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WO2014208755A1 - Composé azine cyclique, son procédé de production et élément électroluminescent organique l'utilisant - Google Patents

Composé azine cyclique, son procédé de production et élément électroluminescent organique l'utilisant Download PDF

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WO2014208755A1
WO2014208755A1 PCT/JP2014/067277 JP2014067277W WO2014208755A1 WO 2014208755 A1 WO2014208755 A1 WO 2014208755A1 JP 2014067277 W JP2014067277 W JP 2014067277W WO 2014208755 A1 WO2014208755 A1 WO 2014208755A1
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pyridyl
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phenyl
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信道 新井
まさみ 銭谷
桂甫 野村
田中　剛
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Tosoh Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present invention relates to a cyclic azine compound characterized by having a specific heteroaromatic group consisting only of carbon atoms, hydrogen atoms, and Group 16 elements of the periodic table, a method for producing the same, and an organic electroluminescent device using the same.
  • An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the excitons that are generated are deactivated, and is applied not only to small displays but also to large televisions and lighting.
  • the hole transport layer is divided into a hole transport layer and a hole injection layer
  • the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer
  • the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured.
  • a co-deposited film doped with a metal, an organic metal compound, or another organic compound may be used as a carrier transport layer (electron transport layer or hole transport layer) of the organic electroluminescence device.
  • organic electroluminescent elements have a higher driving voltage than inorganic light emitting diodes, have low emission luminance and luminous efficiency, have extremely low element lifetime, and have not been put into practical use in a wide range of fields. Furthermore, although recent organic electroluminescence devices have been improved gradually, excellent materials are required for the purpose of further improving the light emission efficiency characteristics, drive voltage characteristics, and long life characteristics. Among them, improvement of element lifetime is an urgent need for widespread use in a wide range of fields, and material development for that is required.
  • An example of an electron transport material having excellent long life for an organic electroluminescence device is the cyclic azine compound disclosed in Patent Document 1. However, further improvements have been demanded in terms of improving the device life.
  • the present invention relates to a specific cyclic azine compound that significantly improves the lifetime of an organic electroluminescent device, a method for producing the same, and an organic material that is excellent in storage stability using the cyclic azine compound as compared with a conventionally known cyclic azine compound.
  • An object is to provide an electroluminescent device. Furthermore, it aims at providing a manufacturing intermediate required in manufacturing the said cyclic azine compound.
  • cyclic azine compound (1) An organic electroluminescent element using a novel cyclic azine compound (hereinafter referred to as cyclic azine compound (1)) characterized by having an electron transport material is significantly longer than when a conventionally known material is used. It has been found that the lifetime is excellent and the driving voltage and power efficiency are excellent, and the present invention has been completed.
  • the present invention relates to a cyclic azine compound represented by the following general formula (1), a production method thereof, and an organic electroluminescence device using the cyclic azine compound.
  • Ar 1 two Ar 1 represent the same substituent, an aromatic hydrocarbon group (fluorine atom number of 6 to 30 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an aromatic having 6 to 18 carbon atoms carbide
  • An aromatic hydrocarbon group (which may have an aromatic hydrocarbon group as a substituent), or a pyridyl group optionally substituted with a phenyl group or a methyl
  • Heteroaromatic group having 4 to 30 prime atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms substituted by a fluorine atom) Substituted with a C3-C13 heteroaromatic group, a C6-C18 aromatic hydrocarbon group substituted with a C3-C13 heteroaromatic group, or a C1-C4 alkyl group. And a heteroaromatic group having 3 to 13 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, may be substituted).
  • the present invention relates to a cyclic azine compound represented by the following general formula (1), a production method thereof, and an organic electroluminescence device using the cyclic azine compound.
  • Ar 1 is .Ar 1 represent the same substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms (fluorine atom, may have a methyl group, a phenyl group or pyridyl group as a substituent) Or a pyridyl group optionally substituted with a phenyl group or a methyl group, Ar 2 is only C, H, and N formed of an aromatic hydrocarbon group having 6 to 18 carbon atoms or a 6-membered ring only And a heteroaromatic group having 3 to 13 carbon atoms (these substituents may be substituted with a fluorine atom, a methyl group or a phenyl group), and each X is independently substituted with a methyl group.
  • Z represents a nitrogen atom.
  • T is a heteroaromatic group having 4 to 20 carbon atoms consisting of only a carbon atom, a hydrogen atom and a group 16 element (a nitrogen-containing complex having 3 to 9 carbon atoms which may have a methyl group, a phenyl group, or a methyl group).
  • An aromatic group may be included as a substituent).
  • heteroaromatic group having 4 to 20 carbon atoms consisting only of carbon atom, hydrogen atom and group 16 element enhances the electron donor property of the compound, and enhances the electron transport ability without impairing the durability and device lifetime of the compound. It becomes possible to improve.
  • the cyclic azine compound of the present invention is used as an electron transport material excellent in durability, driving voltage, and power efficiency. Furthermore, according to the present invention, an organic EL element with low power consumption and excellent element lifetime can be provided.
  • the substituents in the cyclic azine compound (1) of the present invention are defined as follows.
  • two Ar 1 represent the same substituent.
  • Ar 1 is as defined above.
  • the aromatic hydrocarbon group having 6 to 30 carbon atoms in Ar 1 is not particularly limited, but phenyl group, biphenyl group, naphthyl group, phenanthryl group, anthryl group, pyrenyl group, triphenylenyl group, chrysenyl group, fullyl group, An oranthenyl group, an acenaphthylenyl group, a fluorenyl group, a benzofluorenyl group, or the like is preferable.
  • the alkyl group having 1 to 4 carbon atoms in Ar 1 is not particularly limited, but a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, or the like is preferable.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms in Ar 1 is not particularly limited, but includes a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, a triphenylenyl group, a chrysenyl group, a fullyl group.
  • An oranthenyl group, an acenaphthylenyl group, a fluorenyl group, a benzofluorenyl group, or the like is preferable.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom in Ar 1 is not particularly limited, but includes fluorophenyl group, difluorobiphenyl group, fluoronaphthyl, difluoronaphthyl group, fluorophenanthryl.
