WO2014042321A1 - Organic light-emitting compound and organic electroluminescent device using same - Google Patents

Organic light-emitting compound and organic electroluminescent device using same Download PDF

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WO2014042321A1
WO2014042321A1 PCT/KR2013/001025 KR2013001025W WO2014042321A1 WO 2014042321 A1 WO2014042321 A1 WO 2014042321A1 KR 2013001025 W KR2013001025 W KR 2013001025W WO 2014042321 A1 WO2014042321 A1 WO 2014042321A1
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group
compound
substituted
unsubstituted
synthesis
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Korean (ko)
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김충한
연규만
김동연
최태진
송보경
김지이
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주식회사 두산
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Definitions

  • the present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same, and more particularly, a novel organic light emitting compound having excellent light emitting ability, hole transporting ability, electron transporting ability and the like, and the compound in at least one organic material layer.
  • the present invention relates to an organic EL device having improved light emitting efficiency, driving voltage, and lifespan.
  • An organic electroluminescent device (hereinafter referred to as an organic EL device) generally has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic EL device, for example, hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EML), electron transport layer (ETL) ), An electron injection layer (EIL), and the like.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML light emitting layer
  • ETL electron transport layer
  • EIL electron injection layer
  • the light emitting layer forming material of the organic EL device may be classified into blue, green, and red light emitting materials according to light emission colors.
  • yellow and orange light emitting materials are also used as light emitting materials to realize better natural colors.
  • a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
  • carbazole compounds such as CBP (4,4-dicarbazolybiphenyl) are used as the phosphorescent host material, and metal complex compounds containing heavy atoms such as Ir and Pt are widely used as the phosphorescent dopant material. It is used.
  • CBP which is currently used phosphorescent host material, has a low glass transition temperature (T g ) of about 110 ° C., and crystallization within the device is easy, resulting in a very short lifespan of about 150 hours.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide an organic light emitting compound and an organic EL device using the same that can improve the characteristics such as luminous efficiency, driving voltage, thermal stability, life.
  • the present invention provides a compound represented by the following formula (1).
  • X and Y are the same as or different from each other, and each independently N or CH;
  • R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 Alkynyl group of -C 40 , substituted or unsubstituted C 6 -C 40 aryl group, substituted or unsubstituted heteroaryl group of 5 to 40 nuclear atoms, substituted or unsubstituted C 6 -C 40 aryl jade A substituted, unsubstituted or unsubstituted C 1 -C 40 alkyloxy group, -NR 3 R 4 , a substituted or unsubstituted C 3 -C 40 cycloalkyl group, and a substituted or unsubstituted heteroatom having 3 to 40 heteroatoms.
  • R 3 and R 4 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted nucleus selected from the group consisting of atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted C 3 ⁇ C 40 cycloalkyl group and a substituted or unsubstituted number of 3 to 40 hetero-substituted nucleus atoms a cycloalkyl group of or, or they are adjacent A group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with a group,
  • C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 6 -C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 ⁇ C 40 aryloxy group, C 1 ⁇ C 40 alkyloxy group of, C 3 ⁇ cycloalkyl and nuclear atoms, 3 to heterocycloalkyl group 40 of C 40 are each independently a heavy hydrogen, a halogen, a cyano group, C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 6 -C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 -C 40 aryloxy group, C 1 to C 40 alkyloxy group, C 6 to C 40 arylamine group, C 6 to C 40 arylalkyl group, C 3 to C 40 cycloalkyl group, C
  • the present invention also provides an organic EL device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes a compound represented by Formula 1 above.
  • An organic EL device is provided.
  • the organic material layer including the compound represented by Chemical Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer, and specifically, the compound represented by Chemical Formula 1 may be used as a phosphorescent host of the light emitting layer.
  • the compound represented by the formula (1) of the present invention has excellent luminous ability, electron transport ability and hole transport ability. Therefore, the organic EL device including the same may greatly improve characteristics such as light emission performance, driving voltage, and lifetime, and thus may be effectively applied to a full color display panel.
  • the novel organic light emitting compound according to the present invention has a structure represented by Chemical Formula 1 in which various substituents, in particular, N-containing heterocycles, aromatic rings, etc., are connected to a quinoxaline-based mother core.
  • Chemical Formula 1 in which various substituents, in particular, N-containing heterocycles, aromatic rings, etc., are connected to a quinoxaline-based mother core.
  • X and Y are the same as or different from each other, and are each independently N or CH.
  • Y may be N and X is CH, or Y may be CH and X may be N.
  • both X and Y may be CH or N.
  • R 1 and R 2 are the same as or different from each other, and each independently C 1 ⁇ C 40 Alkyl group, C 2 ⁇ C 40 Alkenyl group, C 2 ⁇ C 40 Alkynyl group, C 6 ⁇ C 40 aryl group, nuclear 5 to 40 heteroaryl group, C 6 ⁇ C 40 aryloxy group, C 1 ⁇ C 40 alkyloxy group, -NR 3 R 4 , C 3 ⁇ C 40 cyclo An alkyl group and a heterocycloalkyl group having 3 to 40 nuclear atoms; Or a group in which they combine with adjacent groups to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring.
  • R 3 and R 4 are the same as or different from each other, and each independently C 1 ⁇ C 40 Alkyl group, C 6 ⁇ C 40 An aryl group, a nuclear atom of 5 to 40 heteroaryl group, C 3 ⁇ C 40 cycloalkyl group and heterocycloalkyl group having 3 to 40 nuclear atoms; Or a group in which they combine with adjacent groups to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring.
  • R 1 to R 4 which are substituents in which the term 'substituted or unsubstituted' is described, more specifically in R 1 to R 4 , an alkyl group of C 1 to C 40 , and C 2 to C 40 Alkenyl group, C 2 ⁇ C 40 alkynyl group, C 6 ⁇ C 40 aryl group, 5 to 40 heteroaryl group, C 6 ⁇ C 40 aryloxy group, C 1 ⁇ C 40 Alkyl jade group, C 3 ⁇ C 40 is a cycloalkyl group and nuclear atoms, 3 to heterocycloalkyl group 40, each independently selected from deuterium, halogen, cyano group, C 1 ⁇ alkenyl group of the C 40 alkyl group, C 2 ⁇ C 40 of, C 2 ⁇ C 40 alkynyl group, C 6 ⁇ C 40 aryl group, 5 to 40 heteroaryl group, C 6 ⁇ C 40 aryloxy group
  • R 1 and R 2 are the same as or different from each other, each independently C 6 ⁇ C 40 aryl group, the number of nuclear atoms It is preferred that they are 5 to 40 heteroaryl groups, -NR 3 R 4 , or these functional groups combine with adjacent groups to form condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings.
  • R 1 and R 2 is more preferably in each case a C 6 ⁇ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group or NR 3 R 4 in, and is most preferably in the case of NR 3 R 4.
  • the C 6 ⁇ C 40 aryl group, the heteroaryl group of 5 to 40 nuclear atoms, R 3 , R 4 are each independently deuterium, halogen, cyano group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 to C 40 alkynyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 to C 40 aryloxy group, C 1 to C 40 Alkyloxy group, C 6 -C 40 arylamine group, C 6 -C 40 arylalkyl group, C 3 -C 40 cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C 1 -C 40 alkyl It may be substituted with one or more substituents selected from the group consisting of a silyl group and an arylsilyl group of C 6 to C 40 .
  • the compound of Chemical Formula 1 according to the present invention may be more embodied as any one of the compounds represented by the following Chemical Formulas 2 to 4.
  • R 1 is a C 6 -C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, or NR 3 R 4 ;
  • R 2 , R 3 and R 4 are as defined above.
  • R 2 is preferably a C 6 ⁇ C 40 aryl group or a heteroaryl group having 5 to 40 nuclear atoms.
  • unsubstituted alkyl is a straight or branched chain saturated hydrocarbon of 1 to 40 (10) carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, Hexyl and the like.
  • Unsubstituted aryl means an aromatic moiety having 6 to 40 (8) carbon atoms, singly or in combination of two or more rings. Two or more rings may be attached in a simple or condensed form with one another.
  • Unsubstituted heteroaryl means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 40 (8) nucleoatoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, Substituted by heteroatoms such as O and S. It is understood that two or more rings may be attached in a simple attached or condensed form with each other, and further include condensed forms with aliphatic rings or aromatic rings.
  • Condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combined form thereof.
  • the compound represented by the formula (1) of the present invention described above may be further embodied by the formulas illustrated below. However, the compound represented by the formula (1) of the present invention is not limited by those illustrated below.
  • the compound represented by Formula 2 may be more specifically represented by Compounds 1-1 to 1-22 illustrated below, and the compound represented by Formula 3 may be represented by Compounds 2-1 to 2-22 illustrated below. Can be embodied.
  • the compound represented by the formula (4) may be more specific to the compounds 3-1 to 3-22 exemplified below.
  • the compound of formula 1 of the present invention may be synthesized according to a general synthetic method. Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
  • organic electroluminescent device comprising the compound represented by the formula (1) according to the present invention.
  • the organic electroluminescent device includes an anode; Cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 may include one kind or two or more kinds.
  • the organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer, preferably a light emitting layer, a hole transport layer and / or an electron transport layer. Can be.
  • the light emitting layer of the organic electroluminescent device according to the present invention may contain a host material, wherein any one of the compounds represented by Formula 1 may be used as the host material.
  • a host material such as any one of the compounds represented by Chemical Formula 1
  • organic electroluminescence having excellent efficiency (light emitting efficiency and power efficiency), lifetime, luminance, driving voltage, etc., because the bonding force between holes and electrons in the light emitting layer is increased.
  • An element can be provided.
  • the compound represented by Chemical Formula 1 may be included in the organic light emitting device as a blue, green and / or red phosphorescent host, a fluorescent host, or a dopant material. It can also be used as a dopant material.
  • the structure of the organic electroluminescent element of this invention is not specifically limited, It may be a structure which laminated
  • Non-limiting examples thereof include (i) an anode, a light emitting layer, a cathode; (ii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode; Or (iii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, or a cathode.
  • the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between an electrode and an organic material layer.
  • the organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method.
  • the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
  • the organic EL device according to the present invention forms an organic material layer and an electrode by using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Formula 1 of the present invention. Can be prepared.
  • a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet may be used as the substrate.
  • the anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb
  • Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT),
  • the negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
  • the hole injection layer, the hole transport layer and the electron transport layer is not particularly limited, and conventional materials known in the art may be used.
  • 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) obtained in ⁇ Step 1> was prepared by 9- (4-bromophenyl) -9H-carbazole (21.1g, 104.33mmol), Pd (OAc) 2 (1.28g , 5.73 mmol) and Cs 2 CO 3 (37.38 g, 114.7 mmol) were dissolved in 140 ml of toluene and stirred at room temperature for 15 minutes. Thereafter, tri- (tert-butyl) phosphine (0.31 g, 1.56 mmol) was slowly added dropwise, and the reaction mixture was stirred at reflux for 24 hours.
  • 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) obtained in the ⁇ Step 1> was 3-bromo-9-phenyl-9H-carbazole (10.55g, 52.16mmol), Pd (OAc) 2 (0.64g , 2.86 mmol) and Cs 2 CO 3 (20.39 g, 62.59 mmol) were dissolved in 100 ml of toluene and stirred at room temperature for 15 minutes. Tri- (tert-butyl) phosphine (0.15 g, 0.78 mmol) was then slowly added dropwise and the reaction mixture was stirred at reflux for 24 hours.
  • a compound 3-1 (yield 63%) was synthesized in the same manner as in Synthesis Example 1, except that pyrido [2,3-b] pyrazine was used instead of quinoxaline.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • M-MTDATA 60 nm) / TCTA (80 nm) / Compound 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1 on the prepared ITO transparent electrode -14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14 , 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (each ) And 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) were laminated in order to manufacture a green organic EL device.
  • a green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 1-1 as a light emitting host material when forming the emission layer.
