되는 화합물 118 g을 얻었다. (수율 50 %)In a 5 L round bottom flask, 265 g (0.82 mol) of N-phenyl-3-bromo carbazole and 2500 ml of tetrahydrofuran are added under a stream of nitrogen. The temperature was lowered to −73 ° C., and 670 ml of normal-butyllithium was added dropwise, and when the addition was completed, the mixture was stirred at low temperature for 1 hour, then raised to room temperature and stirred for 2 hours. Lowered to -73 ° C and 182.5 ml of trimethyl borate was added dropwise. Slowly raise to room temperature and add 500 ml of 2M aqueous hydrochloric acid solution dropwise. Extraction with ethyl acetate and water and concentration of the organic layer under reduced pressure and recrystallization from hexane yielded 118 g of the compound represented by [Formula 4-a]. (50% yield)

(2) [화학식 4-b]로 표시되는 화합물의 합성(2) Synthesis of Compound Represented by [Formula 4-b]

하기 [반응식 10]에 의하여 [화학식 4-b]를 합성하였다.[Scheme 4-b] was synthesized by the following [Scheme 10].

[반응식 10]Scheme 10

Figure pat00046
Figure pat00046

[화학식 4-a] [화학식 4-b]         [Formula 4-a] [Formula 4-b]

500 mL 의 둥근 바닥 플라스크에 [화학식4-a]로 표시되는 화합물 44.8 g (0.156 mol), 2-브로모니트로벤젠 26.26 g (0.13 mol), Pd[PPh3]4 3.0 g (0.0026 mol), 탄산칼륨 45 g (0.325 mol), 테트라하이드로퓨란 130 ml, 톨루엔 130 ml, 물 30 ml 를 가한 후, 80 ℃ 에서 12시간 환류시킨다.In a 500 mL round bottom flask, 44.8 g (0.156 mol) of compound represented by [Formula 4-a], 26.26 g (0.13 mol) of 2-bromonitrobenzene, 3.0 g (0.0026 mol) of Pd [PPh3] 4, carbonic acid 45 g (0.325 mol) of potassium, 130 ml of tetrahydrofuran, 130 ml of toluene and 30 ml of water were added, and the mixture was refluxed at 80 DEG C for 12 hours.

반응이 종료되면, 에틸아세테이트 200 ml 와 증류수 100 ml 를 사용하여 추출한다. 2회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드과 헥산으로 재결정하여 [화학식 4-b]로 표시되는 화합물 40.2 g을 얻었다. (수율 85 %)After the reaction was completed, the mixture was extracted using 200 ml of ethyl acetate and 100 ml of distilled water. Repeat twice. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from methylene chloride and hexane to obtain 40.2 g of a compound represented by [Formula 4-b]. (Yield 85%)

(3) [화학식 4-c]로 표시되는 화합물의 합성(3) Synthesis of Compound Represented by [Formula 4-c]

하기 [반응식 11]에 의하여 [화학식 4-c]를 합성하였다.[Scheme 4-c] was synthesized by the following [Scheme 11].

[반응식 11]Scheme 11

Figure pat00047
Figure pat00047

[화학식 4-b] [화학식 4-c]             [Formula 4-b] [Formula 4-c]

500 mL 의 둥근 바닥 플라스크에 [화학식 4-b]로 표시되는 화합물 26.2 g (0.072 mol), 트리페닐포스핀 47.14 g (0.18 mol), 디클로로벤젠 200 ml 를 가한 후, 160 ℃ 에서 12시간 환류시킨다. 반응이 종료되면, 뜨거운 상태에서 여과한 후, 메틸렌클로라이드와 증류수를 사용하여 추출한다.To a 500 mL round bottom flask was added 26.2 g (0.072 mol) of a compound represented by [Formula 4-b], 47.14 g (0.18 mol) of triphenylphosphine, and 200 ml of dichlorobenzene, followed by refluxing at 160 ° C. for 12 hours. . After the reaction is completed, the mixture is filtered while hot and extracted using methylene chloride and distilled water.