  • a fluorofluoranthenyl group, a difluorofluoranthenyl group, a fluoroacenaphthylenyl group, a difluoroacenaphthyl group, or the like is preferable.
  • the heteroaromatic group having 3 to 13 carbon atoms in Ar 1 is not particularly limited.
  • a benzoquinolyl group or an acridyl group is preferred.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a heteroaromatic group having 3 to 13 carbon atoms in Ar 1 is not particularly limited, but includes a pyridylphenyl group, a pyridylbiphenyl group, and a pyridylnaphthyl group.
  • the heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms in Ar 1 is not particularly limited, but is a methylpyridyl group, a methylpyrazyl group, a methylpyrimidyl group, a methylpyridyl group, a methyl group.
  • Triazyl group methylquinolyl group, methylisoquinolyl group, methylphenanthridyl group, methylbenzoquinolyl group, methylacridyl group, dimethylpyridyl group, dimethylpyrazyl group, dimethylpyrimidyl group, dimethylpyridazyl group
  • a dimethyltriazyl group, a dimethylquinolyl group, a dimethylisoquinolyl group, a dimethylphenanthridyl group, a dimethylbenzoquinolyl group, a dimethylacridyl group, or the like is preferable.
  • the aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms in Ar 1 is not particularly limited, but is a methylphenyl group, a methylbiphenyl group, a methylnaphthyl group, a methyl group Phenanthryl group, anthryl group, methylpyrenyl group, methyltriphenylenyl group, methylchrycenyl group, methylfluoranthenyl group, methylacenaphthylenyl group, dimethylphenyl group, dimethylbiphenyl group, dimethylnaphthyl group, dimethylphenanthryl group Anthryl group, dimethylpyrenyl group, dimethyltriphenylenyl group, dimethylchrysenyl group, dimethylfluoranthenyl group, dimethylacenaphthylenyl group, didimethylfluorenyl group, dimethylbenzofluoreny
  • the pyridyl group optionally substituted with a phenyl group or a methyl group in Ar 1 is not particularly limited, but includes a pyridyl group, a 3-phenylpyridin-2-yl group, and a 4-phenylpyridin-2-yl group.
  • 5-phenylpyridin-2-yl group, 3-methylpyridin-2-yl group, 4-methylpyridin-2-yl group, 5-methylpyridin-2-yl group and the like are preferable.
  • Ar 1 is a phenyl group, a biphenyl group, or a naphthyl group (these groups are an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a nitrogen-containing heteroaromatic group having 1 to 13 carbon atoms) in terms of excellent electron transporting material characteristics.
  • Group which may have a group as a substituent
  • a phenyl group which may have a phenyl group, a methyl group or a pyridyl group as a substituent
  • a phenyl group which may have a phenyl group, a methyl group or a pyridyl group as a substituent
  • Ar 1 is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms (which may have a fluorine atom, a methyl group, a phenyl group or a pyridyl group as a substituent), or a phenyl group or a methyl group. It may preferably be a pyridyl group which may be a phenyl group, a biphenyl group or a naphthyl group (these groups may have a fluorine atom, a methyl group, a phenyl group or a pyridyl group as a substituent). More preferred.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms in Ar 1 is not particularly limited, but a phenyl group, a biphenyl group, a naphthyl group, or the like is preferable.
  • Ar 1 examples include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 2,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a mesityl group, and a 2-ethylphenyl group.
  • a phenyl group, a p-tolyl group, a biphenyl-3-yl group, or a biphenyl-4-yl group a 3- (2-
  • Ar 2 is substituted with a hydrogen atom or a nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fluorine atom).
  • Ar 2 is a heteroaromatic group having 3 to 13 carbon atoms consisting of C, H, and N formed only by a 6-membered ring (these groups are substituted with a fluorine atom, a methyl group or a phenyl group) It may preferably be).
  • the following substituents for Ar 2 are the same as the substituents exemplified for Ar 1 .
  • an alkyl group having 1 to 4 carbon atoms (2) an aromatic hydrocarbon group having 6 to 18 carbon atoms, (3) an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, (4) a heteroaromatic group having 3 to 13 carbon atoms, (5) an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a heteroaromatic group having 3 to 13 carbon atoms, (6) a heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, (7) An aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
  • the nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms in Ar 2 is not particularly limited.
  • a quinazolyl group, a quinoxalyl group, a benzoquinolyl group, an acridyl group, a phenanthridyl group, or a phenanthroyl group is preferable.
  • the heteroaromatic group having 3 to 13 carbon atoms composed of only C, H, and N formed only by a 6-membered ring in Ar 2 is not particularly limited, but includes a pyridyl group, a pyrazyl group, a pyrimidyl group, A pyridazyl group, a triazyl group, a quinolyl group, an isoquinolyl group, a naphthyridyl group, a quinazolyl group, a quinoxalyl group, a benzoquinolyl group, an acridyl group, a phenanthridyl group, a phenanthroyl group, and the like are preferable.
  • Ar 2 is preferably a hydrogen atom or a nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms which may be substituted with a phenyl group or a methyl group in terms of excellent electron transporting material properties. Or an unsubstituted nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms.
  • Ar 2 include, but are not limited to, hydrogen atom, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridine-4 -Yl group, 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5 -Yl group, 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-3-yl group, 2,6- Dimethylpyridin-4-yl group, 3,6-dimethylpyridin-2-yl group, 3,6-dimethylpyridin-4-yl group, 3,6-dimethylpyridin-5-yl group, pyridin-6-yl group 5-phenylpyridine-6 -Yl group, 2-phenylpyridin
  • Ar 2 is a hydrogen atom, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-6-yl group, 3-methylpyridine in terms of excellent electron transporting material characteristics.
  • 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidyl group, 4,6-dimethylpyrimidyl group, or pyrazyl group are preferable, and 2-pyridyl group , 3-pyridyl group, 2-quinolyl group, 3-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, or 4-isoquinolyl group are more preferable, a hydrogen atom, 3-pyridyl group, 2- A pyridyl group, a 3-quinolyl group, or a 4-isoquinolyl group is more preferable.
