WO2013069939A1 - Compound for organic electronic element, organic electronic element including the same, electronic device thereof - Google Patents

Compound for organic electronic element, organic electronic element including the same, electronic device thereof Download PDF

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WO2013069939A1
WO2013069939A1 PCT/KR2012/009261 KR2012009261W WO2013069939A1 WO 2013069939 A1 WO2013069939 A1 WO 2013069939A1 KR 2012009261 W KR2012009261 W KR 2012009261W WO 2013069939 A1 WO2013069939 A1 WO 2013069939A1
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mmol
substituted
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aryl
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PCT/KR2012/009261
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French (fr)
Korean (ko)
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박정환
이선희
문성윤
김대성
정화순
김원삼
변지훈
이범성
김동하
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덕산하이메탈(주)
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
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    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Definitions

  • the present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions.
  • the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.
  • a material constituting the organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material.
  • a stable and efficient organic material layer for an organic electric device has not been made sufficiently, and therefore, the development of new materials is still required.
  • An object of the present invention is to provide a compound containing an five-membered hetero ring capable of improving the luminous efficiency, low driving voltage, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device thereof.
  • the present invention provides a compound represented by the following formula.
  • the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
  • the driving voltage of the device can be lowered, and color purity, luminous efficiency and lifetime can be greatly improved.
  • FIG. 1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.
  • halo or halogen as used herein include fluorine, chlorine, bromine, and iodine unless otherwise stated.
  • alkyl or “alkyl group” has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.
  • alkenyl or “alkynyl” has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.
  • cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
  • alkoxy group used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.
  • aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
  • the aryl group or arylene group in the present invention means a monocyclic or heterocyclic aromatic, for example, the aryl group may be a phenyl group, biphenyl group, fluorene group, spirofluorene group.
  • heteroalkyl means an alkyl including one or more heteroatoms unless otherwise indicated.
  • heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 3 to 60 carbon atoms, each of which includes one or more heteroatoms, unless otherwise specified. In addition, it includes not only a single ring but also a heterocycle, and adjacent groups may be formed by bonding.
  • heterocycloalkyl and “heterocyclic group” include one or more heteroatoms, unless otherwise specified, have a carbon number from 2 to 60, and include heterocycles as well as monocycles. Adjacent groups may be formed in combination.
  • heterocyclic group may mean an alicyclic and / or aromatic including a heteroatom.
  • heteroatom refers to at least one of N, O, S, P, and Si unless otherwise indicated.
  • aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
  • aliphatic ring means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
  • saturated or unsaturated ring as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.
  • heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
  • substituted in the term “substituted or unsubstituted” as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ⁇ C 20 alkyl group, C 1 ⁇ C 20 alkoxy group, C 1 ⁇ C 20 alkyl amine group, C 1 ⁇ C 20 coming of the alkyl group, C 6 ⁇ C 20 coming aryl Ti, C 2 ⁇ C 20 alkenyl group, C 2 ⁇ C 20 of the Alkynyl group, C 3 ⁇ C 20 cycloalkyl group, C 6 ⁇ C 60 aryl group, C 6 ⁇ C 20 aryl group substituted with deuterium, C 8 ⁇ C 20 aryl alkenyl group, silane group, boron group, It means that it is substituted with one or more substituents selected from the group consisting of a germanium group, and a C 5 ⁇ C 20 heterocyclic group
  • FIG. 1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
  • the organic electric device 100 includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110.
  • An organic material layer containing a compound represented by the formula (1) between) is provided.
  • the first electrode 120 may be an anode (anode)
  • the second electrode 180 may be a cathode (cathode)
  • the first electrode may be a cathode and the second electrode may be an anode.
  • the organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed.
  • the hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
  • the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
  • the compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as Preferably, the compound of the present invention may be used as the light emitting layer 150, hole transport layer 140 and / or light emitting auxiliary layer 151.
  • the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layers, and thus the lifetime of the organic electric device. And efficiency can be improved at the same time.
  • the organic electroluminescent device may be manufactured using a PVD method.
  • the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon.
  • the organic material layer including the 160 and the electron injection layer 170 it can be prepared by depositing a material that can be used as the cathode 180 thereon.
  • the organic layer may be prepared by using a variety of polymer materials, but not by a deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer. It can be prepared in a number of layers. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
  • the organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
  • the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.
  • OLED organic electroluminescent device
  • OPC organic photoconductor
  • organic TFT organic transistor
  • Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device.
  • the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
  • the compound according to one aspect of the present invention is represented by the following formula (1).
  • R 1 to R 10 is i) independent of each other, hydrogen, deuterium, halogen, C 6 ⁇ aryl group of C 60, a fluorene group, a fused aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60 C 2 -C 60 heterocyclic group including a ring group, O, N, S, Si and P heteroatoms, -LN (R ') (R "), C 1 ⁇ C 50 Alkyl group, Selected from the group consisting of a C 2 to C 20 alkenyl group, a C 1 to C 30 alkoxy group and a C 6 to C 30 aryloxy group, or ii) adjacent groups combine with each other to form at least one ring Where the groups which do not form a ring are as defined in i).
  • R 1 ⁇ R 4 of must be at least one of both is not a hydrogen R 7 ⁇ R 10 hydrogen and, R 7 ⁇ R or at least one hydrogen of 10 R 1 ⁇ R 4 may be all hydrogen, R 1 Except when R 4 and R 7 to R 10 are both hydrogen at the same time.
  • R 1 to R 4 and R 7 to R 10 are all hydrogen at the same time, for example, i) when R 1 to R 4 are all hydrogen, at least one of R 7 to R 10 is hydrogen in the substituent. It means a substituent other than or when adjacent groups of R 7 ⁇ R 10 combine with each other to form a ring, or ii) when R 7 ⁇ R 10 are all hydrogen, at least one of R 1 ⁇ R 4 is The substituent refers to a substituent other than hydrogen or a case in which adjacent groups in R 1 to R 4 combine with each other to form a ring.
  • Adjacent groups of R 1 and R 10 combine with each other to form at least one ring: R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 are bonded to each other, R 8 and R 9 and / or R 9 and R 10 are bonded to each other to form a ring.
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 are bonded to each other
  • R 8 and R 9 and / or R 9 and R 10 are bonded to each other to form a ring.
  • the ring formed by bonding of adjacent groups of R 1 and R 10 to each other may be a monocyclic or polycyclic aromatic ring or a heterocyclic ring containing at least one heteroatom, or a fused aromatic ring with an aliphatic ring.
  • adjacent groups of R 1 and R 10 may be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like.
  • a phenanthrene form may be formed together with the benzene ring of the mother nucleus to which they are bonded.
  • R 1 and R 10 may be bonded to each other to form a hetero ring such as thiophene, furan, pyridine, indole, quinoline, etc., wherein the carbon number may be 2 to 60.
  • the ring may be fused to each other, a plurality of rings may not be fused to each other, or a ring in which the fused and non-fused forms are mixed.
  • X and Y are each independently S, O or SiR 31 R 32 .
  • R 31 and R 32 are independently of each other hydrogen, a C 6 ⁇ C 60 aryl group, C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P, Or a C 1 to C 50 alkyl group.
  • L is a single bond; C 6 ⁇ C 60 arylene group; Fluorenylene groups; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; It is selected from the group consisting of.
  • Ar 1 is a C 2 ⁇ C 60 heterocyclic group, a C 6 ⁇ C 60 aryl group, fluorenyl group or -N (R containing at least one hetero atom of O, N, S, Si and P ') (R ”).
  • R 'and R are independently of each other O, N, S, Si and P containing at least one heteroatom of C 2 ⁇ C 60 heterocyclic group, C 6 ⁇ C 60 aryl group or fluorenyl group Can be.
  • R One ⁇ R 12 , Ar One When R 'and R "are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C One ⁇ C 20 Alkylthio, C One ⁇ C 20 Alkoxyl, C One ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl, C 2 ⁇ C 20 Alkynyl, C 6 ⁇ C 20 Aryl group of C, substituted with deuterium 6 ⁇ C 20 Aryl group, C 2 ⁇ C 20 Heterocyclic group, C 3 ⁇ C 20 Cycloalkyl group, C 7 ⁇ C 20 of Arylalkyl group and C 8 ⁇ C 20 May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
  • R 1 to R 10 , Ar 1 , R ′ and R ′′ are fluorenyl groups, they are deuterium, halogen, silane groups, cyano groups, C 1 to C 20 alkyl groups, and C 2 to C 20 alkenyl groups (alkenyl ), C aryl group of 6 ⁇ C 20, of a C 6 ⁇ C 20 substituted by deuterium aryl group, C 2 ⁇ C 20 of the heterocyclic group and C 3 ⁇ one or more substituents selected from the group consisting of a cycloalkyl group of C 20 May be substituted with
  • R One ⁇ R 1O If is a fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C One ⁇ C 20 Alkylthio, C One ⁇ C 20 Alkoxyl, C One ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl, C 2 ⁇ C 20 Alkynyl, C 6 ⁇ C 20 Aryl group of C, substituted with deuterium 6 ⁇ C 20 Aryl group, C 2 ⁇ C 20 Heterocyclic group, C 3 ⁇ C 20 Cycloalkyl group, C 7 ⁇ C 20 of Arylalkyl group and C 8 ⁇ C 20 May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
  • R One ⁇ R 12 When is an alkyl group, it is halogen, silane group, boron group, cyano group, C One ⁇ C 20 Alkoxyl, C One ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl, C 6 ⁇ C 20 Aryl group of C, substituted with deuterium 6 ⁇ C 20 Aryl group, C 2 ⁇ C 20 Heterocyclic group, C 7 ⁇ C 20 of Arylalkyl group and C 8 ⁇ C 20 May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
  • R One ⁇ R 10 When it is an alkenyl group, it is deuterium, a halogen, a silane group, a cyano group, C One ⁇ C 20 Alkoxyl, C One ⁇ C 20 Alkyl group, C 2 ⁇ C 20 Alkenyl, C 6 ⁇ C 20 Aryl group of C, substituted with deuterium 6 ⁇ C 20 Aryl group, C 2 ⁇ C 20 Heterocyclic group, C 3 ⁇ C 20 Cycloalkyl group, C 7 ⁇ C 20 of Arylalkyl group and C 8 ⁇ C 20 May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
  • R 1 ⁇ R 10 is an alkoxy group, which is heavy hydrogen, a halogen, a silane group, a C 1 ⁇ C 20 alkyl group, C 6 ⁇ C 20 aryl group, a C 6 ⁇ C 20 substituted with a heavy hydrogen of the aryl group, C 2 ⁇ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ⁇ C 20 cycloalkyl group,
  • R 1 ⁇ R 10 is an aryloxy group cases, this deuterium, a silane group, a cyano group, C of 1 ⁇ C 20 alkyl group, a C 6 ⁇ C 20 substituted with an aryl group, a heavy hydrogen of C 6 ⁇ C 20 aryl group , C 2 ⁇ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ⁇ C 20 cycloalkyl group.
  • the compound represented by Chemical Formula 1 may be represented by one of the following chemical formulas.
  • R 1 ⁇ R 10 , X, Y, L and Ar 1 are the same as defined in formula (1).
  • the compound represented by Formula 1 or 2 may be one of the following compounds.
  • R 1 ⁇ R 4 , R 7 ⁇ R 10 , X, Y, L and Ar 1 are as defined in formula (1).
  • a compound according to the present invention may be prepared by reacting Sub 5 with one of Sub 1, Sub 2, Sub 3 or Sub 4, as shown in Scheme 1 below.
  • Scheme 1 the following synthesis examples are only examples, so the scope of the present invention is not limited thereto.
  • Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2 below.
  • Triphenylphosphine (87.53 g, 333.7 mmol) and o -dichlorobenzene in M 1-2'-18 (51.98 g, 133.5 mmol) obtained in the above synthesis were obtained using 33.87 g (yield) of the product using Sub 1-2 synthesis of Example 1. : 71%).
  • Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 5 below.
  • Sub 4 of Scheme 1 may be synthesized by the reaction route of Scheme 9 below.
  • Sub 1, Sub 2, Sub 3, and Sub 4 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.
  • Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 5 (1.2 equiv), Pd 2 (dba) 3 (0.03 equiv), P ( t -Bu) 3 (0.08 equiv), NaO t -Bu (3 equiv) were added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.
  • Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 equiv) was dissolved in dimethyl sulfoxide in a round bottom flask, then Sub 5 (1.1 equiv) and K 2 CO 3 (6 equiv) were added and stirred at 150 ° C. . After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.
  • Sub 1-2 (7.18 g, 18 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 5-7 (8.35 g, 21.6 mmol), Pd 2 (dba) 3 (0.49 g, 0.5 mmol) , 50% P ( t- Bu) 3 (0.7ml, 1.4 mmol), NaO t- Bu (5.18 g, 53.9 mmol) was added and stirred at 100 ° C.
  • An organic light emitting diode was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material of a light emitting layer.
  • a phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm.
  • BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum
  • BAlq is vacuum-deposited to a thickness of 10 nm on the light emitting layer.
  • a stop layer was formed, and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited to a thickness of 40 nm to form an electron transport layer.
  • LiF an alkali metal halide
  • Al an alkali metal halide
  • An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that Comparative Compound 1 was used as a light emitting host material instead of the compound of the present invention to form a light emitting layer.
  • An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the comparative compound 3 (12- (4- (4,6-diphenylpyrimidin-2-yl) phenyl) -12H-benzo [4,5] was used instead of the compound of the present invention. ] thieno [2,3-a] carbazole) was used as a light emitting host material to form a light emitting layer.
  • Electroluminescent (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent device manufactured by Experimental Example 1 and Comparative Examples, and the measurement result was 300 cd / m 2.
  • the T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at the reference luminance.
  • Table 4 below shows device fabrication and evaluation results of Examples and Comparative Examples to which the compound according to the invention is applied.