  • Example 1 Sample Host Drive voltage (V) EL peak (nm) Current efficiency (cd / A) Example 1 1-1 6.78 517 42.4 Example 2 1-2 6.82 515 41.1 Example 3 1-5 6.79 517 40.8 Example 4 1-7 6.79 518 41.0 Example 5 1-9 6.85 516 38.0 Example 6 1-10 6.79 517 40.8 Example 7 1-12 6.93 518 41.0 Example 8 1-14 6.78 517 38.0 Example 9 1-17 6.78 518 42.4 Example 10 1-19 6.82 516 41.1 Example 11 1-20 6.79 517 40.8 Example 12 1-22 6.85 518 41.0 Example 13 2-1 6.79 517 38.0 Example 14 2-2 6.93 518 42.4 Example 15 2-5 6.78 517 41.1 Example 16 2-7 6.79 518 40.8 Example 17 2-9 6.85 516 41.0 Example 18 2-10 6.79 517 41.0 Example 19 2-12 6.93 518 38.0 Example 20 2-14 6.78 517 42.4 Example 21 2-17 6.82 518 41.1 Example 22 2-19 6.79 516 40.8 Example 23 3-1 6.79 5
  • the organic EL device of Examples 1 to 32 using the compound according to the present invention as the light emitting layer of the green organic EL device compared with the green organic EL device of Comparative Example 1 using the conventional CBP It can be seen that the better performance in terms of efficiency and driving voltage.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • a blue organic EL device was manufactured in the same manner as in Example 33, except that CBP was used instead of Compound 1-1 as a light emitting host material when forming the emission layer.
  • Example 33 1-1 7.33 473 5.99
  • Example 34 1-2 7.13 474 6.34
  • Example 35 1-5 7.12 475 6.34
  • Example 36 1-7 7.55 475 5.99
  • Example 37 1-9 7.55 472 5.85
  • Example 38 1-10 7.25 472 5.89
  • Example 39 1-12 7.76 473 5.85
  • Example 40 1-14 7.33 474 6.90
  • Example 41 1-17 7.52 475 6.34
  • Example 42 1-19 7.01 475 6.65
  • Example 43 1-20 7.34 473 5.99
  • Example 46 2-2 7.21 474 6.14
  • Example 47 2-5 7.19 475 5.87
  • Example 48 2-7 7.11 472 5.85
  • Example 49 2-9 7.12 472 5.75
  • Example 50 2-10 7.12 473 5.85
  • Example 51 2-12 7.54 473 6.34
  • Example 52 2-14 7.52 474 6.21
  • Example 53 2-17 7.11 475 5.59
  • Example 54 2-19

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Abstract

The present invention relates to a novel organic light-emitting compound having an excellent light-emitting capability, hole-transport capability, electron-transport capability, etc. The present invention also relates to an organic electroluminescent device comprising one or more organic material layers which contain said compound, thus improving characteristics of the device such as the light-emission efficiency, driving voltage, and lifespan thereof.

Description

유기발광 화합물 및 이를 이용한 유기 전계 발광 소자 Organic light emitting compound and organic electroluminescent device using same
본 발명은 신규의 유기발광 화합물 및 이를 이용한 유기 전계 발광 소자에 관한 것으로, 보다 상세하게는 발광능, 정공 수송능, 전자 수송능 등이 우수한 신규의 유기발광 화합물 및 상기 화합물을 하나 이상의 유기물층에 포함함으로써 발광효율, 구동 전압, 수명 등의 특성이 향상된 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same, and more particularly, a novel organic light emitting compound having excellent light emitting ability, hole transporting ability, electron transporting ability and the like, and the compound in at least one organic material layer. The present invention relates to an organic EL device having improved light emitting efficiency, driving voltage, and lifespan.
유기 전계 발광 소자(organic electroluminescent device) (이하, 유기 EL 소자라 함)는 통상 양극, 음극, 및 이들 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 EL 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공 주입층(HIL), 정공 수송층(HTL), 발광층(EML), 전자 수송층(ETL), 전자 주입층(EIL) 등을 포함할 수 있다. An organic electroluminescent device (hereinafter referred to as an organic EL device) generally has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often formed of a multilayer structure composed of different materials to increase the efficiency and stability of the organic EL device, for example, hole injection layer (HIL), hole transport layer (HTL), light emitting layer (EML), electron transport layer (ETL) ), An electron injection layer (EIL), and the like.
이러한 유기 EL 소자의 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층으로 주입되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다.When voltage is applied between the two electrodes of the organic EL device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet, and the excitons are brought to the ground state. When it falls, it glows.
유기 EL 소자의 발광층 형성재료는 발광색에 따라 청색, 녹색, 적색 발광 재료로 구분될 수 있다. 그밖에, 보다 나은 천연색을 구현하기 위한 발광재료로 노란색 및 주황색 발광재료도 사용된다. 또한, 색순도의 증가와 에너지 전이를 통해 발광 효율을 증가시키기 위하여, 발광 재료로서 호스트/도펀트 계를 사용할 수 있다. 그 원리는 발광층을 주로 구성하는 호스트보다 에너지 대역 간극이 작고 발광 효율이 우수한 도펀트를 발광층에 소량 혼합하면, 호스트에서 발생한 엑시톤이 도펀트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도펀트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다. The light emitting layer forming material of the organic EL device may be classified into blue, green, and red light emitting materials according to light emission colors. In addition, yellow and orange light emitting materials are also used as light emitting materials to realize better natural colors. In addition, in order to increase luminous efficiency through increasing color purity and energy transfer, a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and excellent luminous efficiency than the host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transported to the dopant to give high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
일반적으로 인광 호스트 재료로는 CBP(4,4-dicarbazolybiphenyl) 등의 카바졸계 화합물 등이 사용되며, 인광 도판트 재료로는 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물이 널리 사용되고 있다. 그러나 현재 사용되는 인광 호스트 재료인 CBP의 경우 유리전이온도(Tg)가 110℃ 정도로 낮으며, 소자 내의 결정화가 쉽게 일어나 유기 EL 소자의 수명이 150 시간 정도로 매우 짧은 문제점이 있다.In general, carbazole compounds such as CBP (4,4-dicarbazolybiphenyl) are used as the phosphorescent host material, and metal complex compounds containing heavy atoms such as Ir and Pt are widely used as the phosphorescent dopant material. It is used. However, CBP, which is currently used phosphorescent host material, has a low glass transition temperature (T g ) of about 110 ° C., and crystallization within the device is easy, resulting in a very short lifespan of about 150 hours.
본 발명은 상기한 문제점을 해결하기 위해 안출된 것으로서, 발광효율, 구동전압, 열적 안정성, 수명 등의 특성을 향상시킬 수 있는 유기발광 화합물 및 이를 이용한 유기 EL 소자를 제공하는 것을 목적으로 한다. The present invention has been made to solve the above problems, and an object of the present invention is to provide an organic light emitting compound and an organic EL device using the same that can improve the characteristics such as luminous efficiency, driving voltage, thermal stability, life.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다. In order to achieve the above object, the present invention provides a compound represented by the following formula (1).
화학식 1
Figure PCTKR2013001025-appb-C000001
 Formula 1
Figure PCTKR2013001025-appb-C000001
상기 식에서,Where
X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이고;X and Y are the same as or different from each other, and each independently N or CH;
R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C6~C40의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬옥시기, -NR3R4, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 Alkynyl group of -C 40 , substituted or unsubstituted C 6 -C 40 aryl group, substituted or unsubstituted heteroaryl group of 5 to 40 nuclear atoms, substituted or unsubstituted C 6 -C 40 aryl jade A substituted, unsubstituted or unsubstituted C 1 -C 40 alkyloxy group, -NR 3 R 4 , a substituted or unsubstituted C 3 -C 40 cycloalkyl group, and a substituted or unsubstituted heteroatom having 3 to 40 heteroatoms. Selected from the group consisting of cycloalkyl groups, or groups which form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with adjacent groups,
상기 R3 및 R4는 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 3 and R 4 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted nucleus selected from the group consisting of atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted C 3 ~ C 40 cycloalkyl group and a substituted or unsubstituted number of 3 to 40 hetero-substituted nucleus atoms a cycloalkyl group of or, or they are adjacent A group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with a group,
여기서, 상기 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기는, 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.Wherein the C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 6 -C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 ~ C 40 aryloxy group, C 1 ~ C 40 alkyloxy group of, C 3 ~ cycloalkyl and nuclear atoms, 3 to heterocycloalkyl group 40 of C 40 are each independently a heavy hydrogen, a halogen, a cyano group, C 1 -C 40 alkyl group, C 2 -C 40 alkenyl group, C 2 -C 40 alkynyl group, C 6 -C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 -C 40 aryloxy group, C 1 to C 40 alkyloxy group, C 6 to C 40 arylamine group, C 6 to C 40 arylalkyl group, C 3 to C 40 cycloalkyl group, C 3 to C 40 It may be substituted with one or more substituents selected from the group consisting of a heterocycloalkyl group, a C 1 ~ C 40 alkylsilyl group, and a C 6 ~ C 40 arylsilyl group.
또한, 본 발명은 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 EL 소자로서, 상기 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 EL 소자를 제공한다. The present invention also provides an organic EL device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers includes a compound represented by Formula 1 above. An organic EL device is provided.
이때, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 이루어진 군에서 선택될 수 있으며, 구체적으로 상기 화학식 1로 표시되는 화합물은 발광층의 인광 호스트로 사용될 수 있다.In this case, the organic material layer including the compound represented by Chemical Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer, and specifically, the compound represented by Chemical Formula 1 may be used as a phosphorescent host of the light emitting layer.
본 발명의 화학식 1로 표시되는 화합물은 우수한 발광능, 전자 수송능 및 정공 수송능을 가지고 있다. 따라서, 이를 포함하는 유기 EL 소자는 발광성능, 구동전압, 수명 등의 특성이 크게 향상될 수 있으므로, 풀 칼라 디스플레이 패널 등에 효과적으로 적용될 수 있다. The compound represented by the formula (1) of the present invention has excellent luminous ability, electron transport ability and hole transport ability. Therefore, the organic EL device including the same may greatly improve characteristics such as light emission performance, driving voltage, and lifetime, and thus may be effectively applied to a full color display panel.
이하, 본 발명에 대하여 상세히 설명한다. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
<신규 화합물><New compound>
본 발명에 따른 신규 유기발광 화합물은 퀴녹살린(Quinoxaline)계 모핵에 다양한 치환체, 특히 N-함유 헤테로환, 방향족 고리 등이 연결된 상기 화학식 1로 표시되는 구조를 가진다. 이러한 구조를 통해 충분히 높은 삼중항 에너지 레벨을 달성하여 인광특성을 개선함과 동시에 전자(electron) 및/또는 정공(hole) 수송 능력, 발광효율, 구동전압, 수명 특성 등에서 개선된 효능을 달성할 수 있다.The novel organic light emitting compound according to the present invention has a structure represented by Chemical Formula 1 in which various substituents, in particular, N-containing heterocycles, aromatic rings, etc., are connected to a quinoxaline-based mother core. Through this structure, it is possible to achieve a sufficiently high triplet energy level to improve phosphorescence properties and at the same time to achieve improved efficacy in electron and / or hole transport ability, luminous efficiency, driving voltage, and lifetime characteristics. have.
본 발명의 화학식 1로 표시되는 화합물에서, 상기 X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이다. 일례로, Y가 N이고 X가 CH이거나, 또는 Y가 CH이고 X가 N일 수 있다. 또한 X 및 Y 모두가 CH이거나, 또는 N일 수도 있다. In the compound represented by Formula 1 of the present invention, X and Y are the same as or different from each other, and are each independently N or CH. In one example, Y may be N and X is CH, or Y may be CH and X may be N. In addition, both X and Y may be CH or N.
상기 화학식 1에서, R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, -NR3R4, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나; 또는 이들이 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기일 수 있다. In Formula 1, R 1 and R 2 are the same as or different from each other, and each independently C 1 ~ C 40 Alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 6 ~ C 40 aryl group, nuclear 5 to 40 heteroaryl group, C 6 ~ C 40 aryloxy group, C 1 ~ C 40 alkyloxy group, -NR 3 R 4 , C 3 ~ C 40 cyclo An alkyl group and a heterocycloalkyl group having 3 to 40 nuclear atoms; Or a group in which they combine with adjacent groups to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring.
