KR20140021294A - Novel compounds and organic light emitting device display using the same - Google Patents

Novel compounds and organic light emitting device display using the same Download PDF

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KR20140021294A
KR20140021294A KR1020120087505A KR20120087505A KR20140021294A KR 20140021294 A KR20140021294 A KR 20140021294A KR 1020120087505 A KR1020120087505 A KR 1020120087505A KR 20120087505 A KR20120087505 A KR 20120087505A KR 20140021294 A KR20140021294 A KR 20140021294A
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compound
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김신태
최진석
김용우
윤경민
이도형
노영석
이주동
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희성소재 (주)
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    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/33—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems
    • C07C309/34—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems formed by two rings
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Abstract

The present invention relates to a compound denoted by chemical formula 1, and an organic electroluminescent device containing the same.

Description

신규 화합물 및 이를 이용한 유기전계발광소자{NOVEL COMPOUNDS AND ORGANIC LIGHT EMITTING DEVICE DISPLAY USING THE SAME}New compound and organic electroluminescent device using same {NOVEL COMPOUNDS AND ORGANIC LIGHT EMITTING DEVICE DISPLAY USING THE SAME}

본 발명은 신규 화합물 및 이를 이용한 유기전계발광소자에 관한 것이다.The present invention relates to a novel compound and an organic electroluminescent device using the same.

풀칼라 유기전계발광소자의 특성이 가장 우수한 소자 구조로는 호스트에 도판트를 도핑하여 발광층을 만드는 것으로 알려져 있다. 여기서, 호스트로 이용되는 재료(이하, 호스트 재료)는 고체 상태의 용매와 에너지 전달자의 역할을 한다. 호스트 재료는 순도가 높고 진공 증착이 가능하도록 적당한 분자량을 갖는 것이 바람직하다. 또한, 호스트 재료는 유리전이온도와 열분해 온도가 높아 열적 안정성이 확보되어야 한다. 또한, 호스트 재료는 장수명화를 위해 높은 전기화학적 안정성이 요구된다. 또한, 호스트 재료는 무정형 박막을 형성하기 용이해야 하며, 인접한 다른 층의 재료들과는 접착력이 좋은 반면, 층간 이동은 하지 않아야 한다.A device structure having the best characteristics of a full color organic light emitting diode is known to form a light emitting layer by doping a dopant to a host. Here, the material (hereinafter, host material) used as a host serves as a solvent and an energy transmitter in the solid state. The host material is preferably of high purity and has a suitable molecular weight to enable vacuum deposition. In addition, the host material has a high glass transition temperature and pyrolysis temperature to ensure thermal stability. In addition, host materials require high electrochemical stability for long life. In addition, the host material should be easy to form an amorphous thin film and have good adhesion with materials of other adjacent layers, while not allowing interlayer movement.

이러한 발광층에 최근에는 형광 물질보다 인광 물질이 많이 사용되는 추세이다. 왜냐하면, 인광 물질은 단일항과 삼중항 모두를 빛으로 전환시키는 발광 메커니즘을 가지고 있기 때문이다. 인광 도펀트는 일반적으로 유기물의 중심부에 Ir, Pt, Eu와 같은 무거운 원소(heavy atom)를 포함하며 삼중항에서 단일항으로의 전자 전이확률이 높다. 하지만, 이런 도펀트는 농도 소광 현상으로 급격한 효율감소가 발생하기 때문에, 단독으로 발광층을 구성할 수는 없다. 따라서, 도펀트보다 열안정성 및 삼중항 에너지가 높은 호스트 물질과 함께 발광층을 이루게 된다. Recently, a phosphorescent material is used more than a fluorescent material in such a light emitting layer. This is because the phosphor has a light emitting mechanism that converts both single and triplet to light. Phosphorescent dopants generally contain heavy atoms such as Ir, Pt and Eu in the center of organic material and have a high probability of electron transfer from triplet to singlet. However, such a dopant does not constitute a light emitting layer alone because a sudden efficiency decrease occurs due to concentration quenching. Thus, a luminescent layer is formed together with the host material having higher thermal stability and higher triplet energy than the dopant.

한편, 인광 물질을 포함하는 유기전계발광소자의 발광 프로세스를 간단히 살펴보면, 양극으로부터 주입된 홀과 음극으로부터 주입된 전자가 발광층의 호스트 물질에서 만나게 되고, 호스트에 형성된 단일항 엑시톤은 도펀트의 단일항 또는 삼중항으로 에너지 전이가 일어나며, 삼중항 엑시톤은 도펀트의 삼중항으로 에너지 전이가 일어나게 된다. 도펀트의 단일항으로 전이된 엑시톤은 다시 도펀트의 삼중항으로 전이되기 때문에, 모든 엑시톤의 종착지는 도펀트의 삼중항 준위이다. 이렇게 형성된 엑시톤은 기저상태로 전이되며 빛을 발생한다. 이때, 도펀트로의 효율적인 에너지 전이를 위해 호스트 물질의 삼중항 에너지는 도펀트의 삼중항 에너지보다 반드시 커야 한다.On the other hand, when the light emitting process of the organic light emitting device including the phosphor is briefly examined, holes injected from the anode and electrons injected from the cathode meet in the host material of the light emitting layer, and the singlet excitons formed in the host are the singlet of the dopant or Energy transfer occurs to the triplet, and triplet excitons cause energy transfer to the triplet of the dopant. Since the excitons transferred to a single term of the dopant are again transferred to the triplet of the dopant, all the excitons are terminated at the triplet level of the dopant. The excitons thus formed are transferred to the ground state and generate light. In this case, the triplet energy of the host material must be greater than the triplet energy of the dopant for efficient energy transfer to the dopant.

이러한 목적으로, 분자내에 카바졸을 포함하는 인광물질이 최근에 개발되고 있다.For this purpose, phosphors containing carbazole in the molecule have recently been developed.

예를 들어, 대한민국 공개특허공보 제2007-0004678호에는 아래의 화학식들로 표시되는 인광성 호스트 물질이 개시되어 있다.For example, Korean Patent Publication No. 2007-0004678 discloses a phosphorescent host material represented by the following chemical formula.

Figure pat00001
Figure pat00002
Figure pat00001
Figure pat00002

또한, 대한민국 공개특허공보 제2008-0104025호에는 아래의 화학식들로 표시되는 인광성 호스트 물질이 개시되어 있다.In addition, the Republic of Korea Patent Publication No. 2008-0104025 discloses a phosphorescent host material represented by the following formula.

Figure pat00003
Figure pat00004
Figure pat00003
Figure pat00004

한편, 대한민국 공개특허공보 제2011-0013445호에는 아래의 화학식들로 표시되는 카바졸계 인광성 호스트 물질이 개시되어 있다.Meanwhile, Korean Laid-Open Patent Publication No. 2011-0013445 discloses a carbazole-based phosphorescent host material represented by the following chemical formula.

Figure pat00005
Figure pat00006
Figure pat00005
Figure pat00006

그러나, 상기 특허문헌들의 호스트 물질은 내열성이 약하여 이들을 이용하여 유기전계발광소자를 제조하는 경우 소자 수명이 짧다는 문제점이 계속되고 있다.However, the host material of the above patent documents is weak in heat resistance, and when using the organic electroluminescent device to manufacture them, the problem of short device life continues.

본 발명의 목적은 열적으로 안정하여 이를 이용하는 발광소자의 소자수명이 연장될 수 있는 신규한 화합물을 제공하는 것이다. An object of the present invention is to provide a novel compound that is thermally stable and can extend the device life of the light emitting device using the same.

본 발명의 다른 목적은 이용한 구동 전압을 낮추고, 발광효율, 휘도, 열적 안정성 및 소자 수명이 향상되는, 상기 화합물을 이용한 유기전계발광소자를 제공하는 것이다.Another object of the present invention is to provide an organic electroluminescent device using the compound, which lowers the driving voltage used and improves luminous efficiency, brightness, thermal stability and device life.

본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by the following formula (1): < EMI ID =

<화학식 1>&Lt; Formula 1 >

Figure pat00007
Figure pat00007

상기 화학식 1에서,In Formula 1,

X1 내지 X3는 서로 같거나 다를 수 있으며, 각각 독립적으로 CH 또는 N이고,X 1 to X 3 may be the same as or different from each other, and each independently CH or N,

R1, R2, A1 내지 A4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이고,R 1 , R 2 , A 1 to A 4 may be the same as or different from each other, and each independently hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryl; Substituted or unsubstituted (C5-C60) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C3-C60) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60) alkylsilyl; Substituted or unsubstituted di (C1-C60) alkyl (C6-C60) arylsilyl; Substituted or unsubstituted tri (C6-C60) arylsilyl; Substituted or unsubstituted (C7-C60) bicycloalkyl; Substituted or unsubstituted (C2-C60) alkenyl; Substituted or unsubstituted (C2-C60) alkynyl; Substituted or unsubstituted (C1-C60) alkoxy; Substituted or unsubstituted (C1-C60) alkylamino; Substituted or unsubstituted (C6-C60) arylamino; Substituted or unsubstituted (C6-C60) ar (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryloxy; Substituted or unsubstituted (C6-C60) arylthio; Substituted or unsubstituted (C1-C60) alkylthio; Substituted or unsubstituted (C1-C60) alkoxycarbonyl; Substituted or unsubstituted (C1-C60) alkylcarbonyl; Or (C6-C60) arylcarbonyl,

단, 상기 A1 내지 A4가 모두 수소인 경우는 제외하고,Except that A 1 to A 4 are all hydrogen,

상기 R1, R2, A1 내지 A4는 인접 원소와 융합고리를 포함 또는 미포함하는 치환 또는 비치환된 (C3-C60)알킬렌 또는 (C3-C60)알케닐렌으로 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있다.The R 1 , R 2 , A 1 to A 4 is an alicyclic ring connected to a substituted or unsubstituted (C3-C60) alkylene or (C3-C60) alkenylene containing or not containing a fused ring with an adjacent element, Monocyclic or polycyclic aromatic rings can be formed.

또한, 본 발명은 제 1 전극; 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층; 및 제 2 전극을 포함하는 것을 특징으로 하는 유기전계발광소자를 제공한다.In addition, the present invention is a first electrode; An organic material layer including a compound represented by Chemical Formula 1; And it provides an organic electroluminescent device comprising a second electrode.

본 발명의 화합물은 도펀트보다 큰 삼중항 에너지를 갖는 녹색 인광 호스트 물질로 이용될 수 있다. 본 발명의 화합물을 유기전계발광소자에 적용하면, 구동 전압이 낮아지고, 발광효율, 휘도, 열적 안정성 및 소자 수명이 향상된다.The compounds of the present invention can be used as green phosphorescent host materials with triplet energy greater than dopants. When the compound of the present invention is applied to an organic light emitting device, the driving voltage is lowered, and the luminous efficiency, brightness, thermal stability and device life are improved.

이하에서, 본 발명의 상세한 이해를 위하여 본 발명의 대표 화합물을 예를 들어 본 발명에 따른 화합물, 이의 제조방법 및 유기전계발광소자를 설명하나, 이는 단지 그 실시 양태를 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, for the detailed understanding of the present invention, for example, a compound according to the present invention, a method for preparing the same, and an organic light emitting display device according to the present invention will be described. It does not limit the scope of the invention.

Ⅰ. 화합물Ⅰ. compound

본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).

<화학식 1>&Lt; Formula 1 >

Figure pat00008

Figure pat00008

상기 화학식 1에서,In Formula 1,

X1 내지 X3는 서로 같거나 다를 수 있으며, 각각 독립적으로, CH 또는 N이고, X 1 to X 3 may be the same as or different from each other, and each independently, CH or N,

R1, R2, A1 내지 A4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이고,R 1 , R 2 , A 1 to A 4 may be the same as or different from each other, and each independently hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryl; Substituted or unsubstituted (C5-C60) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C3-C60) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60) alkylsilyl; Substituted or unsubstituted di (C1-C60) alkyl (C6-C60) arylsilyl; Substituted or unsubstituted tri (C6-C60) arylsilyl; Substituted or unsubstituted (C7-C60) bicycloalkyl; Substituted or unsubstituted (C2-C60) alkenyl; Substituted or unsubstituted (C2-C60) alkynyl; Substituted or unsubstituted (C1-C60) alkoxy; Substituted or unsubstituted (C1-C60) alkylamino; Substituted or unsubstituted (C6-C60) arylamino; Substituted or unsubstituted (C6-C60) ar (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryloxy; Substituted or unsubstituted (C6-C60) arylthio; Substituted or unsubstituted (C1-C60) alkylthio; Substituted or unsubstituted (C1-C60) alkoxycarbonyl; Substituted or unsubstituted (C1-C60) alkylcarbonyl; Or (C6-C60) arylcarbonyl,

단, 상기 A1 내지 A4가 모두 수소인 경우는 제외하고,Except that A 1 to A 4 are all hydrogen,

상기 R1, R2, A1 내지 A4는 인접 원소와 융합고리를 포함 또는 미포함하는 치환 또는 비치환된 (C3-C60)알킬렌 또는 (C3-C60)알케닐렌으로 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있다.
The R 1 , R 2 , A 1 to A 4 is an alicyclic ring connected to a substituted or unsubstituted (C3-C60) alkylene or (C3-C60) alkenylene containing or not containing a fused ring with an adjacent element, Monocyclic or polycyclic aromatic rings can be formed.

바람직하게는, 상기 R1, R2, Ar1 내지 Ar4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 수소, 치환 또는 비치환된 (C1-C60)알킬기, 치환 또는 비치환된 (C1-C60)아릴기, 치환 또는 비치환된 (C5-C60)헤테로아릴기, 치환 또는 비치환된 (C1-C60)알킬아미노, 치환 또는 비치환된 (C6-C60)아릴아미노,

Figure pat00009
,
Figure pat00010
,
Figure pat00011
,
Figure pat00012
,
Figure pat00013
,
Figure pat00014
,
Figure pat00015
또는
Figure pat00016
이고,Preferably, R 1 , R 2 , Ar 1 To Ar 4 may be the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted (C1-C60) alkyl group, a substituted or unsubstituted (C1- C60) aryl group, substituted or unsubstituted (C5-C60) heteroaryl group, substituted or unsubstituted (C1-C60) alkylamino, substituted or unsubstituted (C6-C60) arylamino,
Figure pat00009
,
Figure pat00010
,
Figure pat00011
,
Figure pat00012
,
Figure pat00013
,
Figure pat00014
,
Figure pat00015
or
Figure pat00016
ego,

상기 X4 내지 X12은 서로 같거나 다를 수 있으며, 각각 독립적으로 화학결합, 치환 또는 비치환된 CH, CH2, N, NH, O, S 또는 Si이고,X 4 to X 12 may be the same as or different from each other, and each independently a chemical bond, a substituted or unsubstituted CH, CH 2 , N, NH, O, S or Si,

R4 내지 R7은 서로 같거나 다를 수 있고, 각각 독립적으로 수소, (C1-C60)알킬기, (C1-C60)알콕시기 또는 (C6-C60)아릴기이고, R 4 to R 7 may be the same as or different from each other, and each independently hydrogen, a (C1-C60) alkyl group, a (C1-C60) alkoxy group or a (C6-C60) aryl group,

상기 R4 내지 R7은 각각 독립적으로 인접 원소와 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있다.R 4 to R 7 may be independently connected to adjacent elements to form an alicyclic ring, a monocyclic ring, or a polycyclic aromatic ring.

그리고, 상기 치환 또는 비치환된 (C1-C60)아릴기는 하기 구조 중에서 선택될 수 있다: The substituted or unsubstituted (C1-C60) aryl group may be selected from the following structures:

Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023

Figure pat00017
,
Figure pat00018
,
Figure pat00019
,
Figure pat00020
,
Figure pat00021
,
Figure pat00022
,
Figure pat00023

여기서, 상기 R1, R2, A1 내지 A4는 인접 원소와 융합고리를 포함 또는 미포함하는 치환 또는 비치환된 (C3-C60)알킬렌 또는 (C3-C60)알케닐렌으로 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 경우, 1~10개의 고리를 갖는 고리형, 융합 고리형 또는 이들의 혼합형태인 (C3-C60)의 지방족 또는 방향족 고리형 치환체일 수 있으며,Wherein R 1 , R 2 , A 1 to A 4 are alicyclic by being substituted or substituted with (C3-C60) alkylene or (C3-C60) alkenylene with or without adjacent elements and fused rings When forming a ring, monocyclic or polycyclic aromatic ring, it may be an aliphatic or aromatic cyclic substituent of (C3-C60) having a cyclic, fused or mixed form having 1 to 10 rings,

이때, 상기 고리형 치환체는 N, O, S 및 Si로 이루어진 군으로부터 선택되는 이종원소를 고리 내에 하나 이상 포함하는 헤테로형 고리 치환체일 수 있다. In this case, the cyclic substituent may be a heterocyclic ring substituent containing one or more heteroatoms selected from the group consisting of N, O, S and Si in the ring.

상기 고리형 또는 융합 고리형의 치환체로는, 예를 들어, 사이클로펜타디엔, 벤젠, 바이페닐, 터페닐(o-, m- 및 p-형 포함), 나프탈렌, 아세나프탈렌, 안트라센, 디히드로안트라센, 페난트렌, 테트라센, 파이렌, 크리센, 펜타센, 인덴, 플루오렌, 플르오란텐, 트리페닐렌 등으로부터 유도되는 치환체 일 수 있으며, 이에 한정되는 것은 아니다. Examples of the cyclic or fused cyclic substituents include cyclopentadiene, benzene, biphenyl, terphenyl (including o-, m- and p-forms), naphthalene, acenaphthalene, anthracene and dihydroanthracene. , May be a substituent derived from phenanthrene, tetracene, pyrene, chrysene, pentacene, indene, fluorene, fluoranthene, triphenylene and the like, but is not limited thereto.

한편, 이종원소를 하나 이상 포함하는 고리형 또는 융합고리형 치환체로는, 예를 들어, 피롤, 퓨란, 티오펜, 피리딘, 피리미딘, 피리다졸, 피란, 이미다졸, 피라졸, 티아졸, 티아디아졸, 이소티아졸, 옥사졸릴, 이소옥사졸, 옥사디아졸, 트리아진, 테트라진, 트리아졸, 테트르졸릴, 퓨라잔, 피라진, 피리다진 등의 단일고리형; 인돌, 이소인돌, 인다졸, 벤조퓨란, 이소벤조퓨란, 벤조티오펜, 벤즈이미다졸, 벤조티아졸, 벤즈이소옥사졸, 퀴놀린, 이소퀴놀린, 벤즈옥사졸, 퀴나졸리닐, 퀴놀리진 등의 2환 고리형; 또는 카바졸, 디벤조퓨란, 디벤조티오펜, 페난트리딘 등의 3환 고리형으로부터 유도되는 치환체일 수 있으며, 이에 한정되는 것은 아니다.On the other hand, as a cyclic or fused ring substituent containing one or more hetero elements, for example, pyrrole, furan, thiophene, pyridine, pyrimidine, pyridazole, pyran, imidazole, pyrazole, thiazole, thia Monocyclics such as diazole, isothiazole, oxazolyl, isoxazole, oxadiazole, triazine, tetrazine, triazole, tetrzolyl, furazane, pyrazine, pyridazine and the like; 2, such as indole, isoindole, indazole, benzofuran, isobenzofuran, benzothiophene, benzimidazole, benzothiazole, benzisoxazole, quinoline, isoquinoline, benzoxazole, quinazolinyl, quinolyzine Cyclic cyclic; Or a substituent derived from a tricyclic ring such as carbazole, dibenzofuran, dibenzothiophene, phenanthridine, etc., but is not limited thereto.

상기 예시된 고리형 또는 융합고리형의 치환체는 그 골격을 이루는 이중결합 중 일부가 단일결합으로 환원된 것일 수 있다.Substituents of the cyclic or fused ring type exemplified above may be a part of the double bonds constituting the skeleton is reduced to a single bond.

상기 고리형 또는 융합고리형 치환체들은 임의의 탄소, 질소 위치에서 수소라디칼이 제거되어, 그 위치에 치환될 수 있다. The cyclic or fused ring substituents may be substituted at the position by removing the hydrogen radical at any carbon, nitrogen position.

상기 고리형 또는 융합고리형 체환체들은 치환체 전체 내에 존재하는 고리의 수가 10개인 범위 내에서, 보다 바람직하게는 6개인 범위 내에서 상호 조합된 형태일 수 있다.The cyclic or fused ring substituents may be in a form that is combined with each other within the range of 10, more preferably within the range of 6 rings present in the substituent.

상기 고리형 또는 융합고리형 치환체이나 그 조합형태의 치환체는 고리 밖의 치환체를 추가로 가질 수 있다. 상기 고리 밖 치환체는 할로, 시아노, 직쇄상 또는 분지상의 (C1-C10)알킬, 직쇄상 또는 분지상의 (C1-C10)할로알킬, 또는 직쇄상 또는 분지상의 (C1-C10)알콕시 치환체가 바람직하며, 이에 한정되는 것은 아니다. 고리형 또는 융합고리형 화합물이나 그 조합형태의 화합물들은 자신의 고리를 이루는 탄소나 질소와 결합된 임의의 위치의 수소를 대신하여 상기 치환체들과 결합할 수 있다. 그리고, 상기 고리 화합물은 치환 가능한 임의의 위치에서 할로, 시아노, 직쇄상 또는 분지상의 (C1-C10) 알킬, 직쇄상 또는 분지상의 (C1-C10) 할로알킬 및 직쇄상 또는 분지상의 (C1-C10) 알콕시로 구성된 군으로부터 선택되는 하나 이상의 치환체를 고리 밖 치환체로 가질 수 있다.The cyclic or fused ring substituent or a combination thereof may further have a substituent outside the ring. The out-of-ring substituents may be halo, cyano, straight or branched (C 1 -C 10) alkyl, straight or branched (C 1 -C 10) haloalkyl, or straight or branched (C 1 -C 10) alkoxy. Substituents are preferred and are not limited thereto. Cyclic or fused ring compounds or compounds in combination thereof may be bonded to the substituents in place of hydrogen at any position bonded to carbon or nitrogen constituting the ring. And the cyclic compound is halo, cyano, linear or branched (C 1 -C 10) alkyl, linear or branched (C 1 -C 10) haloalkyl and linear or branched at any position that may be substituted It may have one or more substituents selected from the group consisting of (C1-C10) alkoxy as out-of-ring substituents.

상기 화학식 1로 표시되는 화합물의 보다 구체적인 예는 하기와 같을 수 있으며, 이에 한정되는 것은 아니다.
More specific examples of the compound represented by Formula 1 may be as follows, but is not limited thereto.

Figure pat00024
Figure pat00024

Figure pat00025
Figure pat00025

Figure pat00026
Figure pat00027
Figure pat00026
Figure pat00027

Figure pat00028
Figure pat00028

Figure pat00029
Figure pat00029

Figure pat00030
Figure pat00030

Figure pat00031
Figure pat00031

Figure pat00032
Figure pat00032

Figure pat00033
Figure pat00033

Figure pat00034
Figure pat00034

Figure pat00035
Figure pat00035

Figure pat00036
Figure pat00036

Figure pat00037
Figure pat00037

Figure pat00038
Figure pat00038

Figure pat00039
Figure pat00039

Figure pat00040
Figure pat00040

Figure pat00041
Figure pat00041

Figure pat00042
Figure pat00042

Figure pat00043
Figure pat00043

Figure pat00044
Figure pat00044

Figure pat00045
Figure pat00045

Figure pat00046
Figure pat00046

Figure pat00047
Figure pat00047

Figure pat00048
Figure pat00048

Figure pat00049
Figure pat00050
Figure pat00049
Figure pat00050

Figure pat00051
Figure pat00051

Figure pat00052
Figure pat00052

Figure pat00053
Figure pat00053

Figure pat00054
Figure pat00054

Figure pat00055
Figure pat00055

Figure pat00056
Figure pat00056

Figure pat00057
Figure pat00057

Figure pat00058
Figure pat00058

Figure pat00059
Figure pat00060
Figure pat00059
Figure pat00060

Figure pat00061
Figure pat00061

Figure pat00062
Figure pat00062

Figure pat00063
Figure pat00063

Figure pat00064
Figure pat00065
Figure pat00064
Figure pat00065

Figure pat00066
Figure pat00066

Figure pat00067
Figure pat00067

Figure pat00068
Figure pat00068

Figure pat00069
Figure pat00070
Figure pat00069
Figure pat00070

Figure pat00071
Figure pat00071

Figure pat00072
Figure pat00072

Figure pat00073
Figure pat00073

Figure pat00074
Figure pat00074

Figure pat00075
Figure pat00075

Figure pat00076
Figure pat00076

Figure pat00077
Figure pat00077

Figure pat00078
Figure pat00078

Figure pat00079
Figure pat00079

Figure pat00080
Figure pat00080

Figure pat00081
Figure pat00081

Figure pat00082
Figure pat00082

Figure pat00083
Figure pat00083

Figure pat00084
Figure pat00084

Figure pat00085
Figure pat00085

Figure pat00086
Figure pat00086

Figure pat00087
Figure pat00087

Figure pat00088
Figure pat00088

Figure pat00089
Figure pat00090
Figure pat00089
Figure pat00090

Figure pat00091
Figure pat00091

Figure pat00092
Figure pat00093
Figure pat00092
Figure pat00093

Figure pat00094
Figure pat00094

Figure pat00095
Figure pat00095

Figure pat00096
Figure pat00096

Figure pat00097
Figure pat00097

Figure pat00098
Figure pat00098

Figure pat00099
Figure pat00099

Figure pat00100
Figure pat00100

Figure pat00101
Figure pat00101

Figure pat00102
Figure pat00102

Figure pat00103
Figure pat00103

Figure pat00104
Figure pat00104

Figure pat00105
Figure pat00105

Figure pat00106
Figure pat00106

Figure pat00107
Figure pat00107

Figure pat00108
Figure pat00108

Figure pat00109
Figure pat00109

Figure pat00110
Figure pat00110

Figure pat00111
Figure pat00111

Figure pat00112
Figure pat00112

Figure pat00113
Figure pat00113

Figure pat00114
Figure pat00114

Figure pat00115
Figure pat00115

Figure pat00116
Figure pat00116

Figure pat00117
Figure pat00117

Figure pat00118
Figure pat00118

Figure pat00119
Figure pat00119

Figure pat00120
Figure pat00120

Figure pat00121
Figure pat00121

Figure pat00122
Figure pat00122

Figure pat00123

Figure pat00123

본 발명의 화합물은 도펀트보다 큰 삼중항 에너지를 갖는 녹색 인광 호스트 물질로 이용될 수 있다. 본 발명의 화합물을 유기전계발광소자에 적용하면, 구동 전압이 낮아지고, 발광효율, 휘도, 열적 안정성 및 소자 수명이 향상된다.
The compounds of the present invention can be used as green phosphorescent host materials with triplet energy greater than dopants. When the compound of the present invention is applied to an organic light emitting device, the driving voltage is lowered, and the luminous efficiency, brightness, thermal stability and device life are improved.

Ⅱ. Ⅱ. 유기전계발광소자Organic electroluminescent device

본 발명의 유기전계발광소자는 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고, 상기 화학식 1로 표시되는 화합물을 포함하는 유기막을 포함한다. The organic light emitting display device of the present invention comprises: a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including the compound represented by Chemical Formula 1.

상기 청구항 1로 표시되는 화합물은 발광층에 포함되는 녹색 인광 호스트 물질인 것이 바람직하다.The compound represented by claim 1 is preferably a green phosphorescent host material included in the emission layer.

상기 유기물층은 아릴아민계 화합물, 스티릴아릴아민계 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 1종을 더 포함할 수 있다.The organic layer may further include one selected from the group consisting of arylamine-based compounds, styrylarylamine-based compounds, and mixtures thereof.

상기 유기물층은 1족, 2족, 4주기, 5주기 전이금속, 란탄계열 금속 및 d-전이원소의 유기금속으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 더 포함할 수 있다.The organic material layer may further include one or two or more selected from the group consisting of group 1, group 2, 4 cycles, 5 cycle transition metals, lanthanide-based metals and organic metals of d-transition elements.

상기 유기전계발광소자는 필요에 따라, 정공주입층, 정공수송층, 전자저지층, 정공저지층, 전자수송층 및 전자주입층 중 하나 이상의 층을 더 구비할 수 있고, 필요에 따라서는 상기 유기층들을 2층의 유기층으로 형성하는 것도 가능하다.The organic light emitting device may further include one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer and an electron injection layer, if necessary, the organic layers 2 It is also possible to form the organic layer of a layer.

예를 들어, 본 발명을 따르는 유기전계발광소자는 제 1 전극/정공주입층/발광층/제 2 전극, 제 1 전극/정공주입층/정공수송층/발광층/전자수송층/제 2 전극 또는 제 1 전극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/제 2 전극 구조를 가질 수 있다. 또는 상기 유기전계발광소자는 제 1 전극/정공주입 기능 및 정공수송 기능을 동시에 갖는 단일막/발광층/전자수송층/제 2 전극 또는 제 1 전극/정공주입 기능 및 정공 수송 기능을 동시에 갖는 단일막/발광층/전자수송층/전자주입층/제 2 전극 구조를 가질 수 있다.For example, the organic light emitting display device according to the present invention may include a first electrode / hole injection layer / light emitting layer / second electrode, first electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / second electrode or first electrode. It may have a hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode structure. Alternatively, the organic light emitting display device may have a single film / light emitting layer / electron transport layer / second electrode or a first electrode / hole injection function and a hole transport function and a single film / having a hole transport function. It may have a light emitting layer / electron transport layer / electron injection layer / second electrode structure.

본 발명에 따르는 유기전계발광소자는 전면 발광형, 배면 발광형 등 다양한 구조로 적용 가능하다.The organic light emitting display device according to the present invention can be applied in various structures such as a top emission type and a bottom emission type.

본 발명에 따르는 유기전계발광소자의 제조방법을, 제1전극/정공주입층/정공수송층/전자수송층/정자수송층/제2전극의 구조를 갖는 유기전계발광소자를 예로 하여, 이하에 설명한다.A method of manufacturing an organic light emitting display device according to the present invention will be described below using an organic light emitting display device having a structure of a first electrode / hole injection layer / hole transport layer / electron transport layer / sperm transport layer / second electrode as an example.

먼저, 기판 상부에 높은 일함수를 갖는 제 1 전극용 물질을 증착법 또는 스퍼터링법 등에 의해 형성하여 제 1 전극을 형성한다. 상기 제 1 전극은 애노드(Anode) 또는 캐소드(cathode)일 수 있다. 여기에서 기판으로는 통상적인 유기전계발광소자에서 사용되는 기판을 사용하는데 기계적 강도, 열적 안정성, 투명성, 표면 평활성, 취급용이성 및 방수성이 우수한 유리 기판 또는 투명 플라스틱 기판이 바람직하다. 제 1 전극용 물질로는 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO), Al, Ag, Mg 등을 이용할 수 있으며, 투명 전극 또는 반사 전극으로 형성될 수 있다.First, a first electrode material having a high work function on the substrate is formed by a deposition method, a sputtering method, or the like to form a first electrode. The first electrode may be an anode or a cathode. Herein, a substrate used in a conventional organic electroluminescent device is used, but a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the first electrode material, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), Al, Ag, Mg and the like having excellent conductivity may be used. Or a reflective electrode.