  • Ar 2 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms (which may be substituted with a fluorine atom, a methyl group or a phenyl group) from the viewpoint of excellent electron transporting material properties, In combination with the above examples, the following groups can be mentioned.
  • a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthryl group, a fluoranthenyl group, a chrycenyl group or a triphenylenyl group (these groups may be substituted with a methyl group or a phenyl group), or It is preferably a pyridyl group, a pyrimidyl group, a pyrazyl group, a triazyl group, a quinolyl group, an isoquinolyl group, or a phenanthridyl group (these substituents may be substituted with a methyl group or a phenyl group).
  • phenyl group More preferably a triazyl group, a diphenyl-triazyl group (for example, 3,5-diphenyltriazyl group, etc.), a quinolyl group, an isoquinolyl group, or a phenanthrid
  • Ar 2 include, but are not limited to, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-3-yl group, 2-methylpyridin-4-yl group 2-methylpyridin-5-yl group, 2-methylpyridin-6-yl group, 3-methylpyridin-2-yl group, 3-methylpyridin-4-yl group, 3-methylpyridin-5-yl group 3-methylpyridin-6-yl group, 4-methylpyridin-2-yl group, 4-methylpyridin-3-yl group, 2,6-dimethylpyridin-4-yl group, 4,6-dimethylpyridine- 2-yl group, pyridin-6-yl group, 5-phenylpyridin-6-yl group, 2-phenylpyridin-3-yl group, 2-phenylpyridin-5-yl group, 3-phenylpyridin-5-yl Group, 4-phenyl Pyridin-3-yl group, 3-phenylpyridi
  • phenyl group, 1-naphthyl group, 2-naphthyl group, 2-phenanthryl group, 9-phenanthryl group, 9-anthryl group, 1-pyrenyl group, fluoranthene-3 are excellent in electron transporting material characteristics.
  • -Yl group triphenylene-1-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-methylpyridin-6-yl group, 3-methylpyridin-6-yl group, 2-methylpyridine -5-yl group, 2,6-dimethylpyridin-4-yl group, 4,6-dimethylpyridin-2-yl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridin-2 -Yl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 2,4-diphenyltriazin-6-yl group, 2-quinolyl group, - quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group.
  • 4-isoquinolyl group 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidyl group, 4,6-dimethylpyrimidyl group or pyrazyl group are preferred.
  • phenyl group, 9-phenanthryl group, 1-naphthyl group, 2-naphthyl group, 3-pyridyl group, 2-pyridyl group, 2,6-diphenylpyridin-4-yl group, 4,6-diphenylpyridine- 2-yl group, 4,6-dimethylpyrimidin-2-yl group, 1-pyrenyl group, 2-quinolyl group, or 3-quinolyl group are more preferable.
  • Each X independently represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted with a methyl group, or a carbon group having 3 to 13 carbon atoms which may be substituted with a methyl group or a phenyl group.
  • X may be substituted with a methyl group or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group in terms of excellent electron transporting material characteristics.
  • a good divalent nitrogen-containing heteroaromatic group having 5 to 9 carbon atoms is preferable.
  • the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may be substituted with a methyl group in X is not particularly limited, and examples thereof include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrylene group, Anthrylene group, pyrenylene group, triphenylenylene group, chrysenylene group, fluoranthenylene group, acenaphthyleneylene group, fluorenylene group, benzofluorenylene group, dimethylfluorenylene group, or dimethylbenzofluorenylene group are preferable. .
  • the divalent nitrogen-containing heteroaromatic group having 3 to 13 carbon atoms which may be substituted with a methyl group or a phenyl group in X is not particularly limited, and examples thereof include a pyridylene group, a methylpyridylene group, a dimethylpyridene group, and the like.
  • the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a methyl group in X is not particularly limited, but for example, a phenylene group, a tolylene group or a naphthylene group is preferable. .
  • the divalent nitrogen-containing heteroaromatic group having 5 to 9 carbon atoms which may be substituted with a methyl group or a phenyl group in X is not particularly limited, and examples thereof include a pyridylene group, a methylpyridylene group, a dimethylpyrylene group, and the like.
  • Dilene group pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group, dipyrimidylene group, methylpyrimidylene group, phenylpyrimidylene group, pyridazylene group, methylpyridazilene group, triadylene group, methyltriazilene group, phenyl Preferred examples include triadylene group, quinolylene group, methylquinolylene group, isoquinolylene group, methylisoquinolylene group, naphthyridylene group, methylnaphthylidylene group, quinazolylene group, methylquinazolylene group, quinoxalylene group, or methylquinoxalylene group. Cited as
  • each X is independently a phenylene group or a biphenylene group (eg, 4,4′-biphenylene group, 4,3′-biphenylene group, 3,3′-biphenylene group, etc.) ), Naphthylene group, phenanthrylene group, anthrylene group, pyrenylene group, pyridylene group (for example, 2,5-pyridylene group, 3,6-pyridylene group, etc.), methylpyridylene group (for example, 6-methyl-2,5-pyridylene group) 2-methyl-3,6-pyridylene group, etc.), dimethylpyridylene group, pyrazylene group, methylpyrazylene group, dimethylpyrazylene group, pyrimidylene group, methylpyrimidylene group, or dimethylpyrimidylene group (for example, 4,4 6-dimethyl-2,4-pyrimidylene group and
  • each X is independently a phenylene group (1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, etc.) or pyridylene group (for example, 2,5-phenylene group). More preferred are a pyridylene group and a 3,6-pyridylene group).
  • p 0, 1 or 2.
  • P is preferably 0 or 1 in terms of excellent sublimation purification operability.
  • q 0, 1 or 2.
  • Q is preferably 0 or 1 in terms of excellent sublimation purification operability.
  • Z represents a nitrogen atom or a carbon atom.
  • Z is preferably a nitrogen atom from the viewpoint of excellent characteristics of the electron transporting material.