  • the organic electroluminescent device using the organic electroluminescent device material of the present invention as a light emitting host material has remarkably improved color purity, high luminous efficiency and lifetime.
  • the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

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  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a novel compound which comprises a 5-membered heterocycle capable of improving light-emitting efficiency, stability, and lifetime of elements, organic electronic element using the same, and an electronic device thereof.

Description

유기전기소자용 화합물, 이를 포함하는 유기전기소자 및 그 전자 장치Compound for organic electric device, organic electric device comprising same and electronic device thereof
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials such as hole injection materials, hole transport materials, electron transport materials, electron injection materials and the like depending on their functions.
한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투 확산되는 것을 지연시키며, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이 온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 또한 정공 수송층 재료의 낮은 유리전이 온도는 소자 구동시에 박막 표면의 균일도가 무너지는 특성에 따라 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자의 형성에 있어서 증착방법이 주류를 이루고 있으며, 이러한 증착방법에 오랫동안 견딜 수 있는 재료 즉 내열성 특성이 강한 재료가 필요한 실정이다. On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.
전술한 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정하고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이며, 따라서 새로운 재료의 개발이 계속 요구되고 있다.In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric device has not been made sufficiently, and therefore, the development of new materials is still required.
본 발명은 소자의 높은 발광효율, 낮은 구동전압, 색순도, 및 수명을 향상시킬 수 있는 오원자 헤테로 고리를 포함하는 화합물 및 이를 이용한 유기전기소자, 그 전자 장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound containing an five-membered hetero ring capable of improving the luminous efficiency, low driving voltage, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device thereof.
일측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by the following formula.
Figure PCTKR2012009261-appb-I000001
Figure PCTKR2012009261-appb-I000001
다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
본 발명에 따른 화합물을 이용함으로써 소자의 구동전압을 낮출 수 있고, 색순도, 발광효율 및 수명을 크게 향상시킬 수 있다.By using the compound according to the present invention, the driving voltage of the device can be lowered, and color purity, luminous efficiency and lifetime can be greatly improved.
도 1은 본 발명의 일실시예에 따른 유기전기발광소자의 예시도이다. 1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.
이하에서 본 발명의 일부 실시예들을 예시적인 도면을 통해 상세하게 설명한다.Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
또한, 본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a),(b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".
한편, 본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소, 염소, 브롬, 및 요오드를 포함한다. On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise stated.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. As used herein, the term "alkyl" or "alkyl group" has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.
본 발명에 사용된 용어 "알케닐" 또는 "알키닐"은 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 여기에 제한되는 것은 아니다. As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다. The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
본 발명에 사용된 용어 "알콕시기"는 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다. The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
본 발명에서 아릴기 또는 아릴렌기는 단일환 또는 복소환의 방향족을 의미하며, 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다. The aryl group or arylene group in the present invention means a monocyclic or heterocyclic aromatic, for example, the aryl group may be a phenyl group, biphenyl group, fluorene group, spirofluorene group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 3 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다.As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each of which includes one or more heteroatoms, unless otherwise specified. In addition, it includes not only a single ring but also a heterocycle, and adjacent groups may be formed by bonding.
본 발명에 사용된 용어 "헤테로시클로알킬", "헤테로고리기"는 다른 설명이 없는 한 하나 또는 그 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일환뿐만 아니라 복소환을 포함하며, 이웃한 기가 결합하여 형성될 수도 있다. 또한, "헤테로고리기"는 헤테로원자를 포함하는 지환족 및/또는 방향족을 의미할 수 있다.As used herein, the terms "heterocycloalkyl" and "heterocyclic group" include one or more heteroatoms, unless otherwise specified, have a carbon number from 2 to 60, and include heterocycles as well as monocycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 및 Si 중 적어도 하나를 나타낸다. As used herein, the term “heteroatom” refers to at least one of N, O, S, P, and Si unless otherwise indicated.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다. Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "포화 또는 불포화 고리"는 포화 또는 불포화 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 헤테로고리를 의미한다.Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다. Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1~C20의 알킬기, C1~C20의 알콕시기, C1~C20의 알킬아민기, C1~C20의 알킬티오기, C6~C20의 아릴티오기, C2~C20의 알케닐기, C2~C20의 알키닐기, C3~C20의 시클로알킬기, C6~C60의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C8~C20의 아릴알케닐기, 실란기, 붕소기, 게르마늄기, 및 C5~C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, C 1 ~ C 20 alkyl amine group, C 1 ~ C 20 coming of the alkyl group, C 6 ~ C 20 coming aryl Ti, C 2 ~ C 20 alkenyl group, C 2 ~ C 20 of the Alkynyl group, C 3 ~ C 20 cycloalkyl group, C 6 ~ C 60 aryl group, C 6 ~ C 20 aryl group substituted with deuterium, C 8 ~ C 20 aryl alkenyl group, silane group, boron group, It means that it is substituted with one or more substituents selected from the group consisting of a germanium group, and a C 5 ~ C 20 heterocyclic group, and is not limited to these substituents.
도 1은 본 발명에 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(110)과 제 2전극(180) 사이에 화학식 1로 표시되는 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. An organic material layer containing a compound represented by the formula (1) between) is provided. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 발광층(150)을 제외한 나머지 층들이 형성되지 않을 수 있다. 정공저지층, 전자저지층, 발광보조층(151), 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다. The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.
또한, 미도시하였지만, 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다. In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
상기 유기물층에 적용되는 본 발명에 따른 화합물은 정공주입층(130), 정공수송층(140), 전자수송층(160), 전자주입층(170), 발광층(150)의 호스트 또는 도펀트 또는 캐핑층의 재료로 사용될 수 있을 것이다. 바람직하게는, 본 발명의 화합물은 발광층(150), 정공수송층(140) 및/또는 발광보조층(151)으로 사용될 수 있을 것이다.The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as Preferably, the compound of the present invention may be used as the light emitting layer 150, hole transport layer 140 and / or light emitting auxiliary layer 151.
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.
따라서, 본 발명에서는 화학식 1로 표시되는 화합물을 사용하여 발광층을 형성함으로써 각 유기물층 간의 에너지 레벨(level) 및 T1 값, 물질의 고유특성(mobility, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다. Therefore, in the present invention, the light emitting layer is formed using the compound represented by Chemical Formula 1 to optimize the energy level and T1 value between each organic material layer, the intrinsic properties (mobility, interfacial properties, etc.) of the organic layers, and thus the lifetime of the organic electric device. And efficiency can be improved at the same time.
본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic layer may be prepared by using a variety of polymer materials, but not by a deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer. It can be prepared in a number of layers. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
본 발명에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.
또한, 본 발명에 따른 유기전기소자는 유기전기발광소자(OLED), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 단색 또는 백색 조명용 소자 중 하나일 수 있다.In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.
본 발명의 일측면에 따른 화합물은 하기 화학식 1로 표시된다.The compound according to one aspect of the present invention is represented by the following formula (1).
화학식 1
Figure PCTKR2012009261-appb-C000001
 Formula 1
Figure PCTKR2012009261-appb-C000001
상기 화학식 1에서,In Chemical Formula 1,
R1 내지 R10은 i) 서로 독립적으로, 수소, 중수소, 할로겐, C6~C60의 아릴기, 플루오렌일기, C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로 고리기, -L-N(R’)(R”), C1~C50의 알킬기, C2~C20의 알켄일기, C1~C30의 알콕시기 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택되거나, 또는 ii) 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성한다(이때, 고리를 형성하지 않는 기는 i)에서 정의된 것과 같다). R 1 to R 10 is i) independent of each other, hydrogen, deuterium, halogen, C 6 ~ aryl group of C 60, a fluorene group, a fused aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60 C 2 -C 60 heterocyclic group including a ring group, O, N, S, Si and P heteroatoms, -LN (R ') (R "), C 1 ~ C 50 Alkyl group, Selected from the group consisting of a C 2 to C 20 alkenyl group, a C 1 to C 30 alkoxy group and a C 6 to C 30 aryloxy group, or ii) adjacent groups combine with each other to form at least one ring Where the groups which do not form a ring are as defined in i).
단, R1~R4 중 적어도 하나가 수소가 아니면 R7~R10은 모두 수소이어야 하며, R7~R10 중 적어도 하나가 수소가 아니면 R1~R4는 모두 수소이어야 하고, R1~R4와 R7~R10이 모두 동시에 수소인 경우는 제외한다. However, R 1 ~ R 4 of must be at least one of both is not a hydrogen R 7 ~ R 10 hydrogen and, R 7 ~ R or at least one hydrogen of 10 R 1 ~ R 4 may be all hydrogen, R 1 Except when R 4 and R 7 to R 10 are both hydrogen at the same time.
상기 R1~R4 및 R7~R10이 동시에 모두 수소인 경우는 제외한다라는 것은, 예컨대 i) R1~R4가 모두 수소인 경우, R7~R10 중 적어도 하나는 상기 치환기 중 수소 이외의 치환기이거나 R7~R10 중 이웃한 기끼리 서로 결합하여 고리를 형성하는 경우를 의미하거나, 또는 ii) R7~R10가 모두 수소인 경우, R1~R4 중 적어도 하나는 상기 치환기 중 수소 이외의 치환기이거나 R1~R4 중 이웃한 기끼리 서로 결합하여 고리를 형성하는 경우를 의미한다.Except for the case where R 1 to R 4 and R 7 to R 10 are all hydrogen at the same time, for example, i) when R 1 to R 4 are all hydrogen, at least one of R 7 to R 10 is hydrogen in the substituent. It means a substituent other than or when adjacent groups of R 7 ~ R 10 combine with each other to form a ring, or ii) when R 7 ~ R 10 are all hydrogen, at least one of R 1 ~ R 4 is The substituent refers to a substituent other than hydrogen or a case in which adjacent groups in R 1 to R 4 combine with each other to form a ring.
R1과 R10 중 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성한다 함은, R1과 R2끼리, R2와 R3끼리, R3와 R4끼리, R5와 R6끼리, R7과 R8끼리, R8과 R9끼리 및/또는 R9와 R10끼리 서로 결합하여 고리를 형성하는 것을 말한다. 이때, 이웃한 기끼리 서로 결합하여 고리를 형성한다는 자체가 중요하므로, 이들이 어떤 치환기이고 어떤 반응을 통해 고리가 형성되는지에 의해 본 발명의 권리범위가 제한되지는 않는다.Adjacent groups of R 1 and R 10 combine with each other to form at least one ring: R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 are bonded to each other, R 8 and R 9 and / or R 9 and R 10 are bonded to each other to form a ring. At this time, since it is important that the adjacent groups are bonded to each other to form a ring, the scope of the present invention is not limited by what substituents and by what reaction the ring is formed.
R1과 R10 중 이웃한 기끼리 서로 결합하여 형성된 고리는 단환 또는 다환의 방향족고리 또는 헤테로 원자를 적어도 하나 포함하는 헤테로고리일 수 있을 뿐만 아니라 방향족고리와 지방족 고리가 융합된 형태일 수도 있다. 예시적으로, R1과 R10 중 이웃한 기끼리 서로 결합하여 벤젠, 나프탈렌, 페난트렌 등과 같은 방향족고리를 형성할 수 있는데, 이때 형성되는 방향족고리의 핵탄소수는 6 내지 60인 것이 바람직하다. 예컨대, R7과 R8이 서로 결합하여 벤젠고리를 형성하고, R9와 R10이 서로 결합하여 벤젠고리를 형성하면 이들이 결합된 모핵의 벤젠링과 함께 페난트렌 형태가 형성될 수 있을 것이다.The ring formed by bonding of adjacent groups of R 1 and R 10 to each other may be a monocyclic or polycyclic aromatic ring or a heterocyclic ring containing at least one heteroatom, or a fused aromatic ring with an aliphatic ring. For example, adjacent groups of R 1 and R 10 may be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like. For example, when R 7 and R 8 are bonded to each other to form a benzene ring, and R 9 and R 10 are bonded to each other to form a benzene ring, a phenanthrene form may be formed together with the benzene ring of the mother nucleus to which they are bonded.
또한, R1과 R10이 서로 결합하여 싸이오펜, 퓨란, 피리딘, 인돌, 퀴놀린 등과 같은 헤테로고리를 형성할 수 있는데, 이때 핵탄소수는 2 내지 60일 수 있다. 또한, 다환고리인 경우 서로 융합된(fused) 형태일 수도 있고 복수개의 환이 서로 융합되지 않은 형태일 수도 있으며, 융합된 형태와 비융합된 형태가 혼합된 환일 수도 있다.In addition, R 1 and R 10 may be bonded to each other to form a hetero ring such as thiophene, furan, pyridine, indole, quinoline, etc., wherein the carbon number may be 2 to 60. In the case of a polycyclic ring, the ring may be fused to each other, a plurality of rings may not be fused to each other, or a ring in which the fused and non-fused forms are mixed.
상기 화학식 1에서, X와 Y는 서로 독립적으로, S, O 또는 SiR31R32이다. 여기서, R31과 R32는 서로 독립적으로 수소, C6~C60의 아릴기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, 또는 C1~C50의 알킬기일 수 있다. 한편, 상기 화학식에서 m과 n 각각은 0 또는 1일 수 있으나, 단 m과 n이 모두 0인 경우는 제외한다. m+n=1 이상의 정수이어야 하므로, X, Y 중 적어도 하나는 반드시 존재해야 한다.In Formula 1, X and Y are each independently S, O or SiR 31 R 32 . Here, R 31 and R 32 are independently of each other hydrogen, a C 6 ~ C 60 aryl group, C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P, Or a C 1 to C 50 alkyl group. Meanwhile, in the above formula, m and n may each be 0 or 1, except that m and n are both 0. Since m + n = 1 must be an integer, at least one of X and Y must be present.