다음으로, 상기 제 1 전극 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 정공주입층(HIL)을 형성할 수 있다.Next, a hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

진공증착법에 의하여 정공주입층을 형성하는 경우, 그 증착 조건은 정공주입층의 재료로서 사용하는 화합물, 목적으로 하는 정공주입층의 구조 및 열적 특성 등에 따라 다르지만, 일반적으로 증착온도 100 내지 500℃, 진공도 10-8 내지 10-3torr, 증착속도 0.01 내지 100Å/sec, 막 두께는 통상 10Å 내지 5㎛ 범위에서 적절히 선택하는 것이 바람직하다.In the case of forming the hole injection layer by vacuum deposition, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the hole injection layer, and the like. It is preferable that a vacuum degree of 10 -8 to 10 -3 torr, a deposition rate of 0.01 to 100 mW / sec, and a film thickness are usually appropriately selected in the range of 10 mV to 5 m.

스핀코팅법에 의하여 정공주입층을 형성하는 경우, 그 코팅 조건은 정공주입층의 재료로서 사용하는 화합물, 목적하는 하는 정공주입층의 구조 및 열적 특성에 따라 상이하지만, 약 2000 내지 5000rpm의 코팅 속도, 코팅 후 용매 제거를 위한 열처리 온도는 약 80 내지 200℃의 온도 범위에서 적절히 선택하는 것이 바람직하다.In the case of forming the hole injection layer by spin coating, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal characteristics of the desired hole injection layer, but the coating speed is about 2000 to 5000 rpm. , The heat treatment temperature for removing the solvent after coating is preferably selected in the temperature range of about 80 to 200 ℃.

상기 정공주입층 물질로는 공지된 정공주입층 물질을 사용할 수도 있는데, 예를 들면, 미국특허 제4,356,429호에 개시된 구리프탈로시아닌 등의 프탈로시아닌 화합물 또는 Advanced Material, 6, p.677(1994)에 기재되어 있는 스타버스트형 아민 유도체류인 TCTA, m-MTDATA, m-MTDAPB, 용해성이 있는 전도성 고분자인 Pani/DBSA (Polyaniline/Dodecylbenzenesulfonic acid: 폴리아닐린/도데실벤젠술폰산) 또는 PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate):폴리(3,4-에틸렌디옥시티오펜)/폴리(4-스티렌술포네이트)), Pani/CSA (Polyaniline/Camphor sulfonic acid:폴리아닐린/캠퍼술폰산) 또는 PANI/PSS (Polyaniline)/Poly (4-styrene-sulfonate):폴리아닐린)/폴리(4-스티렌술포네이트)) 등을 사용할 수 있다.As the hole injection layer material, a well-known hole injection layer material may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429, or described in Advanced Material, 6, p.677 (1994). Starburst amine derivatives TCTA, m-MTDATA, m-MTDAPB, polyaniline / dodecylbenzenesulfonic acid (polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4) -ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA (Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid) or PANI / PSS (Polyaniline) / Poly (4-styrene-sulfonate): polyaniline) / poly (4-styrenesulfonate)) and the like can be used.

상기 정공주입층의 두께는 약 100 내지 10,000Å 바람직하게는 100 내지 1,000Å일 수 있다. 상기 정공주입층의 두께가 100Å 미만인 경우, 정공주입 특성이 저하될 수 있으며, 상기 정공주입층의 두께가 10,000Å을 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The hole injection layer may have a thickness of about 100 to 10,000 kPa, preferably 100 to 1,000 kPa. This is because when the thickness of the hole injection layer is less than 100 kV, the hole injection characteristic may be reduced, and when the thickness of the hole injection layer exceeds 10,000 kW, the driving voltage may increase.

다음으로 상기 정공주입층 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 정공수송층(HTL)을 형성할 수 있다. 진공증착법 및 스핀팅법에 의하여 정공수송층을 형성하는 경우, 그 증착조건 및 코팅조건은 사용하는 화합물에 따라 다르지만, 일반적으로 정공주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.Next, a hole transport layer (HTL) may be formed on the hole injection layer by various methods such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

상기 정공수송층 물질은 공지된 정공수송층 물질을 이용할 수도 있는데, 예를 들면, N-페닐카바졸, 폴리비닐카바졸 등의 카바졸 유도체, 4,4'-비스[N-(1-나프틸)-N-페닐아미노]비페닐(NPB), N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1-비페닐]-4,4'-디아민(TPD), N,N'-디(나프탈렌-1-일)-N,N'-디페닐 벤지딘(α-NPD) 등의 방향족 축합환을 가지는 통상적인 아민 유도체 등이 사용된 주입층의 형성과 거의 동일한 조건범위 중에서 선택된다.The hole transport layer material may be a known hole transport layer material, for example, carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine (TPD) And the formation of an injection layer in which a conventional amine derivative having an aromatic condensed ring such as N, N'-di (naphthalen-1-yl) -N, N'-diphenyl benzidine (α-NPD), or the like is used. It is selected from the condition range.

다음으로, 상기 정공수송층 상에 발광층으로서 본 발명의 화합물들을 포함하는 유기막을 형성한다. 상기 유기막은 형성은 통상적으로 진공증착법에 의하여 수행된다. 이때, 상기 유기막은 본 발명의 화합물을 호스트로 하고, 공지의 도펀트를 함께 증착함으로써 형성되는 호스트-도펀트 시스템의 발광층일 수 있다. 본 발명의 화합물을 호스트 물질로 하여 조합될 수 있는 도펀트의 대표적인 예로서는 이리듐-트리스(2-페닐피리딘)(Iridium-tris(2-phenylpyidine: Ir(ppy)3)가 있으며, 이에 한정되는 것은 아니다. 증착되는 발광층의 두께는 100 내지 1,000Å의 범위 내에서 조절될 수 있다.Next, an organic film including the compounds of the present invention as a light emitting layer is formed on the hole transport layer. Formation of the organic film is usually carried out by a vacuum deposition method. In this case, the organic layer may be a light emitting layer of a host-dopant system formed by using a compound of the present invention as a host and depositing a known dopant together. Representative examples of dopants that may be combined using the compound of the present invention as a host material include iridium-tris (2-phenylpyidine: Ir (ppy) 3 ), but are not limited thereto. The thickness of the light emitting layer to be deposited may be adjusted within the range of 100 to 1,000Å.

상기 제 1 전극 상부에 진공증착법, 스핀코팅법, 캐스트법, LB법 등과 같은 다양한 방법을 이용하여 전자수송층 및 전자주입층을 형성할 수 있다. An electron transport layer and an electron injection layer may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

전자수송층 역시 공지의 물질을 사용할 수 있다. 당업계 공지의 전자 수송층 물질로서는, 예를 들어, Balq, Alq, Liq 등이 있으나, 이에 한정되는 것은 아니다. 상기 전자수송층의 두께는 통상적으로 10 내지 500Å이며, 그 두께는 조절될 수 있다 The electron transport layer may also use a known material. Examples of electron transport layer materials known in the art include, but are not limited to, Balq, Alq, Liq, and the like. The thickness of the electron transport layer is typically 10 to 500Å, the thickness can be adjusted.

전자주입층의 재료로는 예를 들어, LiF가 당업계 대표적으로 사용되나, 본 발명이 이에 한정되는 것은 아니다.As the material of the electron injection layer, for example, LiF is representatively used in the art, but the present invention is not limited thereto.

상기 전자주입층의 두께는 약 1 내지 100Å 바람직하게는 5 내지 90Å일 수 있다. 상기 전자주입층의 두께가 1Å 미만인 경우, 전자주입 특성이 저하될 수 있으며, 상기 전자주입층의 두께가 100Å을 초과하는 경우, 구동전압이 상승할 수 있기 때문이다.The electron injection layer may have a thickness of about 1 to 100 kPa, preferably 5 to 90 kPa. This is because, when the thickness of the electron injection layer is less than 1 kV, the electron injection characteristic may be degraded, and when the thickness of the electron injection layer exceeds 100 kW, the driving voltage may increase.

마지막으로 전자주입층 상부에 진공증착법이나 스퍼터링법 등의 방법을 이용하여 제 2 전극을 형성할 수 있다. 상기 제 2 전극은 캐소드 또는 애노드로 사용될 수 있다. 상기 제 2 전극 형성용 물질로는 낮은 일함수를 가지는 금속, 합금, 전기전도성 화합물 및 이들의 혼합물을 사용할 수 있다. 구체적인 예로서는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등을 들 수 있다. 또한, 전면 발광 장치를 얻기 위하여 ITO, IZO를 사용한 투명 캐소드를 사용할 수도 있다.Finally, the second electrode may be formed on the electron injection layer by using a method such as vacuum deposition or sputtering. The second electrode may be used as a cathode or an anode. As the material for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, or a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . In addition, a transparent cathode using ITO and IZO may be used to obtain a top light emitting device.

본 발명을 따르는 유기전계발광소자는 다양한 형태의 평판표시장치, 예를 들면 수동 매트릭스 유기발광표시장치 및 능동 매트릭스 유기발광표시장치에 구비될 수 있다. 특히, 능동 매트릭스 유기발광표시장치에 구비되는 경우, 기판 측에 구비된 제 1 전극은 화소 전극으로서 박막 트랜지스터의 소스 전극 또는 드레인 전극과 전기적으로 연결될 수 있다. 또한, 상기 유기전계발광소자는 양면으로 화면을 표시할 수 있는 평판 표시 장치에 구비될 수 있다.
The organic light emitting display device according to the present invention may be provided in various types of flat panel display devices, for example, passive matrix organic light emitting display devices and active matrix organic light emitting display devices. In particular, when provided in the active matrix organic light emitting display device, the first electrode provided on the substrate side may be electrically connected to the source electrode or the drain electrode of the thin film transistor as the pixel electrode. In addition, the organic light emitting display device may be provided in a flat panel display that can display a screen on both sides.

본 발명의 화합물을 유기전계발광소자에 적용하면, 구동 전압이 낮아지고, 발광효율, 휘도, 열적 안정성 및 소자 수명이 향상된다.
When the compound of the present invention is applied to an organic light emitting device, the driving voltage is lowered, and the luminous efficiency, brightness, thermal stability and device life are improved.

Ⅲ. 유기태양전지Ⅲ. Organic solar cell

본 발명의 유기태양 전지는 상기 화학식 1로 표시되는 화합물 유기태양 전지를 포함한다. 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 공지의 유기태양 전지와 동일한 구조를 갖는다.
The organic solar cell of the present invention includes a compound organic solar cell represented by Chemical Formula 1. Except for including the compound represented by the formula (1) has the same structure as a known organic solar cell.

이하에서, 본 발명의 화학식 1로 표시되는 화합물의 합성예 및 실시예를 구체적으로 예시하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.
Hereinafter, the synthesis examples and examples of the compound represented by the formula (1) of the present invention will be specifically illustrated, but the present invention is not limited to the following examples.

<실시예><Examples>

합성예Synthetic example 1: 화합물 1의 제조 1: Preparation of compound 1

하기 화학 반응식 1의 반응 경로를 거쳐 화합물 1을 합성하였다.Compound 1 was synthesized through the reaction route of Chemical Scheme 1 below.

<반응식 1><Reaction Scheme 1>

Figure pat00124
Figure pat00124

(1) 화합물 1-1의 제조 (1) Preparation of Compound 1-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 1-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 9.7 g (30%) of the titled compound 1-1.

(2) 화합물 1-2의 제조 (2) Preparation of Compound 1-2

화합물 1-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 1-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 1-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 1-2.

(3) 화합물 1-3의 제조 (3) Preparation of Compound 1-3

화합물 1-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 1-3 57g (90%)을 얻었다.
Compound 1-2 62.6 g (178.2 mmol), 2-bromo-1-nitrobenzene 30 g (148.5 mmol), Pd (PPh 3 ) 4 17.2 g (149 mmol), And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the title compound 1-3.

(4) 화합물 1-4의 제조 (4) Preparation of Compound 1-4

화합물 1-3 (46.7m㏖), (9,9-디메틸-9H-플루오렌-2-일)보론 산((9,9-dimethyl-9H-fluoren-2-yl)boronic acid) (56.03m㏖, Pd(PPh3)4 (4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 1-4(A3:

Figure pat00125
) 19.8g (89%)을 얻었다.Compound 1-3 (46.7 mmol), (9,9-dimethyl-9H-fluoren-2-yl) boronic acid ((9,9-dimethyl-9H-fluoren-2-yl) boronic acid) (56.03m Mole, Pd (PPh 3 ) 4 (4.67 mmol), and K 2 CO 3 , (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml and stirred at 100 ° C. When the organic layer was extracted, the organic layer was extracted with distilled water and EA, and the organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator, and separated by column chromatography using dichloromethane and hexane as a solvent. A 3 :
Figure pat00125
) 19.8 g (89%).

(5) 화합물 1-5의 제조 (5) Preparation of Compound 1-5

화합물 1-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 1-5(A3:

Figure pat00126
) 11.2g (80%)을 얻었다.
Compound 1-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. When the reaction was complete then cooled to room temperature, by using a vacuum distillation apparatus to remove the 1,2-dichlorobenzene and dichloromethane and purified by column chromatography using hexane as a developing solvent our target compound 1-5 (A 3:
Figure pat00126
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 1-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 4-클로로-2,6-디페닐피리딘(4-chloro-2,6-diphenylpyridine) (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가하고 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하였다. 이에 따라, 최종 화합물로 화합물 1(A1: H, A2: H, A3:

Figure pat00127
, A4: H, X1: CH, X2: CH, X3: N, R1:
Figure pat00128
, R2:
Figure pat00129
. 이하에서는 X1, X2, X3중 하나 이상이 CH일 경우, "C"로만 표시한다)을 수득하였다.NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 1-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 4-chloro-2,6-diphenylpyridine (4-2.6-2,6-diphenylpyridine) (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed by a rotary evaporator, and dichloromethane and hexane were separated by column chromatography using a developing solvent. Accordingly, Compound 1 (A 1 : H, A 2 : H, A 3 :
Figure pat00127
, A 4 : H, X 1 : CH, X 2 : CH, X 3 : N, R 1 :
Figure pat00128
, R 2 :
Figure pat00129
. Hereinafter, when at least one of X 1 , X 2 , and X 3 is CH, only “C” is obtained).

상기 화합물 1의 NMR은 하기 표 1에 기재하였다.
NMR of the compound 1 is shown in Table 1 below.

한편, 상기 반응식 1에서 4-클로로-2,6-디페닐피리딘(4-chloro-2,6-diphenylpyridine,

Figure pat00130
)은 하기 반응식 2에 의해 합성하였다.On the other hand, 4-chloro-2,6-diphenylpyridine (4-chloro-2,6-diphenylpyridine in Scheme 1,
Figure pat00130
) Was synthesized by the following Scheme 2.

<반응식 2><Reaction Scheme 2>

Figure pat00131
Figure pat00131

2,4,6-트리클로로피리딘(2,4,6-trichloropyridine: 1.8g, 9.87m㏖)을 1,2-디메톡시에탄에 용해시킨 후, 페닐보론산(phenylboronic acid: 2.41g, 19.7m㏖)과 수용성 나트륨 카보네이트(aqueous sodium carbonate: 6.48g, 61.2 mmol)와 팔라듐 아세테이트(palladium acetate: 2.5㏖%)와 트리페닐포스핀(triphenylphosphine: 5㏖%)을 넣고 70℃에서 24시간 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물로 4-클로로-2,6-디페닐피리딘 2.31g(85%)을 수득하였다.
2,4,6-trichloropyridine (2,4,6-trichloropyridine: 1.8 g, 9.87 mmol) was dissolved in 1,2-dimethoxyethane, followed by phenylboronic acid (2.41 g, 19.7 m). Mol), water-soluble sodium carbonate (6.48 g, 61.2 mmol), palladium acetate (2.5 mol%) and triphenylphosphine (5 mol%) were added thereto, and the mixture was stirred at 70 ° C for 24 hours. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The solvent was separated using dichloromethane and hexane as a developing solvent, and then separated by column chromatography, and 2.31 g (85%) of 4-chloro-2,6-diphenylpyridine was used as the target compound. ) Was obtained.

합성예Synthetic example 2: 화합물 4의 제조 2: Preparation of Compound 4

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00132
)을 수득하였다. 그리고, 최종 화합물로 화합물 4(A1: H, A2: H, A3:
Figure pat00133
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00134
, R2:
Figure pat00135
)을 수득하였다. 상기 화합물 4의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 1 '(4) Preparation of Compound 1-4', naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene The synthesis was carried out in the same manner except for using). Thus, compound 1-4 (A 3 :
Figure pat00132
) Was obtained. In addition, Compound 4 (A 1 : H, A 2 : H, A 3 :
Figure pat00133
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00134
, R 2 :
Figure pat00135
) Was obtained. NMR of the compound 4 is shown in Table 1 below.

합성예Synthetic example 3: 화합물 5의 제조 3: Preparation of Compound 5

하기 화학 반응식 3의 반응 경로를 거쳐 화합물 5를 합성하였다.Compound 5 was synthesized through the reaction route of Chemical Scheme 3 below.

<반응식 3><Reaction Scheme 3>

Figure pat00136
Figure pat00136

(1) 화합물 2-1의 제조 (1) Preparation of Compound 2-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 2-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 9.7 g (30%) of the title compound 2-1.

(2) 화합물 2-2의 제조 (2) Preparation of Compound 2-2

화합물 2-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 2-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 2-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 2-2.

(3) 화합물 2-3의 제조 (3) Preparation of Compound 2-3

화합물 2-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 2-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 2-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 57 g (90%) of the target compound 2-3.

(4) 화합물 2-4의 제조 (4) Preparation of Compound 2-4

화합물 2-3 (46.7m㏖), (9,9-디메틸-9H-플루오렌-3-일)보론산((9,9-dimethyl-9H-fluoren-3-yl)boronic acid) (56.03m㏖, Pd(PPh3)4 (4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 2-4(A2:

Figure pat00137
) 19.8g (89%)을 얻었다.
Compound 2-3 (46.7 mmol), (9,9-dimethyl-9H-fluoren-3-yl) boronic acid ((9,9-dimethyl-9H-fluoren-3-yl) boronic acid) (56.03m Mole, Pd (PPh 3 ) 4 (4.67 mmol), and K 2 CO 3 , (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml and stirred at 100 ° C. When the organic layer was extracted, the organic layer was extracted with distilled water and EA, and the organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and dichloromethane and hexane as a developing solvent were separated by column chromatography. A 2 :
Figure pat00137
) 19.8 g (89%).

(5) 화합물 2-5의 제조 (5) Preparation of Compound 2-5

화합물 2-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 2-5(A2:

Figure pat00138
) 11.2g (80%)을 얻었다.
Compound 2-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. When the reaction was complete then cooled to room temperature, to remove the 1,2-dichlorobenzene by a vacuum distillation device, and purified by dichloromethane-hexane and the column chromatography as a developing solvent, the desired compound 2-5 (A 2:
Figure pat00138
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 2-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 4-클로로-2,6-디페닐피리딘(4-chloro-2,6-diphenylpyridine) (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 5(A1: H, A2:

Figure pat00139
, A3: H, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00140
, R2:
Figure pat00141
)을 수득하였다. 상기 화합물 5의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 2-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 4-chloro-2,6-diphenylpyridine (4-2.6-2,6-diphenylpyridine) (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated with column chromatography using dichloromethane and hexane as a developing solvent. Compound 5 (A 1 : H, A 2 :
Figure pat00139
, A 3 : H, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00140
, R 2 :
Figure pat00141
) Was obtained. NMR of the compound 5 is shown in Table 1 below.

합성예Synthetic example 4: 화합물 8의 제조 4: Preparation of Compound 8

상기 합성예 3의 합성방법 중 ‘(4) 화합물 2-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 2-4(A3:

Figure pat00142
)을 수득하였다. 그리고, 최종 화합물로 화합물 8(A1: H, A2:
Figure pat00143
, A3: H, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00144
, R2:
Figure pat00145
) 7.7g(51%)을 수득하였다. 상기 화합물 8의 NMR은 하기 표 1에 기재하였다.
In (4) Preparation of Compound 2-4, in the synthesis method of Synthesis Example 3, naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene The synthesis was carried out in the same manner except for using). Thus, compound 2-4 (A 3 :
Figure pat00142
) Was obtained. In addition, Compound 8 (A 1 : H, A 2 :
Figure pat00143
, A 3 : H, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00144
, R 2 :
Figure pat00145
7.7 g (51%) was obtained. NMR of the compound 8 is shown in Table 1 below.

합성예Synthetic example 5: 화합물 9의 제조 5: Preparation of Compound 9

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조[b]티오펜(7-bromobenzo[b]thiophene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00146
)을 수득하였다. 그리고, 최종 화합물로 화합물 9(A1: H, A2: H, A3:
Figure pat00147
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00148
, R2:
Figure pat00149
)을 수득하였다. 상기 화합물 9의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 1 '(4) Preparation of Compound 1-4', 7-bromobenzo [b] thiophene (7-) instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was performed in the same manner except that bromobenzo [b] thiophene) was used. Thus, compound 1-4 (A 3 :
Figure pat00146
) Was obtained. In addition, Compound 9 (A 1 : H, A 2 : H, A 3 :
Figure pat00147
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00148
, R 2 :
Figure pat00149
) Was obtained. NMR of the compound 9 is shown in Table 1 below.

합성예Synthetic example 6: 화합물 11의 제조 6: Preparation of Compound 11

하기 화학 반응식 4의 반응 경로를 거쳐 화합물 11를 합성하였다.Compound 11 was synthesized through the reaction route of Chemical Scheme 4 below.

<반응식 4><Reaction Scheme 4>

Figure pat00150
Figure pat00150

(1) 화합물 3-1의 제조 (1) Preparation of Compound 3-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 3-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 9.7 g (30%) of the title compound 3-1.

(2) 화합물 3-2의 제조 (2) Preparation of Compound 3-2

화합물 3-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 3-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 3-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. The organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, ethyl acetate and hexane were used as a developing solvent, and column chromatography was performed to obtain 31.3 g (89%) of the title compound 3-2.

(3) 화합물 3-3의 제조 (3) Preparation of Compound 3-3

화합물 3-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 3-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 3-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the title compound 3-3.

(4) 화합물 3-4의 제조 (4) Preparation of Compound 3-4

화합물 3-3 20g(46.7m㏖), (9,9-디메틸-9H-플루오렌-2-일)보론산 ((9,9-dimethyl-9H-fluoren-2-yl)boronic acid) (56.03m㏖, Pd(PPh3)4 5.4g(4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 3-4(A4:

Figure pat00151
) 19.8g (89%)을 얻었다.
Compound 3-3 20 g (46.7 mmol), (9,9-dimethyl-9H-fluoren-2-yl) boronic acid ((9,9-dimethyl-9H-fluoren-2-yl) boronic acid) (56.03 Mol, Pd (PPh 3 ) 4 5.4 g (4.67 mmol), and K 2 CO 3 , (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml, and then stirred at 100 ° C. After completion of the reaction, the organic layer was extracted with distilled water and EA, and the organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator, and separated by column chromatography using dichloromethane and hexane as a developing solvent. -4 (A 4 :
Figure pat00151
) 19.8 g (89%).

(5) 화합물 3-5의 제조 (5) Preparation of Compound 3-5

화합물 3-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 3-5(A3:

Figure pat00152
) 11.2g (80%)을 얻었다.
Compound 3-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, cooling to room temperature, by using a vacuum distillation apparatus to remove the 1,2-dichlorobenzene and dichloromethane and purified by a column chromatography using a developing solvent of hexane our target compound 3-5 (A 3:
Figure pat00152
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 3-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 4-클로로-2,6-디페닐피리딘(4-chloro-2,6-diphenylpyridine) (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 11(A1: H, A2: H, A3:

Figure pat00153
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00154
, R2:
Figure pat00155
)을 수득하였다. 상기 화합물 11의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, compound 3-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 4-chloro-2,6-diphenylpyridine (4-2.6-2,6-diphenylpyridine) (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was separated using dichloromethane and hexane as a developing solvent and separated by column chromatography. Compound 11 (A 1 : H, A 2 : H, A 3 :
Figure pat00153
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00154
, R 2 :
Figure pat00155
) Was obtained. NMR of the compound 11 is shown in Table 1 below.

합성예Synthetic example 7: 화합물 12의 제조 7: Preparation of Compound 12

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산 (dibenzo[b,d]thiophen-3-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A4:

Figure pat00156
)을 수득하였다. 그리고, 최종 화합물로 화합물 12(A1: H, A2: H, A3: H, A4:
Figure pat00157
, X1: C, X2: C, X3: N, R1:
Figure pat00158
, R2:
Figure pat00159
)을 수득하였다. 상기 화합물 12의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 6, In Preparation of Compound (4) (3-4), Dibenzo [b, d] thiophen-3-yl is substituted for 2-bromo-9,9-dimethyl-9H-fluorene. Synthesis was carried out in the same manner except for using benzoic acid (dibenzo [b, d] thiophen-3-ylboronic acid). Thus, compound 1-4 (A 4 :
Figure pat00156
) Was obtained. In addition, Compound 12 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00157
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00158
, R 2 :
Figure pat00159
) Was obtained. NMR of the compound 12 is shown in Table 1 below.

합성예Synthetic example 8: 화합물 14의 제조 8: Preparation of Compound 14

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A4:

Figure pat00160
)을 수득하였다. 그리고, 최종 화합물로 화합물 14(A1: H, A2: H, A3: H, A4:
Figure pat00161
, X1: C, X2: C, X3: N, R1:
Figure pat00162
, R2:
Figure pat00163
)을 수득하였다. 상기 화합물 14의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 6 '(4) Preparation of Compound 3-4', naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene The synthesis was carried out in the same manner except for using). Thus, compound 1-4 (A 4 :
Figure pat00160
) Was obtained. In addition, Compound 14 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00161
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00162
, R 2 :
Figure pat00163
) Was obtained. NMR of the compound 14 is shown in Table 1 below.

합성예Synthetic example 9: 화합물 15의 제조 9: Preparation of Compound 15

하기 화학 반응식 5의 반응 경로를 거쳐 화합물 15를 합성하였다.Compound 15 was synthesized through the reaction route of Chemical Scheme 5 below.

<반응식 5><Reaction Scheme 5>

Figure pat00164
Figure pat00164

(1) 화합물 4-1의 제조 (1) Preparation of Compound 4-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 4-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and dichloromethane and hexane were used as a developing solvent, and then separated by column chromatography to obtain 9.7 g (30%) of the title compound 4-1.

(2) 화합물 4-2의 제조 (2) Preparation of Compound 4-2

화합물 4-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 4-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 4-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 4-2.

(3) 화합물 4-3의 제조 (3) Preparation of Compound 4-3

화합물 4-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 4-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 4-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and dichloromethane and hexane were used as a developing solvent, and the resultant was separated by column chromatography to obtain 57 g (90%) of the title compound 4-3.

(4) 화합물 4-4의 제조 (4) Preparation of Compound 4-4

화합물 4-3 20g(46.7m㏖), (9,9-디메틸-9H-플루오렌-3-일)보론산 ((9,9-dimethyl-9H-fluoren-3-yl)boronic acid) (56.03m㏖, Pd(PPh3)4 5.4g(4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 4-4(A1:

Figure pat00165
) 19.8g (89%)을 얻었다.
Compound 4-3 20 g (46.7 mmol), (9,9-dimethyl-9H-fluoren-3-yl) boronic acid ((9,9-dimethyl-9H-fluoren-3-yl) boronic acid) (56.03 Mol, Pd (PPh 3 ) 4 5.4 g (4.67 mmol), and K 2 CO 3 , (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml, and then stirred at 100 ° C. After completion of the reaction, the organic layer was extracted with distilled water and EA, and the organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and dichloromethane and hexane were used as a developing solvent. -4 (A 1 :
Figure pat00165
) 19.8 g (89%).

(5) 화합물 4-5의 제조 (5) Preparation of Compound 4-5

화합물 4-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 4-5(A1:

Figure pat00166
) 11.2g (80%)을 얻었다.
Compound 4-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 1,2-dichlorobenzene was removed using a vacuum distillation apparatus. Purified by column chromatography using dichloromethane and hexane as a developing solvent, target compound 4-5 (A 1 :
Figure pat00166
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 4-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 4-클로로-2,6-디페닐피리딘(4-chloro-2,6-diphenylpyridine) (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 15(A1:

Figure pat00167
, A2: H, A3: H, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00168
, R2:
Figure pat00169
)을 수득하였다. 상기 화합물 15의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 4-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 4-chloro-2,6-diphenylpyridine (4-2.6-2,6-diphenylpyridine) (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent. Compound 15 (A 1 :
Figure pat00167
, A 2 : H, A 3 : H, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00168
, R 2 :
Figure pat00169
) Was obtained. NMR of the compound 15 is shown in Table 1 below.

합성예Synthetic example 10: 화합물 20의 제조 10: Preparation of Compound 20

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조퓨란(7-bromobenzofuran)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A4:

Figure pat00170
)을 수득하였다. 그리고, 최종 화합물로 화합물 20(A1: H, A2: H, A3: H, A4:
Figure pat00171
, X1: C, X2: C, X3: N, R1:
Figure pat00172
, R2:
Figure pat00173
)을 수득하였다. 상기 화합물 20의 NMR은 하기 표 1에 기재하였다.In Synthesis of Synthesis Example 6 '(4) Preparation of Compound 3-4', using 7-bromobenzofuran (7-bromobenzofuran) instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except that. Thus, compound 4-4 (A 4 :
Figure pat00170
) Was obtained. In addition, Compound 20 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00171
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00172
, R 2 :
Figure pat00173
) Was obtained. NMR of the compound 20 is shown in Table 1 below.

합성예Synthetic example 11: 화합물 24의 제조 11: Preparation of Compound 24

상기 합성예 9의 합성방법 중 ‘(4) 화합물 4-4의 제조’에서, 3-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠(1-chloro-4-(trifluoromethyl)benzene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A4:

Figure pat00174
)을 수득하였다. 그리고, 최종 화합물로 화합물 24(A1: H, A2: H, A3: H, A4:
Figure pat00175
, X1: C, X2: C, X3: N, R1:
Figure pat00176
, R2:
Figure pat00177
)을 수득하였다. 상기 화합물 24의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 9 in the preparation of (4) Compound 4-4, 1-chloro-4- (trifluoromethyl) benzene instead of 3-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except that (1-chloro-4- (trifluoromethyl) benzene) was used. Thus, compound 4-4 (A 4 :
Figure pat00174
) Was obtained. In addition, Compound 24 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00175
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00176
, R 2 :
Figure pat00177
) Was obtained. NMR of the compound 24 is shown in Table 1 below.

