WO2015037675A1 - Composé de benzothiénopyrimidine, procédé de production de ce dernier et élément électroluminescent organique contenant ce dernier - Google Patents

Composé de benzothiénopyrimidine, procédé de production de ce dernier et élément électroluminescent organique contenant ce dernier Download PDF

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WO2015037675A1
WO2015037675A1 PCT/JP2014/074122 JP2014074122W WO2015037675A1 WO 2015037675 A1 WO2015037675 A1 WO 2015037675A1 JP 2014074122 W JP2014074122 W JP 2014074122W WO 2015037675 A1 WO2015037675 A1 WO 2015037675A1
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内田　直樹
陽子 本間
尚志 飯田
華奈 藤田
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
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • H—ELECTRICITY
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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
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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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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    • 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
    • H10K50/165—Electron transporting layers comprising dopants
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    • H10K85/30—Coordination compounds

Definitions

  • the present invention relates to a benzothienopyrimidine compound useful as a component of an organic electroluminescent device, a method for producing the same, and an organic electroluminescent device containing the same.
  • An organic electroluminescent element has a basic 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 of the light-emitting layer.
  • This element utilizes light emission (fluorescence or phosphorescence) accompanying exciton deactivation caused by recombination of holes and electrons, and is applied to displays and the like.
  • 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, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured.
  • dibenzothiophene compounds for example, Patent Document 1
  • nitrogen-substituted dibenzothiophene compounds for example, see Patent Document 2-3
  • improvement is desired in that the device has a higher driving voltage and a longer life is required.
  • Organic electroluminescence devices have begun to be used in various display devices, but further improvements in device performance such as longer life, higher luminous efficiency, and lower drive voltage are required. More specifically, there is a demand for the development of a carrier transport material that achieves a long life, high luminous efficiency, low driving voltage, and suppression of voltage rise during driving.
  • the carrier transport materials for the electron injection material and the electron transport material, there are new materials that drive the device at a low voltage due to excellent electron injection properties and electron transport properties, and have high luminous efficiency and drive the device for a long time. It is desired.
  • the organic electroluminescent element material is generally heated to a high temperature in a vacuum at the time of sublimation purification and vapor deposition for producing the organic electroluminescent element, and a material having higher heat resistance is required.
  • the present inventors have found that the benzothienopyrimidine compound represented by the general formula (1) of the present invention has higher electron durability and higher resistance than conventionally known compounds. It has been found that the hole durability is remarkably improved. From such knowledge, when the benzothienopyrimidine compound is used as an electron transport layer in an organic electroluminescent device, the organic electroluminescent device has a longer life than when a known or general-purpose electron transport material is used. The inventors have found that the voltage rise during driving is suppressed, and have completed the present invention.
  • the present inventors have found that by replacing the 2-position and 4-position of benzothienopyrimidine with an aromatic group, the heat resistance of the compound can be improved and the thermal deterioration of the material can be suppressed, and the present invention is completed. It came to.
  • the present invention relates to a benzothienopyrimidine compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), a production method thereof, and an organic electroluminescent device containing the same. .
  • R 1 to R 4 each independently represents an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group)
  • Ar 1 and Ar 2 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group)
  • this invention can provide a very useful manufacturing intermediate in order to manufacture the said compound (1) industrially.
  • the benzothienopyrimidine compound of the present invention is excellent in electron durability and hole durability.
  • the benzothienopyrimidine compound of the present invention is used as an electron transport layer in an organic electroluminescent device, the organic electroluminescent device has a long life, and An increase in voltage during driving is suppressed. Moreover, it is excellent in heat resistance than a conventionally well-known benzothienopyrimidine compound.
  • FIG. 1 is a cross-sectional view of an organic electroluminescent element produced in Evaluation Example 1 or the like.
  • FIG. 2 is a cross-sectional view of an organic electroluminescent element produced in Evaluation Example 10 or the like.
  • the present invention relates to the above compound (1), a production method thereof, and an organic electroluminescence device containing the compound.
  • the present invention also relates to a production intermediate for producing the above compound (1).
  • the aromatic group having 4 to 66 carbon atoms defines only a ring skeleton that may be condensed or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent.
  • the aromatic group having 4 to 66 carbon atoms the aromatic group is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.
  • the aromatic group having 4 to 66 carbon atoms represents an aromatic group having 4 to 66 carbon atoms in the ring skeleton and may be condensed or linked. Note that the aromatic group having 4 to 66 carbon atoms does not include the carbon number of a substituent that may be separately provided.
  • the aromatic group having 4 to 66 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.
  • the aromatic group having 4 to 66 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylbiphenyl group, and a biphenylnaphthyl group.
  • the alkyl group having 3 to 10 carbon atoms is not particularly limited.
  • the alkoxy group having 3 to 10 carbon atoms is not particularly limited, and examples thereof include an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group.
  • Sec-pentyloxy group cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, or phenethyloxy Groups and the like.
  • the halogenated alkyl group having 1 to 3 carbon atoms is not particularly limited, and examples thereof include chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloroethyl group, dichloromethane.
  • Examples include an ethyl group, trichloroethyl group, pentachloroethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group, chloropropyl group, or fluoropropyl group.
  • the halogenated alkoxy group having 1 to 3 carbon atoms is not particularly limited, and examples thereof include a chloromethyloxy group, a dichloromethyloxy group, a trichloromethyloxy group, a fluoromethyloxy group, a difluoromethyloxy group, Fluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, pentafluoroethyloxy group, chloro A propyloxy group, a fluoropropyloxy group, etc. are mentioned.
  • the diarylamino group having 10 to 36 carbon atoms represents an amino group in which two kinds of aryl groups which may be different from each other are bonded, and means a group having 10 to 36 carbon atoms as a whole.
  • the diarylamino group having 10 to 36 carbon atoms is not particularly limited.
  • N, N-diphenylamino group, N-tolyl-N-phenylamino group, N, N-ditolylamino group, or N, N-dibiphenyl is preferable in that the compound (1) has excellent electron transport material characteristics.
  • An amino group is preferred.
  • the sulfide group having 3 to 10 carbon atoms is not particularly limited.
  • the aromatic group having 4 to 66 carbon atoms is each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or a methoxy group.
  • And may have a plurality of substituents. When there are a plurality of substituents, each substituent may be the same or different.
  • the substituent that the aromatic group having 4 to 66 carbon atoms in R 1 to R 4 , Ar 1 , and Ar 2 may have is a methyl group or a carbon number in terms of excellent electron transport material characteristics. 10-36 diarylamino groups are preferred.
  • R 1 to R 4 are each independently an aromatic group having 4 to 30 carbon atoms in terms of excellent electron transport material characteristics (these substituents are each independently a fluorine atom, a methyl group, an ethyl group, A substituent of an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms, preferably a phenyl group, a biphenyl group, a phenanthryl group, Pyrenyl, fluoranthenyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl
  • the aromatic group having 4 to 30 carbon atoms is not particularly limited, but among the substituents exemplified in the aromatic group having 4 to 66 carbon atoms, the total number of carbon atoms is 30 or less. Things can be illustrated.
  • the aromatic group having 4 to 30 carbon atoms defines only a ring skeleton that may be condensed or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent.
  • the aromatic group in the aromatic group having 4 to 30 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a condensed or linked group thereof.
  • the aromatic group having 4 to 30 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylbiphenyl group, and a biphenylnaphthyl group.
