WO2018151479A2 - Heterocyclic compound and organic light emitting element comprising same - Google Patents

Heterocyclic compound and organic light emitting element comprising same Download PDF

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WO2018151479A2
WO2018151479A2 PCT/KR2018/001809 KR2018001809W WO2018151479A2 WO 2018151479 A2 WO2018151479 A2 WO 2018151479A2 KR 2018001809 W KR2018001809 W KR 2018001809W WO 2018151479 A2 WO2018151479 A2 WO 2018151479A2
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group
compound
substituted
formula
light emitting
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WO2018151479A3 (en
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김영석
권혁준
김민준
김공겸
김정범
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주식회사 엘지화학
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Priority to CN201880002765.5A priority Critical patent/CN109476678B/en
Publication of WO2018151479A2 publication Critical patent/WO2018151479A2/en
Publication of WO2018151479A3 publication Critical patent/WO2018151479A3/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • 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
    • C07D495/04—Ortho-condensed systems
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1048—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present specification relates to a heterocyclic compound and an organic light emitting device including the same.
  • organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
  • the organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.
  • the present specification provides a heterocyclic compound and an organic light emitting device including the same.
  • X 1 is O or S
  • L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
  • Y1 and Y3 are N, Y2 is CR13, Y4 is CR14, or Y2 and Y4 are N, Y1 is CR14, Y3 is CR13,
  • R13 is a group which binds to L1
  • R2 and R3, or R3 and R4 is a group which binds to * of the formula (2),
  • R1, R5 to R12, and R14 which do not combine with * in Formula 2 of R2 to R4 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring,
  • n 1 or 2
  • Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • R15 to R18 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring.
  • the heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.
  • FIG. 1 illustrates an organic light emitting device 10 according to an exemplary embodiment of the present specification.
  • FIG. 2 illustrates an organic light emitting device 11 according to another exemplary embodiment of the present specification.
  • FIG. 26 is a mass spectrum of Compound 24 prepared in Synthesis Example 24 of the present specification.
  • the present specification provides a heterocyclic compound represented by Chemical Formula 1.
  • the heterocyclic compound represented by Formula 1 is benzopuro [3,4- d ] pyrimidine, benzopuro [2,3-d] pyrimidine, benzothieno [3, Since position 2 of 4- d ] pyrimidine or benzothieno [2,3-d] pyrimidine is bonded to N of indolocarbazole through L1, the flow of electrons is smooth, and the chemical formula Since Formula 2 is bonded to R2 and R3 or R3 and R4 at 1, the steric hindrance of Formula 1 is reduced and the structure is stable, so that the organic light emitting device including Formula 1 has a low driving voltage, Excellent efficiency and long life.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Carbonyl group; Ester group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted or unsubstituted
  • a substituent to which two or more substituents are linked may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.
  • the halogen group may be fluorine, chlorine, bromine or iodine.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the amide group may be substituted with nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the ester group may be substituted with oxygen of the ester group having a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-o
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, and the like. It is not limited.
  • the amine group is -NH 2 ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30.
  • Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group.
  • Diphenylamine group N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine Groups, N-phenanthrenylfluorenylamine groups, N-biphenylfluorenylamine groups, and the like, but are not limited thereto.
  • the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.
  • the N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted for N in the amine group.
  • the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted for N in the amine group.
  • the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above.
  • the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group
  • the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy, and butyl sulfoxy groups. Etc., but is not limited thereto.
  • the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 30.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.
  • phosphine oxide groups include, but are not limited to, diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like.
  • the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
  • the aryl group is a monocyclic aryl group
  • carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
  • Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.
  • the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
  • adjacent means a substituent substituted on an atom directly connected to an atom to which the substituent is substituted, a substituent positioned closest to the substituent, or another substituent substituted on an atom to which the substituent is substituted.
  • two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups.
  • the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, N-arylalkylamine group, N-arylheteroarylamine group, and arylphosphine group is the same as the examples of the aryl group described above.
  • the aryloxy group may be a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.
  • arylthioxy group examples include a phenylthioxy group and 2- The methylphenyl thioxy group, 4-tert- butylphenyl thioxy group, etc. are mentioned,
  • An aryl sulfoxy group includes a benzene sulfoxy group, p-toluene sulfoxy group, etc., but is not limited to this.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
  • the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic.
  • heterocyclic group examples include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene
  • examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group.
  • the heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group.
  • the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.
  • heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.
  • the arylene group refers to a divalent group having two bonding positions in the aryl group.
  • the description of the aforementioned aryl group can be applied except that they are each divalent.
  • the heteroarylene group means a divalent group having two bonding positions in the heteroaryl group.
  • the description of the aforementioned heteroaryl group can be applied except that they are each divalent.
  • a “ring” means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
  • the hydrocarbon ring may be an aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group except for the above-mentioned monovalent one.
  • the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.
  • the heterocycle includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like.
  • the heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4.
  • X1, L1, n, Y1 to Y4, R1, R2 and R4 to R12 are the same as defined in Formula 1,
  • Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
  • Y1 and Y3 are N, Y2 is CR13, Y4 is CR14.
  • Y2 and Y4 are N, Y1 is CR14, Y3 is CR13.
  • R13 is a group which is bonded to the L1.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-5 to 1-12.
  • Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-13 to 1-20.
  • Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
  • Formula 1 is represented by any one of the following formula 1-21 to 1-28.
  • Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
  • R14 is a substituted or unsubstituted aryl group.
  • R14 is an aryl group.
  • R14 is a phenyl group; Or a naphthyl group.
  • Ar1 is an aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.
  • Ar1 is a phenyl group; Biphenyl group; Naphthyl group; Phenanthryl group; Fluoranthene group; Triphenylenyl group; Pyrenyl group; Pyridyl group; Pyrimidyl groups; Triazinyl group substituted with an aryl group; Or a quinazolyl group unsubstituted or substituted with an aryl group.
  • Ar1 is a phenyl group; Biphenyl group; Naphthyl group; Phenanthryl group; Fluoranthene group; Triphenylenyl group; Pyrenyl group; Pyridyl group; Pyrimidyl groups; Triazinyl group substituted with a phenyl group; Or a quinazolyl group unsubstituted or substituted with a phenyl group or a naphthyl group.
  • Formula 1 is selected from the following compounds.
  • the first electrode A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned heterocyclic compound.
  • the organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.
  • the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
  • 1 illustrates a structure of an organic light emitting device 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20.
  • 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
  • FIG. 2 illustrates a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on a substrate 20.
  • a structure of an organic light emitting device in which 50) is sequentially stacked is illustrated.
  • 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.
  • the organic material layer includes a hole transport layer, and the hole transport layer includes a heterocyclic compound represented by Chemical Formula 1.
  • the organic material layer includes an electron transport layer, an electron injection layer, or a layer for simultaneously transporting and injecting electrons, and the electron transport layer, an electron injection layer, or a layer for simultaneously transporting and injecting an electron It includes the heterocyclic compound.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Formula 1 as a host of the light emitting layer.
  • the organic material layer may include a heterocyclic compound represented by Formula 1 as a host, and may include another organic compound, a metal, or a metal compound as a dopant.
  • the dopant may be one or more selected from the compounds illustrated below, but is not limited thereto.
  • the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • the organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Chemical Formula 1 above. Can be.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a physical vapor deposition PVD: physical vapor deposition
  • PVD physical vapor deposition
  • sputtering e-beam evaporation
  • a metal or conductive metal oxide or an alloy thereof on the substrate
  • It can be prepared by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate.
  • the heterocyclic compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device.
  • the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the anode material a material having a large work function is usually preferred to facilitate hole injection into the organic material layer.
  • the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, Mg / Ag, and the like, but are not limited thereto.
  • the hole injection layer is a layer for injecting holes from an electrode with a hole injection material, and has a capability of transporting holes with a hole injection material, and thus has a hole injection effect at an anode, and an excellent hole injection effect with respect to a light emitting layer or a light emitting material.
  • generated in the light emitting layer to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable.
  • the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer.
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer.
  • the material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
  • the electron blocking layer is a layer that prevents the electrons injected from the electron injection layer from passing through the light emitting layer to the hole injection layer to improve the life and efficiency of the device, and, if necessary, using a known material using a known material It may be formed in a suitable portion between the injection layers.
  • the light emitting material of the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.
  • Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
  • the light emitting layer may include a host material and a dopant material.
  • the host material is a condensed aromatic ring derivative or a hetero ring-containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the dopant material examples include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted.
  • At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted.
  • the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.
  • the hole blocking layer is a layer that can prevent the holes injected from the hole injection layer to pass through the light emitting layer to the electron injection layer to improve the life and efficiency of the device, if necessary, using a known material using a known material and electron It may be formed in a suitable portion between the injection layers.
  • the electron transporting material of the electron transporting layer is a layer for receiving electrons from the electron injection layer and transporting electrons to the light emitting layer.
  • the electron transporting material is a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer. This large material is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used in accordance with the prior art.
  • suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
  • the electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer.
  • the compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
  • Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
  • the heterocyclic compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • the heterocyclic compound according to one embodiment of the present specification may be prepared by the basic synthesis scheme of Schemes 1 to 8, but is not limited thereto.
  • the intermediates A-1 and A-2 may be prepared by the following Schemes 9 and 10, but are not limited thereto.
  • Compound A-1-2 was obtained in the same manner as in Production Example 1, except that 1-naphthylboronic acid was used instead of phenylboronic acid.
  • Compound A-1-3 was obtained in the same manner as in Production Example 1, except that 2-naphthylboronic acid was used instead of phenylboronic acid.
  • Compound A-1-4 was obtained in the same manner as in Production Example 1, except that [1,1'-biphenyl] -4-ylboronic acid was used instead of phenylboronic acid.
  • FIG. 11 is a mass spectrum of Compound 9 prepared in Synthesis Example 9.
  • FIG. 13 is a mass spectrum of Compound 11 prepared in Synthesis Example 11.
  • FIG. 16 is a mass spectrum of Compound 14 prepared in Synthesis Example 14.
  • FIG. 18 is a mass spectrum of Compound 16 prepared in Synthesis Example 16.
  • FIG. 19 is a mass spectrum of Compound 17 prepared in Synthesis Example 17.
  • FIG. 19 is a mass spectrum of Compound 17 prepared in Synthesis Example 17.
  • Example 1 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 1-bromonaphthalene and compound B- (c) -2 instead of compound B- (a) -1.
  • FIG. 21 is a mass spectrum of Compound 19 prepared in Synthesis Example 19.
  • FIG. 25 is a mass spectrum of Compound 23 prepared in Synthesis Example 23.
  • FIG. 26 is a mass spectrum of Compound 24 prepared in Synthesis Example 24.
  • a glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 kPa was put in distilled water in which a dispersant was dissolved, and ultrasonically washed.
  • Fischer Co. product was used as a detergent
  • distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water.
  • the ultrasonic cleaning was repeated twice with distilled water for 10 minutes.
  • ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol was carried out and dried, and then transported to a plasma cleaner.
  • the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
  • the base pressure was 1 X 10 -6 torr, and the organic material was formed as a hole injection and transport layer on the ITO, followed by DNTPD (700 kPa), hole transport and electron blocking layer, NPB (300 kPa).
  • the following CBP which is generally used as a red phosphorescent host material, is used as a host (95 wt%), and the Dp-6 (5 wt%) is co-deposited (300 ⁇ ) as a dopant, and Alq 3 is used as an electron transport layer.
  • (350 kPa) and a cathode were formed in the order of LiF (5 kPa) and Al (1,000 kPa).
  • the deposition rate of the organic material was maintained at 1 ⁇ / sec
  • LiF was 0.2 ⁇ / sec
  • the aluminum was maintained at a deposition rate of 3 to 7 ⁇ / sec.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the following Compounds A to G were used instead of the CBP.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Compounds 1 to 24 prepared in Synthesis Examples 1 to 24 were used instead of the CBP.
  • the driving voltage, current efficiency, and lifetime were measured by applying a current of 10 mA / cm 2 to the organic light emitting diodes manufactured in Comparative Examples 1 to 8 and Examples 1 to 24, and T95 was 95% of the initial luminance. Is measured. The results are shown in Table 1 below.
  • Comparative Example 1 is an organic light emitting device using the CBP used as a conventional light emitting layer host
  • Comparative Examples 2 and 3 are a compound in which Formula 2 is bonded to R1 and R2 of Formula 1 An organic light emitting element used as a host of a light emitting layer.
  • Comparative Examples 4 and 5 are organic light emitting devices using a compound in which carbazole is bonded to the Y 1 position of Chemical Formula 1 of the present application, and Comparative Examples 6 to 8 show an aryl group substituted for indolocarbazole at the Y 3 position of Chemical Formula 1 of the present application An organic light emitting device using the bonded compound as a host of the light emitting layer.
  • Examples 1 to 24 of the organic light emitting device is a host of the light emitting layer of the indolocarbazole in the Y2 or Y3 position of the general formula (1) of the present application, that is, a compound of formula 2 is bonded to R2 and R3, or R3 and R4 of It is the used organic light emitting element.
  • the heterocyclic compound of Formula 1 of the present invention has a stable structure because the electron flow in the molecule is smooth, there are few steric hindrance, the organic light emitting device of Examples 1 to 24 using the same has a driving voltage than the organic light emitting device of Comparative Examples 1 to 8 It was found to be low, excellent in efficiency, and long in life.