합성예Synthetic example 12: 화합물 25의 제조 12: Preparation of Compound 25

상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘(4-chloro-2,6-diphenylpyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 25(A1: H, A2: H, A3:

Figure pat00178
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00179
, R2:
Figure pat00180
)을 수득하였다. 상기 화합물 25의 NMR은 하기 표 1에 기재하였다.In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-diphenylpyrimidine (4-chloro-2, 6-diphenylpyrimidine) was synthesized in the same manner except for using. Accordingly, Compound 25 (A 1 : H, A 2 : H, A 3 :
Figure pat00178
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00179
, R 2 :
Figure pat00180
) Was obtained. NMR of the compound 25 is shown in Table 1 below.

여기서, 상기 4-클로로-2,6-디페닐피리미딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신 2,4,6-트리클로로피리미딘(2,4,6-trichloropyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.
Here, the 4-chloro-2,6-diphenylpyrimidine is 2,4,6-trichloropyridine instead of 2,4,6-trichloropyridine in the synthesis method of 4-chloro-2,6-diphenylpyridine. Synthesis was performed in the same manner except for using midine (2,4,6-trichloropyrimidine).

합성예Synthetic example 13: 화합물 26의 제조 13: Preparation of Compound 26

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산 (dibenzo[b,d]thiophen-3-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00181
)을 수득하였다. In Preparation of Compound (4) (4) in the synthesis method of Synthesis Example 1, dibenzo [b, d] thiophen-3-ylbo instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except for using benzoic acid (dibenzo [b, d] thiophen-3-ylboronic acid). Thus, compound 1-4 (A 3 :
Figure pat00181
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 26(A1: H, A2: H, A3:

Figure pat00182
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00183
, R2:
Figure pat00184
)을 수득하였다. 상기 화합물 26의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 1, '(6) Preparation of the final compound', except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine, Synthesis was carried out by the method. Accordingly, Compound 26 (A 1 : H, A 2 : H, A 3 :
Figure pat00182
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00183
, R 2 :
Figure pat00184
) Was obtained. NMR of the compound 26 is shown in Table 1 below.

합성예Synthetic example 14: 화합물 28의 제조 14: Preparation of Compound 28

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00185
)을 수득하였다. In Synthesis of Synthesis Example 1 '(4) Preparation of Compound 1-4', naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene The synthesis was carried out in the same manner except for using). Thus, compound 1-4 (A 3 :
Figure pat00185
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 28(A1: H, A2: H, A3:

Figure pat00186
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00187
, R2:
Figure pat00188
)을 수득하였다. 상기 화합물 28의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 1, '(6) Preparation of the final compound', except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine, Synthesis was carried out by the method. Accordingly, Compound 28 (A 1 : H, A 2 : H, A 3 :
Figure pat00186
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00187
, R 2 :
Figure pat00188
) Was obtained. NMR of the compound 28 is shown in Table 1 below.

합성예Synthetic example 15: 화합물 38의 제조 15: Preparation of Compound 38

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00189
)을 수득하였다.In Synthesis of Synthesis Example 6 '(4) Preparation of Compound 3-4', naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene The synthesis was carried out in the same manner except for using). Thus, compound 3-4 (A 4 :
Figure pat00189
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 6, '(6) Preparation of the final compound' was the same except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 38(A1: H, A2: H, A3: H, A4:

Figure pat00190
, X1: N, X2: C, X3: N, R1:
Figure pat00191
, R2:
Figure pat00192
)을 수득하였다. 상기 화합물 38의 NMR은 하기 표 1에 기재하였다.
Accordingly, compound 38 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00190
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00191
, R 2 :
Figure pat00192
) Was obtained. NMR of the compound 38 is shown in Table 1 below.

합성예Synthetic example 16: 화합물 39의 제조 16: Preparation of Compound 39

상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 39(A1:

Figure pat00193
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00194
, R2:
Figure pat00195
)을 수득하였다. 상기 화합물 39의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 9, '(6) Preparation of Final Compound', except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was performed. Accordingly, Compound 39 (A 1 :
Figure pat00193
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00194
, R 2 :
Figure pat00195
) Was obtained. NMR of the compound 39 is shown in Table 1 below.

합성예Synthetic example 17: 화합물 42의 제조 17: Preparation of Compound 42

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00196
)을 수득하였다.Synthesis method according to the same method as in Synthesis Example 9 except that naphthalen-2-ylboronic acid was used instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' Proceeded. Thus, compound 4-4 (A 1 :
Figure pat00196
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 9, '(6) Preparation of the final compound' was the same except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 42(A1:

Figure pat00197
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00198
, R2:
Figure pat00199
)을 수득하였다. 상기 화합물 42의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 42 (A 1 :
Figure pat00197
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00198
, R 2 :
Figure pat00199
) Was obtained. NMR of the compound 42 is shown in Table 1 below.

합성예Synthetic example 18: 화합물 45의 제조 18: Preparation of Compound 45

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠(1-chloro-4-(trifluoromethyl)benzene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00200
)을 수득하였다.1-chloro-4- (trifluoromethyl) benzene in place of 3-bromo-9,9-dimethyl-9H-fluorene in the '(4) Preparation of Compound 4-4' in the synthesis method of Synthesis Example 9 Synthesis was performed in the same manner except that 1-chloro-4- (trifluoromethyl) benzene) was used. Thus, compound 4-4 (A 1 :
Figure pat00200
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 9, '(6) Preparation of the final compound' was the same except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 45(A1:

Figure pat00201
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00202
, R2:
Figure pat00203
)을 수득하였다. 상기 화합물 45의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 45 (A 1 :
Figure pat00201
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00202
, R 2 :
Figure pat00203
) Was obtained. NMR of the compound 45 is shown in Table 1 below.

합성예Synthetic example 19: 화합물 48의 제조 19: Preparation of Compound 48

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00204
)을 수득하였다.In the synthesis method of Synthesis Example 6, 1-chloro-4- (trifluoromethyl) benzene was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Synthesis was carried out in the same manner except that used. Thus, compound 3-4 (A 4 :
Figure pat00204
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 6, '(6) Preparation of the final compound' was the same except that 4-chloro-2,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 48(A1: H, A2: H, A3: H, A4:

Figure pat00205
, X1: N, X2: C, X3: N, R1:
Figure pat00206
, R2:
Figure pat00207
)을 수득하였다. 상기 화합물 48의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 48 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00205
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00206
, R 2 :
Figure pat00207
) Was obtained. NMR of the compound 48 is shown in Table 1 below.

합성예Synthetic example 20: 화합물 59의 제조 20: Preparation of Compound 59

상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In Synthesis of Synthesis Example 6, '(6) Preparation of Final Compound', except that 2-chloro-4,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was performed.

이에 따라, 최종 화합물로 화합물 59(A1: H, A2: H, A3: H, A4:

Figure pat00208
, X1: N, X2: N, X3: C, R1:
Figure pat00209
, R2:
Figure pat00210
)을 수득하였다. 상기 화합물 59의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 59 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00208
, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00209
, R 2 :
Figure pat00210
) Was obtained. NMR of the compound 59 is shown in Table 1 below.

합성예Synthetic example 21: 화합물 66의 제조 21: Preparation of Compound 66

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00211
)을 수득하였다.Synthesis method according to the same method as in Synthesis Example 9 except that naphthalen-2-ylboronic acid was used instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' Proceeded. Thus, compound 4-4 (A 1 :
Figure pat00211
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 9, '(6) Preparation of the final compound' was the same except that 2-chloro-4,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 66(A1:

Figure pat00212
, A2: H, A3: H, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00213
, R2:
Figure pat00214
)을 수득하였다. 상기 화합물 66의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 66 (A 1 :
Figure pat00212
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00213
, R 2 :
Figure pat00214
) Was obtained. NMR of the compound 66 is shown in Table 1 below.

합성예Synthetic example 22: 화합물 69의 제조 22: Preparation of Compound 69

상기 합성예 9의 합성방법 중 '(4) 화합물 3-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A1:

Figure pat00215
)을 수득하였다.In the synthesis method of Synthesis Example 9, 1-chloro-4- (trifluoromethyl) benzene was substituted for 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Synthesis was carried out in the same manner except that used. Thus, compound 3-4 (A 1 :
Figure pat00215
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 9, '(6) Preparation of the final compound' was the same except that 2-chloro-4,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 69(A1:

Figure pat00216
, A2: H, A3: H, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00217
, R2:
Figure pat00218
)을 수득하였다. 상기 화합물 69의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 69 (A 1 :
Figure pat00216
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00217
, R 2 :
Figure pat00218
) Was obtained. NMR of the compound 69 is shown in Table 1 below.

합성예Synthetic example 23: 화합물 72의 제조 23: Preparation of Compound 72

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00219
)을 수득하였다.In the synthesis method of Synthesis Example 6, 1-chloro-4- (trifluoromethyl) benzene was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Synthesis was carried out in the same manner except that used. Thus, compound 3-4 (A 4 :
Figure pat00219
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 6, '(6) Preparation of the final compound' was the same except that 2-chloro-4,6-diphenylpyrimidine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

이에 따라, 최종 화합물로 화합물 72(A1: H, A2: H, A3: H, A4:

Figure pat00220
, X1: N, X2: N, X3: C, R1:
Figure pat00221
, R2:
Figure pat00222
)을 수득하였다. 상기 화합물 72의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 72 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00220
, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00221
, R 2 :
Figure pat00222
) Was obtained. NMR of the compound 72 is shown in Table 1 below.

합성예Synthetic example 24: 화합물 76의 제조 24: Preparation of Compound 76

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00223
)을 수득하였다.Synthesis method according to the same method as in Synthesis Example 1 except that naphthalene-2-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in the '(4) Preparation of Compound 1-4' Proceeded. Thus, compound 1-4 (A 3 :
Figure pat00223
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐-1,3,5-트리아진(2-chloro-4,6-diphenyl-1,3,5-triazine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 2-chloro-4,6-diphenyl-1,3,5- Synthesis was performed in the same manner except using triazine (2-chloro-4,6-diphenyl-1,3,5-triazine).

이에 따라, 최종 화합물로 화합물 76(A1: H, A2: H, A3:

Figure pat00224
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00225
, R2:
Figure pat00226
)을 수득하였다. 상기 화합물 76의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 76 (A 1 : H, A 2 : H, A 3 :
Figure pat00224
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00225
, R 2 :
Figure pat00226
) Was obtained. NMR of the compound 76 is shown in Table 1 below.

여기서, 상기 2-클로로-4,6-디페닐-1,3,5-트리아진은 상기 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신 2,4,6-트리클로로-1,3,5-트리아진(2,4,6-trichloro-1,3,5-triazine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.
Here, the 2-chloro-4,6-diphenyl-1,3,5-triazine is 2 instead of 2,4,6-trichloropyridine in the synthesis method of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out in the same manner except for using 4,6-trichloro-1,3,5-triazine (2,4,6-trichloro-1,3,5-triazine).

합성예Synthetic example 25: 화합물 86의 제조 25: Preparation of Compound 86

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00227
)을 수득하였다.Synthesis method was carried out in the same manner as in Synthesis Example 6, except that naphthalen-2-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Proceeded. Thus, compound 3-4 (A 4 :
Figure pat00227
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐-1,3,5-트리아진을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 2-chloro-4,6-diphenyl-1,3,5- Synthesis was performed in the same manner except that triazine was used.

이에 따라, 최종 화합물로 화합물 86(A1: H, A2: H, A3: H, A4:

Figure pat00228
, X1: N, X2: N, X3: N, R1:
Figure pat00229
, R2:
Figure pat00230
)을 수득하였다. 상기 화합물 86의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 86 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00228
, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00229
, R 2 :
Figure pat00230
) Was obtained. NMR of the compound 86 is shown in Table 1 below.

합성예Synthetic example 26: 화합물 90의 제조 26: Preparation of Compound 90

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4 (A1:

Figure pat00231
)을 수득하였다.Synthesis method according to the same method as in Synthesis Example 9 except that naphthalen-2-ylboronic acid was used instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' Proceeded. Thus, compound 4-4 (A 1 :
Figure pat00231
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐-1,3,5-트리아진을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, instead of 4-chloro-2,6-diphenylpyridine 2-chloro-4,6-diphenyl-1,3,5- Synthesis was performed in the same manner except that triazine was used.

이에 따라, 최종 화합물로 화합물 90(A1:

Figure pat00232
, A2: H, A3: H, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00233
, R2:
Figure pat00234
)을 수득하였다. 상기 화합물 90의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 90 (A 1 :
Figure pat00232
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00233
, R 2 :
Figure pat00234
) Was obtained. NMR of the compound 90 is shown in Table 1 below.

합성예Synthetic example 27: 화합물 95의 제조 27: Preparation of Compound 95

상기 합성예 1의 합성방법 중 `(4) 화합물 1-4의 제조`에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00235
)을 수득하였다.1-chloro-4- (trifluoromethyl) benzene was substituted for 2-bromo-9,9-dimethyl-9H-fluorene in `(4) Preparation of Compound 1-4` in the synthesis method of Synthesis Example 1. Synthesis was carried out in the same manner except that used. Thus, compound 1-4 (A 3 :
Figure pat00235
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2-클로로-4,6-디페닐-1,3,5-트리아진을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 2-chloro-4,6-diphenyl-1,3,5- Synthesis was performed in the same manner except that triazine was used.

이에 따라, 최종 화합물로 화합물 95(A1: H, A2: H, A3:

Figure pat00236
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00237
, R2:
Figure pat00238
)을 수득하였다. 상기 화합물 95의 NMR은 하기 표 1에 기재하였다.
Accordingly, compound 95 (A 1 : H, A 2 : H, A 3 :
Figure pat00236
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00237
, R 2 :
Figure pat00238
) Was obtained. NMR of the compound 95 is shown in Table 1 below.

합성예Synthetic example 28: 화합물 105의 제조 28: Preparation of Compound 105

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조[b]티오펜(7-bromobenzo[b]thiophene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00239
)을 수득하였다. 7-bromobenzo [b] thiophene (7-bromobenzo instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 1-4' in the synthesis method of Synthesis Example 1 Synthesis was performed in the same manner except that [b] thiophene) was used. Thus, compound 1-4 (A 3 :
Figure pat00239
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘(2,6-di([1,1'-biphenyl]-4-yl)-4-chloropyridine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except for using -yl) -4-chloropyridine (2,6-di ([1,1'-biphenyl] -4-yl) -4-chloropyridine).

이에 따라, 최종 화합물로 화합물 105(A1: H, A2: H, A3:

Figure pat00240
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00241
, R2:
Figure pat00242
)을 수득하였다. 상기 화합물 105의 NMR은 하기 표 1에 기재하였다.Accordingly, compound 105 (A 1 : H, A 2 : H, A 3 :
Figure pat00240
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00241
, R 2 :
Figure pat00242
) Was obtained. NMR of the compound 105 is shown in Table 1 below.

여기서, 상기 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 페닐보론산 대신 [1,1'-비페닐]-4-일보론산([1,1'-biphenyl]-4-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 2,6-di ([1,1'-biphenyl] -4-yl) -4-chloropyridine is [1] instead of phenylboronic acid in the synthesis method of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out in the same manner except for using [1,1'-biphenyl] -4-ylboronic acid.

합성예Synthetic example 29: 화합물 107의 제조 29: Preparation of Compound 107

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 2-브로모-9,9-디메틸-9H-플루오렌을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00243
)을 수득하였다.In the synthesis method of Synthesis Example 6, in the '(4) Preparation of Compound 3-4', 2-bromo-9,9-dimethyl-9H-flu instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was performed in the same manner except that the orene was used. Thus, compound 3-4 (A 4 :
Figure pat00243
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 107(A1: H, A2: H, A3: H, A4:

Figure pat00244
, X1: C, X2: C, X3: N, R1:
Figure pat00245
, R2:
Figure pat00246
)을 수득하였다. 상기 화합물 107의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 107 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00244
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00245
, R 2 :
Figure pat00246
) Was obtained. NMR of the compound 107 is shown in Table 1 below.

합성예Synthetic example 30: 화합물 109의 제조 30: Preparation of Compound 109

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00247
)을 수득하였다.Dibenzo [b, d] thiophen-3-ylboronic acid in place of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of compound 3-4' in the synthesis method of Synthesis Example 6 Synthesis was carried out in the same manner except using. Thus, compound 3-4 (A 4 :
Figure pat00247
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 109(A1: H, A2: H, A3: H, A4:

Figure pat00248
, X1: C, X2: C, X3: N, R1:
Figure pat00249
, R2:
Figure pat00250
)을 수득하였다. 상기 화합물 109의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 109 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00248
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00249
, R 2 :
Figure pat00250
) Was obtained. NMR of the compound 109 is shown in Table 1 below.

합성예Synthetic example 31: 화합물 110의 제조 31: Preparation of Compound 110

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00251
)을 수득하였다.Synthesis method was carried out in the same manner as in Synthesis Example 6, except that naphthalen-2-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Proceeded. Thus, compound 3-4 (A 4 :
Figure pat00251
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 110(A1: H, A2: H, A3: H, A4:

Figure pat00252
, X1: C, X2: C, X3: N, R1:
Figure pat00253
, R2:
Figure pat00254
)을 수득하였다. 상기 화합물 110의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 110 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00252
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00253
, R 2 :
Figure pat00254
) Was obtained. NMR of the compound 110 is shown in Table 1 below.

합성예Synthetic example 32: 화합물 112의 제조 32: Preparation of Compound 112

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 페난트렌-2-일보론산(phenanthren-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00255
)을 수득하였다.In the synthesis method of Synthesis Example 9, (phen) ren-2-ylboronic acid instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' The synthesis was carried out in the same manner except for using). Thus, compound 4-4 (A 1 :
Figure pat00255
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, instead of 4-chloro-2,6-diphenylpyridine, 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 112(A1:

Figure pat00256
, A2: H, A3: H, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00257
, R2:
Figure pat00258
)을 수득하였다. 상기 화합물 112의 NMR은 하기 표 1에 기재하였다.
Accordingly, compound 112 (A 1 :
Figure pat00256
, A 2 : H, A 3 : H, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00257
, R 2 :
Figure pat00258
) Was obtained. NMR of the compound 112 is shown in Table 1 below.

합성예Synthetic example 33: 화합물 115의 제조 33: Preparation of Compound 115

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조[b]티오펜을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00259
)을 수득하였다.In the synthesis method of Synthesis Example 6, except that 7-bromobenzo [b] thiophene was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in the '(4) Preparation of Compound 3-4' Synthesis was carried out in the same manner. Thus, compound 3-4 (A 4 :
Figure pat00259
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 115(A1: H, A2: H, A3: H, A4:

Figure pat00260
, X1: C, X2: C, X3: N, R1:
Figure pat00261
, R2:
Figure pat00262
)을 수득하였다. 상기 화합물 115의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 115 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00260
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00261
, R 2 :
Figure pat00262
) Was obtained. NMR of the compound 115 is shown in Table 1 below.

합성예Synthetic example 34: 화합물 117의 제조 34: Preparation of Compound 117

상기 합성예 9의 합성방법 중 `(4) 화합물 4-4의 제조`에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-플루오로벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00263
)을 수득하였다.Synthesis method of Synthesis Example 9 was the same as in (4) Preparation of Compound 4-4, except that 1-chloro-4-fluorobenzene was used instead of 3-bromo-9,9-dimethyl-9H-fluorene. Synthesis was carried out by the method. Thus, compound 4-4 (A 1 :
Figure pat00263
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, instead of 4-chloro-2,6-diphenylpyridine, 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 117(A1:

Figure pat00264
, A2: H, A3: H, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00265
, R2:
Figure pat00266
)을 수득하였다. 상기 화합물 117의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 117 (A 1 :
Figure pat00264
, A 2 : H, A 3 : H, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00265
, R 2 :
Figure pat00266
) Was obtained. NMR of the compound 117 is shown in Table 1 below.

합성예Synthetic example 35: 화합물 119의 제조 35: Preparation of Compound 119

상기 합성예 1의 합성방법 중 `(4) 화합물 1-4의 제조`에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00267
)을 수득하였다. 1-chloro-4- (trifluoromethyl) benzene was substituted for 2-bromo-9,9-dimethyl-9H-fluorene in `(4) Preparation of Compound 1-4` in the synthesis method of Synthesis Example 1. Synthesis was carried out in the same manner except that used. Thus, compound 1-4 (A 3 :
Figure pat00267
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,6-디([1,1'-비페닐]-4-일)-4-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 2,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -4-chloropyridine was used.

이에 따라, 최종 화합물로 화합물 119(A1: H, A2: H, A3:

Figure pat00268
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00269
, R2:
Figure pat00270
)을 수득하였다. 상기 화합물 119의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 119 (A 1 : H, A 2 : H, A 3 :
Figure pat00268
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00269
, R 2 :
Figure pat00270
) Was obtained. NMR of the compound 119 is shown in Table 1 below.

합성예Synthetic example 36: 화합물 122의 제조 36: Preparation of Compound 122

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00271
)을 수득하였다. In Synthesis of Synthesis Example 1 '(4) Preparation of Compound 1-4', 1-chloro-4- (trifluoromethyl) benzene instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except using. Thus, compound 1-4 (A 3 :
Figure pat00271
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘(2,4-di([1,1'-biphenyl]-4-yl)-6-chloropyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine, 2,4-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except for using -yl) -6-chloropyrimidine (2,4-di ([1,1'-biphenyl] -4-yl) -6-chloropyrimidine).

이에 따라, 최종 화합물로 화합물 122(A1: H, A2: H, A3:

Figure pat00272
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00273
, R2:
Figure pat00274
)을 수득하였다. 상기 화합물 122의 NMR은 하기 표 1에 기재하였다.Accordingly, as a final compound, Compound 122 (A 1 : H, A 2 : H, A 3 :
Figure pat00272
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00273
, R 2 :
Figure pat00274
) Was obtained. NMR of the compound 122 is shown in Table 1 below.

여기서, 상기 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신 2,4,6-트리클로로피리미딘, 페닐보론산 대신 [1,1'-비페닐]-4-일보론산([1,1'-biphenyl]-4-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 2,4-di ([1,1'-biphenyl] -4-yl) -6-chloropyrimidine is 2,4,6 in the synthesis method of 4-chloro-2,6-diphenylpyridine 2,4,6-trichloropyrimidine instead of trichloropyridine and [1,1'-biphenyl] -4-ylboronic acid ([1,1'-biphenyl] -4-ylboronic acid) instead of phenylboronic acid It synthesize | combined by the same method except having used.

합성예Synthetic example 37: 화합물 125의 제조 37: Preparation of Compound 125

상기 합성예 3의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In Synthesis of Synthesis Example 3, '(6) Preparation of Final Compound', 2,4-di ([1,1'-biphenyl] -4-yl instead of 4-chloro-2,6-diphenylpyridine Synthesis was carried out in the same manner except for using) -6-chloropyrimidine.

이에 따라, 최종 화합물로 화합물 125(A1: H, A2:

Figure pat00275
, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00276
, R2:
Figure pat00277
)을 수득하였다. 상기 화합물 125의 NMR은 하기 표 1에 기재하였다.
Accordingly, compound 125 (A 1 : H, A 2 :
Figure pat00275
, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00276
, R 2 :
Figure pat00277
) Was obtained. NMR of the compound 125 is shown in Table 1 below.

합성예Synthetic example 38: 화합물 129의 제조 38: Preparation of Compound 129

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조[B]티오펜을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00278
)을 수득하였다. In the synthesis method of Synthesis Example 1, except that 7-bromobenzo [B] thiophene was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in the '(4) Preparation of Compound 1-4' Synthesis was carried out in the same manner. Thus, compound 1-4 (A 3 :
Figure pat00278
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine, 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 129(A1: H, A2: H, A3:

Figure pat00279
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00280
, R2:
Figure pat00281
)을 수득하였다. 상기 화합물 129의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 129 (A 1 : H, A 2 : H, A 3 :
Figure pat00279
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00280
, R 2 :
Figure pat00281
) Was obtained. NMR of the compound 129 is shown in Table 1 below.

합성예Synthetic example 39: 화합물 132의 제조 39: Preparation of Compound 132

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00282
)을 수득하였다.Dibenzo [b, d] thiophen-3-ylboronic acid in place of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of compound 3-4' in the synthesis method of Synthesis Example 6 Synthesis was carried out in the same manner except using. Thus, compound 3-4 (A 4 :
Figure pat00282
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 132(A1: H, A2: H, A3: H, A4:

Figure pat00283
, X1: N, X2: C, X3: N, R1:
Figure pat00284
, R2:
Figure pat00285
)을 수득하였다. 상기 화합물 132의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 132 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00283
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00284
, R 2 :
Figure pat00285
) Was obtained. NMR of the compound 132 is shown in Table 1 below.

합성예Synthetic example 40: 화합물 133의 제조 40: Preparation of Compound 133

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00286
)을 수득하였다.Dibenzo [b, d] furan-3-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4' in the synthesis method of Synthesis Example 6. Synthesis was carried out in the same manner except that used. Thus, compound 3-4 (A 4 :
Figure pat00286
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 133(A1: H, A2: H, A3: H, A4:

Figure pat00287
, X1: N, X2: C, X3: N, R1:
Figure pat00288
, R2:
Figure pat00289
)을 수득하였다. 상기 화합물 133의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 133 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00287
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00288
, R 2 :
Figure pat00289
) Was obtained. NMR of the compound 133 is shown in Table 1 below.

합성예Synthetic example 41: 화합물 134의 제조 41: Preparation of Compound 134

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00290
)을 수득하였다.Synthesis method was carried out in the same manner as in Synthesis Example 6, except that naphthalen-2-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Proceeded. Thus, compound 3-4 (A 4 :
Figure pat00290
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 134(A1: H, A2: H, A3: H, A4:

Figure pat00291
, X1: N, X2: C, X3: N, R1:
Figure pat00292
, R2:
Figure pat00293
)을 수득하였다. 상기 화합물 134의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 134 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00291
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00292
, R 2 :
Figure pat00293
) Was obtained. NMR of the compound 134 is shown in Table 1 below.

합성예Synthetic example 42: 화합물 135의 제조 42: Preparation of Compound 135

상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In Synthesis of Synthesis Example 9, '(6) Preparation of Final Compound', 2,4-di ([1,1'-biphenyl] -4-yl instead of 4-chloro-2,6-diphenylpyridine Synthesis was carried out in the same manner except for using) -6-chloropyrimidine.

이에 따라, 최종 화합물로 화합물 135(A1:

Figure pat00294
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00295
, R2:
Figure pat00296
)을 수득하였다. 상기 화합물 135의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 135 (A 1 :
Figure pat00294
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00295
, R 2 :
Figure pat00296
) Was obtained. NMR of the compound 135 is shown in Table 1 below.

합성예Synthetic example 43: 화합물 138의 제조 43: Preparation of Compound 138

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00297
)을 수득하였다.Synthesis method according to the same method as in Synthesis Example 9 except that naphthalen-2-ylboronic acid was used instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' Proceeded. Thus, compound 4-4 (A 1 :
Figure pat00297
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘 을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, instead of 4-chloro-2,6-diphenylpyridine, 2,4-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 138(A1:

Figure pat00298
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00299
, R2:
Figure pat00300
)을 수득하였다. 상기 화합물 138의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 138 (A 1 :
Figure pat00298
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00299
, R 2 :
Figure pat00300
) Was obtained. NMR of the compound 138 is shown in Table 1 below.

합성예Synthetic example 44: 화합물 140의 제조 44: Preparation of Compound 140

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조퓨란을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00301
)을 수득하였다.In the synthesis method of Synthesis Example 6, '(4) Preparation of Compound 3-4' was synthesized in the same manner except that 7-bromobenzofuran was used instead of 2-bromo-9,9-dimethyl-9H-fluorene. Proceeded. Thus, compound 3-4 (A 4 :
Figure pat00301
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 140(A1: H, A2: H, A3: H, A4:

Figure pat00302
, X1: N, X2: C, X3: N, R1:
Figure pat00303
, R2:
Figure pat00304
)을 수득하였다. 상기 화합물 140의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 140 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00302
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00303
, R 2 :
Figure pat00304
) Was obtained. NMR of the compound 140 is shown in Table 1 below.

합성예Synthetic example 45: 화합물 143의 제조 45: Preparation of Compound 143

상기 합성예 1의 합성방법 중 1(4) 화합물 1-4의 제조`에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00305
)을 수득하였다. 1 (4) Compound 1-4 in Preparation Method of Synthesis Example 1 was substituted with 1-chloro-4- (trifluoromethyl) benzene instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except that used. Thus, compound 1-4 (A 3 :
Figure pat00305
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine, 2,4-di ([1,1'-biphenyl] -4 Synthesis was carried out in the same manner except that -yl) -6-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 143(A1: H, A2: H, A3:

Figure pat00306
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00307
, R2:
Figure pat00308
)을 수득하였다. 상기 화합물 143의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 143 (A 1 : H, A 2 : H, A 3 :
Figure pat00306
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00307
, R 2 :
Figure pat00308
) Was obtained. NMR of the compound 143 is shown in Table 1 below.

합성예Synthetic example 46: 화합물 146의 제조 46: Preparation of Compound 146

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00309
)을 수득하였다. Dibenzo [b, d] thiophen-3-ylboronic acid in place of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of compound 1-4' in the synthesis method of Synthesis Example 1 Synthesis was carried out in the same manner except using. Thus, compound 1-4 (A 3 :
Figure pat00309
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘(4,6-di([1,1'-biphenyl]-4-yl)-2-chloropyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 4,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except for using -yl) -2-chloropyrimidine (4,6-di ([1,1'-biphenyl] -4-yl) -2-chloropyrimidine).

이에 따라, 최종 화합물로 화합물 146(A1: H, A2: H, A3:

Figure pat00310
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00311
, R2:
Figure pat00312
)을 수득하였다. 상기 화합물 146의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 146 (A 1 : H, A 2 : H, A 3 :
Figure pat00310
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00311
, R 2 :
Figure pat00312
) Was obtained. NMR of the compound 146 is shown in Table 1 below.

여기서, 상기 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신 2,4,6-트리클로로피리미딘(2,4,6-trichloropyrimidine), 페닐보론산 대신 [1,1'-비페닐]-4-일보론산([1,1'-biphenyl]-4-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Herein, the 4,6-di ([1,1'-biphenyl] -4-yl) -2-chloropyrimidine is 2,4,6 in the synthesis method of 4-chloro-2,6-diphenylpyridine. 2,4,6-trichloropyrimidine instead of trichloropyridine, [1,1'-biphenyl] -4-ylboronic acid ([1,1'-) instead of phenylboronic acid Biphenyl] -4-ylboronic acid) was synthesized in the same manner.

