KR101989952B1 - Novel acridine derivatives and organic electroluminescent devices containing them - Google Patents
Novel acridine derivatives and organic electroluminescent devices containing them Download PDFInfo
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- KR101989952B1 KR101989952B1 KR1020170076644A KR20170076644A KR101989952B1 KR 101989952 B1 KR101989952 B1 KR 101989952B1 KR 1020170076644 A KR1020170076644 A KR 1020170076644A KR 20170076644 A KR20170076644 A KR 20170076644A KR 101989952 B1 KR101989952 B1 KR 101989952B1
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- South Korea
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- acridine derivative
- organic electroluminescent
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- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 title claims abstract description 57
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- 239000010410 layer Substances 0.000 description 86
- 239000000463 material Substances 0.000 description 45
- 125000003118 aryl group Chemical group 0.000 description 44
- 125000001072 heteroaryl group Chemical group 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- -1 Pyridinylpyrimidinyl Chemical group 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 125000000753 cycloalkyl group Chemical group 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 125000003545 alkoxy group Chemical group 0.000 description 17
- 238000002347 injection Methods 0.000 description 16
- 239000007924 injection Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011368 organic material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 11
- 125000000732 arylene group Chemical group 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000003111 delayed effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- TXBFHHYSJNVGBX-UHFFFAOYSA-N (4-diphenylphosphorylphenyl)-triphenylsilane Chemical compound C=1C=CC=CC=1P(C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 TXBFHHYSJNVGBX-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 125000005549 heteroarylene group Chemical group 0.000 description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000032258 transport Effects 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 230000003287 optical effect Effects 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- YPIANBZIVBPMJS-UHFFFAOYSA-N 2-bromo-n,n-diphenylaniline Chemical compound BrC1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 YPIANBZIVBPMJS-UHFFFAOYSA-N 0.000 description 2
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
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Classifications
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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
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
- C07D219/08—Nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- 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
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- Electroluminescent Light Sources (AREA)
Abstract
본 발명은 신규한 아크리딘 유도체 및 이를 포함하는 유기전계발광소자에 관한 것으로, 본 발명의 아크리딘 유도체는 분자 내 전자공여체 및 전자수용체를 가지며, 열안정성이 우수하여 이를 채용한 유기전계발광소자는 우수한 발광효율 및 색순도를 가진다.TECHNICAL FIELD The present invention relates to a novel acridine derivative and an organic electroluminescent device comprising the same. The acridine derivative of the present invention has an electron donor and an electron acceptor in a molecule, has excellent thermal stability, The device has excellent luminous efficiency and color purity.
Description
본 발명은 신규한 아크리딘 유도체 및 이를 포함하는 유기전계발광소자에 관한 것으로, 보다 상세하게는 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)을 나타내는 아크리딘 유도체 및 이를 포함하는 유기전계발광소자에 관한 것이다.The present invention relates to a novel acridine derivative and an organic electroluminescent device including the acridine derivative. More particularly, the present invention relates to an acridine derivative exhibiting thermally activated delayed fluorescence (TADF) and an organic electroluminescent Device.
최근 정보 통신 산업의 발달이 가속화됨에 따라서 가장 중요한 분야의 하나인 디스플레이 소자 분야에 있어서 보다 고도의 성능이 요구되고 있다.As the development of the information communication industry has been accelerated in recent years, higher performance is demanded in the field of display devices, which is one of the most important fields.
이러한 디스플레이 소자는 발광형과 비발광형으로 나눌 수 있으며, 발광형에 속하는 디스플레이 소자는 음극 선관(Cathode Ray Tube: CRT), 전계 발광 소자(Electroluminescene Display: ELD), 전기발광 다이오드(Light Emitting Diode: LED), 플라즈마 소자 패널 (Plazma Display Panel: PDP) 등이 있고, 비발광형 디스플레이 소자로는 액정디스플레이(Liquid Crystal Display: LCD) 등이 있다.Such a display device can be divided into a light emitting type and a non-light emitting type. The display device belonging to the light emitting type includes a cathode ray tube (CRT), an electroluminescence display (ELD), a light emitting diode A light emitting diode (LED), a plasma device panel (PDP) and the like, and a non-light emitting display device includes a liquid crystal display (LCD).
일반적으로 유기 전계 발광 현상이란 유기 물질을 이용하여 전기 에너지를 빛 에너지로 전환시켜 주는 현상을 말한다. 유기전계발광 현상을 이용하는 유기전계발광소자는 통상 양극(anode)과 음극(cathode) 및 이들 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등을 포함 할 수 있다.Generally, organic electroluminescent phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electroluminescent device using organic electroluminescent phenomenon generally has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
앞서 언급한 바와 같이 고도의 성능에 부합하기 위해 상기와 같은 유기전계발광소자의 다양한 구성에 대한 연구가 진행되고 있으며, 그 핵심은 발광층에 포함되는 발광물질이다. As mentioned above, in order to meet the high performance, various studies have been made on the various constitutions of the organic electroluminescent device as described above, and the key is the luminescent material contained in the luminescent layer.
최근 발광물질로 형광물질과 인광물질에 이어, 3 세대 OLED용 물질로 평가받는 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)물질에 대한 관심이 증가되고 있다. 상기 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)물질은 일중항 여기자를 삼중항으로 바꾸어 빛으로 전환하는 인광물질과 달리 삼중항 여기자를 일중항으로 바꾸어 빛으로 전환하는 물질로, 이러한 과정 때문에 지연형광특색을 나타내며, 이론적으로 일중항과 삼중항 여기자를 모두 빛으로 바꿀 수 있기 때문에 100% 내부양자효율이 가능하여 청색 및 적색 인광소재가 가지고 있는 수명과 효율의 한계를 극복할 수 있는 물질로 주목 받으면서 이에 대한 연구가 활성화되고 있는 실정이다.In recent years, interest in thermally activated delayed fluorescence (TADF) materials, which are evaluated as third-generation OLED materials, has been increasing, in addition to fluorescent materials and phosphorescent materials. The thermally activated delayed fluorescence (TADF) material is a material that converts triplet excitons into singletons and converts them into light, unlike a phosphorescent material that converts singlet excitons into triplets and converts them to light. It is a material that can overcome the limitation of lifetime and efficiency of blue and red phosphorescent materials because 100% internal quantum efficiency is possible because it can change both singlet and triplet excitons to light theoretically. Research on this is being activated.
상술한 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)을 나타내는 대표적인 기작은 삼중항-삼중항 소멸 (Triplet-triplet annihilation: TTA)에 의한 것과 역항간교차(Reverse intersystem crossing: RISC)를 통하여 삼중항을 일중항으로 변환에 의한 것이 있다. 이때, 상기 TTA는 현재 효율 높은 형광청색 및 초록색 소자에 활용되고 있으나, 삼중항 2 개가 소멸되어 일중항 1 개가 형성되기 때문에 내부양자효율이 낮아 한계가 있다. 반면 RISC은 이론적으로 모든 삼중항을 일중항으로 바꿀 수 있어 모든 여기자를 빛으로 전환할 수 있어, 높은 내부양자효율을 구현할 수 있다는 장점을 가진다.A representative mechanism of the thermally activated delayed fluorescence ( TADF ) described above is a triplet-triplet annihilation (TTA) and a reverse intersystem crossing (RISC) By converting it into a singular term. At this time, although the TTA is currently used for fluorescent blue and green devices having high efficiency, internal triplet efficiency is low due to the fact that one triplet is formed due to the disappearance of two triplet. On the other hand, RISC has the advantage that all excitons can be converted into light because it can theoretically convert all triplets into singletons, thereby achieving high internal quantum efficiency.
따라서 열활성화지연형광을 나타내는 신규한 화합물에 대한 연구가 요구된다.Therefore, there is a need for new compounds that exhibit thermally activated delayed fluorescence.
본 발명의 목적은 물리적 화학적 특성이 우수하여 향상된 광학적 특성을 가지는 아크리딘 유도체 및 이의 제조방법을 제공한다.An object of the present invention is to provide an acridine derivative having excellent physical and chemical properties and improved optical properties and a method for producing the same.
또한 본 발명은 본 발명의 아크리딘 유도체를 채용함으로써 열안정성이 높고, 우수한 효율 및 광학적 특성을 가지는 유기전계발광소자를 제공한다. The present invention also provides an organic electroluminescent device having high thermal stability and excellent efficiency and optical characteristics by employing the acridine derivative of the present invention.
상기와 같은 목적을 달성하기위해 본 발명자들은 역항간교차(Reverse intersystem crossing: RISC)를 통한 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)을 나타내는 신규한 화합물을 개발하던 중 아크리딘 유도체, 특히 페닐 스피로고리를 치환기로 가지는 아크리딘 유도체를 발견하여 본 발명의 완성하였다. In order to achieve the above object, the present inventors have developed a novel compound showing thermally activated delayed fluorescence (TADF) through reverse intersystem crossing (RISC) An acridine derivative having a phenyl spiro ring as a substituent was discovered and the present invention was completed.
즉, 본 발명은 유기전계발광소자에 이용되어 우수한 광학적 특성을 가지는 하기 화학식 1로 표시되는 아크리딘 유도체를 제공한다.That is, the present invention provides an acridine derivative represented by the following formula (1), which is used in an organic electroluminescent device and has excellent optical properties.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the formula 1,
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
Y는 수소, (C1-C30)알킬, (C1-C30)알콕시 또는 -L-Ar이며;Y is hydrogen, (C1-C30) alkyl, (C1-C30) alkoxy or -L-Ar;
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나 이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
바람직하게 상기 화학식 1에서 L은 하기 구조에서 선택될 수 있다.Preferably, L in formula (1) may be selected from the following structures.
(상기 구조에서,(In the above structure,
상기 R1 내지 R3은 각각 독립적으로 수소, 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴 또는 (C6-C30)아릴이다.)Each of R 1 to R 3 is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C3-C30) heteroaryl or (C6-C30) aryl.
바람직하게 상기 화학식 1에서 Ar은 하기 구조식에서 선택될 수 있다.Preferably, Ar in formula (1) may be selected from the following formulas.
(상기 구조식에서(In the above formula
R11 내지 R18은 서로 독립적으로 수소, 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 또는 (C6-C30)아릴이며;R 11 to R 18 independently from each other are hydrogen, halogen, cyano, nitro, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl or (C6-C30) aryl;
o는 1 내지 2의 정수이며; p는 1 내지 4의 정수이며; q는 1 내지 3의 정수이며; r은 1 내지 5의 정수이며;o is an integer from 1 to 2; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer from 1 to 5;
o, p, q 및 r이 2 이상인 경우 R11 내지 R18은 서로 동일하거나 상이할 수 있다.)When o, p, q and r are 2 or more, R 11 to R 18 may be the same or different from each other.)
