WO2010150988A2 - Anthracene derivatives and organic electroluminescence device using same - Google Patents

Anthracene derivatives and organic electroluminescence device using same Download PDF

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WO2010150988A2
WO2010150988A2 PCT/KR2010/003528 KR2010003528W WO2010150988A2 WO 2010150988 A2 WO2010150988 A2 WO 2010150988A2 KR 2010003528 W KR2010003528 W KR 2010003528W WO 2010150988 A2 WO2010150988 A2 WO 2010150988A2
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WO2010150988A3 (en
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이은정
김경수
김태형
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주식회사 두산
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    • C07D209/04—Indoles; Hydrogenated indoles
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    • H05B33/00—Electroluminescent light sources
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    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
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Definitions

  • the present invention relates to a novel anthracene derivative and an organic electroluminescent device using the same. More specifically, the present invention provides an N, O or S element as a substituent having an electron transfer ability to the core while having a core in which an anthracene moiety having excellent device characteristics and a moiety such as fluorene having excellent fluorescent properties are fused with each other.
  • the novel compounds include the C 2 ⁇ C 40 heteroaryl group is substituted for;
  • it relates to an organic electroluminescent device including the organic material layer containing the compound improved characteristics such as luminous efficiency, brightness, thermal stability, driving voltage, lifespan.
  • organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when the organic material layer is positioned between the anode and the cathode, a voltage is applied between the two electrodes, and holes are injected into the organic material and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.
  • an organic electroluminescent device As one method for making an organic electroluminescent device efficiently, research has been conducted to manufacture an organic material layer in a multi-layer structure instead of a single layer.
  • Tang presented an organic electroluminescent device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer, and most organic electroluminescent devices currently used are hole injections that receive holes as a substrate, an anode, and an anode. It consists of a layer, a hole transport layer for transferring holes, a light emitting layer for recombining holes and electrons to emit light, an electron transport layer for transferring electrons, an electron injection layer for receiving electrons from a cathode, and a cathode.
  • the reason why the organic electroluminescent device is manufactured in multiple layers is that the movement speed of the holes and the electrons is different. Therefore, if the appropriate hole injection layer, the transfer layer, the electron transfer layer, and the electron injection layer are made, the holes and the electrons can be effectively transferred. This is because light emission efficiency can be improved by balancing holes and electrons in the device.
  • the earliest reports on the material of electron transport include oxadiazole derivatives (PBDs). It has since been reported that triazole derivatives (TAZ) and phenanthroline derivatives (BCP) exhibit electron transport properties.
  • PBDs oxadiazole derivatives
  • TEZ triazole derivatives
  • BCP phenanthroline derivatives
  • the electron transport layer is a good candidate for the organic monomolecular materials such as organometallic complexes having excellent electron stability and electron transfer speed, and Alq3 having high stability and electron affinity is the best candidate. Is being used.
  • the electron transport materials disclosed in Japanese Patent Application Laid-Open No. 11-345686 report that they contain oxazole groups and thiazole groups and can be applied to the light emitting layer, but have reached practical use in terms of driving voltage, luminance, and lifetime of the device. I can't.
  • the present invention is to provide a novel compound that can be applied to the organic electroluminescent device.
  • the present invention is to provide an organic electroluminescent device that includes a novel compound is low in driving voltage, the luminous efficiency, brightness, thermal stability, lifespan, and the like.
  • the present invention provides a compound represented by the following formula (1).
  • R 1 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, C 2 ⁇ C 40 heterocycloalkyl group, C 6 ⁇ C 40 aryl group, C 1 ⁇ alkyloxy group of C 40 of the, C 5 ⁇ C 40 An aryloxy group, a C 5 to C 40 arylamino group, a C 5 to C 40 diarylamino group, a C 5 to C 40 aryl group, or a C 2 to C 40 heteroaryl group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group;
  • R 1 , R 2 , R 3 and R 4 is a C 2 to C 40 heteroaryl group containing at least one element selected from the group consisting of N, O and S;
  • Ar 1 to Ar 4 are the same as or different from each other, and are each independently an arylene group of C 5 to C 40 , or a hetero arylene group of C 2 to C 40 ;
  • a, b, c and d are the same as or different from each other, and are each independently an integer of 0 to 3;
  • the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer including the compound represented by Formula 1 of the present invention.
  • An organic electroluminescent device is provided.
  • the organic material layer containing the compound represented by Formula 1 is preferably an electron transport layer.
  • the compound represented by Chemical Formula 1 according to the present invention has excellent electron transport performance, when it is adopted as an electron transport layer material of an organic light emitting device, the compound exhibits superior performance in terms of voltage and efficiency than conventional Alq3. Therefore, the compound represented by Chemical Formula 1 according to the present invention can greatly contribute to improving performance and lifespan of the organic light emitting device, and in particular, the improvement of electron transport performance has a great effect on maximizing performance in a full color organic light emitting panel.
  • the compound represented by Formula 1 of the present invention is a core in which an anthracene moiety having excellent device characteristics and a moiety such as fluorene having excellent fluorescence properties are fused to each other (for example, indenoanthracene ( and a heteroaryl group of C 2 to C 40 containing an N, O or S element as a substituent having an electron transfer capability, and having an indenoanthracene core), and a kind of anthracene derivative.
  • an anthracene moiety having excellent device characteristics and a moiety such as fluorene having excellent fluorescence properties are fused to each other (for example, indenoanthracene ( and a heteroaryl group of C 2 to C 40 containing an N, O or S element as a substituent having an electron transfer capability, and having an indenoanthracene core), and a kind of anthracene derivative.
  • the compound represented by Chemical Formula 1 of the present invention may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material or an electron injection material in an organic light emitting device, preferably an electron transport material, or an electron injection material and It can be used as a transport material.
  • the amino group, the C 5 -C 40 diarylamino group, the C 5 -C 40 aryl group, or the C 2 -C 40 heteroaryl group are each independently deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 1 ⁇ C 40 alkoxy group, C 1
  • At least one of R 1 , R 2 , R 3 and R 4 is at least one element selected from the group consisting of N (nitrogen), O (oxygen) and S (sulfur) C 2 ⁇ C 40 It is a heteroaryl group containing.
  • the heteroaryl group of C 2 ⁇ C 40 is not particularly limited, but may be selected from the group consisting of the structural formulas of Formula 2 below.
  • an aryl group of C 5 ⁇ C 40 in R 1 to R 7 is not particularly limited, but may be selected from the group consisting of the following structural formula (3).
  • Q 1 to Q 4 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen, a nitrile group, a nitro group, C 1 ⁇ alkenyl group of the C 40 alkyl group, C 2 ⁇ C 40 of, C 2 ⁇ C 40 of the alkynyl group, C 1 ⁇ C 40 alkoxy group, C 1 ⁇ C 40 of the amino group, C of 3 ⁇ C 40 cycloalkyl group, C of 3 ⁇ C 40 heterocycloalkyl group, C 6 ⁇ C 40 aryl An alkyl group, a C 5 -C 40 aryl group, or a C 5 -C 40 heteroaryl group.
  • a cycloalkyl group, a C 3 to C 40 heterocycloalkyl group, a C 6 to C 40 aryl group and a C 5 to C 40 heteroaryl group are each independently deuterium, halogen, nitrile group, nitro group, C 1 to C 40 Alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 1 ⁇ C 40 alkoxy group, C 1 ⁇ C 40 amino group, C 3 ⁇ C 40 cycloalkyl group, C 3 ⁇ It may be substituted with a C 40 heterocycloalkyl group, a C 6 ⁇ C 40 arylalkyl group, a C 5 ⁇ C 40 aryl group, or
  • Ar 1 to Ar 4 are each independently a C 5 ⁇ C 40 arylene group or C 2 ⁇ C 40 heteroarylene group, preferably C 5 ⁇ C 40 Arylene group.
  • the arylene group of C 5 ⁇ C 40 may be an arylene group selected from the group consisting of the formula of Formula 3,
  • C 2 ⁇ C 40 heteroarylene group is a heteroaryl selected from the group consisting of the formula It may be a Rengi.
  • the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer including the compound represented by Formula 1 of the present invention.
  • An organic light emitting device is provided.
  • the compound represented by Formula 1 may include one kind or two or more kinds.
  • the organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • the compound represented by Chemical Formula 1 may be included in the organic electroluminescent device as an electron transport material or an electron injection and transport material, in which case the organic electroluminescent device has a low driving voltage, luminous efficiency, luminance, Thermal stability and lifespan can be improved. Therefore, preferably, the organic material layer including the compound represented by Chemical Formula 1 is an electron transport layer.
  • the organic electroluminescent device according to the present invention may include any one or more or all of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer in addition to the organic material layer containing a compound represented by the formula (1) of the present invention. Can be.
  • a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked, and the electron transport layer may be a chemical structure of the organic electroluminescent device according to the present invention. It includes the compound represented by 1.
  • An electron injection layer may be positioned on the electron transport layer.
  • the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between the electrode and the organic material layer.
  • the organic material layer including the compound represented by Chemical Formula 1 may be formed by a vacuum deposition method or a solution coating method.
  • the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
  • the organic electroluminescent device of the present invention is formed using a hole injection layer, a hole using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Formula 1 of the present invention. It can be produced by forming an organic layer and an electrode, such as a transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • Example 1-2 to Example 1-26 Synthesis of Compound of Formula 4-002 to Formula 4-026]
  • the compounds of Formula 4-002 to Formula 4-026 may be synthesized using the same method as in Example 1-1 (Synthesis of Compound of 4-001), respectively, and were obtained as a pale yellow solid. .
  • Example 2-2 to Example 2-14 Synthesis of Compounds of Chemical Formula 5-002 to Chemical Formula 5-014
  • Example 3-2 to Example 3-48 Synthesis of Compounds of Chemical Formula 6-002 to Chemical Formula 6-048
  • the compounds of Formulas 6-002 to 6-648 may be synthesized using the same method as in Example 3-1 (Synthesis of Compounds of Formula 6-001), respectively, and were obtained as a pale yellow solid. .
  • the compounds of Formulas 7-002 to 7-011 were each synthesized using the same method as in Example 4-1 (Synthesis of Compounds of Formula 7-001), and were obtained as a pale yellow solid. .
  • Example 5-1 to Example 5-31 Fabrication of organic light emitting device
  • Product name DS-205 (Doosan Corporation) was vacuum deposited on an ITO transparent electrode to a thickness of 800 kPa to form a hole injection layer, and on top of it, NPB ( N , N- di (naphthalene-1-yl) -N , N- diphenylbenzidine) was deposited to a thickness of 150 ⁇ to form a hole transport layer.
  • ADN (9,10-di (naphthalen-2-yl) anthracene) was used as a host thereon, and a light emitting layer was formed by doping DS-405 (Doosan Co., Ltd.) 5% with a dopant to a thickness of 300 Pa.
  • Each of the electron transporting materials synthesized in Examples 1 to 4 was deposited on the light emitting layer to a thickness of 250 kPa to form an electron transporting layer.
  • 10F thick LiF was deposited on the electron transport layer to form an electron injection layer, and 2,000V thick Al was deposited thereon to form a cathode to manufacture a device.
  • the device When forming the electron transport layer, the device was manufactured in the same manner as in Example 5 except that Alq3 (aluminum tris (8-hydroxyquinoline)) was used instead of the material synthesized in Examples 1 to 4 as the electron transporting material.
  • Alq3 aluminum tris (8-hydroxyquinoline)
  • the organic light emitting device (Examples 5-1 to 5-31) using the compound according to the present invention as an electron transporting material is more voltage and efficiency than the organic light emitting device (Comparative Example 1) using Alq3. We can see that it shows superior performance in.

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Abstract

The present invention relates to anthracene derivatives and an organic electroluminescence device using the same. More specifically, the present invention relates to: a novel compound which has a core (for example, an indenoanthracene core), in which both an anthracene moiety having superior device characteristics and a fluorine moiety having superior fluorescence characteristics are fused, and which is substituted by a C2-C40 heteroaryl group containing an element N, O or S as a substituent with electron transfer capacity; and an organic electroluminenscence device utilizing the novel compound.

Description

안트라센 유도체 및 이를 이용한 유기 전계 발광 소자 Anthracene Derivatives and Organic Electroluminescent Devices Using the Same
본 발명은 신규 안트라센 유도체 및 이를 이용한 유기 전계 발광 소자에 관한 것이다. 보다 구체적으로 본 발명은, 소자 특성이 우수한 안트라센 모이어티와 형광 특성이 우수한 플루오렌 등의 모이어티가 서로 융합된 코어를 가지면서 상기 코어에 전자 전달 능력을 갖는 치환기로서 N, O 또는 S 원소를 포함하는 C2~C40의 헤테로아릴기가 치환된 신규 화합물; 및 상기 화합물을 함유하는 유기물층을 포함하여 발광효율, 휘도, 열적 안정성, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel anthracene derivative and an organic electroluminescent device using the same. More specifically, the present invention provides an N, O or S element as a substituent having an electron transfer ability to the core while having a core in which an anthracene moiety having excellent device characteristics and a moiety such as fluorene having excellent fluorescent properties are fused with each other. the novel compounds include the C 2 ~ C 40 heteroaryl group is substituted for; And it relates to an organic electroluminescent device including the organic material layer containing the compound improved characteristics such as luminous efficiency, brightness, thermal stability, driving voltage, lifespan.