여기서, R3 및 R4는 서로 같거나 또는 상이하며, 각각 독립적으로 C1~C40의 알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나; 또는 이들이 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기일 수 있다.Here, R 3 and R 4 are the same as or different from each other, and each independently C 1 ~ C 40 Alkyl group, C 6 ~ C 40 An aryl group, a nuclear atom of 5 to 40 heteroaryl group, C 3 ~ C 40 cycloalkyl group and heterocycloalkyl group having 3 to 40 nuclear atoms; Or a group in which they combine with adjacent groups to form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring.
한편 본원 화학식 1에서, '치환 또는 비치환된'이라는 용어가 기재된 치환기인 R1~R4, 보다 구체적으로 상기 R1~R4 에서, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기는, 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.Meanwhile, in Formula 1 of the present application, R 1 to R 4 , which are substituents in which the term 'substituted or unsubstituted' is described, more specifically in R 1 to R 4 , an alkyl group of C 1 to C 40 , and C 2 to C 40 Alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, 5 to 40 heteroaryl group, C 6 ~ C 40 aryloxy group, C 1 ~ C 40 Alkyl jade group, C 3 ~ C 40 is a cycloalkyl group and nuclear atoms, 3 to heterocycloalkyl group 40, each independently selected from deuterium, halogen, cyano group, C 1 ~ alkenyl group of the C 40 alkyl group, C 2 ~ C 40 of, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, 5 to 40 heteroaryl group, C 6 ~ C 40 aryloxy group, C 1 ~ C 40 alkyloxy group, C 6 to C 40 arylamine group, C 6 to C 40 arylalkyl group, C 3 to C 40 cycloalkyl group, C 3 to C 40 heterocycloalkyl group, C 1 to C 40 alkylsilyl group, and C 6 is selected from the group consisting of aryl silyl ~ C 40 With one or more substituents may be substituted.
본 발명에 따른 화학식 1로 표기되는 화합물에서, 삼중항 에너지 레벨을 고려했을 때, 상기 R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, -NR3R4 이거나, 또는 이들 작용기가 인접하는 기와 서로 결합하여 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 것이 바람직하다. 이때 R1 및 R2가 각각 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4인 경우가 더욱 바람직하며, NR3R4인 경우가 가장 바람직하다.In the compound represented by Formula 1 according to the present invention, when considering the triplet energy level, R 1 and R 2 are the same as or different from each other, each independently C 6 ~ C 40 aryl group, the number of nuclear atoms It is preferred that they are 5 to 40 heteroaryl groups, -NR 3 R 4 , or these functional groups combine with adjacent groups to form condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings or condensed heteroaromatic rings. Wherein R 1 and R 2 is more preferably in each case a C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group or NR 3 R 4 in, and is most preferably in the case of NR 3 R 4.
여기서, 상기 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, R3, R4는 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다. Herein, the C 6 ~ C 40 aryl group, the heteroaryl group of 5 to 40 nuclear atoms, R 3 , R 4 are each independently deuterium, halogen, cyano group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 to C 40 alkynyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 to C 40 aryloxy group, C 1 to C 40 Alkyloxy group, C 6 -C 40 arylamine group, C 6 -C 40 arylalkyl group, C 3 -C 40 cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C 1 -C 40 alkyl It may be substituted with one or more substituents selected from the group consisting of a silyl group and an arylsilyl group of C 6 to C 40 .
일례로, 상기 C6~C40의 아릴기 또는 핵원자수 5 내지 40의 헤테로아릴기는 페닐, 나프틸, 인덴, 안트라센, 페난트렌, 파이렌, 트리페닐렌, 피리딘, 피리미딘, 피라진, 트리아진, 퀴놀린, 이소퀴놀린, 퀴녹살린, 플루오렌, 카바졸, 디벤조싸이오펜, 디벤조퓨란, 아크리딘, 인돌, 벤조퓨란, 벤조싸이오펜, 벤즈이미다졸, 벤조싸이아졸, 퓨린, 페난트롤린일 수 있다. For example, the C 6 ~ C 40 aryl group or a heteroaryl group having 5 to 40 nuclear atoms, phenyl, naphthyl, indene, anthracene, phenanthrene, pyrene, triphenylene, pyridine, pyrimidine, pyrazine, tri Azine, quinoline, isoquinoline, quinoxaline, fluorene, carbazole, dibenzothiophene, dibenzofuran, acridine, indole, benzofuran, benzothiophene, benzimidazole, benzothiazole, purine, phenanrol It may be lean.
본 발명에 따른 상기 화학식 1의 화합물은 하기 화학식 2 내지 화학식 4로 표시되는 화합물 중 어느 하나로 보다 구체화될 수 있다.The compound of Chemical Formula 1 according to the present invention may be more embodied as any one of the compounds represented by the following Chemical Formulas 2 to 4.
화학식 2
Figure PCTKR2013001025-appb-C000002
 Formula 2
Figure PCTKR2013001025-appb-C000002
화학식 3
Figure PCTKR2013001025-appb-C000003
 Formula 3
Figure PCTKR2013001025-appb-C000003
화학식 4
Figure PCTKR2013001025-appb-C000004
 Formula 4
Figure PCTKR2013001025-appb-C000004
상기 식에서, Where
R1는 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4이고; R 1 is a C 6 -C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, or NR 3 R 4 ;
R2, R3 및 R4는 앞서 정의한 바와 같다.R 2 , R 3 and R 4 are as defined above.
이때 R2는 C6~C40의 아릴기 또는 핵원자수 5 내지 40의 헤테로아릴기인 것이 바람직하다. In this case, R 2 is preferably a C 6 ~ C 40 aryl group or a heteroaryl group having 5 to 40 nuclear atoms.
본 발명에서 사용된 "비치환된 알킬"은 탄소수 1 내지 40(10)의 직쇄 또는 측쇄의 포화 탄화수소이며, 이의 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등을 포함한다.As used herein, “unsubstituted alkyl” is a straight or branched chain saturated hydrocarbon of 1 to 40 (10) carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, Hexyl and the like.
"비치환된 아릴"은 단독 고리 혹은 2 이상의 고리가 조합된, 탄소수 6 내지 40(8)의 방향족 부위를 의미한다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태로 부착될 수 있다."Unsubstituted aryl" means an aromatic moiety having 6 to 40 (8) carbon atoms, singly or in combination of two or more rings. Two or more rings may be attached in a simple or condensed form with one another.
"비치환된 헤테로아릴"은 핵원자수 5 내지 40(8)의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 부위를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O, S와 같은 헤테로원자로 치환된다. 2 이상의 고리가 서로 단순 부착(pendant)되거나 축합된 형태로 부착될 수 있고, 나아가 지방족 고리 또는 방향족 고리와의 축합된 형태도 포함하는 것으로 해석한다."Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 40 (8) nucleoatoms, wherein at least one carbon in the ring, preferably 1 to 3 carbons is N, Substituted by heteroatoms such as O and S. It is understood that two or more rings may be attached in a simple attached or condensed form with each other, and further include condensed forms with aliphatic rings or aromatic rings.
"축합 고리"는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다."Condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combined form thereof.
이상에서 설명한 본 발명의 화학식 1로 표시되는 화합물은 하기 예시된 화학식들로 보다 구체화될 수 있다. 그러나 본 발명의 화학식 1로 표시되는 화합물이 하기 예시된 것들에 의해 한정되는 것은 아니다. The compound represented by the formula (1) of the present invention described above may be further embodied by the formulas illustrated below. However, the compound represented by the formula (1) of the present invention is not limited by those illustrated below.
일례로, 본원 화학식 2로 표시되는 화합물은 하기 예시된 화합물 1-1 내지 1-22 로 보다 구체화될 수 있으며, 상기 화학식 3으로 표시되는 화합물은 하기 예시된 화합물 2-1 내지 2-22로 보다 구체화될 수 있다. 또한 상기 화학식 4로 표시되는 화합물은 하기 예시된 화합물 3-1 내지 3-22로 보다 구체화될 수 있다. For example, the compound represented by Formula 2 may be more specifically represented by Compounds 1-1 to 1-22 illustrated below, and the compound represented by Formula 3 may be represented by Compounds 2-1 to 2-22 illustrated below. Can be embodied. In addition, the compound represented by the formula (4) may be more specific to the compounds 3-1 to 3-22 exemplified below.
Figure PCTKR2013001025-appb-I000001
Figure PCTKR2013001025-appb-I000001
Figure PCTKR2013001025-appb-I000002
Figure PCTKR2013001025-appb-I000002
Figure PCTKR2013001025-appb-I000003
Figure PCTKR2013001025-appb-I000003
Figure PCTKR2013001025-appb-I000004
Figure PCTKR2013001025-appb-I000004
Figure PCTKR2013001025-appb-I000005
Figure PCTKR2013001025-appb-I000005
Figure PCTKR2013001025-appb-I000006
Figure PCTKR2013001025-appb-I000006
본 발명의 화학식 1의 화합물은 일반적인 합성방법에 따라 합성될 수 있다. 본 발명의 화합물에 대한 상세한 합성 과정은 후술하는 합성예에서 구체적으로 기술하도록 한다.The compound of formula 1 of the present invention may be synthesized according to a general synthetic method. Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.
<유기 전계 발광 소자><Organic EL device>
한편, 본 발명의 다른 측면은 상기한 본 발명에 따른 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자(유기 EL 소자)에 관한 것이다. On the other hand, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the formula (1) according to the present invention.
보다 구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode); 음극(cathode); 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다. 이때, 상기 화학식 1로 표시되는 화합물은 1종 또는 2종 이상이 포함될 수 있다.More specifically, the organic electroluminescent device according to the present invention includes an anode; Cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Chemical Formula 1. In this case, the compound represented by Formula 1 may include one kind or two or more kinds.
여기서, 본 발명의 화학식 1로 표시되는 화합물을 포함하는 유기물층은 발광층, 정공주입층, 정공수송층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있으며, 바람직하게는 발광층, 정공수송층 및/또는 전자수송층일 수 있다.Here, the organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer, preferably a light emitting layer, a hole transport layer and / or an electron transport layer. Can be.
본 발명에 따른 유기 전계 발광 소자의 발광층은 호스트 재료를 함유할 수 있는데, 이때 호스트 재료로 상기 화학식 1로 표시되는 화합물 중 어느 하나를 사용할 수 있다. 이와 같이 발광층이 상기 화학식 1로 표시되는 화합물 중 어느 하나를 함유할 경우, 발광층에서 정공과 전자의 결합력이 높아지기 때문에 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등이 우수한 유기 전계 발광 소자를 제공할 수 있다. 상기 화학식 1로 표시되는 화합물은 청색, 녹색 및/또는 적색의 인광 호스트, 형광 호스트, 또는 도펀트 재료로서 유기 발광 소자에 포함될 수 있다. 또한 도펀트 재료로 이용될 수 있다. The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material, wherein any one of the compounds represented by Formula 1 may be used as the host material. As such, when the light emitting layer contains any one of the compounds represented by Chemical Formula 1, organic electroluminescence having excellent efficiency (light emitting efficiency and power efficiency), lifetime, luminance, driving voltage, etc., because the bonding force between holes and electrons in the light emitting layer is increased. An element can be provided. The compound represented by Chemical Formula 1 may be included in the organic light emitting device as a blue, green and / or red phosphorescent host, a fluorescent host, or a dopant material. It can also be used as a dopant material.
본 발명의 유기 EL 소자 구조는 특별히 한정되지 않으나, 전극간에 유기물층을 1층 또는 2층 이상 적층한 구조일 수 있다. 이의 비제한적인 예를 들면 (i) 양극, 발광층, 음극; (ii) 양극, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 음극; 또는 (iii) 양극, 정공주입층, 정공수송층, 발광층, 음극 등의 구조를 들 수 있다.Although the structure of the organic electroluminescent element of this invention is not specifically limited, It may be a structure which laminated | stacked one layer or two or more layers of organic compound layers between electrodes. Non-limiting examples thereof include (i) an anode, a light emitting layer, a cathode; (ii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode; Or (iii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, or a cathode.