  • T represents a heteroaromatic group having 4 to 30 carbon atoms (a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and consisting of only a carbon atom, a hydrogen atom, and a group 16 element; Aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with fluorine atom, heteroaromatic group having 3 to 13 carbon atoms, aromatic having 6 to 18 carbon atoms substituted with heteroaromatic group having 3 to 13 carbon atoms Aromatic hydrocarbon group substituted with an aromatic hydrocarbon group, a C3-C13 heteroaromatic group substituted with a C1-C4 alkyl group, or a C1-C4 alkyl group Which may have a hydrogen group as a substituent.
  • T is a heteroaromatic group having 4 to 20 carbon atoms (having a methyl group, a phenyl group, or a methyl group consisting of only a carbon atom, a hydrogen atom, and a group 16 element because it has excellent characteristics of an electron transporting material. It may preferably have a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms as a substituent.
  • the following substituents for T are the same as the substituents exemplified for Ar 1 .
  • an alkyl group having 1 to 4 carbon atoms (2) an aromatic hydrocarbon group having 6 to 18 carbon atoms, (3) an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, (4) a heteroaromatic group having 3 to 13 carbon atoms, (5) an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a heteroaromatic group having 3 to 13 carbon atoms, (6) a heteroaromatic group having 3 to 13 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, (7) An aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms.
  • Heteroaromatic group having 4 to 30 carbon atoms consisting of only carbon atom, hydrogen atom and group 16 element in T (fluorine atom, alkyl group having 1 to 4 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, fluorine Aromatic hydrocarbon group having 6 to 18 carbon atoms substituted by atom, heteroaromatic group having 3 to 13 carbon atoms, aromatic having 6 to 18 carbon atoms substituted by heteroaromatic group having 3 to 13 carbon atoms
  • Group (which may have a group as a substituent) is not particularly limited, but consists of only carbon atoms, hydrogen atoms and oxygen atoms, only carbon atoms, hydrogen atoms and sulfur atoms, or carbon atom
  • More specific examples include a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, a benzofuranyl group, a thiophenyl group, or a furanyl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, C6-C18 aromatic hydrocarbon group, C6-C18 aromatic hydrocarbon group substituted with a fluorine atom, C3-C13 heteroaromatic group, C3-C13 heteroaromatic group
  • a substituted aromatic hydrocarbon group having 6 to 18 carbon atoms may be used as a substituent.
  • the group includes a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with a fluorine atom, and 3 to 13 carbon atoms.
  • a heteroaromatic group or an aromatic hydrocarbon group having 6 to 18 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms may be used as a substituent.
  • dibenzothiophenyl group dibenzofuranyl group, benzothiophenyl group or benzofuranyl group (these groups are a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aromatic group having 6 to 18 carbon atoms).
  • the aromatic hydrocarbon group may be substituted as a substituent, and a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group or a benzofuranyl group (these groups are a methyl group, a pyridyl group or a phenyl group). May be substituted with a group) is more preferred.
  • the nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms which may have a methyl group is not particularly limited, and examples thereof include imidazolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, Preferred examples include pyrazyl group, pyrimidyl group, dimethylpyrimidyl group, pyridazyl group, triazyl group, quinolyl group, methylquinolyl group, isoquinolyl group, methylisoquinolyl group, naphthyridyl group, quinazolyl group, or quinoxalyl group.
  • imidazolyl group, pyridyl group, methylpyridyl group, dimethylpyridyl group, pyrimidyl group, dimethylpyrimidyl group, quinolyl group, methylquinolyl group, isoquinolyl group, methyl group are preferred because of their excellent electron transport properties.
  • An isoquinolyl group, a quinazolyl group, or a quinoxalyl group is more preferable.
  • T is a heteroaromatic group having 4 to 20 carbon atoms consisting of only a carbon atom, a hydrogen atom and a group 16 element (a nitrogen-containing complex having 3 to 9 carbon atoms which may have a methyl group, a phenyl group or a methyl group).
  • the electron transporting material characteristics in terms of excellent electron transporting material characteristics, it is composed of only a carbon atom, a hydrogen atom and an oxygen atom, or a heteroaromatic group having 4 to 20 carbon atoms (methyl group) consisting of only a carbon atom, a hydrogen atom and a sulfur atom.
  • a nitrogen-containing heteroaromatic group having 3 to 9 carbon atoms which may have a phenyl group or a methyl group may be preferable as a substituent.
  • a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group, or a benzofuranyl group (these groups may have a methyl group, a phenyl group, or a methyl group having 3 carbon atoms.
  • a dibenzothiophenyl group, a dibenzofuranyl group, a benzothiophenyl group or a benzofuranyl group (these groups are a methyl group, a pyridyl group). More preferably a group, optionally substituted with a quinolyl group, a methylpyridyl group, a dimethylpyridyl group, or a phenyl group.
  • thiophen-2-yl thiophen-3-yl, furan-2-yl, furan-3-yl
  • benzothiophen-2-yl benzo Thiophen-3-yl group
  • benzothiophen-4-yl group benzothiophen-5-yl group
  • benzothiophen-6-yl group benzothiophen-7-yl group
  • benzofuran-2-yl group benzofuran-3- Yl group
  • benzofuran-4-yl group benzofuran-5-yl group
  • benzofuran-6-yl group benzofuran-7-yl group
  • dibenzothiophen-1-yl group dibenzothiophen-2-yl group
  • dibenzothiophene- 3-yl group dibenzothiophen-4-yl group, dibenzofuran-1-yl group, dibenzothiophen-2-yl group, dibenzothiophene- 3-yl group, dibenzothiophen-4-yl group,
  • benzothiophen-2-yl group, benzothiophen-3-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, and benzothiophene-6 are excellent in electron transport material characteristics.
  • T is more preferably a substituent represented by the following general formula (T-3) or (T-4) (the bonding position in (T-1) and (T-2) is limited). preferable.
  • W 1 and W 2 each independently represents an oxygen atom or a sulfur atom.
  • Ar 3 represents a hydrogen atom, a methyl group, a pyridyl group, a quinolyl group, a methylpyridyl group, a dimethylpyridyl group, or a phenyl group. * Represents the bonding position.
