WO2015182769A1 - Composés de quinazoline et benzoquinazoline, leur procédé de production et utilisation - Google Patents

Composés de quinazoline et benzoquinazoline, leur procédé de production et utilisation Download PDF

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WO2015182769A1
WO2015182769A1 PCT/JP2015/065650 JP2015065650W WO2015182769A1 WO 2015182769 A1 WO2015182769 A1 WO 2015182769A1 JP 2015065650 W JP2015065650 W JP 2015065650W WO 2015182769 A1 WO2015182769 A1 WO 2015182769A1
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pyrimidyl
phenyl
carbon atoms
pyridyl
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華奈 藤田
陽子 本間
内田　直樹
尚志 飯田
田中　剛
恵理子 太田
裕太 森中
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東ソー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • 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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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

Definitions

  • the present invention relates to a quinazoline and a benzoquinazoline compound for providing a high-efficiency organic electroluminescence device excellent in drivability and light emission characteristics represented by the general formula (1), and a method for producing the same.
  • the organic electroluminescent element has a structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside, and holes injected into the light emitting layer and It is a self-emitting element that utilizes a light emission phenomenon (fluorescence or phosphorescence) when excitons generated by electron recombination are deactivated. Since it is a self-luminous type, it is excellent in visibility, and since it is a completely solid element, it is easy to handle and manufacture. In addition, since it is a thin film type device, it is attracting attention from the viewpoints of space saving and portability, and is applied to displays, lighting, and the like. At present, the organic electroluminescence device has begun to be used for commercial purposes. However, further improvement in light emission efficiency, reduction in driving voltage, and longer life are required for energy saving.
  • Patent Document 1 discloses an electron transport layer host material capable of obtaining an organic EL element having a long emission lifetime and a low driving voltage, and an element using the same.
  • a doped material is indispensable. When used as a single electron transport layer that does not contain a doped material, the device has a higher driving voltage or significantly reduced efficiency, so that improvement can be achieved. It was sought after.
  • Patent Document 2 discloses an electron transport material for providing an organic electroluminescent device having high luminous efficiency.
  • An organic electroluminescent device using a benzoquinazoline compound disclosed in the above document is a benzoquinazoline.
  • Organic electroluminescent elements are used in various display elements, but more efficient light emission is required particularly for practical use of large displays and lighting.
  • An object of the present invention is to provide an electron transporting material which is excellent in the lifetime characteristics of the device and excellent in the light emitting efficiency of the device as compared with a conventionally known electron transporting material for an organic electroluminescence device.
  • an organic electroluminescent device using a quinazoline and benzoquinazoline compound represented by the following general formula (1) as an electron transport layer is a conventionally known material.
  • the inventors have found that the driving voltage is low, the luminous efficiency is improved, and the life is long, and the present invention has been completed.
  • Ar 1 and Ar 2 are each independently a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a benzene ring and / or pyridine)
  • Aromatic groups consisting only of 6 to 6 rings in which 2 to 6 rings are connected and / or condensed ⁇ These groups include a methyl group, a methoxy group, a fluorine atom, a pyrimidyl group (the pyrimidyl group is a methyl group, a carbon number 2-10 alkyl groups and at least one substituent selected from the group consisting of C6-C18 aromatic hydrocarbon groups), or a C2-C10 alkyl group, alkoxy A group, an alkoxyalkyl group, an ester group or an esteralkyl which may be substituted ⁇ .
  • A represents the general formula (2-1), the general formula (2-2), or the general
  • Ar 3 , Ar 4 and Ar 5 are each an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, alkyl group having 2 to 10 carbon atoms, alkoxy group, And may be substituted with an alkoxyalkyl group, an ester group or an ester alkyl group).
  • Ar 6 and Ar 7 are each independently a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, or an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom) Or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 31 , and R 32 are each independently a hydrogen atom Represents a methyl group, a methoxy group, a phenyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
  • each hydrogen atom in the formula may independently be a deuterium atom.
  • Ar 1 and Ar 2 are each independently a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 6 benzene rings and / or pyridine rings.
  • An aromatic group consisting of only six linked and / or condensed six-membered rings ⁇ these groups are a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a fluorine atom, Or a pyrimidyl group (the pyrimidyl group may have at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group).
  • the compound according to [1] which may be substituted ⁇ .
  • Ar 1 and Ar 2 are each independently a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 5 benzene rings and / or pyridine rings.
  • An aromatic group consisting of only six linked and / or condensed six-membered rings ⁇ these groups are a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a fluorine atom, Or a pyrimidyl group (the pyrimidyl group may have at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group).
  • the compound according to [1] which may be substituted.
  • Ar 1 and Ar 2 are each independently a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 4 benzene rings and / or pyridine rings.
  • An aromatic group consisting of only six linked and / or condensed six-membered rings ⁇ these groups are a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a fluorine atom, Or a pyrimidyl group (the pyrimidyl group may have at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group).
  • the compound according to [1] which may be substituted ⁇ .
  • Ar 3 , Ar 4 and Ar 5 are aromatic hydrocarbon groups having 6 to 12 carbon atoms (the group is a methyl group, a methoxy group, an alkyl group or alkoxy group having 2 to 10 carbon atoms, a pyridyl group, a pyrimidyl group, or The compound according to [1], which may be substituted with a fluorine atom.
  • Ar 3 , Ar 4 and Ar 5 are a phenyl group, a naphthyl group, or a biphenyl group (these groups are a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group) A group, an alkoxyalkyl group, an ester group or an esteralkyl group, which may be substituted).
  • Ar 3 , Ar 4 and Ar 5 are a phenyl group, a naphthyl group, or a biphenyl group.