우수한 열안정성 및 광학적 특성을 가지기 위한 측면에서 상기 화학식 1은 하기 화학식 2 또는 화학식 3으로 표시될 수 있다.From the viewpoint of having excellent thermal stability and optical properties, Formula 1 may be represented by Formula 2 or Formula 3 below.
[화학식 2](2)
[화학식 3](3)
(상기 화학식 2 및 3에서,(In the above formulas 2 and 3,
L1 및 L2는 서로 독립적으로 (C6-C30)아릴렌이며;L 1 and L 2 independently of one another are (C 6 -C 30) arylene;
Ar1 및 Ar2는 서로 독립적으로 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar 1 and Ar 2 are, independently of one another, (C6-C30) aryl or (C3-C30) heteroaryl;
L1 및 L2의 아릴렌 및 Ar1 및 Ar2의 아릴 또는 헤테로아릴은 (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)Arylene and aryl or heteroaryl of Ar 1 and Ar 2 of L 1 and L 2 are (C1-C30) alkyl, (C1-C30) alkoxy, (C3-C30) heteroaryl, (C6-C30) aryl (C3 -C30) heteroaryl, and (C6-C30) aryl.
본 발명의 일 실시예에 따른 상기 화학식 2 및 화학식 3에서 바람직하게 L1 및 L2는 서로 독립적으로 (C1-C30)알킬 또는 (C1-C30)알콕시로 치환되거나 치환되지 않은 페닐렌이며;In Formula 2 and Formula 3 according to an embodiment of the present invention, preferably, L 1 and L 2 are each independently phenylene substituted or unsubstituted with (C 1 -C 30) alkyl or (C 1 -C 30) alkoxy;
Ar1 및 Ar2는 서로 독립적으로 (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 치환되거나 치환되지 않은 트리아지닐, 피리디닐 피리미디닐 또는 페닐일 수 있다.Ar 1 and Ar 2 are each independently selected from the group consisting of (C 3 -C 30) heteroaryl, (C 6 -C 30) aryl (C 3 -C 30) heteroaryl and (C 6 -C 30) aryl, , Pyridinylpyrimidinyl, or phenyl.
또한 본 발명은 본 발명의 하기 화학식 11로 표시되는 아크리딘 유도체의 제조방법을 제공하는 것으로, 아크리딘 유도체의 제조방법은, 하기 화학식 12와 하기 화학식 13을 반응시켜 하기 화학식 11의 아크리딘 유도체를 제조하는 단계를 포함한다.The present invention also provides a process for preparing an acridine derivative represented by the following general formula (11), wherein the acridine derivative is produced by reacting the following general formula (12) with the following general formula (13) Amine derivative.
[화학식 11](11)
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
(상기 화학식 11 내지 화학식 13에서,(In the formulas (11) to (13)
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
Y1 및 X1는 서로 독립적으로 할로겐이며;Y 1 and X 1 are independently of each other halogen;
T는 
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
또한 본 발명은 하기 화학식 15와 하기 화학식 16을 반응시켜 하기 화학식 14의 아크리딘 유도체를 제조하는 단계를 포함하는 아크리딘 유도체의 제조방법을 제공한다.The present invention also provides a process for preparing an acridine derivative, which comprises reacting a compound represented by the following formula (15) and (16) to prepare an acridine derivative represented by the following formula (14).
[화학식 14][Chemical Formula 14]
[화학식 15][Chemical Formula 15]
[화학식 16][Chemical Formula 16]
(상기 화학식 14 내지 화학식 16에서,(In the above Chemical Formulas 14 to 16,
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
X2는 서로 독립적으로 할로겐이며;X 2 independently of one another are halogen;
T는 
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
또한 본 발명은 본 발명의 아크리딘 유도체를 포함하는 유기전계발광소자를 제공한다.The present invention also provides an organic electroluminescent device comprising the acridine derivative of the present invention.
바람직하게 본 발명의 일 실시예에 따른 유기전계발광소자에 포함되는 아크리딘 유도체는 유기전계발광소자의 발광층에 포함될 수 있다.Preferably, the acridine derivative included in the organic electroluminescent device according to an embodiment of the present invention may be included in the emission layer of the organic electroluminescent device.
본 발명의 아크리딘 유도체는 분자 내에 전자공여체 및 전자수용체를 동시에 가짐으로써 이를 포함하는 유기전계발광소자의 효율 및 수명특성을 향상시킨다.The acridine derivative of the present invention has both an electron donor and an electron acceptor in the molecule, thereby improving the efficiency and lifetime characteristics of the organic electroluminescent device including the acridine derivative.
또한 본 발명의 아크리딘 유도체는 열안정성이 높아 이를 포함하는 유기전계발광소자의 색순도를 저하시키지 않으면서도 높은 효율 및 수명특성을 가진다. Also, the acridine derivative of the present invention has high thermal stability and thus has high efficiency and lifetime characteristics without lowering the color purity of an organic electroluminescent device including the acridine derivative.
또한 본 발명의 유기전계발광소자는 아크리딘 유도체를 정공수송 재료, 발광 재료(인광 호스트), 특히 열활성화지연형광 도펀트 재료로 포함함으로써 고양자효율 및 장수명 특성을 가진다.Further, the organic electroluminescent device of the present invention has elevator efficiency and long life time characteristics by including an acridine derivative as a hole transporting material, a light emitting material (phosphorescent host), particularly a thermal activation delayed fluorescent dopant material.
본 발명은 열안정성이 우수하고, 특히 삼중항-일중항 에너지 차이가 작아 이를 이용하는 유기전계발광소자의 발광효율 및 색순도를 높일 수 있는 신규한 아크리딘 유도체를 제공하는 것으로, 본 발명의 아크리딘 유도체는 하기 화학식 1로 표시된다.The present invention provides a novel acridine derivative which is excellent in thermal stability, in particular, has a small triene-to-one-to-one energy difference and can increase the luminous efficiency and color purity of an organic electroluminescent device using the same, (1) < / RTI >
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서,(In the formula 1,
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
Y는 수소, (C1-C30)알킬, (C1-C30)알콕시 또는 -L-Ar이며;Y is hydrogen, (C1-C30) alkyl, (C1-C30) alkoxy or -L-Ar;
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나 이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
본 발명의 아크리딘 유도체는 아크리딘 골격의 N에 페닐이 치환되고, 아릴 또는 헤테로아릴이 스피로 고리로 연결된 치환기를 가짐으로써 열안정성이 높으며, 아크리딘 유도체 내에 전자 전자공여체 및 전자수용체를 동시에 포함함으로써 향상된 발광효율을 나타낸다.The acridine derivative of the present invention has a high thermal stability due to the substitution of N in the acridine skeleton with a phenyl and the substitution of the aryl or heteroaryl by a spiro ring and the electron donor and electron acceptor in the acridine derivative And simultaneously exhibits improved luminous efficiency.
발광효율 측면에서 바람직하게 상기 화학식 1에서 L은 하기 구조에서 선택될 수 있다.From the viewpoint of the light emitting efficiency, L in the above formula (1) may be selected from the following structures.
(상기 구조에서,(In the above structure,
상기 R1 내지 R3은 각각 독립적으로 수소, 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 또는 (C6-C30)아릴이다.)Each of R 1 to R 3 is independently selected from the group consisting of hydrogen, halogen, cyano, nitro, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl or (C6-C30) aryl.
바람직하게 상기 R1 내지 R3은 각각 독립적으로 수소 또는 (C1-C30)알킬일 수 있다.Preferably, R 1 to R 3 each independently may be hydrogen or (C 1 -C 30) alkyl.
본 발명의 상기 화학식 1로 표시되는 아크리딘 유도체에서 Ar은 하기 구조식에서 선택될 수 있다.In the acridine derivative represented by Formula 1 of the present invention, Ar may be selected from the following structural formulas.
(상기 구조식에서(In the above formula
R11 내지 R18은 서로 독립적으로 수소, 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 또는 (C6-C30)아릴이며;R 11 to R 18 independently from each other are hydrogen, halogen, cyano, nitro, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl or (C6-C30) aryl;
o는 1 내지 2의 정수이며; p는 1 내지 4의 정수이며; q는 1 내지 3의 정수이며; r은 1 내지 5의 정수이며;o is an integer from 1 to 2; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer from 1 to 5;
o, p, q 및 r이 2 이상인 경우 R11 내지 R18은 서로 동일하거나 상이할 수 있다.)When o, p, q and r are 2 or more, R 11 to R 18 may be the same or different from each other.)
우수한 반응효율 및 수명특성을 가지기 위한 측면에서 바람직하게 상기 구조식에서 R11 내지 R18은 서로 독립적으로 수소, (C3-C30)헤테로아릴 또는 (C6-C30)아릴이며; o는 1 내지 2의 정수이며; p는 1 내지 4의 정수이며; q는 1 내지 3의 정수이며; r은 1 내지 5의 정수이며; o, p, q 및 r이 2 이상인 경우 R11 내지 R18은 서로 동일하거나 상이할 수 있다R 11 to R 18 are independently hydrogen, (C 3 -C 30) heteroaryl or (C 6 -C 30) aryl in the structural formula, in view of having excellent reaction efficiency and life characteristics. o is an integer from 1 to 2; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer from 1 to 5; When o, p, q and r are 2 or more, R 11 to R 18 may be the same or different from each other
보다 구체적으로 상기 화학식 1로 표시되는 아크리딘 유도체에서 Ar은 하기 구조식에서 선택될 수 있다.More specifically, in the acridine derivative represented by the above formula (1), Ar may be selected from the following structural formulas.
바람직하게 본 발명의 상기 화학식 1은 하기 화학식 2 또는 화학식 3으로 표시될 수 있다.Preferably, Formula 1 of the present invention may be represented by Formula 2 or Formula 3 below.
[화학식 2](2)
[화학식 3](3)
(상기 화학식 2 및 3에서,(In the above formulas 2 and 3,
L1 및 L2는 서로 독립적으로 (C6-C30)아릴렌이며;L 1 and L 2 independently of one another are (C 6 -C 30) arylene;
Ar1 및 Ar2는 서로 독립적으로 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar 1 and Ar 2 are, independently of one another, (C6-C30) aryl or (C3-C30) heteroaryl;
L1 및 L2의 아릴렌 및 Ar1 및 Ar2의 아릴 또는 헤테로아릴은 (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)Arylene and aryl or heteroaryl of Ar 1 and Ar 2 of L 1 and L 2 are (C1-C30) alkyl, (C1-C30) alkoxy, (C3-C30) heteroaryl, (C6-C30) aryl (C3 -C30) heteroaryl, and (C6-C30) aryl.