일반적으로 유기 발광 현상이란 유기 물질에 전기에너지를 가했을 때 빛이 나타나는 현상을 말한다. 즉, 양극(anode)과 음극(cathode) 사이에 유기물층을 위치시켰을 때 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되고, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다.In general, organic light emitting phenomenon refers to a phenomenon in which light appears when electric energy is applied to an organic material. That is, when the organic material layer is positioned between the anode and the cathode, a voltage is applied between the two electrodes, and holes are injected into the organic material and electrons are injected into the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall back to the ground, they shine.
유기 전계 발광 소자를 효율적으로 만들기 위한 한 방법으로서 소자 내의 유기물층을 단층 대신 다층 구조로 제조하는 연구가 진행되어 왔다. 1987년 탕(Tang)에 의하여 정공층과 발광층의 기능층으로 나눈 적층구조의 유기 전계 발광 소자가 제시 되었으며, 현재 사용되는 대부분의 유기 전계 발광 소자는 기판, 양극, 양극으로 정공을 받아들이는 정공 주입층, 정공을 전달하는 정공 전달층, 정공과 전자가 재결합하여 빛을 내는 발광층, 전자를 전달하는 전자 전달층, 음극으로부터 전자를 받아들이는 전자 주입층 및 음극으로 이루어져 있다. 이렇게 유기 전계 발광 소자를 다층으로 제작하는 이유는 정공과 전자의 이동속도가 상이하며, 따라서 적절한 정공 주입층 및 전달층, 전자 전달층 및 전자 주입층을 만들어 주면 정공과 전자가 효과적으로 전달될 수 있으며, 소자 내 정공과 전자의 균형이 이루어져 발광 효율을 높일 수 있기 때문이다. As one method for making an organic electroluminescent device efficiently, research has been conducted to manufacture an organic material layer in a multi-layer structure instead of a single layer. In 1987, Tang presented an organic electroluminescent device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer, and most organic electroluminescent devices currently used are hole injections that receive holes as a substrate, an anode, and an anode. It consists of a layer, a hole transport layer for transferring holes, a light emitting layer for recombining holes and electrons to emit light, an electron transport layer for transferring electrons, an electron injection layer for receiving electrons from a cathode, and a cathode. The reason why the organic electroluminescent device is manufactured in multiple layers is that the movement speed of the holes and the electrons is different. Therefore, if the appropriate hole injection layer, the transfer layer, the electron transfer layer, and the electron injection layer are made, the holes and the electrons can be effectively transferred. This is because light emission efficiency can be improved by balancing holes and electrons in the device.
전자 수송의 재료에 관한 최초의 보고는 옥사디아졸 유도체(PBD)를 들 수 있다. 이후 트리아졸 유도체(TAZ) 및 페난스로린 유도체(BCP)가 전자 수송성을 나타낸다고 보고 되었다. 전자 수송층은 유기 단분자 물질로는 전자에 대한 안정도와 전자 이동 속도가 상대적으로 우수한 유기 금속착제들이 좋은 후보들이며, 안정성이 우수하고 전자 친화도가 큰 Alq3가 가장 우수한 것으로 보고 되었으며, 현재에도 가장 기본적으로 사용되고 있다. The earliest reports on the material of electron transport include oxadiazole derivatives (PBDs). It has since been reported that triazole derivatives (TAZ) and phenanthroline derivatives (BCP) exhibit electron transport properties. The electron transport layer is a good candidate for the organic monomolecular materials such as organometallic complexes having excellent electron stability and electron transfer speed, and Alq3 having high stability and electron affinity is the best candidate. Is being used.
또한, 종래의 전자 주입 및 수송층용 물질로는 이미다졸기, 옥사졸기, 티아졸기를 가진 유기 단분자 물질들이 많이 보고되었다. 1996년도에 코닥사에서 발표하고 미국 특허 제5,645,948호에 기재된 TPBI는 이미다졸기를 가진 대표적인 전자 수송층용 물질로 알려져 있으며, 그 구조는 벤젠의 1,3,5 치환 위치에 세 개의 N-페닐 벤즈이미다졸기를 함유하고 기능적으로는 전자를 전달하는 능력뿐 아니라 발광층에서 넘어오는 정공을 차단하는 기능도 있으나, 실제 소자에 적용하기에는 열적 안정성이 낮은 문제점을 가지고 있다. In addition, many organic monomolecular materials having imidazole group, oxazole group, and thiazole group have been reported as materials for the electron injection and transport layer. TPBI, published by Kodak in 1996 and described in US Pat. No. 5,645,948, is known as a representative material for electron transport layers with imidazole groups, and its structure has three N-phenyl benzs at the 1,3,5 substitution positions of benzene. It contains an imidazole group and functionally blocks electrons from the light emitting layer as well as the ability to transfer electrons, but has a problem of low thermal stability for practical application.
또한, 일본 공개특허공보 평11-345686호에 개시된 전자수송용 물질들은 옥사졸기, 티아졸기를 함유하고 있고 발광층에도 적용할 수 있다고 보고하고 있으나, 구동전압, 휘도 및 소자의 수명 측면에서 실용화에 도달하지 못하고 있다.In addition, the electron transport materials disclosed in Japanese Patent Application Laid-Open No. 11-345686 report that they contain oxazole groups and thiazole groups and can be applied to the light emitting layer, but have reached practical use in terms of driving voltage, luminance, and lifetime of the device. I can't.
따라서, 상기와 같은 종래 기술의 문제점을 극복하고 유기 전계 발광 소자의 특성을 더욱 향상시키기 위하여, 유기 전계 발광 소자에서 전자 수송용 물질로 사용될 수 있는 보다 안정적이고 효율적인 재료에 대한 개발이 계속 요구된다.Therefore, in order to overcome the problems of the prior art as described above and to further improve the characteristics of the organic EL device, development of a more stable and efficient material that can be used as an electron transporting material in the OLED is required.
상기 문제점을 해결하고자, 본 발명은 유기 전계 발광 소자에 적용할 수 있는 신규 화합물을 제공하고자 한다. 또한 본 발명은 상기 신규 화합물을 포함하여 구동전압이 낮고, 발광효율, 휘도, 열적 안정성, 수명 등이 향상되는 유기 전계 발광 소자를 제공하고자 한다.In order to solve the above problems, the present invention is to provide a novel compound that can be applied to the organic electroluminescent device. In another aspect, the present invention is to provide an organic electroluminescent device that includes a novel compound is low in driving voltage, the luminous efficiency, brightness, thermal stability, lifespan, and the like.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다. The present invention provides a compound represented by the following formula (1).
화학식 1
Figure PCTKR2010003528-appb-C000001
 Formula 1
Figure PCTKR2010003528-appb-C000001
화학식 1에서, X는 CR6R7, NR6, O, S, S(=O), S(=O)2, 또는 SiR6R7이며;In formula 1, X is CR 6 R 7 , NR 6 , O, S, S (= 0), S (= 0) 2 , or SiR 6 R 7 ;
R1 내지 R7은 서로 같거나 다르고, 각각 독립적으로 수소, 중수소, 할로겐, 니트릴기, 니트로기, 아미노기, 실릴기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C2~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C1~C40의 알킬옥시기, C5~C40의 아릴옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C5~C40의 아릴기, 또는 C2~C40의 헤테로아릴기이거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며;R 1 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, C 2 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, C 1 ~ alkyloxy group of C 40 of the, C 5 ~ C 40 An aryloxy group, a C 5 to C 40 arylamino group, a C 5 to C 40 diarylamino group, a C 5 to C 40 aryl group, or a C 2 to C 40 heteroaryl group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group;
이때 R1, R2, R3 및 R4 중에서 하나 이상은 N, O 및 S로 이루어진 군에서 선택되는 1 이상의 원소를 포함하는 C2~C40의 헤테로아릴기이며;Wherein at least one of R 1 , R 2 , R 3 and R 4 is a C 2 to C 40 heteroaryl group containing at least one element selected from the group consisting of N, O and S;
Ar1 내지 Ar4는 서로 같거나 다르고, 각각 독립적으로 C5~C40의 아릴렌기, 또는 C2~C40의 헤테로아릴렌기이며; Ar 1 to Ar 4 are the same as or different from each other, and are each independently an arylene group of C 5 to C 40 , or a hetero arylene group of C 2 to C 40 ;
a, b, c 및 d는 서로 같거나 다르고, 각각 독립적으로 0~3의 정수이다.a, b, c and d are the same as or different from each other, and are each independently an integer of 0 to 3;
또한, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 본 발명의 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층인 것이 특징인 유기 전계 발광 소자를 제공한다. 본 발명에서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 전자 수송층인 것이 바람직하다.In addition, the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer including the compound represented by Formula 1 of the present invention. An organic electroluminescent device is provided. In the present invention, the organic material layer containing the compound represented by Formula 1 is preferably an electron transport layer.
본 발명에 따른 화학식 1로 표시되는 화합물은 전자 수송 성능이 우수하므로, 이를 유기 발광 소자의 전자 수송층 재료로 채택할 경우 종래 Alq3을 사용하는 경우보다 전압 및 효율 면에서 월등한 성능을 나타낸다. 따라서 본 발명에 따른 화학식 1로 표시되는 화합물은 유기 발광 소자의 성능 개선 및 수명 향상에 크게 기여할 수 있으며, 특히 이러한 전자 수송 성능 향상은 풀 칼라 유기 발광 패널에서의 성능 극대화에도 큰 효과가 있다.Since the compound represented by Chemical Formula 1 according to the present invention has excellent electron transport performance, when it is adopted as an electron transport layer material of an organic light emitting device, the compound exhibits superior performance in terms of voltage and efficiency than conventional Alq3. Therefore, the compound represented by Chemical Formula 1 according to the present invention can greatly contribute to improving performance and lifespan of the organic light emitting device, and in particular, the improvement of electron transport performance has a great effect on maximizing performance in a full color organic light emitting panel.
본 발명의 화학식 1로 표시되는 화합물은 소자 특성이 우수한 안트라센 모이어티(moiety)와 형광 특성이 우수한 플루오렌 등의 모이어티(moiety)가 서로 융합(fused)된 코어 (예를 들면 인데노안트라센(indenoanthracene) 코어)를 가지면서, 전자 전달 능력을 갖는 치환기로서 N, O 또는 S 원소를 포함하는 C2~C40의 헤테로아릴기가 상기 코어에 치환된 화합물이며, 일종의 안트라센 유도체이다. The compound represented by Formula 1 of the present invention is a core in which an anthracene moiety having excellent device characteristics and a moiety such as fluorene having excellent fluorescence properties are fused to each other (for example, indenoanthracene ( and a heteroaryl group of C 2 to C 40 containing an N, O or S element as a substituent having an electron transfer capability, and having an indenoanthracene core), and a kind of anthracene derivative.
따라서, 본 발명의 화학식 1로 표시되는 화합물은 유기 발광 소자에서 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질 또는 전자주입 물질로서 사용될 수 있으며, 바람직하게는 전자수송 물질, 또는 전자주입 및 수송 물질로서 사용할 수 있다.Therefore, the compound represented by Chemical Formula 1 of the present invention may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material or an electron injection material in an organic light emitting device, preferably an electron transport material, or an electron injection material and It can be used as a transport material.
본 발명의 화학식 1로 표시되는 화합물에 있어서, 상기 R1 내지 R7의 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C2~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C1~C40의 알킬옥시기, C5~C40의 아릴옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C5~C40의 아릴기, 또는 C2~C40의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, 아미노기, 실릴기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C5~C40의 아릴기, 또는 C5~C40의 헤테로아릴기로 치환되거나 비치환된 것일 수 있다.In the compound represented by the general formula (I) of the present invention, wherein R 1 to R 7 of C 1 ~ alkyl group of C 40, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 of Cycloalkyl group, C 2 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 arylalkyl group, C 1 ~ C 40 alkyloxy group, C 5 ~ C 40 aryloxy group, C 5 ~ C 40 aryl The amino group, the C 5 -C 40 diarylamino group, the C 5 -C 40 aryl group, or the C 2 -C 40 heteroaryl group are each independently deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 1 ~ C 40 alkoxy group, C 1 ~ C 40 of the amino group, C 3 ~ C 40 cycloalkyl group of It may be unsubstituted or substituted with a C 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 arylalkyl group, C 5 ~ C 40 aryl group, or C 5 ~ C 40 heteroaryl group.
본 발명의 화학식 1로 표시되는 화합물에 있어서, R1, R2, R3 및 R4 중에서 하나 이상은 N(질소), O(산소) 및 S(황)로 이루어진 군에서 선택되는 1 이상의 원소를 포함하는 C2~C40의 헤테로아릴기이다. 상기 C2~C40의 헤테로아릴기는 특별히 한정되지 않으나, 하기 화학식 2의 구조식으로 이루어진 군에서 선택될 수 있다.In the compound represented by the formula (1) of the present invention, at least one of R 1 , R 2 , R 3 and R 4 is at least one element selected from the group consisting of N (nitrogen), O (oxygen) and S (sulfur) C 2 ~ C 40 It is a heteroaryl group containing. The heteroaryl group of C 2 ~ C 40 is not particularly limited, but may be selected from the group consisting of the structural formulas of Formula 2 below.