또한, 본 발명에 따른 유기 EL 소자는 전술한 바와 같이 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입될 수 있다. In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between an electrode and an organic material layer.
본 발명에 따른 유기 EL 소자에 있어서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 진공증착법이나 용액 도포법에 의하여 형성될 수 있다. 상기 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에만 한정되지 않는다. In the organic EL device according to the present invention, the organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
본 발명에 따른 유기 EL 소자는 유기물층 중 1층 이상을 본 발명의 화학식 1로 표시되는 화합물을 포함하도록 형성하는 것을 제외하고는 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 유기물층 및 전극을 형성함으로써 제조될 수 있다. The organic EL device according to the present invention forms an organic material layer and an electrode by using materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Formula 1 of the present invention. Can be prepared.
예컨대, 기판으로는 실리콘 웨이퍼, 석영 또는 유리판, 금속판, 플라스틱 필름이나 시트 등이 사용될 수 있다. For example, a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet may be used as the substrate.
양극 물질로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자; 또는 카본블랙 등이 있으나, 이들에만 한정되는 것은 아니다. The anode material may be a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.
음극 물질로는 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. The negative electrode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or an alloy thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like, but are not limited thereto.
또한, 정공 주입층, 정공 수송층 및 전자 수송층은 특별히 한정되는 것은 아니며, 당 업계에 알려진 통상의 물질이 사용될 수 있다. In addition, the hole injection layer, the hole transport layer and the electron transport layer is not particularly limited, and conventional materials known in the art may be used.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[합성예 1] 화합물 1,4-bis(4-(9H-carbazol-9-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline)의 합성 Synthesis Example 1 Synthesis of Compound 1,4-bis (4- (9H-carbazol-9-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
Figure PCTKR2013001025-appb-I000007
Figure PCTKR2013001025-appb-I000007
<단계 1> 1,2,3,4-tetrahydroquinoxaline 합성Step 1 Synthesis of 1,2,3,4-tetrahydroquinoxaline
Quinoxaline (10g, 74.52mmol)을 테트라하이드로퓨란 100 ㎖에 녹인 다음 NaBH4 (10g, 26.4mmol)을 넣고 교반하였다. 이후, 반응온도를 0℃로 낮추고 트리플루오로아세트산 (10ml, 5.89mmol)을 천천히 30분 동안 적가하였다. 적가가 완료되면 온도를 상온으로 천천히 올린 후 2시간 동안 교반하였다. Quinoxaline (10 g, 74.52 mmol) was dissolved in 100 mL of tetrahydrofuran, and NaBH 4 (10 g, 26.4 mmol) was added thereto and stirred. Thereafter, the reaction temperature was lowered to 0 ° C. and trifluoroacetic acid (10 ml, 5.89 mmol) was slowly added dropwise for 30 minutes. When the dropping was completed, the temperature was slowly raised to room temperature, followed by stirring for 2 hours.
TLC를 이용하여 반응이 종결된 것을 확인한 후 증류수를 투입하고 에틸아세테이트로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(7g, 수율68%)을 얻었다. HRMS [M]+: 134.08After confirming that the reaction was terminated using TLC, distilled water was added and extracted with ethyl acetate. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and purified by column chromatography to obtain the title compound (7 g, yield 68%). HRMS [M] + : 134.08
<단계 2> 1,4-bis(4-(9H-carbazol-9-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline 합성Step 2 Synthesis of 1,4-bis (4- (9H-carbazol-9-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
상기 <단계 1>에서 얻은 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol)을 9-(4-bromophenyl)-9H-carbazole(21.1g, 104.33mmol), Pd(OAc)2(1.28g, 5.73mmol), Cs2CO3 (37.38g, 114.7mmol)과 함께 톨루엔 140ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.31g, 1.56mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) obtained in <Step 1> was prepared by 9- (4-bromophenyl) -9H-carbazole (21.1g, 104.33mmol), Pd (OAc) 2 (1.28g , 5.73 mmol) and Cs 2 CO 3 (37.38 g, 114.7 mmol) were dissolved in 140 ml of toluene and stirred at room temperature for 15 minutes. Thereafter, tri- (tert-butyl) phosphine (0.31 g, 1.56 mmol) was slowly added dropwise, and the reaction mixture was stirred at reflux for 24 hours.
반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물 1-1 (22g, 수율68.5%)을 얻었다. HRMS [M]+: 616.26After the reaction was completed, distilled water was added and extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and purified by column chromatography to obtain the title compound 1-1 (22 g, yield 68.5%). HRMS [M] + : 616.26
[합성예 2] 화합물 1,4-bis(9-phenyl-9H-carbazol-3-yl)-1,2,3,4-tetrahydroquinoxaline 의 합성Synthesis Example 2 Synthesis of Compound 1,4-bis (9-phenyl-9H-carbazol-3-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-2(수율 81%)을 얻었다. HRMS [M]+: 603.73Except for using 3-bromo-9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-2 (yield 81%) ) HRMS [M] + : 603.73
[합성예 3] 화합물 1,4-bis(4,6-diphenylpyridin-2-yl)-1,2,3,4-tetrahydroquinoxaline 의 합성Synthesis Example 3 Synthesis of Compound 1,4-bis (4,6-diphenylpyridin-2-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-3(수율 67%)을 얻었다. HRMS [M]+: 592.73Except for using 2-bromo-4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-3 (yield 67%). Got it. HRMS [M] + : 592.73
[합성예 4] 화합물 3,3'-((5,6-divinyl-2,3-dihydropyrazine-1,4-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole) 의 합성Synthesis Example 4 Compound 3,3 '-((5,6-divinyl-2,3-dihydropyrazine-1,4-diyl) bis (4,1-phenylene)) bis (9-phenyl-9H-carbazole) Synthesis of
9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-4(수율 71%)을 얻었다. HRMS [M]+: 768.94Except for using 3- (4-bromophenyl) -9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-4 (Yield 71%) was obtained. HRMS [M] + : 768.94
[합성예 5] 화합물 1,4-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 5 Synthesis of Compound 1,4-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-5(수율 67%)을 얻었다. HRMS [M]+: 650.85Except for using 4- (4-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-5 ( Yield 67%). HRMS [M] + : 650.85
[합성예 6] 화합물 1,4-di(fluoranthen-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 6 Synthesis of Compound 1,4-di (fluoranthen-3-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-6(수율 64%)을 얻었다. HRMS [M]+: 534.65Except for using 3-bromofluoranthene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to obtain the title compound 1-6 (yield 64%). HRMS [M] + : 534.65
[합성예 7] 화합물 1,4-bis(9,9,10-triphenyl-9,10-dihydroacridin-2-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 7 Synthesis of Compound 1,4-bis (9,9,10-triphenyl-9,10-dihydroacridin-2-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-7(수율 66%)을 얻었다. HRMS [M]+: 949.19The title compound 1 was prepared in the same manner as in Synthesis Example 1, except that 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine was used instead of 9- (4-bromophenyl) -9H-carbazole. -7 (yield 66%) was obtained. HRMS [M] + : 949.19
[합성예 8] 화합물 1-(9,9'-spirobi[fluoren]-2-yl)-4-(9,9'-spirobi[fluoren]-7-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 8 Compound 1- (9,9'-spirobi [fluoren] -2-yl) -4- (9,9'-spirobi [fluoren] -7-yl) -1,2,3,4- Synthesis of tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-8(수율 90%)을 얻었다. HRMS [M]+: 762.94Except for using 2-bromo-9,9'-spirobi [fluorene] instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-8 (yield) 90%). HRMS [M] + : 762.94
[합성예 9] 화합물N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)-9H-fluoren-2-amine)의 합성Synthesis Example 9 Compound N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (4- (9-phenyl-9H-carbazol-3-yl) Synthesis of -3,4-dihydroquinoxalin-1 (2H) -yl) phenyl) -9H-fluoren-2-amine)
Figure PCTKR2013001025-appb-I000008
Figure PCTKR2013001025-appb-I000008
<단계 1> 1,2,3,4-tetrahydroquinoxaline 합성Step 1 Synthesis of 1,2,3,4-tetrahydroquinoxaline
Quinoxaline (10g, 74.5mmol)을 테트라하이드로퓨란 100 ㎖에 녹인 다음 NaBH4 (10g, 26.4mmol)을 넣고 교반하였다. 이후, 반응온도를 0℃로 낮추고 트리플루오로아세트산 (10ml, 5.89mmol)을 천천히 30분 동안 적가하였다. 적가가 완료되면 온도를 상온으로 천천히 올린 후 2시간 동안 교반하였다. Quinoxaline (10 g, 74.5 mmol) was dissolved in 100 mL of tetrahydrofuran, and NaBH 4 (10 g, 26.4 mmol) was added thereto and stirred. Thereafter, the reaction temperature was lowered to 0 ° C. and trifluoroacetic acid (10 ml, 5.89 mmol) was slowly added dropwise for 30 minutes. When the dropping was completed, the temperature was slowly raised to room temperature, followed by stirring for 2 hours.
TLC를 이용하여 반응이 종결된 것을 확인한 후 증류수를 투입하고 에틸아세테이트로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에서 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(7g, 수율68%)을 얻었다. HRMS [M]+: 134.08After confirming that the reaction was terminated using TLC, distilled water was added and extracted with ethyl acetate. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and purified by column chromatography to obtain the title compound (7 g, yield 68%). HRMS [M] + : 134.08
<단계 2> 3-(3,4-dihydroquinoxalin-1(2H)-yl)-9-phenyl-9H-carbazole의 합성Step 2 Synthesis of 3- (3,4-dihydroquinoxalin-1 (2H) -yl) -9-phenyl-9H-carbazole
상기 <단계 1>에서 얻은 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol)을 3-bromo-9-phenyl-9H-carbazole(10.55g, 52.16mmol), Pd(OAc)2(0.64g, 2.86mmol), Cs2CO3 (20.39g, 62.59mmol)과 함께 톨루엔 100ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.15g, 0.78mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. 1,2,3,4-tetrahydroquinoxaline (7g, 52.16mmol) obtained in the <Step 1> was 3-bromo-9-phenyl-9H-carbazole (10.55g, 52.16mmol), Pd (OAc) 2 (0.64g , 2.86 mmol) and Cs 2 CO 3 (20.39 g, 62.59 mmol) were dissolved in 100 ml of toluene and stirred at room temperature for 15 minutes. Tri- (tert-butyl) phosphine (0.15 g, 0.78 mmol) was then slowly added dropwise and the reaction mixture was stirred at reflux for 24 hours.
반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물(6.26g, 수율32%)을 얻었다. HRMS [M]+: 375.17After the reaction was completed, distilled water was added and extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and purified by column chromatography to obtain the title compound (6.26 g, yield 32%). HRMS [M] + : 375.17
<단계 3> N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)-9H-fluoren-2-amine)의 합성<Step 3> N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (4- (9-phenyl-9H-carbazol-3-yl) -3 , 4-dihydroquinoxalin-1 (2H) -yl) phenyl) -9H-fluoren-2-amine)
상기 <단계 2>에서 얻은 3-(3,4-dihydroquinoxalin-1(2H)-yl)-9-phenyl-9H-carbazole (6.26g, 16.68mmol)을 N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine(8.59g, 16.68mmol), Pd(OAc)2(0.20g, 0.91mmol), Cs2CO3 (6.52g, 20mmol)과 함께 톨루엔 100ml에 녹인 상온에서 15분 동안 교반하였다. 이후, 트리-(터트-부틸)포스핀 (0.05g, 0.25mmol)을 천천히 적가한 후 반응 혼합물을 24 시간 동안 환류 교반하였다. 3- (3,4-dihydroquinoxalin-1 (2H) -yl) -9-phenyl-9H-carbazole (6.26g, 16.68mmol) obtained in <Step 2> was replaced with N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine (8.59g, 16.68mmol), Pd (OAc) 2 (0.20g, 0.91mmol), Cs2CO3 ( 6.52g, 20mmol) and was stirred for 15 minutes at room temperature dissolved in 100ml of toluene. Tri- (tert-butyl) phosphine (0.05 g, 0.25 mmol) was then slowly added dropwise and the reaction mixture was stirred at reflux for 24 hours.