L은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 2가의 지방족 탄화수소기;로 이루어진 군에서 선택된다. 이때, 아릴렌기, 플루오렌일렌기, 헤테로고리기 및 지방족 탄화수소기는 니트로기, 시아노기, 할로겐기, C1~C20의 알킬기, C6~C20의 아릴기, C2~C20의 헤테로고리기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환될 수 있다.L is a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; It is selected from the group consisting of. At this time, the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group, nitro group, cyano group, halogen group, C 1 ~ C 20 alkyl group, C 6 ~ C 20 aryl group, C 2 ~ C 20 hetero It may be substituted with one or more substituents selected from the group consisting of a ring group, a C 1 to C 20 alkoxy group and an amino group.
또한, Ar1은 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기, 플루오렌일기 또는 -N(R’)(R”)일 수 있다.In addition, Ar 1 is a C 2 ~ C 60 heterocyclic group, a C 6 ~ C 60 aryl group, fluorenyl group or -N (R containing at least one hetero atom of O, N, S, Si and P ') (R ”).
상기 R'과 R"은 서로 독립적으로 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기 또는 플루오렌일기일 수 있다.R 'and R "are independently of each other O, N, S, Si and P containing at least one heteroatom of C 2 ~ C 60 heterocyclic group, C 6 ~ C 60 aryl group or fluorenyl group Can be.
한편, 상기 R1~R12, Ar1, R' 및 R"이 아릴기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,Meanwhile, ROne~ R12, ArOneWhen R 'and R "are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, COne~ C20Alkylthio, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C2~ C20Alkynyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
상기 R1~R12, Ar1, R' 및 R"가 헤테로고리기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, 니트로기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R12, ArOneWhen R 'and R "are heterocyclic groups, they are deuterium, halogen, silane groups, cyano groups, nitro groups, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
상기 R1~R10, Ar1, R' 및 R"가 플루오렌일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When R 1 to R 10 , Ar 1 , R ′ and R ″ are fluorenyl groups, they are deuterium, halogen, silane groups, cyano groups, C 1 to C 20 alkyl groups, and C 2 to C 20 alkenyl groups (alkenyl ), C aryl group of 6 ~ C 20, of a C 6 ~ C 20 substituted by deuterium aryl group, C 2 ~ C 20 of the heterocyclic group and C 3 ~ one or more substituents selected from the group consisting of a cycloalkyl group of C 20 May be substituted with
상기 R1~R1O가 융합고리기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R1OIf is a fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, COne~ C20Alkylthio, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C2~ C20Alkynyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
상기 R1~R12가 알킬기인 경우, 이는 할로겐, 실란기, 붕소기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R12When is an alkyl group, it is halogen, silane group, boron group, cyano group, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
상기 R1~R10이 알켄일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R10When it is an alkenyl group, it is deuterium, a halogen, a silane group, a cyano group, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
상기 R1~R10이 알콕실기인 경우, 이는 중수소, 할로겐, 실란기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When the R 1 ~ R 10 is an alkoxy group, which is heavy hydrogen, a halogen, a silane group, a C 1 ~ C 20 alkyl group, C 6 ~ C 20 aryl group, a C 6 ~ C 20 substituted with a heavy hydrogen of the aryl group, C 2 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ~ C 20 cycloalkyl group,
상기 R1~R10이 아릴옥시기인 경우, 이는 중수소, 실란기, 시아노기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다.Wherein R 1 ~ R 10 is an aryloxy group cases, this deuterium, a silane group, a cyano group, C of 1 ~ C 20 alkyl group, a C 6 ~ C 20 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 20 aryl group , C 2 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ~ C 20 cycloalkyl group.
상기 화학식 1로 표시되는 화합물은 하기 화학식 중 하나로 표시될 수 있다.The compound represented by Chemical Formula 1 may be represented by one of the following chemical formulas.
Figure PCTKR2012009261-appb-I000002
Figure PCTKR2012009261-appb-I000002
Figure PCTKR2012009261-appb-I000003
Figure PCTKR2012009261-appb-I000003
상기 화학식에서, R1~R10, X, Y, L 및 Ar1은 화학식 1에서 정의된 것과 같다.In the above formula, R 1 ~ R 10 , X, Y, L and Ar 1 are the same as defined in formula (1).
보다 구체적으로, 상기 화학식 1 또는 2로 표시되는 화합물은 하기 화합물 중 하나일 수 있다.More specifically, the compound represented by Formula 1 or 2 may be one of the following compounds.
Figure PCTKR2012009261-appb-I000004
Figure PCTKR2012009261-appb-I000004
Figure PCTKR2012009261-appb-I000005
Figure PCTKR2012009261-appb-I000005
Figure PCTKR2012009261-appb-I000006
Figure PCTKR2012009261-appb-I000006
상기 화학식에서, R1~R4, R7~R10, X, Y, L 및 Ar1은 화학식 1에서 정의된 것과 같다.In the above formula, R 1 ~ R 4 , R 7 ~ R 10 , X, Y, L and Ar 1 are as defined in formula (1).
Figure PCTKR2012009261-appb-I000007
Figure PCTKR2012009261-appb-I000007
Figure PCTKR2012009261-appb-I000008
Figure PCTKR2012009261-appb-I000008
Figure PCTKR2012009261-appb-I000009
Figure PCTKR2012009261-appb-I000009
Figure PCTKR2012009261-appb-I000010
Figure PCTKR2012009261-appb-I000010
Figure PCTKR2012009261-appb-I000011
Figure PCTKR2012009261-appb-I000011
Figure PCTKR2012009261-appb-I000012
Figure PCTKR2012009261-appb-I000012
Figure PCTKR2012009261-appb-I000013
Figure PCTKR2012009261-appb-I000013
Figure PCTKR2012009261-appb-I000014
Figure PCTKR2012009261-appb-I000014
Figure PCTKR2012009261-appb-I000015
Figure PCTKR2012009261-appb-I000015
Figure PCTKR2012009261-appb-I000016
Figure PCTKR2012009261-appb-I000016
Figure PCTKR2012009261-appb-I000017
Figure PCTKR2012009261-appb-I000017
Figure PCTKR2012009261-appb-I000018
Figure PCTKR2012009261-appb-I000018
Figure PCTKR2012009261-appb-I000019
Figure PCTKR2012009261-appb-I000019
Figure PCTKR2012009261-appb-I000020
Figure PCTKR2012009261-appb-I000020
Figure PCTKR2012009261-appb-I000021
Figure PCTKR2012009261-appb-I000021
Figure PCTKR2012009261-appb-I000022
Figure PCTKR2012009261-appb-I000022
Figure PCTKR2012009261-appb-I000023
Figure PCTKR2012009261-appb-I000023
Figure PCTKR2012009261-appb-I000024
Figure PCTKR2012009261-appb-I000024
Figure PCTKR2012009261-appb-I000025
Figure PCTKR2012009261-appb-I000025
Figure PCTKR2012009261-appb-I000026
Figure PCTKR2012009261-appb-I000026
Figure PCTKR2012009261-appb-I000027
Figure PCTKR2012009261-appb-I000027
Figure PCTKR2012009261-appb-I000028
Figure PCTKR2012009261-appb-I000028
Figure PCTKR2012009261-appb-I000029
Figure PCTKR2012009261-appb-I000029
Figure PCTKR2012009261-appb-I000030
Figure PCTKR2012009261-appb-I000030
Figure PCTKR2012009261-appb-I000031
Figure PCTKR2012009261-appb-I000031
Figure PCTKR2012009261-appb-I000032
Figure PCTKR2012009261-appb-I000032
Figure PCTKR2012009261-appb-I000033
Figure PCTKR2012009261-appb-I000033
Figure PCTKR2012009261-appb-I000034
Figure PCTKR2012009261-appb-I000034
Figure PCTKR2012009261-appb-I000035
Figure PCTKR2012009261-appb-I000035
Figure PCTKR2012009261-appb-I000036
Figure PCTKR2012009261-appb-I000036
Figure PCTKR2012009261-appb-I000037
Figure PCTKR2012009261-appb-I000037
Figure PCTKR2012009261-appb-I000038
Figure PCTKR2012009261-appb-I000038
Figure PCTKR2012009261-appb-I000039
Figure PCTKR2012009261-appb-I000039
Figure PCTKR2012009261-appb-I000040
Figure PCTKR2012009261-appb-I000040
Figure PCTKR2012009261-appb-I000041
Figure PCTKR2012009261-appb-I000041
Figure PCTKR2012009261-appb-I000042
Figure PCTKR2012009261-appb-I000042
Figure PCTKR2012009261-appb-I000043
Figure PCTKR2012009261-appb-I000043
Figure PCTKR2012009261-appb-I000044
Figure PCTKR2012009261-appb-I000044
Figure PCTKR2012009261-appb-I000045
Figure PCTKR2012009261-appb-I000045
Figure PCTKR2012009261-appb-I000046
Figure PCTKR2012009261-appb-I000046
Figure PCTKR2012009261-appb-I000047
Figure PCTKR2012009261-appb-I000047
Figure PCTKR2012009261-appb-I000048
Figure PCTKR2012009261-appb-I000048
Figure PCTKR2012009261-appb-I000049
Figure PCTKR2012009261-appb-I000049
Figure PCTKR2012009261-appb-I000050
Figure PCTKR2012009261-appb-I000050
Figure PCTKR2012009261-appb-I000051
Figure PCTKR2012009261-appb-I000051
Figure PCTKR2012009261-appb-I000052
Figure PCTKR2012009261-appb-I000052
Figure PCTKR2012009261-appb-I000053
Figure PCTKR2012009261-appb-I000053
Figure PCTKR2012009261-appb-I000054
Figure PCTKR2012009261-appb-I000054
Figure PCTKR2012009261-appb-I000055
Figure PCTKR2012009261-appb-I000055
Figure PCTKR2012009261-appb-I000056
Figure PCTKR2012009261-appb-I000056
Figure PCTKR2012009261-appb-I000057
Figure PCTKR2012009261-appb-I000057
Figure PCTKR2012009261-appb-I000058
Figure PCTKR2012009261-appb-I000058
Figure PCTKR2012009261-appb-I000059
Figure PCTKR2012009261-appb-I000059
이하에서, 상기 화학식으로 표시되는 본 발명 화합물의 합성예 및 유기전기소자의 제조예에 대하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compounds of the present invention represented by the above formula and the production examples of the organic electric device will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
합성예Synthesis Example
예시적으로, 본 발명에 따른 화합물(final product)은 하기 반응식 1과 같이 Sub 1, Sub 2, Sub 3 또는 Sub 4 중 하나와 Sub 5를 반응시켜 제조할 수 있다. 하지만, 하기 합성예는 실시예에 불과하므로 본 발명의 권리범위가 이에 의해 제한되지는 않는다.In exemplary embodiments, a compound according to the present invention may be prepared by reacting Sub 5 with one of Sub 1, Sub 2, Sub 3 or Sub 4, as shown in Scheme 1 below. However, the following synthesis examples are only examples, so the scope of the present invention is not limited thereto.
<반응식 1><Scheme 1>
Figure PCTKR2012009261-appb-I000060
Figure PCTKR2012009261-appb-I000060
[실시예 1]Example 1
Sub 1의 합성Synthesis of Sub 1
반응식 1의 sub 1은 하기 반응식 2의 반응경로에 의해 합성될 수 있다.Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2 below.
<반응식 2><Scheme 2>
Figure PCTKR2012009261-appb-I000061
Figure PCTKR2012009261-appb-I000061
Sub 1에 속하는 구체적 화합물의 합성예는 다음과 같다Synthesis examples of specific compounds belonging to Sub 1 are as follows.
(1) Sub 1-2 합성예(1) Sub 1-2 Synthesis Example
<반응식 3><Scheme 3>
Figure PCTKR2012009261-appb-I000062
Figure PCTKR2012009261-appb-I000062
Figure PCTKR2012009261-appb-I000063
Figure PCTKR2012009261-appb-I000063
중간체 M 1-1-2 합성Intermediate M 1-1-2 Synthesis
출발물질인 (2-(methylthio)phenyl)boronic acid (72.45 g, 431.2 mmol)를 둥근바닥플라스크에 THF로 녹인 후에, 3-bromo-1-iodonaphthalene (215.36 g, 646.8 mmol), Pd(PPh3)4 (24.91 g, 21.6 mmol), K2CO3 (178.79 g, 1293.6 mmol), 물을 첨가하고 80°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 83.76 g (수율: 59%)를 얻었다.After starting material (2- (methylthio) phenyl) boronic acid (72.45 g, 431.2 mmol) was dissolved in THF in a round bottom flask, 3-bromo-1-iodonaphthalene (215.36 g, 646.8 mmol), Pd (PPh 3 ) 4 (24.91 g, 21.6 mmol), K 2 CO 3 (178.79 g, 1293.6 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was silicagel column and recrystallized to give 83.76 g (yield: 59%) of the product.
중간체 M 1-2-2 합성Intermediate M 1-2-2 Synthesis
상기 합성에서 얻어진 M 1-1-2 (83.76 g, 254.4 mmol)를 둥근바닥플라스크에 acetic acid로 녹인 후에, aqueous 30% H2O2 (25.4ml, 254.4 mmol)를 천천히 적가하고 상온에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출 (Na2S2O3로 유기층 washing)한 후 유기층을 Na2SO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 79.05 g (수율: 90%)를 얻었다.M 1-1-2 (83.76 g, 254.4 mmol) obtained in the above synthesis was dissolved in acetic acid in a round bottom flask, and aqueous 30% H 2 O 2 (25.4ml, 254.4 mmol) was slowly added dropwise and stirred at room temperature. . After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water (Na 2 S 2 O 3, and the organic layer was washed). The organic layer was dried over Na 2 SO 4 and concentrated. : 90%).