  • any one of them is a condensed ring aromatic group having 7 to 18 carbon atoms or any one of the following general formulas (2) to (9), because of excellent electron transport material properties.
  • the substituents represented by these groups are each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, Preferably a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
  • Either one is a condensed aromatic group having 7 to 18 carbon atoms or a substituent represented by any one of the following general formulas (2) to (9) (these substituents are each independently Methyl group or dia having 10 to 36 carbon atoms Ruamino may be substituted with a group.) Is more preferable.
  • Ar 1 and Ar 2 one of them is a condensed aromatic group having 7 to 18 carbon atoms (fluorine atom, methyl group, ethyl group, 3 to 10 carbon atoms, because of excellent electron transport material properties.
  • 18 substituted ring aromatic groups which may be substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms
  • Ar 1 and Ar 2 are each independently a phenyl group, a condensed aromatic group having 7 to 18 carbon atoms, and the following general formulas (2) to (2) to A substituent represented by any one of the general formula (9) (these substituents are each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, It may have an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
  • Ar 1 and Ar 2 are each independently a phenyl group, a condensed aromatic group having 7 to 18 carbon atoms, and the following general formula: Any of (2) to general formula (9) (These substituents may be each independently substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms). It is more preferable.
  • Ar 1 and Ar 2 both are independently a phenyl group, a condensed ring aromatic group having 7 to 18 carbon atoms (a fluorine atom, a methyl group, an ethyl group) because of excellent electron transport material properties.
  • An alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or the number of carbon atoms 10 to 36 diarylamino groups may be substituted.
  • Ar 1 and Both of Ar 2 are each independently a condensed aromatic group having 7 to 18 carbon atoms (which may be substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms) or the following general formula (2 )
  • a substituent represented by any of these is more preferable.
  • each Ar 3 is independently an aromatic group having 4 to 30 carbon atoms (each independently a fluorine atom, methyl group, ethyl group, 3 to 10 carbon atoms) Alkyl group, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino having 10 to 36 carbon atoms And a methyl group, an ethyl group, a methoxy group, an ethoxy group, a diarylamino group having 10 to 36 carbon atoms, or a hydrogen atom.
  • the condensed aromatic group having 7 to 18 carbon atoms defines only the condensed ring skeleton, and the number of carbon atoms of the substituent is not included in the number of carbon atoms of the condensed aromatic group.
  • the condensed ring aromatic group having 7 to 18 carbon atoms is composed of a condensed ring aromatic hydrocarbon group having 7 to 18 carbon atoms and a condensed ring heteroaromatic group having 7 to 18 carbon atoms, and is not particularly limited.
  • the aromatic group having 4 to 30 carbon atoms in the general formulas (2) to (9) has the same definition as the aromatic group having 4 to 30 carbon atoms represented by R 1 to R 4 and is particularly limited. However, the same substituents as those exemplified for R 1 to R 4 can be exemplified.
  • diarylamino group having 10 to 36 carbon atoms in the general formulas (2) to (9) is not particularly limited, but is exemplified in the diarylamino group having 10 to 36 carbon atoms in the general formula (1). The same thing as what was done can be illustrated.
  • the diarylamino group having 10 to 36 carbon atoms is not particularly limited.
  • Ar 1 and Ar 2 are a condensed aromatic group of 7 to 18 or a substituent represented by any one of the general formulas (2) to (9), each independently a fluorine atom, Methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy having 1 to 3 carbon atoms And may have a substituent selected from the group consisting of a group and a diarylamino group having 10 to 36 carbon atoms, and the substituent may be plural. When there are a plurality of substituents, each substituent may be the same or different.
  • Ar 3 is each independently an aromatic group having 4 to 30 carbon atoms (each independently) in terms of excellent electron transport properties.
  • they are each independently an aromatic group having 4 to 24 carbon atoms (each independently having a fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent).
  • Ar 3 is each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenylpyridyl group, diphenylpyridylphenyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl group, Naphtyl, biphenylyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, quinolyl Group, isoquinolyl group, indolyl group, imidazo
  • Ar 3 is each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenylpyridyl group, diphenylpyridylphenyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl.
  • Ar 3 is each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenylpyridyl group, diphenylpyridylphenyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl.
  • the aromatic group having 4 to 24 carbon atoms is an aromatic group having a ring skeleton having 4 to 24 carbon atoms and may be condensed or linked. Note that the aromatic group having 4 to 24 carbon atoms does not include the carbon number of a substituent that may be separately provided.
  • the aromatic group in the aromatic group having 4 to 24 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a condensed or linked group thereof.
  • the aromatic group having 4 to 24 carbon atoms is not particularly limited, but among the substituents exemplified in the aromatic group having 4 to 66 carbon atoms, those having a total number of carbon atoms of 24 or less.
  • benzothienopyrimidine compound represented by the general formula (1) include the following compounds 1 to 140, but the present invention is not limited thereto.
  • the benzothienopyrimidine compound (1) of the present invention is prepared by the following reaction formula (1), reaction formula (2), or reaction formula in the presence of a base, a metal catalyst, or a base and a metal catalyst. It can be produced by the method shown in (12).
  • the compound represented by the general formula (10) is generally referred to as the compound (10).
  • R 1 to R 4 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group)
  • Ar 1 and Ar 2 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group)
  • Ar 11 , Ar 12 and Ar 13 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group). , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
  • X 1 to X 4 each independently represents an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group or an ethoxy group).
  • X 5 to X 6 and Y each independently represent a hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, or 3 to 10 carbon atoms.
  • X 7 represents a leaving group.
  • Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom.
  • the compound (10) used by Reaction formula (1) can be manufactured by the method shown by following Reaction formula (3) or Reaction formula (13) in presence of a base or an acid.
  • the compound (11) can be obtained by the following reaction formula (4) and the method represented by the reaction formula (5), or the reaction formula (14) and the reaction formula (15). It can be produced by the method shown.
  • Ar 11 and Ar 12 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group)
  • R 5 represents a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or an aromatic group having 5 to 10 carbon atoms.
  • X 1 to X 4 are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, It may have an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
  • X 5 to X 6 each independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or an alkoxy having 3 to 10 carbon atoms.
  • X 7 represents a leaving group.
  • Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom.
  • R 5 represents a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or an aromatic group having 5 to 10 carbon atoms.
  • the alkyl group having 3 to 10 carbon atoms has the same definition as above.
  • the aromatic group having 5 to 10 carbon atoms is not particularly limited, and examples thereof include a pyridyl group, a phenyl group, a tolyl group, a tert-butylphenyl group, a naphthyl group, a quinolyl group, and an isoquinolyl group.
  • Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom.
  • a chlorine atom or a bromine atom is preferable in terms of good reaction yield and easy availability.
  • the leaving group represented by X 1 to X 7 and Y is not particularly limited.
  • a metal-containing group for example, Li, Na MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl 2 , AlBr 2 , Al (Me) 2 , Al (Et) 2 , Al ( i Bu) 2 , Sn (Me) 3 ,
  • ZnR 24 examples include ZnCl, ZnBr, ZnI, etc.), Si (R 21 ) 3 (for example, SiMe 3 , SiPh 3 , SiMePh 2 , SiCl 3, SiF 3, Si (OMe ) 3, Si (OEt) 3, Si (OMe) 2 OH , etc.), BF 3 K, B ( OR 22) 2 ( e.g., B OH) 2, B (OMe) 2, B (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the like), B (OR 23) 3, etc.) and the like.