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Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1 and an organic light emitting element comprising the same.

Description

헤테로고리 화합물 및 이를 포함하는 유기 발광 소자Heterocyclic compound and organic light emitting device comprising the same
본 출원은 2017년 2월 14일에 한국특허청에 제출된 한국 특허 출원 제10- 2017-0019961호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application claims the benefit of the filing date of Korean Patent Application No. 10-2017-0019961 filed with the Korea Intellectual Property Office on February 14, 2017, the entire contents of which are incorporated herein.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a heterocyclic compound and an organic light emitting device including the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어 질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.There is a continuing need for the development of new materials for such organic light emitting devices.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자를 제공한다.The present specification provides a heterocyclic compound and an organic light emitting device including the same.
본 명세서의 일 실시상태에 따르면 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.According to an exemplary embodiment of the present specification provides a heterocyclic compound represented by the formula (1).
[화학식 1][Formula 1]
Figure PCTKR2018001809-appb-I000001
Figure PCTKR2018001809-appb-I000001
상기 화학식 1에 있어서,In Chemical Formula 1,
X1은 O 또는 S이고,X 1 is O or S,
L1은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Y1 및 Y3는 N이고, Y2는 CR13이며, Y4는 CR14이거나, Y2 및 Y4는 N이고, Y1은 CR14이고, Y3은 CR13이며,Y1 and Y3 are N, Y2 is CR13, Y4 is CR14, or Y2 and Y4 are N, Y1 is CR14, Y3 is CR13,
상기 R13은 상기 L1과 결합하는 기이고, R13 is a group which binds to L1,
R2 및 R3, 또는 R3 및 R4는 하기 화학식 2의 *와 결합하는 기이며, R2 and R3, or R3 and R4 is a group which binds to * of the formula (2),
상기 R2 내지 R4 중 하기 화학식 2의 *와 결합하지 않는 기, R1, R5 내지 R12 및 R14는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 인접한 기는 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,The groups, R1, R5 to R12, and R14 which do not combine with * in Formula 2 of R2 to R4 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring,
n은 1 또는 2이며,n is 1 or 2,
n이 2 인 경우, 두 개의 L1은 서로 같거나 상이하고,when n is 2, two L1 are the same as or different from each other,
[화학식 2][Formula 2]
Figure PCTKR2018001809-appb-I000002
Figure PCTKR2018001809-appb-I000002
상기 화학식 2에 있어서,In Chemical Formula 2,
*는 상기 화학식 1의 R2 및 R3, 또는 R3 및 R4와 결합하는 부위이며,* Is a site that binds to R2 and R3 of Formula 1, or R3 and R4,
Ar1은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이며,Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R15 내지 R18은 서로 같거나 상이하고, 각각 독립적으로 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 인접한 기는 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.R15 to R18 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring.
또한, 본 명세서의 일 실시상태에 따르면, 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 것인 유기 발광 소자를 제공한다.Further, according to one embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a heterocyclic compound represented by Chemical Formula 1. to provide.
본 명세서의 일 실시상태에 따른 헤테로고리 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있고, 이를 사용함으로써 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성의 향상이 가능하다.The heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.
도 1은 본 명세서의 일 실시상태에 따르는 유기 발광 소자(10)를 도시한 것이다.1 illustrates an organic light emitting device 10 according to an exemplary embodiment of the present specification.
도 2는 본 명세서의 또 하나의 실시상태에 따르는 유기 발광 소자(11)를 도시한 것이다.2 illustrates an organic light emitting device 11 according to another exemplary embodiment of the present specification.
도 3은 본 명세서의 합성예 1에서 제조된 화합물 1의 질량분석 스펙트럼이다.3 is a mass spectrum of Compound 1 prepared in Synthesis Example 1 of the present specification.
도 4은 본 명세서의 합성예 2에서 제조된 화합물 2의 질량분석 스펙트럼이다.4 is a mass spectrum of Compound 2 prepared in Synthesis Example 2 of the present specification.
도 5는 본 명세서의 합성예 3에서 제조된 화합물 3의 질량분석 스펙트럼이다.5 is a mass spectrum of Compound 3 prepared in Synthesis Example 3 of the present specification.
도 6은 본 명세서의 합성예 4에서 제조된 화합물 4의 질량분석 스펙트럼이다.6 is a mass spectrum of Compound 4 prepared in Synthesis Example 4 of the present specification.
도 7은 본 명세서의 합성예 5에서 제조된 화합물 5의 질량분석 스펙트럼이다.7 is a mass spectrum of Compound 5 prepared in Synthesis Example 5 of the present specification.
도 8은 본 명세서의 합성예 6에서 제조된 화합물 6의 질량분석 스펙트럼이다.8 is a mass spectrum of Compound 6 prepared in Synthesis Example 6 of the present specification.
도 9는 본 명세서의 합성예 7에서 제조된 화합물 7의 질량분석 스펙트럼이다.9 is a mass spectrum of Compound 7 prepared in Synthesis Example 7 of the present specification.
도 10은 본 명세서의 합성예 8에서 제조된 화합물 8의 질량분석 스펙트럼이다.10 is a mass spectrum of Compound 8 prepared in Synthesis Example 8 of the present specification.
도 11은 본 명세서의 합성예 9에서 제조된 화합물 9의 질량분석 스펙트럼이다.11 is a mass spectrum of Compound 9 prepared in Synthesis Example 9 of the present specification.
도 12는 본 명세서의 합성예 10에서 제조된 화합물 10의 질량분석 스펙트럼이다.12 is a mass spectrum of Compound 10 prepared in Synthesis Example 10 of the present specification.
도 13은 본 명세서의 합성예 11에서 제조된 화합물 11의 질량분석 스펙트럼이다.13 is a mass spectrum of Compound 11 prepared in Synthesis Example 11 of the present specification.
도 14는 본 명세서의 합성예 12에서 제조된 화합물 12의 질량분석 스펙트럼이다.14 is a mass spectrum of Compound 12 prepared in Synthesis Example 12 of the present specification.
도 15는 본 명세서의 합성예 13에서 제조된 화합물 13의 질량분석 스펙트럼이다.15 is a mass spectrum of Compound 13 prepared in Synthesis Example 13 of the present specification.
도 16은 본 명세서의 합성예 14에서 제조된 화합물 14의 질량분석 스펙트럼이다.16 is a mass spectrum of Compound 14 prepared in Synthesis Example 14 of the present specification.
도 17은 본 명세서의 합성예 15에서 제조된 화합물 15의 질량분석 스펙트럼이다.17 is a mass spectrum of Compound 15 prepared in Synthesis Example 15 of the present specification.
도 18은 본 명세서의 합성예 16에서 제조된 화합물 16의 질량분석 스펙트럼이다.18 is a mass spectrum of Compound 16 prepared in Synthesis Example 16 of the present specification.
도 19는 본 명세서의 합성예 17에서 제조된 화합물 17의 질량분석 스펙트럼이다.19 is a mass spectrum of Compound 17 prepared in Synthesis Example 17 of the present specification.
도 20은 본 명세서의 합성예 18에서 제조된 화합물 18의 질량분석 스펙트럼이다.20 is a mass spectrum of Compound 18 prepared in Synthesis Example 18 of the present specification.
도 21은 본 명세서의 합성예 19에서 제조된 화합물 19의 질량분석 스펙트럼이다.21 is a mass spectrum of Compound 19 prepared in Synthesis Example 19 of the present specification.
도 22는 본 명세서의 합성예 20에서 제조된 화합물 20의 질량분석 스펙트럼이다.22 is a mass spectrum of Compound 20 prepared in Synthesis Example 20 of the present specification.
도 23은 본 명세서의 합성예 21에서 제조된 화합물 21의 질량분석 스펙트럼이다.23 is a mass spectrum of Compound 21 prepared in Synthesis Example 21 of the present specification.
도 24는 본 명세서의 합성예 22에서 제조된 화합물 22의 질량분석 스펙트럼이다.24 is a mass spectrum of Compound 22 prepared in Synthesis Example 22 of the present specification.
도 25는 본 명세서의 합성예 23에서 제조된 화합물 23의 질량분석 스펙트럼이다.25 is a mass spectrum of Compound 23 prepared in Synthesis Example 23 of the present specification.
도 26은 본 명세서의 합성예 24에서 제조된 화합물 24의 질량분석 스펙트럼이다.FIG. 26 is a mass spectrum of Compound 24 prepared in Synthesis Example 24 of the present specification.
[부호의 설명][Description of the code]
10, 11: 유기 발광 소자10, 11: organic light emitting element
20: 기판20: substrate
30: 제1 전극30: first electrode
40: 발광층40: light emitting layer
50: 제2 전극50: second electrode
60: 정공주입층60: hole injection layer
70: 정공수송층70: hole transport layer
80: 전자수송층80: electron transport layer
90: 전자주입층90: electron injection layer
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, this specification is demonstrated in detail.
본 명세서는 상기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.The present specification provides a heterocyclic compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따른 상기 화학식 1로 표시되는 헤테로고리 화합물은 벤조퓨로[3,4-d]피리미딘, 벤조퓨로[2,3-d]피리미딘, 벤조티에노[3,4-d]피리미딘 또는 벤조티에노[2,3-d]피리미딘의 2번 위치가 L1을 통해 인돌로카바졸의 N에 결합되는 구조이므로, 전자의 흐름이 원활하며, 또한, 상기 화학식 1에서 R2 및 R3, 또는 R3 및 R4에 상기 화학식 2가 결합되므로, 상기 화학식 1의 입체 장애(steric hindrance)가 줄어들어 구조가 안정적이므로, 상기 화학식 1을 포함하는 유기 발광 소자는 구동전압이 낮고, 효율이 우수하며, 수명이 길다.The heterocyclic compound represented by Formula 1 according to an exemplary embodiment of the present specification is benzopuro [3,4- d ] pyrimidine, benzopuro [2,3-d] pyrimidine, benzothieno [3, Since position 2 of 4- d ] pyrimidine or benzothieno [2,3-d] pyrimidine is bonded to N of indolocarbazole through L1, the flow of electrons is smooth, and the chemical formula Since Formula 2 is bonded to R2 and R3 or R3 and R4 at 1, the steric hindrance of Formula 1 is reduced and the structure is stable, so that the organic light emitting device including Formula 1 has a low driving voltage, Excellent efficiency and long life.
본 명세서에 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.
본 명세서에 있어서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.
본 명세서에 있어서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of substituents in the present specification are described below, but are not limited thereto.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 니트릴기; 니트로기; 이미드기; 아미드기; 카르보닐기; 에스테르기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 아릴옥시기; 치환 또는 비치환된 알킬티옥시기; 치환 또는 비치환된 아릴티옥시기; 치환 또는 비치환된 알킬술폭시기; 치환 또는 비치환된 아릴술폭시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 아민기; 치환 또는 비치환된 아릴포스핀기; 치환 또는 비치환된 포스핀옥사이드기; 치환 또는 비치환된 아릴기; 및 치환 또는 비치환된 헤테로고리기로 이루어진 군에서 선택된 1 또는 2 이상의 치환기로 치환되었거나 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 바이페닐기일 수 있다. 즉, 바이페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다. As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Carbonyl group; Ester group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.
본 명세서에 있어서,
Figure PCTKR2018001809-appb-I000003
는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,
Figure PCTKR2018001809-appb-I000003
Means a site which is bonded to another substituent or binding moiety.
본 명세서에 있어서, 할로겐기는 불소, 염소, 브롬 또는 요오드가 될 수 있다.In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2018001809-appb-I000004
Figure PCTKR2018001809-appb-I000004
본 명세서에 있어서, 아미드기는 아미드기의 질소가 수소, 탄소수 1 내지 30의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 30의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the amide group may be substituted with nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2018001809-appb-I000005
Figure PCTKR2018001809-appb-I000005
본 명세서에서 카르보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
Figure PCTKR2018001809-appb-I000006
Figure PCTKR2018001809-appb-I000006
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 30의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the ester group may be substituted with oxygen of the ester group having a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2018001809-appb-I000007
Figure PCTKR2018001809-appb-I000007
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 30인 것이 바람직하다. 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 시클로펜틸메틸, 시클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 30인 것이 바람직하며, 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시, 벤질옥시, p-메틸벤질옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, and the like. It is not limited.
본 명세서에 있어서, 아민기는 -NH2; 알킬아민기; N-알킬아릴아민기; 아릴아민기; N-아릴헤테로아릴아민기; N-알킬헤테로아릴아민기 및 헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 1 내지 30인 것이 바람직하다. 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 바이페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, N-페닐나프틸아민기, 디톨릴아민기, N-페닐톨릴아민기, 트리페닐아민기, N-페닐바이페닐아민기, N-페닐나프틸아민기, N-바이페닐나프틸아민기, N-나프틸플루오레닐아민기, N-페닐페난트레닐아민기, N-바이페닐페난트레닐아민기, N-페닐플루오레닐아민기, N-페닐터페닐아민기, N-페난트레닐플루오레닐아민기, N-바이페닐플루오레닐아민기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the amine group is -NH 2 ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine Groups, N-phenanthrenylfluorenylamine groups, N-biphenylfluorenylamine groups, and the like, but are not limited thereto.
본 명세서에 있어서, N-알킬아릴아민기는 아민기의 N에 알킬기 및 아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.
본 명세서에 있어서, N-아릴헤테로아릴아민기는 아민기의 N에 아릴기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted for N in the amine group.