  • Ar 6 and Ar 7 are each independently a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, or an aromatic hydrocarbon group having 6 to 12 carbon atoms (the group is a methyl group, methoxy group, 2 to The compound according to [1], which may be substituted with a 10 alkyl group, an alkoxy group having 2 to 10 carbon atoms, a pyridyl group, a pyrimidyl group, or a fluorine atom.
  • Ar 6 and Ar 7 are each independently a phenyl group, a naphthyl group, or a biphenyl group (these substituents are a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms) , An alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group), a hydrogen atom, a methyl group, a methoxy group, or a fluorine atom.
  • a compound represented by the following general formula (9-1) or general formula (9-2) described below is present in the presence of an oxidizing agent in the presence or absence of an acid, or in the presence of a base or The method for producing a benzoquinazoline compound represented by the general formula (3-1) or the general formula (3-2) according to [15], wherein the reaction is performed in the absence.
  • the compound (1) of the present invention Since the compound (1) of the present invention has good charge injection and transport properties, it is useful as a material for fluorescent or phosphorescent organic electroluminescence devices, and can be used as an electron transport material and a host material, among others.
  • the organic electroluminescent device having an electron transport layer containing the compound (1) of the present invention is superior in organic EL device using a general-purpose electron transport material, has a low driving voltage, excellent luminous efficiency, and has a long lifetime. .
  • the band gap of the compound (1) of the present invention is 3.0 eV or more, and the energy of each of the three primary colors (red: 1.9 eV, green: 2.4 eV, blue: 2.8 eV) constituting the panel is obtained. It is a material with a wide band gap sufficient to confine. Therefore, it can be applied to various elements such as a single color display element, a three primary color display element, and a white element for illumination use. Since the compound (1) of the present invention has a high triplet energy, it can be sufficiently applied to phosphorescence. Furthermore, since the solubility can be controlled by changing the substituent, it can be applied not only to a vapor deposition element but also to a coating element.
  • FIG. 3 is a schematic cross-sectional view of an organic electroluminescent element produced in Test Example-1.
  • Ar 1 and Ar 2 each independently represent a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 6 benzene rings and / or pyridine rings.
  • Aromatic groups consisting only of six-membered rings that are linked and / or condensed ⁇ these groups are methyl, methoxy, fluorine, pyrimidyl (the pyrimidyl is methyl, alkyl of 2 to 10 carbon atoms) And may have at least one substituent selected from the group consisting of an aromatic hydrocarbon group having 6 to 18 carbon atoms), or an alkyl group, alkoxy group, alkoxyalkyl group having 2 to 10 carbon atoms , Optionally substituted with an ester group or an ester alkyl ⁇ .
  • the pyridyl group is not particularly limited, and examples thereof include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.
  • the pyrimidyl group is not particularly limited, and examples thereof include a 2-pyrimidyl group, a 4-pyrimidyl group, and a 5-pyrimidyl group.
  • the pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited, and examples thereof include a 4-phenylpyrimidin-2-yl group, a 5-phenylpyrimidin-2-yl group, 2-phenylpyrimidin-4-yl group, 6-phenylpyrimidin-4-yl group, 2-phenylpyrimidin-5-yl group, 4,6-diphenylpyrimidin-2-yl group, 4-naphthylpyrimidin-2-yl group Group, 5-naphthylpyrimidin-2-yl group, 2-naphthylpyrimidin-4-yl group, 6-naphthylpyrimidin-4-yl group, 2-naphthylpyrimidin-5-yl group, 6-naphthyl-4-phenylpyrimidine -2-yl group, 4-anthracylpyrimidin-2-yl group, 5-anthracylpyrimidin-2-y
  • a pyrimidyl group substituted with a phenyl group, a biphenyl group, or a condensed aromatic hydrocarbon group having 10 to 18 carbon atoms consisting of only a 6-membered ring in terms of good performance as an organic electroluminescent element material.
  • the substituent is not particularly limited, and for example, a pyrimidyl group substituted with a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, or a pyrenyl group is more preferable.
  • the preferred substituents include 5-phenylpyrimidin-2-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, and 4,6-dinaphthylpyrimidin-2-yl. More preferably a group, a 5-phenanthrylpyrimidin-2-yl group, a 5-anthracylpyrimidin-2-yl group, and a 5-pyrenylpyrimidin-2-yl group.
  • a 5-phenylpyrimidin-2-yl group, a 4,6-diphenylpyrimidin-2-yl group, and a 4,6-dinaphthylpyrimidin-2-yl group are more preferable.
  • the aromatic group consisting of only a 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings are linked and / or condensed is not particularly limited.
  • the preferred substituents are (A1) to (A19), (A21), (A28), (A30), (A32), (A36), (A38), (A40), (A42) to (A60). , (A63), (A64), (A66) to (A74), (A76), (A78), (A80), (A82), (A84), (A86) to (A124), (A129), ( A130), (A145) to (A154), and (A156) to (A179) are more preferable.
  • the pyrimidyl group having at least one substituent selected from the group consisting of a methyl group, an alkyl group having 2 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms is not particularly limited, For example, 4-methylpyrimidin-2-yl group, 5-methylpyrimidin-2-yl group, 2-methylpyrimidin-4-yl group, 6-methylpyrimidin-4-yl group, 2-methylpyrimidin-5-yl Group, 4,6-dimethylpyrimidin-2-yl group, 4-ethylpyrimidin-2-yl group, 5-ethylpyrimidin-2-yl group, 2-ethylpyrimidin-4-yl group, 6-ethylpyrimidine-4 -Yl group, 2-ethylpyrimidin-5-yl group, 4,6-diethylpyrimidin-2-yl group, 4-propylpyrimidin-2-yl group, 5-butylpyrimidin-2 Yl group, 2-pentylpyrimidin
  • a pyrimidyl group having at least one substituent selected from the group consisting of a methyl group and an aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable from the viewpoint of good performance as an organic electroluminescent element material.