본 발명의 상기 화학식 2 또는 화학식 3은 특정한 위치에 전자수용체인 
발광효율 및 색순도를 높이기위한 측면에서 바람직하게 상기 화학식 2 및 화학식 3에서, L1 및 L2는 서로 독립적으로 (C1-C30)알킬 또는 (C1-C30)알콕시로 치환되거나 치환되지 않은 페닐렌이며;L 1 and L 2 are each independently phenylene substituted or unsubstituted with (C 1 -C 30) alkyl or (C 1 -C 30) alkoxy, in view of increasing luminous efficiency and color purity ;
Ar1 및 Ar2는 서로 독립적으로 (C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 치환되거나 치환되지 않은 트리아지닐, 피리디닐 피리미디닐 또는 페닐일 수 있다.Ar 1 and Ar 2 may be, independently of one another, substituted or unsubstituted triazinyl, pyridinylpyrimidinyl or phenyl optionally substituted by (C3-C30) heteroaryl and (C6-C30) aryl.
구체적으로 본 발명의 아크리딘 유도체는 하기 화합물에서 선택될 수 있으나, 이에 한정이 있는 것은 아니다.Specifically, the acridine derivatives of the present invention can be selected from the following compounds, but are not limited thereto.
본 발명에 기재된 「알킬」, 「알콕시」 및 그 외 「알킬」부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함하며, 1 내지 30개의 탄소원자 바람직하게는 1 내지 20, 보다 바람직하게는 1 내지 10의 탄소원자를 갖는다. The substituents comprising the "alkyl", "alkoxy", and other "alkyl" moieties described in this invention include both straight-chain or branched forms and are those having 1 to 30 carbon atoms, preferably 1 to 20, more preferably 1 To 10 carbon atoms.
또한 본 발명에 기재된 「아릴」은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐(indenyl), 플루오레닐 등을 포함하지만, 이에 한정되지 않는다. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.
본 발명에 기재된 「헤테로아릴」은 방향족 고리 골격 원자로서 B, N, O, S, P(=O), Si 및 P로부터 선택되는 1 내지 4개의 헤테로원자를 포함하고, 나머지 방향족 고리 골격 원자가 탄소인 아릴 그룹을 의미하는 것으로, 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠환과 축합된 다환식 헤테로아릴이며, 부분적으로 포화될 수도 있다. 또한, 본 발명에서의 헤테로아릴은 하나 이상의 헤테로아릴이 단일결합으로 연결된 형태도 포함한다."Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.
본 발명에 아릴헤테로아릴은 헤테로아릴에 존재하는 하나이상의 수소가 아릴로 치환된 것을 의미하다.In the present invention, arylheteroaryl means that at least one hydrogen present in the heteroaryl is substituted with aryl.
본 발명에 기재된 「시클로알킬」은 3 내지 30개 탄소원자를 갖는 비방향족 일환식(monocyclic) 또는 다환식(multicyclic)고리 계를 의미하는 것으로, 일환식 고리는, 비제한적으로, 시클로프로필, 시클로부틸, 시클로펜틸 및 시클로헥실을 포함한다. 다환식 시클로알킬기의 일례는 퍼히드로나프틸, 퍼히드로인데닐 등을 포함하고; 브리지화된 다환식 시클로알킬기는 아다만틸 및 노르보르닐 등을 포함한다.&Quot; Cycloalkyl " as used in the present invention means a non-aromatic monocyclic or multicyclic ring system having 3 to 30 carbon atoms, and the monocyclic ring includes, but is not limited to, cyclopropyl, cyclobutyl , Cyclopentyl, and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Branched polycyclic cycloalkyl groups include adamantyl and norbornyl and the like.
본 발명에 기재된 「헤테로시클로알킬」은 탄소 원자와 질소, 인, 산소 및 황으로부터 선택된 1 내지 5개 헤테로원자로 이루어진 치환된 또는 비치환된 비방향족 3 내지 15원 고리 라디칼을 의미하며, 헤테로시클로알킬 라디칼은 융합되거나, 브릿지화되거나 또는 스피로 고리 계를 포함할 수 있는 일환식, 이환식 또는 삼환식 고리계일 수 있고, 또 헤테로시클릭 고리 라디칼 중의 질소, 인,탄소, 산소 또는 황 원자는 다양한 산화 상태로 경우에 따라 산화될 수 있다. 또한, 질소 원자는 경우에 따라 4급화 될 수 있다.&Quot; Heterocycloalkyl " as used herein means a substituted or unsubstituted, non-aromatic 3 to 15 membered ring radical consisting of carbon atoms and from 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur and includes heterocycloalkyl The radical may be a fused, bridged or cyclic, bicyclic or tricyclic ring system which may include a spiro ring system, and the nitrogen, phosphorus, carbon, oxygen or sulfur atom in the heterocyclic ring radical may be in various oxidation states If desired. In addition, the nitrogen atom can optionally be quaternized.
또한 본 발명은 본 발명의 아크리딘 유도체의 제조방법을 제공한다.The present invention also provides a process for preparing the acridine derivative of the present invention.
본 발명의 아크리딘 유도체의 제조방법은 두가지 양태로 제공될 수 있으며, 첫번째 양태로 하기 화학식 12와 하기 화학식 13을 반응시켜 하기 화학식 11의 아크리딘 유도체를 제조하는 단계를 포함하는 아크리딘 유도체의 제조방법을 제공한다.The method for preparing an acridine derivative of the present invention can be provided in two embodiments. In a first aspect, the present invention provides a process for producing an acridine derivative represented by the following general formula A method for producing a derivative is provided.
[화학식 11](11)
[화학식 12][Chemical Formula 12]
[화학식 13][Chemical Formula 13]
(상기 화학식 11 내지 화학식 13에서,(In the formulas (11) to (13)
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
Y1 및 X1는 서로 독립적으로 할로겐이며;Y 1 and X 1 are independently of each other halogen;
T는 
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
두번째 양태로 하기 화학식 15와 하기 화학식 16을 반응시켜 하기 화학식 14의 아크리딘 유도체를 제조하는 단계를 포함하는 아크리딘 유도체의 제조방법을 제공한다.In a second aspect, there is provided a process for preparing an acridine derivative, which comprises reacting a compound represented by the following formula (15) with a compound represented by the following formula (16) to prepare an acridine derivative represented by the following formula (14).
[화학식 14][Chemical Formula 14]
[화학식 15][Chemical Formula 15]
[화학식 16][Chemical Formula 16]
(상기 화학식 14 내지 화학식 16에서,(In the above Chemical Formulas 14 to 16,
A1 내지 A4는 서로 독립적으로 CH 또는 N이며;A 1 to A 4 are independently of each other CH or N;
X2는 서로 독립적으로 할로겐이며;X 2 independently of one another are halogen;
T는 
L은 단일결합, (C6-C30)아릴렌 또는 (C3-C30)헤테로아릴렌이며;L is a single bond, (C6-C30) arylene or (C3-C30) heteroarylene;
Ar은 (C6-C30)아릴 또는 (C3-C30)헤테로아릴이며;Ar is (C6-C30) aryl or (C3-C30) heteroaryl;
L의 아릴렌 또는 헤테로아릴렌 및 Ar의 아릴 또는 헤테로아릴은 할로겐, 시아노, 니트로, (C1-C30)알킬, (C1-C30)알콕시, (C3-C30)시클로알킬, (C3-C30)헤테로시클로알킬, (C3-C30)헤테로아릴, (C6-C30)아릴(C3-C30)헤테로아릴 및 (C6-C30)아릴에서 선택되는 하나이상으로 더 치환될 수 있다.)(C3-C30) cycloalkyl, (C3-C30) alkoxy, (C3-C30) cycloalkyl, (C3-C30) heteroaryl, (C6-C30) aryl (C3-C30) heteroaryl and (C6-C30) aryl.
본 발명의 아크리딘 유도체는 스즈키 커플링 반응 또는 스틸레 커플링 반응 등을 통하여 최종 화합물을 제조할 수 있으며, 상기의 제조방법으로 한정하는 것은 아니며, 상기의 제조방법 이외에도 통상의 유기화학 반응에 의하여 제조될 수 있음은 물론이다.The acridine derivative of the present invention can be produced by a Suzuki coupling reaction or a styrene coupling reaction, and the final compound can be prepared. The acridine derivative of the present invention is not limited to the above- Of course.
본 발명의 아크리딘 유도체의 제조방법은 유기용매 하에서 수행되는 것이 바람직하나, 용매를 사용하지 않고 융해된 상태에서 또한 반응이 수행될 수 있음은 물론이다. 상기 유기용매는 반응물을 완벽하게 용해시킬 수 있다면 한정되는 것은 아니나, 이의 구체적인 일예로는 톨루엔, 메탄올, 에탄올, 벤젠, n-햅탄, 테트라하이드로퓨란(THF), 클로로포름 또는 이들의 혼합용매일 수 있다.The method of preparing the acridine derivative of the present invention is preferably carried out in an organic solvent, but it goes without saying that the reaction may be carried out in a melted state without using a solvent. The organic solvent is not limited as long as it can completely dissolve the reactant, but specific examples thereof include toluene, methanol, ethanol, benzene, n-heptane, tetrahydrofuran (THF), chloroform, .
또한 본 발명은 본 발명의 아크리딘 유도체를 포함하는 유기전계발광소자를 제공한다. 이때, 상기 유기전계발광소자는 제1전극; 제2전극; 및 상기 제1전극과 제2전극 사이에 개재되는 1층 이상의 유기물층을 포함하며, 상기 유기물층은 본 발명의 아크리딘 유도체를 포함할 수 있다.The present invention also provides an organic electroluminescent device comprising the acridine derivative of the present invention. Here, the organic electroluminescent device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer may include an acridine derivative of the present invention.
바람직하게 본 발명의 아크리딘 유도체는 유기전계발광소자의 발광층에 포함될 수 있다.Preferably, the acridine derivative of the present invention may be included in the light emitting layer of the organic electroluminescent device.
본 발명의 유기전계발광소자는 당기술분야의 당업자가 인식할 수 있는 범위내에서 가능한 방법으로 제조할 수 있음을 물론이다.It is needless to say that the organic electroluminescent device of the present invention can be manufactured by a method as far as can be recognized by those skilled in the art.
본 발명의 화학식 1로 표시되는 아크리딘 유도체는 다양한 유기전계발광소자에 응용가능하며, 이러한 유기전계발광소자는 평판 디스플레이 장치, 플렉시블 디스플레이 장치, 단색 또는 백색의 평판 조명용 장치 및 단색 또는 백색의 플렉시블 조명용 장치에서 선택되는 장치에 사용될 수 있으나 이에 한정되는 것은 아니다.The acridine derivative represented by the formula (1) of the present invention can be applied to various organic electroluminescent devices. Such organic electroluminescent devices can be used for a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, But it is not limited thereto.