본 명세서에 있어서, N-알킬헤테로아릴아민기는 아민기의 N에 알킬기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted for N in the amine group.
본 명세서에 있어서, 알킬아민기, N-아릴알킬아민기, 알킬티옥시기, 알킬술폭시기, N-알킬헤테로아릴아민기 중의 알킬기는 전술한 알킬기의 예시와 같다. 구체적으로 알킬티옥시기로는 메틸티옥시기, 에틸티옥시기, tert－부틸티옥시기, 헥실티옥시기, 옥틸티옥시기 등이 있고, 알킬술폭시기로는 메실, 에틸술폭시기, 프로필술폭시기, 부틸술폭시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, and the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy, and butyl sulfoxy groups. Etc., but is not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 30인 것이 바람직하다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.
본 명세서에 있어서, 붕소기는 -BR100R101일 수 있으며, 상기 R100 및 R101은 같거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐; 니트릴기; 치환 또는 비치환된 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기; 치환 또는 비치환된 탄소수 1 내지 30의 직쇄 또는 분지쇄의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 및 치환 또는 비치환된 탄소수 2 내지 30의 단환 또는 다환의 헤테로아릴기로 이루어진 군으로부터 선택될 수 있다.In the present specification, the boron group may be -BR 100 R 101 , wherein R 100 and R 101 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms; Substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.
본 명세서에 있어서, 포스핀옥사이드기는 구체적으로 디페닐포스핀옥사이드기, 디나프틸포스핀옥사이드 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, phosphine oxide groups include, but are not limited to, diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하며, 상기 아릴기는 단환식 또는 다환식일 수 있다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.
상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 30인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 트리페닐기, 파이레닐기, 페날레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.
본 명세서에 있어서, 상기 플루오레닐기는 치환될 수 있으며, 인접한 기들이 서로 결합하여 고리를 형성할 수 있다. In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2018001809-appb-I000008
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,
Figure PCTKR2018001809-appb-I000008
And so on. However, the present invention is not limited thereto.
본 명세서에 있어서, "인접한" 기는 해당 치환기가 치환된 원자와 직접 연결된 원자에 치환된 치환기, 해당 치환기와 입체구조적으로 가장 가깝게 위치한 치환기, 또는 해당 치환기가 치환된 원자에 치환된 다른 치환기를 의미할 수 있다. 예컨대, 벤젠고리에서 오르토(ortho)위치로 치환된 2개의 치환기 및 지방족 고리에서 동일 탄소에 치환된 2개의 치환기는 서로 "인접한" 기로 해석될 수 있다.As used herein, the term "adjacent" means a substituent substituted on an atom directly connected to an atom to which the substituent is substituted, a substituent positioned closest to the substituent, or another substituent substituted on an atom to which the substituent is substituted. Can be. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups.
본 명세서에 있어서, 아릴옥시기, 아릴티옥시기, 아릴술폭시기, N-아릴알킬아민기, N-아릴헤테로아릴아민기 및 아릴포스핀기 중의 아릴기는 전술한 아릴기의 예시와 같다. 구체적으로 아릴옥시기로는 페녹시기, p-토릴옥시기, m-토릴옥시기, 3,5-디메틸-페녹시기, 2,4,6-트리메틸페녹시기, p-tert-부틸페녹시기, 3-바이페닐옥시기, 4-바이페닐옥시기, 1-나프틸옥시기, 2-나프틸옥시기, 4-메틸-1-나프틸옥시기, 5-메틸-2-나프틸옥시기, 1-안트릴옥시기, 2-안트릴옥시기, 9-안트릴옥시기, 1-페난트릴옥시기, 3-페난트릴옥시기, 9-페난트릴옥시기 등이 있고, 아릴티옥시기로는 페닐티옥시기, 2－메틸페닐티옥시기, 4－tert－부틸페닐티옥시기 등이 있으며, 아릴술폭시기로는 벤젠술폭시기, p－톨루엔술폭시기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, N-arylalkylamine group, N-arylheteroarylamine group, and arylphosphine group is the same as the examples of the aryl group described above. Specifically, the aryloxy group may be a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like. Examples of the arylthioxy group include a phenylthioxy group and 2- The methylphenyl thioxy group, 4-tert- butylphenyl thioxy group, etc. are mentioned, An aryl sulfoxy group includes a benzene sulfoxy group, p-toluene sulfoxy group, etc., but is not limited to this.
본 명세서에 있어서, 아릴아민기의 예로는 치환 또는 비치환된 모노아릴아민기, 치환 또는 비치환된 디아릴아민기, 또는 치환 또는 비치환된 트리아릴아민기가 있다. 상기 아릴아민기 중의 아릴기는 단환식 아릴기일 수 있고, 다환식 아릴기일 수 있다. 상기 아릴기가 2 이상을 포함하는 아릴아민기는 단환식 아릴기, 다환식 아릴기, 또는 단환식 아릴기와 다환식 아릴기를 동시에 포함할 수 있다. 예컨대, 상기 아릴아민기 중의 아릴기는 전술한 아릴기의 예시 중에서 선택될 수 있다.In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.
본 명세서에 있어서, 헤테로아릴기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 30인 것이 바람직하며, 상기 헤테로아릴기는 단환식 또는 다환식일 수 있다. 헤테로고리기의 예로는 티오펜기, 퓨라닐기, 피롤기, 이미다졸릴기, 티아졸릴기, 옥사졸릴기, 옥사디아졸릴기, 피리딜기, 바이피리딜기, 피리미딜기, 트리아지닐기, 트리아졸릴기, 아크리딜기, 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미딜기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀리닐기, 인돌릴기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤리닐기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.
본 명세서에 있어서, 헤테로아릴아민기의 예로는 치환 또는 비치환된 모노헤테로아릴아민기, 치환 또는 비치환된 디헤테로아릴아민기, 또는 치환 또는 비치환된 트리헤테로아릴아민기가 있다. 상기 헤테로아릴기가 2 이상을 포함하는 헤테로아릴아민기는 단환식 헤테로아릴기, 다환식 헤테로아릴기, 또는 단환식 헤테로아릴기와 다환식 헤테로아릴기를 동시에 포함할 수 있다. 예컨대, 상기 헤테로아릴아민기 중의 헤테로아릴기는 전술한 헤테로아릴기의 예시 중에서 선택될 수 있다.In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.
본 명세서에 있어서, N-아릴헤테로아릴아민기 및 N-알킬헤테로아릴아민기 중의 헤테로아릴기의 예시는 전술한 헤테로아릴기의 예시와 같다.In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.
본 명세서에 있어서, 아릴렌기는 아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 아릴기의 설명이 적용될 수 있다.In the present specification, the arylene group refers to a divalent group having two bonding positions in the aryl group. The description of the aforementioned aryl group can be applied except that they are each divalent.
본 명세서에 있어서, 헤테로아릴렌기는 헤테로아릴기에 결합 위치가 두 개 있는 것 즉 2가기를 의미한다. 이들은 각각 2가기인 것을 제외하고는 전술한 헤테로아릴기의 설명이 적용될 수 있다.In the present specification, the heteroarylene group means a divalent group having two bonding positions in the heteroaryl group. The description of the aforementioned heteroaryl group can be applied except that they are each divalent.
본 명세서에 있어서, 인접한 기가 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 치환 또는 비치환된 탄화수소고리; 또는 치환 또는 비치환된 헤테로고리를 의미한다.In the present specification, in a substituted or unsubstituted ring in which adjacent groups are formed by bonding to each other, a “ring” means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted hetero ring.
본 명세서에 있어서, 탄화수소고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 1가가 아닌 것을 제외하고 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있다.In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group except for the above-mentioned monovalent one.
본 명세서에 있어서, 방향족고리는 단환 또는 다환일 수 있으며, 1가가 아닌 것을 제외하고 상기 아릴기의 예시 중에서 선택될 수 있다.In the present specification, the aromatic ring may be monocyclic or polycyclic, and may be selected from examples of the aryl group except that it is not monovalent.
본 명세서에 있어서, 헤테로고리는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, Se 및 S 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 상기 헤테로고리는 단환 또는 다환일 수 있으며, 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 1가가 아닌 것을 제외하고 상기 헤테로아릴기 또는 헤테로고리기의 예시 중에서 선택될 수 있다.In the present specification, the heterocycle includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocycle may be monocyclic or polycyclic, and may be aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the heteroaryl group or heterocyclic group except that it is not monovalent.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-1 내지 1-4 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4.
Figure PCTKR2018001809-appb-I000009
Figure PCTKR2018001809-appb-I000009
Figure PCTKR2018001809-appb-I000010
Figure PCTKR2018001809-appb-I000010
상기 화학식 1-1 내지 1-4에 있어서,In Chemical Formulas 1-1 to 1-4,
X1, L1, n, Y1 내지 Y4, R1, R2 및 R4 내지 R12의 정의는 상기 화학식 1과 동일하고,X1, L1, n, Y1 to Y4, R1, R2 and R4 to R12 are the same as defined in Formula 1,
Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하다.Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, Y1 및 Y3는 N이고, Y2는 CR13이며, Y4는 CR14이다.According to an exemplary embodiment of the present specification, in the general formula 1, Y1 and Y3 are N, Y2 is CR13, Y4 is CR14.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1에 있어서, Y2 및 Y4는 N이고, Y1은 CR14이고, Y3은 CR13이다.According to an exemplary embodiment of the present specification, in the general formula 1, Y2 and Y4 are N, Y1 is CR14, Y3 is CR13.
본 명세서의 일 실시상태에 따르면, 상기 R13은 상기 L1과 결합하는 기이다.According to an exemplary embodiment of the present disclosure, wherein R13 is a group which is bonded to the L1.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-5 내지 1-12 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-5 to 1-12.
Figure PCTKR2018001809-appb-I000011
Figure PCTKR2018001809-appb-I000011
Figure PCTKR2018001809-appb-I000012
Figure PCTKR2018001809-appb-I000012
Figure PCTKR2018001809-appb-I000013
Figure PCTKR2018001809-appb-I000013
Figure PCTKR2018001809-appb-I000014
Figure PCTKR2018001809-appb-I000014
상기 화학식 1-5 내지 1-12에 있어서,In Chemical Formulas 1-5 to 1-12,
X1, L1, n, R1, R2, R4 내지 R12 및 R14의 정의는 전술한 바와 동일하고,The definitions of X1, L1, n, R1, R2, R4 to R12 and R14 are the same as described above,
Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하다.Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-13 내지 1-20 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-13 to 1-20.
Figure PCTKR2018001809-appb-I000015
Figure PCTKR2018001809-appb-I000015
Figure PCTKR2018001809-appb-I000016
Figure PCTKR2018001809-appb-I000016
Figure PCTKR2018001809-appb-I000017
Figure PCTKR2018001809-appb-I000017
Figure PCTKR2018001809-appb-I000018
Figure PCTKR2018001809-appb-I000018
상기 화학식 1-13 내지 1-20에 있어서,In Chemical Formulas 1-13 to 1-20,
L1, n, R1, R2, R4 내지 R12 및 R14의 정의는 전술한 바와 동일하고,The definitions of L1, n, R1, R2, R4 to R12 and R14 are the same as described above,
Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하다.Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 1-21 내지 1-28 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following formula 1-21 to 1-28.
Figure PCTKR2018001809-appb-I000019
Figure PCTKR2018001809-appb-I000019
Figure PCTKR2018001809-appb-I000020
Figure PCTKR2018001809-appb-I000020
Figure PCTKR2018001809-appb-I000021
Figure PCTKR2018001809-appb-I000021
Figure PCTKR2018001809-appb-I000022
Figure PCTKR2018001809-appb-I000022
상기 화학식 1-21 내지 1-28에 있어서,In Chemical Formulas 1-21 to 1-28,
L1, n, R1, R2, R4 내지 R12 및 R14의 정의는 전술한 바와 동일하고,The definitions of L1, n, R1, R2, R4 to R12 and R14 are the same as described above,
Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하다.Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
본 명세서의 일 실시상태에 따르면, 상기 R14는 치환 또는 비치환된 아릴기이다.According to an exemplary embodiment of the present specification, R14 is a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 R14는 아릴기이다.According to an exemplary embodiment of the present specification, R14 is an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 R14는 페닐기; 또는 나프틸기이다.According to an exemplary embodiment of the present specification, R14 is a phenyl group; Or a naphthyl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar1는 아릴기; 또는 아릴기로 치환 또는 비치환된 헤테로아릴기이다.According to an exemplary embodiment of the present specification, Ar1 is an aryl group; Or a heteroaryl group unsubstituted or substituted with an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar1은 페닐기; 바이페닐기; 나프틸기; 페난트릴기; 플루오란텐기; 트리페닐레닐기; 파이레닐기; 피리딜기; 피리미딜기; 아릴기로 치환된 트리아지닐기; 또는 아릴기로 치환 또는 비치환된 퀴나졸릴기이다.According to an exemplary embodiment of the present specification, Ar1 is a phenyl group; Biphenyl group; Naphthyl group; Phenanthryl group; Fluoranthene group; Triphenylenyl group; Pyrenyl group; Pyridyl group; Pyrimidyl groups; Triazinyl group substituted with an aryl group; Or a quinazolyl group unsubstituted or substituted with an aryl group.