  • the preferred substituents include 5-methylpyrimidin-2-yl group, 4,6-dimethylpyrimidin-2-yl group, 4-phenylpyrimidin-2-yl group, 5-phenylpyrimidin-2-yl group, 2 -Phenylpyrimidin-5-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, 6-naphthyl-4-phenylpyrimidin-2-yl group, 5-anthracylpyrimidine
  • a -2-yl group, a 5-phenanthrylpyrimidin-2-yl group, and a 5-pyrenylpyrimidin-2-yl group are more preferable.
  • a 5-methylpyrimidin-2-yl group, a 4,6-dimethylpyrimidin-2-yl group, a 4-phenylpyrimidin-2-yl group, and a 5-phenylpyrimidin-2-yl group 2-phenylpyrimidin-5-yl group, 4,6-diphenylpyrimidin-2-yl group, and 5-naphthylpyrimidin-2-yl group are more preferable.
  • the alkyl group having 2 to 10 carbon atoms, alkoxy group, alkoxyalkyl group, ester group, or ester alkyl group is not particularly limited, and examples thereof include an ethyl group (-Et), an n-propyl group (n- Pr), i-propyl group (i-Pr), n-butyl group (n-Bu), t-butyl group (t-Bu), pentyl (-Pent), hexyl group (-Hex), heptyl group (- Hept), octyl group (—Oct) (above, alkyl group having 2 to 10 carbon atoms), ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, t-butyloxy group, pentyloxy group Hexyloxy group, heptyloxy group, octyloxy group (above, alkoxy group having 2 to 10 carbon
  • the substituents represented by Ar 1 and Ar 2 are not particularly limited, but the following substituents represented by (B1) to (B137) are exemplified in addition to the substituents shown above. (* Represents a connecting part).
  • a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a compound having an excellent performance as an organic electroluminescent element material or Aromatic groups consisting only of 6-membered rings in which 2 to 6 benzene rings and / or pyridine rings are linked and / or condensed ⁇ these groups are a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, carbon A substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group. It may be substituted with at least one) ⁇ .
  • a phenyl group, a pyridyl group, a pyrimidyl group, a pyrimidyl group substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, or 2 to 5 linked benzene rings and / or pyridine rings and / or Or an aromatic group composed only of a condensed 6-membered ring ⁇ these groups include a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a fluorine atom, or a pyrimidyl group (
  • the pyrimidyl group may be substituted with at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group. It is more preferable
  • An aromatic group consisting of only a 6-membered ring ⁇ these groups are a methyl group, a methoxy group, an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a fluorine atom, or a pyrimidyl group (the pyrimidyl group) May be substituted with at least one substituent selected from the group consisting of a methyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, and a pyrenyl group)
  • Ar 1 and Ar 2 are phenyl, naphthyl, anthracyl, phenanthryl, pyrenyl, pyridyl, pyrimidyl, quinolyl, and isoquinolyl groups in terms of performance as a compound organic electroluminescent device material.
  • Naphthylidyl group benzoquinolyl group, phenanthridyl group, acridyl group, phenanthroyl group, biphenyl group, terphenyl group, naphthylphenyl group, phenanthrylphenyl group, anthracylphenyl group, pyrenylphenyl group, naphthylbiphenyl group, Nantrilbiphenyl, Anthracylbiphenyl, Phenylnaphthyl, Binaphthyl, Phenanthrylnaphthyl, Anthracylnaphthyl, Phenylanthracyl, Phenylphenanthryl, Pyridylphenyl, Pyridylbipheny Group, pyridylnaphthyl group, pyridylanthracyl group, pyridylphenanthryl group, quinolylphenyl
  • the preferred substituents are phenyl, naphthyl, anthracyl, phenanthryl, pyrenyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, naphthyridyl, benzoquinolyl, phenanthridyl, acridyl, phenanthryl Group, biphenyl group, terphenyl group, naphthylphenyl group, phenanthrylphenyl group, anthracylphenyl group, pyrenylphenyl group, naphthylbiphenyl group, phenanthrylbiphenyl group, anthracylbiphenyl group, phenylnaphthyl group, binaphthyl group Phenanthryl naphthyl group, anthracyl naphthyl group, phenyl anthracyl group, phenyl phenanthryl group, pyr
  • the aromatic group consisting of only the 6-membered ring is not particularly limited, but is an aromatic group consisting of only the 6-membered ring in which 2 to 6 benzene rings and / or pyridine rings are connected and / or condensed. Substituents similar to the substituents exemplified for the group can be exemplified.
  • Preferred substituents for Ar 1 and Ar 2 are phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 5-phenylpyrimidine- 2-yl group, 4,6-diphenylpyrimidin-2-yl group, 5-naphthylpyrimidin-2-yl group, 4,6-dinaphthylpyrimidin-2-yl group, 5-phenanthrylpyrimidin-2-yl Group, 5-anthracylpyrimidin-2-yl group, 5-pyrenylpyrimidin-2-yl group, or (A1) to (A19), (A21), (A28), (A30), (A32), ( (A36), (A38), (A40), (A42) to (A60), (A63), (A64), (A66) to (A74), (A76), (A78), (A80), (A82)
  • A represents the above general formula (2-1), general formula (2-2), or general formula (2-3).