2회 반복 후 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드과 헥산으로 컬럼크로마토그래피하여 [화학식 4-c]로 표시되는 화합물 17.9g 을 얻었다. (수율 75 %)After repeating twice, the organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with methylene chloride and hexane to obtain 17.9 g of the compound represented by [Formula 4-c]. (Yield 75%)

(4) [화학식 4-d]로 표시되는 화합물의 합성(4) Synthesis of Compound Represented by [Formula 4-d]

하기 [반응식 12]에 의하여 [화학식 4-d]를 합성하였다.[Scheme 4-d] was synthesized by the following [Scheme 12].

[반응식 12][Reaction Scheme 12]

Figure pat00048
Figure pat00048

[화학식 4-c] [화학식 4-d]           [Formula 4-c] [Formula 4-d]

1 L 의 둥근 바닥 플라스크에 [화학식 4-c]로 표시되는 화합물 13.8 g (0.041 mol), 3-브로모아이오도벤젠 15.2 g (0.054mol), 구리분말 7.9 g (0.124 mol), 18-크라운-6 2.2 g (0.008 mol), 탄산칼륨 28.6 g (0.207 mol)을 순서대로 넣고, 올쏘-디클로로벤젠 150 ml 를 가한 후, 180 ℃ 에서 2일간 환류시킨다.Into a 1 L round bottom flask, 13.8 g (0.041 mol) of compound represented by [Chemical Formula 4-c], 15.2 g (0.054 mol) of 3-bromoiodobenzene, 7.9 g (0.124 mol) of copper powder, 18-crown- 6 2.2 g (0.008 mol) and 28.6 g (0.207 mol) of potassium carbonate are added in this order, and 150 ml of ortho-dichlorobenzene is added thereto, and the mixture is refluxed at 180 ° C. for 2 days.

반응이 종료되면, 메틸렌 클로라이드 300 ml 와 증류수 100 ml 를 사용하여 추출한다. 유기층을 감압농축하여 유기층 용액을 헥산 단독으로 컬럼 크로마토 그래피에서 올쏘-디클로로벤젠을 제거한다. 용매가 제거된 후, 메틸렌 클로라이드를 과량 넣어 불순한 생성물을 얻고, 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼 크로마토그래피하여 [화학식 4-d]로 표시되는 화합물 13 g 을 얻었다. (수율 67 %)After the reaction was completed, the mixture was extracted using 300 ml of methylene chloride and 100 ml of distilled water. The organic layer was concentrated under reduced pressure to remove olso-dichlorobenzene from the column chromatography using hexane alone. After the solvent was removed, an excess of methylene chloride was added to obtain an impure product, and column chromatography was performed with methylene chloride: hexane = 1: 20 to obtain 13 g of a compound represented by [Formula 4-d]. (67% yield)

(5) [화학식 4-e]로 표시되는 화합물의 합성(5) Synthesis of Compound Represented by [Formula 4-e]

하기 [반응식 13]에 의하여 [화학식 4-e]를 합성하였다.[Scheme 4-e] was synthesized by the following [Scheme 13].

[반응식 13]Scheme 13

Figure pat00049
Figure pat00049

[화학식 4-d] [화학식 4-e]           [Formula 4-d] [Formula 4-e]

500 mL 의 둥근 바닥 플라스크에 [화학식 4-d] 25.3 g (0.052 mol), 비스(피나콜라토)디보론 16.2 g (0.063mol), PdCl2(dppf) 1.27 g (0.0016 mol), 칼륨아세테이트 11.8 g (0.156 mol), 디메틸설폭사이드 250 ml 를 가한 후, 110 ℃ 에서 1일간 환류시킨다.In a 500 mL round bottom flask, 25.3 g (0.052 mol) of bis (pinacolato) diboron, 16.2 g (0.063mol) of bis (0.063 mol), 1.27 g (0.0016 mol) of potassium acetate, 11.8 g of potassium acetate (0.156 mol) and 250 ml of dimethyl sulfoxide were added, and the mixture was refluxed at 110 ° C for 1 day.

반응이 종료되면, 메틸렌 클로라이드 100 ml 와 증류수 500 ml 를 사용하여 추출한다. 3회 반복한다. 유기층을 감압농축하여 유기층 용액을 메틸렌클로라이드 : 헥산 = 1 : 20으로 컬럼크로마토그래피하여 [화학식 4-e]로 표시되는 화합물 21.6 g 을 얻었다. (수율 78 %)After the reaction was completed, 100 ml of methylene chloride and 500 ml of distilled water were used for extraction. Repeat three times. The organic layer was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography with methylene chloride: hexane = 1: 20 to obtain 21.6 g of the compound represented by [Formula 4-e]. (Yield 78%)

(6) [SPH39]로 표시되는 화합물의 합성(6) Synthesis of Compound Represented by [SPH39]

하기 [반응식 14]에 의하여 [SPH39]를 합성하였다.[SPH39] was synthesized by the following [Scheme 14].