본 명세서의 일 실시상태에 따르면, 상기 Ar1은 페닐기; 바이페닐기; 나프틸기; 페난트릴기; 플루오란텐기; 트리페닐레닐기; 파이레닐기; 피리딜기; 피리미딜기; 페닐기로 치환된 트리아지닐기; 또는 페닐기, 또는 나프틸기로 치환 또는 비치환된 퀴나졸릴기이다.According to an exemplary embodiment of the present specification, Ar1 is a phenyl group; Biphenyl group; Naphthyl group; Phenanthryl group; Fluoranthene group; Triphenylenyl group; Pyrenyl group; Pyridyl group; Pyrimidyl groups; Triazinyl group substituted with a phenyl group; Or a quinazolyl group unsubstituted or substituted with a phenyl group or a naphthyl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화합물 중에서 선택된다.According to an exemplary embodiment of the present specification, Formula 1 is selected from the following compounds.
Figure PCTKR2018001809-appb-I000023
Figure PCTKR2018001809-appb-I000023
Figure PCTKR2018001809-appb-I000024
Figure PCTKR2018001809-appb-I000024
Figure PCTKR2018001809-appb-I000025
Figure PCTKR2018001809-appb-I000025
Figure PCTKR2018001809-appb-I000026
Figure PCTKR2018001809-appb-I000026
Figure PCTKR2018001809-appb-I000027
Figure PCTKR2018001809-appb-I000027
Figure PCTKR2018001809-appb-I000028
Figure PCTKR2018001809-appb-I000028
Figure PCTKR2018001809-appb-I000029
Figure PCTKR2018001809-appb-I000029
Figure PCTKR2018001809-appb-I000030
Figure PCTKR2018001809-appb-I000030
Figure PCTKR2018001809-appb-I000031
Figure PCTKR2018001809-appb-I000031
Figure PCTKR2018001809-appb-I000032
Figure PCTKR2018001809-appb-I000032
Figure PCTKR2018001809-appb-I000033
Figure PCTKR2018001809-appb-I000033
Figure PCTKR2018001809-appb-I000034
Figure PCTKR2018001809-appb-I000034
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본 명세서의 일 실시상태에 따르면, 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 전술한 헤테로고리 화합물을 포함하는 것인 유기 발광 소자를 제공한다.According to an exemplary embodiment of the present specification, the first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned heterocyclic compound.
본 명세서의 일 실시상태에 따르면, 본 명세서의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로서 정공주입층, 정공수송층, 전자차단층, 발광층, 정공 차단층, 전자수송층, 전자전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적거나 많은 수의 유기층을 포함할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.
예컨대, 본 명세서의 유기 발광 소자의 구조는 도 1 및 도 2에 나타난 것과 같은 구조를 가질 수 있으나 이에만 한정되는 것은 아니다.For example, the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.
도 1에는 기판(20) 위에 제1 전극(30), 발광층(40) 및 제2 전극(50)이 순차적으로 적층된 유기 발광 소자(10)의 구조가 예시 되어 있다. 상기 도 1은 본 명세서의 일 실시상태에 따른 유기 발광 소자의 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.1 illustrates a structure of an organic light emitting device 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
도 2에는 기판(20) 위에 제1 전극(30), 정공주입층(60), 정공수송층(70), 발광층(40), 전자수송층(80), 전자주입층(90) 및 제2 전극(50)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 상기 도 2는 본 명세서의 실시상태에 따른 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.2 illustrates a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, an electron transport layer 80, an electron injection layer 90, and a second electrode on a substrate 20. A structure of an organic light emitting device in which 50) is sequentially stacked is illustrated. 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공수송층을 포함하고, 상기 정공수송층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함한다.According to the exemplary embodiment of the present specification, the organic material layer includes a hole transport layer, and the hole transport layer includes a heterocyclic compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 전자수송층, 전자주입층, 또는 전자 수송 및 주입을 동시에 하는 층을 포함하고, 상기 전자수송층, 전자주입층, 또는 전자 수송 및 주입을 동시에 하는 층은 상기 헤테로고리 화합물을 포함한다.According to one embodiment of the present specification, the organic material layer includes an electron transport layer, an electron injection layer, or a layer for simultaneously transporting and injecting electrons, and the electron transport layer, an electron injection layer, or a layer for simultaneously transporting and injecting an electron It includes the heterocyclic compound.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 발광층의 호스트로서 포함한다.According to an exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound represented by Formula 1 as a host of the light emitting layer.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 상기 화학식 1로 표시되는 헤테로고리 화합물을 호스트로서 포함하고, 다른 유기화합물, 금속 또는 금속화합물을 도펀트로 포함할 수 있다. In one embodiment of the present specification, the organic material layer may include a heterocyclic compound represented by Formula 1 as a host, and may include another organic compound, a metal, or a metal compound as a dopant.
상기 도펀트는 하기 예시하는 화합물 중에서 선택되는 1 이상일 수 있으나, 이에만 한정되는 것은 아니다.The dopant may be one or more selected from the compounds illustrated below, but is not limited thereto.
Figure PCTKR2018001809-appb-I000079
Figure PCTKR2018001809-appb-I000079
Figure PCTKR2018001809-appb-I000080
Figure PCTKR2018001809-appb-I000080
Figure PCTKR2018001809-appb-I000081
Figure PCTKR2018001809-appb-I000081
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택되는 1층 이상을 더 포함할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
본 명세서의 유기 발광 소자는 유기물층 중 1층 이상이 본 명세서의 헤테로고리 화합물, 즉, 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다.The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Chemical Formula 1 above. Can be.
상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 명세서의 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시킴으로써 제조할 수 있다. 이 때 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 물리 증착 방법(PVD: physical Vapor Deposition)을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 제1 전극을 형성하고, 그 위에 정공 주입층, 정공 수송층, 발광층 및 전자 수송층을 포함하는 유기물층을 형성한 후, 그 위에 제2 전극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 제2 전극 물질부터 유기물층, 제1 전극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. 또한, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD: physical vapor deposition) such as sputtering (e-beam evaporation), by depositing a metal or conductive metal oxide or an alloy thereof on the substrate It can be prepared by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the heterocyclic compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이다. According to one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.
본 명세서의 또 하나의 실시상태에 따르면, 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다. According to another exemplary embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2 : Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO 2 : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al, Mg/Ag과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO 2 / Al, Mg / Ag, and the like, but are not limited thereto.
상기 정공주입층은 정공 주입 물질로는 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 구체적인 예로는 금속 포피린(porphyrin), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone)계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정 되는 것은 아니다. The hole injection layer is a layer for injecting holes from an electrode with a hole injection material, and has a capability of transporting holes with a hole injection material, and thus has a hole injection effect at an anode, and an excellent hole injection effect with respect to a light emitting layer or a light emitting material. The compound which prevents the movement of the excitons produced | generated in the light emitting layer to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.
상기 전자 차단층은 전자 주입층으로부터 주입된 전자가 발광층을 지나 정공 주입층으로 진입하는 것을 방지하여 소자의 수명과 효율을 향상시킬 수 있는 층이고, 필요한 경우에 공지의 재료를 사용하여 발광층과 정공 주입층의 사이에 적절한 부분에 형성될 수 있다.The electron blocking layer is a layer that prevents the electrons injected from the electron injection layer from passing through the light emitting layer to the hole injection layer to improve the life and efficiency of the device, and, if necessary, using a known material using a known material It may be formed in a suitable portion between the injection layers.
상기 발광층의 발광 물질로는 정공 수송층과 전자 수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 8-히드록시-퀴놀린 알루미늄 착물(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤즈옥사졸, 벤조티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다. The light emitting material of the light emitting layer is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로 고리 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로 고리 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a hetero ring-containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
상기 도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 시클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.
상기 정공 차단층은 정공 주입층으로부터 주입된 정공이 발광층을 지나 전자 주입층으로 진입하는 것을 방지하여 소자의 수명과 효율을 향상시킬 수 있는 층이고, 필요한 경우에 공지의 재료를 사용하여 발광층과 전자 주입층의 사이에 적절한 부분에 형성될 수 있다.The hole blocking layer is a layer that can prevent the holes injected from the hole injection layer to pass through the light emitting layer to the electron injection layer to improve the life and efficiency of the device, if necessary, using a known material using a known material and electron It may be formed in a suitable portion between the injection layers.
상기 전자수송층의 전자 수송 물질로는 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자 수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transporting material of the electron transporting layer is a layer for receiving electrons from the electron injection layer and transporting electrons to the light emitting layer. The electron transporting material is a material capable of injecting electrons well from the cathode and transferring them to the light emitting layer. This large material is suitable. Specific examples thereof include Al complexes of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.
상기 전자주입층은 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공 주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer is a layer that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer. The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.
본 명세서에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.According to an exemplary embodiment of the present specification, the heterocyclic compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present disclosure may be modified in various other forms, and the scope of the present disclosure is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
본 명세서의 일 실시상태에 따른 헤테로고리 화합물은 하기 반응식 1 내지 8의 기본적인 합성 과정(scheme)에 의하여 제조될 수 있으나, 이에 한정되는 것은 아니다.The heterocyclic compound according to one embodiment of the present specification may be prepared by the basic synthesis scheme of Schemes 1 to 8, but is not limited thereto.
[반응식 1]Scheme 1
Figure PCTKR2018001809-appb-I000082
Figure PCTKR2018001809-appb-I000082
[반응식 2] Scheme 2
Figure PCTKR2018001809-appb-I000083
Figure PCTKR2018001809-appb-I000083
[반응식 3]Scheme 3
Figure PCTKR2018001809-appb-I000084
Figure PCTKR2018001809-appb-I000084
[반응식 4]Scheme 4
Figure PCTKR2018001809-appb-I000085
Figure PCTKR2018001809-appb-I000085
[반응식 5]Scheme 5
Figure PCTKR2018001809-appb-I000086
Figure PCTKR2018001809-appb-I000086
[반응식 6]Scheme 6
Figure PCTKR2018001809-appb-I000087
Figure PCTKR2018001809-appb-I000087
[반응식 7]Scheme 7
Figure PCTKR2018001809-appb-I000088
Figure PCTKR2018001809-appb-I000088
[반응식 8]Scheme 8
Figure PCTKR2018001809-appb-I000089
Figure PCTKR2018001809-appb-I000089
상기 반응식 1 내지 8에 있어서, X1, R14, L1 및 n의 정의는 상기 화학식 1에서 정의한 바와 동일하고, Ar1의 정의는 상기 화학식 2에서 정의한 바와 동일하다.In the above Reaction Schemes 1 to 8, the definition of X1, R14, L1 and n is the same as defined in Formula 1, and the definition of Ar1 is the same as defined in Formula 2.
본 명세서의 일 실시상태에 따르면, 상기 중간체 A-1 및 A-2는 하기 반응식 9 및 10에 의하여 제조될 수 있으나, 이에만 한정되는 것은 아니다.According to an exemplary embodiment of the present specification, the intermediates A-1 and A-2 may be prepared by the following Schemes 9 and 10, but are not limited thereto.
[반응식 9]Scheme 9
Figure PCTKR2018001809-appb-I000090
Figure PCTKR2018001809-appb-I000090
[반응식 10] Scheme 10
Figure PCTKR2018001809-appb-I000091
Figure PCTKR2018001809-appb-I000091
상기 반응식 9 및 10에 있어서, X1 및 R14의 정의는 상기 화학식 1에서 정의한 바와 동일하다.In Schemes 9 and 10, the definition of X1 and R14 is the same as defined in the formula (1).
제조예 1. 화합물 A-1-1의 합성Preparation Example 1 Synthesis of Compound A-1-1
Figure PCTKR2018001809-appb-I000092
Figure PCTKR2018001809-appb-I000092
둥근바닥 플라스크에 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘(10g, 0.04mol), 페닐보론산(4.8g, 0.04mol), 탄산칼슘(8.3g, 0.06mol)과 Pd(PPh3)4(1.8g, 4mol%)을 무수 테트라하이드로퓨란과 물에 녹인 뒤 80℃ 온도조건에서 4시간 동안 환류시켰다. 반응이 종료되면 반응물의 온도를 상온으로 식히고, 클로로포름으로 추출하였다. 추출된 유기층은 무수 황산마그네슘으로 수분제거 후 에틸아세테이트(Ethyl acetate)로 재결정하여 화합물 A-1-1(9.53g, 82%)을 얻었다.In a round bottom flask, 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine (10 g, 0.04 mol), phenylboronic acid (4.8 g, 0.04 mol), calcium carbonate (8.3 g, 0.06 mol) and Pd (PPh 3 ) 4 (1.8 g, 4 mol%) were dissolved in anhydrous tetrahydrofuran and water and refluxed at 80 ° C. for 4 hours. After the reaction was completed, the reaction was cooled to room temperature and extracted with chloroform. The extracted organic layer was removed with anhydrous magnesium sulfate, and then recrystallized with ethyl acetate to obtain compound A-1-1 (9.53 g, 82%).
제조예 2. 화합물 A-1-2의 합성Preparation Example 2 Synthesis of Compound A-1-2
Figure PCTKR2018001809-appb-I000093
Figure PCTKR2018001809-appb-I000093
상기 제조예 1에서 페닐보론산 대신에 1-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-1-2를 얻었다.Compound A-1-2 was obtained in the same manner as in Production Example 1, except that 1-naphthylboronic acid was used instead of phenylboronic acid.