일반적으로 본 발명에 따른 유기전계발광소자에 대해 이하 상세하게 설명하나, 이에 한정이 있는 것은 아니다.In general, the organic electroluminescent device according to the present invention will be described in detail below, but the present invention is not limited thereto.
본 발명의 바람직한 실시예에 따라 제조된 유기전계발광소자(OLED)는 양극, 음극 및 이들 사이에 배치된 유기물층을 포함할 수 있다. An organic electroluminescent device OLED manufactured according to a preferred embodiment of the present invention may include an anode, a cathode, and an organic layer disposed therebetween.
또한 상술한 유기전계발광소자(OLED)의 유기물층은 보조층(버퍼층), 정공주입층, 정공전달층, 발광층, 정공저지층, 전자전달층 및 전자주입층 중 하나 이상을 포함하는 것 일 수 있으며, 상기 화학식 1의 화합물을 상기 유기물층에 포함하는 것을 제외하고는 당 기술분야에 통상의 제조방법 및 재료를 이용하여 당 기술 분야에 알려져 있는 구조로 제조될 수 있음을 물론이다.The organic layer of the organic electroluminescent device OLED may include at least one of an auxiliary layer (buffer layer), a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer , The compound of Formula 1 may be prepared in a manner known in the art using conventional methods and materials in the art, except that the compound of Formula 1 is included in the organic layer.
본 발명에 따른 화학식 1로 표시되는 아크리딘 유도체는 상기 유기물층 중 하나 이상에 포함될 수 있으며, 보다 구체적으로는 상기 유기물층에 있어 보조층(버퍼층), 정공주입층, 정공전달층, 발광층, 정공저지층, 전자전달층 및 전자주입층 중 하나 이상을 대신하여 사용되거나 이들과 함께 층을 형성하여 사용될 수 있다. The acridine derivative represented by the formula (1) according to the present invention may be contained in at least one of the organic material layers. More specifically, the organic material layer may include an auxiliary layer (buffer layer), a hole injecting layer, a hole transporting layer, Layer may be used in place of or more than one of the electron transport layer and the electron injection layer, or may be used by forming a layer with them.
본 발명의 일 실시예에 따른 상기 유기전계발광소자(OLED)는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 하나 이상을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 또한 상기 보조층(버퍼층)은 정공수송층과 발광층 사이 또는 전자수송층과 발광층 상이에 형성될 수 있으며, The organic light emitting diode OLED according to an exemplary embodiment of the present invention may be formed by depositing a metal or a conductive material on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation A metal oxide or an alloy thereof may be deposited to form an anode and an organic layer including 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 may be formed thereon, ≪ / RTI > The auxiliary layer (buffer layer) may be formed between the hole transporting layer and the light emitting layer, or between the electron transporting layer and the light emitting layer,
이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 제조될 수 있음은 물론이며, 상기 유기물층은 보조층(버퍼층), 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. In addition to such a method, the organic layer may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate, and the organic material layer may be formed by sequentially depositing an auxiliary layer (buffer layer), a hole injecting layer, a hole transporting layer, Layer or the like, but it is not limited thereto and may be a single-layer structure.
또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조될 수 있다.In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.
이때, 상기 유기전계발광소자(OLED)에 있어 본 발명의 아크리딘 유도체를 유기물층 중 바람직하게는 발광층에 포함할 수 있으며, 화학식 1로 표시되는 아크리딘 유도체는 청색 발광 재료로써, 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF) 도펀트 물질로 사용될 수 있다.At this time, the acridine derivative of the present invention may be included in the organic layer of the organic electroluminescent device (OLED), and preferably the acridine derivative represented by the formula (1) is a blue light emitting material, (Thermally Activated Delayed Fluorescence, TADF) dopant material.
상기 유기전계발광소자(OLED)에 있어, 상기 기판은 유리 및 석영판 이외에도 PET(polyethylene terephthalate), PEN(polyethylene naphthelate), PP(polyperopylene), PI(polyimide), PC(polycarbornate), PS(polystylene), POM(polyoxyethlene), AS 수지(acrylonitrile styrene copolymer), ABS 수지(acrylonitrile butadiene styrene copolymer) 및 TAC(Triacetyl cellulose) 등을 포함하는 플라스틱과 같은 유연하고 투명한 물질로도 제조될 수 있다. In the organic electroluminescent device OLED, the substrate may be formed of a material selected from the group consisting of polyethylene terephthalate (PEN), polyethylene naphthalate (PEN), polyperopylene (PP), polyimide (PI), polycarbornate (PC) , Plastics including polyoxyethylene (POM), acrylonitrile styrene copolymer (ABS), acrylonitrile butadiene styrene copolymer and TAC (triacetyl cellulose).
상기 기판 위에는 양극이 위치된다. 이러한 양극은 그 위에 위치되는 정공주입층으로 정공을 주입한다. 양극 물질로는 통상 유기물층으로 정공주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐주석 산화물(ITO), 인듐아연산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자; 등이 있으나, 이들에만 한정되는 것은 아니다. On the substrate, an anode is located. Such an anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode material that can be used in the present invention 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 poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; And the like, but are not limited thereto.
상기 양극 위에는 정공주입층이 위치된다. 이러한 정공주입층의 물질로 요구되는 조건은 양극으로부터의 정공주입 효율이 높으며, 주입된 정공을 효율적으로 수송할 수 있어야 한다. 이를 위해서는 이온화 포텐셜이 작고 가시광선에 대한 투명성이 높으며, 정공에 대한 안정성이 우수해야 한다. 정공주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입받을 수 있는 물질로서, 정공주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공주입 물질의 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴 헥사아자트리페닐렌, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 또는 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent. As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.
상기 정공주입층 위에는 정공수송층이 위치된다. 이러한 정공수송층은 정공주입층으로부터 정공을 전달받아 그 위에 위치되는 발광층으로 수송하는 역할을 하며, 높은 정공 이동도와 정공에 대한 안정성 및 전자를 막아주는 역할을 한다. 이러한 일반적 요구 이외에 차체 표시용으로 응용할 경우 소자에 대한 내열성이 요구되며, 유리 전이 온도(Tg)가 70 ℃ 이상의 값을 갖는 재료가 바람직하며, 이와 같은 조건을 만족하는 물질들로는 NPD(혹은 NPB라 함), 스피로-아릴아민계화합물, 페릴렌-아릴아민계화합물, 아자시클로헵타트리엔화합물, 비스(디페닐비닐페닐)안트라센, 실리콘게르마늄옥사이드화합물 또는 실리콘계아릴아민화합물 등이 될 수 있다. A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to a light emitting layer disposed thereon, and plays a role of high hole mobility, stability to holes, and electrons. In addition to these general requirements, materials that require heat resistance to the device and have a glass transition temperature (Tg) of 70 ° C or higher are desirable when used for vehicle display. Materials satisfying such conditions are NPD (or NPB) ), A spiro-arylamine compound, a perylene-arylamine compound, an azacycloheptatriene compound, bis (diphenylvinylphenyl) anthracene, a silicon germanium oxide compound, or a silicon-based arylamine compound.
상기 정공수송층 위에는 발광층이 위치된다. 이러한 유기발광층는 양극과 음극으로부터 각각 주입된 정공과 전자가 재결합하여 발광을 하는 층이며, 양자효율이 높은 물질로 이루어져 있다. 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자효율이 좋은 물질이 바람직하며, 보다 바람직하게 본 발명에 따른 화학식 1로 표시되는 아크리딘 유도체를 포함할 수 있다. 이때, 상술한 발광층은 본 발명의 아크리딘 유도체를 발광층에 포함함으로써, 보다 우수한 발광 효율 및 고색순도를 구현할 수 있다.A light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. As the luminescent material, a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. More preferably, And the acridine derivative represented by the general formula (1) shown below. At this time, by including the acridine derivative of the present invention in the light emitting layer, the above-mentioned light emitting layer can realize more excellent light emitting efficiency and high color purity.
상기 발광층 위에는 전자수송층이 위치된다. 이러한 전자수송층은 그 위에 위치되는 음극으로부터 전자주입 효율이 높고 주입된 전자를 효율적으로 수송할 수 있는 물질이 필요하다. 이를 위해서는 전자 친화력과 전자 이동속도가 크고 전자에 대한 안정성이 우수한 물질로 이루어져야 한다. 이와 같은 조건을 충족시키는 전자수송 물질로는 구체적인 예로 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다.An electron transporting layer is disposed on the light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons. Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.
또한 상기 전자수송층 위에는 전자주입층이 적층될 수 있다. 전자주입층은 Balq, Alq3, Be(bq)2, Zn(BTZ)2, Zn(phq)2, PBD, spiro-PBD, TPBI, Tf-6P 등과 같은 금속착제 화합물; imidazole ring 을 갖는 aromatic화합물; boron화합물; 등을 포함하는 저분자 물질을 이용하여 제작할 수 있으며, 상기 전자주입층은 100Å ~ 300Å의 두께 범위에서 형성되는 것이 바람직하다.An electron injection layer may be laminated on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P; aromatic compounds with imidazole rings; boron compounds; And the electron injecting layer may be formed in a thickness range of 100 to 300 angstroms.
마지막으로 상기 전자주입층 위에는 음극이 위치된다. 이러한 음극은 전자를 주입하는 역할을 하는 것으로, 상기 음극으로 사용하는 재료는 당업계에서 음극에 사용된 재료를 이용하는 것이라면 제한되지 않으며, 효율적인 전자주입을 위해서는 일 함수가 낮은 금속이 보다 바람직하다. 이의 구체적인 일예로는 주석, 마그네슘, 인듐, 칼슘, 나트륨, 리튬, 알루미늄, 은 등의 적당한 금속; 또는 그들의 적절한 합금; 이 사용될 수 있다. 또한 100 ㎛ 이하 두께의 리튬플루오라이드와 알루미늄, 산화리튬과 알루미늄, 스트론튬산화물과 알루미늄 등의 2 층 구조의 전극도 사용될 수 있다.Finally, a cathode is positioned on the electron injection layer. Such a cathode plays a role of injecting electrons. The material used for the cathode is not limited as long as it uses a material used in a cathode in the art, and a metal having a low work function is more preferable for efficient electron injection. Specific examples thereof include suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, and silver; Or their suitable alloys; Can be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.