합성예Synthetic example 47: 화합물 163의 제조 47: Preparation of Compound 163

상기 합성예 6의 합성방법 중 `(4) 화합물 3-4의 제조`에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 3-브로모-1,1-디메틸-1H-인덴(3-bromo-1,1-dimethyl-1H-indene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00313
)을 수득하였다.3-Bromo-1,1-dimethyl-1H-indene instead of 2-bromo-9,9-dimethyl-9H-fluorene in `(4) Preparation of compound 3-4` in the synthesis method of Synthesis Example 6 Synthesis was carried out in the same manner except for using (3-bromo-1,1-dimethyl-1H-indene). Thus, compound 3-4 (A 4 :
Figure pat00313
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 4,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -2-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 163(A1: H, A2: H, A3: H, A4:

Figure pat00314
, X1: N, X2: N, X3: C, R1:
Figure pat00315
, R2:
Figure pat00316
)을 수득하였다. 상기 화합물 163의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 163 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00314
, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00315
, R 2 :
Figure pat00316
) Was obtained. NMR of the compound 163 is shown in Table 1 below.

합성예Synthetic example 48: 화합물 165의 제조 48: Preparation of Compound 165

상기 합성예 9의 합성방법 중 '(4) 화합물 4-4의 제조'에서 3-브로모-9,9-디메틸-9H-플루오렌 대신 4-클로로-1,2-디메틸벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00317
)을 수득하였다.In the synthesis method of Synthesis Example 9, except that 4-chloro-1,2-dimethylbenzene was used instead of 3-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 4-4' Synthesis was carried out in the same manner. Thus, compound 4-4 (A 1 :
Figure pat00317
) Was obtained.

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, 4,6-di ([1,1'-biphenyl] -4 instead of 4-chloro-2,6-diphenylpyridine Synthesis was performed in the same manner except that -yl) -2-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 165(A1:

Figure pat00318
, A2: H, A3: H, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00319
, R2:
Figure pat00320
)을 수득하였다. 상기 화합물 165의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 165 (A 1 :
Figure pat00318
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00319
, R 2 :
Figure pat00320
) Was obtained. NMR of the compound 165 is shown in Table 1 below.

합성예Synthetic example 49: 화합물 167의 제조 49: Preparation of Compound 167

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00321
)을 수득하였다. 1-chloro-4- (trifluoromethyl) benzene instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 1-4' in the synthesis method of Synthesis Example 1 Synthesis was carried out in the same manner except that used. Thus, compound 1-4 (A 3 :
Figure pat00321
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 4,6-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -2-chloropyrimidine was used.

이에 따라, 최종 화합물로 화합물 167(A1: H, A2: H, A3:

Figure pat00322
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00323
, R2:
Figure pat00324
)을 수득하였다. 상기 화합물 167의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 167 (A 1 : H, A 2 : H, A 3 :
Figure pat00322
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00323
, R 2 :
Figure pat00324
) Was obtained. NMR of the compound 167 is shown in Table 1 below.

합성예Synthetic example 50: 화합물 172의 제조 50: Preparation of Compound 172

상기 합성예 1의 합성방법 중 '(4) 화합물 1-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00325
)을 수득하였다. Synthesis method was carried out in the same manner as in Synthesis Example 1 except that naphthalene-2-boronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 1-4'. Proceeded. Thus, compound 1-4 (A 3 :
Figure pat00325
) Was obtained.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로-1,3,5-트리아진(2,4-di([1,1'-biphenyl]-4-yl)-6-chloro-1,3,5-triazine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine, 2,4-di ([1,1'-biphenyl] -4 -Yl) -6-chloro-1,3,5-triazine (2,4-di ([1,1'-biphenyl] -4-yl) -6-chloro-1,3,5-triazine) Synthesis was carried out in the same manner except that used.

이에 따라, 최종 화합물로 화합물 172(A1: H, A2: H, A3:

Figure pat00326
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00327
, R2:
Figure pat00328
)을 수득하였다. 상기 화합물 172의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 172 (A 1 : H, A 2 : H, A 3 :
Figure pat00326
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00327
, R 2 :
Figure pat00328
) Was obtained. NMR of the compound 172 is shown in Table 1 below.

여기서, 상기 4,6-디([1,1'-비페닐]-4-일)-2-클로로피리미딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신 2,4,6-트리클로로피리미딘(2,4,6-trichloropyrimidine), 페닐보론산 대신 [1,1'-비페닐]-4-일보론산([1,1'-biphenyl]-4-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Herein, the 4,6-di ([1,1'-biphenyl] -4-yl) -2-chloropyrimidine is 2,4,6 in the synthesis method of 4-chloro-2,6-diphenylpyridine. 2,4,6-trichloropyrimidine instead of trichloropyridine, [1,1'-biphenyl] -4-ylboronic acid ([1,1'-) instead of phenylboronic acid Biphenyl] -4-ylboronic acid) was synthesized in the same manner.

합성예Synthetic example 51: 화합물 176의 제조 51: Preparation of Compound 176

상기 합성예 3의 합성방법 중 ‘(4) 화합물 2-4의 제조’에서, 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 2-4(A2:

Figure pat00329
)을 수득하였다.In Synthesis of Synthesis Example 3, '(4) Preparation of Compound 2-4', except for using naphthalen-2-ylboronic acid instead of 3-bromo-9,9-dimethyl-9H-fluorene; Synthesis was performed. Thus, compound 2-4 (A 2 :
Figure pat00329
) Was obtained.

그리고, 상기 합성예 3의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로-1,3,5-트리아진을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 3, '(6) Preparation of the final compound', 2,4-di ([1,1'-biphenyl] -4 instead of 4-chloro-2,6-diphenylpyridine Synthesis was performed in the same manner except that -yl) -6-chloro-1,3,5-triazine was used.

이에 따라, 최종 화합물로 화합물 176(A1: H, A2:

Figure pat00330
, A3: H, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00331
, R2:
Figure pat00332
)을 수득하였다. 상기 화합물 176의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 176 (A 1 : H, A 2 :
Figure pat00330
, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00331
, R 2 :
Figure pat00332
) Was obtained. NMR of the compound 176 is shown in Table 1 below.

합성예Synthetic example 52: 화합물 182의 제조 52: Preparation of Compound 182

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 피렌-1-일보론산(pyren-1-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00333
)을 수득하였다.In the synthesis method of Synthesis Example 6 '(4) Preparation of Compound 3-4' pyren-1-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except using. Thus, compound 3-4 (A 4 :
Figure pat00333
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-4-일)-6-클로로-1,3,5-트리아진을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 2,4-di ([1,1'-biphenyl] -4 Synthesis was performed in the same manner except that -yl) -6-chloro-1,3,5-triazine was used.

이에 따라, 최종 화합물로 화합물 182(A1: H, A2: H, A3: H, A4:

Figure pat00334
, X1: N, X2: N, X3: N, R1:
Figure pat00335
, R2:
Figure pat00336
)을 수득하였다. 상기 화합물 182의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 182 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00334
, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00335
, R 2 :
Figure pat00336
) Was obtained. NMR of the compound 182 is shown in Table 1 below.

합성예Synthetic example 53: 화합물 193의 제조 53: Preparation of Compound 193

상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘(4-chloro-2,6-di(naphthalen-1-yl)pyridine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, 4-chloro-2,6-di (naphthalen-1-yl) pyridine (4 instead of 4-chloro-2,6-diphenylpyridine Synthesis was performed in the same manner except that -chloro-2,6-di (naphthalen-1-yl) pyridine) was used.

이에 따라, 최종 화합물로 화합물 193(A1: H, A2: H, A3:

Figure pat00337
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00338
, R2:
Figure pat00339
)을 수득하였다. 상기 화합물 193의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 193 (A 1 : H, A 2 : H, A 3 :
Figure pat00337
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00338
, R 2 :
Figure pat00339
) Was obtained. NMR of the compound 193 is shown in Table 1 below.

여기서, 상기 4-클로로-2,6-디(나프탈렌-1-일)피리딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 페닐보론산 대신 나프탈렌-1-일보론산(naphthalen-1-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 4-chloro-2,6-di (naphthalen-1-yl) pyridine is naphthalen-1-ylboronic acid (naphthalen-1) instead of phenylboronic acid in the synthesis method of 4-chloro-2,6-diphenylpyridine. -ylboronic acid) was synthesized in the same manner.

합성예Synthetic example 54: 화합물 195의 제조 54: Preparation of Compound 195

그리고, 상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라 화합물 1-4(A3:

Figure pat00340
)를 수득하였다.And, in the '(4) Preparation of Compound 1-4' in the synthesis method of Synthesis Example 1, instead of 2-bromo-9,9-dimethyl-9H-fluorene, dibenzo [b, d] furan-3- Synthesis was carried out in the same manner except that ilboronic acid was used. Accordingly, Compound 1-4 (A 3 :
Figure pat00340
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘(4-chloro-2,6-di(naphthalen-1-yl)pyridine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-di (naphthalen-1-yl) pyridine Synthesis was performed in the same manner except that (4-chloro-2,6-di (naphthalen-1-yl) pyridine) was used.

이에 따라, 최종 화합물로 화합물 195(A1: H, A2: H, A3:

Figure pat00341
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00342
, R2:
Figure pat00343
)을 수득하였다. 상기 화합물 195의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 195 (A 1 : H, A 2 : H, A 3 :
Figure pat00341
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00342
, R 2 :
Figure pat00343
) Was obtained. NMR of the compound 195 is shown in Table 1 below.

합성예Synthetic example 55: 화합물 202의 제조 55: Preparation of Compound 202

그리고, 상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조퓨란을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라 화합물 1-4(A3:

Figure pat00344
)를 수득하였다.In the synthesis method of Synthesis Example 1, '(4) Preparation of Compound 1-4' was the same except that 7-bromobenzofuran was used instead of 2-bromo-9,9-dimethyl-9H-fluorene. Synthesis was carried out by the method. Accordingly, Compound 1-4 (A 3 :
Figure pat00344
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-2-일)피리딘(4-chloro-2,6-di(naphthalen-2-yl)pyridine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-di (naphthalen-2-yl) pyridine Synthesis was performed in the same manner except that (4-chloro-2,6-di (naphthalen-2-yl) pyridine) was used.

이에 따라, 최종 화합물로 화합물 202(A1: H, A2: H, A3:

Figure pat00345
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00346
, R2:
Figure pat00347
)을 수득하였다. 상기 화합물 202의 NMR은 하기 표 1에 기재하였다.Accordingly, as the final compound, Compound 202 (A 1 : H, A 2 : H, A 3 :
Figure pat00345
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00346
, R 2 :
Figure pat00347
) Was obtained. NMR of the compound 202 is shown in Table 1 below.

여기서, 상기 4-클로로-2,6-디(나프탈렌-1-일)피리딘은 4-클로로-2,6-디페닐피리딘의 합성방법 중 페닐보론산 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 4-chloro-2,6-di (naphthalen-1-yl) pyridine is naphthalen-2-ylboronic acid (naphthalen-2) instead of phenylboronic acid in the synthesis method of 4-chloro-2,6-diphenylpyridine. -ylboronic acid) was synthesized in the same manner.

합성예Synthetic example 56: 화합물 203의 제조 56: Preparation of Compound 203

상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, 4-chloro-2,6-di (naphthalen-1-yl) pyridine was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out in the same manner except that.

이에 따라, 최종 화합물로 화합물 203(A1: H, A2: H, A3: H, A4:

Figure pat00348
, X1: C, X2: C, X3: N, R1:
Figure pat00349
, R2:
Figure pat00350
)을 수득하였다. 상기 화합물 203의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 203 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00348
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00349
, R 2 :
Figure pat00350
) Was obtained. NMR of the compound 203 is shown in Table 1 below.

합성예Synthetic example 57: 화합물 204의 제조 57: Preparation of Compound 204

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00351
)을 수득하였다.Dibenzo [b, d] thiophen-3-ylboronic acid in place of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of compound 3-4' in the synthesis method of Synthesis Example 6 Synthesis was carried out in the same manner except using. Thus, compound 3-4 (A 4 :
Figure pat00351
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-di (naphthalen-1-yl) pyridine Synthesis was carried out in the same manner except using.

이에 따라, 최종 화합물로 화합물 204(A1: H, A2: H, A3: H, A4:

Figure pat00352
, X1: C, X2: C, X3: N, R1:
Figure pat00353
, R2:
Figure pat00354
)을 수득하였다. 상기 화합물 204의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 204 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00352
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00353
, R 2 :
Figure pat00354
) Was obtained. NMR of the compound 204 is shown in Table 1 below.

합성예Synthetic example 58: 화합물 205의 제조 58: Preparation of Compound 205

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00355
)을 수득하였다.Dibenzo [b, d] furan-3-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4' in the synthesis method of Synthesis Example 6. Synthesis was carried out in the same manner except that used. Thus, compound 3-4 (A 4 :
Figure pat00355
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-di (naphthalen-1-yl) pyridine Synthesis was carried out in the same manner except using.

이에 따라, 최종 화합물로 화합물 205(A1: H, A2: H, A3: H, A4:

Figure pat00356
, X1: C, X2: C, X3: N, R1:
Figure pat00357
, R2:
Figure pat00358
)을 수득하였다. 상기 화합물 205의 NMR은 하기 표 1에 기재하였다.
Accordingly, as the final compound, Compound 205 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00356
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00357
, R 2 :
Figure pat00358
) Was obtained. NMR of the compound 205 is shown in Table 1 below.

합성예Synthetic example 59: 화합물 206의 제조 59: Preparation of Compound 206

상기 합성예 6의 합성방법 중 '(4) 화합물 3-4의 제조'에서 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00359
)을 수득하였다.Synthesis method was carried out in the same manner as in Synthesis Example 6, except that naphthalen-2-ylboronic acid was used instead of 2-bromo-9,9-dimethyl-9H-fluorene in '(4) Preparation of Compound 3-4'. Proceeded. Thus, compound 3-4 (A 4 :
Figure pat00359
) Was obtained.

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-1-일)피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine 4-chloro-2,6-di (naphthalen-1-yl) pyridine Synthesis was carried out in the same manner except using.

이에 따라, 최종 화합물로 화합물 206(A1: H, A2: H, A3: H, A4:

Figure pat00360
, X1: C, X2: C, X3: N, R1:
Figure pat00361
, R2:
Figure pat00362
)을 수득하였다. 상기 화합물 206의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 206 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00360
, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00361
, R 2 :
Figure pat00362
) Was obtained. NMR of the compound 206 is shown in Table 1 below.

합성예Synthetic example 60: 화합물 217의 제조 60: Preparation of Compound 217

상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-2-일)피리미딘(4-chloro-2,6-di(naphthalen-2-yl)pyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine, 4-chloro-2,6-di (naphthalen-2-yl) pyrimidine ( Synthesis was performed in the same manner except that 4-chloro-2,6-di (naphthalen-2-yl) pyrimidine) was used.

이에 따라, 최종 화합물로 화합물 217(A1: H, A2: H, A3:

Figure pat00363
, A4: H, X1: C, X2: N, X3: N, R1:
Figure pat00364
, R2:
Figure pat00365
)을 수득하였다. 상기 화합물 217의 NMR은 하기 표 1에 기재하였다.Accordingly, as the final compound, Compound 217 (A 1 : H, A 2 : H, A 3 :
Figure pat00363
, A 4 : H, X 1 : C, X 2 : N, X 3 : N, R 1 :
Figure pat00364
, R 2 :
Figure pat00365
) Was obtained. NMR of the compound 217 is shown in Table 1 below.

여기서, 상기 4-클로로-2,6-디(나프탈렌-2-일)피리미딘은 상기 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신에 2,4,6-트리클로로피리미딘, 페닐보론산 대신 나프탈렌-2-일보론산(naphthalen-2-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 4-chloro-2,6-di (naphthalen-2-yl) pyrimidine is 2 instead of 2,4,6-trichloropyridine in the synthesis method of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out in the same manner except for using 4,6-trichloropyrimidine and naphthalen-2-ylboronic acid instead of phenylboronic acid.

합성예Synthetic example 61: 화합물 219의 제조 61: Preparation of Compound 219

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조퓨란을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라 화합물 1-4(A3:

Figure pat00366
)를 수득하였다.In the synthesis method of Synthesis Example 1 '(4) Preparation of Compound 1-4', except that 7-bromobenzofuran was used instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was performed. Accordingly, Compound 1-4 (A 3 :
Figure pat00366
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-2-일)피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 219(A1: H, A2: H, A3:

Figure pat00367
, A4: H, X1: C, X2: N, X3: N, R1:
Figure pat00368
, R2:
Figure pat00369
)을 수득하였다. 상기 화합물 219의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 1, '(6) Preparation of the final compound', 4-chloro-2,6-di (naphthalen-2-yl) pyridine instead of 4-chloro-2,6-diphenylpyridine Synthesis was carried out in the same manner except for using midine. Accordingly, as the final compound, Compound 219 (A 1 : H, A 2 : H, A 3 :
Figure pat00367
, A 4 : H, X 1 : C, X 2 : N, X 3 : N, R 1 :
Figure pat00368
, R 2 :
Figure pat00369
) Was obtained. NMR of the compound 219 is shown in Table 1 below.

합성예Synthetic example 62: 화합물 220의 제조 62: Preparation of Compound 220

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라 화합물 1-4(A3:

Figure pat00370
)를 수득하였다.In Synthesis of Synthesis Example 1, '(4) Preparation of Compound 1-4' was the same method as that except for using naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was performed. Accordingly, Compound 1-4 (A 3 :
Figure pat00370
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로-2,6-디(나프탈렌-2-일)피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 1, '(6) Preparation of the final compound', 4-chloro-2,6-di (naphthalen-2-yl) pyridine instead of 4-chloro-2,6-diphenylpyridine Synthesis was carried out in the same manner except for using midine.

이에 따라, 최종 화합물로 화합물 220(A1: H, A2: H, A3:

Figure pat00371
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00372
, R2:
Figure pat00373
)을 수득하였다. 상기 화합물 220의 NMR은 하기 표 1에 기재하였다.
Accordingly, as the final compound, Compound 220 (A 1 : H, A 2 : H, A 3 :
Figure pat00371
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00372
, R 2 :
Figure pat00373
) Was obtained. NMR of the compound 220 is shown in Table 1 below.

합성예Synthetic example 63: 화합물 227의 제조 63: Preparation of Compound 227

상기 합성예 6의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 2,4-디([1,1'-비페닐]-3-일)-6-클로로피리미딘(2,4-di([1,1'-biphenyl]-3-yl)-6-chloropyrimidine)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In Synthesis of Synthesis Example 6, In Preparation of (6) Final Compound, 2,4-di ([1,1'-biphenyl] -3-yl instead of 4-chloro-2,6-diphenylpyridine Synthesis was carried out in the same manner except for using 6-chloropyrimidine (2,4-di ([1,1'-biphenyl] -3-yl) -6-chloropyrimidine).

이에 따라, 최종 화합물로 화합물 227(A1: H, A2: H, A3: H, A4:

Figure pat00374
, X1: C, X2: N, X3: N, R1:
Figure pat00375
, R2:
Figure pat00376
)을 수득하였다. 상기 화합물 227의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 227 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00374
, X 1 : C, X 2 : N, X 3 : N, R 1 :
Figure pat00375
, R 2 :
Figure pat00376
) Was obtained. NMR of the compound 227 is shown in Table 1 below.

여기서, 상기 2,4-디([1,1'-비페닐]-3-일)-6-클로로피리미딘은 상기 4-클로로-2,6-디페닐피리딘의 합성방법 중 2,4,6-트리클로로피리딘 대신에 2,4,6-트리클로로피리미딘, 페닐보론산 대신 [1,1'-비페닐]-3-일보론산([1,1'-biphenyl]-3-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성하였다.
Here, the 2,4-di ([1,1'-biphenyl] -3-yl) -6-chloropyrimidine is 2,4, in the synthesis method of the 4-chloro-2,6-diphenylpyridine 2,4,6-trichloropyrimidine instead of 6-trichloropyridine, [1,1'-biphenyl] -3-ylboronic acid ([1,1'-biphenyl] -3-ylboronic acid instead of phenylboronic acid ) Was synthesized in the same manner except for using.

합성예Synthetic example 64: 화합물 231의 제조 64: Preparation of Compound 231

상기 합성예 9의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산(3,4-dimethylphenyl)boronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, (3,4-dimethylphenyl) boronic acid (3,4-dimethylphenyl) boronic acid instead of 4-chloro-2,6-diphenylpyridine The synthesis was carried out in the same manner except for using).

이에 따라, 최종 화합물로 화합물 231(A1:

Figure pat00377
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00378
, R2:
Figure pat00379
)을 수득하였다. 상기 화합물 231의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 231 (A 1 :
Figure pat00377
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00378
, R 2 :
Figure pat00379
) Was obtained. NMR of the compound 231 is shown in Table 1 below.

합성예Synthetic example 65: 화합물 241의 제조 65: Preparation of Compound 241

상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In Synthesis of Synthesis Example 1, '(6) Preparation of Final Compound', except that (3,4-dimethylphenyl) boronic acid was used instead of 4-chloro-2,6-diphenylpyridine. Proceeded.

이에 따라, 최종 화합물로 화합물 241(A1: H, A2: H, A3:

Figure pat00380
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00381
, R2:
Figure pat00382
)을 수득하였다. 상기 화합물 241의 NMR은 하기 표 1에 기재하였다.
Accordingly, as a final compound, Compound 241 (A 1 : H, A 2 : H, A 3 :
Figure pat00380
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00381
, R 2 :
Figure pat00382
) Was obtained. NMR of the compound 241 is shown in Table 1 below.

합성예Synthetic example 66: 화합물 243의 제조 66: Preparation of Compound 243

그리고, 상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 1, '(4) Preparation of Compound 1-4' was the same except that (3,4-dimethylphenyl) boronic acid was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was carried out by the method.

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, except that (3,4-dimethylphenyl) boronic acid was used instead of 4-chloro-2,6-diphenylpyridine, Synthesis was performed.

이에 따라, 최종 화합물로 화합물 243(A1: H, A2: H, A3:

Figure pat00383
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00384
, R2:
Figure pat00385
)을 수득하였다. 상기 화합물 243의 NMR은 하기 표 1에 기재하였다.
Accordingly, Compound 243 (A 1 : H, A 2 : H, A 3 :
Figure pat00383
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00384
, R 2 :
Figure pat00385
) Was obtained. NMR of the compound 243 is shown in Table 1 below.

합성예Synthetic example 67: 화합물 248의 제조 67: Preparation of Compound 248

상기 합성예 3의 합성방법 중 ‘(4) 화합물 2-4의 제조’에서, 3-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 2-4(A2:

Figure pat00386
)를 수득하였다.In Synthesis of Synthesis Example 3, '(4) Preparation of Compound 2-4', except for using naphthalen-2-ylboronic acid instead of 3-bromo-9,9-dimethyl-9H-fluorene; Synthesis was performed. Thus, compound 2-4 (A 2 :
Figure pat00386
).

그리고, 상기 합성예 3의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 248(A1: H, A2:

Figure pat00387
, A3: H, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00388
, R2:
Figure pat00389
)을 수득하였다. 상기 화합물 248의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 3, '(6) Preparation of the final compound', except that (3,4-dimethylphenyl) boronic acid was used instead of 4-chloro-2,6-diphenylpyridine. Synthesis was performed. Accordingly, Compound 248 (A 1 : H, A 2 :
Figure pat00387
, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00388
, R 2 :
Figure pat00389
) Was obtained. NMR of the compound 248 is shown in Table 1 below.

합성예Synthetic example 68: 화합물 249의 제조 68: Preparation of Compound 249

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 7-브로모벤조[b]티오펜을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A2:

Figure pat00390
)를 수득하였다.In the synthesis method of Synthesis Example 1, '(4) Preparation of Compound 1-4', wherein 7-bromobenzo [b] thiophene was used instead of 2-bromo-9,9-dimethyl-9H-fluorene Other synthesis was carried out in the same manner. Thus, compound 1-4 (A 2 :
Figure pat00390
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (3,4-디메틸페닐)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 249(A1: H, A2: H, A3:

Figure pat00391
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00392
, R2:
Figure pat00393
)을 수득하였다. 상기 화합물 249의 NMR은 하기 표 1에 기재하였다.
In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, except that (3,4-dimethylphenyl) boronic acid was used instead of 4-chloro-2,6-diphenylpyridine, Synthesis was performed. Accordingly, Compound 249 (A 1 : H, A 2 : H, A 3 :
Figure pat00391
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00392
, R 2 :
Figure pat00393
) Was obtained. NMR of the compound 249 is shown in Table 1 below.

합성예Synthetic example 69: 화합물 268의 제조 69: Preparation of Compound 268

상기 합성예 1의 합성방법 중 ‘(4) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00394
)를 수득하였다.In Synthesis of Synthesis Example 1, '(4) Preparation of Compound 1-4' was the same method as that except for using naphthalen-2-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was performed. Thus, compound 1-4 (A 3 :
Figure pat00394
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종 화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 1-클로로-4-플루오로벤젠(1-chloro-4-fluorobenzene)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 268(A1: H, A2: H, A3:

Figure pat00395
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00396
, R2:
Figure pat00397
)을 수득하였다. 상기 화합물 268의 NMR은 하기 표 1에 기재하였다.
And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 1, instead of 4-chloro-2,6-diphenylpyridine 1-chloro-4-fluorobenzene (1-chloro-4-fluorobenzene The synthesis was carried out in the same manner except for using). Accordingly, Compound 268 (A 1 : H, A 2 : H, A 3 :
Figure pat00395
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00396
, R 2 :
Figure pat00397
) Was obtained. NMR of the compound 268 is shown in Table 1 below.

합성예Synthetic example 70: 화합물 271의 제조 70: Preparation of Compound 271

하기 반응식 6의 반응 경로를 거쳐 화합물 271을 합성하였다.Compound 271 was synthesized through the reaction route of Scheme 6 below.

<반응식 6><Reaction Scheme 6>

Figure pat00398
Figure pat00398

(1) 화합물 5-1의 제조 (1) Preparation of Compound 5-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 5-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 9.7 g (30%) of the target compound 5-1.

(2) 화합물 5-2의 제조 (2) Preparation of Compound 5-2

화합물 5-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 5-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 5-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 5-2.

(3) 화합물 5-3의 제조 (3) Preparation of Compound 5-3

화합물 5-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 5-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 5-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the target compound 5-3.

(4) 화합물 5-4의 제조 (4) Preparation of Compound 5-4

화합물 5-3 20g(46.7m㏖), 디벤조[b,d]퓨란-2-일보론산 (56.03m㏖), 페닐보론산 (56.03m㏖), Pd(PPh3)4 5.4g(4.67m㏖), 및 K2CO3, 19.4g(140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 5-4(A2:

Figure pat00399
, A3:
Figure pat00400
) 19.8g (89%)을 얻었다.
Compound 5-3 20 g (46.7 mmol), dibenzo [b, d] furan-2-ylboronic acid (56.03 mmol), phenylboronic acid (56.03 mmol), Pd (PPh 3 ) 4 5.4 g (4.67 m) Mol) and 19.4 g (140.1 mmol) of K 2 CO 3 were dissolved in 200 ml / 40 ml / 40 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent, and the target compound 5-4 (A 2 :
Figure pat00399
, A 3 :
Figure pat00400
) 19.8 g (89%).

(5) 화합물 5-5의 제조 (5) Preparation of Compound 5-5

화합물 5-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 5-5(A2:

Figure pat00401
, A3:
Figure pat00402
) 11.2g (80%)을 얻었다.
Compound 5-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 1,2-dichlorobenzene was removed using a vacuum distillation apparatus. Purified by column chromatography using dichloromethane and hexane as a developing solvent, target compound 5-5 (A 2 :
Figure pat00401
, A 3 :
Figure pat00402
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 5-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 2-클로로-4,6-디페닐-1,3,5-트리아진 (22.6m㏖을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 271(A1: H, A2:

Figure pat00403
, A3:
Figure pat00404
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00405
, R2:
Figure pat00406
)을 수득하였다. 상기 화합물 271의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 5-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 2-chloro-4,6-diphenyl-1,3,5-triazine (22.6 mmol was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the mixture was distilled with water. The organic layer was extracted with EA, the organic layer was dried over MgSO 4 , the solvent was removed using a rotary evaporator, and separated by column chromatography using dichloromethane and hexane as a developing solvent. Compound 271 (A 1 : H, A was used as a final compound). 2 :
Figure pat00403
, A 3 :
Figure pat00404
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00405
, R 2 :
Figure pat00406
) Was obtained. NMR of the compound 271 is shown in Table 1 below.

합성예Synthetic example 71: 화합물 272의 제조 71: Preparation of Compound 272

상기 합성예 70의 합성방법 중 ‘(4) 화합물 5-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 나프탈렌-2-일보론산과 페닐보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 5-4(A2:

Figure pat00407
, A3:
Figure pat00408
)를 수득하였다. 그리고, 최종 화합물로 화합물 272(A1: H, A2:
Figure pat00409
, A3:
Figure pat00410
, A4: H, X1: N, X2: N, X3: N, R1:
Figure pat00411
, R2:
Figure pat00412
)을 수득하였다. 상기 화합물 272의 NMR은 하기 표 1에 기재하였다.In (4) Preparation of Compound 5-4, in the synthesis method of Synthesis Example 70, naphthalen-2-ylboronic acid and phenylboronic acid were used instead of 2-bromo-9,9-dimethyl-9H-fluorene. Other synthesis was carried out in the same manner. Thus, compound 5-4 (A 2 :
Figure pat00407
, A 3 :
Figure pat00408
). In addition, Compound 272 (A 1 : H, A 2 :
Figure pat00409
, A 3 :
Figure pat00410
, A 4 : H, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00411
, R 2 :
Figure pat00412
) Was obtained. NMR of the compound 272 is shown in Table 1 below.

합성예Synthetic example 72: 화합물 282의 제조 72: Preparation of Compound 282

하기 반응식 7의 반응 경로를 거쳐 화합물 283을 합성하였다.Compound 283 was synthesized through the reaction route of Scheme 7 below.

<반응식 7><Reaction Scheme 7>

Figure pat00413
Figure pat00413

(1) 화합물 6-1의 제조 (1) Preparation of Compound 6-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 6-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane as a developing solvent were separated by column chromatography to obtain 9.7 g (30%) of the target compound 6-1.

(2) 화합물 6-2의 제조 (2) Preparation of Compound 6-2

화합물 6-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 6-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 6-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 6-2.

(3) 화합물 6-3의 제조 (3) Preparation of Compound 6-3

화합물 6-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 6-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 6-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the title compound 6-3.