제조예 3. 화합물 A-1-3의 합성Preparation Example 3 Synthesis of Compound A-1-3
Figure PCTKR2018001809-appb-I000094
Figure PCTKR2018001809-appb-I000094
상기 제조예 1에서 페닐보론산 대신에 2-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-1-3를 얻었다.Compound A-1-3 was obtained in the same manner as in Production Example 1, except that 2-naphthylboronic acid was used instead of phenylboronic acid.
제조예 4. 화합물 A-1-4의 합성Preparation Example 4 Synthesis of Compound A-1-4
Figure PCTKR2018001809-appb-I000095
Figure PCTKR2018001809-appb-I000095
상기 제조예 1에서 페닐보론산 대신에 [1,1'-비페닐]-4-일보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-1-4를 얻었다.Compound A-1-4 was obtained in the same manner as in Production Example 1, except that [1,1'-biphenyl] -4-ylboronic acid was used instead of phenylboronic acid.
제조예 5. 화합물 A-2-1의 합성Preparation Example 5 Synthesis of Compound A-2-1
Figure PCTKR2018001809-appb-I000096
Figure PCTKR2018001809-appb-I000096
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[3,2-d]피리미딘을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-2-1를 얻었다.Except that 2,4-dichlorobenzofuro [3,2-d] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1. Compound A-2-1 was obtained in the same manner.
제조예 6. 화합물 A-2-2의 합성Preparation Example 6 Synthesis of Compound A-2-2
Figure PCTKR2018001809-appb-I000097
Figure PCTKR2018001809-appb-I000097
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[3,2-d]피리미딘을 사용하고 페닐보론산 대신 1-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-2-2를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [3,2- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-2-2 was obtained by the same method except that 1-naphthylboronic acid was used instead of the acid.
제조예 7. 화합물 A-2-3의 합성Preparation Example 7 Synthesis of Compound A-2-3
Figure PCTKR2018001809-appb-I000098
Figure PCTKR2018001809-appb-I000098
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[3,2-d]피리미딘을 사용하고 페닐보론산 대신 2-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-2-3를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [3,2- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-2-3 was obtained by the same method except that 2-naphthylboronic acid was used instead of the acid.
제조예 8. 화합물 A-2-4의 합성Preparation Example 8 Synthesis of Compound A-2-4
Figure PCTKR2018001809-appb-I000099
Figure PCTKR2018001809-appb-I000099
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[3,2-d]피리미딘을 사용하고 페닐보론산 대신 [1,1'-비페닐]-4-일보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-2-4를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [3,2- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-2-4 was obtained in the same manner except that [1,1'-biphenyl] -4-ylboronic acid was used instead of the acid.
제조예 9. 화합물 A-3-1의 합성Preparation Example 9 Synthesis of Compound A-3-1
Figure PCTKR2018001809-appb-I000100
Figure PCTKR2018001809-appb-I000100
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조[4,5]티에노[2,3-d]피리미딘을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-3-1를 얻었다.2,4-dichlorobenzo [4,5] thieno [2,3- d ] pyrimidine instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1 Compound A-3-1 was obtained in the same manner except for using.
제조예 10. 화합물 A-3-2의 합성Preparation Example 10 Synthesis of Compound A-3-2
Figure PCTKR2018001809-appb-I000101
Figure PCTKR2018001809-appb-I000101
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조[4,5]티에노[2,3-d]피리미딘을 사용하고 페닐보론산 대신 1-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-3-2를 얻었다.2,4-dichlorobenzo [4,5] thieno [2,3- d ] pyrimidine instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1 Compound A-3-2 was obtained in the same manner except for using 1-naphthylboronic acid instead of phenylboronic acid.
제조예 11. 화합물 A-3-3의 합성Preparation Example 11 Synthesis of Compound A-3-3
Figure PCTKR2018001809-appb-I000102
Figure PCTKR2018001809-appb-I000102
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조[4,5]티에노[2,3-d]피리미딘을 사용하고 페닐보론산 대신 2-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-3-3를 얻었다.2,4-dichlorobenzo [4,5] thieno [2,3- d ] pyrimidine instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1 Compound A-3-3 was obtained in the same manner except for using 2-naphthylboronic acid instead of phenylboronic acid.
제조예 12. 화합물 A-3-4의 합성Preparation Example 12 Synthesis of Compound A-3-4
Figure PCTKR2018001809-appb-I000103
Figure PCTKR2018001809-appb-I000103
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조[4,5]티에노[2,3-d]피리미딘을 사용하고 페닐보론산 대신 [1,1'-비페닐]-4-일보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-3-4를 얻었다.2,4-dichlorobenzo [4,5] thieno [2,3- d ] pyrimidine instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1 Compound A-3-4 was obtained in the same manner except for using [1,1'-biphenyl] -4-ylboronic acid instead of phenylboronic acid.
제조예 13. 화합물 A-4-1의 합성Preparation Example 13 Synthesis of Compound A-4-1
Figure PCTKR2018001809-appb-I000104
Figure PCTKR2018001809-appb-I000104
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[2,3-d]피리미딘을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-4-1를 얻었다.Except that 2,4-dichlorobenzofuro [2,3- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine in Preparation Example 1. Compound A-4-1 was obtained in the same manner.
제조예 14. 화합물 A-4-2의 합성Preparation Example 14 Synthesis of Compound A-4-2
Figure PCTKR2018001809-appb-I000105
Figure PCTKR2018001809-appb-I000105
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[2,3-d]피리미딘을 사용하고 페닐보론산 대신에 1-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-4-2를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [2,3- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-4-2 was obtained in the same manner except that 1-naphthylboronic acid was used instead of the acid.
제조예 15. 화합물 A-4-3의 합성Preparation Example 15 Synthesis of Compound A-4-3
Figure PCTKR2018001809-appb-I000106
Figure PCTKR2018001809-appb-I000106
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[2,3-d]피리미딘을 사용하고 페닐보론산 대신에 2-나프틸보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-4-3를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [2,3- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-4-3 was obtained in the same manner except that 2-naphthylboronic acid was used instead of the acid.
제조예 16. 화합물 A-4-4의 합성Preparation Example 16 Synthesis of Compound A-4-4
Figure PCTKR2018001809-appb-I000107
Figure PCTKR2018001809-appb-I000107
상기 제조예 1에서 2,4-디클로로벤조[4,5]티에노[3,4-d]피리미딘 대신 2,4-디클로로벤조퓨로[2,3-d]피리미딘을 사용하고 페닐보론산 대신에 [1,1'-비페닐]-4-일보론산을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 A-4-4를 얻었다.In Preparation Example 1, 2,4-dichlorobenzofuro [2,3- d ] pyrimidine was used instead of 2,4-dichlorobenzo [4,5] thieno [3,4- d ] pyrimidine and phenylborone. Compound A-4-4 was obtained in the same manner except that [1,1'-biphenyl] -4-ylboronic acid was used instead of the acid.
제조예 17. 화합물 B-(a)-1의 합성Preparation Example 17 Synthesis of Compound B- (a) -1
Figure PCTKR2018001809-appb-I000108
Figure PCTKR2018001809-appb-I000108
둥근바닥 플라스크에 화합물 A-1-1(10g, 0.034mol)과 5,6-디하이드로인돌로[2,3-b]카바졸(8.6g, 0.034mol), 인산칼륨(14.3g, 0.067mol)을 N,N-디메틸아세트아미드(N,N-Dimethylacetamide) 100ml에 녹이고 160℃ 온도조건에서 1시간 동안 환류시켰다. 반응이 종료되면 온도를 상온으로 식히고, 반응물을 물에 부어 고체를 석출시킨 후, 여과하였다. 여과된 고체를 클로로포름에 녹여 추출하였다. 추출된 유기층은 무수 황산마그네슘으로 수분제거 후 에틸아세테이트(Ethyl acetate)로 재결정하여 화합물 B-(a)-1(14.8g, 85%)을 얻었다.Compound A-1-1 (10 g, 0.034 mol), 5,6-dihydroindolo [2,3- b ] carbazole (8.6 g, 0.034 mol) and potassium phosphate (14.3 g, 0.067 mol) in a round bottom flask ) of N, N - dissolved in dimethylacetamide (N, N -Dimethylacetamide) 100ml was refluxed for 1 hour at 160 ℃ temperature conditions. After the reaction was completed, the temperature was cooled to room temperature, the reaction was poured into water to precipitate a solid, and then filtered. The filtered solid was dissolved in chloroform and extracted. The extracted organic layer was dried with anhydrous magnesium sulfate, and then recrystallized with ethyl acetate to obtain compound B- (a) -1 (14.8g, 85%).
제조예 18. 화합물 B-(a)-2의 합성Preparation Example 18 Synthesis of Compound B- (a) -2
Figure PCTKR2018001809-appb-I000109
Figure PCTKR2018001809-appb-I000109
상기 제조예 17에서 화합물 A-1-1 대신 화합물 A-2-2을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(a)-2를 얻었다.Compound B- (a) -2 was obtained in the same manner as in Example 17, except that Compound A-2-2 was used instead of Compound A-1-1.
제조예 19. 화합물 B-(b)-1의 합성Preparation Example 19 Synthesis of Compound B- (b) -1
Figure PCTKR2018001809-appb-I000110
Figure PCTKR2018001809-appb-I000110
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,11-디하이드로인돌로[3,2-b]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-3-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(b)-1를 얻었다.In Preparation Example 17, 5,11-dihydroindolo [3,2- b ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (b) -1 was obtained in the same manner except that compound A-3-2 was used.
제조예 20. 화합물 B-(b)-2의 합성Preparation Example 20 Synthesis of Compound B- (b) -2
Figure PCTKR2018001809-appb-I000111
Figure PCTKR2018001809-appb-I000111
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,11-디하이드로인돌로[3,2-b]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-4-3를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(b)-2를 얻었다.In Preparation Example 17, 5,11-dihydroindolo [3,2- b ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (b) -2 was obtained in the same manner except that compound A-4-3 was used.
제조예 21. 화합물 B-(c)-1의 합성Preparation Example 21 Synthesis of Compound B- (c) -1
Figure PCTKR2018001809-appb-I000112
Figure PCTKR2018001809-appb-I000112
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,8-디하이드로인돌로[2,3-c]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-2-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(c)-1를 얻었다.In Preparation Example 17, 5,8-dihydroindolo [2,3- c ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (c) -1 was obtained in the same manner except that compound A-2-2 was used.
제조예 22. 화합물 B-(c)-2의 합성Preparation Example 22 Synthesis of Compound B- (c) -2
Figure PCTKR2018001809-appb-I000113
Figure PCTKR2018001809-appb-I000113
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,8-디하이드로인돌로[2,3-c]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-3-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(c)-2를 얻었다.In Preparation Example 17, 5,8-dihydroindolo [2,3- c ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (c) -2 was obtained in the same manner except that compound A-3-1 was used.
제조예 23. 화합물 B-(d)-1의 합성Preparation Example 23 Synthesis of Compound B- (d) -1
Figure PCTKR2018001809-appb-I000114
Figure PCTKR2018001809-appb-I000114
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,12-디하이드로인돌로[3,2-a]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-1-3을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(d)-1를 얻었다.In Preparation Example 17, 5,12-dihydroindolo [3,2- a ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (d) -1 was obtained in the same manner except that compound A-1-3 was used.
제조예 24. 화합물 B-(d)-2의 합성Preparation Example 24 Synthesis of Compound B- (d) -2
Figure PCTKR2018001809-appb-I000115
Figure PCTKR2018001809-appb-I000115
상기 제조예 17에서 5,6-디하이드로인돌로[2,3-b]카바졸 대신 5,12-디하이드로인돌로[3,2-a]카바졸을 사용하고 화합물 A-1-1 대신 화합물 A-4-1을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 B-(d)-2를 얻었다.In Preparation Example 17, 5,12-dihydroindolo [3,2- a ] carbazole was used instead of 5,6-dihydroindolo [2,3- b ] carbazole and Compound A-1-1 was used instead. Compound B- (d) -2 was obtained in the same manner except that compound A-4-1 was used.
합성예 1. 화합물 1의 합성 Synthesis Example 1. Synthesis of Compound 1
Figure PCTKR2018001809-appb-I000116
Figure PCTKR2018001809-appb-I000116
둥근바닥 플라스크에 화합물 B-(a)-1(10g, 0.019mol), 1-브로모나프탈렌(4g, 0.019mol)과 인산칼륨(8.2g, 0.038mol)을 넣고 환류시키면서 비스(트라이터셔리부틸포스핀)팔라듐(0.02g, 0.2mol%)을 넣고 추가로 4시간 환류시켰다. 반응이 종료되면 온도를 상온으로 식히고, 석출된 고체를 여과하였다. 이 후, 여과된 고체를 클로로포름에 녹여 추출하였다. 추출된 유기층은 무수 황산마그네슘으로 수분제거 후 에틸아세테이트(Ethyl acetate)로 재결정하여 화합물 1(구체예 1-2) 9.7g(78%)을 얻었다. ([M+H]=643)Compound B- (a) -1 (10 g, 0.019 mol), 1-bromonaphthalene (4 g, 0.019 mol) and potassium phosphate (8.2 g, 0.038 mol) were added to a round-bottomed flask, and the mixture was refluxed. Phosphine) palladium (0.02 g, 0.2 mol%) was added thereto, and the mixture was further refluxed for 4 hours. After the reaction was completed, the temperature was cooled to room temperature, and the precipitated solid was filtered. Thereafter, the filtered solid was dissolved in chloroform and extracted. The extracted organic layer was removed with anhydrous magnesium sulfate, and then recrystallized with ethyl acetate to obtain 9.7 g (78%) of compound 1 (specific example 1-2). ([M + H] = 643)
도 3은 상기 합성예 1에서 제조된 화합물 1의 질량분석 스펙트럼이다.3 is a mass spectrometry spectrum of Compound 1 prepared in Synthesis Example 1.