중간체 M 1-3-2 합성Intermediate M 1-3-2 Synthesis
상기 합성에서 얻어진 M 1-2-2 (79.05 g, 229 mmol)를 둥근바닥플라스크에 triflic acid (607.8ml, 6868.9 mmol)와 함께 넣고 상온에서 24 시간 교반하였다. 이것을 pyridine : H2O = 1 : 5로 2200ml를 첨가하여 30 분간 환류 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 50.92 g (수율: 71%)를 얻었다.M 1-2-2 (79.05 g, 229 mmol) obtained in the above synthesis was added to triflic acid (607.8ml, 6868.9 mmol) in a round bottom flask and stirred at room temperature for 24 hours. 2200 ml of pyridine: H 2 O = 1: 5 was added thereto, followed by stirring for 30 minutes under reflux. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 50.92 g (yield: 71%) of the product.
중간체 M 1-4-2 합성Intermediate M 1-4-2 Synthesis
상기 합성에서 얻어진 M 1-3-2 (50.92 g, 162.6 mmol)를 둥근바닥플라스크에 DMF로 녹인 후에, Bis(pinacolato)diboron (45.41 g, 178.8 mmol), Pd(dppf)Cl2 (3.98 g, 4.9 mmol), KOAc (47.87 g, 487.7 mmol)를 첨가하고 90°C에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 45.69 g (수율: 78%)를 얻었다.M 1-3-2 (50.92 g, 162.6 mmol) obtained in the above synthesis was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (45.41 g, 178.8 mmol) and Pd (dppf) Cl2(3.98 g, 4.9 mmol), KOAc (47.87 g, 487.7 mmol) was added and stirred at 90 ° C. When the reaction is complete, remove DMF by distillation2Cl2And extracted with water. MgSO organic layer4After drying and concentration, the resulting compound was silicagel column and recrystallized to give the product 45.69 g (yield: 78%).
중간체 M 1-5-2 합성Intermediate M 1-5-2 Synthesis
상기 합성에서 얻어진 M 1-4-2 (45.69 g, 126.8 mmol)를 둥근바닥플라스크에 THF로 녹인 후에, 4-bromo-3-nitro-1,1'-biphenyl (52.9 g, 190.2 mmol), Pd(PPh3)4 (7.33 g, 6.3 mmol), K2CO3 (52.58 g, 380.5 mmol), 물을 첨가하고 80°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 47.61 g (수율: 87%)를 얻었다.M 1-4-2 (45.69 g, 126.8 mmol) obtained in the above synthesis was dissolved in THF in a round bottom flask, followed by 4-bromo-3-nitro-1,1'-biphenyl (52.9 g, 190.2 mmol), Pd. (PPh 3 ) 4 (7.33 g, 6.3 mmol), K 2 CO 3 (52.58 g, 380.5 mmol), water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain a product 47.61 g (yield: 87%).
Sub 1-2 합성예Sub 1-2 Synthesis Example
상기 합성에서 얻어진 M 1-5-2 (47.61 g, 110.3 mmol)를 둥근바닥플라스크에 o-dichlorobenzene으로 녹인 후에, triphenylphosphine (72.35 g, 275.8 mmol)을 첨가하고 200°C에서 교반하였다. 반응이 완료되면 증류를 통해 o-dichlorobenzene을 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 33.06 g (수율: 75%)를 얻었다.M 1-5-2 (47.61 g, 110.3 mmol) obtained in the above synthesis was dissolved in o- dichlorobenzene in a round bottom flask, triphenylphosphine (72.35 g, 275.8 mmol) was added and stirred at 200 ° C. After the reaction was completed, o -dichlorobenzene was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was silicagel column and recrystallized to give 33.06 g (yield: 75%) of the product.
(2) Sub 1-18 합성예(2) Synthesis Example of Sub 1-18
반응식 2의 경우, sub 1에 X가 S인 경우를 예시하였다. X가 O인 경우도 동일한 패턴으로 합성된다는 것을 하기 반응식 4의 구체적인 합성예를 통해 보여준다.In the case of Scheme 2, the case where X is S in sub 1 is illustrated. It is shown through the specific synthesis example of the following Scheme 4 that X is synthesized in the same pattern when O.
<반응식 4><Scheme 4>
Figure PCTKR2012009261-appb-I000064
Figure PCTKR2012009261-appb-I000064
중간체 M 1-1'-18 합성Intermediate M 1-1'-18 Synthesis
출발물질인 4-bromodibenzo[b,d]furan (51.61 g, 208.9 mmol)에, Bis(pinacolato)diboron (58.34 g, 229.8 mmol), Pd(dppf)Cl2 (5.12 g, 6.3 mmol), KOAc (61.5 g, 626.6 mmol), DMF를 상기 실시예 1의 M 1-4-2 합성법을 사용하여 생성물 50.99 g (수율: 83%)를 얻었다.4-bromodibenzo starting materialb,d] furan (51.61 g, 208.9 mmol), Bis (pinacolato) diboron (58.34 g, 229.8 mmol), Pd (dppf) Cl2(5.12 g, 6.3 mmol), KOAc (61.5 g, 626.6 mmol) and DMF were obtained using the M 1-4-2 synthesis method of Example 1, to obtain 50.99 g (yield: 83%) of the product.
중간체 M 1-2'-18 합성Intermediate M 1-2'-18 Synthesis
상기 합성에서 얻어진 M 1-1'-18 (50.99 g, 173.3 mmol)에, 9-bromo-10-nitrophenanthrene (78.56 g, 260 mmol), Pd(PPh3)4 (10.02 g, 8.7 mmol), K2CO3 (71.87 g, 520 mmol), THF, 물을 상기 실시예 1의 M 1-5-2 합성법을 사용하여 생성물 51.98 g (수율: 77%)를 얻었다.To M 1-1'-18 (50.99 g, 173.3 mmol) obtained in the above synthesis, 9-bromo-10-nitrophenanthrene (78.56 g, 260 mmol), Pd (PPh 3 ) 4 (10.02 g, 8.7 mmol), K 2 CO 3 (71.87 g, 520 mmol), THF, and water were obtained using the M 1-5-2 synthesis method of Example 1, to obtain 51.98 g (yield: 77%) of the product.
Sub 1-18 합성예Sub 1-18 Synthesis Example
상기 합성에서 얻어진 M 1-2'-18 (51.98 g, 133.5 mmol)에 triphenylphosphine (87.53 g, 333.7 mmol), o-dichlorobenzene을 상기 실시예 1의 Sub 1-2 합성법을 사용하여 생성물 33.87 g (수율: 71%)를 얻었다.Triphenylphosphine (87.53 g, 333.7 mmol) and o -dichlorobenzene in M 1-2'-18 (51.98 g, 133.5 mmol) obtained in the above synthesis were obtained using 33.87 g (yield) of the product using Sub 1-2 synthesis of Example 1. : 71%).
Sub 2의 합성Synthesis of Sub 2
반응식 1의 sub 2는 하기 반응식 5의 반응경로에 의해 합성될 수 있다.Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 5 below.
<반응식 5>Scheme 5
Figure PCTKR2012009261-appb-I000065
Figure PCTKR2012009261-appb-I000065
Sub 2에 속하는 구체적 화합물의 합성예는 다음과 같다.Synthesis examples of specific compounds belonging to Sub 2 are as follows.
(1) Sub 2-18 합성예(1) Synthesis Example of Sub 2-18
<반응식 6><Scheme 6>
Figure PCTKR2012009261-appb-I000066
Figure PCTKR2012009261-appb-I000066
중간체 M 2-1-18 합성Intermediate M 2-1-18 Synthesis
출발물질인 (2-(methylthio)phenyl)boronic acid (73.68 g, 438.5 mmol)에 1-bromo-2-iodobenzene (186.09 g, 657.8 mmol), Pd(PPh3)4 (25.34 g, 21.9 mmol), K2CO3 (181.82 g, 1315.6 mmol), THF, 물을 상기 실시예 1의 M 1-1-2 합성법을 사용하여 생성물 68.56 g (수율: 56%)를 얻었다.In the starting material (2- (methylthio) phenyl) boronic acid (73.68 g, 438.5 mmol), 1-bromo-2-iodobenzene (186.09 g, 657.8 mmol), Pd (PPh 3 ) 4 (25.34 g, 21.9 mmol), K 2 CO 3 (181.82 g, 1315.6 mmol), THF, and water were obtained using the M 1-1-2 synthesis method of Example 1, to obtain 68.56 g (yield: 56%) of the product.
중간체 M 2-2-18 합성Intermediate M 2-2-18 Synthesis
상기 합성에서 얻어진 M 2-1-18 (68.56 g, 245.6 mmol)에 aqueous 30% H2O2 (24.52ml, 245.6 mmol), acetic acid를 상기 실시예 1의 M 1-2-2 합성법을 사용하여 생성물 66.69 g (수율: 92%)를 얻었다.M 2-1-18 (68.56 g, 245.6 mmol) obtained in the above synthesis was added with aqueous 30% H 2 O 2 (24.52 ml, 245.6 mmol) and acetic acid using the M 1-2-2 synthesis method of Example 1. This gave 66.69 g (yield 92%) of product.
중간체 M 2-3-18 합성Intermediate M 2-3-18 Synthesis
상기 합성에서 얻어진 M 2-2-18 (66.69 g, 225.9 mmol)에 triflic acid (600ml, 6777.7 mmol), pyridine : H2O = 1 : 5로 2200ml를 상기 실시예 1의 M 1-3-2 합성법을 사용하여 생성물 41.02 g (수율: 69%)를 얻었다.To M 2-2-18 (66.69 g, 225.9 mmol) obtained in the above synthesis, 2200 ml of triflic acid (600 ml, 6777.7 mmol), pyridine: H 2 O = 1: 1 and M 1-3-2 of Example 1 Synthesis gave 41.02 g of product (yield: 69%).
중간체 M 2-4-18 합성Intermediate M 2-4-18 Synthesis
상기 합성에서 얻어진 M 2-3-18 (41.02 g, 155.9 mmol)에, Bis(pinacolato)diboron (43.54 g, 171.5 mmol), Pd(dppf)Cl2 (3.82 g, 4.7 mmol), KOAc (45.89 g, 467.6 mmol), DMF를 상기 실시예 1의 M 1-4-2 합성법을 사용하여 생성물 35.78 g (수율: 74%)를 얻었다.To M 2-3-18 (41.02 g, 155.9 mmol) obtained in the above synthesis, Bis (pinacolato) diboron (43.54 g, 171.5 mmol), Pd (dppf) Cl2(3.82 g, 4.7 mmol), KOAc (45.89 g, 467.6 mmol) and DMF were obtained using the M 1-4-2 synthesis method of Example 1, to obtain 35.78 g (yield: 74%) of the product.
중간체 M 2-5-18 합성Intermediate M 2-5-18 Synthesis
상기 합성에서 얻어진 M 2-4-18 (35.78 g, 115.3 mmol)에 9-bromo-10-nitrophenanthrene (52.27 g, 173 mmol), Pd(PPh3)4 (6.66 g, 5.8 mmol), K2CO3 (47.82 g, 346 mmol), THF, 물을 상기 실시예 1의 M 1-5-2 합성법을 사용하여 생성물 33.67 g (수율: 72%)를 얻었다.To M 2-4-18 (35.78 g, 115.3 mmol) obtained in the above synthesis, 9-bromo-10-nitrophenanthrene (52.27 g, 173 mmol), Pd (PPh 3 ) 4 (6.66 g, 5.8 mmol), K 2 CO 3 (47.82 g, 346 mmol), THF, water were obtained using the M 1-5-2 synthesis method of Example 1 33.67 g (yield: 72%).
Sub 2-18 합성예Sub 2-18 Synthesis Example
상기 합성에서 얻어진 M 2-5-18 (33.67 g, 83 mmol)에, triphenylphosphine (54.45 g, 207.6 mmol), o-dichlorobenzene을 상기 실시예 1의 Sub 1-2 합성법을 사용하여 생성물 21.71 g (수율: 70%)를 얻었다.To M 2-5-18 (33.67 g, 83 mmol) obtained in the above synthesis, triphenylphosphine (54.45 g, 207.6 mmol) and o- dichlorobenzene were obtained using 21.71 g of the product using the Sub 1-2 synthesis of Example 1 (yield). : 70%).
[실시예 3]Example 3
Sub 3의 합성Synthesis of Sub 3
반응식 1의 sub 3은 하기 반응식 7의 반응경로에 의해 합성될 수 있다.Sub 3 of Scheme 1 may be synthesized by the reaction route of Scheme 7.
<반응식 7>Scheme 7
Figure PCTKR2012009261-appb-I000067
Figure PCTKR2012009261-appb-I000067
Sub 3에 속하는 구체적 화합물의 합성예는 다음과 같다The synthesis example of the specific compound which belongs to Sub3 is as follows.
(1) Sub 3-23 합성예(1) Sub 3-23 Synthesis Example
<반응식 8>Scheme 8
Figure PCTKR2012009261-appb-I000068
Figure PCTKR2012009261-appb-I000068
중간체 M 3-1-23 합성Intermediate M 3-1-23 Synthesis
출발물질인 phenylboronic acid (45.28 g, 371.4 mmol)에 5-bromo-3-iodo-2-nitro-1,1'-biphenyl (225.04 g, 557 mmol), Pd(PPh3)4 (21.46 g, 18.6 mmol), K2CO3 (153.98 g, 1114.1 mmol), THF, 물을 상기 실시예 1의 M 1-1-2 합성법을 사용하여 생성물 81.55 g (수율: 62%)를 얻었다.Starting material phenylboronic acid (45.28 g, 371.4 mmol), 5-bromo-3-iodo-2-nitro-1,1'-biphenyl (225.04 g, 557 mmol), Pd (PPh 3 ) 4 (21.46 g, 18.6 mmol), K 2 CO 3 (153.98 g, 1114.1 mmol), THF, and water were obtained using the M 1-1-2 synthesis method of Example 1, to obtain 81.55 g (yield: 62%).