앞서 설명한 바와 같이 본 발명에 따른 화학식 1로 표시되는 아크리딘 유도체는 보조층(버퍼층) 재료, 정공주입 재료, 정공수송 재료, 발광 재료, 전자수송 재료 또는 전자주입 재료로 사용될 수 있으며, 바람직하게는 정공수송 재료, 발광 재료(인광 호스트) 또는 열활성화지연형광(Thermally Activated Delayed Fluorescence, TADF)용 도펀트 재료로 사용될 수 있으며, 보다 바람직하게는 TADF용 도펀트 재료로 사용되는 것이 좋다.As described above, the acridine derivative represented by Chemical Formula 1 according to the present invention can be used as an auxiliary layer (buffer layer) material, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material or an electron injecting material, May be used as a hole transporting material, a light emitting material (phosphorescent host), or a dopant material for thermally activated delayed fluorescence (TADF), and more preferably used as a dopant material for TADF.
또한 본 발명의 아크리딘 유도체를 포함하는 유기전계발광소자는 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electroluminescent device including the acridine derivative of the present invention may be a top emission type, a back emission type, or a both-sided emission type.
이하, 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 이하의 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.
[실시예 1] 2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-methylphenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene](화합물 1, DTTSAF)의 제조Example 1 Synthesis of 2- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) -2-methylphenyl) -10-phenyl-10H- spiro [acridine- fluorene] (Compound 1, DTTSAF)
[단계 1] 2-bromo-N,N-diphenylaniline (화합물 A)의 제조[Step 1] Preparation of 2-bromo-N, N-diphenylaniline (Compound A)
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 Diphenylamine (15g, 88.638mmol), Pd(OAc)2 1g 및 t-BuONa 21.3g을 넣고 Toluene(300 mL)에 녹였다. Iodobromobenzene 25g 첨가한 후 P(t-Bu)3 1.8g을 첨가하고 110oC에서 12시간 가열환류 시켰다. 반응 종료 후 상온으로 냉각시킨 후 여과하였다. 여과된 용액을 회전식 증발기로 용매를 제거한 다음 MC(메틸렌클로라이드)로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 다시 여과하였다. 잔류물을 N-Hexane:EA (10:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 1 12.93g(45%)을 수득하였다. Diphenylamine (15 g, 88.638 mmol), 1 g of Pd (OAc) 2 and 21.3 g of t-BuONa were placed in a well-dried 100 mL three-neck round bottom flask and dissolved in toluene (300 mL). After adding 25 g of Iodobromobenzene, 1.8 g of P (t-Bu) 3 was added and the mixture was stirred at 110 ° C for 12 hours And the mixture was heated to reflux. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered. The filtrate was extracted with MC (methylene chloride) after removing the solvent with a rotary evaporator. The organic layer was washed with water, dried over MgSO 4 , and filtered again. The residue was separated by column chromatography using a solvent of N- hexane: EA (10: 1) to obtain 12.93 g (45%) of white solid compound 1.
1H-NMR (300 MHz, DMSO-d6)[ppm]: δ = 7.77-7.75 (d, 1H), 7.50-7.45 (t, 1H), 7.29-7.24(m, 6H), 7.00-6.95 (t, 2H), 6.89-6.86 (d, 4H). 1 H-NMR (300 MHz, DMSO-d 6 ) [ppm]:? = 7.77-7.75 (d, 1H), 7.50-7.45 (t, 1H), 7.29-7.24 (m, 6H), 7.00-6.95 t, 2H), 6.89-6.86 (d, 4H).
[단계 2] 10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 C)의 제조[Step 2] Preparation of 10-phenyl-10H-spiro [acridine-9,9'-fluorene (Compound C)
잘 건조시킨 Dropping funnel 장착된 100 mL 삼구 둥근 바닥 플라스크에 2-bromo-N,N-diphenylaniline (10g, 30.843 mmol)을 넣고 THF 300 ml에 녹였다. 도를 -78oC로 낮추고 n-BuLi (2.5M in hexane, 13.57 mL, 33.927 mmol)을 천천히 적가하였다. -78oC에서 2시간동안 교반시킨 다음 THF 200 ml에 녹인 Fluorenone 5.6 g을 Dropping funnel에 넣고 천천히 적가하였다. -78oC에서 2시간동안 교반한 후 서서히 상온으로 올리고 20시간동안 교반시켰다. 회전식 증발기로 용매를 제거한 다음 MC로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 여과하였다. 회전식 증발기로 용매를 제거한 다음 HCl 5 ml과 AcOH 150 ml를 넣고 130oC 에서 4시간동안 가열환류시켰다. 생성된 고체를 여과하여 건조 후 N-Hexane:Ethylacetate (10:1)용매를 사용하여 컬럼 크로마토그래피로 분리하여 고체 화합물 C를 6.41 g (51%)의 수득율로 얻었다. 2-bromo-N, N-diphenylaniline (10 g, 30.843 mmol) was added to a 100 mL three-neck round bottom flask equipped with a well-dried dropping funnel and dissolved in 300 mL of THF. The temperature was lowered to -78 ° C and n- BuLi (2.5 M in hexane, 13.57 mL, 33.927 mmol) was slowly added dropwise. After stirring at -78 ° C for 2 hours, 5.6 g of Fluorenone dissolved in 200 ml of THF was dropped into the dropping funnel and slowly added dropwise. After stirring at -78 ° C for 2 hours, the temperature was gradually raised to room temperature and stirred for 20 hours. Solvent was removed with a rotary evaporator and then extracted with MC. The organic layer was washed with water, dried over MgSO 4 , and filtered. The solvent was removed using a rotary evaporator, 5 ml of HCl and 150 ml of AcOH were added, and the mixture was refluxed at 130 ° C for 4 hours. The resulting solid was filtered off, dried and then separated by column chromatography using a solvent of N- hexane: Ethylacetate (10: 1) to obtain a solid compound C at a yield of 6.41 g (51%).
1H-NMR (300 MHz, CDCl3)[ppm]: δ = 7.84 (d, 2H), 7.74 (t, 2H), 7.60(t, 1H), 7.54 (d, 2H), 7.47 (d, 2H), 7.38 (t, 2H), 7.28 (t, 2H), 6.94 (t, 2H), 6.59 (t, 2H), 6.44 (d, 2H), 6.39 (d, 2H). 1 H-NMR (300 MHz, CDCl 3) [ppm]: δ = 7.84 (d, 2H), 7.74 (t, 2H), 7.60 (t, 1H), 7.54 (d, 2H), 7.47 (d, 2H ), 7.38 (t, 2H), 7.28 (t, 2H), 6.94 (t, 2H), 6.59 (t, 2H), 6.44 (d, 2H), 6.39
[3단계] 2-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 D)의 제조[Step 3] Preparation of 2-bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene (Compound D)
잘 건조시킨 100mL 삼구 둥근 바닥 플라스크에 10-phenyl-10H-spiro[acridine-9,9'-fluorene] (10g, 24.539mmol)을 넣고 Chloroform 250 ml에 녹였다. 온도를 0oC로 낮추고 NBS(N-브로모석신이미드) 3.93g를 5분 간격으로 첨가하였다. 8 ~ 10시간동안 교반한 다음 물로 충분히 씻어준 후 MgSO4로 수분을 제거하고 Silica 도포 후 N-Hexane:Ethylacetate (30:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 D를 8.32 g (60%)의 수득율로 얻었다. 10-phenyl-10H-spiro [acridine-9,9'-fluorene] (10 g, 24.539 mmol) was added to a well-dried 100 mL three-neck round bottom flask and dissolved in 250 mL of chloroform. The temperature was lowered to 0 ° C and 3.93 g of NBS (N-bromosuccinimide) was added at 5 minute intervals. After stirring for 8 to 10 hours, the solid was washed with water, and water was removed with MgSO 4. After silica application, the product was separated by column chromatography using N- hexane: Ethylacetate (30: 1) to obtain 8.32 g (60%).
1H-NMR (300 MHz, CD2Cl2)[ppm]: δ = 7.90-7.87 (d, 2H), 7.80-7.75 (t, 2H), 7.69-7.62(t, 1H), 7.55-7.44 (m, 6H), 7.37-7.31 (t, 2H), 7.07-7.03 (d, 1H), 6.99-6.94 (t, 1H), 6.63-6.58 (t, 1H), 6.49 (s, 1H), 6.41-6.36 (t, 2H), 6.32-6.29 (d, 1H). 1 H-NMR (300 MHz, CD 2 Cl 2) [ppm]: δ = 7.90-7.87 (d, 2H), 7.80-7.75 (t, 2H), 7.69-7.62 (t, 1H), 7.55-7.44 ( (t, 1H), 6.49 (s, 1H), 6.41-6.30 (m, 6H), 7.37-7.31 (t, 2H), 7.07-7.03 6.36 (t, 2 H), 6.32 - 6.29 (d, 1 H).
[4단계] 10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene(화합물 F)의 제조[Step 4] Synthesis of 10-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H- spiro [acridine-9,9'- Manufacturing
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 2-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] (1.0g, 2.06mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (1.57g, 6.17mmol), Pd(dppf)Cl2 (0.10g, 0.082mmol), KOAc (0.61g, 6.17mmol)을 넣고 DMF(15 mL)에 녹였다. 온도를 110oC로 맞추고 12시간 가열환류시켰다. 소량의 물을 넣어 여과한 다음 생성된 고체를 MC로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거하였다. n-Hexane:MC (1:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 F를 0.8 g (72.93 %)의 수득율로 얻었다. To a well-dried 100 mL three-necked round bottom flask was added 2-bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] (1.0 g, 2.06 mmol), 4,4,4 ' (1.57 g, 6.17 mmol), Pd (dppf) CI 2 (0.10 g, 0.082 mmol), KOAc (dicyclohexylcarbodiimide) 0.61 g, 6.17 mmol) were dissolved in DMF (15 mL). Set the temperature to 110 ° C and wait 12 hours And the mixture was heated to reflux. After adding a small amount of water and filtering, the resulting solid was extracted with MC. The organic layer was washed with water, dried with MgSO 4, and then the solvent was removed using a rotary evaporator. The white solid compound F was obtained in a yield of 0.8 g (72.93%) by column chromatography using n- Hexane: MC (1: 1) solvent.
1H-NMR (300 MHz, CD2Cl2) δ = 7.93-7.90 (d, 2H), 7.80-7.75 (t, 2H), 7.67-7.62 (t, 1H), 7.55-7.31 (m, 9H), 6.96-6.91 (t, 1H), 6.75 (s, 1H), 6.61-6.55 (t, 1H), 6.42-6.30 (m, 3H), 1.20 (s, 12H). 1 H-NMR (300 MHz, CD 2 Cl 2) δ = 7.93-7.90 (d, 2H), 7.80-7.75 (t, 2H), 7.67-7.62 (t, 1H), 7.55-7.31 (m, 9H) , 6.96-6.91 (t, 1H), 6.75 (s, 1H), 6.61-6.55 (t, 1H), 6.42-6.30 (m, 3H), 1.20 (s, 12H).