화학식 2
Figure PCTKR2010003528-appb-C000002
 Formula 2
Figure PCTKR2010003528-appb-C000002
Figure PCTKR2010003528-appb-I000001
Figure PCTKR2010003528-appb-I000001
Figure PCTKR2010003528-appb-I000002
Figure PCTKR2010003528-appb-I000002
Figure PCTKR2010003528-appb-I000003
Figure PCTKR2010003528-appb-I000003
Figure PCTKR2010003528-appb-I000004
Figure PCTKR2010003528-appb-I000004
Figure PCTKR2010003528-appb-I000005
Figure PCTKR2010003528-appb-I000005
Figure PCTKR2010003528-appb-I000006
Figure PCTKR2010003528-appb-I000006
또한, R1 내지 R7에서 C5~C40의 아릴기는 특별히 한정되지 않으나, 하기 화학식 3의 구조식으로 이루어진 군에서 선택될 수 있다.In addition, an aryl group of C 5 ~ C 40 in R 1 to R 7 is not particularly limited, but may be selected from the group consisting of the following structural formula (3).
화학식 3
Figure PCTKR2010003528-appb-C000003
 Formula 3
Figure PCTKR2010003528-appb-C000003
상기 화학식 3에서 Q1 내지 Q4는 서로 같거나 상이하고, 각각 독립적으로 수소, 중수소, 할로겐, 니트릴기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C5~C40의 아릴기, 또는 C5~C40의 헤테로아릴기이다.In Formula 3 Q 1 to Q 4 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen, a nitrile group, a nitro group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 of the alkynyl group, C 1 ~ C 40 alkoxy group, C 1 ~ C 40 of the amino group, C of 3 ~ C 40 cycloalkyl group, C of 3 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 aryl An alkyl group, a C 5 -C 40 aryl group, or a C 5 -C 40 heteroaryl group.
또한, 상기 Q1 내지 Q4에 있어서의 C1~C40의 알킬기, C2~C40의 알케닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴기 및 C5~C40의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C5~C40의 아릴기, 또는 C5~C40의 헤테로아릴기로 치환될 수 있다.Further, the Q 1 to Q 4 alkoxy group of C 1 ~ a C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 1 ~ C 40 of the in, C 1 ~ C 40 of the amino group, C 3 ~ C 40 A cycloalkyl group, a C 3 to C 40 heterocycloalkyl group, a C 6 to C 40 aryl group and a C 5 to C 40 heteroaryl group are each independently deuterium, halogen, nitrile group, nitro group, C 1 to C 40 Alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 1 ~ C 40 alkoxy group, C 1 ~ C 40 amino group, C 3 ~ C 40 cycloalkyl group, C 3 ~ It may be substituted with a C 40 heterocycloalkyl group, a C 6 ~ C 40 arylalkyl group, a C 5 ~ C 40 aryl group, or a C 5 ~ C 40 heteroaryl group.
본 발명의 화학식 1로 표시되는 화합물에 있어서, Ar1 내지 Ar4는 각각 독립적으로 C5~C40의 아릴렌기 또는 C2~C40의 헤테로아릴렌기이며, 바람직하게는 C5~C40의 아릴렌기이다. 상기 C5~C40의 아릴렌기는 상기 화학식 3의 구조식으로 이루어진 군에서 선택되는 아릴렌기일 수 있고, C2~C40의 헤테로아릴렌기는 상기 화학식 2의 구조식으로 이루어진 군에서 선택되는 헤테로아릴렌기일 수 있다.In the compound represented by the formula (1) of the present invention, Ar 1 to Ar 4 are each independently a C 5 ~ C 40 arylene group or C 2 ~ C 40 heteroarylene group, preferably C 5 ~ C 40 Arylene group. The arylene group of C 5 ~ C 40 may be an arylene group selected from the group consisting of the formula of Formula 3, C 2 ~ C 40 heteroarylene group is a heteroaryl selected from the group consisting of the formula It may be a Rengi.
아래 화합물들은 본 발명의 화학식 1로 표시되는 화합물의 대표적인 예들이나, 본 발명의 화학식 1로 표시되는 화합물이 하기 예시된 것들에 한정되는 것은 아니다.The following compounds are representative examples of the compound represented by Formula 1 of the present invention, but the compound represented by Formula 1 of the present invention is not limited to those illustrated below.
Figure PCTKR2010003528-appb-I000007
Figure PCTKR2010003528-appb-I000007
Figure PCTKR2010003528-appb-I000008
Figure PCTKR2010003528-appb-I000008
Figure PCTKR2010003528-appb-I000009
Figure PCTKR2010003528-appb-I000009
Figure PCTKR2010003528-appb-I000010
Figure PCTKR2010003528-appb-I000010
Figure PCTKR2010003528-appb-I000011
Figure PCTKR2010003528-appb-I000011
Figure PCTKR2010003528-appb-I000012
Figure PCTKR2010003528-appb-I000012
Figure PCTKR2010003528-appb-I000013
Figure PCTKR2010003528-appb-I000013
Figure PCTKR2010003528-appb-I000014
Figure PCTKR2010003528-appb-I000014
Figure PCTKR2010003528-appb-I000015
Figure PCTKR2010003528-appb-I000015
Figure PCTKR2010003528-appb-I000016
Figure PCTKR2010003528-appb-I000016
Figure PCTKR2010003528-appb-I000017
Figure PCTKR2010003528-appb-I000017
Figure PCTKR2010003528-appb-I000018
Figure PCTKR2010003528-appb-I000018
Figure PCTKR2010003528-appb-I000019
Figure PCTKR2010003528-appb-I000019
Figure PCTKR2010003528-appb-I000020
Figure PCTKR2010003528-appb-I000020
Figure PCTKR2010003528-appb-I000021
Figure PCTKR2010003528-appb-I000021
Figure PCTKR2010003528-appb-I000022
Figure PCTKR2010003528-appb-I000022
Figure PCTKR2010003528-appb-I000023
Figure PCTKR2010003528-appb-I000023
Figure PCTKR2010003528-appb-I000024
Figure PCTKR2010003528-appb-I000024
한편, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 본 발명의 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층인 것이 특징인 유기 발광 소자를 제공한다. 이때, 상기 화학식 1로 표시되는 화합물은 1종 또는 2종 이상이 포함될 수 있다.On the other hand, the present invention is an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer including the compound represented by Formula 1 of the present invention. An organic light emitting device is provided. In this case, the compound represented by Formula 1 may include one kind or two or more kinds.
본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있다. 바람직하게는, 상기 화학식 1로 표시되는 화합물은 전자수송 물질, 또는 전자주입 및 수송 물질로서 유기 전계 발광 소자에 포함될 수 있고, 이 경우 유기 전계 발광 소자는 구동전압이 낮아지고, 발광효율, 휘도, 열적 안정성 및 수명이 향상될 수 있다. 따라서, 바람직하게는, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 전자 수송층이다.The organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. Preferably, the compound represented by Chemical Formula 1 may be included in the organic electroluminescent device as an electron transport material or an electron injection and transport material, in which case the organic electroluminescent device has a low driving voltage, luminous efficiency, luminance, Thermal stability and lifespan can be improved. Therefore, preferably, the organic material layer including the compound represented by Chemical Formula 1 is an electron transport layer.
또한, 본 발명에 따른 유기 전계 발광 소자는, 본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기물층 이외에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나 이상 또는 모두를 포함할 수 있다.In addition, the organic electroluminescent device according to the present invention may include any one or more or all of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer in addition to the organic material layer containing a compound represented by the formula (1) of the present invention. Can be.
본 발명에 따른 유기 전계 발광 소자 구조의 비제한적인 예를 들면, 기판, 양극, 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 음극이 순차적으로 적층된 것일 수 있으며, 이때 상기 전자 수송층은 상기 화학식 1로 표시되는 화합물을 포함하는 것이다. 상기 전자 수송층 위에는 전자 주입층이 위치할 수도 있다.For example, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode may be sequentially stacked, and the electron transport layer may be a chemical structure of the organic electroluminescent device according to the present invention. It includes the compound represented by 1. An electron injection layer may be positioned on the electron transport layer.
또한, 본 발명에 따른 유기 전계 발광 소자는 전술한 바와 같이 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입될 수 있다.In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between the electrode and the organic material layer.
본 발명의 유기 전계 발광 소자에 있어서, 상기 화학식 1로 표시되는 화합물을 포함하는 상기 유기물층은 진공증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에만 한정되지 않는다. In the organic electroluminescent device of the present invention, the organic material layer including the compound represented by Chemical Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
본 발명의 유기 전계 발광 소자는, 유기물층 중 1층 이상을 본 발명의 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는, 당 기술 분야에 알려진 재료 및 방법을 이용하여 정공 주입층, 정공 수송층, 발광층, 전자 수송층, 전자 주입층 등의 유기물층 및 전극을 형성함으로써 제조될 수 있다.The organic electroluminescent device of the present invention is formed using a hole injection layer, a hole using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Formula 1 of the present invention. It can be produced by forming an organic layer and an electrode, such as a transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[실시예 1: 화학식 4-001 내지 화학식 4-026의 화합물 합성]Example 1 Compound Synthesis of Formulas 4-001 to 4-026
하기 화학식 4-001 내지 화학식 4-026으로 표시되는 화합물을 합성하기 위해 다음과 같은 방법을 사용하였다.To synthesize the compound represented by the following formula 4-001 to formula 4-026 was used the following method.
[반응식 1]Scheme 1
Figure PCTKR2010003528-appb-I000025
Figure PCTKR2010003528-appb-I000025
[합성예 1-1: 화합물 1-2의 합성]Synthesis Example 1-1: Synthesis of Compound 1-2
화합물 1-1인 2-bromofluorene 30g을 디메틸 설폭사이드 500mL에 녹이고, 디메틸 설폭사이드 20ml에 녹인 수산화칼륨 94g을 첨가하였다. 0℃ 하에서 요오드화메탄 76g을 서서히 적가한 다음 상온으로 올려 12시간 교반하였다. 반응 종료 후 반응 용액을 1L 증류수에 쏟고 30분 정도 교반한 후 생성된 고체를 여과하였다. 얻은 고체를 컬럼 크로마토그래피를 통하여 불순물을 제거하고 화합물 1-2 34g (수율 91%)을 수득하였다.30 g of 2-bromofluorene as compound 1-1 was dissolved in 500 mL of dimethyl sulfoxide, and 94 g of potassium hydroxide dissolved in 20 mL of dimethyl sulfoxide was added. 76 g of methane iodide was slowly added dropwise at 0 ° C., and then stirred at room temperature for 12 hours. After the reaction was completed, the reaction solution was poured into 1 L distilled water, stirred for about 30 minutes, and the resulting solid was filtered. The obtained solid was removed by column chromatography to obtain 34 g of a compound 1-2 (yield 91%).
[합성예 1-2: 화합물 1-4의 합성]Synthesis Example 1-2: Synthesis of Compound 1-4
화합물 1-2 30g과 화합물 1-3인 phthalic anhydride 18g (1.1 당량)을 디클로로메탄에 녹여 상온에서 교반하다가 염화알루미늄 22g (1.5 당량)을 0℃ 하에서 천천히 넣어주었다. 안정화되면 반응물을 40℃에서 6시간 환류 교반 시킨 후, 농축하여 컬럼 크로마토그래피로 불순물을 제거하고, 디클로로메탄에 녹여 n-헥산에서 침전시켜 여과하였다. 여과로 얻은 고체를 감압 건조하여 화합물 1-4 21.9g (수율 47.3%)을 수득하였다.30 g of compound 1-2 and 18 g (1.1 equiv) of phthalic anhydride (compound 1-3) were dissolved in dichloromethane, stirred at room temperature, and 22 g (1.5 equiv) of aluminum chloride was slowly added thereto at 0 ° C. After stabilization, the reaction was stirred under reflux at 40 ° C. for 6 hours, concentrated to remove impurities by column chromatography, dissolved in dichloromethane, precipitated in n-hexane, and filtered. The solid obtained by filtration was dried under reduced pressure to give 21.9 g of a compound 1-4 (yield 47.3%).
[합성예 1-3: 화합물 1-5의 합성]Synthesis Example 1-3: Synthesis of Compound 1-5
화합물 1-4 21g에 폴리인산 125mL를 넣어주고 130℃로 3시간 가열 교반 후, 상온에서 얼음물 500mL 넣어 고체를 여과하고 메탄올로 씻었다. 여과로 얻은 고체를 감압 건조하여 화합물 1-5 16.6g (수율 82.6%)을 합성하였다.125 mL of polyphosphoric acid was added to 21 g of Compound 1-4, and the mixture was heated and stirred at 130 ° C. for 3 hours, 500 mL of ice water was added at room temperature, and the solid was filtered and washed with methanol. The solid obtained by filtration was dried under reduced pressure to synthesize 16.6 g (yield 82.6%) of compound 1-5.
[합성예 1-4: 화합물 1-7의 합성]Synthesis Example 1-4: Synthesis of Compound 1-7
화합물 1-6 25.6g(3 당량)을 질소 하에서 테트라하이드로퓨란 300mL에 녹였다. 이 반응물에 n-부틸리튬 85mL를 -78℃ 하에 서서히 적가하였다. -78℃ 하에서 1시간 교반한 후 화합물 1-5 16.6g을 넣었다. 천천히 상온으로 올려 교반한 후 포화 염화암모늄 용액을 넣어 디클로로메탄으로 추출하였다. 추출물을 농축하고, n-헥산에서 침전시킨 후 여과하여 고체 21.7g (수율 80%)을 얻었다.25.6 g (3 equivalents) of compound 1-6 was dissolved in 300 mL of tetrahydrofuran under nitrogen. 85 mL of n-butyllithium was slowly added dropwise to the reaction at -78 ° C. After stirring for 1 hour at -78 ° C, 16.6 g of Compound 1-5 was added. After slowly raising to room temperature, the mixture was added with saturated ammonium chloride solution and extracted with dichloromethane. The extract was concentrated, precipitated in n-hexane and filtered to give 21.7 g of solid (80% yield).