중간체 M 3-2-23 합성Intermediate M 3-2-23 Synthesis
상기 합성에서 얻어진 M 3-1-23 (81.55 g, 230.2 mmol)에, triphenylphosphine (150.97 g, 575.6 mmol), o-dichlorobenzene을 상기 실시예 1의 Sub 1-2 합성법을 사용하여 생성물 51.19 g (수율: 69%)를 얻었다.To M 3-1-23 (81.55 g, 230.2 mmol) obtained in the above synthesis, triphenylphosphine (150.97 g, 575.6 mmol) and o- dichlorobenzene were obtained using 51.19 g (yield) of the product using the Sub 1-2 synthesis of Example 1. : 69%).
중간체 M 3-3-23 합성Intermediate M 3-3-23 Synthesis
(2-(methylthio)-5-(naphthalen-2-yl)phenyl)boronic acid (31.16 g, 105.9 mmol)에 상기 합성에서 얻어진 M 3-2-23 (51.19 g, 158.9 mmol), Pd(PPh3)4 (6.12 g, 5.3 mmol), K2CO3 (43.92 g, 317.8 mmol), THF, 물을 상기 실시예 1의 M 1-1-2 합성법을 사용하여 생성물 43.22 g (수율: 83%)를 얻었다.(2- (methylthio) -5- (naphthalen-2-yl) phenyl) boronic acid (31.16 g, 105.9 mmol) in M 3-2-23 (51.19 g, 158.9 mmol), Pd (PPh 3 ) obtained in the above synthesis ) 4 (6.12 g, 5.3 mmol), K 2 CO 3 (43.92 g, 317.8 mmol), THF, water, 43.22 g (Yield: 83%) using M 1-1-2 synthesis in Example 1 above Got.
중간체 M 3-4-23 합성Intermediate M 3-4-23 Synthesis
상기 합성에서 얻어진 M 3-3-23 (43.22 g, 87.9 mmol)에 aqueous 30% H2O2 (8.78ml, 87.9 mmol), acetic acid를 상기 실시예 1의 M 1-2-2 합성법을 사용하여 생성물 40.16 g (수율: 90%)를 얻었다.M 3-3-23 (43.22 g, 87.9 mmol) obtained in the above synthesis was added with aqueous 30% H 2 O 2 (8.78ml, 87.9 mmol) and acetic acid using the M 1-2-2 synthesis method of Example 1 This gave 40.16 g (yield: 90%) of product.
Sub 3-23 합성예Sub 3-23 Synthesis Example
상기 합성에서 얻어진 M 3-4-23 (40.16 g, 79.1 mmol)에 triflic acid (210ml, 2373.3 mmol), pyridine : H2O = 1 : 5로 770ml를 상기 실시예 1의 M 1-3-2 합성법을 사용하여 생성물 27.09 g (수율: 72%)를 얻었다.770ml of triflic acid (210ml, 2373.3mmol), pyridine: H 2 O = 1: 5 in M 3-4-23 (40.16 g, 79.1 mmol) obtained in the above synthesis. Synthesis gave 27.09 g (yield: 72%) of product.
[실시예 4]Example 4
Sub 4의 합성Synthesis of Sub 4
반응식 1의 sub 4은 하기 반응식 9의 반응경로에 의해 합성될 수 있다.Sub 4 of Scheme 1 may be synthesized by the reaction route of Scheme 9 below.
<반응식 9>Scheme 9
Figure PCTKR2012009261-appb-I000069
Figure PCTKR2012009261-appb-I000069
Sub 4에 속하는 구체적 화합물의 합성예는 다음과 같다Synthesis examples of specific compounds belonging to Sub 4 are as follows.
(1) Sub 4-43 합성예(1) Sub 4-43 Synthesis Example
<반응식 10>Scheme 10
Figure PCTKR2012009261-appb-I000070
Figure PCTKR2012009261-appb-I000070
중간체 M 4-1-43 합성Intermediate M 4-1-43 Synthesis
출발물질인 phenylboronic acid (39.57 g, 324.5 mmol)에 3-bromo-4-iodo-5-nitro-1,1':4',1''-terphenyl (233.71 g, 486.8 mmol), Pd(PPh3)4 (18.75 g, 16.2 mmol), K2CO3 (134.56 g, 973.6 mmol), THF, 물을 상기 실시예 1의 M 1-1-2 합성법을 사용하여 생성물 89.37 g (수율: 64%)를 얻었다.In the starting material phenylboronic acid (39.57 g, 324.5 mmol), 3-bromo-4-iodo-5-nitro-1,1 ': 4', 1 ''-terphenyl (233.71 g, 486.8 mmol), Pd (PPh 3 ) 4 (18.75 g, 16.2 mmol), K 2 CO 3 (134.56 g, 973.6 mmol), THF, water using the M 1-1-2 synthesis of Example 1 above 89.37 g (yield: 64%) Got.
중간체 M 4-2-43 합성Intermediate M 4-2-43 Synthesis
상기 합성에서 얻어진 M 4-1-43 (89.37 g, 207.7 mmol)에, triphenylphosphine (136.19 g, 519.2 mmol), o-dichlorobenzene을 상기 실시예 1의 Sub 1-2 합성법을 사용하여 생성물 55.42 g (수율: 67%)를 얻었다.To M 4-1-43 (89.37 g, 207.7 mmol) obtained in the above synthesis, triphenylphosphine (136.19 g, 519.2 mmol) and o -dichlorobenzene were obtained using 55.42 g of the product using the Sub 1-2 synthesis of Example 1 (yield). : 67%).
중간체 M 4-3-43 합성Intermediate M 4-3-43 Synthesis
(10-(methylthio)phenanthren-9-yl)boronic acid (24.88 g, 92.8 mmol)에 상기 합성에서 얻어진 M 4-2-43 (55.42 g, 139.2 mmol), Pd(PPh3)4 (5.36 g, 4.6 mmol), K2CO3 (38.46 g, 278.3 mmol), THF, 물을 상기 실시예 1의 M 1-1-2 합성법을 사용하여 생성물 42.71 g (수율: 85%)를 얻었다.To (10- (methylthio) phenanthren-9-yl) boronic acid (24.88 g, 92.8 mmol), M 4-2-43 (55.42 g, 139.2 mmol), Pd (PPh 3 ) 4 (5.36 g, 4.6 mmol), K 2 CO 3 (38.46 g, 278.3 mmol), THF, and water were obtained using the M 1-1-2 synthesis method of Example 1, yielding 42.71 g (yield: 85%) of the product.
중간체 M 4-4-43 합성Intermediate M 4-4-43 Synthesis
상기 합성에서 얻어진 M 4-3-43 (42.71 g, 78.8 mmol)에 aqueous 30% H2O2 (7.87ml, 78.8 mmol), acetic acid를 상기 실시예 1의 M 1-2-2 합성법을 사용하여 생성물 40.45 g (수율: 92%)를 얻었다.M 4-3-43 (42.71 g, 78.8 mmol) obtained in the above synthesis was added with aqueous 30% H 2 O 2 (7.87 ml, 78.8 mmol) and acetic acid using the M 1-2-2 synthesis method of Example 1 This gave 40.45 g (yield: 92%) of the product.
Sub 4-43 합성예Sub 4-43 Synthesis Example
상기 합성에서 얻어진 M 4-4-43 (40.45 g, 72.5 mmol)에 triflic acid (192.6ml, 2175.9 mmol), pyridine : H2O = 1 : 5로 700ml를 상기 실시예 1의 M 1-3-2 합성법을 사용하여 생성물 25.93 g (수율: 68%)를 얻었다.To M 4-4-43 (40.45 g, 72.5 mmol) obtained in the above synthesis, 700 ml of triflic acid (192.6 ml, 2175.9 mmol), pyridine: H 2 O = 1: 1 and M 1-3- in Example 1 25.93 g (yield: 68%) of product was obtained using the 2 synthesis method.
한편, Sub 1, Sub 2, Sub 3 및 Sub 4의 예시는 아래와 같으나, 이에 한정되는 것은 아니며, 이들의 FD-MS는 하기 표 1과 같다.Examples of Sub 1, Sub 2, Sub 3, and Sub 4 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 1 below.
Figure PCTKR2012009261-appb-I000071
Figure PCTKR2012009261-appb-I000071
Figure PCTKR2012009261-appb-I000072
Figure PCTKR2012009261-appb-I000072
Figure PCTKR2012009261-appb-I000073
Figure PCTKR2012009261-appb-I000073
Figure PCTKR2012009261-appb-I000074
Figure PCTKR2012009261-appb-I000074
[표 1]TABLE 1
Figure PCTKR2012009261-appb-I000075
Figure PCTKR2012009261-appb-I000075
Figure PCTKR2012009261-appb-I000076
Figure PCTKR2012009261-appb-I000076
Figure PCTKR2012009261-appb-I000077
Figure PCTKR2012009261-appb-I000077
[실시예 5]Example 5
Product 합성Product Synthesis
Method 1Method 1
Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 당량)을 둥근바닥플라스크에 toluene으로 녹인 후에, Sub 5 (1.2 당량), Pd2(dba)3 (0.03 당량), P(t-Bu)3 (0.08 당량), NaOt-Bu (3 당량)을 첨가하고 100°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Final products를 얻었다.Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 5 (1.2 equiv), Pd 2 (dba) 3 (0.03 equiv), P ( t -Bu) 3 (0.08 equiv), NaO t -Bu (3 equiv) were added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.
Method 2Method 2
Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 당량)을 둥근바닥플라스크에 dimethyl sulfoxide로 녹인 후에, Sub 5 (1.1 당량), K2CO3 (6 당량)을 첨가하고 150°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Final products를 얻었다.Sub 1 or Sub 2 or Sub 3 or Sub 4 (1 equiv) was dissolved in dimethyl sulfoxide in a round bottom flask, then Sub 5 (1.1 equiv) and K 2 CO 3 (6 equiv) were added and stirred at 150 ° C. . After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.
한편, Sub 5의 Ar1-L-X (X= Br, Cl, F) 예시는 아래와 같으나, 이에 한정되는 것은 아니며, 이들의 FD-MS는 하기 표 2와 같다.Meanwhile, examples of Ar 1 -LX (X = Br, Cl, F) of Sub 5 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.
Figure PCTKR2012009261-appb-I000078
Figure PCTKR2012009261-appb-I000078
[표 2]TABLE 2
Figure PCTKR2012009261-appb-I000079
Figure PCTKR2012009261-appb-I000079
(1)(One) Product 1-10 합성예Product 1-10 Synthesis Example
<반응식 11> Scheme 11
Figure PCTKR2012009261-appb-I000080
Figure PCTKR2012009261-appb-I000080
상기 합성에서 얻어진 Sub 1-2 (7.18 g, 18 mmol)을 둥근바닥플라스크에 toluene으로 녹인 후에, Sub 5-7 (8.35 g, 21.6 mmol), Pd2(dba)3 (0.49 g, 0.5 mmol), 50% P(t-Bu)3 (0.7ml, 1.4 mmol), NaOt-Bu (5.18 g, 53.9 mmol)을 첨가하고 100°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 9.26 g (수율: 73%)를 얻었다.Sub 1-2 (7.18 g, 18 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 5-7 (8.35 g, 21.6 mmol), Pd 2 (dba) 3 (0.49 g, 0.5 mmol) , 50% P ( t- Bu) 3 (0.7ml, 1.4 mmol), NaO t- Bu (5.18 g, 53.9 mmol) was added and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 9.26 g (yield: 73%) of the product.
(2) Product 2-5 합성예(2) Product 2-5 Synthesis Example
<반응식 12> Scheme 12
Figure PCTKR2012009261-appb-I000081
Figure PCTKR2012009261-appb-I000081
상기 합성에서 얻어진 Sub 1-15 (7.32 g, 22.6 mmol)에 Sub 5-11 (7.24 g, 27.2 mmol), Pd2(dba)3 (0.62 g, 0.7 mmol), 50% P(t-Bu)3 (0.9ml, 1.8 mmol), NaOt-Bu (6.53 g, 67.9 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 8.77 g (수율: 70%)를 얻었다.Sub 1-15 (7.32 g, 22.6 mmol) obtained in the above synthesis in Sub 5-11 (7.24 g, 27.2 mmol), Pd 2 (dba) 3 (0.62 g, 0.7 mmol), 50% P ( t -Bu) 3 (0.9 ml, 1.8 mmol), NaO t -Bu (6.53 g, 67.9 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 8.77 g (yield: 70%) of the product.
(3) Product 2-35 합성예(3) Example of Product 2-35 Synthesis
<반응식 13> Scheme 13
Figure PCTKR2012009261-appb-I000082
Figure PCTKR2012009261-appb-I000082
상기 합성에서 얻어진 Sub 1-17 (7.01 g, 18.8 mmol)에 Sub 5-11 (6.01 g, 22.5 mmol), Pd2(dba)3 (0.52 g, 0.6 mmol), 50% P(t-Bu)3 (0.7ml, 1.5 mmol), NaOt-Bu (5.41 g, 56.3 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 8.5 g (수율: 75%)를 얻었다.To Sub 1-17 (7.01 g, 18.8 mmol) obtained in the above synthesis, Sub 5-11 (6.01 g, 22.5 mmol), Pd 2 (dba) 3 (0.52 g, 0.6 mmol), 50% P ( t -Bu) 3 (0.7 ml, 1.5 mmol), NaO t -Bu (5.41 g, 56.3 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 8.5 g (yield: 75%) of the product.
(4) Product 2-44 합성예(4) Product 2-44 Synthesis Example
<반응식 14> Scheme 14
Figure PCTKR2012009261-appb-I000083
Figure PCTKR2012009261-appb-I000083
상기 합성에서 얻어진 Sub 1-18 (6.89 g, 19.3 mmol)에 Sub 5-3 (5.39 g, 23.1 mmol), Pd2(dba)3 (0.53 g, 0.6 mmol), 50% P(t-Bu)3 (0.8ml, 1.5 mmol), NaOt-Bu (5.56 g, 57.8 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.66 g (수율: 78%)를 얻었다.Sub 1-18 (6.89 g, 19.3 mmol) obtained in the above synthesis in Sub 5-3 (5.39 g, 23.1 mmol), Pd 2 (dba) 3 (0.53 g, 0.6 mmol), 50% P ( t -Bu) 3 (0.8 ml, 1.5 mmol), NaO t -Bu (5.56 g, 57.8 mmol), toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.66 g (yield: 78%) of the product.