  • the cyclic azine compound (1) of the present invention can be produced by any one of the following reaction formulas (1) to (4), optionally in the presence of a base and in the presence of a palladium catalyst.
  • Y 1 and Y 2 each independently represent a leaving group described later.
  • M 1 and M 2 represents each independently a substituent described later.
  • the compound (3) used in the reaction formula (1) or the reaction formula (2) is obtained by using, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2008-280330 or Japanese Patent Application Laid-Open No. 2001-335516. Can be manufactured.
  • Examples of compound (3) include (B-1) to (B-26) below, but are not limited thereto.
  • Examples of ZnR 1 and MgR 2 represented by M 1 include ZnCl, ZnBr, ZnI, MgCl, MgBr, and MgI.
  • Examples of Sn (R 3 ) 3 represented by M 1 include Sn (Me) 3 and Sn (Bu) 3 .
  • Examples of B (OR 4 ) 2 represented by M 1 include B (OH) 2 , B (OMe) 2 , B (O i Pr) 2 , and B (OBu) 2 .
  • Examples of B (OR 4 ) 2 in the case where two R 4 are combined to form a ring containing an oxygen atom and a boron atom include the following (C-1) to (C-6): The group shown can be exemplified, and the group shown by (C-2) is desirable from the viewpoint of good yield.
  • the compound (4) used in the reaction formula (1) or the reaction formula (2) is disclosed in, for example, the method disclosed in Japanese Patent Application Laid-Open No. 2008-280330 or Japanese Patent Application Laid-Open No. 2001-335516. It can be manufactured using the method. Specific examples of the compound (4) include the following (D-1) to (D-30), but are not limited thereto. M 2 of the compound (4) can exemplify the same substituent as M 1 described above.
  • the compound (6) used in the reaction formula (3) can be exemplified by a compound in which M 2 in the compound (4) is replaced with Y 3 .
  • the compound (8) used in the reaction formula (4) can be exemplified by a compound in which M 1 of the compound (3) is replaced with Y 4 .
  • the Y 4 of Y 3 and compounds of the compound (6) (8), a leaving group independently is not particularly limited, and for example, a chlorine atom, a bromine atom, an iodine atom or a triflate and the like .
  • a bromine atom or a chlorine atom is preferable in that the reaction yield is good.
  • Y 1 and Y 2 of the compound (2) each independently represent a leaving group and are not particularly limited, and examples thereof include a chlorine atom, a bromine atom, an iodine atom, and a triflate. Among these, a bromine atom or a chlorine atom is preferable in that the reaction yield is good. In order to improve the selectivity of the reaction, Y 1 and Y 2 are more preferably different leaving groups.
  • Step 1 of the reaction formula (1), the compound (2) is reacted with the compound (3) in the presence of a palladium catalyst in the presence of a base in some cases, and the compound (9) as a synthetic intermediate is reacted.
  • reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained with good yield.
  • Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Furthermore, ⁇ -allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Examples include complex compounds such as fino) ferrocene) palladium.
  • a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and in terms of a good reaction yield, a palladium complex having triphenylphosphine as a ligand. Is particularly preferred.
  • the palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound.
  • the tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5.
  • 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl or triphenylphosphine is preferred because it is easily available and the reaction yield is good.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 from the viewpoint of good reaction yield.
  • Bases that can be used in “Step 1” include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, fluorine. Examples thereof include cesium chloride. Potassium carbonate is desirable in terms of good yield.
  • the molar ratio of the base and the compound (3) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of a good yield.
  • the molar ratio of the compound (2) and the compound (3) used in “Step 1” is preferably 1: 2 to 5: 1, and more preferably 1: 2 to 2: 1 in terms of a good yield.
  • Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. You may use it combining suitably. From the viewpoint of good yield, it is desirable to use a mixed solvent of dioxane or THF (tetrahydrofuran) and water.
  • Step 1 can be carried out at a temperature appropriately selected from 0 to 150 ° C., and is more preferably carried out at 50 to 100 ° C. in terms of a good yield.
  • Compound (9) can be obtained by carrying out a usual treatment after completion of “Step 1”. You may refine
  • Step 2 is a method in which the compound (9) is reacted with the compound (4) in the presence of a base and in the presence of a palladium catalyst to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions of general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the target product can be obtained in high yield.
  • reaction conditions are not necessarily the same as those in “Step 1”.
  • compound (4) can be added and reacted in the reaction system of “Step 1” without isolating compound (9), which is a synthetic intermediate, to synthesize cyclic azine compound (1).
  • the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
  • the compound (9) is excellent for industrially supplying a compound such as the compound (1) that remarkably improves the low driving voltage property, the high light emission efficiency, and the long life property of the organic electroluminescence device. It is an intermediate material for manufacturing and is very useful industrially.
  • Step 3 of the reaction formula (2), the compound (2) is reacted with the compound (4) in the presence of a palladium catalyst, optionally in the presence of a base, to give a compound (10) as a synthetic intermediate.
  • reaction conditions of general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc.
  • the desired product can be obtained with good yield.
  • the same reaction conditions as those mentioned in “Step 1” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 1”.
  • the obtained compound (10) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
  • Step 4 is a method in which the compound (10) is reacted with the compound (3) in the presence of a palladium catalyst in the presence of a base in some cases to obtain the cyclic azine compound (1) of the present invention. -By applying reaction conditions of general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the target product can be obtained in high yield.
  • reaction conditions are not necessarily the same as those in “Step 1”.
  • the compound (3) can be added to the reaction system of “Step 3” and reacted to synthesize the cyclic azine compound (1) without isolating the compound (10) which is a synthetic intermediate. .
  • the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
  • Step 5 is a reaction for synthesizing a general organometallic compound from Compound (9) (for example, Angew. Chem. Int. Ed. 2007, 46, 5359-5363).
  • Step 5 is a method in which the compound (5) is reacted with the compound (6) in the presence of a palladium catalyst, optionally in the presence of a base, to obtain the cyclic azine compound (1) of the present invention.
  • reaction conditions of general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc.