(4) 화합물 6-4의 제조 (4) Preparation of Compound 6-4

화합물 6-3 (46.7m㏖), 나프탈렌-2-일보론산 (56.03m㏖), 페닐보론산 (56.03m㏖), Pd(PPh3)4 5.4g(4.67m㏖), 및 K2CO3, 19.4g(140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 6-4(A1:

Figure pat00414
, A4:
Figure pat00415
) 19.8g (89%)을 얻었다.
Compound 6-3 (46.7 mmol), naphthalen-2-ylboronic acid (56.03 mmol), phenylboronic acid (56.03 mmol), Pd (PPh 3 ) 4 5.4 g (4.67 mmol), and K 2 CO 3 And 19.4 g (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200 mL / 40 mL / 40 mL, and then stirred at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent, and the target compound 6-4 (A 1 :
Figure pat00414
, A 4 :
Figure pat00415
) 19.8 g (89%).

(5) 화합물 6-5의 제조 (5) Preparation of Compound 6-5

화합물 6-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 6-5(A1:

Figure pat00416
, A4:
Figure pat00417
) 11.2g (80%)을 얻었다.
Compound 6-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 1,2-dichlorobenzene was removed using a vacuum distillation apparatus. Purified by column chromatography using dichloromethane and hexane as a developing solvent, the target compound 6-5 (A 1 :
Figure pat00416
, A 4 :
Figure pat00417
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 6-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 2-클로로-4,6-디페닐-1,3,5-트리아진 (22.6m㏖) 을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 282(A1:

Figure pat00418
, A2: H, A3: H, A4:
Figure pat00419
, X1: N, X2: N, X3: N, R1:
Figure pat00420
, R2:
Figure pat00421
)을 수득하였다. 상기 화합물 282의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 6-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 2-chloro-4,6-diphenyl-1,3,5-triazine (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent. Compound 282 (A 1 :
Figure pat00418
, A 2 : H, A 3 : H, A 4 :
Figure pat00419
, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00420
, R 2 :
Figure pat00421
) Was obtained. NMR of the compound 282 is shown in Table 1 below.

합성예Synthetic example 73: 화합물 283의 제조 73: Preparation of Compound 283

상기 합성예 72의 합성방법 중 ‘(4) 화합물 6-4의 제조’에서, 나프탈렌-2-일보론산 대신 벤조[b]티오펜-7-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 6-4(A1:

Figure pat00422
, A4:
Figure pat00423
)를 수득하였다. 그리고, 최종 화합물로 화합물 283(A1:
Figure pat00424
, A2: H, A3: H, A4:
Figure pat00425
, X1: N, X2: N, X3: N, R1:
Figure pat00426
, R2:
Figure pat00427
)을 수득하였다. 상기 화합물 283의 NMR은 하기 표 1에 기재하였다.
Synthesis was carried out in the same manner as in Synthesis Example 72 except that benzo [b] thiophen-7-ylboronic acid was used instead of naphthalen-2-ylboronic acid in the preparation of Compound (4-4). . Thus, compound 6-4 (A 1 :
Figure pat00422
, A 4 :
Figure pat00423
). In addition, Compound 283 (A 1 :
Figure pat00424
, A 2 : H, A 3 : H, A 4 :
Figure pat00425
, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00426
, R 2 :
Figure pat00427
) Was obtained. NMR of the compound 283 is shown in Table 1 below.

합성예Synthetic example 74: 화합물 326의 제조 74: Preparation of Compound 326

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 나프탈렌-2-일보론산 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A4:

Figure pat00428
)를 수득하였다.In Synthesis of Synthesis Example 6, '(4) Preparation of Compound 3-4' was carried out in the same manner except for using naphthalen-2-ylboronic acid instead of naphthalen-2-ylboronic acid. Thus, compound 3-4 (A 4 :
Figure pat00428
).

상기 합성예 6의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 [1,1':2',1''-터페닐]-4'-일보론산([1,1':2',1''-terphenyl]-4'-ylboronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 326(A1: H, A2: H, A3: H, A4:

Figure pat00429
, X1: N, X2: C, X3: N, R1:
Figure pat00430
, R2:
Figure pat00431
)을 수득하였다. 상기 화합물 326의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 6 '(6) Preparation of the final compound', instead of 4-chloro-2,6-diphenylpyridine [1,1 ': 2', 1 ''-terphenyl] -4 ' Synthesis was carried out in the same manner except for using -ilboronic acid ([1,1 ': 2', 1 ''-terphenyl] -4'-ylboronic acid). Accordingly, Compound 326 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00429
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00430
, R 2 :
Figure pat00431
) Was obtained. NMR of the compound 326 is shown in Table 1 below.

합성예Synthetic example 75: 화합물 330의 제조 75: Preparation of Compound 330

상기 합성예 8의 합성방법 중 ‘(4) 화합물 4-4의 제조’에서, 나프탈렌-2-일보론산 대신 나프탈렌-2-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00432
)를 수득하였다.In Synthesis of Synthesis Example 8, (4) Preparation of Compound 4-4, except that naphthalene-2-ylboronic acid was used instead of naphthalene-2-ylboronic acid, synthesis was carried out in the same manner. Thus, compound 4-4 (A 1 :
Figure pat00432
).

상기 합성예 8의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 [1,1':2',1''-터페닐]-4'-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 330(A1:

Figure pat00433
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00434
, R2:
Figure pat00435
)을 수득하였다. 상기 화합물 326의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 8 '(6) Preparation of the final compound', instead of 4-chloro-2,6-diphenylpyridine [1,1 ': 2', 1 ''-terphenyl] -4 ' Synthesis was performed in the same manner except that ilboronic acid was used. Accordingly, Compound 330 (A 1 :
Figure pat00433
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00434
, R 2 :
Figure pat00435
) Was obtained. NMR of the compound 326 is shown in Table 1 below.

합성예Synthetic example 76: 화합물 333의 제조 76: Preparation of Compound 333

상기 합성예 8의 합성방법 중 ‘(4) 화합물 4-4의 제조’에서, 나프탈렌-2-일보론산 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00436
)를 수득하였다.Synthesis was carried out in the same manner as in Synthesis Example 8 except that 1-chloro-4- (trifluoromethyl) benzene was used instead of naphthalen-2-ylboronic acid in '(4) Preparation of Compound 4-4'. Proceeded. Thus, compound 4-4 (A 1 :
Figure pat00436
).

상기 합성예 8의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 [1,1':2',1''-터페닐]-4'-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 333(A1:

Figure pat00437
, A2: H, A3: H, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00438
, R2:
Figure pat00439
)을 수득하였다. 상기 화합물 333의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 8 '(6) Preparation of the final compound', instead of 4-chloro-2,6-diphenylpyridine [1,1 ': 2', 1 ''-terphenyl] -4 ' Synthesis was performed in the same manner except that ilboronic acid was used. Accordingly, Compound 333 (A 1 :
Figure pat00437
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00438
, R 2 :
Figure pat00439
) Was obtained. NMR of the compound 333 is shown in Table 1 below.

합성예Synthetic example 77: 화합물 336의 제조 77: Preparation of Compound 336

상기 합성예 6의 합성방법 중 ‘(4) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 1-클로로-4-(트리플루오로메틸)벤젠을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A1:

Figure pat00440
)를 수득하였다.In Synthesis of Synthesis Example 6, '(4) Preparation of Compound 3-4', 1-chloro-4- (trifluoromethyl) benzene instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except using. Thus, compound 3-4 (A 1 :
Figure pat00440
).

상기 합성예 6의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 [1,1':2',1''-터페닐]-4'-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 336(A1: H, A2: H, A3: H, A4:

Figure pat00441
, X1: N, X2: C, X3: N, R1:
Figure pat00442
, R2:
Figure pat00443
)을 수득하였다. 상기 화합물 336의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 6 '(6) Preparation of the final compound', instead of 4-chloro-2,6-diphenylpyridine [1,1 ': 2', 1 ''-terphenyl] -4 ' Synthesis was performed in the same manner except that ilboronic acid was used. Accordingly, Compound 336 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00441
, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00442
, R 2 :
Figure pat00443
) Was obtained. NMR of the compound 336 is shown in Table 1 below.

합성예Synthetic example 78: 화합물 337의 제조 78: Preparation of Compound 337

상기 합성예 1의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로벤조니트릴(4-chlorobenzonitrile)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 337(A1: H, A2: H, A3:

Figure pat00444
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00445
, R2:
Figure pat00446
)을 수득하였다. 상기 화합물 337의 NMR은 하기 표 1에 기재하였다.
In Synthesis of Synthesis Example 1, '(6) Preparation of Final Compound', except that 4-chlorobenzonitrile was used instead of 4-chloro-2,6-diphenylpyridine. Proceeded. Accordingly, compound 337 (A 1 : H, A 2 : H, A 3 :
Figure pat00444
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00445
, R 2 :
Figure pat00446
) Was obtained. NMR of the compound 337 is shown in Table 1 below.

합성예Synthetic example 79: 화합물 339의 제조 79: Preparation of Compound 339

상기 합성예 1의 합성방법 중 ‘(6) 화합물 1-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 1-4(A3:

Figure pat00447
)를 수득하였다.In Synthesis of Synthesis Example 1, In Preparation of (6) Compound 1-4, Dibenzo [b, d] furan-3-ylboronic acid instead of 2-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except using. Thus, compound 1-4 (A 3 :
Figure pat00447
).

그리고, 상기 합성예 1의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 4-클로로벤조니트릴을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 339(A1: H, A2: H, A3:

Figure pat00448
, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00449
, R2:
Figure pat00450
)을 수득하였다. 상기 화합물 339의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 1, '(6) Preparation of the final compound' was carried out in the same manner except for using 4-chlorobenzonitrile instead of 4-chloro-2,6-diphenylpyridine. Accordingly, compound 339 (A 1 : H, A 2 : H, A 3 :
Figure pat00448
, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00449
, R 2 :
Figure pat00450
) Was obtained. NMR of the compound 339 is shown in Table 1 below.

합성예Synthetic example 80: 화합물 348의 제조 80: Preparation of Compound 348

상기 합성예 6의 합성방법 중 ‘(6) 화합물 3-4의 제조’에서, 2-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 3-4(A3:

Figure pat00451
)를 수득하였다.In Synthesis of Synthesis Example 6, In Preparation of (6) Compound 3-4, Dibenzo [b, d] thiophen-3-yl is substituted for 2-bromo-9,9-dimethyl-9H-fluorene. Synthesis was carried out in the same manner except for using lonic acid. Thus, compound 3-4 (A 3 :
Figure pat00451
).

그리고, 상기 합성예 6의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (4-(티오펜-2-일)페닐)보론산((4-(thiophen-2-yl)phenyl)boronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 348(A1: H, A2: H, A3: H, A4:

Figure pat00452
, X1: N, X2: N, X3: C, R1:
Figure pat00453
, R2:
Figure pat00454
)을 수득하였다. 상기 화합물 348의 NMR은 하기 표 1에 기재하였다.
And, in the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 6, instead of 4-chloro-2,6-diphenylpyridine (4- (thiophen-2-yl) phenyl) boronic acid (( Synthesis was carried out in the same manner except that 4- (thiophen-2-yl) phenyl) boronic acid) was used. Accordingly, Compound 348 (A 1 : H, A 2 : H, A 3 : H, A 4 :
Figure pat00452
, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00453
, R 2 :
Figure pat00454
) Was obtained. NMR of the compound 348 is shown in Table 1 below.

합성예Synthetic example 81: 화합물 353의 제조 81: Preparation of Compound 353

상기 합성예 9의 합성방법 중 ‘(4) 화합물 4-4의 제조’에서, 3-브로모-9,9-디메틸-9H-플루오렌 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 4-4(A1:

Figure pat00455
)를 수득하였다.In Preparation of Compound (4-4) in Synthesis Example 9, Dibenzo [b, d] furan-3-ylboronic acid instead of 3-bromo-9,9-dimethyl-9H-fluorene Synthesis was carried out in the same manner except using. Thus, compound 4-4 (A 1 :
Figure pat00455
).

그리고, 상기 합성예 9의 합성방법 중 ‘(6) 최종화합물의 제조’에서, 4-클로로-2,6-디페닐피리딘 대신 (4-(티오펜-2-일)페닐)보론산((4-(thiophen-2-yl)phenyl)boronic acid)을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 353(A1:

Figure pat00456
, A2: H, A3: H, A4: H, X1: N, X2: N, X3: C, R1:
Figure pat00457
, R2:
Figure pat00458
)을 수득하였다. 상기 화합물 353의 NMR은 하기 표 1에 기재하였다.
In the '(6) Preparation of the final compound' in the synthesis method of Synthesis Example 9, instead of 4-chloro-2,6-diphenylpyridine, (4- (thiophen-2-yl) phenyl) boronic acid (( Synthesis was carried out in the same manner except that 4- (thiophen-2-yl) phenyl) boronic acid) was used. Thus, Compound 353 (A 1 :
Figure pat00456
, A 2 : H, A 3 : H, A 4 : H, X 1 : N, X 2 : N, X 3 : C, R 1 :
Figure pat00457
, R 2 :
Figure pat00458
) Was obtained. NMR of the compound 353 is shown in Table 1 below.

합성예Synthetic example 82: 화합물 373의 제조 82: Preparation of Compound 373

하기 반응식 8의 반응 경로를 거쳐 화합물 373을 합성하였다.Compound 373 was synthesized through the reaction route of Scheme 8 below.

<반응식 8><Reaction Scheme 8>

Figure pat00459
Figure pat00459

(1) 화합물 7-1의 제조 (1) Preparation of Compound 7-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the resultant was separated by column chromatography to obtain 9.7 g (30%) of the title compound 7-1.

(2) 화합물 7-2의 제조 (2) Preparation of Compound 7-2

화합물 7-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 7-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 7-2.

(3) 화합물 7-3의 제조 (3) Preparation of Compound 7-3

화합물 7-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 7-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the title compound 7-3.

(4) 화합물 7-4의 제조 (4) Preparation of Compound 7-4

화합물 7-3 (46.7m㏖), 디벤조[b,d]퓨란-3-일보론산 9.64g(56.03m㏖), 페닐보론산 (56.03m㏖), Pd(PPh3)4 5.4g(4.67m㏖), 및 K2CO3, 19.4g(140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 7-4(A2:

Figure pat00460
, A4:
Figure pat00461
) 19.8g (89%)을 얻었다.
Compound 7-3 (46.7 mmol), 9.64 g (56.03 mmol) of dibenzo [b, d] furan-3-ylboronic acid, phenylboronic acid (56.03 mmol), Pd (PPh 3 ) 4 5.4 g (4.67) mmol), and 19.4 g (140.1 mmol) of K 2 CO 3 were dissolved in 200 ml / 40 ml / 40 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent, and the target compound 7-4 (A 2 :
Figure pat00460
, A 4 :
Figure pat00461
) 19.8 g (89%).

(5) 화합물 7-5의 제조 (5) Preparation of Compound 7-5

화합물 7-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 7-5(A2:

Figure pat00462
, A4:
Figure pat00463
) 11.2g (80%)을 얻었다.
Compound 7-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 1,2-dichlorobenzene was removed using a vacuum distillation apparatus. Purified by column chromatography using dichloromethane and hexane as a developing solvent, the target compound 7-5 (A 2 :
Figure pat00462
, A 4 :
Figure pat00463
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 7-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 나프탈렌-2-일보론산 (22.6m㏖) 을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 373(A1: H, A2:

Figure pat00464
, A3: H, A4:
Figure pat00465
, X1: N, X2: N, X3: N, R1:
Figure pat00466
, R2:
Figure pat00467
)을 수득하였다. 상기 화합물 373의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 7-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, naphthalen-2-ylboronic acid (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was separated using dichloromethane and hexane as a developing solvent, and separated by column chromatography. Compound 373 (A 1 : H, A 2 :
Figure pat00464
, A 3 : H, A 4 :
Figure pat00465
, X 1 : N, X 2 : N, X 3 : N, R 1 :
Figure pat00466
, R 2 :
Figure pat00467
) Was obtained. NMR of the compound 373 is shown in Table 1 below.

합성예Synthetic example 83: 화합물 385의 제조 83: Preparation of Compound 385

하기 반응식 9의 반응 경로를 거쳐 화합물 385을 합성하였다.Compound 385 was synthesized through the reaction route of Scheme 9 below.

<반응식 9><Reaction Scheme 9>

Figure pat00468
Figure pat00468

(1) 화합물 8-1의 제조 (1) Preparation of Compound 8-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 8-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 9.7 g (30%) of the titled Compound 8-1.

(2) 화합물 8-2의 제조 (2) Preparation of Compound 8-2

화합물 8-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 8-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 8-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 8-2.

(3) 화합물 8-3의 제조 (3) Preparation of Compound 8-3

화합물 8-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 8-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 8-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 57 g (90%) of the title compound 8-3.

(4) 화합물 8-4의 제조 (4) Preparation of Compound 8-4

화합물 8-3 (46.7m㏖), 나프탈렌-1-일보론산 (56.03m㏖), 3-클로로피리딘(56.03m㏖), Pd(PPh3)4 (4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 8-4(A2:

Figure pat00469
, A3:
Figure pat00470
) 19.8g (89%)을 얻었다.
Compound 8-3 (46.7 mmol), naphthalen-1-ylboronic acid (56.03 mmol), 3-chloropyridine (56.03 mmol), Pd (PPh 3 ) 4 (4.67 mmol), and K 2 CO 3 , (140.1 mmol) was dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml and stirred at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent, and the target compound 8-4 (A 2 :
Figure pat00469
, A 3 :
Figure pat00470
) 19.8 g (89%).

(5) 화합물 8-5의 제조 (5) Preparation of Compound 8-5

화합물 8-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 8-5(A2:

Figure pat00471
, A3:
Figure pat00472
) 11.2g (80%)을 얻었다.
Compound 8-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 ml of 1,2-dichlorobenzene and stirred at 180 ° C. When the reaction was complete then cooled to room temperature, to remove the 1,2-dichlorobenzene by a vacuum distillation device, and purified by dichloromethane-hexane and the column chromatography as a developing solvent, the desired compound 8-5 (A 2:
Figure pat00471
, A 3 :
Figure pat00472
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 8-5 10g(22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, 4-클로로-2,6-디페닐피리딘 (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 385(A1: H, A2:

Figure pat00473
, A3:
Figure pat00474
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00475
, R2:
Figure pat00476
)을 수득하였다. 상기 화합물 385의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, 10 g (22.6 mmol) of Compound 8-5 was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, 4-chloro-2,6-diphenylpyridine (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. The reaction mixture was separated with column chromatography using dichloromethane and hexane as a developing solvent. Compound 385 (A 1 : H, A 2 :
Figure pat00473
, A 3 :
Figure pat00474
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00475
, R 2 :
Figure pat00476
) Was obtained. NMR of the compound 385 is shown in Table 1 below.

합성예Synthetic example 84: 화합물 386의 제조 84: Preparation of Compound 386

상기 합성예 83의 합성방법 중 '(4) 화합물 8-4의 제조'에서 3-클로로피리딘 대신 2-브로모-9,9-디메틸-9H-플루오렌을 이용한 것 이외에는 동일한 방법으로 합성하였다. 이에 따라, 화합물 8-4(A2:

Figure pat00477
, A3:
Figure pat00478
)를 수득하였다. 그리고, 최종 화합물로 화합물 386(A1: H, A2:
Figure pat00479
, A3:
Figure pat00480
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00481
, R2:
Figure pat00482
)을 수득하였다. 상기 화합물 386의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 83, '(4) Preparation of Compound 8-4' was synthesized in the same manner except that 2-bromo-9,9-dimethyl-9H-fluorene was used instead of 3-chloropyridine. Thus, compound 8-4 (A 2 :
Figure pat00477
, A 3 :
Figure pat00478
). In addition, Compound 386 (A 1 : H, A 2 :
Figure pat00479
, A 3 :
Figure pat00480
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00481
, R 2 :
Figure pat00482
) Was obtained. NMR of the compound 386 is shown in Table 1 below.

합성예Synthetic example 85: 화합물 387의 제조 85: preparation of compound 387

상기 합성예 83의 합성방법 중 '(4) 화합물 8-4의 제조'에서 3-클로로피리딘 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성하였다. 이에 따라, 화합물 8-4(A2:

Figure pat00483
, A3:
Figure pat00484
)를 수득하였다. 그리고, 최종 화합물로 화합물 387(A1: H, A2:
Figure pat00485
, A3:
Figure pat00486
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00487
, R2:
Figure pat00488
)을 수득하였다. 상기 화합물 387의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 83, '(4) Preparation of Compound 8-4' was synthesized in the same manner except that dibenzo [b, d] thiophen-3-ylboronic acid was used instead of 3-chloropyridine. Thus, compound 8-4 (A 2 :
Figure pat00483
, A 3 :
Figure pat00484
). In addition, Compound 387 (A 1 : H, A 2 :
Figure pat00485
, A 3 :
Figure pat00486
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00487
, R 2 :
Figure pat00488
) Was obtained. NMR of the compound 387 is shown in Table 1 below.

합성예Synthetic example 86: 화합물 388의 제조 86: Preparation of Compound 388

상기 합성예 83의 합성방법 중 '(4) 화합물 8-4의 제조'에서 3-클로로피리딘 대신 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성하였다. 이에 따라, 화합물 8-4(A2:

Figure pat00489
, A3:
Figure pat00490
)를 수득하였다. 그리고, 최종 화합물로 화합물 387(A1: H, A2:
Figure pat00491
, A3:
Figure pat00492
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00493
, R2:
Figure pat00494
)을 수득하였다. 상기 화합물 387의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 83, '(4) Preparation of Compound 8-4' was synthesized in the same manner except for using dibenzo [b, d] furan-3-ylboronic acid instead of 3-chloropyridine. Thus, compound 8-4 (A 2 :
Figure pat00489
, A 3 :
Figure pat00490
). In addition, Compound 387 (A 1 : H, A 2 :
Figure pat00491
, A 3 :
Figure pat00492
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00493
, R 2 :
Figure pat00494
) Was obtained. NMR of the compound 387 is shown in Table 1 below.

합성예Synthetic example 87: 화합물 389의 제조 87: Preparation of Compound 389

상기 합성예 83의 합성방법 중 '(4) 화합물 8-4의 제조'에서 3-클로로피리딘을 이용하지 않은 것 이외에는 동일한 방법으로 합성하였다. 이에 따라, 화합물 8-4(A2:

Figure pat00495
, A3:
Figure pat00496
)를 수득하였다. 그리고, 최종 화합물로 화합물 389(A1: H, A2:
Figure pat00497
, A3:
Figure pat00498
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00499
, R2:
Figure pat00500
)을 수득하였다. 상기 화합물 389의 NMR은 하기 표 1에 기재하였다.
Synthesis was carried out in the same manner as in Synthesis Example 83, except that 3-chloropyridine was not used in '(4) Preparation of Compound 8-4'. Thus, compound 8-4 (A 2 :
Figure pat00495
, A 3 :
Figure pat00496
). In addition, Compound 389 (A 1 : H, A 2 :
Figure pat00497
, A 3 :
Figure pat00498
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00499
, R 2 :
Figure pat00500
) Was obtained. NMR of the compound 389 is shown in Table 1 below.

합성예Synthetic example 88: 화합물 390의 제조 88: preparation of compound 390

하기 화학 반응식 10의 반응 경로를 거쳐 화합물 390을 합성하였다.Compound 390 was synthesized through the reaction route of Chemical Scheme 10 below.

<반응식 10><Reaction formula 10>

Figure pat00501
Figure pat00501

(1) 화합물 9-1의 제조 (1) Preparation of Compound 9-1

트리페닐렌(Triphenylene) 19g(83m㏖)을 니트로벤젠(Nitrobenzene) 600㎖에 녹인 후, 철 파우더(Iron powder) 0.07g(1.25 m㏖)을 넣고, 아이스 배스(Ice bath)에 넣고 0℃에서 교반하였다. 그 후, 이를 브로민(Bromine) 20g(125m㏖)을 니트로벤젠(Nitrobenzene) 50㎖에 용해시켜 천천히 넣고, 이를 아이스 배스에서 5시간 동안 교반하였다. 반응이 완결된 후, Na2SO3 용액을 넣었다. 이어서, 증류수와 디클로로메탄으로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 9-1 9.7g (30%)을 얻었다.
19 g (83 mmol) of triphenylene was dissolved in 600 ml of nitrobenzene, and then 0.07 g (1.25 mmol) of iron powder was added thereto, and placed in an ice bath at 0 ° C. Stirred. Thereafter, 20 g (125 mmol) of bromine was dissolved in 50 ml of nitrobenzene and slowly added thereto, and the mixture was stirred for 5 hours in an ice bath. After the reaction was completed, Na 2 SO 3 solution was added. Then, the organic layer was extracted with distilled water and dichloromethane. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and column chromatography was performed to obtain 9.7 g (30%) of the target compound 9-1.

(2) 화합물 9-2의 제조 (2) Preparation of Compound 9-2

화합물 8-1 38.7g(100m㏖)을 THF 200㎖ 녹인 후 -78℃에서 교반하였다. 2.5M BuLi 48㎖(120m㏖)을 천천히 첨가하고, 한시간 정도 교반하였다. 트리-이소-프로필 보레이트(Tri-iso-propyl borate) 24.5g(130m㏖)를 넣은 후, 상온에서 하루 정도 교반하였다. HCl 200㎖(2.0M)과 증류수를 넣어 반응을 완결하였다. 에틸 이써(Ethyl ether)을 이용하여 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후, 회전 증발기로 용매를 제거하고, 에틸아세테이트와 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 9-2 31.3g (89%)을 얻었다.
38.7 g (100 mmol) of Compound 8-1 was dissolved in 200 mL of THF, followed by stirring at -78 ° C. 48 mL (120 mmol) of 2.5M BuLi was slowly added and stirred for about 1 hour. 24.5 g (130 mmol) of tri-iso-propyl borate was added thereto, followed by stirring at room temperature for one day. 200 ml (2.0 M) of HCl and distilled water were added to complete the reaction. The organic layer was extracted using ethyl ether. After drying the organic layer with MgSO 4 , the solvent was removed by a rotary evaporator, ethyl acetate and hexane as a developing solvent was separated by column chromatography to give 31.3 g (89%) of the title compound 9-2.

(3) 화합물 9-3의 제조 (3) Preparation of Compound 9-3

화합물 9-2 62.6g(178.2m㏖), 2-브로모-1-니트로벤젠(2-Bromo-1-nitrobenzene) 30g(148.5m㏖), Pd(PPh3)4 17.2g(149m㏖), 및 K2CO3 61.6g(445.5 m㏖)을 톨루엔/에탄올/증류수 300㎖/60㎖/60㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 에틸아세테이트로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 9-3 57g (90%)을 얻었다.
62.6 g (178.2 mmol) of compound 9-2, 30 g (148.5 mmol) of 2-Bromo-1-nitrobenzene, 17.2 g (149 mmol) of Pd (PPh 3 ) 4 , And 61.6 g (445.5 mmol) of K 2 CO 3 were dissolved in 300 ml / 60 ml / 60 ml of toluene / ethanol / distilled water, followed by stirring at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and ethyl acetate. The organic layer was dried over MgSO 4 , and the solvent was removed using a rotary evaporator. Dichloromethane and hexane were used as a developing solvent, and the residue was separated by column chromatography to obtain 57 g (90%) of the title compound 9-3.

(4) 화합물 9-4의 제조 (4) Preparation of Compound 9-4

화합물 9-3 (46.7m㏖), 3-브로모-1,1-디메틸-1H-인덴 (56.03m㏖), 3-클로로피리딘 (56.03m㏖), Pd(PPh3)4 (4.67m㏖), 및 K2CO3, (140.1m㏖)을 톨루엔/에탄올/증류수 200㎖/40㎖/40㎖에 녹인 후, 100℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 상기 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 목적화합물 9-4(A1:

Figure pat00502
, A3:
Figure pat00503
) 19.8g (89%)을 얻었다.
Compound 9-3 (46.7 mmol), 3-bromo-1,1-dimethyl-1H-indene (56.03 mmol), 3-chloropyridine (56.03 mmol), Pd (PPh 3 ) 4 (4.67 mmol ) And K 2 CO 3 , (140.1 mmol) were dissolved in toluene / ethanol / distilled water 200ml / 40ml / 40ml and stirred at 100 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The reaction mixture was separated by column chromatography using dichloromethane and hexane as a developing solvent, and the target compound 9-4 (A 1 :
Figure pat00502
, A 3 :
Figure pat00503
) 19.8 g (89%).

(5) 화합물 9-5의 제조 (5) Preparation of Compound 9-5

화합물 9-4 (31.5m㏖)과 PPh3 (78.9m㏖)을 1,2-디클로로벤젠 (1,2-dichlorobenzene) 100㎖에 녹인 후, 180℃에서 교반하였다. 반응이 완결되면 상온까지 냉각시킨 후, 진공증류장치를 이용하여 1,2-디클로로벤젠을 제거하고 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 정제하여 목적화합물 9-5(A1:

Figure pat00504
, A3:
Figure pat00505
) 11.2g (80%)을 얻었다.
Compound 9-4 (31.5 mmol) and PPh 3 (78.9 mmol) were dissolved in 100 mL of 1,2-dichlorobenzene and stirred at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, and then 1,2-dichlorobenzene was removed using a vacuum distillation apparatus. Purified by column chromatography using dichloromethane and hexane as a developing solvent, target compound 9-5 (A 1 :
Figure pat00504
, A 3 :
Figure pat00505
) 11.2 g (80%) was obtained.

(6) 최종 화합물의 제조(6) Preparation of Final Compound

NaH(60% in 미네럴 오일) (28.2m㏖)을 DMF 20㎖에 녹였다. 그 후, 화합물 9-5 (22.6m㏖)을 DMF 60㎖에 녹인 후, 상기 용액에 첨가하였다. 그 후, 한시간 동안 상온에서 교반하였다. 이어서, [1,1'-비페닐]-3-일보론산 (22.6m㏖)을 DMF 50㎖에 녹인 후 상기 용액에 첨가한 후 150℃에서 교반하였다. 반응이 완결되면 증류수와 EA로 유기층을 추출하였다. 유기층을 MgSO4로 건조시킨 후 회전 증발기로 용매를 제거하고, 디클로로메탄과 헥산을 전개용매로 하여 컬럼크로마토그래피로 분리하고 최종 화합물로 화합물 390(A1:

Figure pat00506
, A2: H, A3:
Figure pat00507
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00508
, R2:
Figure pat00509
)을 수득하였다. 상기 화합물 390의 NMR은 하기 표 1에 기재하였다.
NaH (60% in mineral oil) (28.2 mmol) was dissolved in 20 mL of DMF. Thereafter, Compound 9-5 (22.6 mmol) was dissolved in 60 mL of DMF, and then added to the solution. Then, the mixture was stirred at room temperature for one hour. Subsequently, [1,1'-biphenyl] -3-ylboronic acid (22.6 mmol) was dissolved in 50 mL of DMF, added to the solution, and stirred at 150 ° C. When the reaction was completed, the organic layer was extracted with distilled water and EA. The organic layer was dried over MgSO 4 and the solvent was removed using a rotary evaporator. The solvent was separated using dichloromethane and hexane as a developing solvent and separated by column chromatography. Compound 390 (A 1 :
Figure pat00506
, A 2 : H, A 3 :
Figure pat00507
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00508
, R 2 :
Figure pat00509
) Was obtained. NMR of the compound 390 is shown in Table 1 below.