[합성예 1-5: 화합물 1-8의 합성]Synthesis Example 1-5: Synthesis of Compound 1-8
화합물 1-7 21.7g과 요오드화칼륨 54.7g (10 당량), 차아인산나트륨 수화물 70g (20 당량)을 아세트산 300mL에 분산시킨 후 2시간 동안 환류 교반하였다. 상온으로 냉각 후, 물 500mL에 붓고 여과하여 물과 메탄올로 씻은 다음 감압 건조 하여 화합물 1-8 19.6g (수율 95%)을 수득하였다.21.7 g of Compound 1-7, 54.7 g (10 equivalents) of potassium iodide, and 70 g (20 equivalents) of sodium hypophosphite hydrate were dispersed in 300 mL of acetic acid, followed by stirring under reflux for 2 hours. After cooling to room temperature, poured into 500mL of water, filtered, washed with water and methanol and dried under reduced pressure to give 19.6g (yield 95%) of compound 1-8.
[실시예 1-1: 화학식 4-001의 화합물의 합성]Example 1-1: Synthesis of Compound of Chemical Formula 4-001
화합물 1-8 19.6g과 화합물 1-9에 해당하는 4-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenylboronic acid, 12.8g (1.2 당량)을 톨루엔 300mL에 녹이고 테트라키스트라이페닐포스핀팔라듐 1g과 2N 탄산칼륨 100mL를 넣고 13시간 환류 교반 하였다. 상온으로 냉각시키고 유기층과 물층을 분리한 후, 물과 포화 염화나트륨 용액으로 씻어주고 무수 황산나트륨으로 건조하여 농축하였다. 컬럼 크로마토그래피 (n-헥산 ~ n-헥산/디클로로메탄=9/1 ~ n-헥산/초산에틸=8/2)로 불순물을 제거한 후, n-헥산에서 침전을 시키고 여과하여 연한 노란색 고체의 화학식 4-001의 화합물 10.8g(41%)을 얻었다.19.6 g of compound 1-8 and 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid corresponding to compound 1-9, 12.8 g (1.2 equivalents), were added to 300 mL of toluene. After dissolving, 1 g of tetrakistriphenylphosphinepalladium and 100 mL of 2 N potassium carbonate were added thereto, and the mixture was stirred under reflux for 13 hours. After cooling to room temperature, the organic layer and the water layer were separated, washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. After removing impurities by column chromatography (n-hexane to n-hexane / dichloromethane = 9/1 to n-hexane / ethyl acetate = 8/2), the precipitate was precipitated in n-hexane and filtered to give a pale yellow solid. 10.8 g (41%) of 4-001 compound were obtained.
[화학식 4-001][Formula 4-001]
Figure PCTKR2010003528-appb-I000026
Figure PCTKR2010003528-appb-I000026
1H NMR (500MHz, THF-d8) : 7.48 7.50 7.48 7.50 7.48 7.3 7.55 7.53 7.55 7.3 7.25 7.54 7.54 7.25 8.11 7.59 7.59 8.01 7.58 7.92 7.73 8.11 7.59 7.59 8.01 7.58 7.92 7.73 1.73 1.73 7.83 7.66 8.12 7.76 8.07 7.91 7.91 7.39 7.39 1H NMR (500MHz, THF-d8): 7.48 7.50 7.48 7.50 7.48 7.3 7.55 7.53 7.55 7.3 7.25 7.54 7.54 7.25 8.11 7.59 7.59 8.01 7.58 7.92 7.73 8.11 7.59 7.59 8.01 7.58 7.92 7.73 1.73 1.73 7.83 7.66 8.12 7.76 8.07 7.91 7.91 7.39 7.39
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[실시예 1-2 ~ 실시예 1-26: 화학식 4-002 ~ 화학식 4-026의 화합물의 합성][Example 1-2 to Example 1-26: Synthesis of Compound of Formula 4-002 to Formula 4-026]
하기 화학식 4-002의 화합물 내지 화학식 4-026의 화합물은 각각 상기 실시예 1-1(화학식 4-001의 화합물의 합성)과 동일한 방법을 이용하여 합성할 수 있었으며, 연한 노란색 고체로 얻을 수 있었다.The compounds of Formula 4-002 to Formula 4-026 may be synthesized using the same method as in Example 1-1 (Synthesis of Compound of 4-001), respectively, and were obtained as a pale yellow solid. .
[화학식 4-002][Formula 4-002]
Figure PCTKR2010003528-appb-I000027
Figure PCTKR2010003528-appb-I000027
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[화학식 4-003][Formula 4-003]
Figure PCTKR2010003528-appb-I000028
Figure PCTKR2010003528-appb-I000028
Exact Mass: 842.37, Elemental Analysis: C, 91.18; H, 5.50; N, 3.32Exact Mass: 842.37, Elemental Analysis: C, 91.18; H, 5.50; N, 3.32
[화학식 4-004][Formula 4-004]
Figure PCTKR2010003528-appb-I000029
Figure PCTKR2010003528-appb-I000029
Mass: 737.31, Elemental Analysis: C, 92.77; H, 5.33; N, 1.90Mass: 737.31, Elemental Analysis: C, 92.77; H, 5. 33; N, 1.90
[화학식 4-005][Formula 4-005]
Figure PCTKR2010003528-appb-I000030
Figure PCTKR2010003528-appb-I000030
Mass: 661.28, Elemental Analysis: C, 92.55; H, 5.33; N, 2.12Mass: 661.28, Elemental Analysis: C, 92.55; H, 5. 33; N, 2.12
[화학식 4-006][Formula 4-006]
Figure PCTKR2010003528-appb-I000031
Figure PCTKR2010003528-appb-I000031
Mass: 661.28, Elemental Analysis: C, 92.55; H, 5.33; N, 2.12Mass: 661.28, Elemental Analysis: C, 92.55; H, 5. 33; N, 2.12
[화학식 4-007][Formula 4-007]
Figure PCTKR2010003528-appb-I000032
Figure PCTKR2010003528-appb-I000032
Mass: 661.28, Elemental Analysis: C, 92.55; H, 5.33; N, 2.12Mass: 661.28, Elemental Analysis: C, 92.55; H, 5. 33; N, 2.12
[화학식 4-008][Formula 4-008]
Figure PCTKR2010003528-appb-I000033
Figure PCTKR2010003528-appb-I000033
Mass: 661.28, Elemental Analysis: C, 92.55; H, 5.33; N, 2.12Mass: 661.28, Elemental Analysis: C, 92.55; H, 5. 33; N, 2.12
[화학식 4-009][Formula 4-009]
Figure PCTKR2010003528-appb-I000034
Figure PCTKR2010003528-appb-I000034
Mass: 674.27, Elemental Analysis: C, 90.77; H, 5.08; N, 4.15Mass: 674.27, Elemental Analysis: C, 90.77; H, 5.08; N, 4.15
[화학식 4-010][Formula 4-010]
Figure PCTKR2010003528-appb-I000035
Figure PCTKR2010003528-appb-I000035
Mass: 624.26, Elemental Analysis: C, 90.35; H, 5.16; N, 4.48Mass: 624.26, Elemental Analysis: C, 90.35; H, 5. 16; N, 4.48
[화학식 4-011][Formula 4-011]
Figure PCTKR2010003528-appb-I000036
Figure PCTKR2010003528-appb-I000036
Mass: 638.27, Elemental Analysis: C, 90.25; H, 5.36; N, 4.39Mass: 638.27, Elemental Analysis: C, 90.25; H, 5. 36; N, 4.39
[화학식 4-012][Formula 4-012]
Figure PCTKR2010003528-appb-I000037
Figure PCTKR2010003528-appb-I000037
Mass: 654.27, Elemental Analysis: C, 88.04; H, 5.23; N, 4.28; O, 2.44Mass: 654.27, Elemental Analysis: C, 88.04; H, 5. 23; N, 4.28; O, 2.44
[화학식 4-013][Formula 4-013]
Figure PCTKR2010003528-appb-I000038
Figure PCTKR2010003528-appb-I000038
Mass: 700.29, Elemental Analysis: C, 90.83; H, 5.18; N, 4.00Mass: 700.29, Elemental Analysis: C, 90.83; H, 5. 18; N, 4.00
[화학식 4-014][Formula 4-014]
Figure PCTKR2010003528-appb-I000039
Figure PCTKR2010003528-appb-I000039
Mass: 624.26, Elemental Analysis: C, 90.35; H, 5.16; N, 4.48Mass: 624.26, Elemental Analysis: C, 90.35; H, 5. 16; N, 4.48
[화학식 4-015][Formula 4-015]
Figure PCTKR2010003528-appb-I000040
Figure PCTKR2010003528-appb-I000040
Mass: 624.26, Elemental Analysis: C, 90.35; H, 5.16; N, 4.48Mass: 624.26, Elemental Analysis: C, 90.35; H, 5. 16; N, 4.48
[화학식 4-016][Formula 4-016]
Figure PCTKR2010003528-appb-I000041
Figure PCTKR2010003528-appb-I000041
Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72
[화학식 4-017][Formula 4-017]
Figure PCTKR2010003528-appb-I000042
Figure PCTKR2010003528-appb-I000042
Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72
[화학식 4-018][Formula 4-018]
Figure PCTKR2010003528-appb-I000043
Figure PCTKR2010003528-appb-I000043
Mass: 611.26, Elemental Analysis: C, 92.27; H, 5.44; N, 2.29Mass: 611.26, Elemental Analysis: C, 92.27; H, 5. 44; N, 2.29
[화학식 4-019][Formula 4-019]
Figure PCTKR2010003528-appb-I000044
Figure PCTKR2010003528-appb-I000044
Mass: 687.29, Elemental Analysis: C, 92.54; H, 5.42; N, 2.04Mass: 687.29, Elemental Analysis: C, 92.54; H, 5. 42; N, 2.04
[화학식 4-020][Formula 4-020]
Figure PCTKR2010003528-appb-I000045
Figure PCTKR2010003528-appb-I000045
Mass: 614.24, Elemental Analysis: C, 87.92; H, 4.92; N, 4.56; O, 2.60Mass: 614.24, Elemental Analysis: C, 87.92; H, 4.92; N, 4.56; O, 2.60
[화학식 4-021][Formula 4-021]
Figure PCTKR2010003528-appb-I000046
Figure PCTKR2010003528-appb-I000046
Mass: 630.21, Elemental Analysis: C, 85.68; H, 4.79; N, 4.44; S, 5.08Mass: 630.21, Elemental Analysis: C, 85.68; H, 4.79; N, 4.44; S, 5.08
[화학식 4-022][Formula 4-022]
Figure PCTKR2010003528-appb-I000047
Figure PCTKR2010003528-appb-I000047
Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86
[화학식 4-023][Formula 4-023]
Figure PCTKR2010003528-appb-I000048
Figure PCTKR2010003528-appb-I000048
Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86
[화학식 4-024][Formula 4-024]
Figure PCTKR2010003528-appb-I000049
Figure PCTKR2010003528-appb-I000049
Mass: 762.3, Elemental Analysis: C, 91.31; H, 5.02; N, 3.67Mass: 762.3, Elemental Analysis: C, 91.31; H, 5.02; N, 3.67
[화학식 4-025][Formula 4-025]
Figure PCTKR2010003528-appb-I000050
Figure PCTKR2010003528-appb-I000050
Mass: 763.3, Elemental Analysis: C, 89.62; H, 4.88; N, 5.50Mass: 763.3, Elemental Analysis: C, 89.62; H, 4.88; N, 5.50
[화학식 4-026][Formula 4-026]
Figure PCTKR2010003528-appb-I000051
Figure PCTKR2010003528-appb-I000051
Mass: 763.32, Elemental Analysis: C, 92.76; H, 5.41; N, 1.83Mass: 763.32, Elemental Analysis: C, 92.76; H, 5.41; N, 1.83
[실시예 2: 화학식 5-001 내지 화학식 5-014의 화합물 합성]Example 2 Synthesis of Compounds of Formula 5-001 to Formula 5-014
하기 화학식 5-001 내지 화학식 5-014로 표시되는 화합물을 합성하기 위해 다음과 같은 방법을 사용하였다.The following method was used to synthesize the compounds represented by Formula 5-001 to Formula 5-014.
[반응식 2]Scheme 2
Figure PCTKR2010003528-appb-I000052
Figure PCTKR2010003528-appb-I000052
[합성예 2-1: 화합물 2-3의 합성]Synthesis Example 2-1: Synthesis of Compound 2-3
화합물 2-1인 fluorene 27.8g과 화합물 2-2인 4-bromophthalic anhydride 48.7g을 디클로로메탄 700mL에 녹여 상온에서 교반하다가 염화알루미늄 28.7g을 0℃ 하에서 천천히 넣었다. 이어서 반응물을 40℃에서 6시간 환류 교반 시킨 후 농축하여 컬럼 크로마토그래피로 불순물을 제거하고 디클로로메탄에 녹여 n-헥산에서 침전시켜 여과하였다. 여과로 얻은 고체를 감압 건조하여 화합물 2-3 30g (수율 50%)을 수득하였다.27.8 g of fluorene compound 2-1 and 48.7 g of 4-bromophthalic anhydride compound 2-2 were dissolved in 700 mL of dichloromethane, stirred at room temperature, and 28.7 g of aluminum chloride was slowly added at 0 ° C. Subsequently, the reaction was stirred under reflux at 40 ° C. for 6 hours, concentrated to remove impurities by column chromatography, dissolved in dichloromethane, precipitated in n-hexane, and filtered. The solid obtained by filtration was dried under reduced pressure to give 30 g of a compound 2-3 (yield 50%).