[5단계] 2-(4-bromo-3-methylphenyl)-4,6-diphenyl-1,3,5-triazine(화합물 G)의 제조[Step 5] Preparation of 2- (4-bromo-3-methylphenyl) -4,6-diphenyl-1,3,5-triazine (Compound G)
잘 건조시킨 1L 삼구 둥근 바닥 플라스크에 1-bromo-4-iodo-2-methylbenzene (15.0g, 50.52mmol)를 넣고 THF(300mL) 에 녹였다. 온도를 -90oC 로 낮추고 n-BuLi(2.5M in hexane, 22.78mL, 40.41mmol)을 천천히 적가하였다. 질소 기류 하에서 40 분 동안 교반시킨 다음 온도를 -78oC 로 올리고 2-chloro-4,6-diphenyl-1,3,5-triazine(13.5g, 50.51mmol)을 THF(150mL)에 녹여서 천천히 적가하고, 30 분 동안 교반한 후 서서히 상온으로 올려서 10 시간 동안 교반시켰다. 소량의 물을 넣어 quenching 하고 회전식 증발기를 이용하여 THF 를 제거하고, MC로 추출하고 유기층을 물로 씻어준 다음 MgSO4로 건조시킨 후 회전식 증발기를 사용하여 용매를 제거하였다. n-Hexane:Toluene (9:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 G를 4.6 g (22.63%)의 수득율로 얻었다. 1-bromo-4-iodo-2-methylbenzene (15.0 g, 50.52 mmol) was added to a well-dried 1 L three-neck round bottom flask and dissolved in THF (300 mL). The temperature was reduced to -90 ° C and n- BuLi (2.5 M in hexane, 22.78 mL, 40.41 mmol) was slowly added dropwise. The mixture was stirred for 40 minutes under a stream of nitrogen, then the temperature was raised to -78 ° C and 2-chloro-4,6-diphenyl-1,3,5-triazine (13.5 g, 50.51 mmol) was dissolved in THF (150 mL) , Stirred for 30 minutes, then slowly warmed to room temperature and stirred for 10 hours. The mixture was quenched with a small amount of water, and THF was removed using a rotary evaporator. The organic layer was extracted with MC, washed with water, dried over MgSO 4, and then evaporated using a rotary evaporator. The white solid compound G was obtained in a yield of 4.6 g (22.63%) using a solvent of n- Hexane: Toluene (9: 1) and separated by column chromatography.
1H-NMR (300 MHz, CD2Cl2) δ = 8.80-8.77 (m, 4H), 8.64 (s, 1H), 8.48-8.44 (d, 1H), 7.76-7.73 (d, 1H), 7.65-7.57 (m, 6H), 2.60 (s, 3H). 1 H-NMR (300 MHz, CD 2 Cl 2 )? = 8.80-8.77 (m, 4H), 8.64 (s, 1H), 8.48-8.44 (d, 1H), 7.76-7.73 -7.57 (m, 6 H), 2.60 (s, 3 H).
[6단계] 2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-methylphenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene의 제조[Step 6] Preparation of 2- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) -2-methylphenyl) -10-phenyl-10H- spiro [acridine-9,9'-fluorene Manufacturing
잘 건조시킨 100mL 삼구 둥근 바닥 플라스크에 10-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-10H-spiro[acridine-9,9'-fluorene] (1.0g, 1.875mmol), 2-(4-bromo-3-methylphenyl)-4,6-diphenyl-1,3,5-triazine (0.75g, 1.875mmol), Pd(pph3)4 (0.108g, 0.094 mmol)을 넣고 Toluene(20 mL) 에 녹였다. 2M K2CO3 (5mL) 넣는다. 온도를 95oC로 가열환류시켰다. 소량의 물과 Methanol을 넣어 교반하고 여과한 후 생성된 고체를 MC에 녹여서 Silica로 도포하고 n-Hexane/MC (5/1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 고체 화합물 1을 1.1 g (80.88 %)의 수득율로 얻었다. A well-dried 100 mL three-neck round bottom flask was charged with 10-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H- spiro [acridine- 3-methylphenyl) -4,6-diphenyl-1,3,5-triazine (0.75 g, 1.875 mmol), Pd (PPh 3 ) 4 ( 0.108 g, 0.094 mmol) was dissolved in toluene (20 mL). Add 2M K 2 CO 3 (5 mL). The temperature was refluxed to 95 ° C. A small amount of water and methanol were added to the solution and the mixture was stirred and filtered. The resulting solid was dissolved in MC, applied with silica, and separated by column chromatography using n- hexane / MC (5/1) 80.88%).
1H-NMR (300 MHz, CD2Cl2) δ = 8.79-8.76 (m, 4H), 8.53-8.47 (m, 2H), 7.87-7.79(m, 4H), 7.70-7.58 (m, 9H), 7.55-7.52 (d, 2H), 7.47-7.41 (m, 2H), 7.38-7.33(m, 2H), 7.22-7.19 (d, 1H), 7.09-6.97 (m, 2H), 6.66-6.61 (m, 1H), 6.53-6.44 (m, 4H), 2.12 (s, 3H). 13C-NMR (500 MHz, CDCl3) δ = 171.52, 171.49, 156.62, 145.49, 141.25, 140.99, 140.56, 139.24, 136.35, 135.74, 134.35, 132.97, 132.39, 131.18, 130.85, 129.82, 128.93, 128.59, 128.37, 127.92, 127.88, 127.67, 127.29, 126.36, 125.77, 124.80, 124.57, 120.77, 120.00, 114.75, 114.53, 56.85, 20.69. MS ES+(m/e): 728.29 (M+, 100%). 1 H-NMR (300 MHz, CD 2 Cl 2) δ = 8.79-8.76 (m, 4H), 8.53-8.47 (m, 2H), 7.87-7.79 (m, 4H), 7.70-7.58 (m, 9H) , 7.55-7.52 (d, 2H), 7.47-7.41 (m, 2H), 7.38-7. 33 (m, 2H), 7.22-7.19 m, 1 H), 6.53 - 6.44 (m, 4 H), 2.12 (s, 3 H). 13 C-NMR (500 MHz, CDCl 3 ) 隆 = 171.52, 171.49, 156.62, 145.49, 141.25, 140.99, 140.56, 139.24, 136.35, 135.74, 134.35, 132.97, 132.39, 131.18, 130.85, 129.82, 128.93, 128.59, 128.37 , 127.92, 127.88, 127.67, 127.29, 126.36, 125.77, 124.80, 124.57, 120.77, 120.00, 114.75, 114.53, 56.85, 20.69. MS ES + (m / e): 728.29 (M < + >, 100%).
[실시예 2] 2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2,5-dimethylphenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 2, DTXSAF)의 제조Example 2 Synthesis of 2- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) -2,5-dimethylphenyl) -10-phenyl-10H-spiro [acridine- '-fluorene (Compound 2, DTXSAF)
[1단계] 2-(4-bromo-2,5-dimethylphenyl)-4,6-diphenyl-1,3,5-triazine의 제조[Step 1] Preparation of 2- (4-bromo-2,5-dimethylphenyl) -4,6-diphenyl-1,3,5-triazine
실시예 1의 5단계에서 1-bromo-4-iodo-2-methylbenzene (15.0g, 50.52mmol)대신 1,4-dibromo-2,5-dimethylbenzene (20.0g, 75.77 mmol)을 사용한 것을 제외하고는 실시예 1의 5단계와 동일하게 실시하여 흰색 고체 화합물 H를 14.4 g (45.65%)의 수득율로 얻었다. Except that 1,4-dibromo-2,5-dimethylbenzene (20.0 g, 75.77 mmol) was used instead of 1-bromo-4-iodo-2-methylbenzene (15.0 g, 50.52 mmol) in the fifth step of Example 1 The procedure of Step 5 of Example 1 was repeated to obtain a white solid compound H in a yield of 14.4 g (45.65%).
1H-NMR (300 MHz, CD2Cl2) δ = 8.76-8.73 (m, 4H), 8.22 (s, 1H), 7.64-7.57 (m, 7H), 2.81(s, 3H), 2.52 (s, 3H). 1 H-NMR (300 MHz, CD 2 Cl 2) δ = 8.76-8.73 (m, 4H), 8.22 (s, 1H), 7.64-7.57 (m, 7H), 2.81 (s, 3H), 2.52 (s , 3H).
[2단계] 2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2,5-dimethylphenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 2)의 제조[Step 2] Synthesis of 2- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) -2,5-dimethylphenyl) -10- -fluorene (Compound 2)
실시예 1의 6단계에서 화합물 G 대신 화합물 H를 사용한 것을 제외하고는 실시예 1의 6단계와 동일하게 실시하여 화합물 2를 64.75 %의 수득율로 얻었다.Compound 6 was obtained in a yield of 64.75% in the same manner as in Step 6 of Example 1, except that Compound H was used instead of Compound G in Step 6 of Example 1.
1H-NMR (300 MHz, CD2Cl2) δ = 8.75-8.71 (m, 4H), 8.10 (s, 1H), 7.87-7.79 (m, 4H), 7.69-7.52 (m, 11H), 7.46-7.32 (m, 4H), 7.07-6.96 (m, 3H), 6.66-6.60 (t, 1H), 6.52-6.44 (m, 4H), 2.73 (s, 3H), 2.03 (s, 3H). 13C-NMR (500 MHz, CDCl3) δ = 174.31, 171.15, 156.64, 144.02, 141.30, 141.04, 140.46, 139.25, 136.36, 136.18, 134.15, 133.11, 133.05, 132.97, 132.41, 131.20, 131.15, 128.95, 128.63, 128.58, 128.35, 127.94, 127.76, 127.28, 125.76, 124.80, 124.51, 120.73, 119.99, 114.73, 114.55, 56.86, 21.85, 19.95. MS ES+(m/e): 742.30 (M+, 100%). 1 H-NMR (300 MHz, CD 2 Cl 2) δ = 8.75-8.71 (m, 4H), 8.10 (s, 1H), 7.87-7.79 (m, 4H), 7.69-7.52 (m, 11H), 7.46 (M, 4H), 2.73 (s, 3H), 2.03 (s, 3H). 13 C-NMR (500 MHz, CDCl 3 )? = 174.31, 171.15, 156.64, 144.02, 141.30, 141.04, 140.46, 139.25, 136.36, 136.18, 134.15, 133.11, 133.05, 132.97, 132.41, 131.20, 131.15, 128.95, 128.63 , 128.58, 128.35, 127.94, 127.76, 127.28, 125.76, 124.80, 124.51, 120.73, 119.99, 114.73, 114.55, 56.86, 21.85, 19.95. MS ES + (m / e): 742.30 (M < + >, 100%).