[반응식 14][Reaction Scheme 14]

Figure pat00050
Figure pat00050

[화학식 4-e] [SPH39]           [Formula 4-e] [SPH39]

250 mL 의 둥근 바닥 플라스크에 [화학식4-e]로 표시되는 화합물 13 g (0.028 mol), 클로로디페닐트리아진 5.9 g (0.022 mol), Pd[PPh3]4 1.02 g (0.0008 mol), 탄산칼륨 9.2 g (0.066 mol), 테트라하이드로퓨란 40 ml, 1,4-디옥세인 40 ml, 물 15 ml 를 가한 후, 80 ℃ 에서 12시간 환류시킨다.In a 250 mL round bottom flask, 13 g (0.028 mol) of the compound represented by [Formula 4-e], 5.9 g (0.022 mol) of chlorodiphenyltriazine, 1.02 g (0.0008 mol) of Pd [PPh3] 4, potassium carbonate 9.2 g (0.066 mol), 40 ml of tetrahydrofuran, 40 ml of 1,4-dioxane and 15 ml of water were added, and the mixture was refluxed at 80 DEG C for 12 hours.

반응이 종료되면, 에틸아세테이트 100 ml 와 증류수 50 ml 를 사용하여 추출한다. 유기층을 감압농축하여 유기층 용액을 테트라하이드로퓨란과 헥산으로 재결정을 반복하여 [SPH39]로 표시되는 화합물 2.25 g을 얻었다. (수율16 %)After the reaction was completed, 100 ml of ethyl acetate and 50 ml of distilled water were used for extraction. The organic layer was concentrated under reduced pressure, and the organic layer solution was recrystallized from tetrahydrofuran and hexane to obtain 2.25 g of the compound represented by [SPH39]. (16% yield)

MS(MALDI-TOF):m/z= 639.24 [M]+ MS (MALDI-TOF): m / z = 639.24 [M] +

EA(Elemental analysis) : 이론값 - C. 84.48 % ; H. 4.57 % ; N. 10.95 %Elemental analysis (EA): theoretical value-C. 84.48%; H. 4.57%; N. 10.95%

실제값 - C. 84.16 % ; H. 4.85 % ; N. 10.99 %;
Found-C. 84.16%; H. 4.85%; N. 10.99%;

<합성예 5> [SPH75]로 표시되는 화합물의 합성Synthesis Example 5 Synthesis of Compound Represented by [SPH75]

상기 <합성예 4>의 [반응식 14]에서 사용된 클로로디페닐트리아진 대신 1-클로로-3-디페닐아민-5-페닐트리아진을 사용한 것을 제외하고는, 동일한 상기 <합성예 4>와 동일한 합성 방법으로 [SPH75]로 표시되는 화합물을 합성하였다.<Synthesis Example 4> is the same as in <Synthesis Example 4>, except that 1-chloro-3-diphenylamine-5-phenyltriazine is used instead of chlorodiphenyltriazine. By the same synthesis method, the compound represented by [SPH75] was synthesized.

MS(MALDI-TOF):m/z= 730.28 [M]+ MS (MALDI-TOF): m / z = 730.28 [M] +

EA(Elemental analysis) : 이론값 - C. 83.81 % ; H. 4.57 % ; N. 10.95 %Elemental analysis (EA): theoretical value-C. 83.81%; H. 4.57%; N. 10.95%

실제값 - C. 84.16 % ; H. 4.85 % ; N. 10.99 %;
Found-C. 84.16%; H. 4.85%; N. 10.99%;

<실시예 1 내지 5> 상기 합성예 1 내지 5에 의해서 합성된 화합물을 포함한 유기전계발광소자의 제조<Examples 1 to 5> Preparation of an organic electroluminescent device comprising a compound synthesized in Synthesis Examples 1 to 5