  • Ar 3 , Ar 4 and Ar 5 are each an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, alkyl group having 2 to 10 carbon atoms, alkoxy group, And may be substituted with an alkoxyalkyl group, an ester group or an ester alkyl group).
  • the aromatic hydrocarbon group having 6 to 12 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenyl group, a 3-biphenyl group, and a 4- Biphenyl group etc. are mentioned.
  • the pyridyl group and pyrimidyl group can be exemplified the same substituents as the substituents exemplified for Ar 1 and Ar 2.
  • alkyl group having 2 to 10 carbon atoms, alkoxy group, alkoxyalkyl group, ester group, or ester alkyl group is not particularly limited, but the same substituents as those exemplified for Ar 1 and Ar 2 are exemplified. can do.
  • the substituents represented by Ar 3 , Ar 4 and Ar 5 are not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, 2, 3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl Group, 3-ethylphenyl group, 4-ethylphenyl group, 2-ethyl-3-methylphenyl group, 2-ethyl-4-methylphenyl group, 2-ethyl-5-methylphenyl group, 2-ethyl-6- Methylphenyl group, 3-ethyl-2-methylphenyl group, 3-ethyl-4-methylphenyl group, 3-ethyl-5-methylphenyl group, 3-ethyl-6-
  • Ar 3 , Ar 4, and Ar 5 are aromatic hydrocarbon groups having 6 to 12 carbon atoms (methyl group, methoxy group, alkyl group having 2 to 10 carbon atoms or An alkoxy group, a pyridyl group, a pyrimidyl group, or a fluorine atom, which may be substituted).
  • the preferred substituent is more preferably a phenyl group, a naphthyl group, or a biphenyl group (these groups may be substituted with a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, or a fluorine atom). preferable.
  • phenyl group 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, or 2-naphthyl group It is more preferable that
  • Ar 3 , Ar 4, and Ar 5 are phenyl, naphthyl, or biphenyl groups (these groups are methyl, methoxy, pyridyl, pyrimidyl, etc.) because they have good performance as organic electroluminescent device materials.
  • Ar 6 and Ar 7 are each independently a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, or an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom) Or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
  • Aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine atom, or alkyl group, alkoxy group, alkoxyalkyl group, ester group or ester alkyl group having 2 to 10 carbon atoms) Can be substituted with the same substituents as exemplified for Ar 3 , Ar 4 and Ar 5 .
  • Ar 6 and Ar 7 are a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, or an aromatic hydrocarbon group having 6 to 12 carbon atoms (methyl group, methoxy group) in terms of good performance as an organic electroluminescent element material.
  • an alkyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, a pyridyl group, a pyrimidyl group, or a fluorine atom which may be substituted.
  • a phenyl group, a naphthyl group, or a biphenyl group (these groups may be substituted with a methyl group, a methoxy group, a pyridyl group, a pyrimidyl group, or a fluorine atom), a hydrogen atom, a methyl group It is more preferably a group, a methoxy group, or a fluorine atom.
  • a hydrogen atom, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-biphenyl group, 4-biphenyl group, 1-naphthyl group, or 2 -It is more preferably a naphthyl group.
  • a hydrogen atom, a phenyl group, a 3-biphenyl group, and a 4-biphenyl group are more preferable.
  • Ar 6 and Ar 7 are phenyl group, naphthyl group, or biphenyl group (these groups are methyl group, methoxy group, pyridyl group, pyrimidyl group, fluorine, etc.) in terms of good performance as an organic electroluminescent element material.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 31 and R 32 are each independently a hydrogen atom, It represents a methyl group, a methoxy group, a phenyl group, a fluorine atom, or an alkyl group having 2 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, an ester group or an ester alkyl group.
  • the alkyl group, the alkoxy group, the alkoxyalkyl group, the ester group, or the ester alkyl group is not particularly limited, and examples thereof are the same as those exemplified for Ar 1 and Ar 2 .
  • the organic electroluminescent element of the compound In terms of good performance as a material, each is preferably independently a hydrogen atom, a methyl group, a methoxy group, a phenyl group, or a fluorine atom, and more preferably a hydrogen atom, a methyl group, a methoxy group, or a phenyl group. Preferably, it is a hydrogen atom.
  • each hydrogen atom in the compound (1) may be independently a deuterium atom.
  • Compound (1) is not particularly limited, but can be exemplified by the following (C1) to (C1076).
  • the compound (1) of the present invention has the following reaction formula
  • Z 1 and Z 2 each independently represent a leaving group
  • M 1 and M 2 each independently represent a metal group
  • compound (3) the compound represented by the general formula (3) is referred to as a compound (3).
  • compound (4) and compound (5) can be produced, for example, using the method disclosed in JP 2008-280330 A [0061] to [0076].
  • Examples of the compound (3) include the following (D1) to (D81), but the present invention is not limited to these.
  • Z 1 and Z 2 each independently represent a leaving group described later.
  • M 1 represents a metal group, a boronic acid group, or a boronic acid ester group.
  • Step 1 is a step of synthesizing compound (1).
  • Compound (1) is synthesized by reacting compound (3) with compound (4) in the presence of a metal catalyst or in the presence of a metal catalyst and a base, and then reacting compound (5).
  • reaction conditions for general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc., the desired product can be obtained in high yield.
  • Step 1 the reaction order of the compound (4) and the compound (5) may be reversed.
  • the compound (4) and the compound (5) may be reacted sequentially in one pot, or the intermediate product may be taken out once in the stage where the compound (4) is reacted, and the compound (5) may be reacted separately. .
  • M 1 and M 2 in the compound (4) and the compound (5) are not particularly limited.