합성예 2. 화합물 2의 합성 Synthesis Example 2 Synthesis of Compound 2
Figure PCTKR2018001809-appb-I000117
Figure PCTKR2018001809-appb-I000117
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로피리미딘을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 2(구체예 1-12)를 얻었다. ([M+H]=595)Compound 2 (Specific Example 1-12) was obtained in the same manner as in Synthesis Example 1, except that 2-chloropyrimidine was used instead of 1-bromonaphthalene. ([M + H] = 595)
도 4는 상기 합성예 2에서 제조된 화합물 2의 질량분석 스펙트럼이다.4 is a mass spectrum of Compound 2 prepared in Synthesis Example 2.
합성예 3. 화합물 3의 합성 Synthesis Example 3 Synthesis of Compound 3
Figure PCTKR2018001809-appb-I000118
Figure PCTKR2018001809-appb-I000118
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로-4,6-디페닐-1,3,5-트리아진을 사용한 것을 제외하고는 같은 방법으로 하여 화합물 3(구체예 1-17)을 얻었다. ([M+H]=748)Compound 3 (Specific Example 1-17) was prepared in the same manner as in Synthesis Example 1, except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 1-bromonaphthalene. Got it. ([M + H] = 748)
도 5는 상기 합성예 3에서 제조된 화합물 3의 질량분석 스펙트럼이다.5 is a mass spectrometry spectrum of Compound 3 prepared in Synthesis Example 3.
합성예 4. 화합물 4의 합성 Synthesis Example 4 Synthesis of Compound 4
Figure PCTKR2018001809-appb-I000119
Figure PCTKR2018001809-appb-I000119
상기 합성예 1에서 1-브로모나프탈렌 대신 1-브로모벤젠을 사용하고 화합물 B-(a)-1 대신 화합물 B-(a)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 4(구체예 1-120)를 얻었다. ([M+H]=628)Compound 4 (spheres) in the same manner as in Synthesis Example 1 except that 1-bromobenzene was used instead of 1-bromonaphthalene and compound B- (a) -2 was used instead of compound B- (a) -1 Example 1-120) was obtained. ([M + H] = 628)
도 6은 상기 합성예 4에서 제조된 화합물 4의 질량분석 스펙트럼이다.6 is a mass spectrum of Compound 4 prepared in Synthesis Example 4.
합성예 5. 화합물 5의 합성 Synthesis Example 5 Synthesis of Compound 5
Figure PCTKR2018001809-appb-I000120
Figure PCTKR2018001809-appb-I000120
상기 합성예 1에서 1-브로모나프탈렌 대신 9-브로모페난트렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(a)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 5(구체예 1-124)를 얻었다. ([M+H]=727)Compound 5 (In the same manner as in Synthesis Example 1 except that 9-bromophenanthrene was used instead of 1-bromonaphthalene and compound B- (a) -2 was used instead of compound B- (a) -1) Example 1-124) was obtained. ([M + H] = 727)
도 7은 상기 합성예 5에서 제조된 화합물 5의 질량분석 스펙트럼이다.7 is a mass spectrum of Compound 5 prepared in Synthesis Example 5.
합성예 6. 화합물 6의 합성 Synthesis Example 6 Synthesis of Compound 6
Figure PCTKR2018001809-appb-I000121
Figure PCTKR2018001809-appb-I000121
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로-4-페닐퀴나졸린을 사용하고 화합물 B-(a)-1 대신 화합물 B-(a)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 6(구체예 1-134)을 얻었다. ([M+H]=755)In the same manner as in Synthesis Example 1 except that 2-chloro-4-phenylquinazoline was used instead of 1-bromonaphthalene and compound B- (a) -2 was used instead of compound B- (a) -1. Compound 6 (specific example 1-134) was obtained. ([M + H] = 755)
도 8은 상기 합성예 6에서 제조된 화합물 6의 질량분석 스펙트럼이다.8 is a mass spectrum of Compound 6 prepared in Synthesis Example 6.
합성예 7. 화합물 7의 합성 Synthesis Example 7 Synthesis of Compound 7
Figure PCTKR2018001809-appb-I000122
Figure PCTKR2018001809-appb-I000122
상기 합성예 1에서 1-브로모나프탈렌 대신 3-클로로플루오란텐을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 7(구체예 2-74)을 얻었다. ([M+H]=768)Compound 7 (In the same manner as in Synthesis Example 1 except that 3-chlorofluoranthene was used instead of 1-bromonaphthalene and compound B- (b) -1 was used instead of compound B- (a) -1) Example 2-74) was obtained. ([M + H] = 768)
도 9는 상기 합성예 7에서 제조된 화합물 7의 질량분석 스펙트럼이다.9 is a mass spectrum of Compound 7 prepared in Synthesis Example 7.
합성예 8. 화합물 8의 합성 Synthesis Example 8 Synthesis of Compound 8
Figure PCTKR2018001809-appb-I000123
Figure PCTKR2018001809-appb-I000123
상기 합성예 1에서 1-브로모나프탈렌 대신 1-브로모파이렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 8(구체예 2-76)을 얻었다. ([M+H]=768)Compound 8 (In the same manner as in Synthesis Example 1 except that 1-bromopyrene was used instead of 1-bromonaphthalene and compound B- (b) -1 was used instead of compound B- (a) -1) Example 2-76) was obtained. ([M + H] = 768)
도 10은 상기 합성예 8에서 제조된 화합물 8의 질량분석 스펙트럼이다.10 is a mass spectrum of Compound 8 prepared in Synthesis Example 8.
합성예 9. 화합물 9의 합성 Synthesis Example 9. Synthesis of Compound 9
Figure PCTKR2018001809-appb-I000124
Figure PCTKR2018001809-appb-I000124
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로-4-(나프탈렌-2-일)퀴나졸린을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 9(구체예 2-84)를 얻었다. ([M+H]=822)Except for using 2-chloro-4- (naphthalen-2-yl) quinazolin instead of 1-bromonaphthalene in Synthesis Example 1 and using compound B- (b) -1 instead of compound B- (a) -1 In the same manner, compound 9 (specific example 2-84) was obtained. ([M + H] = 822)
도 11은 상기 합성예 9에서 제조된 화합물 9의 질량분석 스펙트럼이다.FIG. 11 is a mass spectrum of Compound 9 prepared in Synthesis Example 9.
합성예 10. 화합물 10의 합성 Synthesis Example 10 Synthesis of Compound 10
Figure PCTKR2018001809-appb-I000125
Figure PCTKR2018001809-appb-I000125
상기 합성예 1에서 1-브로모나프탈렌 대신 1-브로모벤젠을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-2를 사용한 것을 제외하고는 상기 3-1)과 같은 방법으로 하여 화합물 10(구체예 2-188)을 얻었다. ([M+H]=628)The same method as in 3-1) except that 1-bromobenzene was used instead of 1-bromonaphthalene and compound B- (b) -2 was used instead of compound B- (a) -1 in Synthesis Example 1. Compound 10 (specific example 2-188) was obtained. ([M + H] = 628)
도 12는 상기 합성예 10에서 제조된 화합물 10의 질량분석 스펙트럼이다.12 is a mass spectrum of Compound 10 prepared in Synthesis Example 10.
합성예 11. 화합물 11의 합성 Synthesis Example 11. Synthesis of Compound 11
Figure PCTKR2018001809-appb-I000126
Figure PCTKR2018001809-appb-I000126
상기 합성예 1에서 1-브로모나프탈렌 대신 2-브로모트라이페닐렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 11(구체예 2-194)을 얻었다. ([M+H]=778) Compound 11 was prepared in the same manner as in Synthesis Example 1, except that 2-bromotriphenylene was used instead of 1-bromonaphthalene and compound B- (b) -2 was used instead of compound B- (a) -1. (Specific Example 2-194) was obtained. ([M + H] = 778)
도 13은 상기 합성예 11에서 제조된 화합물 11의 질량분석 스펙트럼이다.FIG. 13 is a mass spectrum of Compound 11 prepared in Synthesis Example 11.
합성예 12. 화합물 12의 합성 Synthesis Example 12 Synthesis of Compound 12
Figure PCTKR2018001809-appb-I000127
Figure PCTKR2018001809-appb-I000127
상기 합성예 1에서 1-브로모나프탈렌 대신 4-클로로피리미딘을 사용하고 화합물 B-(a)-1 대신 화합물 B-(b)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 12(구체예 2-200)를 얻었다. ([M+H]=629)Compound 12 (spheres) was prepared in the same manner as in Synthesis Example 1, except that 4-chloropyrimidine was used instead of 1-bromonaphthalene and compound B- (b) -2 was used instead of compound B- (a) -1. Example 2-200) was obtained. ([M + H] = 629)
도 14는 상기 합성예 12에서 제조된 화합물 12의 질량분석 스펙트럼이다.14 is a mass spectrum of Compound 12 prepared in Synthesis Example 12.
합성예 13. 화합물 13의 합성 Synthesis Example 13 Synthesis of Compound 13
Figure PCTKR2018001809-appb-I000128
Figure PCTKR2018001809-appb-I000128
상기 합성예 1에서 1-브로모나프탈렌 대신 2-브로모나프탈렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 13(구체예 3-122)를 얻었다. ([M+H]=678)Compound 13 (Sphere) was prepared in the same manner as in Synthesis Example 1, except that 2-bromonaphthalene was used instead of 1-bromonaphthalene and compound B- (c) -1 was used instead of compound B- (a) -1. Example 3-122) was obtained. ([M + H] = 678)
도 15는 상기 합성예 13에서 제조된 화합물 13의 질량분석 스펙트럼이다.15 is a mass spectrum of Compound 13 prepared in Synthesis Example 13.
합성예 14. 화합물 14의 합성 Synthesis Example 14 Synthesis of Compound 14
Figure PCTKR2018001809-appb-I000129
Figure PCTKR2018001809-appb-I000129
상기 합성예 1에서 1-브로모나프탈렌 대신 3-클로로피리딘 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 14(구체예 3-129)를 얻었다. ([M+H]=628)Compound 14 (Synthesis Example 3) was used in the same manner as in Synthesis Example 1, except that 3-chloropyridine was used instead of 1-bromonaphthalene and compound B- (c) -1 was used instead of compound B- (a) -1. -129). ([M + H] = 628)
도 16은 상기 합성예 14에서 제조된 화합물 14의 질량분석 스펙트럼이다.FIG. 16 is a mass spectrum of Compound 14 prepared in Synthesis Example 14.
합성예 15. 화합물 15의 합성 Synthesis Example 15 Synthesis of Compound 15
Figure PCTKR2018001809-appb-I000130
Figure PCTKR2018001809-appb-I000130
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로퀴나졸린을 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 15(구체예 3-133)를 얻었다. ([M+H]=679)Compound 15 (Sphere) was synthesized in the same manner as in Synthesis Example 1, except that 2-chloroquinazolin was used instead of 1-bromonaphthalene and compound B- (c) -1 was used instead of compound B- (a) -1. Example 3-133) was obtained. ([M + H] = 679)
도 17은 상기 합성예 15에서 제조된 화합물 15의 질량분석 스펙트럼이다.17 is a mass spectrum of Compound 15 prepared in Synthesis Example 15.
합성예 16. 화합물 16의 합성 Synthesis Example 16 Synthesis of Compound 16
Figure PCTKR2018001809-appb-I000131
Figure PCTKR2018001809-appb-I000131
상기 합성예 1에서 1-브로모나프탈렌 대신 9-브로모페난트렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 16(구체예 3-56)를 얻었다. ([M+H]=693)Compound 16 (In the same manner as in Synthesis Example 1 except that 9-bromophenanthrene was used instead of 1-bromonaphthalene and compound B- (c) -2 was used instead of compound B- (a) -1) Example 3-56) was obtained. ([M + H] = 693)
도 18은 상기 합성예 16에서 제조된 화합물 16의 질량분석 스펙트럼이다.FIG. 18 is a mass spectrum of Compound 16 prepared in Synthesis Example 16.
합성예 17. 화합물 17의 합성 Synthesis Example 17 Synthesis of Compound 17
Figure PCTKR2018001809-appb-I000132
Figure PCTKR2018001809-appb-I000132
상기 합성예 1에서 1-브로모나프탈렌 대신 4-클로로피리딘 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 17(구체예 3-62)을 얻었다. ([M+H]=595)Compound 17 (Synthesis example 3) in the same manner as in Synthesis Example 1, except that 4-chloropyridine was used instead of 1-bromonaphthalene and compound B- (c) -2 was used instead of compound B- (a) -1. -62). ([M + H] = 595)
도 19는 상기 합성예 17에서 제조된 화합물 17의 질량분석 스펙트럼이다.19 is a mass spectrum of Compound 17 prepared in Synthesis Example 17. FIG.