ITO 글래스의 발광 면적이 2mm × 2mm 크기가 되도록 패터닝한 후 세정하였다. 기판을 진공 챔버에 장착한 후 베이스 압력이 1 × 10-6torr가 되도록 한 후 유기물을 상기 ITO 위에 DNTPD(700Å), NPD(300Å), 본 발명에 의해 제조된 화합물 + Ir(ppy)3(10%)(300Å), Alq3(350Å), LiF(5Å), Al(1,000Å)의 순서로 성막하였으며, 0.4mA에서 측정을 하였다.The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in the vacuum chamber, the base pressure is 1 × 10 -6 torr and the organic material is placed on the ITO DNTPD (700 kPa), NPD (300 kPa), the compound + Ir (ppy) 3 (prepared by the present invention) 10%) (300 mW), Alq 3 (350 mW), LiF (5 mW), and Al (1,000 mW) were formed in this order and measured at 0.4 mA.

[DNTPD][DNTPD]

Figure pat00051
Figure pat00051

[NPD][NPD]

Figure pat00052
Figure pat00052

[Ir(ppy)3][Ir (ppy) 3 ]

Figure pat00053
Figure pat00053

[Alq3][Alq 3 ]

Figure pat00054
Figure pat00054

<비교예 1>Comparative Example 1

비교예를 위한 유기전계발광소자는 상기 실시예의 소자 구조에서 발명에 의해 제조된 화합물 대신 하기 구조식의 CBP를 사용한 점을 제외하고 동일하게 제작하였다.An organic light emitting display device for a comparative example was manufactured in the same manner except for using CBP having the following structural formula instead of the compound prepared by the invention in the device structure of the above example.

[CBP][CBP]

Figure pat00055
Figure pat00055

구분division 호스트Host 도펀트Dopant 도핑농도(%)Doping Concentration (%) ETLETL VV Cd/ACd / A COLORCOLOR 비교예1Comparative Example 1 CBPCBP Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 7.27.2 36.2436.24 GREENGREEN 실시예1Example 1 SPH10SPH10 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 3.413.41 41.7441.74 GREENGREEN 실시예2Example 2 SPH34SPH34 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 3.453.45 45.4645.46 GREENGREEN 실시예3Example 3 SPH35SPH35 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 3.683.68 43.1343.13 GREENGREEN 실시예4Example 4 SPH39SPH39 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 3.493.49 42.2142.21 GREENGREEN 실시예5Example 5 SPH75SPH75 Ir(ppy)3 Ir (ppy) 3 1010 Alq3 Alq 3 3.583.58 41.9641.96 GREENGREEN

상기 <실시예 1 내지 5>, <비교예 1> 및 [표 1]의 결과로부터, 본 발명에 따른 [화학식 1]로 표시되는 화합물은 인광발광재료로 많이 쓰이는 CBP에 비하여 구동 전압, 발광효율 등이 우수한 특성을 보이므로, 표시소자, 디스플레이 소자 및 조명 등에 유용하게 사용될 수 있음을 알 수 있다.From the results of <Examples 1 to 5>, <Comparative Example 1> and [Table 1], the compound represented by [Formula 1] according to the present invention is a driving voltage, luminous efficiency compared to CBP which is used a lot as a phosphorescent material Since the light shows excellent properties, it can be seen that it can be usefully used for display devices, display devices, and lighting.

Claims (8)

하기 [화학식 1]로 표시되는 인돌로카바졸 유도체:
[화학식 1]
Figure pat00056

(상기 식에서, n은 1부터 5까지의 정수이며,
n이 1인 경우, A는 1개 이상의 질소를 포함하는 치환 또는 비치환의 탄소수 3 - 40의 헤테로아릴기이고,
n이 2 이상인 경우, A는 각각 독립적으로 동일 또는 상이할 수 있으며, 수소원자, 중수소원자, 할로겐원자, 치환 또는 비치환의 헤테로아릴아미노기, 치환 또는 비치환의 탄소수 6 - 40의 아릴기, 치환 또는 비치환의 탄소수 3 - 40의 헤테로아릴기로부터 선택되고, 이때, 1개 이상의 질소를 포함하는 헤테로아릴기가 적어도 1개 이상 반드시 포함하며,
상기 A의 치환기는 수소원자, 중수소 원자, 시아노기, 할로겐원자, 히드록시기, 니트로기, 탄소수 1 - 40의 알킬기, 탄소수 1 - 40의 알콕시기, 탄소수 1 - 40의 알킬아미노기, 탄소수 6 - 40의 아릴아미노기, 탄소수 3 - 40의 헤테로아릴아미노기, 탄소수 1 - 40의 알킬실릴기, 탄소수 6 - 40의 아릴실릴기, 탄소수 6 - 40의 아릴기, 탄소수 3 - 40의 아릴옥시기, 탄소수 3 - 40의 헤테로아릴기로 이루어진 군으로부터 선택된 어느 하나임.)Indolocarbazole derivatives represented by the following [Formula 1]:
[Formula 1]
Figure pat00056