  • Si (R 21 ) 3 for example, SiMe 3 , SiPh 3 , SiMePh 2 , SiCl 3, SiF 3, Si (OMe ) 3, Si (OEt) 3, Si (OMe) 2 OH , etc.
  • B ( OR 22) 2 e.g., B OH) 2, B (OMe) 2, B (O i Pr) 2, B (OBu
  • the metal-containing group represented by X 1 to X 7 and Y may be coordinated with a ligand such as ethers or amines. There is no limit as long as it does not.
  • Examples of B (OR 23 ) 3 include those represented by the following (I) to (III).
  • chlorine atom, bromine atom, triflate, iodine atom, B (OR 22 ) 2 , or B (OR 23 ) 3 is selected from the viewpoint of ease of post-reaction treatment and raw material procurement. preferable.
  • reaction formula (1) As shown in the reaction of the reaction formula (1), the compound (1) of the present invention is obtained by reacting the compound (10) or the compound (11) with the compound (21) in the presence of a metal catalyst or in the presence of a base and a metal catalyst. And can be synthesized by performing a coupling reaction.
  • a metal catalyst is a palladium catalyst, a nickel catalyst, or a copper catalyst in reaction of Reaction formula (1) at the point which the efficiency etc. of a coupling reaction are excellent.
  • X 1 to X 7 and Y are a hydrogen atom, a chlorine atom, a bromine atom, a triflate, an iodine atom, B (OR 22 ) 2 , or Si (R 21 ) 3 , it is essential to add a base. .
  • phase transfer catalyst can be added in the reaction of the reaction formula (1).
  • the phase transfer catalyst is not particularly limited.
  • 18-crown-6-ether or the like can be used.
  • the amount added is an arbitrary amount within a range that does not significantly inhibit the reaction.
  • the metal catalyst used in the reaction of the reaction formula (1) is not particularly limited, and examples thereof include a palladium catalyst, a copper catalyst, and a nickel catalyst.
  • the palladium catalyst is not particularly limited, and examples thereof include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Further, ⁇ -allyl palladium chloride dimer, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert Examples include -butyl) phosphine palladium and dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium.
  • a palladium complex having a tertiary phosphine as a ligand such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert-butyl) phosphinepalladium, is preferable in terms of high yield, and is available. In terms of ease, tri (tert-butyl) phosphine palladium is more preferable.
  • the copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper triflate. Among these, copper oxide and copper iodide are preferable from the viewpoint of excellent coupling reaction results, and copper oxide is more preferable from the viewpoint of easy availability.
  • the nickel catalyst is not particularly limited.
  • dichloro [1,1′-bis (diphenylphosphino) ferrocene] nickel Examples of the four include nickel complexes having tertiary phosphine as a ligand) and dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel.
  • dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, and dichloro (N, N, N ', N'-tetramethylethylenediamine) nickel have excellent coupling reaction results.
  • dichloro (dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable in terms of easy availability.
  • a tertiary phosphine is added to a palladium salt, nickel salt or complex thereof. Can be adjusted. The adjustment can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.
  • the tertiary phosphine is not particularly limited.
  • triphenylphosphine trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl.
  • (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl is preferred because it is readily available and yields are good.
  • the addition amount of the tertiary phosphine is 1 mol of palladium salt, nickel salt or complex thereof (in terms of palladium or nickel atom).
  • the amount is preferably 0.1 to 10 times mol, and more preferably 0.3 to 5 times mol in terms of good yield.
  • a ligand separately to said copper catalyst.
  • the ligand added to the copper catalyst is not particularly limited.
  • 2,2′-bipyridine, 1,10-phenanthroline, N, N, N ′, N′-tetramethylethylenediamine, triphenyl Examples include phosphine, 2- (dicyclohexylphosphino) biphenyl, and the like. Of these, 1,10-phenanthroline is preferred because it is readily available and yields are good.
  • the base that can be used is not particularly limited.
  • potassium carbonate, potassium phosphate, or sodium hydroxide is preferable in terms of a good yield.
  • the reaction of reaction formula (1) is preferably carried out in a solvent.
  • the solvent is not particularly limited, and examples thereof include water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol or xylene. These may be exemplified, and these may be used in appropriate combination. Of these, a mixed solvent of 1,4-dioxane, xylene, toluene and butanol or a mixed solvent of xylene and butanol is preferable in terms of a good yield.
  • the compound (21) in the reaction formula (1) is not particularly limited, but examples thereof include the compounds represented by the following 4-1 to 4-63.
  • substituents are each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, or 1 to 3 carbon atoms.
  • a halogenated methyl group, a halogenated methoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms may be used as a substituent.
  • Y is the same definition as Y in the general formula (21).
  • substituents are each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, or 1 to 3 carbon atoms.
  • a halogenated methyl group, a halogenated methoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms may be used as a substituent.
  • Y is the same definition as Y in the general formula (21).
  • Compound (21) is, for example, J. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal 16: Journal of Japan. 10, 941-944, 2008, or Chemistry of Materials, 20, 595-15953, 2008.
  • any hydrogen atom in compound (21) may be substituted with a deuterium atom.
  • the compound (10) or (11) is reacted with the compound (21) in the presence or absence of a base in the presence of a metal catalyst to produce the compound (1) of the present invention.
  • the target product can be obtained in good yield.
  • the amount of the metal catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1% with respect to 1 mol of the compound (10) or (11) in terms of good yield. It is preferred that the amount be 0.01 mol (converted to metal atoms).
  • the amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times by mole, and 1 to 4 times by mole in terms of good yield, relative to 1 mole of compound (21). Is more preferable.
  • the compound (10) and the compound (11) industrially supply a compound such as the compound (1) that is remarkably excellent in low driving voltage property, high light emission efficiency, and long life of the organic electroluminescence device. Therefore, it is an excellent material and is very valuable industrially.
  • reaction formulas (2), (3) and (4) will be described.
  • the reactions of the reaction formulas (2), (3) and (4) can be carried out by subjecting the compounds described in the respective reaction formulas to a ring condensation reaction in the presence of a base or an acid, respectively.
  • the base that can be used in the reactions of the reaction formulas (2), (3) and (4) is not particularly limited, and examples thereof include potassium tert-butoxide, sodium hydroxide, potassium hydroxide and sodium carbonate.
  • potassium tert-butoxide is preferred because of its good yield.
  • the acid that can be used in the reaction is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, benzoic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and p-toluenesulfone.
  • Examples include acids and various Lewis acids.
  • sulfuric acid is preferred because of its good yield.
  • the reactions of reaction formulas (2), (3) and (4) are preferably carried out in a solvent.
  • the solvent is not particularly limited, and examples thereof include water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol or xylene. These may be exemplified, and these may be used in appropriate combination. Of these, THF, DMF, and xylene are preferable in terms of good yield.
  • the amount of the base used is not particularly limited, but is preferably 0.5 to 10-fold mol per mol of the compounds (13), (16) and (19), and the yield is good. More preferably, it is 1.1 to 4.0 moles.
  • reaction formula (2) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (6) and (7).
  • Ar 1 , Ar 2 , R 1 to R 4 , and Z have the same definitions as those in Reaction Formula (2).
  • Compounds (12) to (14) used in the reaction of reaction formula (2) can be produced using a known production method, or commercially available products can be used.