합성예Synthetic example 89: 화합물 391의 제조 89: Preparation of Compound 391

상기 합성예 88의 합성방법 중 '(4) 화합물 9-4의 제조'에서 3-클로로피리딘 대신 (9,9-디메틸-9,10-디하이드로안트라센-2-일)보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 9-4(A1:

Figure pat00510
, A2: H, A3:
Figure pat00511
)를 수득하였다. 그리고, 최종 화합물로 화합물 391(A1:
Figure pat00512
, A2: H, A3:
Figure pat00513
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00514
, R2:
Figure pat00515
)을 수득하였다. 상기 화합물 391의 NMR은 하기 표 1에 기재하였다.
Except for using (9,9-dimethyl-9,10-dihydroanthracen-2-yl) boronic acid instead of 3-chloropyridine in '(4) Preparation of Compound 9-4' in the synthesis method of Synthesis Example 88 Synthesis was carried out in the same manner. Thus, compound 9-4 (A 1 :
Figure pat00510
, A 2 : H, A 3 :
Figure pat00511
). In addition, Compound 391 (A 1 :
Figure pat00512
, A 2 : H, A 3 :
Figure pat00513
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00514
, R 2 :
Figure pat00515
) Was obtained. NMR of the compound 391 is shown in Table 1 below.

합성예Synthetic example 90: 화합물 392의 제조 90: Preparation of Compound 392

상기 합성예 88의 합성방법 중 '(4) 화합물 9-4의 제조'에서 3-클로로피리딘 대신 디벤조[b,d]티오펜-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 9-4(A1:

Figure pat00516
, A3:
Figure pat00517
)를 수득하였다. 그리고, 최종 화합물로 화합물 392(A1:
Figure pat00518
, A2: H, A3:
Figure pat00519
, A4: H, X1: C, X2: C, X3: N, R1:
Figure pat00520
, R2:
Figure pat00521
)을 수득하였다. 상기 화합물 392의 NMR은 하기 표 1에 기재하였다.
Synthesis was carried out in the same manner as in Synthesis Example 88 except that dibenzo [b, d] thiophen-3-ylboronic acid was used instead of 3-chloropyridine in '(4) Preparation of Compound 9-4'. . Thus, compound 9-4 (A 1 :
Figure pat00516
, A 3 :
Figure pat00517
). And as a final compound, Compound 392 (A 1 :
Figure pat00518
, A 2 : H, A 3 :
Figure pat00519
, A 4 : H, X 1 : C, X 2 : C, X 3 : N, R 1 :
Figure pat00520
, R 2 :
Figure pat00521
) Was obtained. NMR of the compound 392 is shown in Table 1 below.

합성예Synthetic example 91: 화합물 400의 제조 91: Preparation of Compound 400

상기 합성예 70의 합성방법 중 '(4) 화합물 5-4의 제조"에서 디벤조[b,d]퓨란-2-일보론산과 브로모벤젠 대신 티오펜-2-일보론산과 3-클로로피리딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 9-4(A2:

Figure pat00522
, A3:
Figure pat00523
)를 수득하였다.In the synthesis method of Synthesis Example 70, thiophen-2-ylboronic acid and 3-chloropyridine in place of dibenzo [b, d] furan-2-ylboronic acid and bromobenzene in "(4) Preparation of compound 5-4" Synthesis was carried out in the same manner except that Compound 9-4 (A 2 :
Figure pat00522
, A 3 :
Figure pat00523
).

그리고, 상기 합성예 70의 합성방법 중 '(6) 최종 화합물의 제조"에서 2-클로로-4-6-디페닐-1,3,5-트리아진 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 최종 화합물로 화합물 400(A1: H, A2:

Figure pat00524
, A3:
Figure pat00525
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00526
, R2:
Figure pat00527
)을 수득하였다. 상기 화합물 400의 NMR은 하기 표 1에 기재하였다.
In the synthesis method of Synthesis Example 70, 4-chloro-2,6-diphenyl instead of 2-chloro-4-6-diphenyl-1,3,5-triazine in the 'preparation of the final compound (6)' Synthesis was carried out in the same manner except that pyrimidine was used, and as a result, compound 400 (A 1 : H, A 2 :
Figure pat00524
, A 3 :
Figure pat00525
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00526
, R 2 :
Figure pat00527
) Was obtained. NMR of the compound 400 is shown in Table 1 below.

합성예Synthetic example 92: 화합물 403의 제조 92: Preparation of Compound 403

상기 합성예 70의 합성방법 중 '(4) 화합물 5-4의 제조'에서 디벤조[b,d]퓨란-2-일보론산과 브로모벤젠 대신 티오펜-2-일보론산과 디벤조[b,d]퓨란-3-일보론산을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다. 이에 따라, 화합물 9-4(A2:

Figure pat00528
, A3:
Figure pat00529
)를 수득하였다.In the synthesis method of Synthesis Example 70, thiophen-2-ylboronic acid and dibenzo [b instead of dibenzo [b, d] furan-2-ylboronic acid and bromobenzene in the '(4) Preparation of Compound 5-4' , d] Synthesis was performed in the same manner except using furan-3-ylboronic acid. Thus, compound 9-4 (A 2 :
Figure pat00528
, A 3 :
Figure pat00529
).

그리고, 상기 합성예 70의 합성방법 중 '(6) 최종 화합물의 제조'에서 2-클로로-4-6-디페닐-1,3,5-트리아진 대신 4-클로로-2,6-디페닐피리미딘을 이용한 것 이외에는 동일한 방법으로 합성을 진행하였다.In the synthesis method of Synthesis Example 70, 4-chloro-2,6-diphenyl instead of 2-chloro-4-6-diphenyl-1,3,5-triazine in '(6) Preparation of the final compound' Synthesis was performed in the same manner except that pyrimidine was used.

이에 따라, 최종 화합물로 화합물 403(A1: H, A2:

Figure pat00530
, A3:
Figure pat00531
, A4: H, X1: N, X2: C, X3: N, R1:
Figure pat00532
, R2:
Figure pat00533
)을 수득하였다. 상기 화합물 403의 NMR은 하기 표 1에 기재하였다.Accordingly, Compound 403 (A 1 : H, A 2 :
Figure pat00530
, A 3 :
Figure pat00531
, A 4 : H, X 1 : N, X 2 : C, X 3 : N, R 1 :
Figure pat00532
, R 2 :
Figure pat00533
) Was obtained. NMR of the compound 403 is shown in Table 1 below.