[실시예 3] 2,7-bis(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 3, BDTPSAF)의 제조Example 3 Preparation of 2,7-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10-phenyl-10H- spiro [acridine- fluorene (Compound 3, BDTPSAF)
[1단계] 2,7-dibromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene의 제조[Step 1] Preparation of 2,7-dibromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 10-phenyl-10H-spiro[acridine-9,9'-fluorene] (2.3g, 5.644mmol)을 넣고 Chloroform 100 ml로 녹였다. 0oC에서 NBS 4.01g을 수차례 나누어 첨가하였다. 0oC에서 2시간동안 교반시키고 상온에서 12시간동안 교반시켰다. 물로 충분히 씻어준 다음 MgSO4로 수분제거하고 Silica 도포 후 N-Hexane/Ethylacetate (10/1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 J를 1.5 g (47%)의 수득율로 얻었다. 10-phenyl-10H-spiro [acridine-9,9'-fluorene] (2.3 g, 5.644 mmol) was added to a well-dried 100 mL three-neck round bottom flask and dissolved in 100 mL of chloroform. NBS 4.01g was added in several portions at 0 ° C. The mixture was stirred at 0 ° C for 2 hours and at room temperature for 12 hours. After washing thoroughly with water, water was removed with MgSO 4 , applied with silica, and then separated by column chromatography using N- hexane / Ethylacetate (10/1) solvent to obtain white solid compound J at a yield of 1.5 g (47%).
1H-NMR (300 MHz, CDCl3)[ppm]: δ = 7.85 (d, 2H), 7.75 (t, 2H), 7.62 (t, 1H), 7.49-7.40 (m, 6H), 7.34-7.32 (d, 2H), 7.04 (d, 2H), 6.48 (s, 2H), 6.26 (d, 2H). 1 H-NMR (300 MHz, CDCl 3) [ppm]: δ = 7.85 (d, 2H), 7.75 (t, 2H), 7.62 (t, 1H), 7.49-7.40 (m, 6H), 7.34-7.32 (d, 2H), 7.04 (d, 2H), 6.48 (s, 2H), 6.26 (d, 2H).
[2단계] 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine의 제조Preparation of 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine
잘 건조시킨 100 mL 삼구 둥근 바닥 플라스크에 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine(20g, 51.511mmol) 및 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane)(39.24g, 154.532mmol)을 KOAc(15g, 154.532 mmol)와 Pd(dppf)Cl2 1.68g넣고 DMF 280ml에 녹인 다음 130oC에서 가열환류시켰다. 상온으로 냉각한 후 찬물에 붓고 교반시킨 후 생성되는 파우더를 여과하고 충분히 물로 씻어주었다. 고체를 MC에 녹이고 물로 충분히 씻어주며 잔여 DMF를 최대한 제거한 후 MgSO4로 수분제거하고 Silica로 도포한 후 N-Hexane/MC (10/1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 K를 16.8 g (75 %)의 수득율로 얻었다. To a well-dried 100 mL three-neck round bottom flask was added 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (20 g, 51.511 mmol) and 4,4,4 ' 1.68 g of KOAc (15 g, 154.532 mmol) and Pd (dppf) Cl 2 were added to a solution of 5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (39.24 g, 154.532 mmol) Dissolved in 280 ml of DMF, and then heated to reflux at 130 ° C. The mixture was cooled to room temperature, poured into cold water and stirred, and the resulting powder was filtered and sufficiently washed with water. The solids were dissolved in MC, washed thoroughly with water, and the remaining DMF was removed as much as possible. The water was removed with MgSO 4 and applied with silica. The product was separated by column chromatography using N- hexane / MC (10/1) Was obtained with a yield of 16.8 g (75%).
1H-NMR (300 MHz, CD2Cl2) δ = 8.83-8.77 (m, 6H), 8.04-8.02 (d, 2H), 7.65-7.58 (m, 6H), 1.42 (s, 12H). 1 H-NMR (300 MHz, CD 2 Cl 2 )? = 8.83-8.77 (m, 6H), 8.04-8.02 (d, 2H), 7.65-7.58 (m, 6H), 1.42 (s, 12H).
[3단계] 2,7-bis(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 3)의 제조[Step 3] Preparation of 2,7-bis (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -10-phenyl-10H- spiro [acridine-9,9'-fluorene (Compound 3)
잘 건조시킨 100mL 삼구 둥근 바닥 플라스크에 2,7-dibromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene] (2.0g, 3.538mmol) 및 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (3.39g, 7.783mmol)을 넣고 Toluene로 녹인 후 Pd(PPh3)4 0.2g을 넣었다. 2M K2CO3 수용액 5.3ml을 넣고 온도를 100oC로 맞추어 24시간동안 교반시켰다. 상온으로 냉각하고 Methanol를 첨가하였다. 생성된 고체를 여과한 다음 MC에 녹이고 물로 충분히 씻어준 후 MgSO4로 수분을 제거하고 Silica로 도포 후 N-Hexane:Ethylacetate (10:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 3을 0.8 g (72.93 %)의 수득율로 얻었다. 10-spiro [acridine-9,9'-fluorene] (2.0 g, 3.538 mmol) and 2,4-diphenyl-6- (4 - (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,5-triazine (3.39 g, 7.783 mmol) were dissolved in toluene. 3 ) 4 were added thereto. 5.3 ml of 2M K 2 CO 3 aqueous solution was added thereto, and the mixture was stirred at a temperature of 100 ° C for 24 hours. Cool to room temperature and add methanol. The resulting solid was filtered and then dissolved in MC. After washing thoroughly with water, the water was removed with MgSO 4 , applied with silica, and separated by column chromatography using a solvent of N- hexane: Ethylacetate (10: 1) Was obtained in a yield of 0.8 g (72.93%).
1H-NMR (300 MHz, CDCl3)[ppm]: δ = 8.78-8.75 (d, 8H), 8.69-8.67 (d, 4H) 7.91-7.89(d, 2H), 7.82 (t, 2H), 7.64-7.55 (m, 17H), 7.50-7.34 (m, 10H), 6.86 (d, 2H), 6.58 (d, 2H). 13C-NMR (500 MHz, CDCl3) [ppm]: δ = 171.51, 156.09, 144.37, 141.20, 140.73, 139.34, 136.33, 134.21, 132.41, 131.29, 130.94, 128.93, 128.59, 126.48, 126.27, 125.71, 120.26, 115.39, 57.05 1 H-NMR (300 MHz, CDCl 3) [ppm]: δ = 8.78-8.75 (d, 8H), 8.69-8.67 (d, 4H) 7.91-7.89 (d, 2H), 7.82 (t, 2H), 7.64-7.55 (m, 17H), 7.50-7.34 (m, 10H), 6.86 (d, 2H), 6.58 (d, 2H). 13 C-NMR (500 MHz, CDCl 3 ) [ppm]: δ = 171.51, 156.09, 144.37, 141.20, 140.73, 139.34, 136.33, 134.21, 132.41, 131.29, 130.94, 128.93, 128.59, 126.48, 126.27, 125.71, , 115.39, 57.05
[실시예 4] 2-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-methylphenyl)-10-phenyl-10H-spiro[acridine-9,9'-fluorene](화합물 4, DTPSAF)의 제조Example 4 Synthesis of 2- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) -2-methylphenyl) -10-phenyl-10H- spiro [acridine- fluorene] (Compound 4, DTPSAF)
잘 건조시킨 100mL 삼구 둥근 바닥 플라스크에 2-bromo-10-phenyl-10H-spiro[acridine-9,9'-fluorene(화합물 D) (2.0g, 4.11 mmol) 및 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine(화합물 K) (1.61g, 3.70 mmol)을 넣고 Toluene 100 ml로 녹인 후 Pd(PPh3)4 0.24g을 넣었다. 2M K2CO3 수용액 5 ml을 넣고 온도를 100oC로 맞추어 24시간동안 교반시켰다. 상온으로 냉각하고 Methanol를 첨가하였다. 생성된 고체를 여과한 다음 MC에 녹이고 물로 충분히 씻어준 후 MgSO4로 수분을 제거하고 Silica로 도포 후 N-Hexane:dichloromethane (5:1)용매를 사용하여 컬럼 크로마토그래피로 분리해서 흰색 고체 화합물 을 2.1 g (72.23 %)의 수득율로 얻었다.Acridine-9,9'-fluorene (Compound D) (2.0 g, 4.11 mmol) and 2,4-diphenyl-6- ( Phenyl) -1,3,5-triazine (Compound K) (1.61 g, 3.70 mmol) was added to a solution of Toluene 100 was dissolved in ml were added to Pd (PPh 3) 4 0.24g. 5 ml of 2M K 2 CO 3 aqueous solution was added, the temperature was adjusted to 100 ° C, and the mixture was stirred for 24 hours. Cool to room temperature and add methanol. The resulting solid was filtered and then dissolved in MC. After washing with water, the water was removed with MgSO 4 , applied with silica, and then separated by column chromatography using N- hexane: dichloromethane (5: 1) 2.1 g (72.23%).
1H-NMR (300 MHz, CD2Cl2) δ = 8.79-8.76 (m, 4H), 8.68-8.65 (d, 2H), 7.93-7.90 (d, 2H), 7.84-7.79 (t, 2H), 7.70-7.58 (m, 9H), 7.55-7.34 (m, 9H), 7.03-6.97 (t, 1H), 6.81-6.80 (d, 1H), 6.67-6.62 (t, 1H), 6.57-6.54 (d, 1H), 6.48-6.44 (d, 2H). 1 H-NMR (300 MHz, CD 2 Cl 2) δ = 8.79-8.76 (m, 4H), 8.68-8.65 (d, 2H), 7.93-7.90 (d, 2H), 7.84-7.79 (t, 2H) , 7.70-7.58 (m, 9H), 7.55-7.34 (m, 9H), 7.03-6.97 (t, 1H), 6.81-6.80 (d, 1H), 6.67-6.62 d, 1 H), 6.48 - 6.44 (d, 2 H).