  • the compound (12) is not particularly limited, and examples thereof include the following compounds represented by 5-1 to 5-38.
  • the compound (13) is not particularly limited, and examples thereof include the compounds represented by the following 6-1 to 6-15.
  • the compound (14) is not particularly limited, and examples thereof include the compounds represented by the following 7-1 to 7-39.
  • Reaction formula (2) can be decomposed into reaction formulas (6) and (7). That is, in this reaction, compound (12) is produced by reacting compound (12) with compound (13) in the presence of a base. The compound (22) is reacted with the compound (14) as represented by the reaction formula (7) to obtain the compound (1) of the present invention.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times mol per mol of the compound (13), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (12) and the compound (13) used in the reaction formula (6) is not particularly limited, but the compound (12) is 0.1 to 10-fold mol per mol of the compound (13).
  • the compound (22) In terms of a good yield of the compound (22), it is preferably 1.1 to 2.0 moles. There is no particular limitation on the molar ratio of the compound (22) and the compound (14) used in the reaction formula (7), but the compound (14) is 0.1 to 20-fold mol with respect to 1 mol of the compound (22). In view of a good yield of the benzothienopyrimidine compound (1) of the present invention, 1.0 to 5 times is preferable.
  • reaction formula (12) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (16) and (17).
  • Ar 1 , Ar 2 , R 1 to R 4 , and Z have the same definitions as those in Reaction Formula (2).
  • Compounds (12) to (14) used in the reaction of reaction formula (2) can be produced using a known production method, or commercially available products can be used.
  • the compound (25) is not particularly limited, and examples thereof include the compounds represented by the following 25-1 to 25-38.
  • the compound (26) is not particularly limited, and examples thereof include the compounds represented by the following 26-1 to 26-15.
  • Compound (14) is not particularly limited, and examples thereof include the same compounds as those in Reaction Formula (2).
  • Reaction formula (2) can be decomposed into reaction formulas (16) and (17). That is, in this reaction, compound (22) is produced by reacting compound (25) with compound (26) in the presence of a base.
  • Compound (1) of the present invention is obtained by reacting Compound (22) with Compound (14) as represented by Reaction Formula (17).
  • the amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (26), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (25) and the compound (26) used in the reaction formula (16) is not particularly limited, but the compound (25) is 0.1 to 10-fold mol per mol of the compound (26).
  • the compound (22) In terms of a good yield of the compound (22), it is preferably 1.1 to 2.0 moles. There is no particular limitation on the molar ratio of the compound (22) and the compound (14) used in the reaction formula (17), but the compound (14) is 0.1 to 20-fold mol with respect to 1 mol of the compound (22). In view of a good yield of the benzothienopyrimidine compound (1) of the present invention, 1.0 to 5 times is preferable.
  • reaction formula (3) can be carried out in one pot, but can also be carried out stepwise as shown in the following reaction formulas (8) and (9).
  • Ar 11 , Ar 12 , X 1 to X 6 , and Z have the same definitions as in reaction formula (3).
  • Compounds (15) to (17) can be produced using known methods, or commercially available products can also be used.
  • the compound (15) is not particularly limited, and examples thereof include the compounds represented by the following 8-1 to 8-10.
  • the compound (16) is not particularly limited, and examples thereof include the compounds represented by the following 9-1 to 9-5.
  • the compound (17) is not particularly limited, and examples thereof include the compounds represented by the following 10-1 to 10-12.
  • Reaction formula (3) is a method for producing the compound (10) of the present invention by reacting the compound (15), the compound (16) and the compound (17) in the presence of a base or an acid.
  • Reaction formula (3) can be decomposed into reaction formulas (8) and (9). That is, in this reaction, compound (23) is produced by reacting compound (15) with compound (16) in the presence of a base.
  • the compound (10) of the present invention is obtained by reacting the compound (23) with the compound (17) as represented by the reaction formula (9). Although the compound (23) may be isolated, it may be used for the reaction (9) which is the next step in one pot without isolation.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times by mole with respect to 1 mole of the compound (16), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (15) and the compound (16) used in the reaction formula (8) is not particularly limited, but the compound (15) is 0.1 to 10-fold mol per mol of the compound (16). In terms of good yield of compound (23), it is preferably 1.1 to 2.0 moles. There is no particular limitation on the molar ratio of the compound (23) and the compound (17) used in the reaction formula (9), but the compound (17) is 0.1 to 20-fold mol with respect to 1 mol of the compound (23). In view of good yield of the compound (10) of the present invention, 1.0 to 5 times is preferable.
  • Reaction formula (13) can be performed in one pot, but can also be performed stepwise as shown in reaction formulas (18) and (19) below.
  • reaction formulas (18) and (19) In the general formula, Ar 11 , Ar 12 , X 1 to X 6 , and Z have the same definitions as in reaction formula (3).
  • Compounds (27) to (28) can be produced using known methods, or commercially available products can also be used.
  • the compound (27) is not particularly limited, and examples thereof include the compounds represented by the following 27-1 to 27-10.
  • the compound (28) is not particularly limited, and examples thereof include the compounds represented by the following 28-1 to 28-5.
  • Compound (17) is not particularly limited, and examples thereof include the same compounds as those in Reaction Formula (3).
  • Reaction formula (13) is a method for producing compound (10) of the present invention by reacting compound (27), compound (28) and compound (17) in the presence of a base or acid.
  • Reaction formula (13) can be decomposed into reaction formulas (18) and (19). That is, in this reaction, compound (23) is produced by reacting compound (27) with compound (28) in the presence of a base.
  • the compound (10) of the present invention is obtained by reacting the compound (23) with the compound (17) as represented by the reaction formula (9). Although the compound (23) may be isolated, it may be used for the reaction (9) which is the next step in one pot without isolation.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (28), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (27) and the compound (28) used in the reaction formula (18) is not particularly limited, but the compound (27) is 0.1 to 10 moles per 1 mole of the compound (28). In terms of good yield of compound (23), it is preferably 1.1 to 2.0 moles.
  • the molar ratio of the compound (23) and the compound (17) used in the reaction formula (19) is not particularly limited, but the compound (17) is 0.1 to 20-fold mol with respect to 1 mol of the compound (23). In view of good yield of the compound (10) of the present invention, 1.0 to 5 times is preferable.
  • reaction formula (4) will be described.
  • the reaction formula (4) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (10) and (11).
  • Ar 12 , X 1 to X 4 , X 6 , X 7 , Z, and R 5 have the same definitions as in Reaction Formula (4).
  • Reaction formula (4) is a method for producing compound (20) by reacting compound (18), compound (19) and compound (17) in the presence of a base or acid.
  • the compound (18) is not particularly limited, and examples thereof include compounds represented by methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, phenyl acetate, and naphthyl acetate. can do.
  • Reaction formula (4) can be decomposed into reaction formulas (10) and (11). That is, in this reaction, Compound (24) is produced by reacting Compound (18) with Compound (19) in the presence of a base.
  • the compound (20) of the present invention is obtained by reacting the compound (24) with the compound (17) as represented by the reaction formula (11).
  • the compound (24) may be isolated, it may be used for the reaction (11) which is the next step in one pot without isolation.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (18), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (18) and the compound (19) used in the reaction formula (10) is not particularly limited, but the compound (18) is 0.1 to 10-fold mol per mol of the compound (19). In terms of good yield of compound (24), it is preferably 1.1 to 2.0 moles.