  • Examples of the palladium catalyst that can be used in “Step 5” include the same palladium catalysts as those mentioned in “Step 1”. Among them, a palladium complex having a tertiary phosphine as a ligand is more preferable in terms of a good reaction yield, is easily available, and has a triphenylphosphine as a ligand in terms of a good reaction yield. Palladium complexes are particularly preferred.
  • the palladium complex having tertiary phosphine as a ligand can also be prepared in a reaction system by adding tertiary phosphine to a palladium salt or complex compound.
  • tertiary phosphine examples include the same tertiary phosphine as that described in “Step 1”.
  • 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl or triphenylphosphine is preferred because it is easily available and the reaction yield is good.
  • the molar ratio of the tertiary phosphine to the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 from the viewpoint of good reaction yield.
  • Examples of the base that can be used in “Step 5” include the same bases as those mentioned in “Step 1”.
  • the molar ratio of base to compound (5) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of good yield.
  • the molar ratio of the compound (5) and the compound (6) used in “Step 5” is preferably 1: 5 to 2: 1, and more preferably 1: 1 to 1: 3 in terms of a good yield.
  • Step 5 examples include the same solvents as those mentioned in “Step 1”. From the viewpoint of good yield, it is desirable to use dioxane or a mixed solvent of THF and water. “Step 5” can be performed at a temperature appropriately selected from 0 to 150 ° C., and is more preferably performed at 50 to 100 ° C. in terms of a good yield. After completion of “Step 5”, the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
  • Step 6 is a reaction for synthesizing a general organometallic compound from Compound (10) (for example, Angew. Chem. Int. Ed. 2007, 46, 5359). -5363).
  • Step 6 is a method in which the compound (7) is reacted with the compound (8) in the presence of a base, optionally in the presence of a palladium catalyst, to obtain the cyclic azine compound (1) of the present invention.
  • reaction conditions of general coupling reactions such as Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the target product can be obtained in high yield.
  • Step 6 the same reaction conditions as those described in “Step 5” can be selected. However, the reaction conditions are not necessarily the same as those in “Step 5”.
  • the obtained cyclic azine compound (1) may be purified by recrystallization, column chromatography, sublimation or the like, if necessary.
  • the compound (7) is excellent for industrially supplying a compound such as the compound (1) that significantly improves the low driving voltage property, the high light emission efficiency, and the long life property of the organic electroluminescence device. It is a production intermediate material and is very useful industrially.
  • the cyclic azine compound (1) of the present invention is preferably used as a part of the components of the organic electroluminescence device.
  • effects such as longer life, higher efficiency, and lower voltage can be obtained than conventional devices.
  • it can also be used as a co-deposited film with any organic metal species, organic compound or inorganic compound.
  • the cyclic azine compound (1) of the present invention is preferable as a material for an organic thin film layer having electron transport properties such as a light-emitting layer, an electron transport layer, and an electron injection layer in an organic electroluminescence device because it exhibits good electron transport properties. Can be used.
  • the film-forming by a vacuum evaporation method is possible. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus.
  • the vacuum degree of the vacuum chamber when forming a film by the vacuum deposition method is determined by taking into account the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device, and commonly used diffusion pumps, turbo molecular pumps, cryopumps, etc. Is preferably about 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 6 Pa, more preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 6 Pa.
  • the deposition rate is preferably 0.005 to 1.0 nm / second, and more preferably 0.01 to 0.3 nm / second, depending on the thickness of the film to be formed.
  • the cyclic azine compound (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran, or the like, a spin coating method using a general-purpose apparatus, Film formation by an inkjet method, a cast method, a dip method, or the like is also possible.
  • a typical structure of the organic electroluminescent device capable of obtaining the effects of the present invention includes a substrate, an anode, a hole injection layer, a hole transport layer light emitting layer, an electron transport layer, and a cathode.
  • the anode and cathode of the organic electroluminescent element are connected to a power source through an electrical conductor.
  • the organic electroluminescent device operates by applying a potential between the anode and the cathode. Holes are injected into the organic electroluminescent device from the anode, and electrons are injected into the organic electroluminescent device at the cathode.
  • the organic electroluminescent device is typically placed on a substrate, and the anode or cathode can be in contact with the substrate.
  • the electrode in contact with the substrate is called the lower electrode for convenience.
  • the lower electrode is an anode, but the organic electroluminescent element of the present invention is not limited to such a form.
  • the substrate may be light transmissive or opaque depending on the intended emission direction.
  • the light transmission property can be confirmed by electroluminescence emission through the substrate.
  • transparent glass or plastic is employed as such a substrate.
  • the substrate may be a composite structure including multiple material layers. When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.
  • anode Common transparent anode (anode) materials used in the present invention include indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide. Further, other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also preferably used. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can also be used as the anode. The anode can be modified with plasma deposited fluorocarbon.
  • ITO indium-tin oxide
  • IZO indium-zinc oxide
  • tin oxide other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also preferably used.
  • metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or
  • the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used.
  • Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum, and the like.
  • the hole injection layer can be provided between the anode and the hole transport layer.
  • the material of the hole injection layer is useful for improving the film formation characteristics of an organic material layer such as a hole transport layer and a hole injection layer, and facilitating injection of holes into the hole transport layer.
  • Examples of materials suitable for use in the hole injection layer include porphyrin compounds, plasma deposited fluorocarbon polymers, and amines having aromatic rings such as biphenyl groups and carbazole groups, such as m-MTDATA (4,4 ′ , 4 ′′ -tris [(3-methylphenyl) phenylamino] triphenylamine), 2T-NATA (4,4 ′, 4 ′′ -tris [(N-naphthalen-2-yl) -N-phenylamino ] Triphenylamine), triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N, N′N′-tetrakis (4-methylphenyl) -1,1′-biphenyl-4,4′-diamine, MeO-TPD N, N, N′
  • the hole transport layer of the organic electroluminescence device preferably contains one or more hole transport compounds (hole transport materials) such as aromatic tertiary amines.