[합성예 2-2: 화합물 2-4의 합성]Synthesis Example 2-2: Synthesis of Compound 2-4
화합물 2-3 18.5g에 폴리인산 50mL를 넣고 130℃로 3시간 가열 교반 후, 상온에서 얼음물 300mL 넣어 고체를 여과하고 메탄올로 씻었다. 여과로 얻은 고체를 감압 건조하여 화합물 2-4 11g (수율 62%)을 합성하였다.50 mL of polyphosphoric acid was added to 18.5 g of the compound 2-3, and the mixture was heated and stirred at 130 ° C. for 3 hours, 300 mL of ice water was added at room temperature, and the solid was filtered and washed with methanol. The solid obtained by filtration was dried under reduced pressure to synthesize 11 g of a compound 2-4 (yield 62%).
[합성예 2-3: 화합물 2-5의 합성]Synthesis Example 2-3: Synthesis of Compound 2-5
화합물 1-6 17g을 질소 하에서 테트라하이드로퓨란 300mL에 녹였다. 이 반응물에 n-부틸 리튬 56mL를 -78℃ 하에 서서히 적가하였다. -78℃ 하에서 1시간 교반한 후 화합물 2-4 11g을 넣었다. 천천히 상온으로 올려 교반한 후 포화 염화암모늄 용액을 넣어 디클로로메탄으로 추출하였다. 농축하여 n-헥산에서 침전시켜 여과하여 고체 상태의 화합물2-5 12g (수율 67%)을 얻었다.17 g of compound 1-6 was dissolved in 300 mL of tetrahydrofuran under nitrogen. 56 mL of n-butyl lithium was slowly added dropwise to the reaction at -78 ° C. After stirring for 1 hour at -78 ° C, 11 g of Compound 2-4 was added. After slowly raising to room temperature, the mixture was added with saturated ammonium chloride solution and extracted with dichloromethane. Concentrated, precipitated in n-hexane and filtered to give 12g (yield 67%) of compound 2-5 in a solid state.
[합성예 2-4: 화합물 2-6의 합성]Synthesis Example 2-4: Synthesis of Compound 2-6
화합물 2-5 12g과 요오드화칼륨 30g, 차아인산나트륨 수화물 35g을 아세트산 200mL에 분산시킨 후 2시간 동안 환류 교반하였다. 상온으로 냉각 후 물 300mL에 붓고 여과하여 물과 메탄올로 씻은 다음, 감압 건조하여 화합물 2-6 8g (수율 71%)을 수득하였다.12 g of Compound 2-5, 30 g of potassium iodide, and 35 g of sodium hypophosphite hydrate were dispersed in 200 mL of acetic acid and stirred under reflux for 2 hours. After cooling to room temperature, poured into 300mL of water, filtered, washed with water and methanol, and dried under reduced pressure to give 8 g of compound 2-6 (yield 71%).
[실시예 2-1: 화학식 5-001의 화합물의 합성]Example 2-1: Synthesis of Compound of Chemical Formula 5-001
화합물 2-6 8g과 화합물 1-9에 해당하는 4-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenylboronic acid 5.2g을 톨루엔 100mL에 녹이고 테트라키스트라이페닐포스핀팔라듐 0.4g과 2N 탄산칼륨 25mL를 넣고 13시간 환류 교반하였다. 상온으로 냉각시키고 유기층과 물층을 분리한 후, 물과 포화 염화나트륨 용액으로 씻어주고, 무수 황산나트륨으로 건조한 후 농축하였다. 컬럼 크로마토그래피 (n-헥산 ~ n-헥산/디클로로메탄=9/1 ~ n-헥산/초산에틸=8/2)로 불순물을 제거한 후, n-헥산에서 침전을 시키고 여과하여 연한 노란색 고체의 화학식 5-001의 화합물 4g(37%)을 얻었다.8 g of compound 2-6 and 5.2 g of 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid corresponding to compound 1-9 were dissolved in 100 mL of toluene and tetrakistriphenylphosphate. 0.4 g of pinpalladium and 25 mL of 2 N potassium carbonate were added thereto, and the mixture was stirred under reflux for 13 hours. After cooling to room temperature, the organic layer and the water layer were separated, washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. After removing impurities by column chromatography (n-hexane to n-hexane / dichloromethane = 9/1 to n-hexane / ethyl acetate = 8/2), the precipitate was precipitated in n-hexane and filtered to give a pale yellow solid. 4 g (37%) of 5-001 were obtained.
[화학식 5-001][Formula 5-001]
Figure PCTKR2010003528-appb-I000053
Figure PCTKR2010003528-appb-I000053
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[실시예 2-2 ~ 실시예 2-14: 화학식 5-002 ~ 화학식 5-014의 화합물의 합성]Example 2-2 to Example 2-14: Synthesis of Compounds of Chemical Formula 5-002 to Chemical Formula 5-014
하기 화학식 5-002의 화합물 내지 화학식 5-014의 화합물은 각각 상기 실시예 2-1(화학식 5-001의 화합물의 합성)과 동일한 방법을 이용하여 합성할 수 있었으며, 연한 노란색 고체로 얻을 수 있었다.Compounds of the formula 5-002 to the compound of the formula 5-014 could be synthesized using the same method as in Example 2-1 (synthesis of the compound of Formula 5-001), respectively, and could be obtained as a pale yellow solid. .
[화학식 5-002][Formula 5-002]
Figure PCTKR2010003528-appb-I000054
Figure PCTKR2010003528-appb-I000054
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[화학식 5-003][Formula 5-003]
Figure PCTKR2010003528-appb-I000055
Figure PCTKR2010003528-appb-I000055
Mass: 737.31, Elemental Analysis: C, 92.77; H, 5.33; N, 1.90Mass: 737.31, Elemental Analysis: C, 92.77; H, 5. 33; N, 1.90
[화학식 5-004][Formula 5-004]
Figure PCTKR2010003528-appb-I000056
Figure PCTKR2010003528-appb-I000056
Mass: 674.27, Elemental Analysis: C, 90.77; H, 5.08; N, 4.15Mass: 674.27, Elemental Analysis: C, 90.77; H, 5.08; N, 4.15
[화학식 5-005][Formula 5-005]
Figure PCTKR2010003528-appb-I000057
Figure PCTKR2010003528-appb-I000057
Mass: 700.29, Elemental Analysis: C, 90.83; H, 5.18; N, 4.00Mass: 700.29, Elemental Analysis: C, 90.83; H, 5. 18; N, 4.00
[화학식 5-006][Formula 5-006]
Figure PCTKR2010003528-appb-I000058
Figure PCTKR2010003528-appb-I000058
Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72Mass: 625.25, Elemental Analysis: C, 88.29; H, 4.99; N, 6.72
[화학식 5-007][Formula 5-007]
Figure PCTKR2010003528-appb-I000059
Figure PCTKR2010003528-appb-I000059
Mass: 614.24, Elemental Analysis: C, 87.92; H, 4.92; N, 4.56; O, 2.60Mass: 614.24, Elemental Analysis: C, 87.92; H, 4.92; N, 4.56; O, 2.60
[화학식 5-008][Formula 5-008]
Figure PCTKR2010003528-appb-I000060
Figure PCTKR2010003528-appb-I000060
Mass: 630.21, Elemental Analysis: C, 85.68; H, 4.79; N, 4.44; S, 5.08Mass: 630.21, Elemental Analysis: C, 85.68; H, 4.79; N, 4.44; S, 5.08
[화학식 5-009][Formula 5-009]
Figure PCTKR2010003528-appb-I000061
Figure PCTKR2010003528-appb-I000061
Mass: 687.29, Elemental Analysis: C, 92.54; H, 5.42; N, 2.04Mass: 687.29, Elemental Analysis: C, 92.54; H, 5. 42; N, 2.04
[화학식 5-010][Formula 5-010]
Figure PCTKR2010003528-appb-I000062
Figure PCTKR2010003528-appb-I000062
Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86
[화학식 5-011][Formula 5-011]
Figure PCTKR2010003528-appb-I000063
Figure PCTKR2010003528-appb-I000063
Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86Mass: 724.29, Elemental Analysis: C, 91.13; H, 5.01; N, 3.86
[화학식 5-012][Formula 5-012]
Figure PCTKR2010003528-appb-I000064
Figure PCTKR2010003528-appb-I000064
Mass: 762.3, Elemental Analysis: C, 91.31; H, 5.02; N, 3.67Mass: 762.3, Elemental Analysis: C, 91.31; H, 5.02; N, 3.67
[화학식 5-013][Formula 5-013]
Figure PCTKR2010003528-appb-I000065
Figure PCTKR2010003528-appb-I000065
Mass: 713.28, Elemental Analysis: C, 89.17; H, 4.94; N, 5.89Mass: 713.28, Elemental Analysis: C, 89.17; H, 4.94; N, 5.89
[화학식 5-014][Formula 5-014]
Figure PCTKR2010003528-appb-I000066
Figure PCTKR2010003528-appb-I000066
Mass: 763.32, Elemental Analysis: C, 92.76; H, 5.41; N, 1.83Mass: 763.32, Elemental Analysis: C, 92.76; H, 5.41; N, 1.83
[실시예 3: 화학식 6-001 내지 화학식 6-048의 화합물 합성]Example 3: Synthesis of Compounds of Chemical Formulas 6-001 to 6-048
하기 화학식 6-001 내지 화학식 6-048로 표시되는 화합물을 합성하기 위해 다음과 같은 방법을 사용하였다.To synthesize the compounds represented by the following Chemical Formulas 6-001 to 6-048, the following method was used.
[반응식 3]Scheme 3
Figure PCTKR2010003528-appb-I000067
Figure PCTKR2010003528-appb-I000067
[합성예 3-1: 화합물 3-1의 합성]Synthesis Example 3-1: Synthesis of Compound 3-1
화합물 2-1인 fluorene 20g과 화합물 1-3인 phthalic anhydride 23g을 디클로로메탄에 녹여 상온에서 교반하다가 염화알루미늄 20.5g을 0℃ 하에서 천천히 넣었다. 안정화되면 반응물을 40℃에서 6시간 환류 교반 시킨 후 농축하여 컬럼 크로마토그래피로 불순물을 제거하고 디클로로메탄에 녹여 n-헥산에서 침전시켜 여과하였다. 여과로 얻은 고체를 감압 건조하여 화합물 3-1 27g (수율 76%)을 수득하였다.20 g of fluorene compound 2-1 and 23 g of phthalic anhydride compound 1-3 were dissolved in dichloromethane, and stirred at room temperature. Then, 20.5 g of aluminum chloride was slowly added at 0 ° C. After stabilization, the reaction was stirred under reflux at 40 ° C. for 6 hours, concentrated to remove impurities by column chromatography, dissolved in dichloromethane, precipitated in n-hexane, and filtered. The solid obtained by filtration was dried under reduced pressure to give 27 g of compound 3-1 (yield 76%).
[합성예 3-2: 화합물 3-2의 합성]Synthesis Example 3-2: Synthesis of Compound 3-2
화합물 3-1 27g에 폴리인산 50mL를 넣어주고 130℃로 3시간 가열 교반 후, 상온에서 얼음물 400mL 넣어 고체를 여과하고 메탄올로 씻었다. 여과로 얻은 고체를 감압 건조하여 화합물 3-2 19g (수율 74%)을 합성하였다.50 mL of polyphosphoric acid was added to 27 g of the compound 3-1, and the mixture was heated and stirred at 130 ° C. for 3 hours, 400 mL of ice water was added at room temperature, and the solid was filtered and washed with methanol. The solid obtained by filtration was dried under reduced pressure to synthesize 19 g of a compound 3-2 (yield 74%).
[합성예 3-3: 화합물 3-3의 합성]Synthesis Example 3-3: Synthesis of Compound 3-3
화합물 3-2 64g을 메탄올 2L에 분산시키고, 이 반응물에 sodium borohydride 30g을 0℃ 하에서 세 번에 나누어 천천히 넣었다. 0℃ 하에서 3시간 교반한 후 물 3L를 넣어 생긴 고체를 여과했다. 물로 충분히 씻어주고 자연 건조하였다.64 g of compound 3-2 was dispersed in 2 L of methanol, and 30 g of sodium borohydride was added to the reaction in three portions at 0 ° C. After stirring for 3 hours at 0 ° C, 3L of water was added to the resulting solid. Washed sufficiently with water and dried naturally.
[합성예 3-4: 화합물 3-4의 합성]Synthesis Example 3-4: Synthesis of Compound 3-4
위 합성예에서 얻은 화합물 3-3을 5N HCl 300mL에 분산시키고 20시간 동안 환류 교반하였다. 상온으로 내린 후 물을 넣고 고체를 여과하여 물로 충분히 씻었다. 감압 건조하여 화합물 3-4 60.3g (두 단계 수율 98.5%)을 수득하였다.Compound 3-3 obtained in the above synthesis example was dispersed in 300 mL of 5N HCl and stirred at reflux for 20 hours. After cooling to room temperature, water was added, and the solid was filtered and washed with water sufficiently. Drying under reduced pressure afforded 60.3 g of compound 3-4 (two steps yield 98.5%).