  • the molar ratio of the compound (24) and the compound (17) used in the reaction formula (11) is not particularly limited, but the compound (17) is 0.1 to 20-fold mol with respect to 1 mol of the compound (24). In view of good yield of the compound (20), 1.0 to 5 times is preferable.
  • Reaction formula (5) is a method for producing compound (11) by reacting compound (20) with a halogenating agent or sulfonylating agent in the presence or absence of a base.
  • the halogenating agent is not particularly limited, and examples thereof include thienyl chloride, thienyl bromide, thienyl iodide, phosphoryl chloride, phosphoryl bromide, and phosphoryl iodide.
  • the sulfonylating agent is not particularly limited, and examples thereof include trifluoromethanesulfonic acid anhydride, toluenesulfonic acid anhydride, toluenesulfonic acid chloride, methanesulfonic acid chloride, and nitrobenzenesulfonic acid chloride.
  • a base used by Reaction formula (5) The same thing as the base shown by Reaction formula (2), (3) and (4) can be used.
  • the amount of the reactant is preferably 0.1 to 20 moles per mole of the compound (20). From the viewpoint of good yield of the benzothienopyrimidine compound (11) of the present invention, 1.0 to 5 times is preferable.
  • reaction formula (14) will be described.
  • the reaction formula (14) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (20) and (11).
  • Ar 12 , X 1 to X 4 , X 6 , X 7 , Z, and R 5 have the same definitions as in Reaction Formula (4).
  • Reaction formula (14) is a method for producing compound (20) by reacting compound (29), compound (28) and compound (17) in the presence of a base or acid. Although it does not specifically limit as compound (29), For example, methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, pentyl thioglycolate, hexyl thioglycolate, phenyl thioglycolate And compounds represented by benzylthioglycolate and naphthylthioglycolate. Reaction formula (14) can be decomposed into reaction formulas (20) and (11).
  • compound (29) reacts with compound (28) in the presence of a base to produce compound (24).
  • the compound (20) of the present invention is obtained by reacting the compound (24) with the compound (17) as represented by the reaction formula (11). Although the compound (24) may be isolated, it may be used for the reaction (11) which is the next step in one pot without isolation.
  • the amount of the base to be used is not particularly limited, but is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (28), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.
  • the molar ratio of the compound (29) and the compound (28) used in the reaction formula (20) is not particularly limited.
  • the compound (24) In terms of good yield of compound (24), it is preferably 1.1 to 2.0 moles.
  • the molar ratio of the compound (24) and the compound (17) used in the reaction formula (11) is not particularly limited, but the compound (17) is 0.1 to 20-fold mol with respect to 1 mol of the compound (24). In view of good yield of the compound (20), 1.0 to 5 times is preferable.
  • the purity of the compounds (1), (10) and (11) of the present invention can be increased by carrying out treatments such as reprecipitation, concentration, filtration and purification after the completion of each reaction.
  • purification may be performed by recrystallization, silica gel column chromatography, sublimation, or the like, if necessary.
  • the present invention is an organic electroluminescence device containing a benzothienopyrimidine compound represented by the general formula (1), and the benzothienopyrimidine compound is preferably used for an electron transport layer, an electron injection layer, or a light emitting layer.
  • the benzothienopyrimidine compound represented by the general formula (1) can be preferably used as an electron transporting material (electron transporting material, electron injecting material, etc.) of an organic electroluminescence device.
  • electron transporting material electron transporting material, electron injecting material, etc.
  • anode for the anode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the light emitting layer dopant, the light emitting layer host, the cathode, and the like used in combination, generally known materials are selected by those skilled in the art. Can be used.
  • the configuration of the organic electroluminescent element may be any conventionally known one, and is not particularly limited.
  • 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 (1) can also be manufactured by the solution coating method.
  • the compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, ink jet method, casting method or Film formation by a dip method or the like is also possible.
  • the benzothienopyrimidine compound represented by the general formula (1) of the present invention has high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran, etc.
  • a general-purpose apparatus was used. Film formation by a spin coat method, an ink jet method, a cast method, a dip method or the like is also possible.
  • a typical structure of the organic electroluminescence device that can obtain the effects of the present invention includes a substrate, an anode, a hole injection 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 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 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. The light transmission characteristics can be confirmed by electroluminescence emission through the substrate. Generally, transparent glass or plastic is used as the substrate.
  • the substrate may be a composite structure including multiple material layers.
  • the anode When the electroluminescent emission is confirmed through the anode, the anode is formed by passing or substantially passing through the emission.
  • Common transparent anode (anode) materials used in the present invention include indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide.
  • 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 metal sulfides such as zinc sulfide can be used as the anode.
  • the anode can be modified with plasma deposited fluorocarbon.
  • the transmission characteristics of the anode are not important, 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, 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.
  • Aromatic tertiary amines are compounds that contain one or more trivalent nitrogen atoms that are bonded only to carbon atoms, and one or more of these carbon atoms have an aromatic ring. Forming.
  • the aromatic tertiary amine can be an arylamine, such as a monoarylamine, diarylamine, triarylamine, or a polymeric arylamine.
  • a benzothienopyrimidine compound represented by the general formula (1) can be used as a hole transport material, and an aromatic tertiary amine having one or more amino groups can be used as another material. Can do. Furthermore, a polymeric hole transport material can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and the like can be used.
  • PVK poly (N-vinylcarbazole)
  • PVK polythiophene
  • polypyrrole polyaniline and the like
  • 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 methane (F 4 -TCNQ) or the like may be provided, and the hole transport layer may be doped with these compounds.
  • 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 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.
  • a benzothienopyrimidine compound represented by the general formula (1) can be used as the host material of the light emitting layer.
  • examples of other materials include a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, Examples thereof include compounds having a pyrenyl group or an anthranyl group, and these materials can be used alone or in combination with a benzothienopyrimidine compound represented by the general formula (1).
  • 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
  • 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, or a combination of these materials
  • fluorescent dopants include pyrene, 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, carbostyryl compounds, and compounds that exhibit thermally activated delayed fluorescence.
  • Examples of useful phosphorescent dopants include organometallic complexes of transition metals such as iridium, platinum, palladium, osmium.
  • Examples of dopants 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.
  • a benzothienopyrimidine compound represented by the general formula (1) of the present invention can be used as the thin film forming material used to form the electron transport layer of the organic electroluminescence device 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.
  • Preferred compounds 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- (phenylphenolato) aluminum), bis (10-hydroxybenzo [h] quinolinato) beryllium) and the like.
  • 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).
  • Preferred compounds for the electron injection layer include benzothienopyrimidine compounds represented by the general formula (1), fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, and perylenetetracarboxylic acid. Examples include acid, fluorenylidenemethane, anthraquinodimethane, and anthrone.
  • the above-mentioned 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, GeO X, LiO X, LiON, TiO X, TiON, TaO X, TaON, TaN X, various oxides of C, etc. may be used an inorganic compound such as a nitride, and oxynitride.
  • 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.
  • compound B-1 (1.36 g), 4- (2-pyridyl) phenylboronic acid (1.43 g), palladium acetate (13.5 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ , 6'-Triisopropylbiphenyl (85.8 mg) was added to toluene (30 mL), and 3M aqueous potassium carbonate solution (4.8 mL) and 1-butanol (4.8 mL) were added, followed by heating for 2.5 hours. Refluxed. The reaction mixture was allowed to cool to room temperature, and water and methanol were added.