(5) Product 3-5 합성예(5) Product 3-5 Synthesis Example
<반응식 15> Scheme 15
Figure PCTKR2012009261-appb-I000084
Figure PCTKR2012009261-appb-I000084
상기 합성에서 얻어진 Sub 1-19 (6.84 g, 18.3 mmol)에 Sub 5-11 (5.86 g, 22 mmol), Pd2(dba)3 (0.5 g, 0.5 mmol), 50% P(t-Bu)3 (0.7ml, 1.5 mmol), NaOt-Bu (5.28 g, 54.9 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.85 g (수율: 71%)를 얻었다.Sub 1-19 (6.84 g, 18.3 mmol) obtained in the above synthesis to Sub 5-11 (5.86 g, 22 mmol), Pd 2 (dba) 3 (0.5 g, 0.5 mmol), 50% P ( t -Bu) 3 (0.7 ml, 1.5 mmol), NaO t -Bu (5.28 g, 54.9 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.85 g (yield: 71%) of the product.
(6) Product 3-35 합성예(6) Product 3-35 Synthesis Example
<반응식 16>Scheme 16
Figure PCTKR2012009261-appb-I000085
Figure PCTKR2012009261-appb-I000085
상기 합성에서 얻어진 Sub 1-21 (7.71 g, 18.2 mmol)에 Sub 5-11 (5.83 g, 21.8 mmol), Pd2(dba)3 (0.5 g, 0.5 mmol), 50% P(t-Bu)3 (0.7ml, 1.5 mmol), NaOt-Bu (5.25 g, 54.6 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 8.09 g (수율: 68%)를 얻었다.Sub 1-21 (7.71 g, 18.2 mmol) obtained in the synthesis above, Sub 5-11 (5.83 g, 21.8 mmol), Pd 2 (dba) 3 (0.5 g, 0.5 mmol), 50% P ( t -Bu) 3 (0.7 ml, 1.5 mmol), NaO t -Bu (5.25 g, 54.6 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 8.09 g (yield: 68%) of the product.
(7) Product 1-1'합성예(7) Product 1-1 'Synthesis Example
<반응식 17>Scheme 17
Figure PCTKR2012009261-appb-I000086
Figure PCTKR2012009261-appb-I000086
상기 합성에서 얻어진 Sub 3-1 (8.35 g, 25.5 mmol)에 Sub 5-1 (4.8 g, 30.6 mmol), Pd2(dba)3 (0.7 g, 0.8 mmol), 50% P(t-Bu)3 (1ml, 2 mmol), NaOt-Bu (7.35 g, 76.5 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.62 g (수율: 74%)를 얻었다.Sub 3-1 (8.35 g, 25.5 mmol) obtained in the above synthesis to Sub 5-1 (4.8 g, 30.6 mmol), Pd 2 (dba) 3 (0.7 g, 0.8 mmol), 50% P ( t -Bu) 3 (1 ml, 2 mmol), NaO t -Bu (7.35 g, 76.5 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.62 g (yield: 74%) of the product.
(8) Product 1-11' 합성예(8) Product 1-11 'Synthesis Example
<반응식 18>Scheme 18
Figure PCTKR2012009261-appb-I000087
Figure PCTKR2012009261-appb-I000087
상기 합성에서 얻어진 Sub 3-10 (7.26 g, 16.1 mmol)에 Sub 5-8 (7.5 g, 19.4 mmol), Pd2(dba)3 (0.44 g, 0.5 mmol), 50% P(t-Bu)3 (0.6ml, 1.3 mmol), NaOt-Bu (4.66 g, 48.4 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 8.42 g (수율: 69%)를 얻었다.Sub 3-10 (7.26 g, 16.1 mmol) obtained in the above synthesis in Sub 5-8 (7.5 g, 19.4 mmol), Pd 2 (dba) 3 (0.44 g, 0.5 mmol), 50% P ( t -Bu) 3 (0.6 ml, 1.3 mmol), NaO t -Bu (4.66 g, 48.4 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 8.42 g (yield: 69%) of product.
(9) Product 1-44'합성예(9) Product 1-44 'Synthesis Example
<반응식 19>Scheme 19
Figure PCTKR2012009261-appb-I000088
Figure PCTKR2012009261-appb-I000088
상기 합성에서 얻어진 Sub 3-23 (8.83 g, 18.6 mmol)에 Sub 5-1 (3.5 g, 22.3 mmol), Pd2(dba)3 (0.51 g, 0.6 mmol), 50% P(t-Bu)3 (0.7ml, 1.5 mmol), NaOt-Bu (5.35 g, 55.7 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.48 g (수율: 73%)를 얻었다.To Sub 3-23 (8.83 g, 18.6 mmol) obtained in the above synthesis Sub 5-1 (3.5 g, 22.3 mmol), Pd 2 (dba) 3 (0.51 g, 0.6 mmol), 50% P ( t -Bu) 3 (0.7 ml, 1.5 mmol), NaO t -Bu (5.35 g, 55.7 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.48 g (yield: 73%) of the product.
(10) Product 1-46' 합성예(10) Product 1-46 'Synthesis Example
<반응식 20>Scheme 20
Figure PCTKR2012009261-appb-I000089
Figure PCTKR2012009261-appb-I000089
상기 합성에서 얻어진 Sub 3-25 (8.47 g, 19.7 mmol)에 Sub 5-1 (3.72 g, 23.7 mmol), Pd2(dba)3 (0.54 g, 0.6 mmol), 50% P(t-Bu)3 (0.8ml, 1.6 mmol), NaOt-Bu (5.69 g, 59.2 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.08 g (수율: 71%)를 얻었다.To Sub 3-25 (8.47 g, 19.7 mmol) obtained in the above synthesis Sub 5-1 (3.72 g, 23.7 mmol), Pd 2 (dba) 3 (0.54 g, 0.6 mmol), 50% P ( t -Bu) 3 (0.8 ml, 1.6 mmol), NaO t -Bu (5.69 g, 59.2 mmol) and toluene were obtained by using the Product 1-10 synthesis method of Example 5, which obtained 7.08 g (yield: 71%) of the product.
(11) Product 1-59' 합성예(11) Product 1-59 'Synthesis Example
<반응식 21>Scheme 21
Figure PCTKR2012009261-appb-I000090
Figure PCTKR2012009261-appb-I000090
상기 합성에서 얻어진 Sub 4-25 (8.35 g, 19.5 mmol)에 Sub 5-1 (3.68 g, 23.4 mmol), Pd2(dba)3 (0.54 g, 0.6 mmol), 50% P(t-Bu)3 (0.8ml, 1.6 mmol), NaOt-Bu (5.63 g, 58.6 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 6.69 g (수율: 68%)를 얻었다.To Sub 4-25 (8.35 g, 19.5 mmol) obtained in the above synthesis, Sub 5-1 (3.68 g, 23.4 mmol), Pd 2 (dba) 3 (0.54 g, 0.6 mmol), 50% P ( t -Bu) 3 (0.8 ml, 1.6 mmol), NaO t -Bu (5.63 g, 58.6 mmol), toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 6.69 g (yield: 68%) of product.
(12) Product 2-4'합성예(12) Product 2-4 'Synthesis Example
<반응식 22>Scheme 22
Figure PCTKR2012009261-appb-I000091
Figure PCTKR2012009261-appb-I000091
상기 합성에서 얻어진 Sub 3-35 (6.97 g, 15.5 mmol)에 Sub 5-10 (4.98 g, 18.6 mmol), Pd2(dba)3 (0.43 g, 0.5 mmol), 50% P(t-Bu)3 (0.6ml, 1.2 mmol), NaOt-Bu (4.47 g, 46.5 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 6.86 g (수율: 65%)를 얻었다.To Sub 3-35 (6.97 g, 15.5 mmol) obtained in the above synthesis, Sub 5-10 (4.98 g, 18.6 mmol), Pd 2 (dba) 3 (0.43 g, 0.5 mmol), 50% P ( t -Bu) 3 (0.6 ml, 1.2 mmol), NaO t -Bu (4.47 g, 46.5 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 6.86 g (yield: 65%) of the product.
(13) Product 2-15' 합성예(13) Product 2-15 'Synthesis Example
<반응식 23>Scheme 23
Figure PCTKR2012009261-appb-I000092
Figure PCTKR2012009261-appb-I000092
상기 합성에서 얻어진 Sub 3-39 (7.41 g, 24.1 mmol)에 Sub 5-3 (6.74 g, 28.9 mmol), Pd2(dba)3 (0.66 g, 0.7 mmol), 50% P(t-Bu)3 (0.9ml, 1.9 mmol), NaOt-Bu (6.95 g, 72.3 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.98 g (수율: 72%)를 얻었다.To Sub 3-39 (7.41 g, 24.1 mmol) obtained in the above synthesis, Sub 5-3 (6.74 g, 28.9 mmol), Pd 2 (dba) 3 (0.66 g, 0.7 mmol), 50% P ( t -Bu) 3 (0.9 ml, 1.9 mmol), NaO t -Bu (6.95 g, 72.3 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.98 g (yield: 72%) of the product.
(14) Product 3-9'합성예(14) Product 3-9 'Synthesis Example
<반응식 24>Scheme 24
Figure PCTKR2012009261-appb-I000093
Figure PCTKR2012009261-appb-I000093
상기 합성에서 얻어진 Sub 3-40 (6.27 g, 16.8 mmol)에 Sub 5-6 (7.82 g, 20.1 mmol), Pd2(dba)3 (0.46 g, 0.5 mmol), 50% P(t-Bu)3 (0.7ml, 1.3 mmol), NaOt-Bu (4.84 g, 50.4 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 8.34 g (수율: 73%)를 얻었다.To Sub 3-40 (6.27 g, 16.8 mmol) obtained in the above synthesis Sub 5-6 (7.82 g, 20.1 mmol), Pd 2 (dba) 3 (0.46 g, 0.5 mmol), 50% P ( t -Bu) 3 (0.7 ml, 1.3 mmol), NaO t -Bu (4.84 g, 50.4 mmol) and toluene were obtained by using the Product 1-10 synthesis method of Example 5 to give 8.34 g (yield: 73%) of product.
(15) Product 3-21' 합성예(15) Product 3-21 'Synthesis Example
<반응식 25>Scheme 25
Figure PCTKR2012009261-appb-I000094
Figure PCTKR2012009261-appb-I000094
상기 합성에서 얻어진 Sub 4-43 (7.33 g, 13.9 mmol)에 Sub 5-7 (6.48 g, 16.7 mmol), Pd2(dba)3 (0.38 g, 0.4 mmol), 50% P(t-Bu)3 (0.5ml, 1.1 mmol), NaOt-Bu (4.02 g, 41.8 mmol), toluene을 상기 실시예 5의 Product 1-10 합성법을 사용하여 생성물 7.38 g (수율: 70%)를 얻었다.To Sub 4-43 (7.33 g, 13.9 mmol) obtained in the above synthesis, Sub 5-7 (6.48 g, 16.7 mmol), Pd 2 (dba) 3 (0.38 g, 0.4 mmol), 50% P ( t -Bu) 3 (0.5 ml, 1.1 mmol), NaO t -Bu (4.02 g, 41.8 mmol) and toluene were obtained using the Product 1-10 synthesis method of Example 5 to obtain 7.38 g (yield: 70%) of the product.
(16) Product 2-52 합성예(16) Product 2-52 Synthesis Example
<반응식 26>Scheme 26
Figure PCTKR2012009261-appb-I000095
Figure PCTKR2012009261-appb-I000095
상기 합성에서 얻어진 Sub 2-18 (7.71 g, 20.6 mmol)을 둥근바닥플라스크에 dimethyl sulfoxide로 녹인 후에, Sub 5-13 (5.68 g, 22.7 mmol)을 첨가하고 150°C에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 8.85 g (수율: 71%)를 얻었다.Sub 2-18 (7.71 g, 20.6 mmol) obtained in the above synthesis was dissolved in dimethyl sulfoxide in a round bottom flask, then Sub 5-13 (5.68 g, 22.7 mmol) was added and stirred at 150 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 8.85 g (yield: 71%).
한편, 상기와 같은 합성예에 따라 제조된 본 발명의 화합물 1-1~1-40, 2-1~2-60, 3-1~3-60, 1-1'~1-64', 2-1~2-32' 및 3-1~3-32'의 FD-MS 값은 하기 표 3과 같다 Meanwhile, the compounds 1-1 to 1-40, 2-1 to 2-60, 3-1 to 3-60, 1-1 'to 1-64' of the present invention prepared according to the synthesis examples as described above. FD-MS values of -1 to 2-32 'and 3-1 to 3-32' are shown in Table 3 below.