[합성예 3-5: 화합물 3-5의 합성]Synthesis Example 3-5 Synthesis of Compound 3-5
화합물 3-4 60.3g을 이소프로판올 1.5L에 분산시키고 sodium borohydride 36.7g을 첨가하였다. 22시간 동안 환류 교반시킨 후, 상온으로 냉각하였다. 이어서 붉은 반응물을 물 2L에 쏟아 교반한 후 고체를 여과하고 물로 충분히 씻어주어 황토색 고체를 얻었다. 물을 제거하고 컬럼 크로마토그래피를 통해 불순물을 제거하여 밝은 연두색 고체의 화합물 3-5 27.9g (수율 48.7%)을 얻었다. 60.3 g of compound 3-4 were dispersed in 1.5 L of isopropanol and 36.7 g of sodium borohydride were added. After stirring for 22 hours at reflux, the mixture was cooled to room temperature. Subsequently, the red reactant was poured into 2 L of water, stirred, and the solid was filtered and washed with water to obtain an ocher solid. Water was removed and impurities were removed via column chromatography to give 27.9 g (yield 48.7%) of compound 3-5 as a light yellow green solid.
[합성예 3-6: 화합물 3-6의 합성]Synthesis Example 3-6: Synthesis of Compound 3-6
화합물 3-5 27.9g을 디메틸포름아미드 400mL에 녹이고 N-bromosuccinimide 18.5g을 넣었다. 상온에서 1시간 교반한 후 물 1L에 쏟아 생긴 고체를 여과하였다. 물과 메탄올로 충분히 씻어주고 감압 건조하여 연노랑 고체의 화합물 3-6 33.3g (수율 94.2%)을 얻었다.27.9 g of compound 3-5 was dissolved in 400 mL of dimethylformamide, and 18.5 g of N-bromosuccinimide was added thereto. After stirring for 1 hour at room temperature, the solid poured into 1L of water was filtered. After washing sufficiently with water and methanol and drying under reduced pressure, 33.3 g (yield 94.2%) of a light yellow solid compound 3-6 was obtained.
[합성예 3-7: 화합물 3-8의 합성]Synthesis Example 3-7: Synthesis of Compound 3-8
화합물 3-6 33.3g과 화합물 3-7에 해당하는 2-naphthaleneboronic acid 23g을 톨루엔 400mL에 녹이고 테트라키스트라이페닐포스핀팔라듐 3.1g과 2N 탄산칼륨 100mL를 넣고 22시간 환류 교반하였다. 상온으로 냉각시키고 유기층과 물층을 분리한 후 물과 포화 염화나트륨 용액으로 씻어주고 무수 황산나트륨으로 건조하여 농축하였다. 컬럼 크로마토그래피 (n-헥산 ~ n-헥산/디클로로메탄=9/1)로 불순물을 제거하여 연한 노란색 고체의 화합물 3-8 35.3g(수율 94.1%)을 얻었다.33.3 g of compound 3-6 and 23 g of 2-naphthaleneboronic acid corresponding to compound 3-7 were dissolved in 400 mL of toluene, and 3.1 g of tetrakistriphenylphosphine palladium and 100 mL of 2N potassium carbonate were added and stirred under reflux for 22 hours. After cooling to room temperature, the organic layer and the water layer were separated, washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. Impurities were removed by column chromatography (n-hexane to n-hexane / dichloromethane = 9/1) to give 35.3 g (yield 94.1%) of compound 3-8 as a pale yellow solid.
[합성예 3-8: 화합물 3-9의 합성]Synthesis Example 3-8: Synthesis of Compound 3-9
화합물 3-8 35.3g을 디메틸포름아미드 400mL에 녹이고 N-bromosuccinimide 16.4g을 넣었다. 상온에서 1시간 교반한 후 물 1.5L에 쏟아 교반한 후 생긴 고체를 여과하였다. 물과 메탄올로 충분히 씻어주고 감압 건조하여 연노랑 고체의 화합물 3-9 39.1g (수율 93.3%)을 얻었다. 35.3 g of compound 3-8 was dissolved in 400 mL of dimethylformamide, and 16.4 g of N-bromosuccinimide was added thereto. After stirring for 1 hour at room temperature and poured into 1.5L of water, the resulting solid was filtered. The mixture was washed with water and methanol sufficiently and dried under reduced pressure to obtain 39.1 g (yield 93.3%) of compound 3-9 as a light yellow solid.
[실시예 3-1: 화학식 6-001의 화합물의 합성]Example 3-1: Synthesis of Compound of Chemical Formula 6-001
화합물 3-9 39.1g과 화합물 1-9에 해당하는 4-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenylboronic acid 34.7g을 톨루엔 500mL에 녹이고 에탄올 150mL를 첨가하였다. 테트라키스트라이페닐포스핀팔라듐 2.7g과 2N 탄산칼륨 150mL를 넣고 22시간 환류 교반하였다. 상온으로 냉각시키고 유기층과 물층을 분리한 후, 물과 포화 염화나트륨 용액으로 씻어주고, 무수 황산나트륨으로 건조하여 농축하였다. 컬럼 크로마토그래피 (n-헥산 ~ n-헥산/디클로로메탄=9/1 ~ n-헥산/초산에틸=5/5)로 불순물을 제거한 후, n-헥산에서 침전을 시키고 여과하여 연한 노란색 고체의 화학식 6-001의 화합물 32g(57.1%)을 얻었다.39.1 g of compound 3-9 and 34.7 g of 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid corresponding to compound 1-9 were dissolved in 500 mL of toluene and 150 mL of ethanol was added. It was. 2.7 g of tetrakistriphenylphosphinepalladium and 150 mL of 2N potassium carbonate were added and stirred under reflux for 22 hours. After cooling to room temperature, the organic layer and the water layer were separated, washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. After removing impurities by column chromatography (n-hexane to n-hexane / dichloromethane = 9/1 to n-hexane / ethyl acetate = 5/5), the precipitate was precipitated in n-hexane and filtered to give a pale yellow solid. 32 g (57.1%) of 6-001 were obtained.
[화학식 6-001][Formula 6-001]
Figure PCTKR2010003528-appb-I000068
Figure PCTKR2010003528-appb-I000068
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[실시예 3-2 ~ 실시예 3-48: 화학식 6-002 ~ 화학식 6-048의 화합물의 합성]Example 3-2 to Example 3-48: Synthesis of Compounds of Chemical Formula 6-002 to Chemical Formula 6-048
하기 화학식 6-002의 화합물 내지 화학식 6-048의 화합물은 각각 상기 실시예 3-1(화학식 6-001의 화합물의 합성)과 동일한 방법을 이용하여 합성할 수 있었으며, 연한 노란색 고체로 얻을 수 있었다.The compounds of Formulas 6-002 to 6-648 may be synthesized using the same method as in Example 3-1 (Synthesis of Compounds of Formula 6-001), respectively, and were obtained as a pale yellow solid. .
[화학식 6-002][Formula 6-002]
Figure PCTKR2010003528-appb-I000069
Figure PCTKR2010003528-appb-I000069
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-003][Formula 6-003]
Figure PCTKR2010003528-appb-I000070
Figure PCTKR2010003528-appb-I000070
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-004][Formula 6-004]
Figure PCTKR2010003528-appb-I000071
Figure PCTKR2010003528-appb-I000071
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-005][Formula 6-005]
Figure PCTKR2010003528-appb-I000072
Figure PCTKR2010003528-appb-I000072
Mass: 665.28, Elemental Analysis: C, 88.39; H, 5.30; N, 6.31Mass: 665.28, Elemental Analysis: C, 88.39; H, 5. 30; N, 6.31
[화학식 6-006][Formula 6-006]
Figure PCTKR2010003528-appb-I000073
Figure PCTKR2010003528-appb-I000073
Mass: 665.28, Elemental Analysis: C, 88.39; H, 5.30; N, 6.31Mass: 665.28, Elemental Analysis: C, 88.39; H, 5. 30; N, 6.31
[화학식 6-007][Formula 6-007]
Figure PCTKR2010003528-appb-I000074
Figure PCTKR2010003528-appb-I000074
Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37
[화학식 6-008][Formula 6-008]
Figure PCTKR2010003528-appb-I000075
Figure PCTKR2010003528-appb-I000075
Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37
[화학식 6-009][Formula 6-009]
Figure PCTKR2010003528-appb-I000076
Figure PCTKR2010003528-appb-I000076
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-010][Formula 6-010]
Figure PCTKR2010003528-appb-I000077
Figure PCTKR2010003528-appb-I000077
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-011][Formula 6-011]
Figure PCTKR2010003528-appb-I000078
Figure PCTKR2010003528-appb-I000078
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-012][Formula 6-012]
Figure PCTKR2010003528-appb-I000079
Figure PCTKR2010003528-appb-I000079
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-013][Formula 6-013]
Figure PCTKR2010003528-appb-I000080
Figure PCTKR2010003528-appb-I000080
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-014][Formula 6-014]
Figure PCTKR2010003528-appb-I000081
Figure PCTKR2010003528-appb-I000081
Mass: 741.31, Elemental Analysis: C, 89.04; H, 5.30; N, 5.66Mass: 741.31, Elemental Analysis: C, 89.04; H, 5. 30; N, 5.66
[화학식 6-015][Formula 6-015]
Figure PCTKR2010003528-appb-I000082
Figure PCTKR2010003528-appb-I000082
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-016][Formula 6-016]
Figure PCTKR2010003528-appb-I000083
Figure PCTKR2010003528-appb-I000083
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-017][Formula 6-017]
Figure PCTKR2010003528-appb-I000084
Figure PCTKR2010003528-appb-I000084
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-018][Formula 6-018]
Figure PCTKR2010003528-appb-I000085
Figure PCTKR2010003528-appb-I000085
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-019][Formula 6-019]
Figure PCTKR2010003528-appb-I000086
Figure PCTKR2010003528-appb-I000086
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-020][Formula 6-020]
Figure PCTKR2010003528-appb-I000087
Figure PCTKR2010003528-appb-I000087
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-021][Formula 6-021]
Figure PCTKR2010003528-appb-I000088
Figure PCTKR2010003528-appb-I000088
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-022][Formula 6-022]
Figure PCTKR2010003528-appb-I000089
Figure PCTKR2010003528-appb-I000089
Mass: 791.33, Elemental Analysis: C, 89.48; H, 5.22; N, 5.31Mass: 791.33, Elemental Analysis: C, 89.48; H, 5. 22; N, 5.31
[화학식 6-023][Formula 6-023]
Figure PCTKR2010003528-appb-I000090
Figure PCTKR2010003528-appb-I000090
Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49
[화학식 6-024][Formula 6-024]
Figure PCTKR2010003528-appb-I000091
Figure PCTKR2010003528-appb-I000091
Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49
[화학식 6-025][Formula 6-025]
Figure PCTKR2010003528-appb-I000092
Figure PCTKR2010003528-appb-I000092
Mass: 815.33, Elemental Analysis: C, 89.79; H, 5.06; N, 5.15Mass: 815.33, Elemental Analysis: C, 89.79; H, 5.06; N, 5.15
[화학식 6-026][Formula 6-026]
Figure PCTKR2010003528-appb-I000093
Figure PCTKR2010003528-appb-I000093
Mass: 815.33, Elemental Analysis: C, 89.79; H, 5.06; N, 5.15Mass: 815.33, Elemental Analysis: C, 89.79; H, 5.06; N, 5.15
[화학식 6-027][Formula 6-027]
Figure PCTKR2010003528-appb-I000094
Figure PCTKR2010003528-appb-I000094
Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32
[화학식 6-028][Formula 6-028]
Figure PCTKR2010003528-appb-I000095
Figure PCTKR2010003528-appb-I000095
Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32