  • compound B-1 (1.12 g), 9-phenanthreneboronic acid (581 mg), and tetrakis (triphenylphosphine) palladium (57.8 mg) were added to THF (24 mL), and 4N-sodium hydroxide was added. Aqueous solution (1.9 mL) was added and then heated to reflux for 16 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid.
  • compound B-2 (1.14 g), 4- (2-pyridyl) phenylboronic acid (497 mg), palladium acetate (9.4 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (59.5 mg) was added to toluene (21 mL), 3M aqueous potassium carbonate solution (2.1 mL) and 1-butanol (2.1 mL) were added, and the mixture was heated to reflux for 3 hours. After allowing the reaction mixture to cool, water and methanol were added.
  • compound B-1 (2.50 g), 4- (2-pyridyl) phenylboronic acid (1.32 g), and tetrakis (triphenylphosphine) palladium (128 mg) were added to THF (55 mL), and 3M aqueous potassium carbonate solution (4.4 mL) was added, and then the mixture was heated to reflux for 23 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid.
  • compound B-3 (1.32 g), 1-pyreneboronic acid (738 mg), palladium acetate (11.2 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl ( 47.7 mg) was added to THF (50 mL), 3M-potassium carbonate aqueous solution (5.0 mL) was added, and the mixture was heated to reflux for 2 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid.
  • 1 H-NMR (CDCl 3 ), ⁇ (ppm): 7.30-7.34 (m, 1H), 7.57-7.65 (m, 4H), 7.70 (dd, J 8.
  • compound B-3 (1.32 g), 3-fluorantheneboronic acid (738 mg), palladium acetate (11.2 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropyl biphenyl (47.7 mg) was added to THF (50 mL), 3M-potassium carbonate aqueous solution (5.0 mL) was further added, and the mixture was heated to reflux for 6 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid.
  • compound B-4 (1.44 g), 4- (2-pyridyl) phenylboronic acid (640 mg), palladium acetate (12.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (76.6 mg) was added to THF (27 mL), 3M-potassium carbonate aqueous solution (2.1 mL) was further added, and the mixture was heated to reflux for 17 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid.
  • compound B-5 (1.71 g), 2-bromopyridine (493 mg), copper (I) oxide (18.6 mg), 1,10-phenanthroline (46.9 mg), potassium carbonate (719 mg), And 18-crown-6-ether (137 mg) was added to xylene and heated to reflux for 17 hours.
  • the reaction product was allowed to cool to room temperature, and water and methanol were added.
  • the precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a brown solid.
  • compound B-6 (1.75 g), 4- (2-pyridyl) phenylboronic acid (1.85 g), palladium acetate (17.4 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ , 6'-Triisopropylbiphenyl (73.8 mg) was added to THF (39 mL), 3M aqueous potassium carbonate solution (6.2 mL) was added thereto, and then the mixture was heated to reflux for 16 hours. After allowing the reaction mixture to cool, water and methanol were added.
  • compound B-9 (496 mg), 9-phenanthreneboronic acid (533 mg), and tetrakis (triphenylphosphine) palladium (23.1 mg) were added to THF (20 mL), and 3M aqueous potassium carbonate solution was added thereto. (1.6 mL) was added and then heated to reflux for 19 hours. The reaction mixture was allowed to cool to room temperature, and water and methanol were added.
  • compound B-3 (470 mg), bispinacolatodiboron (295 mg), tris (dibenzylideneacetone) dipalladium (16.0 mg), 2-dicyclohexylphosphino-2 ', 4', 6'- Triisopropylbiphenyl (17.0 mg) and potassium acetate (175 mg) were suspended in 1,4-dioxane (30.0 mL), and the mixture was heated and stirred at 80 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-13 (240 mg), 5-bromo-2,2′-bipyridine (110 mg), palladium acetate (1.8 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropylbiphenyl (7.4 mg) was suspended in 1,4-dioxane (13.0 mL), 3M-potassium carbonate aqueous solution (0.26 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-14 (700 mg), 4- (2-pyridyl) phenylboronic acid (581 mg), palladium acetate (18.0 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-tri Isopropyl biphenyl (76.0 mg) was suspended in 1,4-dioxane (44.0 mL), 3M-potassium carbonate aqueous solution (0.89 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 5 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-15 (500 mg), 4- (2-pyridyl) phenylboronic acid (436 mg), palladium acetate (11.0 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropylbiphenyl (47.5 mg) was suspended in 1,4-dioxane (33.0 mL), 3M-potassium carbonate aqueous solution (0.66 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-16 (1.01 g), 4- (2-pyridyl) phenylboronic acid (876 mg), palladium acetate (9.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (57.2 mg) was suspended in THF (40.0 mL), 3M-potassium carbonate aqueous solution (2.9 mL) was further added, and the mixture was heated to reflux for 60 hours. The reaction mixture was allowed to cool, water and methanol were added, and the precipitated solid was collected by filtration.
  • compound B-2 (1.50 g), 4- (3-pyridyl) phenylboronic acid (652 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M-potassium carbonate aqueous solution (1.82 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-2 (10.0 g), bis (binacolato) diboron (5.95 g), tris (dibenzylideneacetone) bispalladium (286 mg), 2-dicyclohexylphosphino-2 ', 4', 6 '-Triisopropylbiphenyl (297 mg) and potassium acetate (3.06 g) were suspended in 1,4-dioxane (310 mL), and the mixture was heated and stirred at 80 ° C. for 24 hours. The reaction mixture was allowed to cool, and the solvent was evaporated under reduced pressure.
  • compound B-17 (1.75 g), 3-chloro-6-phenylpyridine (622 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- Triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M-potassium carbonate aqueous solution (1.82 mL) was further added, and the mixture was heated and stirred at 95 ° C. for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-17 (1.75 g), 5-bromo-2,2′-bipyridine (771 mg), and tetrakis (triphenylphosphino) palladium (63.0 mg) were added to 1,4-dioxane ( (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was added, and the mixture was stirred with heating at 95 ° C. for 18 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-2 (1.50 g), 4-isoquinolylboronic acid (567 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-tri Isopropyl biphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M-potassium carbonate aqueous solution (1.8 mL) was further added, and the mixture was stirred with heating at 90 ° C. for 20 hr. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-2 (1.50 g), 8-quinolylboronic acid (567 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl ( 78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was stirred with heating at 90 ° C. for 20 hr. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-1 (1.81 g), phenylboronic acid (1.17 g), palladium acetate (18.0 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl ( 114 mg) was suspended in THF (40 mL), 3M aqueous potassium carbonate solution (6.4 mL) was added, and the mixture was heated to reflux for 26 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-10 (1.23 g), 4- (4,6-diphenylpyridin-2-yl) phenylboronic acid (1.15 g), palladium acetate (12.3 mg), and 2-dicyclohexylphosphine Fino-2 ′, 4 ′, 6′-triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), and further 3M-potassium carbonate aqueous solution (1.82 mL) was added. The mixture was stirred at 7 ° C. for 7 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-10 (1.23 g), 4- (2,6-diphenylpyridin-4-yl) phenylboronic acid (1.15 g), palladium acetate (12.3 mg), and 2-dicyclohexylphosphine Fino-2 ′, 4 ′, 6′-triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), and further 3M-potassium carbonate aqueous solution (1.82 mL) was added. The mixture was stirred at 7 ° C. for 7 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-17 (1.75 g), 2-bromopyridine (518 mg), and tetrakis (triphenylphosphino) palladium (63.0 mg) were suspended in 1,4-dioxane (55.0 mL). Further, 3M-potassium carbonate aqueous solution (1.82 mL) was added, and the mixture was heated and stirred at 95 ° C. for 123 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-19 (1.59 g), 4- (2-pyridyl) phenylboronic acid (1.43 g), and tetrakis (triphenylphosphino) palladium (69.3 mg) were added to THF (60 mL). The suspension was suspended, 3M aqueous potassium carbonate solution (4.8 mL) was added, and the mixture was heated to reflux for 24 hours. The reaction mixture was allowed to cool to room temperature, and water and methanol were added.