반응이 종결된 후 증류수를 넣고 다이클로로메틸용액으로 추출하였다. 유기층을 Na2SO4 로 건조하고 감압하에 증류한 다음 컬럼 크로마토그래피로 정제하여 표제 화합물 1-19 (9.19g, 수율68%)을 얻었다. HRMS [M]+: 810.37After the reaction was completed, distilled water was added and extracted with dichloromethyl solution. The organic layer was dried over Na 2 SO 4 , distilled under reduced pressure and purified by column chromatography to give the title compound 1-19 (9.19 g, yield 68%). HRMS [M] + : 810.37
[합성예 10] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydroquinoxalin-1(2H)-yl)phenyl)naphthalen-1-amine의 합성Synthesis Example 10 Compound N-phenyl-N- (4- (4- (9-phenyl-9H-carbazol-3-yl) -3,4-dihydroquinoxalin-1 (2H) -yl) phenyl) naphthalen-1 -amine synthesis
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 표제 화합물 1-9(수율 57%)을 얻었다. HRMS [M]+: 668.83Except for using N- (4-bromophenyl) -N-phenylnaphthalen-2-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 9 was carried out to provide the title compound 1-9. (Yield 57%) was obtained. HRMS [M] + : 668.83
[합성예 11] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 11 Synthesis of Compound N, N '-((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-2-amine)
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 표제 화합물 1-10(수율 75%)을 얻었다. HRMS [M]+: 668.83Except for using N- (4-bromophenyl) -N-phenylnaphthalen-1-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 9 was carried out to provide the title compound 1-10. (Yield 75%) was obtained. HRMS [M] + : 668.83
[합성예 12] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 12 Synthesis of Compound N, N '-((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-2-amine)
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-11(수율 88%)을 얻었다. HRMS [M]+: 720.9Except for using N- (4-bromophenyl) -N-phenylnaphthalen-2-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-11. (Yield 88%) was obtained. HRMS [M] + : 720.9
[합성예 13] 화합물 N,N'-((2,3-dihydroquinoxaline-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 13 Synthesis of Compound N, N '-((2,3-dihydroquinoxaline-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-1-amine)
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-12(수율 78%)을 얻었다. HRMS [M]+: 720.9Except for using N- (4-bromophenyl) -N-phenylnaphthalen-1-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-12 (Yield 78%) was obtained. HRMS [M] + : 720.9
[합성예 14] 화합물 1,4-bis(6-(9H-carbazol-9-yl)pyridin-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 14 Synthesis of Compound 1,4-bis (6- (9H-carbazol-9-yl) pyridin-3-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-13(수율 59%)을 얻었다. HRMS [M]+: 681.73Except for using 9- (5-bromopyridin-2-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-13 (Yield 59%) was obtained. HRMS [M] + : 681.73
[합성예 15] 화합물 1,4-bis(9,9-dimethyl-9H-fluoren-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 15 Synthesis of Compound 1,4-bis (9,9-dimethyl-9H-fluoren-3-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물1-14(수율 60%)을 얻었다. HRMS [M]+: 518.69Except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to give the title compound 1-14 (Yield) 60%). HRMS [M] + : 518.69
[합성예 16] 화합물 1,4-bis(5-(9H-carbazol-9-yl)pyridin-3-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 16 Synthesis of Compound 1,4-bis (5- (9H-carbazol-9-yl) pyridin-3-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-15(수율 48%)을 얻었다. HRMS [M]+: 618.73Except for using 9- (5-bromopyridin-3-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-15. (Yield 48%) was obtained. HRMS [M] + : 618.73
[합성예 17] 화합물 1,4-bis(3-(9H-carbazol-9-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 17 Synthesis of Compound 1,4-bis (3- (9H-carbazol-9-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-16(수율 50%)을 얻었다. HRMS [M]+: 616.75Except for using 9- (3-bromophenyl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-16 (yield 50%). ) HRMS [M] + : 616.75
[합성예 18] 화합물 1,4-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 18 Synthesis of Compound 1,4-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-17(수율 77%)을 얻었다. HRMS [M]+: 518.61Except for using 2- (3-bromophenyl) imidazo [1,2-a] pyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1- 17 (yield 77%) was obtained. HRMS [M] + : 518.61
[합성예 19] 화합물 1,4-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 19 Synthesis of Compound 1,4-bis (3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-18(수율 65%)을 얻었다. HRMS [M]+: 670.8The same procedure as in Synthesis Example 1 was conducted except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used instead of 9- (4-bromophenyl) -9H-carbazole. Compound 1-18 (yield 65%) was obtained. HRMS [M] + : 670.8
[합성예 20] 화합물 1,4-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 20 Synthesis of Compound 1,4-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-20(수율 50%)을 얻었다. HRMS [M]+: 744.92Except for using 2- (4-bromophenyl) -4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-20 (yield) 50%). HRMS [M] + : 744.92
[합성예 21] 화합물 1,4-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 21 Synthesis of Compound 1,4-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-21(수율 70%)을 얻었다. HRMS [M]+: 650.85Except for using 4- (3-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 1 was carried out to provide the title compound 1-21 ( Yield 70%). HRMS [M] + : 650.85
[합성예 22] 화합물 1,4-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-1,2,3,4-tetrahydroquinoxaline의 합성Synthesis Example 22 Synthesis of Compound 1,4-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -1,2,3,4-tetrahydroquinoxaline
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 표제 화합물 1-22(수율 72%)을 얻었다. HRMS [M]+: 596.68The title compound 1 was prepared in the same manner as in Synthesis Example 1, except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used instead of 9- (4-bromophenyl) -9H-carbazole. -22 (yield 72%) was obtained. HRMS [M] + : 596.68
[합성예 23] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9H-carbazole)의 합성Synthesis Example 23 Synthesis of Compound 9,9 '-((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9H-carbazole)
Figure PCTKR2013001025-appb-I000009
Figure PCTKR2013001025-appb-I000009
Quinoxaline 대신 pteridine를 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 2-1 (수율 50%)을 합성하였다. Except for using pteridine instead of quinoxaline, Compound 2-1 (yield 50%) was synthesized in the same manner as in Synthesis Example 1.
HRMS [M]+: 618.25HRMS [M] + : 618.25
[합성예 24] 화합물 3,3'-(6,7-dihydropteridine-5,8-diyl)bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 24 Synthesis of Compound 3,3 '-(6,7-dihydropteridine-5,8-diyl) bis (9-phenyl-9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-2(수율 78%)을 얻었다. HRMS [M]+: 618.73Except for using 3-bromo-9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-2 (yield 78%). ) HRMS [M] + : 618.73
[합성예 25] 화합물 5,8-bis(4,6-diphenylpyridin-2-yl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 25 Synthesis of Compound 5,8-bis (4,6-diphenylpyridin-2-yl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예23과 동일한 과정을 수행하여 표제 화합물 2-3(수율 80%)을 얻었다. HRMS [M]+: 594.71Except for using 2-bromo-4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-3 (Yield 80%). Got it. HRMS [M] + : 594.71
[합성예 26] 화합물 3,3'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 26 Synthesis of Compound 3,3 '-((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9-phenyl-9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-4(수율 76%)을 얻었다. HRMS [M]+: 770.92Except for using 3- (4-bromophenyl) -9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-4. (Yield 76%) was obtained. HRMS [M] + : 770.92
[합성예 27] 화합물 5,8-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 27 Synthesis of Compound 5,8-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-5(수율 77%)을 얻었다. Except for using 4- (4-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-5 ( Yield 77%).
HRMS [M]+: 652.83HRMS [M] + : 652.83
[합성예 28] 화합물 5,8-di(fluoranthen-3-yl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 28 Synthesis of Compound 5,8-di (fluoranthen-3-yl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-6(수율 83%)을 얻었다. HRMS [M]+: 536.62Except for using 3-bromofluoranthene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to obtain the title compound 2-6 (yield 83%). HRMS [M] + : 536.62
[합성예 29] 화합물 2,2'-(6,7-dihydropteridine-5,8-diyl)bis(9,9,10-triphenyl-9,10-dihydroacridine)의 합성Synthesis Example 29 Synthesis of Compound 2,2 '-(6,7-dihydropteridine-5,8-diyl) bis (9,9,10-triphenyl-9,10-dihydroacridine)
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-7(수율 76%)을 얻었다. HRMS [M]+: 951.16Except for using 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to obtain the title compound 2 -7 (yield 76%) was obtained. HRMS [M] + : 951.16
[합성예 30] 화합물 5-(9,9'-spirobi[fluoren]-2-yl)-8-(9,9'-spirobi[fluoren]-7-yl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 30 Compound 5- (9,9'-spirobi [fluoren] -2-yl) -8- (9,9'-spirobi [fluoren] -7-yl) -5,6,7,8- Synthesis of tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-8(수율 86%)을 얻었다. HRMS [M]+: 764.91Except for using 2-bromo-9,9'-spirobi [fluorene] instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-8 (yield) 86%). HRMS [M] + : 764.91
[합성예 31] 화합물N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)-9H-fluoren-2-amine의 합성Synthesis Example 31 Compound N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (8- (9-phenyl-9H-carbazol-3-yl) Synthesis of -7,8-dihydropteridin-5 (6H) -yl) phenyl) -9H-fluoren-2-amine
Figure PCTKR2013001025-appb-I000010
Figure PCTKR2013001025-appb-I000010
Quinoxaline 대신 pteridine를 사용하는 것을 제외하고는, 상기 합성예 9와 동일한 과정을 수행하여 화합물 2-19 (수율 21%)를 합성하였다. Except for using pteridine instead of quinoxaline, the same procedure as in Synthesis Example 9 was carried out to synthesize compound 2-19 (yield 21%).