[화학식 6-029][Formula 6-029]
Figure PCTKR2010003528-appb-I000096
Figure PCTKR2010003528-appb-I000096
Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32
[화학식 6-030][Formula 6-030]
Figure PCTKR2010003528-appb-I000097
Figure PCTKR2010003528-appb-I000097
Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32Mass: 789.31, Elemental Analysis: C, 89.70; H, 4.98; N, 5.32
[화학식 6-031][Formula 6-031]
Figure PCTKR2010003528-appb-I000098
Figure PCTKR2010003528-appb-I000098
Mass: 891.36, Elemental Analysis: C, 90.21; H, 5.08; N, 4.71Mass: 891.36, Elemental Analysis: C, 90.21; H, 5.08; N, 4.71
[화학식 6-032][Formula 6-032]
Figure PCTKR2010003528-appb-I000099
Figure PCTKR2010003528-appb-I000099
Mass: 891.36, Elemental Analysis: C, 90.21; H, 5.08; N, 4.71Mass: 891.36, Elemental Analysis: C, 90.21; H, 5.08; N, 4.71
[화학식 6-033][Formula 6-033]
Figure PCTKR2010003528-appb-I000100
Figure PCTKR2010003528-appb-I000100
Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49
[화학식 6-034][Formula 6-034]
Figure PCTKR2010003528-appb-I000101
Figure PCTKR2010003528-appb-I000101
Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49Mass: 765.31, Elemental Analysis: C, 89.38; H, 5.13; N, 5.49
[화학식 6-035][Formula 6-035]
Figure PCTKR2010003528-appb-I000102
Figure PCTKR2010003528-appb-I000102
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[화학식 6-036][Formula 6-036]
Figure PCTKR2010003528-appb-I000103
Figure PCTKR2010003528-appb-I000103
Mass: 841.35, Elemental Analysis: C, 89.86; H, 5.15; N, 4.99Mass: 841.35, Elemental Analysis: C, 89.86; H, 5. 15; N, 4.99
[화학식 6-037][Formula 6-037]
Figure PCTKR2010003528-appb-I000104
Figure PCTKR2010003528-appb-I000104
Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50
[화학식 6-038][Formula 6-038]
Figure PCTKR2010003528-appb-I000105
Figure PCTKR2010003528-appb-I000105
Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50
[화학식 6-039][Formula 6-039]
Figure PCTKR2010003528-appb-I000106
Figure PCTKR2010003528-appb-I000106
1H NMR (500MHz, THF-d8) : 8.07(d, 1H), 8.06(d, 1H), 7.91(m, 2H), 7.76(d, 1H), 7.61(m, 1H), 7.55(m, 4H), 7.54(m, 4H), 7.53(m, 2H), 7.50(m, 4H), 7.48(m, 6H), 7.44(m, 1H), 7.39(d, 2H), 7.3(d, 4H), 7.25(m, 4H), 7.24(m, 1H), 1.73(s, 6H) 1H NMR (500MHz, THF-d8): 8.07 (d, 1H), 8.06 (d, 1H), 7.91 (m, 2H), 7.76 (d, 1H), 7.61 (m, 1H), 7.55 (m, 4H ), 7.54 (m, 4H), 7.53 (m, 2H), 7.50 (m, 4H), 7.48 (m, 6H), 7.44 (m, 1H), 7.39 (d, 2H), 7.3 (d, 4H) , 7.25 (m, 4H), 7.24 (m, 1H), 1.73 (s, 6H)
Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50
[화학식 6-040][Formula 6-040]
Figure PCTKR2010003528-appb-I000107
Figure PCTKR2010003528-appb-I000107
Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50Mass: 884.36, Elemental Analysis: C, 85.49; H, 5.01; N, 9.50
[화학식 6-041][Formula 6-041]
Figure PCTKR2010003528-appb-I000108
Figure PCTKR2010003528-appb-I000108
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-042][Formula 6-042]
Figure PCTKR2010003528-appb-I000109
Figure PCTKR2010003528-appb-I000109
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-043][Formula 6-043]
Figure PCTKR2010003528-appb-I000110
Figure PCTKR2010003528-appb-I000110
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-044][Formula 6-044]
Figure PCTKR2010003528-appb-I000111
Figure PCTKR2010003528-appb-I000111
Mass: 715.3, Elemental Analysis: C, 88.92; H, 5.21; N, 5.87Mass: 715.3, Elemental Analysis: C, 88.92; H, 5. 21; N, 5.87
[화학식 6-045][Formula 6-045]
Figure PCTKR2010003528-appb-I000112
Figure PCTKR2010003528-appb-I000112
Mass: 665.28, Elemental Analysis: C, 88.39; H, 5.30; N, 6.31Mass: 665.28, Elemental Analysis: C, 88.39; H, 5. 30; N, 6.31
[화학식 6-046][Formula 6-046]
Figure PCTKR2010003528-appb-I000113
Figure PCTKR2010003528-appb-I000113
Mass: 665.28, Elemental Analysis: C, 88.39; H, 5.30; N, 6.31Mass: 665.28, Elemental Analysis: C, 88.39; H, 5. 30; N, 6.31
[화학식 6-047][Formula 6-047]
Figure PCTKR2010003528-appb-I000114
Figure PCTKR2010003528-appb-I000114
Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37
[화학식 6-048][Formula 6-048]
Figure PCTKR2010003528-appb-I000115
Figure PCTKR2010003528-appb-I000115
Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37Mass: 781.35, Elemental Analysis: C, 89.08; H, 5.54; N, 5.37
[실시예 4: 화학식 7-001 내지 화학식 7-011의 화합물 합성]Example 4 Compound Synthesis of Formulas 7-001 to 7-011
하기 화학식 7-001 내지 화학식 7-011로 표시되는 화합물을 합성하기 위해 다음과 같은 방법을 사용하였다.To synthesize the compounds represented by the following Chemical Formulas 7-001 to 7-011, the following method was used.
[반응식 4]Scheme 4
Figure PCTKR2010003528-appb-I000116
Figure PCTKR2010003528-appb-I000116
[합성예 4-1: 화합물 4-1의 합성]Synthesis Example 4-1: Synthesis of Compound 4-1
화합물 1-2 10g과 화합물 2-2인 4-bromophthalic anhydride 12.46g을 디클로로메탄 300mL에 녹여 상온에서 교반하다가 0℃ 하에서 염화알루미늄 10.6g을 천천히 넣었다. 안정화되면 반응물을 40℃에서 6시간 환류 교반 시킨 후 농축하여 컬럼 크로마토그래피로 불순물을 제거하고, n-헥산에서 침전시켜 여과하였다. 여과로 얻은 고체를 감압 건조하여 화합물 4-1 20g (수율 74%)을 수득하였다.10 g of compound 1-2 and 12.46 g of 4-bromophthalic anhydride (compound 2-2) were dissolved in 300 mL of dichloromethane, stirred at room temperature, and then slowly added 10.6 g of aluminum chloride at 0 ° C. When stabilized, the reaction was stirred at reflux at 40 ° C. for 6 hours, concentrated to remove impurities by column chromatography, precipitated in n-hexane, and filtered. The solid obtained by filtration was dried under reduced pressure to give 20 g of a compound 4-1 (yield 74%).
[합성예 4-2: 화합물 4-2의 합성]Synthesis Example 4-2: Synthesis of Compound 4-2
화합물 4-1 20g에 폴리인산 40mL를 넣어주고 130℃로 3시간 가열 교반 후 50℃이하까지 식혔다. 이어서 증류수 500mL 서서히 넣어 생성된 고체를 여과하고 메탄올로 씻었다. 여과로 얻은 고체를 감압 건조하여 화합물 4-2 14g (수율 73%)을 합성하였다.40 mL of polyphosphoric acid was added to 20 g of the compound 4-1, and the mixture was cooled to 130 ° C. or lower after heating and stirring at 130 ° C. for 3 hours. Subsequently, 500 mL of distilled water was slowly added thereto, and the resulting solid was filtered and washed with methanol. The solid obtained by filtration was dried under reduced pressure to synthesize 14 g of compound 4-2 (yield 73%).
[합성예 4-3: 화합물 4-3의 합성]Synthesis Example 4-3 Synthesis of Compound 4-3
화합물 1-6인 2-bromonaphthrene 18g을 질소 하에서 테트라하이드로퓨란 200mL에 녹였다. 이 반응물에 n-부틸 리튬 60mL를 -78℃ 하에 서서히 적가하였다. -78℃ 하에서 1시간 교반한 후 화합물 4-2 18.5g을 넣었다. 천천히 상온으로 올려 20시간 교반한 후 포화 염화암모늄 용액을 넣어 디클로로메탄으로 추출하였다. 추출물을 농축한 후, n-헥산에서 침전시키고 여과하여 고체 화합물 4-3 16g (수율 75%)을 얻었다.18 g of 2-bromonaphthrene, Compound 1-6, was dissolved in 200 mL of tetrahydrofuran under nitrogen. 60 mL of n-butyl lithium was slowly added dropwise to the reaction at -78 ° C. After stirring at −78 ° C. for 1 hour, 18.5 g of Compound 4-2 was added thereto. After slowly raising to room temperature and stirring for 20 hours, saturated ammonium chloride solution was added and extracted with dichloromethane. The extract was concentrated, precipitated in n-hexane and filtered to give 16 g (75% yield) of solid compound 4-3.
[합성예 4-4: 화합물 4-4의 합성]Synthesis Example 4-4: Synthesis of Compound 4-4
화합물 4-3 16g과 요오드화칼륨 36.5g 차아인산나트륨 수화물 43.2g을 아세트산 250mL에 분산시킨 후 2시간 동안 환류 교반하였다. 상온으로 냉각 후 물 400mL에 붓고 여과하였다. 이어서 물과 메탄올로 씻은 다음 감압 건조하여 화합물 4-4 11g (수율 71%)을 수득하였다.16 g of Compound 4-3 and 43.2 g of potassium iodide 343 g sodium hypophosphite hydrate were dispersed in acetic acid 250mL and stirred under reflux for 2 hours. After cooling to room temperature, poured into 400mL of water and filtered. Then washed with water and methanol and dried under reduced pressure to give 11 g (yield 71%) of compound 4-4.
[실시예 4-1: 화학식 7-001의 화합물의 합성]Example 4-1: Synthesis of Compound of Chemical Formula 7-001
화합물 4-4 11g과 화합물 1-9에 해당하는 4-(4,5-diphenyl-4H-1,2,4-triazol-3-yl)phenylboronic acid 13.3g을 톨루엔 150mL에 녹이고 테트라키스트라이페닐포스핀팔라듐 0.54g과 2N 탄산칼륨 50mL를 넣고 13시간 환류 교반하였다. 상온으로 냉각시키고 유기층과 물층을 분리한 후, 물과 포화 염화나트륨 용액으로 씻어주고 무수 황산나트륨으로 건조하여 농축하였다. 컬럼 크로마토그래피 (n-헥산 ~ n-헥산/디클로로메탄=9/1 ~ n-헥산/초산에틸=5/5)로 불순물을 제거한 후, n-헥산에서 침전을 시키고 여과하여 연한 노란색 고체의 화학식 7-001의 화합물 8.3g(47%)을 얻었다.11 g of compound 4-4 and 13.3 g of 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid corresponding to compound 1-9 were dissolved in 150 mL of toluene and tetrakistriphenylphosphate. 0.54 g of pinpalladium and 50 mL of 2N potassium carbonate were added thereto, and the mixture was stirred under reflux for 13 hours. After cooling to room temperature, the organic layer and the water layer were separated, washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated. After removing impurities by column chromatography (n-hexane to n-hexane / dichloromethane = 9/1 to n-hexane / ethyl acetate = 5/5), the precipitate was precipitated in n-hexane and filtered to give a pale yellow solid. 8.3g (47%) of compound of 7-001 was obtained.
[화학식 7-001][Formula 7-001]
Figure PCTKR2010003528-appb-I000117
Figure PCTKR2010003528-appb-I000117
Mass: 1136.46, Elemental Analysis: C, 87.65; H, 4.96; N, 7.39Mass: 1136.46, Elemental Analysis: C, 87.65; H, 4.96; N, 7.39
[실시예 4-2 ~ 실시예 4-11: 화학식 7-002 ~ 화학식 7-011의 화합물의 합성][Example 4-2 to Example 4-11: Synthesis of the compound of Formula 7-002 to Formula 7-011]
하기 화학식 7-002의 화합물 내지 화학식 7-011의 화합물은 각각 상기 실시예 4-1(화학식 7-001의 화합물의 합성)과 동일한 방법을 이용하여 합성할 수 있었으며, 연한 노란색 고체로 얻을 수 있었다.The compounds of Formulas 7-002 to 7-011 were each synthesized using the same method as in Example 4-1 (Synthesis of Compounds of Formula 7-001), and were obtained as a pale yellow solid. .