  • the precipitated solid is purified by column chromatography (developing solvent: chloroform), whereby 6-chloro-2- [4,4 ′′ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ′ '] -Terphenyl-5'-yl] -4-phenyl [1] benzothieno [3,2-d] pyrimidine (B-20) yellow powder (yield 1.57 g, 77% yield), and 6- Chloro-2- [5-bromo-4 '-(2-pyridyl) biphenyl-3-yl] -4-phenyl [1] benzothieno [3,2-d] pyrimidine (B-21) yellow powder (Yield 0 .153 g, yield 8.5%).
  • compound B-22 (800 mg), 4- (2-pyridyl) phenylboronic acid (860 mg), palladium acetate (8.8 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- Triisopropylbiphenyl (56.0 mg) was suspended in 1,4-dioxane (40.0 mL), 3M-potassium carbonate aqueous solution (2.6 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 23 hours. After allowing to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-1 (904 mg), carbazole (702 mg), palladium acetate (9.0 mg), potassium carbonate (1.16 g), and 18-crown-6-ether (106 mg) were added to xylene (20 mL). The suspension was further added, and a 1M-toluene solution (120 ⁇ L) of tri (tert-butyl) phosphine was added, and the mixture was heated to reflux for 5 hours.
  • compound B-17 (1.75 g), 1-chloroisoquinoline (537 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl ( 78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M-potassium carbonate aqueous solution (1.82 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-17 (1.75 g), 2-chloro-4,6-diphenylpyridine (872 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (78.9 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was stirred with heating at 85 ° C. for 16 hr. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration.
  • compound B-24 (1.34 g), 4- (2-pyridyl) phenylboronic acid (1.24 g), palladium acetate (12.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ , 6'-Triisopropylbiphenyl (76.3 mg) was suspended in THF (53.0 mL), 3M-potassium carbonate aqueous solution (5.3 mL) was added, and the mixture was heated to reflux for 22 hours.
  • compound B-17 (1.28 g), 8- (4-chlorophenyl) quinoline (527 mg), palladium acetate (9.0 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- Triisopropylbiphenyl (57.2 mg) was suspended in THF (22.0 mL), 3M-potassium carbonate aqueous solution (1.33 mL) was further added, and the mixture was heated to reflux for 17 hours. The reaction mixture was allowed to cool, water and methanol were added, and the precipitated solid was collected by filtration.
  • Example 1 Compound C-1 yellow powder (1.58 g, purity 99.7% before sublimation) was sublimated by heating to a vaporization section temperature of 330 ° C. and a collection section temperature of 280 ° C. under a vacuum of 1.0 ⁇ 10 ⁇ 3 Pa. Purification gave white powder of compound C-1 (yield 1.20 g, yield 76%, purity 99.8%).
  • Comparative Purification Example 1 Compound ETL-3 gray powder (1.54 g, purity 99.7% before sublimation) was sublimated by heating to a vaporization section temperature of 240 ° C. and a collection section temperature of 220 ° C. under a vacuum of 5.0 ⁇ 10 ⁇ 4 Pa. Purification gave white powder of compound ETL-3 (yield 1.20 g, yield 78%, purity 99.4%).
  • Evaluation Example 1 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. 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 deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 2 a first hole transport layer 3, a second hole transport layer 4, a light emitting layer 5, an electron transport layer are formed as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 6 and the electron injection layer 7 were sequentially formed, and then the cathode layer 8 was formed.
  • all the materials which comprise each layer of an organic electroluminescent element were vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited at a film thickness of 0.025 nm / second to a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited with a film thickness of 10 nm at a film formation rate of 0.15 nm / second.
  • the electron transport layer 6 the compound C-1 synthesized in Example 2 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.
  • Liq was vacuum-deposited with a film thickness of 0.005 nm / second and a film thickness of 0.5 nm.
  • a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 8 was formed.
  • the cathode layer 8 is formed by vacuum-depositing magnesium / silver (weight ratio 80/20) and silver in this order at film thicknesses of 80 nm and 20 nm at a film formation rate of 0.5 nm / second and 0.2 nm / second, respectively.
  • a two-layer structure was adopted. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • 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.
  • Evaluation Example 2 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1 except that Compound C-2 synthesized in Example 3 was used instead of Compound C-1. .
  • Evaluation Example 3 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescence device was produced in the same manner as in Evaluation Example 1, except that Compound C-3 synthesized in Example 4 was used instead of Compound C-1. .
  • Evaluation Example 4 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent device was produced in the same manner as in Evaluation Example 1 except that Compound C-4 synthesized in Example 5 was used instead of Compound C-1. .
  • Evaluation Example 5 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1 except that Compound C-5 synthesized in Example 6 was used instead of Compound C-1. .
  • Evaluation Example 6 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1 except that Compound C-14 synthesized in Example 19 was used instead of Compound C-1. .
  • Evaluation Example 7 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1 except that Compound C-15 synthesized in Example 20 was used instead of Compound C-1. .
  • Evaluation Example 8 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1, except that Compound C-18 synthesized in Example 25 was used instead of Compound C-1. .
  • Evaluation Example 9 In the electron transport layer 6 of Evaluation Example 1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1, except that Compound C-23 synthesized in Example 32 was used instead of Compound C-1. .
  • a direct current was applied to the organic electroluminescent devices produced in Evaluation Examples 1 to 9 and Reference Example 1, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON.
  • the lifetime characteristic (h) the luminance decay time during continuous lighting when a current density of 10 mA / cm 2 was passed was measured. Further, the time when the luminance (cd / m 2 ) was reduced by 20% and the drive voltage increase when the device was driven for 20 hours were measured.
  • Table 1 shows the measurement results together with the initial voltage (V) and the initial current efficiency (cd / A) when a current density of 10 mA / cm 2 was passed.
  • the element lifetime (h) of each evaluation example is expressed as a relative value with the time (h) when the luminance (cd / m 2 ) of the element in Reference Example 1 is reduced by 20% from the initial value being 100. .
  • Evaluation Example 10 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. 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 deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15 and an electron transport layer are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. 16 were sequentially formed, and then the cathode layer 17 was formed.
  • all the materials which comprise each layer of an organic electroluminescent element were vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited at a film formation rate of 0.15 nm / second to a film thickness of 10 nm.
  • the cathode layer 17 is formed by vacuum-depositing magnesium / silver (weight ratio 80/20) and silver in this order at film thicknesses of 80 nm and 20 nm at a film formation rate of 0.5 nm / second and 0.2 nm / second, respectively.
  • a two-layer structure was adopted. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • DEKTAK stylus type film thickness meter
  • 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.