HRMS [M]+: 812.36HRMS [M] + : 812.36
[합성예 32] 화합물 N-phenyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)naphthalen-2-amine의 합성Synthesis Example 32 Compound N-phenyl-N- (4- (8- (9-phenyl-9H-carbazol-3-yl) -7,8-dihydropteridin-5 (6H) -yl) phenyl) naphthalen-2 -amine synthesis
N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 2-9(수율 79%)을 얻었다. HRMS [M]+: 671.8N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine instead of N- (4-bromophenyl) -N-phenylnaphthalen Except for using 2-amine, the same procedure as in Synthesis Example 31 was carried out to obtain the title compound 2-9 (yield 79%). HRMS [M] + : 671.8
[합성예 33] 화합물 N-phenyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)naphthalen-1-amine 의 합성Synthesis Example 33 Compound N-phenyl-N- (4- (8- (9-phenyl-9H-carbazol-3-yl) -7,8-dihydropteridin-5 (6H) -yl) phenyl) naphthalen-1 Synthesis of -amine
N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 2-10(수율 58%)을 얻었다. HRMS [M]+: 670.8N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine instead of N- (4-bromophenyl) -N-phenylnaphthalen Except for using -1-amine, the same procedure as in Synthesis Example 31 was carried out to obtain the title compound 2-10 (yield 58%). HRMS [M] + : 670.8
[합성예 34] 화합물 N,N'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine) 의 합성Synthesis Example 34 Synthesis of Compound N, N '-((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-2-amine)
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-11(수율 62%)을 었다. HRMS [M]+:722.8Except for using N- (4-bromophenyl) -N-phenylnaphthalen-2-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-11. (Yield 62%). HRMS [M] + : 722.8
[합성예 35] 화합물 N,N'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 35 Synthesis of Compound N, N '-((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-1-amine)
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-12(수율 49%)을 얻었다. HRMS [M]+: 722.8Except for using N- (4-bromophenyl) -N-phenylnaphthalen-1-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-12 (Yield) 49%). HRMS [M] + : 722.8
[합성예 36] 화합물 9,9'-(5,5'-(6,7-dihydropteridine-5,8-diyl)bis(pyridine-5,2-diyl))bis(9H-carbazole) 의 합성Synthesis Example 36 Synthesis of Compound 9,9 '-(5,5'-(6,7-dihydropteridine-5,8-diyl) bis (pyridine-5,2-diyl)) bis (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-13(수율 79%)을 얻었다. HRMS [M]+: 620.7Except for using 9- (5-bromopyridin-2-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-13. (Yield 79%) was obtained. HRMS [M] + : 620.7
[합성예 37] 화합물 5,8-bis(9,9-dimethyl-9H-fluoren-3-yl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 37 Synthesis of Compound 5,8-bis (9,9-dimethyl-9H-fluoren-3-yl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물2-14(수율 56%)을 얻었다. HRMS [M]+: 520.67Except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-14 (Yield) 56%). HRMS [M] + : 520.67
[합성예 38] 화합물 9,9'-(5,5'-(6,7-dihydropteridine-5,8-diyl)bis(pyridine-5,3-diyl))bis(9H-carbazole) 의 합성Synthesis Example 38 Synthesis of Compound 9,9 '-(5,5'-(6,7-dihydropteridine-5,8-diyl) bis (pyridine-5,3-diyl)) bis (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-15(수율 65%)을 얻었다. HRMS [M]+: 620.7Except for using 9- (5-bromopyridin-3-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-15. (Yield 65%) was obtained. HRMS [M] + : 620.7
[합성예 39] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(3,1-phenylene))bis(9H-carbazole) 의 합성Synthesis Example 39 Synthesis of Compound 9,9 '-((6,7-dihydropteridine-5,8-diyl) bis (3,1-phenylene)) bis (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-16(수율 70%)을 얻었다. HRMS [M]+: 520.67Except for using 9- (3-bromophenyl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-16 (yield 70%). ) HRMS [M] + : 520.67
[합성예 40] 화합물 5,8-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 40 Synthesis of Compound 5,8-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-17(수율 46%)을 얻었다. HRMS [M]+: 607.69Except for using 2- (3-bromophenyl) imidazo [1,2-a] pyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2- 17 (yield 46%) was obtained. HRMS [M] + : 607.69
[합성예 41] 화합물 5,8-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 41 Synthesis of Compound 5,8-bis (3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-18(수율 55%)을 얻었다. HRMS [M]+: 672.78The same procedure as in Synthesis Example 23 was conducted except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used instead of 9- (4-bromophenyl) -9H-carbazole. Compound 2-18 (yield 55%) was obtained. HRMS [M] + : 672.78
[합성예 42] 화합물 5,8-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 42 Synthesis of Compound 5,8-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-20(수율 60%)을 얻었다. HRMS [M]+: 746.9Except for using 2- (4-bromophenyl) -4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-20 (yield) 60%). HRMS [M] + : 746.9
[합성예 43] 화합물 5,8-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-5,6,7,8-tetrahydropteridine 의 합성Synthesis Example 43 Synthesis of Compound 5,8-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-21(수율 54%)을 얻었다. HRMS [M]+: 652.83Except for using 4- (3-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 2-21 ( Yield 54%). HRMS [M] + : 652.83
[합성예 44] 화합물 5,8-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-5,6,7,8-tetrahydropteridine의 합성Synthesis Example 44 Synthesis of Compound 5,8-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -5,6,7,8-tetrahydropteridine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 2-22(수율 35%)을 얻었다. HRMS [M]+: 598.66Except for using 2-bromo-4,6-diphenyl-1,3,5-triazine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to obtain the title compound 2 -22 (yield 35%) was obtained. HRMS [M] + : 598.66
[합성예 45] 화합물 9,9'-((6,7-dihydropteridine-5,8-diyl)bis(4,1-phenylene))bis(9H-carbazole)의 합성Synthesis Example 45 Synthesis of Compound 9,9 '-((6,7-dihydropteridine-5,8-diyl) bis (4,1-phenylene)) bis (9H-carbazole)
Figure PCTKR2013001025-appb-I000011
Figure PCTKR2013001025-appb-I000011
Quinoxaline 대신 pyrido[2,3-b]pyrazine을 사용하는 것을 제외하고는, 상기 합성예 1과 동일한 과정을 수행하여 화합물 3-1 (수율 63%)을 합성하였다. A compound 3-1 (yield 63%) was synthesized in the same manner as in Synthesis Example 1, except that pyrido [2,3-b] pyrazine was used instead of quinoxaline.
HRMS [M]+: 617.74HRMS [M] + : 617.74
[합성예 46] 3,3'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 46 Synthesis of 3,3 '-(2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (9-phenyl-9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9-phenyl-9H-carbazole 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-2(수율 59%)을 얻었다. HRMS [M]+: 617.74Except for using 3-bromo-9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-2 (yield 59% ) HRMS [M] + : 617.74
[합성예 47] 화합물 1,4-bis(4,6-diphenylpyridin-2-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 47 Synthesis of Compound 1,4-bis (4,6-diphenylpyridin-2-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예23과 동일한 과정을 수행하여 표제 화합물3-3(수율 650%)을 얻었다. HRMS [M]+: 593.72Except for using 2-bromo-4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the title compound 3-3 (Yield 650%) was obtained in the same manner as in Synthesis Example 23 above. Got it. HRMS [M] + : 593.72
[합성예 48] 화합물 3,3'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(9-phenyl-9H-carbazole)의 합성Synthesis Example 48 Compound 3,3 '-((2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (4,1-phenylene)) bis (9-phenyl-9H- synthesis of carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 3-(4-bromophenyl)-9-phenyl-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물3-4(수율 70%)을 얻었다. HRMS [M]+: 769.93Except for using 3- (4-bromophenyl) -9-phenyl-9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-4. (Yield 70%) was obtained. HRMS [M] + : 769.93
[합성예 49] 화합물 1,4-bis(4-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 49 Synthesis of Compound 1,4-bis (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 4-(4-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-5(수율 63%)을 얻었다. HRMS [M]+: 651.84Except for using 4- (4-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-5 ( Yield 63%). HRMS [M] + : 651.84
[합성예 50] 화합물 1,4-di(fluoranthen-3-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 50 Synthesis of Compound 1,4-di (fluoranthen-3-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 3-bromofluoranthene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-6(수율 70%)을 얻었다. HRMS [M]+: 535.64Except for using 3-bromofluoranthene instead of 9- (4-bromophenyl) -9H-carbazole, the title compound 3-6 (yield 70%) was obtained in the same manner as in Synthesis Example 23. HRMS [M] + : 535.64
[합성예 51] 화합물 2,2'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(9,9,10-triphenyl-9,10-dihydroacridine)의 합성Synthesis Example 51 Synthesis of Compound 2,2 '-(2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (9,9,10-triphenyl-9,10-dihydroacridine)
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-7(수율 70%)을 얻었다. HRMS [M]+: 950.18Except for using 2-bromo-9,9,10-triphenyl-9,10-dihydroacridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3 -7 (yield 70%) was obtained. HRMS [M] + : 950.18
[합성예 52] 화합물 1-(9,9'-spirobi[fluoren]-2-yl)-4-(9,9'-spirobi[fluoren]-7-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 52 Compound 1- (9,9'-spirobi [fluoren] -2-yl) -4- (9,9'-spirobi [fluoren] -7-yl) -1,2,3,4- Synthesis of tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-9,9'-spirobi[fluorene]를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-8(수율 77%)을 얻었다. HRMS [M]+: 763.92Except for using 2-bromo-9,9'-spirobi [fluorene] instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-8 (yield) 77%). HRMS [M] + : 763.92
[합성예 53] 화합물N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(8-(9-phenyl-9H-carbazol-3-yl)-7,8-dihydropteridin-5(6H)-yl)phenyl)-9H-fluoren-2-amine의 합성Synthesis Example 53 Compound N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (8- (9-phenyl-9H-carbazol-3-yl) Synthesis of -7,8-dihydropteridin-5 (6H) -yl) phenyl) -9H-fluoren-2-amine
Figure PCTKR2013001025-appb-I000012
Figure PCTKR2013001025-appb-I000012
Quinoxaline 대신 pyrido[2,3-b]pyrazine를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 화합물 3-19 (수율 40%)를 합성하였다. Except for using pyrido [2,3-b] pyrazine instead of quinoxaline, Compound 3-19 (yield 40%) was synthesized in the same manner as in Synthesis Example 31 above.