[화학식 7-002][Formula 7-002]
Figure PCTKR2010003528-appb-I000118
Figure PCTKR2010003528-appb-I000118
Mass: 1136.46, Elemental Analysis: C, 87.65; H, 4.96; N, 7.39Mass: 1136.46, Elemental Analysis: C, 87.65; H, 4.96; N, 7.39
[화학식 7-003][Formula 7-003]
Figure PCTKR2010003528-appb-I000119
Figure PCTKR2010003528-appb-I000119
Mass: 928.38, Elemental Analysis: C, 91.78; H, 5.21; N, 3.01Mass: 928.38, Elemental Analysis: C, 91.78; H, 5. 21; N, 3.01
[화학식 7-004][Formula 7-004]
Figure PCTKR2010003528-appb-I000120
Figure PCTKR2010003528-appb-I000120
Mass: 802.31, Elemental Analysis: C, 88.25; H, 4.77; N, 6.98Mass: 802.31, Elemental Analysis: C, 88.25; H, 4.77; N, 6.98
[화학식 7-005][Formula 7-005]
Figure PCTKR2010003528-appb-I000121
Figure PCTKR2010003528-appb-I000121
Mass: 854.34, Elemental Analysis: C, 88.50; H, 4.95; N, 6.55Mass: 854.34, Elemental Analysis: C, 88.50; H, 4.95; N, 6.55
[화학식 7-006][Formula 7-006]
Figure PCTKR2010003528-appb-I000122
Figure PCTKR2010003528-appb-I000122
Mass: 702.28, Elemental Analysis: C, 87.15; H, 4.88; N, 7.97Mass: 702.28, Elemental Analysis: C, 87.15; H, 4.88; N, 7.97
[화학식 7-007][Formula 7-007]
Figure PCTKR2010003528-appb-I000123
Figure PCTKR2010003528-appb-I000123
Mass: 704.27, Elemental Analysis: C, 83.50; H, 4.58; N, 11.92Mass: 704.27, Elemental Analysis: C, 83.50; H, 4.58; N, 11.92
[화학식 7-008][Formula 7-008]
Figure PCTKR2010003528-appb-I000124
Figure PCTKR2010003528-appb-I000124
Mass: 682.24, Elemental Analysis: C, 82.68; H, 4.43; N, 8.21; O, 4.69Mass: 682.24, Elemental Analysis: C, 82.68; H, 4. 43; N, 8.21; O, 4.69
[화학식 7-009][Formula 7-009]
Figure PCTKR2010003528-appb-I000125
Figure PCTKR2010003528-appb-I000125
Mass: 714.19, Elemental Analysis: C, 78.96; H, 4.23; N, 7.84; S, 8.97Mass: 714.19, Elemental Analysis: C, 78.96; H, 4. 23; N, 7.84; S, 8.97
[화학식 7-010][Formula 7-010]
Figure PCTKR2010003528-appb-I000126
Figure PCTKR2010003528-appb-I000126
Mass: 902.34, Elemental Analysis: C, 89.11; H, 4.69; N, 6.20Mass: 902.34, Elemental Analysis: C, 89.11; H, 4.69; N, 6.20
[화학식 7-011][Formula 7-011]
Figure PCTKR2010003528-appb-I000127
Figure PCTKR2010003528-appb-I000127
Mass: 902.34, Elemental Analysis: C, 89.11; H, 4.69; N, 6.20Mass: 902.34, Elemental Analysis: C, 89.11; H, 4.69; N, 6.20
[실시예 5-1 내지 실시예 5-31: 유기 발광 소자 제조][Example 5-1 to Example 5-31: Fabrication of organic light emitting device]
ITO 투명 전극 위에 제품명 DS-205 (두산社)를 800Å의 두께로 진공 증착하여 정공 주입층을 형성하고, 그 위에 정공 이송 물질인 NPB (N, N-di(naphthalene-1-yl)-N, N-diphenylbenzidine)를 150Å의 두께로 증착하여 정공 수송층을 형성하였다. 그 위에 호스트로 ADN (9,10-di(naphthalen-2-yl)anthracene)을 사용하고 도판트로 DS-405(두산社)를 5% 도핑하여 300Å 두께로 증착하여 발광층을 형성하였다. 발광층 위에 실시예 1~4에서 합성된 각각의 전자 이송 물질을 250Å의 두께로 증착하여 전자 수송층을 형성하였다. 상기 전자 수송층 위에 10 Å 두께의 LiF를 증착하여 전자 주입층을 형성하였고, 그 위에 2,000Å 두께의 Al을 증착하여 음극을 형성하여 소자를 제조하였다. Product name DS-205 (Doosan Corporation) was vacuum deposited on an ITO transparent electrode to a thickness of 800 kPa to form a hole injection layer, and on top of it, NPB ( N , N- di (naphthalene-1-yl) -N , N- diphenylbenzidine) was deposited to a thickness of 150 Å to form a hole transport layer. ADN (9,10-di (naphthalen-2-yl) anthracene) was used as a host thereon, and a light emitting layer was formed by doping DS-405 (Doosan Co., Ltd.) 5% with a dopant to a thickness of 300 Pa. Each of the electron transporting materials synthesized in Examples 1 to 4 was deposited on the light emitting layer to a thickness of 250 kPa to form an electron transporting layer. 10F thick LiF was deposited on the electron transport layer to form an electron injection layer, and 2,000V thick Al was deposited thereon to form a cathode to manufacture a device.
[비교예 1: 유기 발광 소자 제조]Comparative Example 1: Fabrication of Organic Light-Emitting Element
전자 수송층을 형성할 때, 전자 이송 물질로서 실시예 1~4에서 합성된 물질 대신 Alq3 (aluminum tris(8-hydroxyquinoline))을 사용한 것을 제외하고는 실시예 5와 동일한 방법으로 소자를 제조하였다.When forming the electron transport layer, the device was manufactured in the same manner as in Example 5 except that Alq3 (aluminum tris (8-hydroxyquinoline)) was used instead of the material synthesized in Examples 1 to 4 as the electron transporting material.
실시예 5-1 내지 실시예 5-31 및 비교예 1에서 각각 제작된 유기 발광 소자의 특성은 표 1에 기재하였다.The characteristics of the organic light emitting diodes manufactured in Examples 5-1 to 5-35 and Comparative Example 1 are shown in Table 1 below.
표 1
전자이송물질 구동 전압(V) 발광 효율(cd/A) 전자이송물질 구동 전압(V) 발광 효율(cd/A)
화학식 4-001 5.1 7.3 화학식 6-037 5.3 6.9
화학식 4-002 5.2 7.1 화학식 6-038 5.6 6.7
화학식 4-003 5.5 6.8 화학식 6-047 4.8 7.1
화학식 4-004 5.6 6.7 화학식 6-048 5.1 6.9
화학식 4-005 5.5 6.5 화학식 7-001 5.5 5.5
화학식 4-006 5.6 6.3 화학식 7-002 5.6 5.7
화학식 4-007 5.7 6.2 화학식 7-003 6.1 5.6
화학식 5-001 5.6 6.9 화학식 7-004 6.7 5.6
화학식 5-002 5.9 6.3 화학식 7-005 6.1 5.8
화학식 6-001 4.9 7.5 화학식 7-006 6.1 5.6
화학식 6-002 5.1 7.1 화학식 7-007 6.4 5.9
화학식 6-007 4.9 7.7 화학식 7-008 6.2 5.7
화학식 6-008 5.3 7.2 화학식 7-009 6.2 5.8
화학식 6-011 4.8 7.2 화학식 7-010 6.5 6.4
화학식 6-017 4.9 7.1 화학식 7-011 6.6 6.6
화학식 6-023 5.1 7 Alq3 5.7 6
Table 1
Electron transport material Drive voltage (V) Luminous Efficiency (cd / A) Electron transport material Drive voltage (V) Luminous Efficiency (cd / A)
Formula 4-001 5.1 7.3 Formula 6-037 5.3 6.9
Formula 4-002 5.2 7.1 Formula 6-038 5.6 6.7
Formula 4-003 5.5 6.8 Formula 6-047 4.8 7.1
Formula 4-004 5.6 6.7 Formula 6-048 5.1 6.9
Formula 4-005 5.5 6.5 Formula 7-001 5.5 5.5
Formula 4-006 5.6 6.3 Formula 7-002 5.6 5.7
Formula 4-007 5.7 6.2 Formula 7-003 6.1 5.6
Formula 5-001 5.6 6.9 Formula 7-004 6.7 5.6
Formula 5-002 5.9 6.3 Formula 7-005 6.1 5.8
Formula 6-001 4.9 7.5 Formula 7-006 6.1 5.6
Formula 6-002 5.1 7.1 Formula 7-007 6.4 5.9
Formula 6-007 4.9 7.7 Formula 7-008 6.2 5.7
Formula 6-008 5.3 7.2 Formula 7-009 6.2 5.8
Formula 6-011 4.8 7.2 Formula 7-010 6.5 6.4
Chemical Formula 6-017 4.9 7.1 Formula 7-011 6.6 6.6
Formula 6-023 5.1 7 Alq3 5.7 6
표 1과 같이, 전자 이송 물질로서 본 발명에 따른 화합물을 사용한 유기 발광 소자(실시예 5-1 내지 실시예 5-31)는 종래 Alq3을 사용한 유기 발광 소자(비교예 1) 보다 전압 및 효율 면에서 월등한 성능을 나타내는 것을 확인할 수 있었다.As shown in Table 1, the organic light emitting device (Examples 5-1 to 5-31) using the compound according to the present invention as an electron transporting material is more voltage and efficiency than the organic light emitting device (Comparative Example 1) using Alq3. We can see that it shows superior performance in.
이상을 통해 본 발명의 바람직한 실시예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. It is natural to belong.

Claims (5)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2010003528-appb-I000128
    Figure PCTKR2010003528-appb-I000128
    화학식 1에서, X는 CR6R7, NR6, O, S, S(=O), S(=O)2, 또는 SiR6R7이며;In formula 1, X is CR 6 R 7 , NR 6 , O, S, S (= 0), S (= 0) 2 , or SiR 6 R 7 ;
    R1 내지 R7은 서로 같거나 다르고, 각각 독립적으로 수소, 중수소, 할로겐, 니트릴기, 니트로기, 아미노기, 실릴기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C2~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C1~C40의 알킬옥시기, C5~C40의 아릴옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C5~C40의 아릴기, 또는 C2~C40의 헤테로아릴기이거나; 또는 인접하는 기와 축합(fused) 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며;R 1 to R 7 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, C 2 ~ C 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, C 1 ~ alkyloxy group of C 40 of the, C 5 ~ C 40 An aryloxy group, a C 5 to C 40 arylamino group, a C 5 to C 40 diarylamino group, a C 5 to C 40 aryl group, or a C 2 to C 40 heteroaryl group; Or a group which forms a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring or a fused heteroaromatic ring with an adjacent group;
    이때 R1, R2, R3 및 R4 중에서 하나 이상은 N, O 및 S로 이루어진 군에서 선택되는 1 이상의 원소를 포함하는 C2~C40의 헤테로아릴기이며;Wherein at least one of R 1 , R 2 , R 3 and R 4 is a C 2 to C 40 heteroaryl group containing at least one element selected from the group consisting of N, O and S;
    Ar1 내지 Ar4는 서로 같거나 다르고, 각각 독립적으로 C5~C40의 아릴렌기, 또는 C2~C40의 헤테로아릴렌기이며; Ar 1 to Ar 4 are the same as or different from each other, and are each independently an arylene group of C 5 to C 40 , or a hetero arylene group of C 2 to C 40 ;
    a, b, c 및 d는 서로 같거나 다르고, 각각 독립적으로 0~3의 정수이다.a, b, c and d are the same as or different from each other, and are each independently an integer of 0 to 3;
  2. 제1항에 있어서, R1, R2, R3 및 R4 중에서 하나 이상은 하기 화학식 2의 구조식으로 이루어진 군에서 선택되는 C2~C40의 헤테로아릴기인 것이 특징인 화학식 1로 표시되는 화합물:The compound of claim 1 , wherein at least one of R 1 , R 2 , R 3, and R 4 is a C 2 to C 40 heteroaryl group selected from the group consisting of the following structural formulas: :
    [화학식 2][Formula 2]
    Figure PCTKR2010003528-appb-I000129
    Figure PCTKR2010003528-appb-I000129
    Figure PCTKR2010003528-appb-I000130
    Figure PCTKR2010003528-appb-I000130
    Figure PCTKR2010003528-appb-I000131
    Figure PCTKR2010003528-appb-I000131
    Figure PCTKR2010003528-appb-I000132
    Figure PCTKR2010003528-appb-I000132
    Figure PCTKR2010003528-appb-I000133
    Figure PCTKR2010003528-appb-I000133
    Figure PCTKR2010003528-appb-I000134
    Figure PCTKR2010003528-appb-I000134
    Figure PCTKR2010003528-appb-I000135
    Figure PCTKR2010003528-appb-I000135
  3. 제1항에 있어서, 상기 R1 내지 R7의 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, C2~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C1~C40의 알킬옥시기, C5~C40의 아릴옥시기, C5~C40의 아릴아미노기, C5~C40의 디아릴아미노기, C5~C40의 아릴기, 또는 C2~C40의 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 니트릴기, 니트로기, 아미노기, 실릴기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C1~C40의 알콕시기, C1~C40의 아미노기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C6~C40의 아릴알킬기, C5~C40의 아릴기, 또는 C5~C40의 헤테로아릴기로 치환되거나 비치환된 것이 특징인 화학식 1로 표시되는 화합물.The method of claim 1, wherein the R 1 to R 7 of C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 of the cycloalkyl group, C 2 ~ C 40 of the heterocycloalkyl group, C 6 ~ C 40 aryl group, C 1 ~ alkyloxy group of C 40 of, C 5 ~ C 40 aryloxy group, C 5 ~ C 40 aryl group, C 5 ~ C 40 diarylamino group, C 5 ~ C 40 aryl group, or C 2 ~ C 40 heteroaryl group each independently deuterium, halogen, nitrile group, nitro group, amino group, silyl group, C 1 ~ C 40 alkyl group , C 2 ~ C 40 alkenyl group, C 2 ~ C 40 of the alkynyl group, C 1 ~ C 40 alkoxy group, C 1 ~ C 40 of the amino group, C 3 ~ C 40 cycloalkyl group, C 3 ~ C 40 A compound represented by the formula (1) characterized by being unsubstituted or substituted with a heterocycloalkyl group, a C 6 to C 40 arylalkyl group, a C 5 to C 40 aryl group, or a C 5 to C 40 heteroaryl group.
  4. 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서,anode; cathode; And one or more organic material layers interposed between the anode and the cathode.
    상기 1층 이상의 유기물층 중 적어도 하나는 제1항 내지 제3항 중 어느 한 항에 따른 화학식 1로 표시되는 화합물을 포함하는 유기물층인 것이 특징인 유기 전계 발광 소자.At least one of the one or more organic material layer is an organic electroluminescent device, characterized in that the organic material layer containing a compound represented by the formula (1) according to any one of claims 1 to 3.
  5. 제4항에 있어서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 전자 수송층인 것이 특징인 유기 전계 발광 소자.The organic electroluminescent device according to claim 4, wherein the organic material layer including the compound represented by Chemical Formula 1 is an electron transport layer.
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