Wherein n is an integer from 1 to 5,
when n is 1, A is a substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms containing one or more nitrogen,
When n is 2 or more, A may be the same or different from each other independently, and a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted heteroarylamino group, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, substituted or unsubstituted Selected from a heteroaryl group having 3 to 40 carbon atoms in the ring, wherein at least one heteroaryl group including one or more nitrogens is necessarily included;
The substituent of A is a hydrogen atom, a deuterium atom, a cyano group, a halogen atom, a hydroxyl group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, a group having 6 to 40 carbon atoms Arylamino group, C3-C40 heteroarylamino group, C1-C40 alkylsilyl group, C6-C40 arylsilyl group, C6-C40 aryl group, C3-C40 aryloxy group, C3- Any one selected from the group consisting of 40 heteroaryl groups.) 제1항에 있어서,
n이 2 이상인 경우 상기 A는 각각 결합하여 포화 또는 불포화 고리 또는 헤테로 원자를 갖는 고리를 형성하는 것을 특징으로 하는 인돌로카바졸 유도체.The method of claim 1,
when n is 2 or more, said A each binds to form a saturated or unsaturated ring or a ring having a hetero atom. 제1항에 있어서,
상기 A의 치환기는 서로 결합하여 포화 혹은 불포화 고리를 형성하거나, 펜던트 방법으로 함께 부착 또는 융합(fused)되는 것을 특징으로 하는 인돌로카바졸 유도체.The method of claim 1,
The substituents of A bind to each other to form a saturated or unsaturated ring, or indolocarbazole derivatives, characterized in that attached or fused together by a pendant method. 제1항에 있어서,
하기 화학식 [SPH01] 내지 화학식 [SPH99]로 표시되는 군으로부터 선택된 어느 하나의 화합물인 것을 특징으로 하는 인돌로카바졸 유도체:
Figure pat00057

[SPH01] [SPH02] [SPH03]
Figure pat00058

[SPH04] [SPH05] [SPH06]
Figure pat00059

[SPH07] [SPH08] [SPH09]
Figure pat00060

[SPH10] [SPH11] [SPH12]
Figure pat00061

[SPH13] [SPH14] [SPH15]
Figure pat00062

[SPH16] [SPH17] [SPH18]
Figure pat00063

[SPH19] [SPH20] [SPH21]
Figure pat00064

[SPH22] [SPH23] [SPH24]
Figure pat00065

[SPH25] [SPH26] [SPH27]
Figure pat00066

[SPH28] [SPH29] [SPH30]
Figure pat00067

[SPH31] [SPH32] [SPH33]
Figure pat00068

[SPH34] [SPH35] [SPH36]
Figure pat00069

[SPH37] [SPH38] [SPH39]
Figure pat00070

[SPH40] [SPH41] [SPH42]
Figure pat00071

[SPH43] [SPH44] [SPH45]
Figure pat00072

[SPH46] [SPH47] [SPH48]
Figure pat00073

[SPH49] [SPH50] [SPH51]
Figure pat00074

[SPH52] [SPH53] [SPH54]
Figure pat00075

[SPH55] [SPH56] [SPH57]
Figure pat00076

[SPH58] [SPH59] [SPH60]
Figure pat00077

[SPH61] [SPH62] [SPH63]
Figure pat00078

[SPH64] [SPH65] [SPH66]
Figure pat00079

[SPH67] [SPH68] [SPH69]
Figure pat00080

[SPH70] [SPH71] [SPH72]
Figure pat00081

[SPH73] [SPH74] [SPH75]
Figure pat00082

[SPH76] [SPH77] [SPH78]
Figure pat00083

[SPH79] [SPH80] [SPH81]
Figure pat00084

[SPH82] [SPH83] [SPH84]
Figure pat00085

[SPH85] [SPH86] [SPH87]
Figure pat00086

[SPH88] [SPH89] [SPH90]
Figure pat00087

[SPH91] [SPH92] [SPH93]
Figure pat00088

[SPH94] [SPH95] [SPH96]
Figure pat00089

[SPH97] [SPH98] [SPH99]The method of claim 1,
An indolocarbazole derivative, which is any one compound selected from the group represented by the following formulas [SPH01] to [SPH99]:
Figure pat00057