13C-NMR (500 MHz, CDCl3) δ = 171.48, 171.33, 156.35, 144.44, 141.48, 141.09, 140.92, 139.30, 136.34, 132.40, 132.16, 131.19, 131.08, 129.26, 128.92, 128.67, 128.58, 128.48, 127.80, 127.32, 126.47, 126.21, 126.02, 125.77, 125.57, 124.99, 120.97, 120.08, 115.21, 114.82, 56.96. 13 C-NMR (500 MHz, CDCl 3 )? = 171.48, 171.33, 156.35, 144.44, 141.48, 141.09, 140.92, 139.30, 136.34, 132.40, 132.16, 131.19, 131.08, 129.26, 128.92, 128.67, 128.58, 128.48, , 127.32, 126.47, 126.21, 126.02, 125.77, 125.57, 124.99, 120.97, 120.08, 115.21, 114.82, 56.96.
MS ES+(m/e): 714.27 (M+, 100%).MS ES + (m / e): 714.27 (M < + >, 100%).
[실시예 5] 유기전계발광소자의 제작[Example 5] Fabrication of organic electroluminescent device
OLED용 글래스로부터 얻어진 투명전극 ITO 박막 cell을 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다. Transparent electrode ITO thin film cells obtained from glass for OLED were ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use.
소자의 구성은 Glass / indiumtin oxide (ITO) / 4 % ReO3: mCP (45 nm) / mCP(15 nm)/ mCP : TSPO1 : 16 wt% 실시예의 아크리딘 유도체(본 발명의 화합물 1)(15 nm)/ TSPO1 (15 nm) / 4 wt% Rb2CO3:TSPO1 (50 nm) / Al 이다. The composition of the device was an acridine derivative (compound 1 of the present invention) of the present invention (glass / indium tin oxide (ITO) / 4% ReO 3 : mCP (45 nm) / mCP (15 nm) / mCP: TSPO1: 15 nm) / TSPO 1 (15 nm) / 4 wt% Rb 2 CO 3 : TSPO 1 (50 nm) / Al.
ITO 박막 4% ReO3: mCP 을 증착하여 45 nm의 정공주입층을 형성 후 1,3-Bis(N-carbazolyl)benzene (mCP)을 증착하여 15 nm의 정공 전달층을 형성하였으며, 발광층의 호스트 물질로 9-(3-(9H-carbazol-9-yl)phenyl)-3-(diphenylphosphoryl)-9H-carbazole (mCP): diphenyl(4-(triphenylsilyl)phenyl)phosphine oxide(TSPO1)을 사용하였고, 실시예 1 내지 4의 화합물(청색 발광 재료, 본 발명의 화합물)을 발광층의 도판트로 사용하였으며, co-host와 도판트의 농도는 16 wt%로 하여 (mCP: TSPO1: 본 발명의 아크리딘 유도체(본 발명의 화합물 1 내지 화합물 4) 각각을 15 nm 진공증착하여 발광층을 형성하였다. 전자전달층으로 TSPO1를 15 nm 증착하고, 전자주입층으로 4 wt% Rb2CO3:TSPO1 를 50 nm 증착하고, 상기 전자주입 및 전자전달층 위에 Al을 증착하여 음극을 형성함으로써 유기전계발광소자를 제조하였다. 제조된 유기전계발광소자의 특성을 측정하여 하기 표 1에 나타내었다.ITO thin film 4% ReO 3 : mCP was deposited to form a 45 nm hole injecting layer, and 1,3-bis (N-carbazolyl) benzene (mCP) was deposited to form a 15 nm hole transporting layer. (Triphenylsilyl) phenyl) phosphine oxide (TSPO1) was used as the starting material, and 9- (9H-carbazol-9-yl) phenyl) -3- (diphenylphosphoryl) The compounds of Examples 1 to 4 (blue light emitting material, compound of the present invention) were used as a dopant of the light emitting layer, and the concentrations of co-host and dopant were 16 wt% (mCP: TSPO1: acridine derivative (compound 1 to compound 4 of the present invention), respectively to form a light emitting layer to 15 nm vacuum-deposited 4 wt% Rb 2 CO 3 to TSPO1 with a 15 nm deposited, and an electron injecting layer an electron transport layer: the TSPO1 50 nm And an Al was deposited on the electron injecting and electron transporting layer to form a cathode. An organic electroluminescent device was fabricated, To the characteristics of the measurement are shown in Table 1 below.
(nm) λ EL a)
(nm)
(nm)FWHM b)
(nm)
(V)V on d)
(V)
(lm/W)PE Max ./500/1000 e)
(lm / W)
(%) EQE Max ./500/1000 f)
(%)
EQEMax . g) (%) Calculated
EQE Max . g) (%)
(DTPSAF )Compound 4
(DTPSAF)
(DTTSAF) Compound 1
(DTTSAF)
(DTXSAF) Compound 2
(DTXSAF)
7.78
(BDTPSAF) Compound 3
(BDTPSAF)
9.51
a) EL peak at 500 cd/m2. b) Full width half maximum at 500 cd/m2. c) CIE 1931 coordinates at 500 cd/m2. d) Turn on voltage at 1 cd/m2. e) Power efficiency. Maximum, at 500 cd/m2, and at 1000 cd/m2. f) External quantum efficiency. Maximum, at 500 cd/m2, and at 1000 cd/m2. g) Calculated EQEMax by optical simulation. a) EL peak at 500 cd / m 2 . b) Full width half maximum at 500 cd / m 2 . c) CIE 1931 coordinates at 500 cd / m 2 . d) Turn on voltage at 1 cd / m 2 . e) Power efficiency. Maximum, at 500 cd / m 2 , and at 1000 cd / m 2 . f) External quantum efficiency. Maximum, at 500 cd / m 2 , and at 1000 cd / m 2 . g) Calculated EQE Max by optical simulation.
표 1에서 보이는 바와 같이 본 발명의 유기전계발광소자는 본 발명의 아크리딘 유도체를 전자 주게로, 트리아진 유도체를 전자 받게로 도입하여 bipolar한 특성을 갖는 화합물로, 비대칭 스피로아크리딘 유도체의 경우 donor unit과 acceptor unit사이에 위치하는 linker group의 torsion angle이 증가함에 따라 비틀린 구조일수록 HOMO, LUMO의 분리가 원활하여 TADF 소자의 효율향상과 높은 색순도를 나타내었다. 또한, 양쪽에 트리아진 유도체를 도입한 대칭형 스피로아크리딘 유도체의 경우, 전자 받게-전자 주게-전자 받게 타입의 형태로 비대칭 스피로아크리딘 유도체에 비해 planar한 구조를 가지며 전하의 이동이 원활하여 비대칭 유도체에 비해 보다 낮은 구동전압을 가지며 외부양자효율이 현저히 향상되었음을 알 수 있다.As shown in Table 1, the organic electroluminescent device of the present invention is a compound having bipolar characteristics by introducing an acridine derivative of the present invention as an electron donor, a triazine derivative as an electron acceptor, and an asymmetric spiroacridine derivative As the torsion angle of the linker group located between the donor unit and the acceptor unit increases, the efficiency of the TADF device is improved and the color purity is improved as the twisted structure is smoothly separated from HOMO and LUMO. In addition, in the case of the symmetric spiroacridine derivatives incorporating both triazine derivatives, they have a planar structure in the form of an electron acceptor-electron donor-electron acceptor type and have a smooth charge transfer It can be seen that the device has a lower driving voltage than the asymmetric derivative and the external quantum efficiency is significantly improved.
Claims (9)
[화학식 1]
상기 화학식 1에서,
A1 내지 A4는 CH이며,
Y는 수소이며,
L은
여기서 R1 내지 R3는 메틸기이며,
Ar은 하기로 구성되는 군으로부터 선택되는 어느 하나이다.
[Chemical Formula 1]
In Formula 1,
A 1 to A 4 are CH,
Y is hydrogen,
L is
Wherein R 1 to R 3 are methyl groups,
Ar is any one selected from the group consisting of
[화학식 2]
상기 화학식 2에서,
L1 및 L2는 서로 동일하고, 하기로 구성되는 군으로부터 선택되는 어느 하나이며,
여기서 R1 내지 R3는 메틸기이며;
Ar1 및 Ar2는 서로 동일하고, 하기로 구성되는 군으로부터 선택되는 어느 하나이다.
(2)
In Formula 2,
L 1 and L 2 are the same as each other and are any one selected from the group consisting of:
Wherein R 1 to R 3 are methyl groups;
Ar 1 and Ar 2 are the same as each other and are any one selected from the group consisting of
[화학식 11]
[화학식 12]
[화학식 13]
상기 화학식 11 내지 화학식 13에서,
A1 내지 A4는 CH이며,
Y1 및 X1는 서로 독립적으로 할로겐이며,
T는
L은 하기로 구성되는 군으로부터 선택되는 어느 하나이며,
여기서 R1 내지 R3는 메틸기이며,
Ar은 하기로 구성되는 군으로부터 선택되는 어느 하나이다.
(11)
[Chemical Formula 12]
[Chemical Formula 13]
In the above Chemical Formulas 11 to 13,
A 1 to A 4 are CH,
Y 1 and X 1 are each independently halogen,
T is
L is any one selected from the group consisting of:
Wherein R 1 to R 3 are methyl groups,
Ar is any one selected from the group consisting of
[화학식 14]
[화학식 15]
[화학식 16]
상기 화학식 14 내지 화학식 16에서,
A1 내지 A4는 CH이며;
X2는 할로겐이며;
T는
L은
여기서 R1 내지 R3는 메틸기이며,
Ar은 하기로 구성되는 군으로부터 선택되는 어느 하나이다.
[Chemical Formula 14]
[Chemical Formula 15]
[Chemical Formula 16]
In the above Chemical Formulas 14 to 16,
A 1 to A 4 are CH;
X 2 is halogen;
T is
L is
Wherein R 1 to R 3 are methyl groups,
Ar is any one selected from the group consisting of
상기 아크리딘 유도체는 유기전계발광소자의 발광층에 포함되는 것인 유기전계발광소자.9. The method of claim 8,
Wherein the acridine derivative is contained in the light emitting layer of the organic electroluminescent device.
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| KR102633124B1 (en) * | 2019-10-07 | 2024-02-01 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102524743B1 (en) * | 2019-10-18 | 2023-04-24 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
| KR102633769B1 (en) * | 2019-10-18 | 2024-02-02 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102639657B1 (en) * | 2019-10-18 | 2024-02-21 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102633801B1 (en) * | 2019-10-23 | 2024-02-02 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR20230109467A (en) | 2022-01-13 | 2023-07-20 | 주식회사 센텀머티리얼즈 | Spiro benzoquinolino acridine compound and organic light emitting device comprising the same |
| KR20230109821A (en) | 2022-01-13 | 2023-07-21 | 주식회사 센텀머티리얼즈 | Spiro benzoquinolino acridine compound and organic light emitting device comprising the same |
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