  • ZnX 1 , MgX 2 , Sn (X 3 ) 3 , B (OX 4 ) 2 Etc examples of M 1 and M 2 each independently represent a chlorine atom, a bromine atom or an iodine atom
  • X 3 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group
  • X 4 represents a hydrogen atom and 1 carbon atom. represents an alkyl group or a phenyl group having 4
  • B (OX 4) 2 two X 4 2 may be the same or different.
  • two X 4 can also form a ring containing an oxygen atom and a boron atom together.
  • B (OX 4 ) 2 in the compound (4) and the compound (5) is not particularly limited.
  • B (OH) 2 , B (OMe) 2 , B (O i Pr) 2 , B (OBu) 2 , B (OPh) 2 and the like can be exemplified.
  • B (OX 4 ) 2 in the case where two X 4 are united to form a ring containing an oxygen atom and a boron atom include groups represented by the following (F1) to (F6): The group represented by (F2) is preferable because it can be exemplified and the yield is good.
  • the leaving group represented by Z 1 and Z 2 in the compound (3) is not particularly limited, and examples thereof include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy (OTf) group, and methane. Examples thereof include a sulfonyloxy group, a chloromethanesulfonyloxy group, and a p-toluenesulfonyloxy group.
  • Examples of the metal catalyst that can be used in “Step 1” include a palladium catalyst and a nickel catalyst.
  • the palladium catalyst that can be used in “Step 1” is not particularly limited, and examples thereof include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like.
  • a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield.
  • a 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 in this case is not particularly limited. For example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine.
  • 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 in terms of good reaction yield.
  • the nickel catalyst that can be used in “Step 1” is not particularly limited.
  • the base that can be used in “Step 1” is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, and phosphoric acid.
  • Sodium, sodium fluoride, potassium fluoride, cesium fluoride and the like can be exemplified, and tripotassium phosphate is desirable in terms of a good yield.
  • the molar ratio of the base to the compound (3), the compound (4) and the compound (5) is preferably 1: 2 to 10: 1, and more preferably 1: 1 to 3: 1 in terms of a good yield.
  • a solvent can be used, and it is preferable to use a solvent from the viewpoint of controlling the reaction.
  • the solvent that can be used in “Step 1” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. These may be used in appropriate combination. It is desirable to use a mixed solvent of dioxane and water and a mixed solvent of tetrahydrofuran and water in terms of a good yield.
  • Step 1 can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 80 ° C. to 100 ° C. in terms of a good yield.
  • Compound (1) can be obtained by performing a normal treatment (separation operation or the like) performed by those skilled in the art after completion of “Step 1”. Furthermore, you may refine
  • the compound (3) of the present invention can also be represented as general formula (3-1), general formula (3-2) and general formula (3-3).
  • the compound represented by the general formula (3-1) is referred to as a compound (3-1). The same applies to compound (3-2) and compound (3-3).
  • Compound (3-1), Compound (3-2) and Compound (3-3) can be produced by the method shown by the following reaction formula.
  • Step 2 is a step of obtaining compound (3-1), compound (3-2) or compound (3-3).
  • Compound (3-1) is present in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • a catalyst in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • Compound (3-2) is present in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • a catalyst in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • Compound (3-3) is present in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • a catalyst in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source.
  • Examples of substituents necessary for carrying out the pyrimidine ring formation reaction represented by W 21 , W 22 , W 23 , W 31 , W 32 and W 33 are not particularly limited. Examples include formyl group, carbonyl group, carboxyl group, ester group, amide group, amino group, imino group, amidyl group or its hydrochloride, nitrile group, and halogen. Of these, an amidyl group or a hydrochloride thereof, a formyl group, a nitrile group, a carbonyl group, an amino group, and an imino group are preferable from the viewpoint of ease of synthesis.
  • the leaving group represented by Z 11 , Z 12 , Z 21 , Z 22 , Z 31 and Z 32 in the compound (3-1), the compound (3-2) or the compound (3-3) is particularly limited. not intended to be, but can be exemplified the same substituents as the substituents exemplified for Z 1 and Z 2.
  • the acid that can be used in “Step 2” is not particularly limited.
  • examples thereof include sulfonic acid and p-toluenesulfonic acid.
  • the base that can be used in “Step 2” is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, tripotassium phosphate, and phosphoric acid. Examples include trisodium, sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and the like.
  • the catalyst that can be used in “Step 2” is not particularly limited, and examples thereof include halogens, Lewis acids, Lewis bases, or catalytic amounts of the above acids and bases.
  • halogen include iodine, bromine, and chlorine.
  • Lewis acid and the Lewis base include metal complexes such as indium, ytterbium, zinc, copper, iron, hafnium, and aluminum.
  • the nitrogen source that can be used in “Step 2” is not particularly limited, and examples thereof include ammonium acetate, ammonium chloride, ammonium formate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium iodide, ammonium fluoride, and hydrogen carbonate. Examples thereof include ammonium, ammonium dihydrogen phosphate, ammonium benzenesulfonate, and ammonium p-toluenesulfonate.
  • a solvent can be used, and it is preferable to use a solvent from the viewpoint of reaction control.
  • the solvent that can be used in “Step 2” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene. .
  • Step 2 can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C.
  • the compound (3-1), the compound (3-2) and the compound (3-3) can be obtained by performing a usual treatment (separation operation or the like) performed by those skilled in the art after completion of “Step 2”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.
  • Step 3 is a step of obtaining the compound (9-1) or the compound (9-2).
  • Compound (9-1) is prepared in the presence or absence of a nitrogen source in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base. Is synthesized by reacting compound (6-1) with compound (8-1).