[표 3]TABLE 3
Figure PCTKR2012009261-appb-I000096
Figure PCTKR2012009261-appb-I000096
Figure PCTKR2012009261-appb-I000097
Figure PCTKR2012009261-appb-I000097
Figure PCTKR2012009261-appb-I000098
Figure PCTKR2012009261-appb-I000098
Figure PCTKR2012009261-appb-I000099
Figure PCTKR2012009261-appb-I000099
Figure PCTKR2012009261-appb-I000100
Figure PCTKR2012009261-appb-I000100
한편, 상기에서는 화학식 1로 표시되는 본 발명의 예시적 합성예를 설명하였지만, 이들은 모두 Suzuki cross-coupling 반응, Miyaura boration 반응, Buchwald-Hartwig cross coupling 반응 및 aromatic nucleophilic substitution 반응 (Ultrasonic Sonochemistry, 2003, 10, 265) 등에 기초한 것으로 구체적 합성예에 명시된 치환기 이외에 화학식 1에 정의된 다른 치환기 (R1 내지 R10, L, Ar1 등의 치환기)가 결합되더라도 상기 반응이 진행된다는 것을 당업자라면 쉽게 이해할 수 있을 것이다. 예컨대, 반응식 2에서 출발물질 -> M 1-1, M 1-4 -> M 1-5, 반응식 5에서 출발물질 -> M 2-1, M 2-4 -> M 2-5, 반응식 7에서 출발물질 -> M 3-1, M 3-2 -> M 3-3, 반응식 9에서 출발물질 -> M 4-1, M 4-2 -> M 4-3 반응 등은 모두 Suzuki cross-coupling 반응에 기초한 것이고, 반응식 2에서 M 1-3 -> M 1-4, 반응식 5에서 M 2-3 -> M 2-4 반응 등은 Miyaura boration 반응에 기초한 것이며, Product 합성 반응식은 Buchwald-Hartwig cross coupling 반응 (반응식 11 내지 반응식 25)과 aromatic nucleophilic substitution 반응 (반응식 26)에 기초한 것으로, 이들에 구체적으로 명시되지 않은 치환기가 결합되더라도 상기 반응들이 진행할 것이다.On the other hand, in the above described an exemplary synthetic example of the present invention represented by the formula (1), these are all Suzuki cross-coupling reaction, Miyaura boration reaction, Buchwald-Hartwig cross coupling reaction and aromatic nucleophilic substitution reaction ( Ultrasonic Sonochemistry , 2003, 10 , 265) and the like, it will be readily understood by those skilled in the art that the reaction proceeds even if other substituents (substituents such as R 1 to R 10 , L, Ar 1, etc.) defined in Formula 1 are combined in addition to the substituents specified in the specific synthesis examples. will be. For example, starting materials in Scheme 2-> M 1-1, M 1-4-> M 1-5, starting materials in Scheme 5-> M 2-1, M 2-4-> M 2-5, Scheme 7 Starting materials at-M 3-1, M 3-2-> M 3-3, starting materials at reaction 9-> M 4-1, M 4-2-> M 4-3 reactions are all Suzuki cross- Based on coupling reaction, M 1-3-> M 1-4 in Scheme 2, M 2-3-> M 2-4 reaction in Scheme 5 are based on Miyaura boration reaction, and the product synthesis scheme is Buchwald-Hartwig Based on cross coupling reactions (Scheme 11 to Scheme 25) and aromatic nucleophilic substitution reactions (Scheme 26), the reactions will proceed even if they have a substituent that is not specifically specified.
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
[실험예 1]Experimental Example 1
합성을 통해 얻은 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 위에 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께의 정공주입층을 형성하였다. 이어서, 정공주입층 상에 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 -NPD로 약기함)을 20 nm 두께로 진공 증착하여 정공수송층을 형성하였다. An organic light emitting diode was manufactured according to a conventional method using a compound obtained through synthesis as a light emitting host material of a light emitting layer. First, on the ITO layer (anode) formed on the glass substrate, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. .
다음으로, 정공 수송층 상부에 본 발명의 화합물을 호스트 물질로, Ir(ppy)3 [tris(2-phenylpyridine)-iridium] 을 도펀트물질로 사용하여 95:5 중량으로 도핑함으로써 상기 정공수송층 위에 30nm 두께의 발광층을 형성하였다. Next, 30 nm thick on the hole transport layer by doping at 95: 5 weight using the compound of the present invention as a host material on the hole transport layer and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as a dopant material. The light emitting layer of was formed.
그리고, 상기 발광층 상에 (1,1’-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄 (이하 BAlq로 약기함)을 10 nm 두께로 진공증착하여 정공저지층을 형성하고고, 트리스(8-퀴놀리놀)알루미늄 (이하 Alq3로 약기함)을 40 nm 두께로 성막하여 전자수송층을 형성하였다. 이후, 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150 nm의 두께로 증착하여 음극을 형성함으로써 유기전계발광소자를 제작하였다.In addition, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) is vacuum-deposited to a thickness of 10 nm on the light emitting layer. A stop layer was formed, and tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq 3 ) was deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting display device.
[비교예 1]Comparative Example 1
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 하기 비교 화합물 1을 발광호스트 물질로 사용하여 발광층을 형성하였다.An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that Comparative Compound 1 was used as a light emitting host material instead of the compound of the present invention to form a light emitting layer.
<비교 화합물 1><Comparative Compound 1>
Figure PCTKR2012009261-appb-I000101
Figure PCTKR2012009261-appb-I000101
[비교예 2]Comparative Example 2
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 비교 화합물 2(12-(5-phenylpyrimidin-2-yl)-12H-benzo[4,5]thieno[3,2-a]carbazole)을 발광호스트 물질로 사용하여 발광층을 형성하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but Comparative Compound 2 (12- (5-phenylpyrimidin-2-yl) -12H-benzo [4,5] thieno [3,2- was used instead of the compound of the present invention. a] carbazole) was used as a light emitting host material to form a light emitting layer.
<비교 화합물 2><Comparative Compound 2>
Figure PCTKR2012009261-appb-I000102
Figure PCTKR2012009261-appb-I000102
[비교예 3]Comparative Example 3
상기 실험예 1과 동일하게 유기전계발광소자를 제작하되, 본 발명의 화합물 대신 비교 화합물 3(12-(4-(4,6-diphenylpyrimidin-2-yl)phenyl)-12H-benzo[4,5]thieno[2,3-a]carbazole)을 발광호스트 물질로 사용하여 발광층을 형성하였다.An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, except that the comparative compound 3 (12- (4- (4,6-diphenylpyrimidin-2-yl) phenyl) -12H-benzo [4,5] was used instead of the compound of the present invention. ] thieno [2,3-a] carbazole) was used as a light emitting host material to form a light emitting layer.
<비교 화합물 3> Comparative Compound 3
Figure PCTKR2012009261-appb-I000103
Figure PCTKR2012009261-appb-I000103
상기 실험예 1 및 비교예들에 의해 제조된 유기전기발광소자에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 300cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표 4는 발명에 따른 화합물을 적용한 실시예 및 비교예에 대한 소자제작 및 그 평가 결과를 나타낸다.Electroluminescent (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent device manufactured by Experimental Example 1 and Comparative Examples, and the measurement result was 300 cd / m 2. The T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at the reference luminance. Table 4 below shows device fabrication and evaluation results of Examples and Comparative Examples to which the compound according to the invention is applied.
표 4에서, 본 발명의 실험예 1에 따라 제조된 유기전기소자를 실시예 1 내지 실시예 288로 표시하였다.In Table 4, the organic electric device manufactured according to Experimental Example 1 of the present invention is shown as Examples 1 to 288.
[표 4]TABLE 4
Figure PCTKR2012009261-appb-I000104
Figure PCTKR2012009261-appb-I000104
Figure PCTKR2012009261-appb-I000105
Figure PCTKR2012009261-appb-I000105
Figure PCTKR2012009261-appb-I000106
Figure PCTKR2012009261-appb-I000106
Figure PCTKR2012009261-appb-I000107
Figure PCTKR2012009261-appb-I000107
Figure PCTKR2012009261-appb-I000108
Figure PCTKR2012009261-appb-I000108
Figure PCTKR2012009261-appb-I000109
Figure PCTKR2012009261-appb-I000109
Figure PCTKR2012009261-appb-I000110
Figure PCTKR2012009261-appb-I000110
상기 표의 결과로부터 알 수 있듯이, 본 발명의 유기전계발광소자용 재료를 발광 호스트 물질로 사용한 유기전계발광소자는 색순도, 높은 발광효율 및 수명이현저히 개선되었다. 본 발명의 화합물들을 유기전계발광소자의 다른 유기물층들, 예를 들어 발광 보조층, 전자주입층, 전자수송층, 및 정공주입층에 사용되더라도 동일한 효과를 얻을 수 있는 것은 자명하다.As can be seen from the results of the above table, the organic electroluminescent device using the organic electroluminescent device material of the present invention as a light emitting host material has remarkably improved color purity, high luminous efficiency and lifetime. When the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시 예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시 예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited thereto. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2011년 11월 07일 한국에 출원한 특허출원번호 제 10-2011-0115427 호, 2011년 12월 05일 한국에 출원한 특허출원번호 제 10-2011-0129127 호 및 2012년 10월 30일 한국에 출원한 특허출원번호 제 10-2012-0121380 호에 대해 미국 특허법 119(a)조 (35 U.S.C § 119(a))에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application is filed with the Korean Patent Application No. 10-2011-0115427 filed in Korea on November 07, 2011, the patent application No. 10-2011-0129127 filed in Korea on December 05, 2011, and October 2012. Priority is claimed to Korean Patent Application No. 10-2012-0121380 filed with Korea on the 30th in accordance with US Patent Act Article 119 (a) (35 USC § 119 (a)), all of which are hereby incorporated by reference. Incorporated into the application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물.A compound represented by the following formula (1).
    <화학식 1><Formula 1>
    Figure PCTKR2012009261-appb-I000111
    Figure PCTKR2012009261-appb-I000111
    상기 화학식 1에서,In Chemical Formula 1,
    R1 내지 R10은 i) 서로 독립적으로, 수소, 중수소, 할로겐, C6~C60의 아릴기, 플루오렌일기, C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로 고리기, -L-N(R’)(R”), C1~C50의 알킬기, C2~C20의 알켄일기, C1~C30의 알콕시기 및 C6~C30의 아릴옥시기로 이루어진 군에서 선택되거나, 또는 ii) 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성하며(이때, 고리를 형성하지 않는 기는 i)에서 정의된 것과 같음), R 1 to R 10 is i) independent of each other, hydrogen, deuterium, halogen, C 6 ~ aryl group of C 60, a fluorene group, a fused aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60 C 2 -C 60 heterocyclic group including a ring group, O, N, S, Si and P heteroatoms, -LN (R ') (R "), C 1 ~ C 50 Alkyl group, C 2 ~ C 20 Alkenyl group, C 1 ~ C 30 Alkoxy group and C 6 ~ C 30 It is selected from the group consisting of aryloxy group, or ii) adjacent groups are bonded to each other to form at least one ring (Where a group that does not form a ring is as defined in i)),
    단, R1~R4 중 적어도 하나가 수소가 아니면 R7~R10은 모두 수소이어야 하며, R7~R10 중 적어도 하나가 수소가 아니면 R1~R4는 모두 수소이어야 하며, R1~R4와 R7~R10이 모두 동시에 수소인 경우는 제외하며,However, R 1 ~ R 4 at least one is not a hydrogen of R 7 ~ R 10 must be a both hydrogen, R 7 ~ R, at least one of the 10 is not a hydrogen R 1 ~ R 4 may be all hydrogen and, R 1 Except when ~ R 4 and R 7 ~ R 10 are both hydrogen at the same time,
    X와 Y는 서로 독립적으로, S, O 또는 -Si(R11)(R12)이며(여기서, R11과 R12는 서로 독립적으로 수소, C6~C60의 아릴기, O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, 또는 C1~C50의 알킬기임), m과 n 각각은 0 또는 1이며(단, m+n=1 이상의 정수임),X and Y are independently of each other, S, O, or -Si (R 11 ) (R 12 ) (wherein R 11 and R 12 are independently of each other hydrogen, an aryl group of C 6 ~ C 60 , O, N, A C 2 to C 60 heterocyclic group or a C 1 to C 50 alkyl group comprising at least one heteroatom of S, Si and P, wherein m and n are each 0 or 1, provided that m + n Is an integer greater than or equal to = 1),
    L은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; 및 2가의 지방족 탄화수소기;로 이루어진 군에서 선택되며(이때, 아릴렌기, 플루오렌일렌기, 헤테로고리기 및 지방족 탄화수소기는 니트로기, 시아노기, 할로겐기, C1~C20의 알킬기, C6~C20의 아릴기, C2~C20의 헤테로고리기, C1~C20의 알콕시기 및 아미노기로 이루어진 군에서 선택되는 하나 이상의 치환기로 치환될 수 있음),L is a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And a divalent aliphatic hydrocarbon group; wherein the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group are nitro group, cyano group, halogen group, C 1 ~ C 20 alkyl group, C 6 May be substituted with one or more substituents selected from the group consisting of an aryl group of ~ C 20 , a heterocyclic group of C 2 ~ C 20 , an alkoxy group of C 1 ~ C 20 , and an amino group),
    Ar1은 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기, 플루오렌일기 또는 -N(R’)(R”)이고,Ar 1 is a C 2 ~ C 60 heterocyclic group, C 6 ~ C 60 aryl group, fluorenyl group or -N (R ') containing at least one heteroatom of O, N, S, Si and P (R ”),
    상기 R'과 R"은 서로 독립적으로 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기, C6~C60의 아릴기 또는 플루오렌일기이다.R 'and R "are independently of each other O, N, S, Si and P containing at least one heteroatom of C 2 ~ C 60 heterocyclic group, C 6 ~ C 60 aryl group or fluorenyl group to be.