합성예 18. 화합물 18의 합성 Synthesis Example 18 Synthesis of Compound 18
Figure PCTKR2018001809-appb-I000133
Figure PCTKR2018001809-appb-I000133
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로-4,6-디페닐-1,3,5-트리아진을 사용하고 화합물 B-(a)-1 대신 화합물 B-(c)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 18(구체예 3-68)을 얻었다. ([M+H]=749)In Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of 1-bromonaphthalene and compound B- (c) -2 instead of compound B- (a) -1. Compound 18 (Specific Example 3-68) was obtained in the same manner except for using. ([M + H] = 749)
도 20은 상기 합성예 18에서 제조된 화합물 18의 질량분석 스펙트럼이다.20 is a mass spectrometry spectrum of Compound 18 prepared in Synthesis Example 18.
합성예 19. 화합물 19의 합성 Synthesis Example 19 Synthesis of Compound 19
Figure PCTKR2018001809-appb-I000134
Figure PCTKR2018001809-appb-I000134
상기 합성예 1에서 1-브로모나프탈렌 대신 2-브로모나프탈렌을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 19(구체예 4-37)를 얻었다. ([M+H]=693)Compound 19 (spheres) in the same manner as in Synthesis Example 1 except that 2-bromonaphthalene was used instead of 1-bromonaphthalene and compound B- (d) -1 was used instead of compound B- (a) -1 Example 4-37) was obtained. ([M + H] = 693)
도 21은 상기 합성예 19에서 제조된 화합물 19의 질량분석 스펙트럼이다.FIG. 21 is a mass spectrum of Compound 19 prepared in Synthesis Example 19.
합성예 20. 화합물 20의 합성Synthesis Example 20 Synthesis of Compound 20
Figure PCTKR2018001809-appb-I000135
Figure PCTKR2018001809-appb-I000135
상기 합성예 1에서 1-브로모나프탈렌 대신 4-브로모-1,1'-비페닐을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 20(구체예 4-38)을 얻었다. ([M+H]=719)Except for the use of 4-bromo-1,1'-biphenyl instead of 1-bromonaphthalene in Synthesis Example 1 and compound B- (d) -1 instead of compound B- (a) -1 Compound 20 (specific example 4-38) was obtained by the method. ([M + H] = 719)
도 22는 상기 합성예 20에서 제조된 화합물 20의 질량분석 스펙트럼이다.22 is a mass spectrum of Compound 20 prepared in Synthesis Example 20.
합성예 21. 화합물 21의 합성 Synthesis Example 21 Synthesis of Compound 21
Figure PCTKR2018001809-appb-I000136
Figure PCTKR2018001809-appb-I000136
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로-4-페닐퀴나졸린을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-1를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 21(구체예 4-49)을 얻었다. ([M+H]=772)In the same manner as in Synthesis Example 1 except that 2-chloro-4-phenylquinazoline was used instead of 1-bromonaphthalene and compound B- (d) -1 was used instead of compound B- (a) -1. Compound 21 (specific example 4-49) was obtained. ([M + H] = 772)
도 23은 상기 합성예 21에서 제조된 화합물 21의 질량분석 스펙트럼이다.23 is a mass spectrum of Compound 21 prepared in Synthesis Example 21.
합성예 22. 화합물 22의 합성 Synthesis Example 22 Synthesis of Compound 22
Figure PCTKR2018001809-appb-I000137
Figure PCTKR2018001809-appb-I000137
상기 합성예 1에서 1-브로모나프탈렌 대신 4-브로모-1,1'-비페닐을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 22(구체예 4-157)를 얻었다. ([M+H]=654)Except for using 4-bromo-1,1'-biphenyl instead of 1-bromonaphthalene in Synthesis Example 1 and compound B- (d) -2 instead of compound B- (a) -1 Compound 22 (specific example 4-157) was obtained by the method. ([M + H] = 654)
도 24는 상기 합성예 22에서 제조된 화합물 22의 질량분석 스펙트럼이다.24 is a mass spectrometry spectrum of Compound 22 prepared in Synthesis Example 22.
합성예 23. 화합물 23의 합성 Synthesis Example 23 Synthesis of Compound 23
Figure PCTKR2018001809-appb-I000138
Figure PCTKR2018001809-appb-I000138
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로피리딘을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 23(구체예 4-162)를 얻었다. ([M+H]=578)Compound 23 (Synthesis example) was used in the same manner as in Synthesis Example 1, except that 2-chloropyridine was used instead of 1-bromonaphthalene and compound B- (d) -2 was substituted for compound B- (a) -1. 4-162). ([M + H] = 578)
도 25는 상기 합성예 23에서 제조된 화합물 23의 질량분석 스펙트럼이다.FIG. 25 is a mass spectrum of Compound 23 prepared in Synthesis Example 23.
합성예 24. 화합물 24의 합성 Synthesis Example 24 Synthesis of Compound 24
Figure PCTKR2018001809-appb-I000139
Figure PCTKR2018001809-appb-I000139
상기 합성예 1에서 1-브로모나프탈렌 대신 2-클로로피리미딘을 사용하고 화합물 B-(a)-1 대신 화합물 B-(d)-2를 사용한 것을 제외하고는 같은 방법으로 하여 화합물 24(구체예 4-165)를 얻었다. ([M+H]=579)Compound 24 (Sphere) was prepared in the same manner as in Synthesis Example 1, except that 2-chloropyrimidine was used instead of 1-bromonaphthalene and compound B- (d) -2 was used instead of compound B- (a) -1. Example 4-165) was obtained. ([M + H] = 579)
도 26은 상기 합성예 24에서 제조된 화합물 24의 질량분석 스펙트럼이다.FIG. 26 is a mass spectrum of Compound 24 prepared in Synthesis Example 24.
<유기 발광 소자의 제작><Production of Organic Light-Emitting Element>
비교예 1Comparative Example 1
ITO(인듐 주석 산화물)가 1,000 Å의 두께로 박막 코팅된 유리 기판을 분산제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀리포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후, 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후, 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 kPa was put in distilled water in which a dispersant was dissolved, and ultrasonically washed. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol was carried out and dried, and then transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.
기판을 진공 챔버에 장착한 후 베이스 압력이 1 X 10-6 torr가 되도록 한 후 유기물을 상기 ITO위에 정공 주입 및 수송층으로 하기 DNTPD (700 Å), 정공수송 및 전자차단층으로 하기 NPB (300Å), 일반적으로 적색 인광 호스트 물질로 많이 사용되고 있는 하기 CBP를 호스트로서(95 wt%) 사용하고, 도판트로서 상기 Dp-6 (5 wt%)를 공증착(300 Å)하며, 전자수송층으로 Alq3 (350 Å), 음극으로 LiF (5 Å), Al (1,000 Å)의 순서로 성막하였다. 상기의 과정에서 유기물의 증착속도는 1 Å/sec를 유지하였고, LiF는 0.2 Å/sec, 알루미늄은 3~7 Å/sec의 증착속도를 유지하였다. After mounting the substrate in the vacuum chamber, the base pressure was 1 X 10 -6 torr, and the organic material was formed as a hole injection and transport layer on the ITO, followed by DNTPD (700 kPa), hole transport and electron blocking layer, NPB (300 kPa). The following CBP, which is generally used as a red phosphorescent host material, is used as a host (95 wt%), and the Dp-6 (5 wt%) is co-deposited (300 Å) as a dopant, and Alq 3 is used as an electron transport layer. (350 kPa) and a cathode were formed in the order of LiF (5 kPa) and Al (1,000 kPa). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, LiF was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3 to 7 Å / sec.
Figure PCTKR2018001809-appb-I000140
Figure PCTKR2018001809-appb-I000140
비교예 2 내지 8Comparative Examples 2 to 8
상기 비교예 1에서 상기 CBP 대신 하기 화합물 A 내지 G를 각각 사용한 것을 제외하고는 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the following Compounds A to G were used instead of the CBP.
Figure PCTKR2018001809-appb-I000141
Figure PCTKR2018001809-appb-I000141
실시예 1 내지 24Examples 1 to 24
상기 비교예 1에서 상기 CBP 대신 상기 합성예 1 내지 24에서 제조된 화합물 1 내지 24를 각각 사용한 것을 제외하고는 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that Compounds 1 to 24 prepared in Synthesis Examples 1 to 24 were used instead of the CBP.
상기 비교예 1 내지 8 및 실시예 1 내지 24에서 제작한 유기 발광 소자에 10mA/cm2의 전류를 인가하여, 구동전압, 전류효율 및 수명을 측정하였으며, T95는 초기 휘도 대비 95%가 되는 시간을 측정한 것이다. 그 결과를 하기 표 1에 나타내었다.The driving voltage, current efficiency, and lifetime were measured by applying a current of 10 mA / cm 2 to the organic light emitting diodes manufactured in Comparative Examples 1 to 8 and Examples 1 to 24, and T95 was 95% of the initial luminance. Is measured. The results are shown in Table 1 below.
호스트 물질Host substance 구동전압(V)Driving voltage (V) 전류효율(cd/A)Current efficiency (cd / A) 수명(T95%@10mA/cm2)Lifespan (T95% @ 10mA / cm 2 )
비교예 1Comparative Example 1 CBPCBP 7.557.55 13.0713.07 5858
비교예 2Comparative Example 2 화합물 ACompound A 4.824.82 18.1218.12 7878
비교예 3Comparative Example 3 화합물 BCompound B 4.744.74 18.4218.42 7676
비교예 4Comparative Example 4 화합물 CCompound C 4.924.92 17.2517.25 8181
비교예 5Comparative Example 5 화합물 DCompound d 4.984.98 17.0317.03 8888
비교예 6Comparative Example 6 화합물 ECompound E 5.025.02 16.2216.22 9090
비교예 7Comparative Example 7 화합물 FCompound F 5.115.11 16.1016.10 9595
비교예 8Comparative Example 8 화합물 GCompound G 5.865.86 15.9615.96 9999
실시예 1Example 1 화합물 1Compound 1 4.274.27 22.8722.87 189189
실시예 2Example 2 화합물 2Compound 2 4.324.32 23.5923.59 178178
실시예 3Example 3 화합물 3Compound 3 4.154.15 24.0024.00 170170
실시예 4Example 4 화합물 4Compound 4 4.264.26 22.0522.05 195195
실시예 5Example 5 화합물 5Compound 5 4.164.16 23.7723.77 181181
실시예 6Example 6 화합물 6Compound 6 4.404.40 20.9920.99 198198
실시예 7Example 7 화합물 7Compound 7 4.244.24 24.5324.53 156156
실시예 8Example 8 화합물 8Compound 8 4.504.50 25.4425.44 120120
실시예 9Example 9 화합물 9Compound 9 4.104.10 19.2219.22 201201
실시예 10Example 10 화합물 10Compound 10 4.344.34 20.1320.13 179179
실시예 11Example 11 화합물 11Compound 11 4.124.12 22.1022.10 165165
실시예 12Example 12 화합물 12Compound 12 4.384.38 24.7324.73 133133
실시예 13Example 13 화합물 13Compound 13 4.134.13 22.1522.15 176176
실시예 14Example 14 화합물 14Compound 14 4.114.11 22.8422.84 170170
실시예 15Example 15 화합물 15Compound 15 4.164.16 23.0023.00 162162
실시예 16Example 16 화합물 16Compound 16 4.234.23 25.5725.57 124124
실시예 17Example 17 화합물 17Compound 17 4.284.28 25.8825.88 119119
실시예 18Example 18 화합물 18Compound 18 4.214.21 24.9924.99 135135
실시예 19Example 19 화합물 19Compound 19 3.873.87 27.9027.90 245245
실시예 20Example 20 화합물 20Compound 20 4.014.01 26.3126.31 203203
실시예 21Example 21 화합물 21Compound 21 4.114.11 27.1027.10 184184
실시예 22Example 22 화합물 22Compound 22 4.084.08 25.1125.11 188188
실시예 23Example 23 화합물 23Compound 23 4.134.13 26.2026.20 172172
실시예 24Example 24 화합물 24Compound 24 4.104.10 26.0426.04 177177
상기 표 1에 있어서, 상기 비교예 1은 종래의 발광층 호스트로 사용되는 상기 CBP를 사용한 유기 발광 소자이며, 상기 비교예 2 및 3은 상기 화학식 1의 R1 및 R2에 상기 화학식 2가 결합되는 화합물을 발광층의 호스트로 사용한 유기 발광 소자이다.In Table 1, Comparative Example 1 is an organic light emitting device using the CBP used as a conventional light emitting layer host, Comparative Examples 2 and 3 are a compound in which Formula 2 is bonded to R1 and R2 of Formula 1 An organic light emitting element used as a host of a light emitting layer.
또한, 비교예 4 및 5는 본원 화학식 1의 Y1위치에 카바졸이 결합되는 화합물을 사용한 유기 발광 소자이며, 비교예 6 내지 8은 본원 화학식 1의 Y3 위치에 인돌로카바졸 대신 치환된 아릴기가 결합된 화합물을 발광층의 호스트로 사용한 유기 발광 소자이다.Further, Comparative Examples 4 and 5 are organic light emitting devices using a compound in which carbazole is bonded to the Y 1 position of Chemical Formula 1 of the present application, and Comparative Examples 6 to 8 show an aryl group substituted for indolocarbazole at the Y 3 position of Chemical Formula 1 of the present application An organic light emitting device using the bonded compound as a host of the light emitting layer.