[SPH01] [SPH02] [SPH03]
Figure pat00058

[SPH04] [SPH05] [SPH06]
Figure pat00059

[SPH07] [SPH08] [SPH09]
Figure pat00060

[SPH10] [SPH11] [SPH12]
Figure pat00061

[SPH13] [SPH14] [SPH15]
Figure pat00062

[SPH16] [SPH17] [SPH18]
Figure pat00063

[SPH19] [SPH20] [SPH21]
Figure pat00064

[SPH22] [SPH23] [SPH24]
Figure pat00065

[SPH25] [SPH26] [SPH27]
Figure pat00066

[SPH28] [SPH29] [SPH30]
Figure pat00067

[SPH31] [SPH32] [SPH33]
Figure pat00068

[SPH34] [SPH35] [SPH36]
Figure pat00069

[SPH37] [SPH38] [SPH39]
Figure pat00070

[SPH40] [SPH41] [SPH42]
Figure pat00071

[SPH43] [SPH44] [SPH45]
Figure pat00072

[SPH46] [SPH47] [SPH48]
Figure pat00073

[SPH49] [SPH50] [SPH51]
Figure pat00074

[SPH52] [SPH53] [SPH54]
Figure pat00075

[SPH55] [SPH56] [SPH57]
Figure pat00076

[SPH58] [SPH59] [SPH60]
Figure pat00077

[SPH61] [SPH62] [SPH63]
Figure pat00078

[SPH64] [SPH65] [SPH66]
Figure pat00079

[SPH67] [SPH68] [SPH69]
Figure pat00080

[SPH70] [SPH71] [SPH72]
Figure pat00081

[SPH73] [SPH74] [SPH75]
Figure pat00082

[SPH76] [SPH77] [SPH78]
Figure pat00083

[SPH79] [SPH80] [SPH81]
Figure pat00084

[SPH82] [SPH83] [SPH84]
Figure pat00085

[SPH85] [SPH86] [SPH87]
Figure pat00086

[SPH88] [SPH89] [SPH90]
Figure pat00087

[SPH91] [SPH92] [SPH93]
Figure pat00088

[SPH94] [SPH95] [SPH96]
Figure pat00089

[SPH97] [SPH98] [SPH99] 애노드;
캐소드; 및
상기 애노드 및 캐소드 사이에 개재되며, 제1항 또는 제4항 중 어느 한 항에 따른 인돌로카바졸 유도체를 포함하는 층을 구비한 유기전계발광소자.Anode;
Cathode; And
An organic electroluminescent device comprising a layer comprising an indolocarbazole derivative according to any one of claims 1 to 4, interposed between the anode and the cathode. 제5항에 있어서,
상기 애노드 및 캐소드 사이에 발광층, 정공주입층, 정공수송층, 정공저지층, 전자수송층, 전자주입층 및 전자저지층으로 이루어진 군으로부터 선택된 하나 이상의 층을 더 포함하는 것을 특징으로 하는 유기전계발광소자. The method of claim 5,
An organic electroluminescent device further comprising at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer and an electron blocking layer between the anode and the cathode. 제6항에 있어서,
상기 인돌로카바졸 유도체는 상기 애노드 및 캐소드 사이의 발광층 중에 포함되는 것을 특징으로 하는 유기전계발광소자. The method of claim 6,
The indolocarbazole derivative is an organic electroluminescent device, characterized in that contained in the light emitting layer between the anode and the cathode. 제7항에 있어서,
상기 발광층의 두께는 50 내지 2,000 Å인 것을 특징으로 하는 유기전계발광소자. The method of claim 7, wherein
The thickness of the light emitting layer is an organic light emitting device, characterized in that 50 to 2,000 kPa.
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