HRMS [M]+: 812.01HRMS [M] + : 812.01
[합성예 54] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydropyrido[2,3-b]pyrazin-1(2H)-yl)phenyl)naphthalen-2-amine의 합성Synthesis Example 54 Compound N-phenyl-N- (4- (4- (9-phenyl-9H-carbazol-3-yl) -3,4-dihydropyrido [2,3-b] pyrazin-1 (2H) Synthesis of -yl) phenyl) naphthalen-2-amine
N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 3-9(수율 67%)을 얻었다. HRMS [M]+: 681.844N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine instead of N- (4-bromophenyl) -N-phenylnaphthalen Except for using 2-amine, the same procedure as in Synthesis Example 31 was carried out to obtain the title compound 3-9 (yield 67%). HRMS [M] + : 681.844
[합성예 55] 화합물 N-phenyl-N-(4-(4-(9-phenyl-9H-carbazol-3-yl)-3,4-dihydropyrido[2,3-b]pyrazin-1(2H)-yl)phenyl)naphthalen-1-amine의 합성Synthesis Example 55 Compound N-phenyl-N- (4- (4- (9-phenyl-9H-carbazol-3-yl) -3,4-dihydropyrido [2,3-b] pyrazin-1 (2H) Synthesis of -yl) phenyl) naphthalen-1-amine
N-([1,1'-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 31과 동일한 과정을 수행하여 표제 화합물 3-10(수율 61%)을 얻었다. HRMS [M]+: 669.81N-([1,1'-biphenyl] -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine instead of N- (4-bromophenyl) -N-phenylnaphthalen Except for using -1-amine, the same procedure as in Synthesis Example 31 was carried out to obtain the title compound 3-10 (yield 61%). HRMS [M] + : 669.81
[합성예 56] 화합물 N,N'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-2-amine)의 합성Synthesis Example 56 Compound N, N '-((2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-2- Synthesis of amines
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-2-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-11(수율 78%)을 얻었다. HRMS [M]+: 669.81Except for using N- (4-bromophenyl) -N-phenylnaphthalen-2-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-11. (Yield 78%) was obtained. HRMS [M] + : 669.81
[합성예 57] 화합물 N,N'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(4,1-phenylene))bis(N-phenylnaphthalen-1-amine)의 합성Synthesis Example 57 Compound N, N '-((2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (4,1-phenylene)) bis (N-phenylnaphthalen-1- Synthesis of amines
9-(4-bromophenyl)-9H-carbazole 대신 N-(4-bromophenyl)-N-phenylnaphthalen-1-amine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-12(수율 91%)을 얻었다. HRMS [M]+: 721.89Except for using N- (4-bromophenyl) -N-phenylnaphthalen-1-amine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-12. (Yield 91%) was obtained. HRMS [M] + : 721.89
[합성예 58] 화합물 9,9'-(5,5'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(pyridine-5,2-diyl))bis(9H-carbazole)의 합성Synthesis Example 58 Compound 9,9 '-(5,5'-(2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (pyridine-5,2-diyl)) bis Synthesis of (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-2-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-13(수율 80%)을 얻었다. HRMS [M]+: 721.89Except for using 9- (5-bromopyridin-2-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-13 (Yield 80%) was obtained. HRMS [M] + : 721.89
[합성예 59] 화합물 1,4-bis(9,9-dimethyl-9H-fluoren-3-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 59 Synthesis of Compound 1,4-bis (9,9-dimethyl-9H-fluoren-3-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 3-bromo-9,9-dimethyl-9H-fluorene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물3-14(수율 87%)을 얻었다. HRMS [M]+: 619.72Except for using 3-bromo-9,9-dimethyl-9H-fluorene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-14 (Yield) 87%). HRMS [M] + : 619.72
[합성예 60] 화합물 9,9'-(5,5'-(2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(pyridine-5,3-diyl))bis(9H-carbazole)의 합성Synthesis Example 60 Compound 9,9 '-(5,5'-(2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (pyridine-5,3-diyl)) bis Synthesis of (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(5-bromopyridin-3-yl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-15(수율 54%)을 얻었다. HRMS [M]+: 617.74Except for using 9- (5-bromopyridin-3-yl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-15. (Yield 54%) was obtained. HRMS [M] + : 617.74
[합성예 61] 화합물 9,9'-((2,3-dihydropyrido[2,3-b]pyrazine-1,4-diyl)bis(3,1-phenylene))bis(9H-carbazole) 의 합성Synthesis Example 61 Synthesis of Compound 9,9 '-((2,3-dihydropyrido [2,3-b] pyrazine-1,4-diyl) bis (3,1-phenylene)) bis (9H-carbazole)
9-(4-bromophenyl)-9H-carbazole 대신 9-(3-bromophenyl)-9H-carbazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-16(수율 77%)을 얻었다. HRMS [M]+: 519.6Except for using 9- (3-bromophenyl) -9H-carbazole instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-16 (yield 77%) ) HRMS [M] + : 519.6
[합성예 62] 화합물 1,4-bis(3-(imidazo[1,2-a]pyridin-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 62 Compound 1,4-bis (3- (imidazo [1,2-a] pyridin-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine synthesis
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)imidazo[1,2-a]pyridine 를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-17(수율 69%)을 얻었다. HRMS [M]+: 671.79Except for using 2- (3-bromophenyl) imidazo [1,2-a] pyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3- 17 (yield 69%) was obtained. HRMS [M] + : 671.79
[합성예 63] 화합물 1,4-bis(3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 63 Compound 1,4-bis (3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3-b] synthesis of pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 2-(3-bromophenyl)-1-phenyl-1H-benzo[d]imidazole를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-18(수율 86%)을 얻었다. HRMS [M]+: 519.6The same procedure as in Synthesis Example 23 was conducted except that 2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole was used instead of 9- (4-bromophenyl) -9H-carbazole. Compound 3-18 (yield 86%) was obtained. HRMS [M] + : 519.6
[합성예 64] 화합물 1,4-bis(4-(4,6-diphenylpyridin-2-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 64 Synthesis of Compound 1,4-bis (4- (4,6-diphenylpyridin-2-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 2-(4-bromophenyl)-4,6-diphenylpyridine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-20(수율 69%)을 얻었다. HRMS [M]+: 745.91Except for using 2- (4-bromophenyl) -4,6-diphenylpyridine instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-20 (yield) 69%). HRMS [M] + : 745.91
[합성예 65] 화합물 1,4-bis(3-(dibenzo[b,d]thiophen-4-yl)phenyl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine 의 합성Synthesis Example 65 Synthesis of Compound 1,4-bis (3- (dibenzo [b, d] thiophen-4-yl) phenyl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 4-(3-bromophenyl)dibenzo[b,d]thiophene를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-21(수율 71%)을 얻었다. HRMS [M]+: 651.84Except for using 4- (3-bromophenyl) dibenzo [b, d] thiophene instead of 9- (4-bromophenyl) -9H-carbazole, the same procedure as in Synthesis Example 23 was carried out to provide the title compound 3-21 ( Yield 71%). HRMS [M] + : 651.84
[합성예 66] 화합물 1,4-bis(4,6-diphenyl-1,3,5-triazin-2-yl)-1,2,3,4-tetrahydropyrido[2,3-b]pyrazine의 합성Synthesis Example 66 Synthesis of Compound 1,4-bis (4,6-diphenyl-1,3,5-triazin-2-yl) -1,2,3,4-tetrahydropyrido [2,3-b] pyrazine
9-(4-bromophenyl)-9H-carbazole 대신 2-bromo-4,6-diphenyl-1,3,5-triazine를 사용하는 것을 제외하고는, 상기 합성예 23과 동일한 과정을 수행하여 표제 화합물 3-22(수율 57%)을 얻었다. HRMS [M]+: 597.67The title compound 3 was prepared in the same manner as in Synthesis Example 23, except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used instead of 9- (4-bromophenyl) -9H-carbazole. -22 (yield 57%) was obtained. HRMS [M] + : 597.67
[실시예 1 ~ 32] 녹색 유기 EL 소자의 제작Examples 1 to 32 Fabrication of Green Organic EL Devices
앞서 합성예에서 합성된 각 화합물 (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19)을 통상적으로 알려진 방법으로 고순도 승화정제를 수행한 후 아래의 과정에 따라 녹색 유기 EL 소자를 제작하였다.Each compound synthesized in the above synthesis example (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1 -20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1 , 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19) A green organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/TCTA (80 nm)/ 화합물 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (각각) + 10 % Ir(ppy)3 (300nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 녹색 유기 EL 소자를 제작하였다. M-MTDATA (60 nm) / TCTA (80 nm) / Compound 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1 on the prepared ITO transparent electrode -14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14 , 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (each ) And 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) were laminated in order to manufacture a green organic EL device.
m-MTDATA, TCTA, Ir(ppy)3, CBP 및 BCP의 구조는 하기와 같다.The structures of m-MTDATA, TCTA, Ir (ppy) 3 , CBP and BCP are as follows.
Figure PCTKR2013001025-appb-I000013
Figure PCTKR2013001025-appb-I000013
Figure PCTKR2013001025-appb-I000014
Figure PCTKR2013001025-appb-I000014
[비교예 1] 녹색 유기 EL 소자의 제작Comparative Example 1 Fabrication of Green Organic EL Device
발광층 형성시 발광 호스트 물질로서 화합물 1-1 대신 CBP를 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 과정으로 녹색 유기 EL 소자를 제작하였다.A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 1-1 as a light emitting host material when forming the emission layer.
[평가예 1][Evaluation Example 1]
실시예 1-32 및 비교예 1에서 제작한 각각의 녹색 유기 EL 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.For each of the green organic EL devices produced in Examples 1-32 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.
표 1
샘플 호스트 구동 전압(V) EL 피크(nm) 전류효율(cd/A)
실시예 1 1-1 6.78 517 42.4
실시예 2 1-2 6.82 515 41.1
실시예 3 1-5 6.79 517 40.8
실시예 4 1-7 6.79 518 41.0
실시예 5 1-9 6.85 516 38.0
실시예 6 1-10 6.79 517 40.8
실시예 7 1-12 6.93 518 41.0
실시예 8 1-14 6.78 517 38.0
실시예 9 1-17 6.78 518 42.4
실시예 10 1-19 6.82 516 41.1
실시예 11 1-20 6.79 517 40.8
실시예 12 1-22 6.85 518 41.0
실시예 13 2-1 6.79 517 38.0
실시예 14 2-2 6.93 518 42.4
실시예 15 2-5 6.78 517 41.1
실시예 16 2-7 6.79 518 40.8
실시예 17 2-9 6.85 516 41.0
실시예 18 2-10 6.79 517 41.0
실시예 19 2-12 6.93 518 38.0
실시예 20 2-14 6.78 517 42.4
실시예 21 2-17 6.82 518 41.1
실시예 22 2-19 6.79 516 40.8
실시예 23 3-1 6.79 517 41.0
실시예 24 3-2 6.79 517 38.0
실시예 25 3-5 6.85 518 42.4
실시예 26 3-7 6.79 516 41.0
실시예 27 3-9 6.93 517 41.0
실시예 28 3-10 6.78 518 38.0
실시예 29 3-12 6.82 516 42.4
실시예 30 3-14 6.82 517 41.1
실시예 31 3-17 6.79 518 40.8
실시예 32 3-19 6.85 517 41.0
비교예 1 CBP 6.93 516 38.2
Table 1
Sample Host Drive voltage (V) EL peak (nm) Current efficiency (cd / A)
Example 1 1-1 6.78 517 42.4
Example 2 1-2 6.82 515 41.1
Example 3 1-5 6.79 517 40.8
Example 4 1-7 6.79 518 41.0
Example 5 1-9 6.85 516 38.0
Example 6 1-10 6.79 517 40.8
Example 7 1-12 6.93 518 41.0
Example 8 1-14 6.78 517 38.0
Example 9 1-17 6.78 518 42.4
Example 10 1-19 6.82 516 41.1
Example 11 1-20 6.79 517 40.8
Example 12 1-22 6.85 518 41.0
Example 13 2-1 6.79 517 38.0
Example 14 2-2 6.93 518 42.4
Example 15 2-5 6.78 517 41.1
Example 16 2-7 6.79 518 40.8
Example 17 2-9 6.85 516 41.0
Example 18 2-10 6.79 517 41.0
Example 19 2-12 6.93 518 38.0
Example 20 2-14 6.78 517 42.4
Example 21 2-17 6.82 518 41.1
Example 22 2-19 6.79 516 40.8
Example 23 3-1 6.79 517 41.0
Example 24 3-2 6.79 517 38.0
Example 25 3-5 6.85 518 42.4
Example 26 3-7 6.79 516 41.0
Example 27 3-9 6.93 517 41.0
Example 28 3-10 6.78 518 38.0
Example 29 3-12 6.82 516 42.4
Example 30 3-14 6.82 517 41.1
Example 31 3-17 6.79 518 40.8
Example 32 3-19 6.85 517 41.0
Comparative Example 1 CBP 6.93 516 38.2
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화합물을 녹색 유기 EL 소자의 발광층으로 사용하는 실시예 1~32의 유기 EL 소자는 종래 CBP를 사용하는 비교예 1의 녹색 유기 EL 소자와 비교해 볼 때 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 1, the organic EL device of Examples 1 to 32 using the compound according to the present invention as the light emitting layer of the green organic EL device, compared with the green organic EL device of Comparative Example 1 using the conventional CBP It can be seen that the better performance in terms of efficiency and driving voltage.
[실시예 33~64] 청색 유기 EL 소자의 제조Examples 33 to 64 Fabrication of Blue Organic EL Devices
앞서 합성예에서 합성된 각 화합물 (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19)을 통상적으로 알려진 방법으로 고순도 승화정제를 수행한 후 아래의 과정에 따라 청색 유기 EL 소자를 제작하였다.Each compound synthesized in the above synthesis example (1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1 -20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1 , 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19) A blue organic EL device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.
이렇게 준비된 ITO 투명 전극 위에 CuPc (10 nm)/ TPAC (30 nm)/ 화합물 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2-17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (각각) + 7 % Flrpic (30nm)/ Alq3 (30 nm)/ LiF (0.2 nm)/Al (150 nm) 순으로 적층하여 청색 유기 EL 소자를 제작하였다. Thus prepared CuPc (10 nm) / TPAC (30 nm) / compound 1-1, 1-2, 1-5, 1-7, 1-9, 1-10, 1-12, 1-14 , 1-17, 1-19, 1-20, 1-22, 2-1, 2-2, 2-5, 2-7, 2-9, 2-10, 2-12, 2-14, 2 -17, 2-19, 3-1, 3-2, 3-5, 3-7, 3-9, 3-10, 3-12, 3-14, 3-17, 3-19 (each) + A blue organic EL device was fabricated by stacking 7% Flrpic (30 nm) / Alq 3 (30 nm) / LiF (0.2 nm) / Al (150 nm).
CuPc, TPAC, Flrpic의 구조는 하기와 같다.The structures of CuPc, TPAC, and Flrpic are as follows.
Figure PCTKR2013001025-appb-I000015
Figure PCTKR2013001025-appb-I000015
[비교예 2] 유기 EL 소자의 제작Comparative Example 2 Fabrication of Organic EL Device
발광층 형성시 발광 호스트 물질로서 화합물 1-1 대신 CBP를 사용하는 것을 제외하고는 실시예 33과 동일한 과정으로 청색 유기 EL 소자를 제작하였다.A blue organic EL device was manufactured in the same manner as in Example 33, except that CBP was used instead of Compound 1-1 as a light emitting host material when forming the emission layer.