  • Compound (9-2) is prepared in the presence of a catalyst, in the presence of an acid, in the presence of a base, in the presence of a catalyst and an acid, or in the presence of a catalyst and a base, in the presence or absence of a nitrogen source. Is synthesized by reacting compound (6-2) with compound (8-2).
  • the compound (9-1) or compound (9-2) obtained in “Step 3” is purified without refining or by recrystallization, column chromatography or sublimation, etc. Can be used as
  • step 4 will be described with specific examples, but the present invention is not limited to these.
  • Step 4 is a step of obtaining compound (3-1) or compound (3-2).
  • the compound (3-1) is synthesized by oxidizing the dihydrobenzoquinazolyl group of the compound (9-1) in the presence of an oxidizing agent and in the presence of an acid or a base.
  • Compound (3-2) is synthesized by oxidizing the dihydrobenzoquinazolyl group of compound (9-2) in the presence of an oxidizing agent and in the presence of an acid or a base.
  • Examples of the oxidizing agent that can be used in “Step 4” include potassium permanganate, manganese dioxide, chromium (IV) oxide, sodium dichromate, potassium dichromate, potassium chromate, chromate ester, hydrogen peroxide, 2, Examples include 3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (chloranil), tetrachloro-1,2-benzoquinone (o-chloranil), or nitrobenzene. It is done.
  • DDQ 3-dichloro-5,6-dicyano-1,4-benzoquinone
  • chloranil tetrachloro-1,4-benzoquinone
  • o-chloranil tetrachloro-1,2-benzoquinone
  • a solvent can be used, and it is preferable to use a solvent from the viewpoint of controlling the reaction.
  • the solvent that can be used in “Step 4” is not particularly limited, and examples thereof include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene.
  • Step 4 can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C.
  • the compound (3-1) and the compound (3-2) can be obtained by performing a usual treatment (separation operation or the like) performed by those skilled in the art after completion of “Step 4”. Furthermore, you may refine
  • the compound (1) of the present application is suitably used as a material for an organic electroluminescence device.
  • the compound (1) of the present application is suitably used as an electron transport material or an electron injection material for an organic electroluminescence device.
  • the film-forming by a vacuum evaporation method can be mentioned as a preferable example.
  • 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 evaporation method is such that the production tact time for producing the organic electroluminescent element is short and the production cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, cryogenic pumps are used.
  • the thin film for organic electroluminescent elements which consists of a compound A can also be manufactured by the solution coating method.
  • compound A is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, or tetrahydrofuran, and spin coating, ink jet, casting, or dip using a general-purpose apparatus. It is also possible to form a film by, for example.
  • organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, or tetrahydrofuran
  • the typical structure of the organic electroluminescent element that can obtain the effects of the present invention includes a substrate, an anode, a hole-in layer, a hole transport layer, a 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 element 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 electroluminescence device 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. Light transmission properties are desirable for viewing electroluminescent emission through a substrate. Transparent glass or plastic is generally employed as such a substrate.
  • the substrate may be a composite structure including multiple material layers.
  • anode should pass or substantially pass the emission.
  • Common transparent anode (anode) materials used in the present invention are indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide, but other metal oxides such as Aluminum or indium doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also useful.
  • metal nitrides such as gallium nitride, metal selenides such as zinc selenide, or metal sulfides such as zinc sulfide can be used as the anode.
  • the anode can be modified with plasma deposited fluorocarbon.
  • the transmission properties of the anode are not critical and any conductive material that is transparent, opaque or reflective can be used.
  • conductors for this application include gold, iridium, molybdenum, palladium and platinum.
  • a hole injection layer can be provided between the anode and the hole transport layer.
  • the hole injection material can serve to improve the film forming properties of the subsequent organic layer and to facilitate injection of holes into the hole transport layer.
  • 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,
  • the hole transport layer of the organic electroluminescence device preferably contains one or more hole transport compounds such as aromatic tertiary amines.
  • Aromatic tertiary amine means that the compound contains one or more trivalent nitrogen atoms, the trivalent nitrogen atoms being bonded only to carbon atoms, one or more of these carbon atoms being An aromatic ring is formed.
  • the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine.
  • hole transport material an aromatic tertiary amine having one or more amine groups can be used.
  • 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
  • TPBi 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl)
  • 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. In this case, light emission occurs as a result of recombination of electron-hole pairs in this region.
  • the emissive layer may consist of a single material including both small molecules and polymers, but more commonly consists of a host material doped with a guest compound, in which case the emission is mainly from the dopant. Occurs and can have any color.
  • 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 (carbazole-9) -Yl) biphenyl
  • CDBP 4,4′-bis (carbazol-9-yl) -2,2′-dimethylbiphenyl
  • the host material in the light emitting layer may be an electron transport material as defined below, a hole transport material as defined above, or another material that supports hole-electron recombination, or a combination of these materials.
  • fluorescent dopants examples include anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium or thiapyrylium compounds, fluorene derivatives, perifanthene derivatives, indeno Examples include perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, and carbostyryl compounds.
  • An example of a useful phosphorescent dopant is an organometallic complex of a transition metal of iridium, platinum, palladium, or osmium.
  • dopants examples include Alq 3 (tris (8-hydroxyquinoline) aluminum)), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) 3 ( And 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 compound (1) of the present application.
  • the electron transporting layer may contain another electron transporting material, and examples of the electron transporting material include alkali metal complexes, alkaline earth metal complexes, and earth metal complexes. Desirable alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinate lithium (Liq), bis (8-hydroxyquinolinato) zinc, and 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 for the hole element 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 the electron injection property and improving device characteristics (for example, light emission efficiency, constant voltage drive, or high durability).