    (상기 R1~R12, Ar1, R' 및 R"이 아릴기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,(R aboveOne~ R12, ArOneWhen R 'and R "are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, COne~ C20Alkylthio, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C2~ C20Alkynyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
    상기 R1~R12, Ar1, R' 및 R"가 헤테로고리기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, 니트로기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R12, ArOneWhen R 'and R "are heterocyclic groups, they are deuterium, halogen, silane groups, cyano groups, nitro groups, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
    상기 R1~R10, Ar1, R' 및 R"가 플루오렌일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When R 1 to R 10 , Ar 1 , R ′ and R ″ are fluorenyl groups, they are deuterium, halogen, silane groups, cyano groups, C 1 to C 20 alkyl groups, and C 2 to C 20 alkenyl groups (alkenyl ), C aryl group of 6 ~ C 20, of a C 6 ~ C 20 substituted by deuterium aryl group, C 2 ~ C 20 of the heterocyclic group and C 3 ~ one or more substituents selected from the group consisting of a cycloalkyl group of C 20 May be substituted with
    상기 R1~R1O가 융합고리기인 경우, 이는 중수소, 할로겐, 실란기, 붕소기, 게르마늄기, 시아노기, 니트로기, C1~C20의 알킬싸이오기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C2~C20의 알카인일기(alkynyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R1OIf is a fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, COne~ C20Alkylthio, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C2~ C20Alkynyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
    상기 R1~R12가 알킬기인 경우, 이는 할로겐, 실란기, 붕소기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R12When is an alkyl group, it is halogen, silane group, boron group, cyano group, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
    상기 R1~R10이 알켄일기인 경우, 이는 중수소, 할로겐, 실란기, 시아노기, C1~C20의 알콕실기, C1~C20의 알킬기, C2~C20의 알켄일기(alkenyl), C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기, C3~C20의 시클로알킬기, C7~C20의 아릴알킬기 및 C8~C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,ROne~ R10When it is an alkenyl group, it is deuterium, a halogen, a silane group, a cyano group, COne~ C20Alkoxyl, COne~ C20Alkyl group, C2~ C20Alkenyl, C6~ C20Aryl group of C, substituted with deuterium6~ C20Aryl group, C2~ C20Heterocyclic group, C3~ C20Cycloalkyl group, C7~ C20of Arylalkyl group and C8~ C20May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,
    상기 R1~R10이 알콕실기인 경우, 이는 중수소, 할로겐, 실란기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있고,When the R 1 ~ R 10 is an alkoxy group, which is heavy hydrogen, a halogen, a silane group, a C 1 ~ C 20 alkyl group, C 6 ~ C 20 aryl group, a C 6 ~ C 20 substituted with a heavy hydrogen of the aryl group, C 2 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ~ C 20 cycloalkyl group,
    상기 R1~R10이 아릴옥시기인 경우, 이는 중수소, 실란기, 시아노기, C1~C20의 알킬기, C6~C20의 아릴기, 중수소로 치환된 C6~C20의 아릴기, C2~C20의 헤테로고리기 및 C3~C20의 시클로알킬기로 이루어진 군에서 선택된 하나 이상의 치환기로 치환될 수 있다)Wherein R 1 ~ R 10 is an aryloxy group cases, this deuterium, a silane group, a cyano group, C of 1 ~ C 20 alkyl group, a C 6 ~ C 20 substituted with an aryl group, a heavy hydrogen of C 6 ~ C 20 aryl group , C 2 ~ C 20 It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and C 3 ~ C 20 cycloalkyl group)
  2. 제 1항에 있어서,The method of claim 1,
    하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.Compound represented by one of the following formula.
    Figure PCTKR2012009261-appb-I000112
    Figure PCTKR2012009261-appb-I000112
    Figure PCTKR2012009261-appb-I000113
    Figure PCTKR2012009261-appb-I000113
    (상기 화학식에서, R1~R10, X, Y, L 및 Ar1은 화학식 1에서 정의된 것과 같다)(In the above formula, R 1 ~ R 10 , X, Y, L and Ar 1 are the same as defined in formula 1)
  3. 제 1항에 있어서,The method of claim 1,
    하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물.Compound represented by one of the following formula.
    Figure PCTKR2012009261-appb-I000114
    Figure PCTKR2012009261-appb-I000114
    Figure PCTKR2012009261-appb-I000115
    Figure PCTKR2012009261-appb-I000115
    Figure PCTKR2012009261-appb-I000116
    Figure PCTKR2012009261-appb-I000116
    (상기 화학식에서, R1~R4, R7~R10, X, Y, L 및 Ar1은 화학식 1에서 정의된 것과 같다) (In the above formula, R 1 ~ R 4 , R 7 ~ R 10 , X, Y, L and Ar 1 are the same as defined in Formula 1)
  4. 제 1항에 있어서,The method of claim 1,
    하기 화합물 중 하나인 것을 특징으로 하는 화합물.Compound which is one of the following compounds.
    Figure PCTKR2012009261-appb-I000117
    Figure PCTKR2012009261-appb-I000117
    Figure PCTKR2012009261-appb-I000118
    Figure PCTKR2012009261-appb-I000118
    Figure PCTKR2012009261-appb-I000119
    Figure PCTKR2012009261-appb-I000119
    Figure PCTKR2012009261-appb-I000120
    Figure PCTKR2012009261-appb-I000120
    Figure PCTKR2012009261-appb-I000121
    Figure PCTKR2012009261-appb-I000121
    Figure PCTKR2012009261-appb-I000122
    Figure PCTKR2012009261-appb-I000122
    Figure PCTKR2012009261-appb-I000123
    Figure PCTKR2012009261-appb-I000123
    Figure PCTKR2012009261-appb-I000124
    Figure PCTKR2012009261-appb-I000124
    Figure PCTKR2012009261-appb-I000125
    Figure PCTKR2012009261-appb-I000125
    Figure PCTKR2012009261-appb-I000126
    Figure PCTKR2012009261-appb-I000126
    Figure PCTKR2012009261-appb-I000127
    Figure PCTKR2012009261-appb-I000127
    Figure PCTKR2012009261-appb-I000128
    Figure PCTKR2012009261-appb-I000128
    Figure PCTKR2012009261-appb-I000129
    Figure PCTKR2012009261-appb-I000129
    Figure PCTKR2012009261-appb-I000130
    Figure PCTKR2012009261-appb-I000130
    Figure PCTKR2012009261-appb-I000131
    Figure PCTKR2012009261-appb-I000131
    Figure PCTKR2012009261-appb-I000132
    Figure PCTKR2012009261-appb-I000132
    Figure PCTKR2012009261-appb-I000133
    Figure PCTKR2012009261-appb-I000133
    Figure PCTKR2012009261-appb-I000134
    Figure PCTKR2012009261-appb-I000134
    Figure PCTKR2012009261-appb-I000135
    Figure PCTKR2012009261-appb-I000135
    Figure PCTKR2012009261-appb-I000136
    Figure PCTKR2012009261-appb-I000136
    Figure PCTKR2012009261-appb-I000137
    Figure PCTKR2012009261-appb-I000137
    Figure PCTKR2012009261-appb-I000138
    Figure PCTKR2012009261-appb-I000138
    Figure PCTKR2012009261-appb-I000139
    Figure PCTKR2012009261-appb-I000139
    Figure PCTKR2012009261-appb-I000140
    Figure PCTKR2012009261-appb-I000140
    Figure PCTKR2012009261-appb-I000141
    Figure PCTKR2012009261-appb-I000141
    Figure PCTKR2012009261-appb-I000142
    Figure PCTKR2012009261-appb-I000142
    Figure PCTKR2012009261-appb-I000143
    Figure PCTKR2012009261-appb-I000143
    Figure PCTKR2012009261-appb-I000144
    Figure PCTKR2012009261-appb-I000144
    Figure PCTKR2012009261-appb-I000145
    Figure PCTKR2012009261-appb-I000145
    Figure PCTKR2012009261-appb-I000146
    Figure PCTKR2012009261-appb-I000146
    Figure PCTKR2012009261-appb-I000147
    Figure PCTKR2012009261-appb-I000147
    Figure PCTKR2012009261-appb-I000148
    Figure PCTKR2012009261-appb-I000148
    Figure PCTKR2012009261-appb-I000149
    Figure PCTKR2012009261-appb-I000149
    Figure PCTKR2012009261-appb-I000150
    Figure PCTKR2012009261-appb-I000150
    Figure PCTKR2012009261-appb-I000151
    Figure PCTKR2012009261-appb-I000151
    Figure PCTKR2012009261-appb-I000152
    Figure PCTKR2012009261-appb-I000152
    Figure PCTKR2012009261-appb-I000153
    Figure PCTKR2012009261-appb-I000153
    Figure PCTKR2012009261-appb-I000154
    Figure PCTKR2012009261-appb-I000154
    Figure PCTKR2012009261-appb-I000155
    Figure PCTKR2012009261-appb-I000155
    Figure PCTKR2012009261-appb-I000156
    Figure PCTKR2012009261-appb-I000156
    Figure PCTKR2012009261-appb-I000157
    Figure PCTKR2012009261-appb-I000157
    Figure PCTKR2012009261-appb-I000158
    Figure PCTKR2012009261-appb-I000158
    Figure PCTKR2012009261-appb-I000159
    Figure PCTKR2012009261-appb-I000159
    Figure PCTKR2012009261-appb-I000160
    Figure PCTKR2012009261-appb-I000160
    Figure PCTKR2012009261-appb-I000161
    Figure PCTKR2012009261-appb-I000161
    Figure PCTKR2012009261-appb-I000162
    Figure PCTKR2012009261-appb-I000162
    Figure PCTKR2012009261-appb-I000163
    Figure PCTKR2012009261-appb-I000163
    Figure PCTKR2012009261-appb-I000164
    Figure PCTKR2012009261-appb-I000164
    Figure PCTKR2012009261-appb-I000165
    Figure PCTKR2012009261-appb-I000165
    Figure PCTKR2012009261-appb-I000166
    Figure PCTKR2012009261-appb-I000166
    Figure PCTKR2012009261-appb-I000167
    Figure PCTKR2012009261-appb-I000167
    Figure PCTKR2012009261-appb-I000168
    Figure PCTKR2012009261-appb-I000168
    Figure PCTKR2012009261-appb-I000169
    Figure PCTKR2012009261-appb-I000169
  5. 제 1전극, 제 2전극, 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층을 포함하는 유기전기소자에 있어서,In an organic electric device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,
    상기 유기물층은 제 1항 내지 제 4항 중 어느 한 항의 화합물을 함유하는 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electric device, characterized in that it contains a compound of any one of claims 1 to 4.
  6. 제 5항에 있어서,The method of claim 5,
    상기 화합물을 용액공정(soluble process)에 의해 상기 유기물층으로 형성하는 것을 특징으로 하는 유기전기소자. And forming the compound into the organic material layer by a soluble process.
  7. 제 5항에 있어서,The method of claim 5,
    상기 유기물층은 발광층, 정공 주입층, 정공 수송층, 발광보조층, 전자 주입층 및 전자 수송층 중 적어도 하나인 것을 특징으로 하는 유기전기소자.And the organic material layer is at least one of a light emitting layer, a hole injection layer, a hole transporting layer, a light emitting auxiliary layer, an electron injection layer, and an electron transporting layer.
  8. 제 7항에 있어서,The method of claim 7, wherein
    상기 발광층은 상기 화합물로 형성되는 것을 특징으로 하는 유기전기소자.And the light emitting layer is formed of the compound.
  9. 제 5항의 유기전기소자를 포함하는 디스플레이장치; 및A display device comprising the organic electroluminescent device of claim 5; And
    상기 디스플레이장치를 구동하는 제어부; 를 포함하는 전자장치.A controller for driving the display device; Electronic device comprising a.
  10. 제 9항에 있어서,The method of claim 9,
    상기 유기전기소자는 유기전기발광소자(OLED ), 유기태양전지, 유기감광체(OPC), 유기트랜지스터(유기 TFT), 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467450A (en) * 2013-09-04 2013-12-25 吉林奥来德光电材料股份有限公司 Novel organic electroluminescent (EL) material and application thereof in devices
EP2772493A1 (en) * 2013-02-28 2014-09-03 Samsung Display Co., Ltd. Condensed benzoindoles and organic light emitting device comprising the same
WO2014200244A1 (en) * 2013-06-11 2014-12-18 Rohm And Haas Electronic Materials Korea Ltd. Novel organic electroluminescent compounds and organic electroluminescent device comprising the same
WO2016119992A1 (en) * 2015-01-30 2016-08-04 Merck Patent Gmbh Materials for electronic devices
CN107406381A (en) * 2015-09-14 2017-11-28 株式会社Lg化学 Heterocyclic compound and the organic luminescent device for including it
CN107849442A (en) * 2015-07-10 2018-03-27 德山新勒克斯有限公司 Organic electric element compound, organic electric element and its electronic installation using it
WO2018158659A1 (en) * 2017-03-03 2018-09-07 株式会社半導体エネルギー研究所 Organic compound, light-emitting element, light-emitting device, electronic apparatus, and illumination device
CN108779120A (en) * 2016-03-24 2018-11-09 德山新勒克斯有限公司 Organic electronic element compound, organic electronic element and its electronic device using the compound
CN108948028A (en) * 2018-08-22 2018-12-07 宇瑞(上海)化学有限公司 A kind of organic electro-optic device of oxygen-containing thia ring triarylamine compounds and its application
CN109326741A (en) * 2017-08-01 2019-02-12 江苏三月光电科技有限公司 A kind of organic luminescent device containing azines compound
CN110446714A (en) * 2017-03-16 2019-11-12 德山金属株式会社 Compound for organic electronic element, the organic electronic element and its electronic equipment using the compound

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131855A2 (en) * 2009-05-13 2010-11-18 덕산하이메탈(주) Compound containing a 5-membered heterocycle and organic light-emitting diode using same, and terminal for same
KR20100122798A (en) * 2009-05-13 2010-11-23 덕산하이메탈(주) Compound containing 5-membered heterocycle and organic electronic element using the same, terminal thereof
KR20110016288A (en) * 2009-08-11 2011-02-17 덕산하이메탈(주) Compound containing 5-membered heterocycle and organic electronic element using the same, terminal thereof
KR20110100877A (en) * 2010-03-05 2011-09-15 덕산하이메탈(주) Compound containing 5-membered heterocycle and organic electronic element using the same, terminal thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010131855A2 (en) * 2009-05-13 2010-11-18 덕산하이메탈(주) Compound containing a 5-membered heterocycle and organic light-emitting diode using same, and terminal for same
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