  • An aromatic tertiary amine is a compound containing one or more trivalent nitrogen atoms, which are bonded only to carbon atoms, and one or more of these carbon atoms have an aromatic ring. Forming.
  • the aromatic tertiary amine is an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine.
  • An aromatic tertiary amine having one or more amine groups can be used as the hole transport material.
  • a polymeric hole transport material can be used.
  • PVK poly (N-vinylcarbazole)
  • PVK polythiophene
  • polypyrrole polyaniline
  • NPD N, N′-bis (naphthalen-1-yl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine
  • ⁇ -NPD N, N '-Di (1-naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine
  • TPBi 1,3,5-tris (1-phenyl-1H-benzimidazole) 2-yl) benzene
  • TPD N, N′-bis (3-methylphenyl) -N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine
  • a layer containing (HAT-CN) may be provided.
  • the light emitting layer of the organic electroluminescent element contains a phosphorescent material or a fluorescent material, and emits light as a result of recombination of electron / hole pairs in this region.
  • the light-emitting layer may be formed from a single material that includes both small molecules and polymers, but more commonly is formed from a host material doped with a guest compound, where light emission is primarily from a dopant, Any color can be emitted.
  • Examples of the host material for the light emitting layer include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group.
  • DPVBi 4,4′-bis (2,2-diphenylvinyl) -1,1′-biphenyl
  • BCzVBi 4,4′-bis (9-ethyl-3-carbazovinylene) 1,1 '-Biphenyl
  • TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene
  • ADN (9,10-di (2-naphthyl) anthracene)
  • CBP 4,4'-bis ( Carbazol-9-yl) biphenyl
  • CDBP 4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl
  • 9,10-bis (biphenyl) anthracene and the like.
  • the host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, another material that supports hole / electron recombination (support), or a combination of
  • fluorescent dopants examples include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium or thiapyrylium compound, fluorene derivative, perifuranthene derivative, indenoperylene derivative, Examples thereof include bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.
  • an organometallic complex of a transition metal such as iridium, platinum, palladium, or osmium can be given.
  • dopants include Alq 3 (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) 3 (Tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III)) and the like.
  • the thin film forming material used for forming the electron transport layer of the organic electroluminescence device of the present invention is the cyclic azine compound (1) of the present invention.
  • the electron transporting layer may contain other electron transporting materials.
  • other electron transporting materials include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Desirable alkali metal complexes, alkaline earth metal complexes, or earth metal complexes include, for example, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinate).
  • a hole blocking layer may be provided between the light emitting layer and the electron transport layer for the purpose of improving carrier balance.
  • Desirable compounds as a material for the hole blocking layer include BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2-methyl-8-quinolinolato) -4- (phenylphenolate) aluminum) or bis (10-hydroxybenzo [h] quinolinato) beryllium).
  • an electron injection layer may be provided for the purpose of improving electron injection properties and improving device characteristics (for example, light emission efficiency, low voltage driving, or high durability).
  • Desirable compounds as the material for the electron injection layer are fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, or And anthrone.
  • the above metal complexes alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO x , AlO x , SiN x , SiON, AlON, inorganic compounds such as GeO X, LiO X, LiON, TiO X, TiON, TaO X, TaON, TaN X, various oxides such as C, nitrides, and oxynitrides may be used.
  • the cathode used in the organic electroluminescent device of the present invention can be formed from any conductive material.
  • Desirable cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.
  • phenacylpyridinium bromide (3.00 g, 8.40 mmol), (E) -chalcone (1.75 g, 8.40 mmol), ammonium acetate (32.3 g, 420 mmol), acetic acid (120 mL) and dimethylformamide (95 mL) was added to a 500 mL four-necked flask and stirred at 160 ° C. for 3 hours. After allowing to cool to room temperature, water (300 mL) was added to the reaction mixture, and the precipitate was collected by filtration. The precipitate collected by filtration was washed with pure water to obtain a white powder.
  • 2-dibenzothiopheneboronic acid (3.00 g, 13.2 mmol), p-bromochlorobenzene (2.51 g, 13.2 mmol), tetrakistriphenylphosphine palladium (456 mg, 0.394 mmol) and potassium carbonate ( 5.45 g, 39.5 mmol) was suspended in a mixed solvent of tetrahydrofuran (79 mL) and water (39 mL), and the mixture was stirred at 70 ° C. for 17 hours. After cooling to room temperature, water (100 mL) and chloroform (200 mL) were added to the reaction mixture. After the obtained mixture was shaken and mixed, only the organic layer was taken out.
  • the obtained organic layer was dehydrated with magnesium sulfate, and then the low boiling point component was distilled off.
  • Synthesis Example-10 The target product, 5-chloro-2- (2-naphthyl) pyridine, was synthesized under the same reaction conditions and method as in Synthesis Example-8.
  • the obtained organic layer was dehydrated with magnesium sulfate, and then the low boiling point component was distilled off.
  • Element Example-1 As the substrate, a glass substrate with an ITO transparent electrode in which a 2 mm-wide indium-tin oxide (ITO) film was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in the sectional view of FIG. Each organic material was formed by a resistance heating method.
  • ITO indium-tin oxide
  • the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa. Then, as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 1, a hole injection layer 2, a charge generation layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and an electron injection layer 7 and the cathode layer 8 were both formed by vacuum vapor deposition while being laminated in this order. As the hole injection layer 2, a sublimated HIL film having a thickness of 65 nm was formed at a rate of 0.15 nm / second.
  • HAT sublimation-purified HAT was deposited to a thickness of 5 nm at a rate of 0.05 nm / second.
  • HTL was formed to a thickness of 10 nm at a rate of 0.15 nm / second.
  • EML-1 and EML-2 were deposited at a ratio of 95: 5 (weight ratio) to 25 nm (deposition rate of 0.18 nm / second).
  • the cathode layer 7 is formed of silver / magnesium (weight ratio 1/10) and silver in this order at 80 nm (film formation rate 0.5 nm / second) and 20 nm (film formation rate 0.2 nm / second), respectively. And a two-layer structure.
  • Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.