  • Evaluation Example 11 An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that Compound C-2 synthesized in Example 3 was used instead of Compound C-1 in the electron transport layer 16 of Evaluation Example 10. .
  • Evaluation Example 12 An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that Compound C-3 synthesized in Example 4 was used in place of Compound C-1 in the electron transport layer 16 of Evaluation Example 10. .
  • Evaluation Example 13 An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that Compound C-4 synthesized in Example 5 was used in place of Compound C-1 in the electron transport layer 16 of Evaluation Example 10. .
  • Evaluation Example 14 An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that Compound C-10 synthesized in Example 15 was used in place of Compound C-1 in the electron transport layer 16 of Evaluation Example 10. .
  • Evaluation Example 15 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescence device was produced in the same manner as in Evaluation Example 10 except that Compound C-12 synthesized in Example 17 was used instead of Compound C-1. .
  • Evaluation Example 16 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10, except that Compound C-13 synthesized in Example 18 was used instead of Compound C-1. .
  • Evaluation Example 17 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10 except that Compound C-15 synthesized in Example 20 was used instead of Compound C-1. .
  • Evaluation Example 18 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescence device was produced in the same manner as in Evaluation Example 10 except that Compound C-17 synthesized in Example 23 was used instead of Compound C-1. .
  • Evaluation Example 19 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescence device was produced in the same manner as in Evaluation Example 10 except that Compound C-20 synthesized in Example 28 was used instead of Compound C-1. .
  • Evaluation Example 20 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10, except that Compound C-21 synthesized in Example 29 was used instead of Compound C-1. .
  • Evaluation Example 21 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10 except that Compound C-22 synthesized in Example 31 was used instead of Compound C-1. .
  • Evaluation Example 22 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10 except that Compound C-23 synthesized in Example 32 was used instead of Compound C-1. .
  • Evaluation Example 23 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescent element was produced in the same manner as in Evaluation Example 10, except that Compound C-24 synthesized in Example 34 was used instead of Compound C-1. .
  • Evaluation Example 24 In the electron transport layer 16 of Evaluation Example 10, an organic electroluminescence device was produced in the same manner as in Evaluation Example 10 except that Compound C-25 synthesized in Example 35 was used instead of Compound C-1. .
  • a direct current was applied to the organic electroluminescence devices produced in Evaluation Examples 10 to 24, Reference Example 2 and Reference Example 3, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. did.
  • the lifetime characteristic (h) the luminance decay time during continuous lighting when a current density of 10 mA / cm 2 was passed was measured. Further, the time when the luminance (cd / m 2 ) was reduced by 10% and the drive voltage increase when the device was driven for 50 hours were measured.
  • Table 2 shows the measurement results together with the initial voltage (V) and the initial current efficiency (cd / A) when a current density of 10 mA / cm 2 was passed.
  • the driving voltage (V) and current efficiency (cd / A) of each evaluation example are shown as relative values when the measured value in Reference Example 2 (ETL-1) is 100.
  • the element lifetime (h) of each evaluation example is shown as a relative value with the time (h) when the luminance (cd / m 2 ) of the element in Reference Example 2 is reduced by 10% from the initial value being 100.
  • Evaluation Example 25 As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. 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 deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm 2 as shown in FIG. First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 ⁇ 10 ⁇ 4 Pa.
  • ITO indium-tin oxide
  • a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15 and an electron transport layer are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. 16 were sequentially formed, and then the cathode layer 17 was formed.
  • all the materials which comprise each layer of an organic electroluminescent element were vacuum-deposited by the resistance heating system.
  • HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.
  • HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.
  • HTL-2 was vacuum-deposited at a film formation rate of 0.15 nm / second to a film thickness of 10 nm.
  • the cathode layer 17 is formed by vacuum-depositing magnesium / silver (weight ratio 80/20) and silver in this order at film thicknesses of 80 nm and 20 nm at a film formation rate of 0.5 nm / second and 0.2 nm / second, respectively.
  • a two-layer structure was adopted. Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
  • DEKTAK stylus type film thickness meter
  • 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.
  • Evaluation Comparative Example 1 An organic electroluminescent element was produced in the same manner as in Evaluation Example 25 except that ETL-3 synthesized in Synthesis Example 1 was used in place of C-26 in the electron transport layer 16 of Evaluation Example 25.
  • Evaluation Comparative Example 2 An organic electroluminescent device was produced in the same manner as in Evaluation Example 25 except that ETL-4 synthesized in Synthesis Example 2 was used in place of C-26 in the electron transport layer 16 of Evaluation Example 25.
  • a direct current was applied to the organic electroluminescent elements produced in Evaluation Example 25, Evaluation Comparative Example 1 and Evaluation Comparative Example 2, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. did.
  • the initial voltage (V) and the initial current efficiency (cd / A) when a current density of 5 mA / cm 2 was passed were measured.
  • Table 3 shows the results of measuring the drive voltage rise when the device was driven for 50 hours when a current density of 40 mA / cm 2 was passed and the device was continuously lit.
  • the drive voltage (V) and current efficiency (cd / A) in each evaluation example are shown as relative values when the measured value in Evaluation Comparative Example 2 (ETL-4) is 100.
  • the organic electroluminescent device using the benzothienopyrimidine compound of the present invention has a low driving voltage, excellent current efficiency, and excellent driving voltage rise suppression effect. It was.
  • the organic electroluminescent device using the benzothienopyrimidine compound of the present invention can be driven for a long time compared to the organic electroluminescent device using the existing material.
  • the benzothienopyrimidine compound of the present invention can be applied to a light emitting host layer and the like in addition to the electron transport layer of this example.
  • the present invention can be applied not only to an element using a fluorescent light emitting material but also to various organic electroluminescent elements using a phosphorescent light emitting material.
  • the benzothienopyrimidine compound of the present invention has high solubility, and it is possible to produce an element using not only a vacuum deposition method but also a coating method. Furthermore, it is useful not only for applications such as flat panel displays but also for illumination applications that require low power consumption.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention porte sur un nouveau matériau de transport d'électrons qui a une excellente résistance à la chaleur et une haute efficacité lumineuse et qui permet à un élément d'être excité à une faible tension par ses excellentes propriétés d'injection d'électrons et caractéristiques de transport d'électrons, tout en permettant à l'élément d'être excité pendant longtemps. Selon l'invention, un composé de benzothiénopyrimidine représenté par la formule générale (1) est utilisé. (Dans la formule, chacun de R1-R4 représente indépendamment un groupe aromatique qui peut être substitué par un substituant particulier et comprenant 4 à 66 atomes de carbone, un atome d'hydrogène, un atome de deutérium, un atome de fluor, un groupe méthyle, un groupe éthyle, un groupe alkyle comprenant 3 à 10 atomes de carbone, un groupe méthoxy, un groupe éthoxy, un groupe alcoxy comprenant 3 à 10 atomes de carbone, un groupe méthylthio, un groupe éthylthio, un groupe sulfure comprenant 3 à 10 atomes de carbone ou un groupe diarylamino comprenant 10 à 36 atomes de carbone ; et chacun de Ar1 et Ar2 représente indépendamment un groupe aromatique qui peut être substitué par un substituant particulier et comprenant 4 à 66 atomes de carbone.)
PCT/JP2014/074122 2013-09-11 2014-09-11 Composé de benzothiénopyrimidine, procédé de production de ce dernier et élément électroluminescent organique contenant ce dernier WO2015037675A1 (fr)

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