  • Preferred compounds for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, or anthrone. Etc.
  • the cathode used in the present invention can be formed from almost 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.
  • ⁇ -Tetralone 7.31 g (50.0 mmol) and benzaldehyde 5.31 g (50.0 mmol) were added to 100 mL of acetic acid, and 24.5 g (250 mmol) of concentrated sulfuric acid was added thereto, followed by stirring for 14 hours. Subsequently, 200 mL of water was added to the reaction mixture. The precipitated solid was collected by filtration and washed with water to give the target 2-benzylidene-3,4-dihydro-2H-naphthalen-1-one (A-1) as a light brown powder (yield 10.6 g, yield) 91%).
  • 6-chloro-4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] quinazoline ( J-2) 1.41 g (2.26 mmol), phenylboronic acid 331 mg (2.72 mmol), palladium acetate 10.1 mg (0.0452 mmol), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- 33.1 mg (0.0904 mmol) of triisopropylbiphenyl was added to 45 mL of THF, and 1.5 mL of 3M-potassium carbonate aqueous solution was further added, and the mixture was heated to reflux for 5.5 hours.
  • Test Example-1 Preparation and evaluation of the organic electroluminescent element were performed as follows.
  • the substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning.
  • Each layer was vacuum-deposited on the cleaned substrate by a vacuum evaporation method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG.
  • 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. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate indicated by 1 in FIG. Filmed.
  • sublimation-purified HIL was vacuum-deposited with a film thickness of 65 nm.
  • HAT and HTL were vacuum-deposited with a thickness of 5 nm and 10 nm, respectively.
  • EML-1 and EML-2 were vacuum-deposited at a thickness of 25 nm at a ratio of 954: 46 (mass%).
  • Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.6 to 3.0 nm / second.
  • 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.
  • a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin manufactured by Nagase ChemteX Corporation were used. The structural formulas and abbreviations of the compounds used are shown below.
  • 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 / m 2 luminance
  • cd / A current efficiency
  • lm / W power efficiency
  • Test Example-2 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 4-phenyl-2- [5- (1-pyrenyl) -4 ′-(2-pyridyl) biphenyl-3-yl obtained in Experimental Example 4 instead of benzo [h] quinazoline (A-4) An organic electroluminescent device was produced in the same manner as in Test Example 1 except that benzo [h] quinazoline (B-2) was used, and evaluated in the same manner as in Test Example-1.
  • Test Example 3 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • An organic electroluminescent element was produced in the same manner as in Test Example 1 except that phenylbenzo [h] quinazoline (C-2) was used, and evaluated in the same manner as in Test Example-1.
  • Test Example 4 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • quinazoline (A-4) 2- [3- (9-phenanthryl) -5- (3-pyridyl) phenyl] -4-phenylbenzo [h] obtained in Experimental Example-7
  • An organic electroluminescent device was produced in the same manner as in Test Example 1 except that quinazoline (C-4) was used, and evaluated in the same manner as in Test Example-1.
  • Test Example-5 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 4-phenyl-2- [4- (4,6-diphenylpyridin-2-yl) -1,1 ′ obtained in Experimental Example-9 in place of benzo [h] quinazoline (A-4): 3
  • An organic electroluminescent device was prepared in the same manner as in Test Example 1 except that “, 1 ′′ -terphenyl-5′-yl] -benzo [h] quinazoline (E-2) was used. Evaluation was performed in the same manner as in 1.
  • Test Example-6 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [4- (5-phenylpyridin-2-yl) -1,1 ′: 3 ′ obtained in Experimental Example-10 An organic electroluminescent device was prepared in the same manner as in Test Example 1 except that 1 ′′ -terphenyl-5′-yl] benzo [h] quinazoline (F-2) was used, and the same as in Test Example-1. Evaluated.
  • Test Example-7 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [4- (6-phenylpyridin-2-yl) -1,1 ′ obtained in Experimental Example-11, 3 ′, An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′′ -terphenyl-5′-yl] benzo [h] quinazoline (F-3) was used, and the same as in Test Example-1. Evaluated.
  • Test Example-8 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [5- (6-phenylpyridin-3-yl) -1,1 ′ obtained in Experimental Example-12, 4 ′, An organic electroluminescent device was prepared in the same manner as in Test Example 1 except that 1 ′′ -terphenyl-3-yl] benzo [h] quinazoline (G-2) was used. evaluated.
  • Test Example-9 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • 4-phenyl-2- [4- (4-isoquinolyl) -1,1 ′: 3 ′, 1 ′′: 4 obtained in Experimental Example-13 ”, 1 ′ ′′-Quaterphenyl-5′-yl] benzo [h] quinazoline (H-2) was used, and an organic electroluminescence device was prepared and tested in the same manner as in Test Example 1. Evaluation was performed in the same manner as in Example-1.
  • Test Example-10 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [4- (8-quinolyl) -1,1 ′: 3 ′, 1 ′′: 4 obtained in Experimental Example-14 ”, 1 ′ ′′-Quaterphenyl-5′-yl] benzo [h] quinazoline (H-3) was used, and an organic electroluminescent device was prepared and tested in the same manner as in Test Example-1. Evaluation was performed in the same manner as in Example-1.
  • Test Example-11 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [5- (5-phenylpyridin-2-yl) -1,1 ′: 4 ′ obtained in Experimental Example-15 An organic electroluminescent device was prepared in the same manner as in Test Example 1 except that 1 ′′ -terphenyl-3-yl] benzo [h] quinazoline (H-4) was used. evaluated.