[평가예 2][Evaluation Example 2]
실시예 33~64 및 비교예 2에서 제작한 각각의 청색 유기 EL 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 2에 나타내었다.For each of the blue organic EL devices produced in Examples 33 to 64 and Comparative Example 2, the driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below.
표 2
샘플 호스트 구동 전압(V) EL 피크(nm) 전류효율(cd/A)
실시예 33 1-1 7.33 473 5.99
실시예 34 1-2 7.13 474 6.34
실시예 35 1-5 7.12 475 6.34
실시예 36 1-7 7.55 475 5.99
실시예 37 1-9 7.55 472 5.85
실시예 38 1-10 7.25 472 5.89
실시예 39 1-12 7.76 473 5.85
실시예 40 1-14 7.33 474 6.90
실시예 41 1-17 7.52 475 6.34
실시예 42 1-19 7.01 475 6.65
실시예 43 1-20 7.34 473 5.99
실시예 44 1-22 7.37 474 5.85
실시예 45 2-1 7.22 473 6.34
실시예 46 2-2 7.21 474 6.14
실시예 47 2-5 7.19 475 5.87
실시예 48 2-7 7.11 472 5.85
실시예 49 2-9 7.12 472 5.75
실시예 50 2-10 7.12 473 5.85
실시예 51 2-12 7.54 473 6.34
실시예 52 2-14 7.52 474 6.21
실시예 53 2-17 7.11 475 5.59
실시예 54 2-19 7.13 472 5.99
실시예 55 3-1 7.12 472 5.85
실시예 56 3-2 7.44 473 6.90
실시예 57 3-5 7.34 474 6.34
실시예 58 3-7 7.18 475 5.99
실시예 59 3-9 7.13 472 5.85
실시예 60 3-10 7.12 472 6.34
실시예 61 3-12 7.21 473 5.78
실시예 62 3-14 7.55 474 5.85
실시예 63 3-17 7.41 475 6.90
실시예 64 3-19 7.13 474 6.34
비교예 2 CBP 7.80 474 5.80
TABLE 2
Sample Host Drive voltage (V) EL peak (nm) Current efficiency (cd / A)
Example 33 1-1 7.33 473 5.99
Example 34 1-2 7.13 474 6.34
Example 35 1-5 7.12 475 6.34
Example 36 1-7 7.55 475 5.99
Example 37 1-9 7.55 472 5.85
Example 38 1-10 7.25 472 5.89
Example 39 1-12 7.76 473 5.85
Example 40 1-14 7.33 474 6.90
Example 41 1-17 7.52 475 6.34
Example 42 1-19 7.01 475 6.65
Example 43 1-20 7.34 473 5.99
Example 44 1-22 7.37 474 5.85
Example 45 2-1 7.22 473 6.34
Example 46 2-2 7.21 474 6.14
Example 47 2-5 7.19 475 5.87
Example 48 2-7 7.11 472 5.85
Example 49 2-9 7.12 472 5.75
Example 50 2-10 7.12 473 5.85
Example 51 2-12 7.54 473 6.34
Example 52 2-14 7.52 474 6.21
Example 53 2-17 7.11 475 5.59
Example 54 2-19 7.13 472 5.99
Example 55 3-1 7.12 472 5.85
Example 56 3-2 7.44 473 6.90
Example 57 3-5 7.34 474 6.34
Example 58 3-7 7.18 475 5.99
Example 59 3-9 7.13 472 5.85
Example 60 3-10 7.12 472 6.34
Example 61 3-12 7.21 473 5.78
Example 62 3-14 7.55 474 5.85
Example 63 3-17 7.41 475 6.90
Example 64 3-19 7.13 474 6.34
Comparative Example 2 CBP 7.80 474 5.80
상기 표 2에 나타낸 바와 같이, 본 발명에 따른 화합물을 청색 유기 EL 소자의 발광층으로 사용하는 실시예 33~64의 유기 EL 소자는 종래 CBP를 사용하는 비교예 2의 청색 유기 EL 소자와 비교해 볼 때 효율 및 구동전압 면에서 보다 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 2 above, the organic EL devices of Examples 33 to 64 using the compound according to the present invention as the light emitting layer of the blue organic EL device were compared with the blue organic EL device of Comparative Example 2 using the conventional CBP. It can be seen that the better performance in terms of efficiency and driving voltage.

Claims (8)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2013001025-appb-I000016
    Figure PCTKR2013001025-appb-I000016
    상기 식에서,Where
    X 및 Y는 서로 같거나 또는 상이하며, 각각 독립적으로 N 또는 CH이고;X and Y are the same as or different from each other, and each independently N or CH;
    R1 및 R2은 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C2~C40의 알케닐기, 치환 또는 비치환된 C2~C40의 알키닐기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C6~C40의 아릴옥시기, 치환 또는 비치환된 C1~C40의 알킬옥시기, -NR3R4, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 1 and R 2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 2 to C 40 alkenyl group, a substituted or unsubstituted C 2 Alkynyl group of -C 40 , substituted or unsubstituted C 6 -C 40 aryl group, substituted or unsubstituted heteroaryl group of 5 to 40 nuclear atoms, substituted or unsubstituted C 6 -C 40 aryl jade A substituted, unsubstituted or unsubstituted C 1 -C 40 alkyloxy group, -NR 3 R 4 , a substituted or unsubstituted C 3 -C 40 cycloalkyl group, and a substituted or unsubstituted heteroatom having 3 to 40 heteroatoms. Selected from the group consisting of cycloalkyl groups, or groups which form a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with adjacent groups,
    상기 R3 및 R4는 서로 같거나 또는 상이하며, 각각 독립적으로 치환 또는 비치환된 C1~C40의 알킬기, 치환 또는 비치환된 C6~C40의 아릴기, 치환 또는 비치환된 핵원자수 5 내지 40의 헤테로아릴기, 치환 또는 비치환된 C3~C40의 시클로알킬기 및 치환 또는 비치환된 핵원자수 3 내지 40의 헤테로시클로알킬기로 이루어진 군에서 선택되거나, 또는 이들이 인접하는 기와 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리 또는 축합 헤테로방향족 고리를 형성하는 기이며, R 3 and R 4 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 40 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted nucleus selected from the group consisting of atoms of 5 to 40 heteroaryl group, a substituted or unsubstituted C 3 ~ C 40 cycloalkyl group and a substituted or unsubstituted number of 3 to 40 hetero-substituted nucleus atoms a cycloalkyl group of or, or they are adjacent A group which forms a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring or a condensed heteroaromatic ring with a group,
    상기 C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C3~C40의 시클로알킬기 및 핵원자수 3 내지 40의 헤테로시클로알킬기는, 각각 독립적으로 중수소, 할로겐, 시아노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C6~C40의 아릴옥시기, C1~C40의 알킬옥시기, C6~C40의 아릴아민기, C6~C40의 아릴알킬기, C3~C40의 시클로알킬기, C3~C40의 헤테로시클로알킬기, C1~C40의 알킬실릴기, 및 C6~C40의 아릴실릴기로 이루어진 군으로부터 선택되는 하나 이상의 치환기로 치환될 수 있다.The C 1 ~ C 40 Alkyl group, C 2 ~ C 40 Alkenyl group, C 2 ~ C 40 Alkynyl group, C 6 ~ C 40 Aryl group, nuclear atom 5 to 40 heteroaryl group, C 6 ~ aryloxy group of C 40, C 1 ~ C 40 alkyloxy group of, C 3 ~ heterocycloalkyl group of C 40 cycloalkyl group and nuclear atoms, 3 to 40 are each independently a heavy hydrogen, a halogen, cyano group, C 1 a ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 6 ~ C 40 aryl group, the number of nuclear atoms of 5 to 40 heteroaryl group, C 6 ~ C 40 of the aryloxy group, C 1 ~ C 40 alkyloxy group of, C 6 ~ C 40 aryl amine group, C 6 ~ C 40 aryl group, C of 3 ~ C 40 cycloalkyl group, C 3 ~ heterocycloalkyl of C 40 It may be substituted with one or more substituents selected from the group consisting of an alkyl group, a C 1 ~ C 40 alkylsilyl group, and a C 6 ~ C 40 arylsilyl group.
  2. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 화학식 4로 표시되는 화합물 중에서 선택되는 어느 하나의 화합물인 것을 특징으로 하는 화합물:The compound of claim 1, wherein the compound represented by Chemical Formula 1 is any one compound selected from the compounds represented by the following Chemical Formulas 2 to 4.
    [화학식 2][Formula 2]
    Figure PCTKR2013001025-appb-I000017
    Figure PCTKR2013001025-appb-I000017
    [화학식 3][Formula 3]
    Figure PCTKR2013001025-appb-I000018
    Figure PCTKR2013001025-appb-I000018
    [화학식 4][Formula 4]
    Figure PCTKR2013001025-appb-I000019
    Figure PCTKR2013001025-appb-I000019
    상기 식에서, Where
    R1 및 R2는 서로 같거나 또는 상이하며, 각각 독립적으로 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4 이고;R 1 and R 2 are the same as or different from each other, and are each independently a C 6 to C 40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, or NR 3 R 4 ;
    R3, 및 R4는 제1항에서 정의된 바와 같다. R 3 , and R 4 are as defined in claim 1.
  3. 제1항에 있어서, 상기 R1은 각각 독립적으로 C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기 또는 NR3R4 이고, According to claim 1, wherein R 1 are each independently C 6 ~ C 40 An aryl group, a nuclear atom of 5 to 40 heteroaryl group or NR 3 R 4 ,
    R2는 C6~C40의 아릴기 또는 핵원자수 5 내지 40의 헤테로아릴기인 것을 특징으로 하는 화합물.R 2 is a C 6 ~ C 40 An aryl group or a heteroaryl group having 5 to 40 nuclear atoms.
  4. 제2항에 있어서, 상기 화학식 2로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 화합물:The compound of claim 2, wherein the compound represented by Chemical Formula 2 is selected from the group of compounds represented by the following chemical formulas:
    Figure PCTKR2013001025-appb-I000020
    Figure PCTKR2013001025-appb-I000020
    Figure PCTKR2013001025-appb-I000021
    Figure PCTKR2013001025-appb-I000021
  5. 제2항에 있어서, 상기 화학식 3으로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 화합물:The compound of claim 2, wherein the compound represented by Chemical Formula 3 is selected from the group of compounds represented by the following chemical formulas:
    Figure PCTKR2013001025-appb-I000022
    Figure PCTKR2013001025-appb-I000022
    Figure PCTKR2013001025-appb-I000023
    Figure PCTKR2013001025-appb-I000023
  6. 제2항에 있어서, 상기 화학식 4로 표시되는 화합물은 하기 화학식으로 표시된 화합물 군에서 선택되는 것을 특징으로 하는 화합물:The compound of claim 2, wherein the compound represented by Chemical Formula 4 is selected from the group of compounds represented by the following chemical formulas:
    Figure PCTKR2013001025-appb-I000024
    Figure PCTKR2013001025-appb-I000024
    Figure PCTKR2013001025-appb-I000025
    Figure PCTKR2013001025-appb-I000025
  7. 양극, 음극, 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode.
    상기 1층 이상의 유기물층 중에서 적어도 하나는 제1항 내지 제6항 중 어느 한 항에 따른 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자. At least one of the one or more organic material layer comprises an compound according to any one of claims 1 to 6 characterized in that the organic electroluminescent device.
  8. 제 7 항에 있어서, 상기 화합물은 발광층, 전자 수송층 및 정공 수송층으로 구성된 군으로부터 선택된 적어도 하나의 층에 포함되는 것을 특징으로 하는 유기 전계 발광 소자. The organic electroluminescent device according to claim 7, wherein the compound is included in at least one layer selected from the group consisting of a light emitting layer, an electron transporting layer, and a hole transporting layer.
PCT/KR2013/001025 2012-09-11 2013-02-08 Organic light-emitting compound and organic electroluminescent device using same WO2014042321A1 (en)

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