화합물
번호compound
number NMRNMR FoundFound calculatedcalculated 1One d=8.99(1H, d), 8.93(2H, d), 8.34-8.30(5H, m), 8.12-8.10(4H, m), 7.93-7.77(5H, m), 7.63-7.38(11H, m), 7.29-7.28(2H, s), 1.72(6H, s). d = 8.99 (1H, d), 8.93 (2H, d), 8.34-8.30 (5H, m), 8.12-8.10 (4H, m), 7.93-7.77 (5H, m), 7.63-7.38 (11H, m ), 7.29-7.28 (2H, s), 1.72 (6H, s). 738.91738.91 738.30738.30 44 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.30(4H, d), 8.12-8.10(4H, t), 8.00(2H, d), 7.92-7.82(3H, m), 7.73(1H, s), 7.47(2H, t), 7.29(1H, t), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.30 (4H, d), 8.12-8.10 (4H, t), 8.00 (2H, d), 7.92-7.82 ( 3H, m), 7.73 (1H, s), 7.47 (2H, t), 7.29 (1H, t), 7.05 (2H, s). 672.81672.81 672.26672.26 55 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.06(1H, s), 8.04(1H, d), 7.88-7.82(3H, t), 7.61-7.28(14H, m), 7.05(2H, s), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.06 (1H, s), 8.04 (1H, d) , 7.88-7.82 (3H, t), 7.61-7.28 (14H, m), 7.05 (2H, s), 1.72 (6H, s). 738.91738.91 738.30738.30 88 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, s), 8.00(2H, d), 7.92-7.73(4H, m), 7.63-7.47(11H, m), 7.29(1H, s), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, s), 8.00 (2H, d) , 7.92-7.73 (4H, m), 7.63-7.47 (11H, m), 7.29 (1H, s), 7.05 (2H, s). 672.81672.81 672.26672.26 99 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.30(4H, d), 8.20(1H, d), 8.12(3H, d), 8.10(1H, d), 7.88-7.75(4H, m), 7.65-7.47(10H, m), 7.29(1H, t), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.30 (4H, d), 8.20 (1H, d), 8.12 (3H, d), 8.10 (1H, d) , 7.88-7.75 (4H, m), 7.65-7.47 (10H, m), 7.29 (1H, t), 7.05 (2H, s). 678.84678.84 678.21678.21 1111 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 7.93-7.77(5H, t), 7.63(2H, d), 7.55-7.28(11H, m), 7.05(2H, s), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 7.93-7.77 (5H, t), 7.63 (2H, d), 7.55-7.28 (11 H, m), 7.05 (2H, s), 1.72 (6H, s). 738.91738.91 738.30738.30 1212 d=9.15(1H, s), 8.93(2H, d), 8.45(1H, d), 8.30(4H, d), 8.18(1H, d), 8.12-7.98(8H, m), 7.63-7.47(10H, m), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.45 (1H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12-7.98 (8H, m), 7.63-7.47 ( 10H, m), 7.29 (1H, t), 7.05 (2H, s). 728.90728.90 728.23728.23 1414 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.04-7.73(7H, m), 7.63-7.47(11H, m), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04-7.73 (7H, m), 7.63-7.47 ( 11 H, m), 7.29 (1 H, t), 7.05 (2 H, s). 672.81672.81 672.26672.26 1515 d=8.99(1H, d), 8.93(2H, d), 8.34(1H,s), 8.30(4H, d), 8.12-8.00(5H, t), 7.88-7.82(3H, m), 7.63-7.28(14H, m), 7.05(2H, s), 1.72(6H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.30 (4H, d), 8.12-8.00 (5H, t), 7.88-7.82 (3H, m), 7.63- 7.28 (14H, m), 7.05 (2H, s), 1.72 (6H, s). 738.91738.91 738.30738.30 2020 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 7.88(1H, t), 7.85(1H, d), 7.82(1H, t), 7.81(1H, d), 7.63-7.29(11H, m), 7.05(2H, s), 6.66(1H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 7.88 (1H, t) , 7.85 (1H, d), 7.82 (1H, t), 7.81 (1H, d), 7.63-7.29 (11H, m), 7.05 (2H, s), 6.66 (1H, d). 662.78662.78 662.24662.24 2424 d=9.15(1H, s), 8.93(2H, d), 8.30(4H, d), 8.18-8.04(5H, d), 7.88(1H, t), 7.82(1H, t), 7.68(2H, d), 7.63(1H, d), 7.54(4H, t), 7.50(1H, t), 7.47(2H, t), 7.38-7.29(3H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (4H, d), 8.18-8.04 (5H, d), 7.88 (1H, t), 7.82 (1H, t), 7.68 (2H, d), 7.63 (1H, d), 7.54 (4H, t), 7.50 (1H, t), 7.47 (2H, t), 7.38-7.29 (3H, t), 7.05 (2H, s). 690.75690.75 690.23690.23 2525 d=8.99(1H, d), 8.93(2H, d), 8.34(1H,s), 8.28(2H, d), 8.12-8.10(4H, d), 7.93-7.77(7H, m), 7.63(2H, d), 7.55(1H, d), 7.51(4H, t), 7.50(1H, t), 7.41-7.28(6H, m), 1.72(6H, s). d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12-8.10 (4H, d), 7.93-7.77 (7H, m), 7.63 ( 2H, d), 7.55 (1H, d), 7.51 (4H, t), 7.50 (1H, t), 7.41-7.28 (6H, m), 1.72 (6H, s). 739.90739.90 739.30739.30 2626 d=8.99(1H, d), 8.93(2H, d), 8.45(1H, d), 8.34(1H, s), 8.28(2H, d), 8.12(3H, d), 8.11-7.98(5H, d), 7.79(2H, d), 7.88(1H, t), 7.82(1H, t), 7.63(1H, d), 7.52(1H, t), 7.51(4H, m), 7.50(2H, t), 7.41(2H, m), 7.32(1H, s), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.45 (1H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12 (3H, d), 8.11-7.98 (5H, d), 7.79 (2H, d), 7.88 (1H, t), 7.82 (1H, t), 7.63 (1H, d), 7.52 (1H, t), 7.51 (4H, m), 7.50 (2H, t ), 7.41 (2H, m), 7.32 (1H, s), 7.29 (1H, t). 729.89729.89 729.22729.22 2828 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(2H, d), 8.12-8.10(4H, d), 8.00-7.73(8H, m), 7.63-7.41(11H, m), 7.32(1H, s), 7.29(1H, t). d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12-8.10 (4H, d), 8.00-7.73 (8H, m), 7.63- 7.41 (11 H, m), 7.32 (1 H, s), 7.29 (1 H, t). 673.80673.80 673.25673.25 3838 d=9.15(1H, s), 8.93(2H, d), 8.28(2H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 8.00(2H, d), 7.92-7.73(6H, m), 7.63-7.41 (11H, m), 7.32(1H, s), 7.29(1H, t).d = 9.15 (1H, s), 8.93 (2H, d), 8.28 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 8.00 (2H, d) , 7.92-7.73 (6H, m), 7.63-7.41 (11H, m), 7.32 (1H, s), 7.29 (1H, t). 673.80673.80 673.25673.25 3939 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(2H, d), 8.12(3H, d), 8.10(1H, d), 8.00(1H, s), 7.88-7.79(5H, m), 7.63(1H, d), 7.61(1H, d), 7.55(1H, d), 7.53(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12 (3H, d), 8.10 (1H, d), 8.00 (1H, s) , 7.88-7.79 (5H, m), 7.63 (1H, d), 7.61 (1H, d), 7.55 (1H, d), 7.53 (1H, d), 7.51 (4H, m), 7.50 (1H, t ), 7.41 (2H, t), 7.32 (1H, s), 7.29 (1H, t). 739.90739.90 739.30739.30 4242 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(2H, d), 8.12-8.10(4H, d), 8.00(2H, d), 7.92-7.79(6H, m), 7.63(1H, d), 7.59(2H, m), 7.58(1H, s), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12-8.10 (4H, d), 8.00 (2H, d), 7.92-7.79 ( 6H, m), 7.63 (1H, d), 7.59 (2H, m), 7.58 (1H, s), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.32 (1H) , s), 7.29 (1 H, t). 673.80673.80 673.25673.25 4545 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(2H, d), 8.12-8.10(4H, d), 7.88(1H, t), 7.82(1H, t), 7.79(2H, d), 7.68(2H, d), 7.63(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.38(2H, d), 7.32(1H, s), 7.29(1H, d). d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (2H, d), 8.12-8.10 (4H, d), 7.88 (1H, t), 7.82 (1H, t), 7.79 (2H, d), 7.68 (2H, d), 7.63 (1H, d), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.38 (2H, d ), 7.32 (1 H, s), 7.29 (1 H, d). 691.74691.74 691.22691.22 4848 d=9.15(1H, s), 8.93(2H, d), 8.28(2H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 7.88(1H, t), 7.82(1H, t), 7.79(2H, d), 7.68(2H, d), 7.63(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.38(2H, d), 7.32(1H, s), 7.29(1H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.28 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 7.88 (1H, t) , 7.82 (1H, t), 7.79 (2H, d), 7.68 (2H, d), 7.63 (1H, d), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.38 (2H, d), 7.32 (1 H, s), 7.29 (1 H, d). 691.74691.74 691.22691.22 5959 d=9.15(1H, s), 8.93(2H, d), 8.63(1H, s), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 7.93-7.82(4H, m), 7.79(4H, d), 7.77(1H, s), 7.63(2H, d), 7.55(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.38-7.28(3H, m), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.63 (1H, s), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d), 7.93-7.82 (4H, m), 7.79 (4H, d), 7.77 (1H, s), 7.63 (2H, d), 7.55 (1H, d), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t ), 7.38-7.28 (3H, m), 1.72 (6H, s). 739.90739.90 739.30739.30 6666 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12(3H, d), 8.10(1H, d), 8.00(2H, d), 7.92-7.82(3H, m), 7.79(4H, t), 7.73(1H, d), 7.63(1H, d), 7.59(2H, m), 7.58(1H, s), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12 (3H, d), 8.10 (1H, d), 8.00 (2H, d) , 7.92-7.82 (3H, m), 7.79 (4H, t), 7.73 (1H, d), 7.63 (1H, d), 7.59 (2H, m), 7.58 (1H, s), 7.51 (4H, m ), 7.50 (1H, t), 7.41 (2H, t), 7.29 (1H, t). 673.80673.80 673.25673.25 6969 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12-8.10(4H, m), 7.88(1H, t), 7.79(4H, m), 7.82(1H, t), 7.68(2H, d), 7.63(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.38(2H, d), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12-8.10 (4H, m), 7.88 (1H, t), 7.79 (4H, m), 7.82 (1H, t), 7.68 (2H, d), 7.63 (1H, d), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.38 (2H, d ), 7.29 (1 H, t). 691.74691.74 691.22691.22 7272 d=9.15(1H, s), 8.93(2H, d), 8.63(1H, s), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 7.88(1H, d), 7.82(1H, d), 7.79(4H, d), 7.68(2H, d), 7.63(1H, d), 7.51(4H, m), 7.50(1H, d), 7.41(2H, t), 7.38(2H, d), 7.29(1H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.63 (1H, s), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 7.88 (1H, d) , 7.82 (1H, d), 7.79 (4H, d), 7.68 (2H, d), 7.63 (1H, d), 7.51 (4H, m), 7.50 (1H, d), 7.41 (2H, t), 7.38 (2H, d), 7.29 (1 H, d). 691.74691.74 691.22691.22 7676 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(4H, d), 8.12-8.10(4H, m), 8.00(2H, d), 7.92-7.82(3H, m), 7.63(1H, d), 7.59(2H, d), 7.58(1H, s), 7.51(4H, t), 7.50(1H, t), 7.41(2H, t), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (4H, d), 8.12-8.10 (4H, m), 8.00 (2H, d), 7.92-7.82 ( 3H, m), 7.63 (1H, d), 7.59 (2H, d), 7.58 (1H, s), 7.51 (4H, t), 7.50 (1H, t), 7.41 (2H, t), 7.29 (1H) , t). 674.79674.79 674.25674.25 8686 d=9.15(1H, s), 8.93(2H, d), 8.28(4H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 8.00(2H, d), 7.92-7.73(4H, m), 7.63(1H, d), 7.59(2H, m), 7.58(1H, s), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.29(1H, t).d = 9.15 (1H, s), 8.93 (2H, d), 8.28 (4H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 8.00 (2H, d) , 7.92-7.73 (4H, m), 7.63 (1H, d), 7.59 (2H, m), 7.58 (1H, s), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t ), 7.29 (1 H, t). 674.79674.79 674.25674.25 9090 d=.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.28(4H, d), 8.12-8.10(4H, m), 8.00(2H, d), 7.92-7.82(3H, m), 7.73(1H, d), 7.63(1H, d), 7.59(2H, d), 7.58(1H, s), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t).d = .99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.28 (4H, d), 8.12-8.10 (4H, m), 8.00 (2H, d), 7.92-7.82 (3H, m), 7.73 (1H, d), 7.63 (1H, d), 7.59 (2H, d), 7.58 (1H, s), 7.51 (4H, m), 7.50 (1H, t), 7.41 ( 2H, t). 674.79674.79 674.25674.25 9595 d=8.99(1H, s), 8.93(2H, d), 8.34(1H, s), 8.28(4H, d), 8.12-8.10(4H, m), 7.88(1H, t), 7.82(1H, t), 7.68(2H, d), 7.63(1H, d), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.38(2H, d), 7.29(1H, t).d = 8.99 (1H, s), 8.93 (2H, d), 8.34 (1H, s), 8.28 (4H, d), 8.12-8.10 (4H, m), 7.88 (1H, t), 7.82 (1H, t), 7.68 (2H, d), 7.63 (1H, d), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.38 (2H, d), 7.29 (1H, t ). 692.73692.73 692.22692.22 105105 d=8.99(1H, d), 8.93(2H, d), 8.81(4H, d), 8.34(1H, s), 8.20(1H, d), 8.12-8.10(4H, m), 7.88(5H, d), 7.82(1H, t), 7.78(1H, d), 7.75(1H, d), 7.65-7.58(3H, m), 7.52(4H, d), 7.51(4H, t), 7.50(1H, d), 7.41(2H, t), 7.29(1H, t), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.81 (4H, d), 8.34 (1H, s), 8.20 (1H, d), 8.12-8.10 (4H, m), 7.88 (5H, d), 7.82 (1H, t), 7.78 (1H, d), 7.75 (1H, d), 7.65-7.58 (3H, m), 7.52 (4H, d), 7.51 (4H, t), 7.50 (1H , d), 7.41 (2H, t), 7.29 (1H, t), 7.05 (2H, s). 831.03831.03 830.28830.28 107107 d=9.15(1H, s), 8.93(2H, d), 8.81(4H, d), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 7.93(1H, d), 7.88(5H, d), 7.87(1H, d), 7.82(1H, t), 7.77(1H, s), 7.63(2H, d), 7.55(1H, d), 7.52(4H, d), 7.51(4H, t), 7.50(1H, t), 7.41(2H, d), 7.38(1H, t), 7.29(1H, t), 7.28(1H, t), 7.05(2H, s), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.81 (4H, d), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d), 7.93 (1H, d) , 7.88 (5H, d), 7.87 (1H, d), 7.82 (1H, t), 7.77 (1H, s), 7.63 (2H, d), 7.55 (1H, d), 7.52 (4H, d), 7.51 (4H, t), 7.50 (1H, t), 7.41 (2H, d), 7.38 (1H, t), 7.29 (1H, t), 7.28 (1H, t), 7.05 (2H, s), 1.72 (6H, s). 891.11891.11 890.37890.37 109109 d=9.15(1H, s), 8.93(2H, d), 8.81(4H, d), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 7.95(1H, d), 7.89(1H, d), 7.88(5H, m), 7.82(1H, t), 7.75(1H, d), 7.66-7.63(3H, m), 7.52(4H, d), 7.51(4H, t), 7.50(1H, t), 7.41(2H, t), 7.38-7.29(3H, m), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.81 (4H, d), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d), 7.95 (1H, d) , 7.89 (1H, d), 7.88 (5H, m), 7.82 (1H, t), 7.75 (1H, d), 7.66-7.63 (3H, m), 7.52 (4H, d), 7.51 (4H, t ), 7.50 (1H, t), 7.41 (2H, t), 7.38-7.29 (3H, m), 7.05 (2H, s). 865.03865.03 864.31864.31 110110 d=9.15(1H, s), 8.93(2H, d), 8.81(4H, d), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 8.00(2H, d), 7.92(1H, d), 7.88(5H, t), 7.82(1H, t), 7.73(1H, d), 7.63(1H, d), 7.59(2H, m), 7.58(1H, s), 7.52(4H, s), 7.51(4H, t), 7.50(1H, t), 7.41(2H, t), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.81 (4H, d), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d), 8.00 (2H, d) , 7.92 (1H, d), 7.88 (5H, t), 7.82 (1H, t), 7.73 (1H, d), 7.63 (1H, d), 7.59 (2H, m), 7.58 (1H, s), 7.52 (4H, s), 7.51 (4H, t), 7.50 (1H, t), 7.41 (2H, t), 7.29 (1H, t), 7.05 (2H, s). 825.01825.01 824.32824.32 112112 d=8.99(2H, d), 8.93(3H, d), 8.81(4H, d), 8.34(2H, s), 8.12(4H, d), 8.10(2H, d), 7.88(6H, m), 7.82(2H, t), 7.71(2H, s), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.29(1H, t), 7.05(2H, s). d = 8.99 (2H, d), 8.93 (3H, d), 8.81 (4H, d), 8.34 (2H, s), 8.12 (4H, d), 8.10 (2H, d), 7.88 (6H, m) , 7.82 (2H, t), 7.71 (2H, s), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.29 (1H, t), 7.05 (2H, s ). 875.06875.06 874.33874.33 115115 d=9.15(1H, s), 8.93(2H, d), 8.81(4H, d), 8.20(1H, d), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 7.88(5H, m), 7.82(1H, t), 7.78-7.75(2H, m), 7.65-7.41(14H, m), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.81 (4H, d), 8.20 (1H, d), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d) , 7.88 (5H, m), 7.82 (1H, t), 7.78-7.75 (2H, m), 7.65-7.41 (14H, m), 7.29 (1H, t), 7.05 (2H, s). 831.03831.03 830.28830.28 117117 d=8.99(1H, d), 8.93(2H, d), 8.81(4H, d), 8.34(1H, s), 8.12-8.10(4H, d), 7.88(5H, t), 7.82(1H, t), 7.63(1H, d), 7.52-7.50(9H, m), 7.41-7.29(7H, m), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.81 (4H, d), 8.34 (1H, s), 8.12-8.10 (4H, d), 7.88 (5H, t), 7.82 (1H, t), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41-7.29 (7H, m), 7.05 (2H, s). 792.94792.94 792.29792.29 119119 d=8.99(1H, d), 8.93(2H, d), 8.81(4H, d), 8.34(1H, s), 8.12-8.10(4H, d), 7.88(5H, m), 7.82(1H, t), 7.68(2H, d), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.38(2H, d), 7.29(1H, t), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.81 (4H, d), 8.34 (1H, s), 8.12-8.10 (4H, d), 7.88 (5H, m), 7.82 (1H, t), 7.68 (2H, d), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.38 (2H, d), 7.29 (1H, t), 7.05 (2H , s). 842.94842.94 842.29842.29 122122 d=8.99(1H, d), 8.93(2H, d), 8.45(1H, d), 8.34(1H, s), 8.30(2H, d), 8.12-7.88(8H, m), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.63(1H, d), 7.52-7.50(11H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 8.99 (1H, d), 8.93 (2H, d), 8.45 (1H, d), 8.34 (1H, s), 8.30 (2H, d), 8.12-7.88 (8H, m), 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.63 (1H, d), 7.52-7.50 (11H, m), 7.41 (2H, t), 7.32 (1H, s), 7.29 (1H) , t), 7.25 (2H, d). 882.08882.08 881.29881.29 125125 d=9.15(1H, s), 8.93(2H, d), 8.30(2H, d), 8.18(1H, d), 8.12(3H, d), 8.06(1H, s), 8.04(1H, d), 7.88(1H, t), 7.87(1H, d), 7.85(4H, m), 7.82(1H, t), 7.63-7.50(13H, m), 7.41(2H, t), 7.38-7.25(6H, m), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.06 (1H, s), 8.04 (1H, d) , 7.88 (1H, t), 7.87 (1H, d), 7.85 (4H, m), 7.82 (1H, t), 7.63-7.50 (13H, m), 7.41 (2H, t), 7.38-7.25 (6H m), 1.72 (6H, s). 892.06892.06 891.36891.36 129129 d=8.99(1H, s), 8.93(2H, d), 8.34(1H, s), 8.30(2H, d), 8.20(1H, d), 8.12(3H, d), 8.10(1H, d), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.78(1H, d), 7.75(1H, d), 7.65-7.58(3H, m), 7.52-7.50(9H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 8.99 (1H, s), 8.93 (2H, d), 8.34 (1H, s), 8.30 (2H, d), 8.20 (1H, d), 8.12 (3H, d), 8.10 (1H, d) , 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.78 (1H, d), 7.75 (1H, d), 7.65-7.58 (3H, m), 7.52-7.50 (9H m), 7.41 (2H, t), 7.32 (1H, s), 7.29 (1H, t), 7.25 (2H, d). 832.02832.02 831.27831.27 132132 d=9.15(1H, s), 8.93(2H, d), 8.45(1H, d), 8.30(2H, d), 8.18(1H, d), 8.12-8.04(7H, m), 7.98(1H, d), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.63(1H, d), 7.52-7.50(11H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.45 (1H, d), 8.30 (2H, d), 8.18 (1H, d), 8.12-8.04 (7H, m), 7.98 (1H, d), 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.63 (1H, d), 7.52-7.50 (11H, m), 7.41 (2H, t), 7.32 (1H) , s), 7.29 (1 H, t), 7.25 (2 H, d). 882.08882.08 881.29881.29 133133 d=9.15(1H, s), 8.93(2H, d), 8.30(2H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, t), 7.95(1H, d), 7.89(1H, d), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.75(1H, d), 7.66-7.63(3H, m), 7.52-7.50(9H, m), 7.41(2H, t), 7.38(1H, t), 7.32(2H, t), 7.29(1H, t), 7.25(2H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, t), 7.95 (1H, d) , 7.89 (1H, d), 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.75 (1H, d), 7.66-7.63 (3H, m), 7.52-7.50 (9H m), 7.41 (2H, t), 7.38 (1H, t), 7.32 (2H, t), 7.29 (1H, t), 7.25 (2H, d). 866.01866.01 865.31865.31 134134 d=9.15(1H, s), 8.93(2H, d), 8.30(2H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, t), 8.00(2H, d), 7.92(1H, d), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.73(1H, d), 7.63(1H, d), 7.59-7.50(12H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, t), 8.00 (2H, d) , 7.92 (1H, d), 7.88 (1H, t), 7.85 (4H, m), 7.82 (1H, t), 7.73 (1H, d), 7.63 (1H, d), 7.59-7.50 (12H, m ), 7.41 (2H, t), 7.32 (1H, s), 7.29 (1H, t), 7.25 (2H, d). 825.99825.99 825.31825.31 135135 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.30(2H, d), 8.12-8.06(5H, m), 7.88(1H, t), 7.87(1H, d), 7.85(4H, d), 7.82(1H, t), 7.63-7.50(13H, m), 7.41(2H, t), 7.38(1H, t), 7.32(1H, s), 7.29-7.28(2H, t), 7.25(2H, d), 1.72(6H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.30 (2H, d), 8.12-8.06 (5H, m), 7.88 (1H, t), 7.87 (1H, d), 7.85 (4H, d), 7.82 (1H, t), 7.63-7.50 (13H, m), 7.41 (2H, t), 7.38 (1H, t), 7.32 (1H, s), 7.29-7.28 (2H, t), 7.25 (2H, d), 1.72 (6H, s). 892.09892.09 891.36891.36 138138 d=8.99(1H, s), 8.93(2H, d), 8.34(1H, s), 8.30(2H, d), 8.12(3H, d), 8.10(1H, d), 8.00(2H, d), 7.92(1H, d), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 8.99 (1H, s), 8.93 (2H, d), 8.34 (1H, s), 8.30 (2H, d), 8.12 (3H, d), 8.10 (1H, d), 8.00 (2H, d) , 7.92 (1H, d), 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (2H, t ), 7.32 (1 H, s), 7.29 (1 H, t), 7.25 (2 H, d). 825.99825.99 825.31825.31 140140 d=9.15(1H, s), 8.93(2H, d), 8.30(2H, d), 8.18(1H, s), 8.12(3H, d), 8.04(1H, d), 7.88(1H, t), 7.85(5H, m), 7.82-7.81(2H, t), 7.63(1H, d), 7.52-7.50(10H, m), 7.41(2H, t), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d), 6.66(1H, d).d = 9.15 (1H, s), 8.93 (2H, d), 8.30 (2H, d), 8.18 (1H, s), 8.12 (3H, d), 8.04 (1H, d), 7.88 (1H, t) , 7.85 (5H, m), 7.82-7.81 (2H, t), 7.63 (1H, d), 7.52-7.50 (10H, m), 7.41 (2H, t), 7.32 (1H, s), 7.29 (1H) , t), 7.25 (2H, d), 6.66 (1 H, d). 815.96815.96 815.29815.29 143143 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.30(2H, d), 8.12-8.10(4H, m), 7.88-7.82(6H, m), 7.68(2H, d), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.38(2H, d), 7.32(1H, s), 7.29(1H, t), 7.25(2H, d).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.30 (2H, d), 8.12-8.10 (4H, m), 7.88-7.82 (6H, m), 7.68 ( 2H, d), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.38 (2H, d), 7.32 (1H, s), 7.29 (1H, t), 7.25 (2H, d). 843.93843.93 843.29843.29 146146 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.45(1H, d), 8.34(1H, s), 8.30(4H, d), 8.12-7.98(8H, m), 7.88(1H, t), 7.85(4H, d), 7.82(1H, t), 7.63(1H, d), 7.52-7.50(11H, m), 7.41(2H, t), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.45 (1H, d), 8.34 (1H, s), 8.30 (4H, d), 8.12-7.98 (8H, m), 7.88 (1H, t), 7.85 (4H, d), 7.82 (1H, t), 7.63 (1H, d), 7.52-7.50 (11H, m), 7.41 (2H, t), 7.29 (1H) , t). 882.08882.08 881.29881.29 163163 d=8.97(1H, s), 8.93(2H, d), 8.63(1H, s), 8.30(4H, d), 8.12(3H, d), 8.07(1H, s), 7.88(1H, m), 7.86(1H, d), 7.85(4H, m), 7.82(1H, t), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.309-7.22(5H, m), 6.75(1H, s), 1.69(6H, s).d = 8.97 (1H, s), 8.93 (2H, d), 8.63 (1H, s), 8.30 (4H, d), 8.12 (3H, d), 8.07 (1H, s), 7.88 (1H, m) , 7.86 (1H, d), 7.85 (4H, m), 7.82 (1H, t), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.309-7.22 (5H m), 6.75 (1 H, s), 1.69 (6 H, s). 842.04842.04 841.35841.35 165165 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.30(4H, m), 8.12-8.10(4H, m), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.67(1H, d), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.29(1H, t), 7.17(1H, m), 7.14(1H, d), 2.34(6H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.30 (4H, m), 8.12-8.10 (4H, m), 7.88 (1H, t), 7.85 (4H, m), 7.82 (1H, t), 7.67 (1H, d), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.29 (1H) , t), 7.17 (1 H, m), 7.14 (1 H, d), 2.34 (6 H, s). 803.99803.99 803.33803.33 167167 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.30(4H, m), 8.12(3H, d), 8.10(1H, d), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.68(2H, m), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.38(2H, m), 7.29(1H, t). d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.30 (4H, m), 8.12 (3H, d), 8.10 (1H, d) , 7.88 (1H, t), 7.85 (4H, m), 7.82 (1H, t), 7.68 (2H, m), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t ), 7.38 (2H, m), 7.29 (1H, t). 843.93843.93 843.29843.29 172172 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.12-8.10(4H, m), 8.00(2H, m), 7.92(1H, d), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(2H, t), 7.29(1H, t), 7.25(4H, m).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.12-8.10 (4H, m), 8.00 (2H, m), 7.92 (1H, d), 7.88 (1H, t), 7.85 (4H, m), 7.82 (1H, t), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (2H, t), 7.29 (1H, t), 7.25 (4H , m). 826.98826.98 826.31826.31 176176 d=9.15(1H, s), 8.93(2H, d), 8.18(1H, d), 8.12(3H, d), 8.00(2H, d), 7.92(1H, d), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(2H, t), 7.29(1H, t), 7.25(4H, m).d = 9.15 (1H, s), 8.93 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.00 (2H, d), 7.92 (1H, d), 7.88 (1H, t) , 7.85 (4H, m), 7.82 (1H, t), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (2H, t), 7.29 (1H, t), 7.25 (4H, m ). 826.98826.98 826.31826.31 182182 d=9.15(1H, s), 8.93(2H, d), 8.18(2H, d), 8.12(4H, d), 8.04(2H, d), 7.88(2H, t), 7.85(4H, m), 7.82(2H, t), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(2H, t), 7.29(1H, t), 7.25(4H, m).d = 9.15 (1H, s), 8.93 (2H, d), 8.18 (2H, d), 8.12 (4H, d), 8.04 (2H, d), 7.88 (2H, t), 7.85 (4H, m) , 7.82 (2H, t), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (2H, t), 7.29 (1H, t), 7.25 (4H, m). 901.06901.06 900.33900.33 193193 d=8.99(1H, d), 8.93(2H, d), 8.55(2H, d), 8.46(2H, d), 8.34(1H, s), 8.12-8.08(8H, m), 7.93(1H, d), 7.88-7.77(4H, m), 7.64-7.50(10H, m), 7.38(1H, t), 7.29(1H, t), 7.28(1H, t), 7.05(2H, s), 1.72(6H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.55 (2H, d), 8.46 (2H, d), 8.34 (1H, s), 8.12-8.08 (8H, m), 7.93 (1H, d), 7.88-7.77 (4H, m), 7.64-7.50 (10H, m), 7.38 (1H, t), 7.29 (1H, t), 7.28 (1H, t), 7.05 (2H, s), 1.72 (6H, s). 839.03839.03 838.33838.33 195195 d=8.99(1H, d), 8.93(2H, d), 8.55(2H, d), 8.46(2H, d), 8.34(1H, s), 8.12-8.08(8H, m), 7.95-7.75(5H, m), 7.66-7.50(10H, m), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t), 7.05(2H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.55 (2H, d), 8.46 (2H, d), 8.34 (1H, s), 8.12-8.08 (8H, m), 7.95-7.75 ( 5H, m), 7.66-7.50 (10H, m), 7.38 (1H, t), 7.32 (1H, t), 7.29 (1H, t), 7.05 (2H, s). 812.95812.95 812.28812.28 202202 d=8.99(1H, d), 8.93(2H, d), 8.85(2H, s), 8.38(2H, d), 8.34(1H, s), 8.12-7.82(14H, m), 7.63-7.50(7H, m), 7.38(1H, t), 7.29(1H, t), 7.05(2H, s), 6.66(1H, d).d = 8.99 (1H, d), 8.93 (2H, d), 8.85 (2H, s), 8.38 (2H, d), 8.34 (1H, s), 8.12-7.82 (14H, m), 7.63-7.50 ( 7H, m), 7.38 (1H, t), 7.29 (1H, t), 7.05 (2H, s), 6.66 (1H, d). 762.89762.89 762.27762.27 203203 d=9.15(1H, s), 8.93(2H, d), 8.85(2H, d), 8.38(2H, d), 8.18-7.82(16H, m), 7.63-7.50(8H, m), 7.38(1H, t), 7.29(1H, t), 7.28(1H, t), 7.05(2H, s), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.85 (2H, d), 8.38 (2H, d), 8.18-7.82 (16H, m), 7.63-7.50 (8H, m), 7.38 ( 1H, t), 7.29 (1H, t), 7.28 (1H, t), 7.05 (2H, s), 1.72 (6H, s). 839.03839.03 838.33838.33 204204 d=9.15(1H, s), 8.93(2H, d), 8.85(2H, s), 8.45(1H, d), 8.38(2H, d), 8.18-7.82(17H, m), 7.63-7.50(8H, m), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.85 (2H, s), 8.45 (1H, d), 8.38 (2H, d), 8.18-7.82 (17H, m), 7.63-7.50 ( 8H, m), 7.29 (1H, t), 7.05 (2H, s). 829.02829.02 828.26828.26 205205 d=9.15(1H, s), 8.93(2H, d), 8.85(2H, s), 8.38(2H, d), 8.18-7.82(16H, m), 7.66-7.50(8H, m), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.85 (2H, s), 8.38 (2H, d), 8.18-7.82 (16H, m), 7.66-7.50 (8H, m), 7.38 ( 1H, t), 7.32 (1H, t), 7.29 (1H, t), 7.05 (2H, s). 812.95812.95 812.28812.28 206206 d=9.15(1H, s), 8.93(2H, d), 8.85(2H, s), 8.38(2H, d), 8.18(1H, d), 8.12(3H, d), 8.04-7.82(12H, m), 7.73(1H, d), 7.63-7.50(9H, m), 7.29(1H, m), 7.05(2H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.85 (2H, s), 8.38 (2H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04-7.82 (12H, m), 7.73 (1H, d), 7.63-7.50 (9H, m), 7.29 (1H, m), 7.05 (2H, s). 772.93772.93 772.29772.29 217217 d=9.09(1H, s), 8.99(1H, d), 8.93(2H, d), 8.49(1H, d), 8.34(2H, s), 8.12(3H, d), 8.10(1H, d), 8.00-7.77(12H, m), 7.63-7.50(8H, m), 7.38(1H, t), 7.32(1H, s), 7.29(1H, t), 7.28(1H, t), 1.72(6H, s).d = 9.09 (1H, s), 8.99 (1H, d), 8.93 (2H, d), 8.49 (1H, d), 8.34 (2H, s), 8.12 (3H, d), 8.10 (1H, d) , 8.00-7.77 (12H, m), 7.63-7.50 (8H, m), 7.38 (1H, t), 7.32 (1H, s), 7.29 (1H, t), 7.28 (1H, t), 1.72 (6H , s). 840.02840.02 839.33839.33 219219 d=9.09(1H, s), 8.99(1H, d), 8.93(2H, d), 8.49(1H, d), 8.34(2H, s), 8.12-7.75(16H, m), 7.66(1H, d), 7.64(1H, s), 7.63-7.50(6H, m), 7.38(1H, t), 7.32(2H, t), 7.29(1H, t).d = 9.09 (1H, s), 8.99 (1H, d), 8.93 (2H, d), 8.49 (1H, d), 8.34 (2H, s), 8.12-7.75 (16H, m), 7.66 (1H, d), 7.64 (1H, s), 7.63-7.50 (6H, m), 7.38 (1H, t), 7.32 (2H, t), 7.29 (1H, t). 813.94813.94 813.28813.28 220220 d=9.09(1H, s), 8.99(1H, d), 8.93(2H, d), 8.49(1H, d), 8.34(2H, s), 8.12(3H, d), 8.10(1H, d), 8.00-7.82(12H, m), 7.73(1H, d), 7.63-7.50(9H, m), 7.32(1H, s), 7.29(1H, t).d = 9.09 (1H, s), 8.99 (1H, d), 8.93 (2H, d), 8.49 (1H, d), 8.34 (2H, s), 8.12 (3H, d), 8.10 (1H, d) 8.00-7.82 (12H, m), 7.73 (1H, d), 7.63-7.50 (9H, m), 7.32 (1H, s), 7.29 (1H, t). 773.92773.92 773.28773.28 227227 d=9.15(1H, s), 8.93(2H, d), 8.24(1H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 7.93-7.70(8H, m), 7.63-7.48(16H, m), 7.41(2H, t), 7.38(1H, t), 7.32(1H, s), 7.29(1H, t), 7.28(1H, t), 1.72(6H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.24 (1H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 7.93-7.70 (8H, m), 7.63-7.48 (16H, m), 7.41 (2H, t), 7.38 (1H, t), 7.32 (1H, s), 7.29 (1H, t), 7.28 (1H, t), 1.72 (6H , s). 892.29892.29 891.36891.36 231231 d=8.99(1H, s), 8.93(2H, d), 8.34(1H, s), 8.33(1H, d), 8.12(3H, d), 8.10(1H, d), 8.06(1H, s), 7.88(1H, t), 7.87(1H, d), 7.82(1H, t), 7.67-7.48(8H, m), 7.38(1H, t), 7.32(1H, s), 7.29(1H, t), 7.28(1H, t), 7.17(2H, d), 2.34(12H, s), 1.72(6H, s).d = 8.99 (1H, s), 8.93 (2H, d), 8.34 (1H, s), 8.33 (1H, d), 8.12 (3H, d), 8.10 (1H, d), 8.06 (1H, s) , 7.88 (1H, t), 7.87 (1H, d), 7.82 (1H, t), 7.67-7.48 (8H, m), 7.38 (1H, t), 7.32 (1H, s), 7.29 (1H, t ), 7.28 (1H, t), 7.17 (2H, d), 2.34 (12H, s), 1.72 (6H, s). 796.01796.01 795.36795.36 241241 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12(3H, d), 8.10(1H, d), 7.93-7.77(5H, m), 7.67(2H, d), 7.63(2H, d), 7.55(1H, d), 7.50(1H, t), 7.48(2H, d), 7.29(1H, t), 7.28(1H, t), 7.17(2H, d), 2.34(12H, s), 1.72(6H, s). d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12 (3H, d), 8.10 (1H, d), 7.93-7.77 (5H, m), 7.67 (2H, d), 7.63 (2H, d), 7.55 (1H, d), 7.50 (1H, t), 7.48 (2H, d), 7.29 (1H, t), 7.28 (1H, t) ), 7.17 (2H, d), 2.34 (12H, s), 1.72 (6H, s). 796.01796.01 795.36795.36 243243 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12(3H, d), 8.10(1H, d), 7.95-7.82(4H, m), 7.75(1H, d), 7.67-7.63(5H, m), 7.50(1H, t), 7.48(2H, d), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t), 7.17(2H, d), 2.34(12H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12 (3H, d), 8.10 (1H, d), 7.95-7.82 (4H, m), 7.75 (1H, d), 7.67-7.63 (5H, m), 7.50 (1H, t), 7.48 (2H, d), 7.38 (1H, t), 7.32 (1H, t), 7.29 (1H) , t), 7.17 (2H, d), 2.34 (12H, s). 796.93796.93 796.31796.31 248248 d=9.15(1H, s), 8.93(2H, d), 8.63(1H, s), 8.18(1H, d), 8.12(3H, d), 8.04(1H, d), 8.00(2H, d), 7.92(1H, d), 7.88(1H, t), 7.82(1H, t), 7.73(1H, d), 7.67(2H, s), 7.63(1H, d), 7.59-7.58(3H, m), 7.50(1H, t), 7.48(2H, d), 7.29(1H, t), 7.17(2H, d), 2.34(12H, s).d = 9.15 (1H, s), 8.93 (2H, d), 8.63 (1H, s), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, d), 8.00 (2H, d) , 7.92 (1H, d), 7.88 (1H, t), 7.82 (1H, t), 7.73 (1H, d), 7.67 (2H, s), 7.63 (1H, d), 7.59-7.58 (3H, m ), 7.50 (1H, t), 7.48 (2H, d), 7.29 (1H, t), 7.17 (2H, d), 2.34 (12H, s). 729.91729.91 729.31729.31 249249 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.20(1H, d), 8.12(3H, d), 8.10(1H, d), 7.88-7.75(4H, m), 7.67-7.48(8H, m), 7.29(1H, t), 7.17(2H, d), 2.34(12H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.20 (1H, d), 8.12 (3H, d), 8.10 (1H, d) , 7.88-7.75 (4H, m), 7.67-7.48 (8H, m), 7.29 (1H, t), 7.17 (2H, d), 2.34 (12H, s). 735.94735.94 735.27735.27 268268 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.12(3H, d), 8.10(2H, d), 8.00(2H, d), 7.92(1H, d), 7.88(1H, d), 7.82(1H, t), 7.77(4H, m), 7.73(1H, d), 7.63-7.50(5H, m), 7.30(4H, m), 7.29(1H, t). d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.12 (3H, d), 8.10 (2H, d), 8.00 (2H, d), 7.92 (1H, d) , 7.88 (1H, d), 7.82 (1H, t), 7.77 (4H, m), 7.73 (1H, d), 7.63-7.50 (5H, m), 7.30 (4H, m), 7.29 (1H, t ). 710.77710.77 710.23710.23 271271 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.34(1H, s), 8.28(4H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.04(1H, d), 7.89(1H, d), 7.81(1H, d), 7.72(1H, d), 7.71(1H, s), 7.66(1H, d), 7.63(1H, d), 7.52-7.50(9H, m), 7.41(3H, t), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.34 (1H, s), 8.28 (4H, d), 8.18 (1H, d), 8.12 (2H, d) , 8.10 (1H, d), 8.04 (1H, d), 7.89 (1H, d), 7.81 (1H, d), 7.72 (1H, d), 7.71 (1H, s), 7.66 (1H, d), 7.63 (1H, d), 7.52-7.50 (9H, m), 7.41 (3H, t), 7.38 (1H, t), 7.32 (1H, t), 7.29 (1H, t). 790.91790.91 790.27790.27 272272 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.34(1H, s), 8.28(4H, d), 8.18-7.92(8H, m), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(3H, t), 7.29(1H, t).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.34 (1H, s), 8.28 (4H, d), 8.18-7.92 (8H, m), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (3H, t), 7.29 (1H, t). 750.89750.89 750.28750.28 282282 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.34(1H, s), 8.28(4H, d), 8.18-7.92(8H, m), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(3H, t), 7.29(1H, s).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.34 (1H, s), 8.28 (4H, d), 8.18-7.92 (8H, m), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (3H, t), 7.29 (1H, s). 750.89750.89 750.28750.28 283283 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.34(1H, s), 8.28(4H, d), 8.20(1H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.04(1H, d), 7.78(1H, d), 7.75(1H, d), 7.65-7.50(12H, m), 7.41(3H, t), 7.29(1H, t). d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.34 (1H, s), 8.28 (4H, d), 8.20 (1H, d), 8.18 (1H, d) , 8.12 (2H, d), 8.10 (1H, d), 8.04 (1H, d), 7.78 (1H, d), 7.75 (1H, d), 7.65-7.50 (12H, m), 7.41 (3H, t ), 7.29 (1 H, t). 756.91756.91 756.23756.23 326326 d=9.15(1H, s), 8.93(2H, d), 8.26(1H, d), 8.18(1H, d), 8.12(3H, d), 8.04-7.73(20H, m), 7.63(1H, d), 7.59(2H, t), 7.58(1H, s), 7.51(8H, m), 7.50(1H, t), 7.41(3H, t), 7.32(1H, s), 7.29(1H, t).d = 9.15 (1H, s), 8.93 (2H, d), 8.26 (1H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04-7.73 (20H, m), 7.63 (1H, d), 7.59 (2H, t), 7.58 (1H, s), 7.51 (8H, m), 7.50 (1H, t), 7.41 (3H, t), 7.32 (1H, s), 7.29 (1H, t) ). 978.19978.19 977.38977.38 330330 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.26(1H, d), 8.12(3H, d), 8.10(1H, d), 8.00(2H, d), 7.92(1H, d), 7.91(2H, d), 7.88(1H, t), 7.82(1H, t), 7.81(1H, d), 7.79(8H, m), 7.76(2H, s), 7.73(1H, d), 7.63-7.50(13H, m), 7.41(4H, t), 7.32(1H, s), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.26 (1H, d), 8.12 (3H, d), 8.10 (1H, d), 8.00 (2H, d) , 7.92 (1H, d), 7.91 (2H, d), 7.88 (1H, t), 7.82 (1H, t), 7.81 (1H, d), 7.79 (8H, m), 7.76 (2H, s), 7.73 (1H, d), 7.63-7.50 (13H, m), 7.41 (4H, t), 7.32 (1H, s), 7.29 (1H, t). 978.19978.19 977.38977.38 333333 d=8.99(1H, d), 8.93(2H, d), 8.34(1H, s), 8.26(1H, d), 8.12(3H, d), 8.10(1H, d), 7.91-7.76(15H, m), 7.68(2H, d), 7.63(1H, d), 7.51(8H, m), 7.50(1H, t), 7.41(4H, t), 7.38(2H, d), 7.32(1H, s), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.34 (1H, s), 8.26 (1H, d), 8.12 (3H, d), 8.10 (1H, d), 7.91-7.76 (15H, m), 7.68 (2H, d), 7.63 (1H, d), 7.51 (8H, m), 7.50 (1H, t), 7.41 (4H, t), 7.38 (2H, d), 7.32 (1H, s ), 7.29 (1 H, t). 996.12996.12 995.35995.35 336336 d=9.15(1H, s), 8.93(2H, d), 8.26(1H, d), 8.18(1H, d), 8.12(3H, d), 8.04(1H, s), 7.91(2H, d), 7.88(1H, t), 7.82(1H, t), 7.81(1H, d), 7.79(8H, m), 7.76(2H, s), 7.68(2H, d), 7.63(1H, d), 7.51(8H, m), 7.50(1H, t), 7.41(4H, t), 7.38(2H, d), 7.32(1H, s), 7.29(1H, t).d = 9.15 (1H, s), 8.93 (2H, d), 8.26 (1H, d), 8.18 (1H, d), 8.12 (3H, d), 8.04 (1H, s), 7.91 (2H, d) , 7.88 (1H, t), 7.82 (1H, t), 7.81 (1H, d), 7.79 (8H, m), 7.76 (2H, s), 7.68 (2H, d), 7.63 (1H, d), 7.51 (8H, m), 7.50 (1H, t), 7.41 (4H, t), 7.38 (2H, d), 7.32 (1H, s), 7.29 (1H, t). 996.12996.12 995.35995.35 337337 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12(3H, d), 8.10(1H, d), 7.97-7.82(12H, m), 7.77(1H, s), 7.63(2H, d), 7.55(1H, d), 7.50(1H, t), 7.38(1H, t), 7.29(1H, t), 7.28(1H, t), 1.72(6H, s).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12 (3H, d), 8.10 (1H, d), 7.97-7.82 (12H, m), 7.77 (1H, s), 7.63 (2H, d), 7.55 (1H, d), 7.50 (1H, t), 7.38 (1H, t), 7.29 (1H, t), 7.28 (1H, t) ), 1.72 (6H, s). 789.92789.92 798.29798.29 339339 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.12(3H, d), 8.10(1H, d), 7.97-7.82(12H, m), 7.75(1H, d), 7.66(1H, d), 7.64(1H, s), 7.63(1H, d), 7.50(1H, t), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t).d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.12 (3H, d), 8.10 (1H, d), 7.97-7.82 (12H, m), 7.75 (1H, d), 7.66 (1H, d), 7.64 (1H, s), 7.63 (1H, d), 7.50 (1H, t), 7.38 (1H, t), 7.32 (1H, t ), 7.29 (1 H, t). 763.84763.84 763.24763.24 348348 d=9.15(1H, s), 8.93(2H, d), 8.63(1H, s), 8.45(1H, d), 8.30(4H, d), 8.18(1H, d), 8.12(3H, d), 8.08-7.98(4H, m), 7.88(1H, t), 7.85(4H, m), 7.82(1H, t), 7.69(2H, d), 7.63(1H, d), 7.52(1H, t), 7.50(2H, t), 7.40(2H, d), 7.29(1H, t), 7.17(2H, t). d = 9.15 (1H, s), 8.93 (2H, d), 8.63 (1H, s), 8.45 (1H, d), 8.30 (4H, d), 8.18 (1H, d), 8.12 (3H, d) , 8.08-7.98 (4H, m), 7.88 (1H, t), 7.85 (4H, m), 7.82 (1H, t), 7.69 (2H, d), 7.63 (1H, d), 7.52 (1H, t ), 7.50 (2H, t), 7.40 (2H, d), 7.29 (1H, t), 7.17 (2H, t). 894.13894.13 893.20893.20 353353 d=8.99(1H, d), 8.93(2H, d), 8.63(1H, s), 8.34(1H, s), 8.30(4H, m), 8.12(3H, d), 8.10(1H, d), 7.89-7.81(8H, m), 7.72-7.63(6H, m), 7.50(1H, t), 7.40(2H, d), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t), 7.17(2H, t). d = 8.99 (1H, d), 8.93 (2H, d), 8.63 (1H, s), 8.34 (1H, s), 8.30 (4H, m), 8.12 (3H, d), 8.10 (1H, d) , 7.89-7.81 (8H, m), 7.72-7.63 (6H, m), 7.50 (1H, t), 7.40 (2H, d), 7.38 (1H, t), 7.32 (1H, t), 7.29 (1H , t), 7.17 (2H, t). 878.07878.07 877.22877.22 373373 d=9.15(2H, s), 8.93(1H, s), 8.18(2H, d), 8.12(2H, d), 8.04(2H, d), 8.00(4H, m), 7.95-7.85(8H, m), 7.75(1H, d), 7.73(2H, d), 7.66-7.50(14H, m), 7.41(1H, t), 7.38-7.25(7H, m). d = 9.15 (2H, s), 8.93 (1H, s), 8.18 (2H, d), 8.12 (2H, d), 8.04 (2H, d), 8.00 (4H, m), 7.95-7.85 (8H, m), 7.75 (1H, d), 7.73 (2H, d), 7.66-7.50 (14H, m), 7.41 (1H, t), 7.38-7.25 (7H, m). 1043.221043.22 1042.371042.37 385385 d=9.24(1H, s), 9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.70(1H, d), 8.55(1H, d), 8.42(2H, d), 8.34(1H,s), 8.30(4H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.08(1H, d), 8.04(2H, d), 7.63(1H, d), 7.61(1H, t), 7.57(1H, t), 7.55(2H, m), 7.54(4H, t), 7.50(1H, t), 7.47(2H, t), 7.29(1H, t), 7.05(2H, s). d = 9.24 (1H, s), 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.70 (1H, d), 8.55 (1H, d), 8.42 (2H, d) , 8.34 (1H, s), 8.30 (4H, d), 8.18 (1H, d), 8.12 (2H, d), 8.10 (1H, d), 8.08 (1H, d), 8.04 (2H, d), 7.63 (1H, d), 7.61 (1H, t), 7.57 (1H, t), 7.55 (2H, m), 7.54 (4H, t), 7.50 (1H, t), 7.47 (2H, t), 7.29 (1H, t), 7.05 (2H, s). 749.90749.90 749.28749.28 386386 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.55(1H, d), 8.42(1H, d), 8.34(1H, s), 8.30(4H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.08(1H, d), 8.04(2H, d), 7.93(1H, d), 7.87(1H, d), 7.77(1H, s), 7.63(2H, d), 7.61(1H, s), 7.55(3H, d), 7.54(4H, t), 7.50(1H, t), 7.47(2H, t), 7.38-7.29(3H, m), 7.05(2H, s), 1.72(6H, s).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.55 (1H, d), 8.42 (1H, d), 8.34 (1H, s), 8.30 (4H, d) , 8.18 (1H, d), 8.12 (2H, d), 8.10 (1H, d), 8.08 (1H, d), 8.04 (2H, d), 7.93 (1H, d), 7.87 (1H, d), 7.77 (1H, s), 7.63 (2H, d), 7.61 (1H, s), 7.55 (3H, d), 7.54 (4H, t), 7.50 (1H, t), 7.47 (2H, t), 7.38 -7.29 (3H, m), 7.05 (2H, s), 1.72 (6H, s). 865.07865.07 864.35864.35 387387 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.55(1H, d), 8.45(1H, d), 8.42(1H, d), 8.34(1H, s), 8.30(4H, d), 8.18-8.10(5H, m), 8.08(2H, d), 8.05(1H, d), 8.04(2H, d), 7.98(1H, d), 7.63(1H, d), 7.61(1H, t), 7.55(2H, t), 7.54(4H, d), 7.52(1H, t), 7.50(2H, t), 7.47(2H, t), 7.29(1H, t), 7.05(2H, s). d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.55 (1H, d), 8.45 (1H, d), 8.42 (1H, d), 8.34 (1H, s) , 8.30 (4H, d), 8.18-8.10 (5H, m), 8.08 (2H, d), 8.05 (1H, d), 8.04 (2H, d), 7.98 (1H, d), 7.63 (1H, d ), 7.61 (1H, t), 7.55 (2H, t), 7.54 (4H, d), 7.52 (1H, t), 7.50 (2H, t), 7.47 (2H, t), 7.29 (1H, t) , 7.05 (2H, s). 855.05855.05 854.28854.28 388388 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.55(1H, d), 8.42(1H, d), 8.34(1H, s), 8.30(4H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.08(1H, d), 8.04(2H, d), 7.95(1H, d), 7.89(1H , d), 7.75(1H, d), 7.66(1H, d), 7.64(1H, s), 7.63(1H, d), 7.61(1H, t), 7.55(2H, t), 7.54(4H, t), 7.50(1H, t), 7.47(2H, t), 7.38(1H, t), 7.32(1H, t), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.55 (1H, d), 8.42 (1H, d), 8.34 (1H, s), 8.30 (4H, d) , 8.18 (1H, d), 8.12 (2H, d), 8.10 (1H, d), 8.08 (1H, d), 8.04 (2H, d), 7.95 (1H, d), 7.89 (1H, d), 7.75 (1H, d), 7.66 (1H, d), 7.64 (1H, s), 7.63 (1H, d), 7.61 (1H, t), 7.55 (2H, t), 7.54 (4H, t), 7.50 (1H, t), 7.47 (2H, t), 7.38 (1H, t), 7.32 (1H, t), 7.29 (1H, t), 7.05 (2H, s). 838.99838.99 838.30838.30 389389 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.55(1H, d), 8.42(1H, d), 8.34(1H, s), 8.30(4H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.08(1H, d), 8.04(2H, d), 8.00(2H, d), 7.92(1H, d), 7.73(1H, d), 7.63(1H, d), 7.61(1H, t), 7.59(2H, t), 7.58(1H, s), 7.55(2H, t), 7.54(4H, t), 7.50(1H, t), 7.47(2H, t), 7.29(1H, t), 7.05(2H, s).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.55 (1H, d), 8.42 (1H, d), 8.34 (1H, s), 8.30 (4H, d) , 8.18 (1H, d), 8.12 (2H, d), 8.10 (1H, d), 8.08 (1H, d), 8.04 (2H, d), 8.00 (2H, d), 7.92 (1H, d), 7.73 (1H, d), 7.63 (1H, d), 7.61 (1H, t), 7.59 (2H, t), 7.58 (1H, s), 7.55 (2H, t), 7.54 (4H, t), 7.50 (1H, t), 7.47 (2H, t), 7.29 (1H, t), 7.05 (2H, s). 798.97798.97 798.30798.30 390390 d=9.24(1H, s), 8.99(1H, d), 8.93(1H, s), 8.88(1H, d), 8.81(4H, d), 8.70(1H, d), 8.42(1H, d), 8.34(1H, s), 8.16(1H, s), 8.12(2H, d), 8.10(1H, d), 7.88(4H, d), 7.63(1H, d), 7.57(1H, t), 7.52-7.41(11H, m), 7.29(2H, t), 7.05(2H, s), 5.96(1H, s), 5.90-5.80(4H, m), 2.99(1H, d), 2.59(1H, d), 1.25(6H, s).d = 9.24 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.88 (1H, d), 8.81 (4H, d), 8.70 (1H, d), 8.42 (1H, d) , 8.34 (1H, s), 8.16 (1H, s), 8.12 (2H, d), 8.10 (1H, d), 7.88 (4H, d), 7.63 (1H, d), 7.57 (1H, t), 7.52-7.41 (11H, m), 7.29 (2H, t), 7.05 (2H, s), 5.96 (1H, s), 5.90-5.80 (4H, m), 2.99 (1H, d), 2.59 (1H, d), 1.25 (6 H, s). 920.15920.15 919.39919.39 391391 d=8.99(1H, d), 8.93(1H, s), 8.88(1H, d), 8.81(4H, d), 8.34(1H, s), 8.16(1H, s), 8.12(2H, d), 8.10(1H, d), 7.92(1H, d), 7.88(4H, d), 7.63(1H, d), 7.53(1H, s), 7.52-7.51(8H, m), 7.50(1H, t), 7.41(3H, m), 7.37(1H, d), 7.31(2H, d), 7.30(1H, d), 7.29(1H, t), 7.25-7.19(5H, m), 7.05(2H, s), 6.75(1H, s), 3.91(2H, s), 1.72(6H, s), 1.69(6H, s).d = 8.99 (1H, d), 8.93 (1H, s), 8.88 (1H, d), 8.81 (4H, d), 8.34 (1H, s), 8.16 (1H, s), 8.12 (2H, d) , 8.10 (1H, d), 7.92 (1H, d), 7.88 (4H, d), 7.63 (1H, d), 7.53 (1H, s), 7.52-7.51 (8H, m), 7.50 (1H, t ), 7.41 (3H, m), 7.37 (1H, d), 7.31 (2H, d), 7.30 (1H, d), 7.29 (1H, t), 7.25-7.19 (5H, m), 7.05 (2H, s), 6.75 (1H, s), 3.91 (2H, s), 1.72 (6H, s), 1.69 (6H, s). 1047.331047.33 1046.461046.46 392392 d=8.99(1H, d), 8.93(1H, s), 8.88(1H, d), 8.81(4H, d), 8.45(1H, d), 8.34(1H, s), 8.16(1H, s), 8.12(2H, d), 8.11(1H, d), 8.10(1H, d), 8.08(1H, s), 8.05(1H, d), 7.98(1H, d), 7.92(1H, d), 7.88(4H, d), 7.63(1H, d), 7.52-7.41(13H, m), 7.30(1H, d), 7.29(1H, t), 7.25-7.22(3H, m), 7.05(2H, s), 6.75(1H, s), 1.69(6H, s). d = 8.99 (1H, d), 8.93 (1H, s), 8.88 (1H, d), 8.81 (4H, d), 8.45 (1H, d), 8.34 (1H, s), 8.16 (1H, s) , 8.12 (2H, d), 8.11 (1H, d), 8.10 (1H, d), 8.08 (1H, s), 8.05 (1H, d), 7.98 (1H, d), 7.92 (1H, d), 7.88 (4H, d), 7.63 (1H, d), 7.52-7.41 (13H, m), 7.30 (1H, d), 7.29 (1H, t), 7.25-7.22 (3H, m), 7.05 (2H, s), 6.75 (1 H, s), 1.69 (6 H, s). 1023.291023.29 1022.371022.37 400400 d=9.24(1H, s), 9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.70(1H, d), 8.42(1H, d), 8.34(1H, s), 8.28(2H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.04(1H, d), 7.79(2H, d), 7.69(1H, d), 7.63(1H, d), 7.57(1H, t), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.40(1H, d), 7.32(1H, s), 7.29(1H, t), 7.17(1H, t), d = 9.24 (1H, s), 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.70 (1H, d), 8.42 (1H, d), 8.34 (1H, s) , 8.28 (2H, d), 8.18 (1H, d), 8.12 (2H, d), 8.10 (1H, d), 8.04 (1H, d), 7.79 (2H, d), 7.69 (1H, d), 7.63 (1H, d), 7.57 (1H, t), 7.51 (4H, m), 7.50 (1H, t), 7.41 (2H, t), 7.40 (1H, d), 7.32 (1H, s), 7.29 (1H, t), 7.17 (1H, t), 706.85706.85 706.22706.22 403403 d=9.15(1H, s), 8.99(1H, d), 8.93(1H, s), 8.34(1H, s), 8.28(2H, d), 8.18(1H, d), 8.12(2H, d), 8.10(1H, d), 8.04(1H, d), 7.95(1H, d), 7.89(1H, d), 7.79-7.63(7H, m), 7.51(4H, m), 7.50(1H, t), 7.41(2H, t), 7.40(1H, d), 7.38-7.29(4H, m), 7.17(1H, t).d = 9.15 (1H, s), 8.99 (1H, d), 8.93 (1H, s), 8.34 (1H, s), 8.28 (2H, d), 8.18 (1H, d), 8.12 (2H, d) , 8.10 (1H, d), 8.04 (1H, d), 7.95 (1H, d), 7.89 (1H, d), 7.79-7.63 (7H, m), 7.51 (4H, m), 7.50 (1H, t ), 7.41 (2H, t), 7.40 (1H, d), 7.38-7.29 (4H, m), 7.17 (1H, t). 795.95795.95 795.23795.23