  • Test Example-12 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • 1 ′′ ′′-kinkphenyl-5 ′′ -yl) -4-phenylbenzo [h] quinazoline (H-6) was used to produce an organic electroluminescent device in the same manner as in Test Example-1. Then, evaluation was made in the same manner as in Test Example-1.
  • Test Example-13 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 Instead of benzo [h] quinazoline (A-4), 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′ obtained in Experimental Example-19 An organic electroluminescent device was produced in the same manner as in Test Example 1 except that 1 ′′ -terphenyl-5′-yl] quinazoline (I-2) was used, and evaluated in the same manner as in Test Example-1.
  • Test Example-14 (Example) 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1 4,6-diphenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′ obtained in Experimental Example-21 in place of benzo [h] quinazoline (A-4): 3
  • An organic electroluminescent device was produced in the same manner as in Test Example 1 except that “, 1 ′′ -terphenyl-5′-yl] quinazoline (J-3) was used, and evaluated in the same manner as in Test Example-1. did.
  • Reference Example-1 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • An organic electroluminescent device obtained by vacuum-depositing ', 1''-terphenyl-5'-yl] -1,3,5-triazine (represented by the following formula) was prepared and measured in the same manner as in Test Example-1. did.
  • Comparative Example-1 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • Comparative Example-2 4-phenyl-2- [4,4 ′′ -bis (2-pyridyl) -1,1 ′: 3 ′, 1 ′′ -terphenyl-5′-yl] of the electron transport layer 5 of Test Example-1
  • benzo [h] quinazoline (A-4) an organic electroluminescent device in which 2,4-diphenylquinazoline (represented by the following formula) contained in Patent No. WO2006 / 104118 was vacuum-deposited was tested in Test Example 1. It produced and measured similarly.
  • Test Examples-1 to 14 The measurement results of Test Examples-1 to 14, Reference Example-1, and Comparative Examples-1 and 2 are summarized in the table below.
  • the thin film comprising the compound (1) of the present invention exhibits high thin film stability, heat resistance, electron transport properties, hole blocking ability, redox resistance, water resistance, oxygen resistance, electron injection properties, etc.
  • a material of an electroluminescent element it can use suitably as an electron transport material.
  • the compound (1) of the present invention has a wide energy gap and triplet energy, and can be used in combination with a fluorescent or phosphorescent organic electroluminescent material.
  • the compound (1) of this invention can be used for a light emission host layer other than an electron carrying layer from the characteristic. Moreover, it can be used even if it mixes or laminates with another compound as an electron carrying layer.
  • this compound has high solubility, and can be used for coating elements in addition to vapor deposition. From these effects, these elements are expected to have significant effects such as suppression of battery consumption by reducing power consumption, improvement of product life by extending life, and reduction of burden on the drive circuit.

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

Abstract

Cette invention concerne des composés représentés par la formule générale (1) à titre de dispositif électroluminescent organique à rendement élevé, basse tension d'attaque, et longue durée de vie et un matériau le permettant, en particulier un matériau de transport d'électrons, des procédés de production desdits composés, et un dispositif électroluminescent organique les utilisant. (Dans la formule, Ar1 et Ar2 sont tels que définis dans la description, A représente la formule générale (2-1), la formule générale (2-2), ou la formule générale (2-3) où ＊ représente un site de liaison, et Ar3-Ar7, R11-R16, R21-R26, R31, et R32 sont tels que définis dans la description).
PCT/JP2015/065650 2014-05-29 2015-05-29 Composés de quinazoline et benzoquinazoline, leur procédé de production et utilisation WO2015182769A1 (fr)

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JP2014111639 2014-05-29
JP2014-111639 2014-05-29
JP2014124117 2014-06-17
JP2014-124117 2014-06-17
JP2014-125801 2014-06-18
JP2014125801 2014-06-18

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CN110143952A (zh) * 2019-06-17 2019-08-20 上海天马有机发光显示技术有限公司 一种化合物、显示面板及显示装置
CN111377904A (zh) * 2018-12-29 2020-07-07 北京鼎材科技有限公司 有机电致发光材料及器件

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WO2013069762A1 (fr) * 2011-11-11 2013-05-16 東ソー株式会社 Composé d'azine cyclique comportant un groupe aromatique condensé contenant de l'azote, son procédé de production, et élément électroluminescent organique l'utilisant en tant que composant constituant
WO2013180376A1 (fr) * 2012-05-30 2013-12-05 Alpha Chem Co., Ltd. Nouveau matériau de transport d'électrons et dispositif organique électroluminescent l'utilisant
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JP2003045662A (ja) * 2001-08-01 2003-02-14 Konica Corp 有機エレクトロルミネッセンス素子及び表示装置
WO2004039786A1 (fr) * 2002-10-30 2004-05-13 Ciba Specialty Chemicals Holding Inc. Dispositif electroluminescent
WO2006104118A1 (fr) * 2005-03-29 2006-10-05 Konica Minolta Holdings, Inc. Dispositif electroluminescent organique, dispositif d’affichage et dispositif d’eclairage
JP2011063584A (ja) * 2009-08-21 2011-03-31 Tosoh Corp トリアジン誘導体、その製造方法、及びそれを構成成分とする有機電界発光素子
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WO2013180376A1 (fr) * 2012-05-30 2013-12-05 Alpha Chem Co., Ltd. Nouveau matériau de transport d'électrons et dispositif organique électroluminescent l'utilisant
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CN111377904A (zh) * 2018-12-29 2020-07-07 北京鼎材科技有限公司 有机电致发光材料及器件
CN110143952A (zh) * 2019-06-17 2019-08-20 上海天马有机发光显示技术有限公司 一种化合物、显示面板及显示装置

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