상기 실시예 1 내지 24의 유기 발광 소자는 본원 화학식 1의 Y2 또는 Y3 위치에 인돌로카바졸 즉, 상기 화학식 1의 R2 및 R3, 또는 R3 및 R4에 화학식 2가 결합되는 화합물을 발광층의 호스트로 사용한 유기 발광 소자이다.Examples 1 to 24 of the organic light emitting device is a host of the light emitting layer of the indolocarbazole in the Y2 or Y3 position of the general formula (1) of the present application, that is, a compound of formula 2 is bonded to R2 and R3, or R3 and R4 of It is the used organic light emitting element.
본원 화학식 1의 헤테로고리 화합물은 분자 내 전자 흐름이 원활하며, 입체장애가 적어 구조가 안정적이므로, 이를 사용한 상기 실시예 1 내지 24의 유기 발광 소자는 비교예 1 내지 8의 유기 발광 소자 보다 구동전압이 낮고, 효율이 우수하며, 수명이 긴 것을 알 수 있었다.The heterocyclic compound of Formula 1 of the present invention has a stable structure because the electron flow in the molecule is smooth, there are few steric hindrance, the organic light emitting device of Examples 1 to 24 using the same has a driving voltage than the organic light emitting device of Comparative Examples 1 to 8 It was found to be low, excellent in efficiency, and long in life.

Claims (10)

  1. 하기 화학식 1로 표시되는 헤테로고리 화합물:Heterocyclic compounds represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2018001809-appb-I000142
    Figure PCTKR2018001809-appb-I000142
    상기 화학식 1에 있어서,In Chemical Formula 1,
    X1은 O 또는 S이고,X 1 is O or S,
    L1은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 헤테로아릴렌기이며,L 1 is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
    Y1 및 Y3는 N이고, Y2는 CR13이며, Y4는 CR14이거나, Y2 및 Y4는 N이고, Y1은 CR14이고, Y3은 CR13이며,Y1 and Y3 are N, Y2 is CR13, Y4 is CR14, or Y2 and Y4 are N, Y1 is CR14, Y3 is CR13,
    상기 R13은 상기 L1과 결합하는 기이고, R13 is a group which binds to L1,
    R2 및 R3, 또는 R3 및 R4는 하기 화학식 2의 *와 결합하는 기이며, R2 and R3, or R3 and R4 is a group which binds to * of the formula (2),
    상기 R2 내지 R4 중 하기 화학식 2의 *와 결합하지 않는 기, R1, R5 내지 R12 및 R14는 서로 같거나 상이하고, 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 인접한 기는 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있고,The groups, R1, R5 to R12, and R14 which do not combine with * in Formula 2 of R2 to R4 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring,
    n은 1 또는 2이며,n is 1 or 2,
    n이 2 인 경우, 두 개의 L1은 서로 같거나 상이하고,when n is 2, two L1 are the same as or different from each other,
    [화학식 2][Formula 2]
    Figure PCTKR2018001809-appb-I000143
    Figure PCTKR2018001809-appb-I000143
    상기 화학식 2에 있어서,In Chemical Formula 2,
    *는 상기 화학식 1의 R2 및 R3, 또는 R3 및 R4와 결합하는 부위이며,* Is a site that binds to R2 and R3 of Formula 1, or R3 and R4,
    Ar1은 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이며,Ar1 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
    R15 내지 R18은 서로 같거나 상이하고, 각각 독립적으로 각각 독립적으로 수소; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이거나, 인접한 기는 서로 결합하여 치환 또는 비치환된 고리를 형성할 수 있다.R15 to R18 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or adjacent groups may combine with each other to form a substituted or unsubstituted ring.
  2. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 1-1 내지 1-4 중 어느 하나로 표시되는 것인 헤테로고리 화합물:The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 1-1 to 1-4:
    Figure PCTKR2018001809-appb-I000144
    Figure PCTKR2018001809-appb-I000144
    Figure PCTKR2018001809-appb-I000145
    Figure PCTKR2018001809-appb-I000145
    상기 화학식 1-1 내지 1-4에 있어서,In Chemical Formulas 1-1 to 1-4,
    X1, L1, n, Y1 내지 Y4, R1, R2 및 R4 내지 R12의 정의는 상기 화학식 1과 동일하고,X1, L1, n, Y1 to Y4, R1, R2 and R4 to R12 are the same as defined in Formula 1,
    Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하다.Ar 1 and R 15 to R 18 have the same definitions as in Formula 2 above.
  3. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 1-5 내지 1-12 중 어느 하나로 표시되는 것인 헤테로고리 화합물:The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 1-5 to 1-12:
    Figure PCTKR2018001809-appb-I000146
    Figure PCTKR2018001809-appb-I000146
    Figure PCTKR2018001809-appb-I000147
    Figure PCTKR2018001809-appb-I000147
    Figure PCTKR2018001809-appb-I000148
    Figure PCTKR2018001809-appb-I000148
    Figure PCTKR2018001809-appb-I000149
    Figure PCTKR2018001809-appb-I000149
    상기 화학식 1-5 내지 1-12에 있어서,In Chemical Formulas 1-5 to 1-12,
    X1, L1, n, R1, R2 및 R4 내지 R12의 정의는 상기 화학식 1과 동일하고,X1, L1, n, R1, R2 and R4 to R12 are the same as defined in Formula 1,
    Ar1 및 R15 내지 R18의 정의는 상기 화학식 2와 동일하며,Ar1 and R15 to R18 are the same as defined in Formula 2,
    R14는 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이다.R14 is a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.
  4. 청구항 1에 있어서, 상기 R14는 아릴기인 것인 헤테로고리 화합물.The heterocyclic compound according to claim 1, wherein R 14 is an aryl group.
  5. 청구항 1에 있어서, 상기 Ar1은 아릴기; 또는 아릴기로 치환 또는 비치환된 헤테로아릴기인 것인 헤테로고리 화합물.The method according to claim 1, wherein Ar1 is an aryl group; Or a heteroaryl group which is unsubstituted or substituted with an aryl group.
  6. 청구항 1에 있어서, 상기 화학식 1은 하기 화합물 중에서 선택되는 것인 헤테로고리 화합물:The heterocyclic compound according to claim 1, wherein Formula 1 is selected from the following compounds:
    Figure PCTKR2018001809-appb-I000150
    Figure PCTKR2018001809-appb-I000150
    Figure PCTKR2018001809-appb-I000151
    Figure PCTKR2018001809-appb-I000151
    Figure PCTKR2018001809-appb-I000152
    Figure PCTKR2018001809-appb-I000152
    Figure PCTKR2018001809-appb-I000153
    Figure PCTKR2018001809-appb-I000153
    Figure PCTKR2018001809-appb-I000154
    Figure PCTKR2018001809-appb-I000154
    Figure PCTKR2018001809-appb-I000155
    Figure PCTKR2018001809-appb-I000155
    Figure PCTKR2018001809-appb-I000156
    Figure PCTKR2018001809-appb-I000156
    Figure PCTKR2018001809-appb-I000157
    Figure PCTKR2018001809-appb-I000157
    Figure PCTKR2018001809-appb-I000158
    Figure PCTKR2018001809-appb-I000158
    Figure PCTKR2018001809-appb-I000159
    Figure PCTKR2018001809-appb-I000159
    Figure PCTKR2018001809-appb-I000160
    Figure PCTKR2018001809-appb-I000160
    Figure PCTKR2018001809-appb-I000161
    Figure PCTKR2018001809-appb-I000161
    Figure PCTKR2018001809-appb-I000162
    Figure PCTKR2018001809-appb-I000162
    Figure PCTKR2018001809-appb-I000163
    Figure PCTKR2018001809-appb-I000163
    Figure PCTKR2018001809-appb-I000164
    Figure PCTKR2018001809-appb-I000164
    Figure PCTKR2018001809-appb-I000165
    Figure PCTKR2018001809-appb-I000165
    Figure PCTKR2018001809-appb-I000166
    Figure PCTKR2018001809-appb-I000166
    Figure PCTKR2018001809-appb-I000167
    Figure PCTKR2018001809-appb-I000167
    Figure PCTKR2018001809-appb-I000168
    Figure PCTKR2018001809-appb-I000168
    Figure PCTKR2018001809-appb-I000169
    Figure PCTKR2018001809-appb-I000169
    Figure PCTKR2018001809-appb-I000170
    Figure PCTKR2018001809-appb-I000170
    Figure PCTKR2018001809-appb-I000171
    Figure PCTKR2018001809-appb-I000171
    Figure PCTKR2018001809-appb-I000172
    Figure PCTKR2018001809-appb-I000172
    Figure PCTKR2018001809-appb-I000173
    Figure PCTKR2018001809-appb-I000173
    Figure PCTKR2018001809-appb-I000174
    Figure PCTKR2018001809-appb-I000174
    Figure PCTKR2018001809-appb-I000175
    Figure PCTKR2018001809-appb-I000175
    Figure PCTKR2018001809-appb-I000176
    Figure PCTKR2018001809-appb-I000176
    Figure PCTKR2018001809-appb-I000177
    Figure PCTKR2018001809-appb-I000177
    Figure PCTKR2018001809-appb-I000178
    Figure PCTKR2018001809-appb-I000178
    Figure PCTKR2018001809-appb-I000179
    Figure PCTKR2018001809-appb-I000179
    Figure PCTKR2018001809-appb-I000180
    Figure PCTKR2018001809-appb-I000180
    Figure PCTKR2018001809-appb-I000181
    Figure PCTKR2018001809-appb-I000181
    Figure PCTKR2018001809-appb-I000182
    Figure PCTKR2018001809-appb-I000182
    Figure PCTKR2018001809-appb-I000183
    Figure PCTKR2018001809-appb-I000183
    Figure PCTKR2018001809-appb-I000184
    Figure PCTKR2018001809-appb-I000184
    Figure PCTKR2018001809-appb-I000185
    Figure PCTKR2018001809-appb-I000185
    Figure PCTKR2018001809-appb-I000186
    Figure PCTKR2018001809-appb-I000186
    Figure PCTKR2018001809-appb-I000187
    Figure PCTKR2018001809-appb-I000187
    Figure PCTKR2018001809-appb-I000188
    Figure PCTKR2018001809-appb-I000188
    Figure PCTKR2018001809-appb-I000189
    Figure PCTKR2018001809-appb-I000189
    Figure PCTKR2018001809-appb-I000190
    Figure PCTKR2018001809-appb-I000190
    Figure PCTKR2018001809-appb-I000191
    Figure PCTKR2018001809-appb-I000191
    Figure PCTKR2018001809-appb-I000192
    Figure PCTKR2018001809-appb-I000192
    Figure PCTKR2018001809-appb-I000193
    Figure PCTKR2018001809-appb-I000193
    Figure PCTKR2018001809-appb-I000194
    Figure PCTKR2018001809-appb-I000194
    Figure PCTKR2018001809-appb-I000195
    Figure PCTKR2018001809-appb-I000195
    Figure PCTKR2018001809-appb-I000196
    Figure PCTKR2018001809-appb-I000196
    Figure PCTKR2018001809-appb-I000197
    Figure PCTKR2018001809-appb-I000197
    Figure PCTKR2018001809-appb-I000198
    Figure PCTKR2018001809-appb-I000198
    Figure PCTKR2018001809-appb-I000199
    Figure PCTKR2018001809-appb-I000199
    Figure PCTKR2018001809-appb-I000200
    Figure PCTKR2018001809-appb-I000200
    Figure PCTKR2018001809-appb-I000201
    Figure PCTKR2018001809-appb-I000201
    Figure PCTKR2018001809-appb-I000202
    Figure PCTKR2018001809-appb-I000202
    Figure PCTKR2018001809-appb-I000203
    Figure PCTKR2018001809-appb-I000203
    Figure PCTKR2018001809-appb-I000204
    Figure PCTKR2018001809-appb-I000204
    Figure PCTKR2018001809-appb-I000205
    Figure PCTKR2018001809-appb-I000205
  7. 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1 층 이상은 청구항 1 내지 6 중 어느 한 항의 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound according to any one of claims 1 to 6. device.
  8. 청구항 7에 있어서, 상기 유기물층은 정공수송층을 포함하고, 상기 정공수송층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 7, wherein the organic material layer includes a hole transport layer, and the hole transport layer includes the heterocyclic compound.
  9. 청구항 7에 있어서, 상기 유기물층은 전자수송층, 전자주입층, 또는 전자 수송 및 주입을 동시에 하는 층을 포함하고, 상기 전자수송층, 전자주입층, 또는 전자 수송 및 주입을 동시에 하는 층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The method according to claim 7, wherein the organic layer comprises an electron transport layer, an electron injection layer, or a layer for simultaneously transport and injection, the electron transport layer, an electron injection layer, or a layer for simultaneously transporting and injecting the heterocyclic compound Organic light emitting device comprising a.
  10. 청구항 7에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The organic light emitting device of claim 7, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound.
PCT/KR2018/001809 2017-02-14 2018-02-12 Heterocyclic compound and organic light emitting element comprising same WO2018151479A2 (en)

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WO2023172069A1 (en) * 2022-03-11 2023-09-14 에스에프씨 주식회사 Organic compound and organic light-emitting device comprising same
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CN112218861A (en) * 2018-10-22 2021-01-12 株式会社Lg化学 Polycyclic compound and organic light-emitting element comprising same
CN112218861B (en) * 2018-10-22 2023-08-04 株式会社Lg化学 Polycyclic compound and organic light-emitting device containing same
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WO2024194264A1 (en) 2023-03-20 2024-09-26 Merck Patent Gmbh Materials for organic electroluminescent devices

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