제조예Manufacturing example 1 내지 92,  1 to 92, 비교제조예Comparative Manufacturing Example 1: 본 발명의 화합물을 이용한  1: using the compound of the present invention 유기전계발광소자의The organic electroluminescent device 제조 Produce

우선, OLED용 글래스(삼성-코닝사 제조)로부터 얻어진 투명전극 ITO 박막을, 트리클로로에틸렌, 아세톤, 에탄올, 증류수를 순차적으로 사용하여 초음파 세척을 실시한 후, 이소프로판올에 넣어 보관한 후 사용하였다.First, the transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning Co., Ltd.) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water in sequence, and then stored in isopropanol and used.

다음으로, 진공 증착 장비의 기판 폴더에 ITO 기판을 설치하고, 진공 증착 장비 내의 셀에 하기 4,4',4"-트리스(N,N-(2-나프틸)-페닐아미노)트리페닐 아민(4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine: 2-TNATA)을 넣었다.Next, an ITO substrate was placed in the substrate folder of the vacuum deposition equipment, and the following 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine was added to the cells in the vacuum deposition equipment. (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2-TNATA) was added.

Figure pat00534
Figure pat00534

이어서, 챔버 내의 진공도가 10-6torr에 도달할 때까지 배기시킨 후, 셀에 전류를 인가하여 2-TNATA를 증발시켜 ITO 기판 상에 200Å 두께의 정공 주입층을 증착하였다. 진공 증착 장비 내의 다른 셀에 하기 N,N'-비스(α-나프틸)-N,N'-디페닐-4,4'-디아민(N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine: NPB)을 넣고, 셀에 전류를 인가하여 증발시켜 정공주입층 위에 600Å 두께의 정공수송층을 증착하였다.Subsequently, after evacuating the chamber until the vacuum reached 10 −6 torr, a current was applied to the cell to evaporate 2-TNATA to deposit a 200 Å thick hole injection layer on the ITO substrate. N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine (N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine: NPB) was added, and a 600 Å thick hole transport layer was deposited on the hole injection layer by evaporation by applying a current to the cell.

Figure pat00535
Figure pat00535

상기 정공주입층, 정공수송층을 형성시킨 후, 그 위에 발광층을 다음과 같이 증착시켰다. 진공 증착 장비 내의 한쪽 셀에 발광 재료로 하기 표 3에 기재된 호스트를 넣고, 다른 셀에는 도펀트로 이리듐-트리스(2-페닐피리딘)(Iridium-tris(2-phenylpyidine: Ir(ppy)3)를 넣었다.After the hole injection layer and the hole transport layer were formed, a light emitting layer was deposited thereon as follows. In one cell of the vacuum deposition equipment, a host shown in Table 3 was used as a light emitting material, and in another cell, iridium-tris (2-phenylpyidine: Ir (ppy) 3 ) was added as a dopant. .

이어서, 두 셀을 같이 가열, 상기 도펀트의 증착속도 비율을 10중량%(호스트:도펀트= 90:10)로 증착함으로써 상기 정공 전달층 위에 400Å의 두께로로 발광층을 증착하였다. 이어서, 전자수송층으로서 하기 트리스(8-하이드록시퀴놀린)알루미늄(Ⅲ)(tris(8-hydroxyquinoline)aluminum(Ⅲ): Alq)를 200Å 두께로 증착하였다. Subsequently, the two cells were heated together, and the light emitting layer was deposited to a thickness of 400 kPa on the hole transport layer by depositing the deposition rate ratio of the dopant at 10 wt% (host: dopant = 90: 10). Subsequently, the following tris (8-hydroxyquinoline) aluminum (III): Alq was deposited to a thickness of 200 Å as an electron transport layer.

Figure pat00536
Figure pat00536

그 후, 전자주입층으로 하기 화합물 리튬 플루오라이드(lithium fluoride: LiF)를 10Å 두께로 증착하였다. 그리고, Al 음극을 1000Å의 두께로 증착하여 OLED를 제작하였다.Thereafter, the following compound lithium fluoride (LiF) was deposited as an electron injecting layer to a thickness of 10 Å. And an Al cathode was deposited to a thickness of 1000 Å to produce an OLED.

한편, OLED 소자 제작에 필요한 모든 유기 화합물은 재료 별로 각각 10-6~10-8torr 하에서 진공 승화 정제하여 OLED 제작에 사용하였다.On the other hand, all the organic compounds required for OLED device fabrication were vacuum sublimated and refined under 10 -6 ~ 10 -8 torr for each material, and used for OLED fabrication.

　 녹색 인광 호스트 재료Green phosphorescent host material 제조예 1Production Example 1 합성예 1Synthesis Example 1 제조예 2Production Example 2 합성예 2Synthesis Example 2 제조예 3Production Example 3 합성예 3Synthesis Example 3 제조예 4Production Example 4 합성예 4Synthesis Example 4 제조예 5Production Example 5 합성예 5Synthesis Example 5 제조예 6Production Example 6 합성예 6Synthesis Example 6 제조예 7Production Example 7 합성예 7Synthesis Example 7 제조예 8Production Example 8 합성예 8Synthesis Example 8 제조예 9Production Example 9 합성예 9Synthesis Example 9 제조예 10Production Example 10 합성예 10Synthesis Example 10 제조예 11Production Example 11 합성예 11Synthesis Example 11 제조예 12Production Example 12 합성예 12Synthesis Example 12 제조예 13Production Example 13 합성예 13Synthesis Example 13 제조예 14Production Example 14 합성예 14Synthesis Example 14 제조예 15Production Example 15 합성예 15Synthesis Example 15 제조예 16Production Example 16 합성예 16Synthesis Example 16 제조예 17Production Example 17 합성예 17Synthesis Example 17 제조예 18Production Example 18 합성예 18Synthesis Example 18 제조예 19Production Example 19 합성예 19Synthesis Example 19 제조예 20Production example 20 합성예 20Synthesis Example 20 제조예 21Production Example 21 합성예 21Synthesis Example 21 제조예 22Production Example 22 합성예 22Synthesis Example 22 제조예 23Production Example 23 합성예 23Synthesis Example 23 제조예 24Production Example 24 합성예 24Synthesis Example 24 제조예 25Production example 25 합성예 25Synthesis Example 25 제조예 26Production Example 26 합성예 26Synthesis Example 26 제조예 27Production Example 27 합성예 27Synthesis Example 27 제조예 28Production Example 28 합성예 28Synthesis Example 28 제조예 29Production Example 29 합성예 29Synthesis Example 29 제조예 30Production Example 30 합성예 30Synthesis Example 30 제조예 31Production Example 31 합성예 31Synthesis Example 31 제조예 32Production example 32 합성예 32Synthesis Example 32 제조예 33Production Example 33 합성예 33Synthesis Example 33 제조예 34Production example 34 합성예 34Synthesis Example 34 제조예 35Production example 35 합성예 35Synthesis Example 35 제조예 36Production Example 36 합성예 36Synthesis Example 36 제조예 37Production example 37 합성예 37Synthesis Example 37 제조예 38Production Example 38 합성예 38Synthesis Example 38 제조예 39Production example 39 합성예 39Synthesis Example 39 제조예 40Production example 40 합성예 40Synthesis Example 40 제조예 41Production example 41 합성예 41Synthesis Example 41 제조예 42Production example 42 합성예 42Synthesis Example 42 제조예 43Production Example 43 합성예 43Synthesis Example 43 제조예 44Production example 44 합성예 44Synthesis Example 44 제조예 45Production example 45 합성예 45Synthesis Example 45 제조예 46Production example 46 합성예 46Synthesis Example 46 제조예 47Production example 47 합성예 47Synthesis Example 47 제조예 48Production Example 48 합성예 48Synthesis Example 48 제조예 49Production Example 49 합성예 49Synthesis Example 49 제조예 50Production Example 50 합성예 50Synthesis Example 50 제조예 51Production example 51 합성예 51Synthesis Example 51 제조예 52Production example 52 합성예 52Synthesis Example 52 제조예 53Production Example 53 합성예 53Synthesis Example 53 제조예 54Production example 54 합성예 54Synthesis Example 54 제조예 55Production example 55 합성예 55Synthesis Example 55 제조예 56Production example 56 합성예 56Synthesis Example 56 제조예 57Production Example 57 합성예 57Synthesis Example 57 제조예 58Production Example 58 합성예 58Synthesis Example 58 제조예 59Production example 59 합성예 59Synthesis Example 59 제조예 60Production example 60 합성예 60Synthesis Example 60 제조예 61Production example 61 합성예 61Synthesis Example 61 제조예 62Production example 62 합성예 62Synthesis Example 62 제조예 63Production Example 63 합성예 63Synthesis Example 63 제조예 64Production example 64 합성예 64Synthesis Example 64 제조예 65Production example 65 합성예 65Synthesis Example 65 제조예 66Production example 66 합성예 66Synthesis Example 66 제조예 67Production example 67 합성예 67Synthesis Example 67 제조예 68Production example 68 합성예 68Synthesis Example 68 제조예 69Production Example 69 합성예 69Synthesis Example 69 제조예 70Production example 70 합성예 70Synthesis Example 70 제조예 71Preparation Example 71 합성예 71Synthesis Example 71 제조예 72Preparation Example 72 합성예 72Synthesis Example 72 제조예 73Preparation Example 73 합성예 73Synthesis Example 73 제조예 74Production example 74 합성예 74Synthesis Example 74 제조예 75Preparation 75 합성예 75Synthesis Example 75 제조예 76Production Example 76 합성예 76Synthesis Example 76 제조예 77Production Example 77 합성예 77Synthesis Example 77 제조예 78Production Example 78 합성예 78Synthesis Example 78 제조예 79Production Example 79 합성예 79Synthesis Example 79 제조예 80Production example 80 합성예 80Synthesis Example 80 제조예 81Production example 81 합성예 81Synthesis Example 81 제조예 82Production example 82 합성예 82Synthesis Example 82 제조예 83Production Example 83 합성예 83Synthesis Example 83 제조예 84Production Example 84 합성예 84Synthesis Example 84 제조예 85Production Example 85 합성예 85Synthesis Example 85 제조예 86Production example 86 합성예 86Synthesis Example 86 제조예 87Production Example 87 합성예 87Synthesis Example 87 제조예 88Production example 88 합성예 88Synthesis Example 88 제조예 89Production example 89 합성예 89Synthesis Example 89 제조예 90Production Example 90 합성예 90Synthesis Example 90 제조예 91Production example 91 합성예 91Synthesis Example 91 제조예 92Production Example 92 합성예 92Synthesis Example 92 비교제조예 1Comparative Preparation Example 1 징크 비스(2-(2-하이드록시페닐)벤조티아졸레이트
Zinc bis(2-(2-hydroxyphenyl)benzothiazolate: Zn(BTZ)2)Zinc bis (2- (2-hydroxyphenyl) benzothiazolate
Zinc bis (2- (2-hydroxyphenyl) benzothiazolate: Zn (BTZ) 2 )

시험예Test Example 1:  One: OLEDOLED 의 특성 평가Characterization of

제조예 1 내지 제조예65, 비교제조예 1의 OLED소자의 전력효율 및 구동 수명을 1,000cd/m2 에서 그리고, 효율이 50%까지 떨어질 때까지의 시간을 하기 표 4에 기재하였다.The power efficiency and driving life of the OLED devices of Preparation Examples 1 to 65 and Comparative Production Example 1 are shown in Table 4 below at 1,000 cd / m 2 and the time until the efficiency drops to 50%.

　 Cd/A @1000cd/m2 Cd / A @ 1000 cd / m 2 수명(T50)Life (T 50 ) 제조예1Production Example 1 4545 630630 제조예2Production Example 2 4747 650650 제조예3Production Example 3 5050 520520 제조예4Production Example 4 4444 590590 제조예5Production Example 5 4646 650650 제조예6Production Example 6 4848 680680 제조예7Production Example 7 5050 550550 제조예8Production Example 8 4444 610610 제조예9Production Example 9 4646 520520 제조예10Production Example 10 4848 480480 제조예11Production Example 11 4141 550550 제조예12Production Example 12 4444 620620 제조예13Production Example 13 4545 490490 제조예14Production Example 14 4141 550550 제조예15Production Example 15 4646 680680 제조예16Production Example 16 4949 720720 제조예17Production Example 17 5252 560560 제조예18Preparation Example 18 4545 650650 제조예19Preparation Example 19 4646 480480 제조예20Preparation Example 20 4848 460460 제조예21Preparation Example 21 4141 610610 제조예22Preparation Example 22 4040 600600 제조예23Preparation Example 23 4141 590590 제조예24Preparation Example 24 4040 550550 제조예25Preparation Example 25 4646 600600 제조예26Preparation Example 26 4747 610610 제조예27Preparation Example 27 5151 550550 제조예28Preparation Example 28 4646 580580 제조예29Preparation Example 29 4848 670670 제조예30Preparation Example 30 5050 680680 제조예31Preparation Example 31 5151 590590 제조예32Preparation Example 32 4848 610610 제조예33Preparation Example 33 4545 510510 제조예34Preparation Example 34 4646 490490 제조예35Preparation Example 35 4545 550550 제조예36Preparation Example 36 4646 590590 제조예37Preparation Example 37 5050 500500 제조예38Preparation Example 38 4545 500500 제조예39Preparation Example 39 4848 690690 제조예40Preparation Example 40 5151 690690 제조예41Preparation Example 41 5353 600600 제조예42Preparation Example 42 4848 650650 제조예43Preparation Example 43 4646 480480 제조예44Preparation Example 44 4848 450450 제조예45Preparation Example 45 4141 610610 제조예46Preparation Example 46 4141 580580 제조예47Preparation Example 47 4040 550550 제조예48Preparation Example 48 4141 530530 제조예49Preparation Example 49 4747 610610 제조예50Preparation Example 50 4646 610610 제조예51Preparation Example 51 5151 540540 제조예52Preparation Example 52 4545 550550 제조예53Preparation Example 53 4949 680680 제조예54Preparation Example 54 5151 690690 제조예55Preparation Example 55 5151 600600 제조예56Preparation Example 56 4848 620620 제조예57Preparation Example 57 4444 530530 제조예58Preparation Example 58 4545 490490 제조예59Preparation Example 59 4545 560560 제조예60Preparation Example 60 4444 610610 제조예61Preparation Example 61 5151 520520 제조예62Preparation Example 62 4545 510510 제조예63Preparation Example 63 5050 500500 비교제조예1Comparative Preparation Example 1 3838 450450

상기 표 3에서 나타난 바와 같이, 본 발명에 따른 화합물을 녹색 인광 호스트로 이용하면, 유기전계발광소자의 전력효율과 수명이 우수한 것을 알 수 있다.
As shown in Table 3, when the compound according to the present invention is used as a green phosphorescent host, it can be seen that the power efficiency and lifespan of the organic light emitting display device are excellent.

Claims (8)

하기 화학식 1로 표시되는 화합물:
<화학식 1>
Figure pat00537

상기 화학식 1에서,
X1 내지 X3는 서로 같거나 다를 수 있으며, 각각 독립적으로, CH 또는 N이고,
R1, R2, A1 내지 A4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 수소; 할로겐 원자; 아다만틸; 나이트로; 하이드록시; 시아노; 치환 또는 비치환된 (C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴; 치환 또는 비치환된 (C5-C60)헤테로아릴; N, O, S 및 Si로부터 선택된 1종 또는 2종 이상을 포함하는 5원 또는 6원의 헤테로시클로알킬; 치환 또는 비치환된 (C3-C60)시클로알킬; 치환 또는 비치환된 트리(C1-C60)알킬실릴; 치환 또는 비치환된 디(C1-C60)알킬(C6-C60)아릴실릴; 치환 또는 비치환된 트리(C6-C60)아릴실릴; 치환 또는 비치환된 (C7-C60)바이시클로알킬; 치환 또는 비치환된 (C2-C60)알케닐; 치환 또는 비치환된 (C2-C60)알키닐; 치환 또는 비치환된 (C1-C60)알콕시; 치환 또는 비치환된 (C1-C60)알킬아미노; 치환 또는 비치환된 (C6-C60)아릴아미노; 치환 또는 비치환된 (C6-C60)아르(C1-C60)알킬; 치환 또는 비치환된 (C6-C60)아릴옥시; 치환 또는 비치환된 (C6-C60)아릴티오; 치환 또는 비치환된 (C1-C60)알킬티오; 치환 또는 비치환된 (C1-C60)알콕시카보닐; 치환 또는 비치환된 (C1-C60)알킬카보닐; 또는 (C6-C60)아릴카보닐이고,
단, 상기 A1 내지 A4가 모두 수소인 경우는 제외하고,
상기 R1, R2, A1 내지 A4는 인접 원소와 융합고리를 포함 또는 미포함하는 치환 또는 비치환된 (C3-C60)알킬렌 또는 (C3-C60)알케닐렌으로 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있다.A compound represented by the following formula (1):
&Lt; Formula 1 >
Figure pat00537

In Formula 1,
X 1 to X 3 may be the same as or different from each other, and each independently, CH or N,
R 1 , R 2 , A 1 to A 4 may be the same as or different from each other, and each independently hydrogen; A halogen atom; Adamantyl; Nitro; Hydroxy; Cyano; Substituted or unsubstituted (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryl; Substituted or unsubstituted (C5-C60) heteroaryl; 5- or 6-membered heterocycloalkyl including one or two or more selected from N, O, S and Si; Substituted or unsubstituted (C3-C60) cycloalkyl; Substituted or unsubstituted tri (C 1 -C 60) alkylsilyl; Substituted or unsubstituted di (C1-C60) alkyl (C6-C60) arylsilyl; Substituted or unsubstituted tri (C6-C60) arylsilyl; Substituted or unsubstituted (C7-C60) bicycloalkyl; Substituted or unsubstituted (C2-C60) alkenyl; Substituted or unsubstituted (C2-C60) alkynyl; Substituted or unsubstituted (C1-C60) alkoxy; Substituted or unsubstituted (C1-C60) alkylamino; Substituted or unsubstituted (C6-C60) arylamino; Substituted or unsubstituted (C6-C60) ar (C1-C60) alkyl; Substituted or unsubstituted (C6-C60) aryloxy; Substituted or unsubstituted (C6-C60) arylthio; Substituted or unsubstituted (C1-C60) alkylthio; Substituted or unsubstituted (C1-C60) alkoxycarbonyl; Substituted or unsubstituted (C1-C60) alkylcarbonyl; Or (C6-C60) arylcarbonyl,
Except that A 1 to A 4 are all hydrogen,
The R 1 , R 2 , A 1 to A 4 is an alicyclic ring connected to a substituted or unsubstituted (C3-C60) alkylene or (C3-C60) alkenylene containing or not containing a fused ring with an adjacent element, Monocyclic or polycyclic aromatic rings can be formed. 청구항 1에 있어서,
상기 R1, R2, Ar1 내지 Ar4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 수소, 치환 또는 비치환된 (C1-C60)알킬기, 치환 또는 비치환된 (C1-C60)아릴기, 치환 또는 비치환된 (C5-C60)헤테로아릴기, 치환 또는 비치환된 (C1-C60)알킬아미노, 치환 또는 비치환된 (C6-C60)아릴아미노,
Figure pat00538
,
Figure pat00539
,
Figure pat00540
,
Figure pat00541
,
Figure pat00542
,
Figure pat00543
,
Figure pat00544
또는
Figure pat00545
이고,
상기 X4 내지 X12은 서로 같거나 다를 수 있으며, 각각 독립적으로 화학결합, 치환 또는 비치환된 CH, CH2, N, NH, O, S 또는 Si이고,
R4 내지 R7은 서로 같거나 다를 수 있고, 각각 독립적으로 수소, (C1-C60)알킬기, (C1-C60)알콕시기 또는 (C6-C60)아릴기이고,
상기 R4 내지 R7은 각각 독립적으로 인접 원소와 연결되어 지환족 고리, 단일환 또는 다환의 방향족 고리를 형성할 수 있는 것을 특징으로 하는 화합물.The method according to claim 1,
R 1 , R 2 , Ar 1 to Ar 4 may be the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted (C1-C60) alkyl group, a substituted or unsubstituted (C1-C60) aryl group , A substituted or unsubstituted (C5-C60) heteroaryl group, a substituted or unsubstituted (C1-C60) alkylamino, a substituted or unsubstituted (C6-C60) arylamino,
Figure pat00538
,
Figure pat00539
,
Figure pat00540
,
Figure pat00541
,
Figure pat00542
,
Figure pat00543
,
Figure pat00544
or
Figure pat00545
ego,
X 4 to X 12 may be the same as or different from each other, and each independently a chemical bond, a substituted or unsubstituted CH, CH 2 , N, NH, O, S or Si,
R 4 to R 7 may be the same as or different from each other, and each independently hydrogen, a (C1-C60) alkyl group, a (C1-C60) alkoxy group or a (C6-C60) aryl group,
R 4 to R 7 are each independently connected to an adjacent element to form an alicyclic ring, a monocyclic or polycyclic aromatic ring, characterized in that. 청구항 1에 있어서,
상기 R1, R2, A1 내지 A4는 서로 같거나 다를 수 있으며, 각각 독립적으로, 상기 (C1-C60)알킬기, (C1-C60)아릴기, (C5-C60)헤테로아릴기 또는 (C6-C60)아릴아미노는 CF3, 할로겐 원자, 시아노, (C1-C60)알킬기, (C1-C60)알콕시기, (C6-C60)아릴기 또는
Figure pat00546
로 치환되고,
X13는 치환 또는 비치환된 C, N, O, S 또는 Si인 것을 특징으로 하는 화합물.The method according to claim 1,
R 1 , R 2 , A 1 to A 4 may be the same as or different from each other, and each independently, the (C1-C60) alkyl group, (C1-C60) aryl group, (C5-C60) heteroaryl group or ( C 6 -C 60) arylamino is CF 3 , halogen atom, cyano, (C1-C60) alkyl group, (C1-C60) alkoxy group, (C6-C60) aryl group or
Figure pat00546
Substituted with
X 13 is a substituted or unsubstituted C, N, O, S or Si characterized in that the compound. 제 1 전극; 제 2 전극; 및 상기 제 1 전극과 제 2 전극 사이에 위치하고, 청구항 1의 기재의 화합물을 포함하는 유기막을 포함하는 것을 특징으로 하는 유기전계발광소자.A first electrode; A second electrode; And an organic film disposed between the first electrode and the second electrode, the organic film comprising the compound of claim 1. 청구항 4에 있어서,
상기 화합물은 녹색 인광 호스트 물질인 것을 특징으로 하는 유기전계발광소자.The method of claim 4,
The compound is an organic electroluminescent device, characterized in that the green phosphorescent host material. 청구항 4에 있어서,
상기 화합물을 포함하는 유기막은 발광층인 것을 특징으로 하는 유기전계발광소자.The method of claim 4,
The organic film containing the compound is an organic light emitting device, characterized in that the light emitting layer. 청구항 4에 있어서,
상기 유기막은 정공주입층, 정공수송층, 전자수송층 및 전자주입층으로 이루어진 군에서 선택되는 1종 또는 2종 이상을 더 포함하는 것을 특징으로 하는 유기전계발광소자.The method of claim 4,
The organic film is an organic electroluminescent device further comprising one or two or more selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer. 청구항 1 기재의 화합물을 포함하는 것을 특징으로 하는 유기태양 전지.An organic solar cell comprising the compound of claim 1.
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Cited By (5)

* Cited by examiner, † Cited by third party
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KR20160013338A (en) * 2014-07-24 2016-02-04 삼성디스플레이 주식회사 An organic light emitting device
US9929349B2 (en) 2014-12-08 2018-03-27 Samsung Display Co., Ltd. Organic light emitting device and display device including the same
US10069083B2 (en) 2014-06-02 2018-09-04 Samsung Display Co., Ltd. Condensed cyclic compounds and organic light-emitting devices including the same
CN109665937A (en) * 2018-10-31 2019-04-23 山东瑞辰新材料有限公司 The synthetic method of 2,7- of one kind bis- bromo- benzo [9,10] phenanthrene
US11108001B2 (en) * 2019-01-17 2021-08-31 Luminescence Technology Corp. Organic compound and organic electroluminescence device using the same

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10069083B2 (en) 2014-06-02 2018-09-04 Samsung Display Co., Ltd. Condensed cyclic compounds and organic light-emitting devices including the same
US10608189B2 (en) 2014-06-02 2020-03-31 Samsung Display Co., Ltd. Condensed cyclic compounds and organic light-emitting devices including the same
KR20160013338A (en) * 2014-07-24 2016-02-04 삼성디스플레이 주식회사 An organic light emitting device
US9929349B2 (en) 2014-12-08 2018-03-27 Samsung Display Co., Ltd. Organic light emitting device and display device including the same
CN109665937A (en) * 2018-10-31 2019-04-23 山东瑞辰新材料有限公司 The synthetic method of 2,7- of one kind bis- bromo- benzo [9,10] phenanthrene
CN109665937B (en) * 2018-10-31 2021-03-23 山东瑞辰新材料有限公司 Synthetic method of 2, 7-dibromo-benzo [9,10] phenanthrene
US11108001B2 (en) * 2019-01-17 2021-08-31 Luminescence Technology Corp. Organic compound and organic electroluminescence device using the same

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