  • Element Example-7 In device example-1, 2- ⁇ 3- (dibenzofuran-4-yl) -5- [6- (2-naphthyl) pyridin-3-yl] obtained in synthesis example-9 was formed on the electron transport layer 6. ] An organic electroluminescent device was produced in the same manner as in Device Example 1 except that phenyl ⁇ -4,6-diphenyl-1,3,5-triazine (Compound A-493) was used.
  • Element Example-8 In device example-1, 2- [4 ′-(4-dibenzofuran) -5- (3-pyridyl) -biphenyl-3-yl] -4, obtained in synthesis example-12 was formed on the electron transport layer 6. An organic electroluminescent device was produced in the same manner as in Device Example 1 except that 6-diphenyl-1,3,5-triazine (Compound A-556) was used.
  • Element Example-14 In device example-1, 2- [5- (dibenzothiophen-2-yl)-[1,1 ′: 4 ′, 1 ′′]-telomer obtained in synthesis example-13 was formed on the electron transport layer 6. An organic electroluminescent device was produced in the same manner as in Device Example 1 except that phenyl-3-yl] -4,6-difer-1,3,5-triazine (Compound A-98) was used.
  • Device reference example-1 In device example-1, 2- [5- (9-phenanthryl) -4 ′-(2-pyrimidyl) biphenyl-3-yl] -4 described in Japanese Patent Application Laid-Open No. 2010-183145 is used for the electron transport layer 6.
  • An organic electroluminescence device was produced in the same manner as in Device Example 1 except that, 6-diphenyl-1,3,5-triazine (the above formula, represented by ETL-1) was used.
  • a direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • V voltage
  • cd / A current efficiency
  • the luminance decay time during continuous lighting when the initial luminance was driven at 800 cd / m 2 was measured.
  • the time when the luminance (cd / m 2 ) is reduced by 30% is shown as the element lifetime (h) below.
  • Device comparison example-1 In Device Example-1, 2- [3,5-bis (dibenzothiophen-2-yl)]-3,5-diphenyl-pyrimidine (in the above formula, disclosed in Japanese Patent Application No. 2007-550166) was used for the electron transport layer 6.
  • An organic electroluminescent device was produced in the same manner as in the device example-1 except that ETL-2) was used.
  • ETL-2 the initial luminance was driven at 800 cd / m 2 and the luminance decay time during continuous lighting was measured, the time when the luminance (cd / m 2 ) was reduced by 30% was 192 hours. This result can be said that there is a large difference in device lifetime as compared with the compound of the present invention.
  • the organic electroluminescent device using the azine compound of the present invention has improved characteristics in voltage, current efficiency and device lifetime as compared with the device reference example.
  • the cyclic azine compound of the present invention has a high Tg and good thermal stability during sublimation purification, and can be provided as a material with excellent impurities in sublimation purification and less impurities.
  • a material for a light-emitting element it is used as an electron transport material having little element deterioration, good stability of a deposited film, excellent heat resistance, and particularly excellent durability, driving voltage, and power efficiency.
  • the thin film comprising the cyclic azine compound (1) of the present invention has high surface smoothness, amorphousness, heat resistance, electron transport ability, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection characteristics, etc. Therefore, it is useful as a material for organic electroluminescent elements.
  • it can be used as an electron transport agent, a hole blocking material, a light emitting host material, and the like, and since the cyclic azine compound (1) is a wide band gap material, it can be used not only for conventional fluorescent device applications but also to phosphorescent devices. There is also the possibility of application.
  • the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-136249 filed on June 28, 2013 and Japanese Patent Application No. 2013-259774 filed on December 17, 2013. The entire contents of this document are hereby incorporated by reference as the disclosure of the specification of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention porte sur un composé azine cyclique qui est utilisé pour des éléments électroluminescents organiques qui peuvent atteindre une efficience lumineuse améliorée et une plus longue durée de vie utile en même temps. Plus précisément, l'invention porte sur un composé azine cyclique représenté par la formule générale (1) ; sur un procédé pour la production du composé azine cyclique ; et sur un élément électroluminescent organique qui utilise le composé azine cyclique. (Dans la formule, deux fractions Ar1 représentent des substituants identiques et chaque Ar1 représente un groupe hydrocarboné aromatique ayant 6 à 10 atomes de carbone (qui peuvent avoir un atome de fluor, un groupe méthyle, un groupe phényle ou un groupe pyridyle en tant que substituant) ; Ar2 représente un groupe hydrocarboné aromatique ayant 6 à 18 atomes de carbone ou similaire ; chaque X représente indépendamment un groupe hydrocarboné aromatique divalent ayant 6 à 10 atomes de carbone, qui peut être substitué par un groupe méthyle, ou similaire ; chacun de p et q représente indépendamment 0, 1 ou 2 ; Z représente un atome d'azote ; et T représente un groupe hétéroaromatique ayant 4 à 20 atomes de carbone qui n'est composé que d'atomes de carbone, d'atomes d'hydrogène et d'éléments du groupe 16 (et qui peut avoir, comme substituant, un groupe méthyle, un groupe phényle ou un groupe hétéroaromatique contenant de l'azote ayant 3 à 9 atomes de carbone, qui peuvent avoir un groupe méthyle) ou similaire.)
PCT/JP2014/067277 2013-06-28 2014-06-27 Composé azine cyclique, son procédé de production et élément électroluminescent organique l'utilisant Ceased WO2014208755A1 (fr)

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WO2018043761A1 (fr) 2016-09-05 2018-03-08 Idemitsu Kosan Co.,Ltd. Aza-dibenzofuranes et aza-dibenzothiophènes spécifiquement substitués pour dispositifs électroniques organiques
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CN113024526A (zh) * 2021-03-26 2021-06-25 宁波卢米蓝新材料有限公司 一种有机电致发光材料及其应用
CN114702508B (zh) * 2022-02-23 2024-10-15 京东方科技集团股份有限公司 一种三嗪衍生物、发光器件和显示装置
CN114702508A (zh) * 2022-02-23 2022-07-05 京东方科技集团股份有限公司 一种三嗪衍生物、发光器件和显示装置

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