WO2005014755A1 - Alkynyl group-substituted condensed heterocyclic compound, method for producing same, and organic electroluminescent device using same - Google Patents

Alkynyl group-substituted condensed heterocyclic compound, method for producing same, and organic electroluminescent device using same Download PDF

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WO2005014755A1
WO2005014755A1 PCT/JP2004/011337 JP2004011337W WO2005014755A1 WO 2005014755 A1 WO2005014755 A1 WO 2005014755A1 JP 2004011337 W JP2004011337 W JP 2004011337W WO 2005014755 A1 WO2005014755 A1 WO 2005014755A1
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group
formula
represented
compound
substituted
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Osamu Fujimura
Mitsuhiro Tanaka
Kenji Fukunaga
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Ube Industries, Ltd.
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Priority to JP2005512964A priority Critical patent/JP4479656B2/en
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom

Definitions

  • Alkynyl-substituted condensed heterocyclic compound process for producing the same, and organic electroluminescent device using the same
  • the present invention provides the following formula (1) useful for a blue light-emitting material for an electroluminescent device (organic electroluminescent device):
  • n 1 represents an integer of 13; and when n 1 is 1, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylene group, an aralkyl group, an alkylsilyl group, or a heterocyclic group. And when n 1 is 2 or 3, A represents a divalent or trivalent aryl or heterocyclic group, and X and Y represent CH or N, respectively.
  • the present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1), an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) used in the device, and a method for producing the same.
  • the present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1), which emits strong blue light under ultraviolet irradiation, and the above formula (1)
  • the present invention provides a novel alkynyl group-substituted condensed heterocyclic compound which is included in the alkynyl group-substituted condensed heterocyclic compound.
  • the present invention also relates to an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1), which shows strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescent device.
  • a method for synthesizing with good yield is provided.
  • the present inventors have conducted intensive studies and as a result, have found that an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) emits blue-white light when a voltage is applied. In addition, they found that the alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) showed strong blue light emission by ultraviolet irradiation in a chloroform solution, and was extremely useful as an organic electroluminescent device material. The present invention has been achieved.
  • the present inventors have derived a hydroxy-substituted condensed heterocyclic compound into the corresponding trifluoromethanesulfonic acid ester (formula (5) shown below), and then used a zero-valent palladium catalyst to prepare various terminal groups. It has been found that the alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1) can be produced in good yield by reacting with the acetylene conjugate.
  • the present invention is as follows.
  • the first invention is an organic electroluminescent device having an organic compound thin layer between a pair of electrodes, wherein the organic compound layer has the following formula (1):
  • n 1 represents an integer of 13; when n 1 is 1, A represents a hydrogen atom, an alkyl group, Represents an alkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n 1 is 2 or 3, A represents a divalent or trivalent aryl group or a heterocyclic group. , X and Y each represent CH or N;
  • the present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula:
  • a second invention provides the following formula (1 '):
  • ⁇ 1 is as defined above, and when ⁇ 1 is 1, R 1 is an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a hetero group. When ⁇ 1 is 2 or 3, R 1 represents a divalent or trivalent aryl group or a heterocyclic group, and X and ⁇ are as defined above;
  • the present invention relates to an alkynyl group-substituted fused heterocyclic compound represented by the formula:
  • the third invention uses a zero-valent palladium compound as a catalyst and uses the following formula (5):
  • the present invention relates to a method for producing the alkynyl group-substituted fused heterocyclic compound represented by the formula (1).
  • a fourth invention uses a zero-valent palladium compound as a catalyst and a trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound represented by the formula (5) and an alkylsilylacetylene in a basic solvent. Reacting with a compound of formula (I) to form an alkylsilyl-etul group-substituted condensed heterocyclic compound (compound wherein n 1 is 1 and A is an alkylsilyl group in the above formula (1)), and then hydrolyzes.
  • the present invention relates to a process for producing a condensed heterocyclic compound substituted with an ethur group represented by the formula (compound wherein n 1 is 1 and A is a hydrogen atom in the formula (1)).
  • a fifth invention relates to an ethynyl group-substituted fused heterocyclic compound represented by the above formula (7) and the following formula (9):
  • X ′ represents a halogen atom
  • R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acinole group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group.
  • n 3 is an integer of 1 one 5
  • the present invention relates to a process for producing a fused heterocyclic compound substituted with a phenylethur group represented by the formula:
  • FIG. 1 is a cross-sectional view of an organic EL device in Example 16, in which reference numeral 1 indicates a glass substrate, 2 indicates a square, 3 indicates a hole injection layer, and 4 indicates a hole injection layer.
  • eta 1 represents an integer of 1 one 3
  • ⁇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n 1 is 2 or 3, A is divalent or trivalent.
  • X and Y each represent CH or N;
  • alkyl group examples include a C11-C10 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. No. These substituents include isomers thereof.
  • cycloalkyl group examples include a cycloalkyl group having 3 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • a cycloalkyl group having 3 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a dimethylnaphthyl group. These substituents include isomers thereof.
  • aralkyl group examples include a benzyl group, a phenyl group, a phenylpropyl group, a phenylbutyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylmethyl group, a diphenylmethyl group, and the like.
  • alkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a methyldiisopropylsilyl group, a t-butyldimethylsilinole group, a methyldi-t-butylsilyl group, and the like.
  • heterocyclic group examples include a quinolinole group, a quinazolinyl group, a quinoxalinyl group, an imidazolyl group
  • An imidazolidinyl group an imidazolinyl group, a pyrazolyl group, a pyridinole group, a piperidyl group and the like.
  • A is a divalent aryl group or a divalent heterocyclic group
  • A is a trivalent aryl group or a trivalent hetero ring group. It is a ring group.
  • These groups include the divalent or trivalent groups of the above aryl groups or heterocyclic groups.
  • the hydrogen atom bonded to the carbon atom may further be a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom;
  • An amino group preferably a dialkylamino group having 2 to 10 carbon atoms such as a dimethinoleamino group, a getylamino group, a dipropylamino group;
  • an aryloxy group preferably a phenoxy group, a trioxy group, a xyloxy group, a naphthoxy group, or a dimethylnaphthoxy group;
  • An aryloxy group having 614 carbon atoms such as a group; an alkoxy group, preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentaoxy group, a hexoxy group,
  • alkoxy group having 1 to 10 carbon atoms an alkenyl group, preferably a vinylinole group, Alkenyl groups having 2 to 20, especially 2 to 12 carbon atoms such as benzyl, butyr, pentenyl, hexenyl, heptenyl, otathenyl, nonenyl, decenyl, pendecenyl and dodecenyl; Acetyl group, preferably aromatic group such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, aromatic group such as benzoyl group or benzoyl group of C 17 aliphatic acid such as valiroyl group; , A cyano group, or an alkyl group, a cycloalkyl group, or an aryl group as defined above. These substituents include isomers thereof.
  • alkynyl group-substituted condensed heterocyclic compound examples include 8-phenylethynylquinoline, 1,4-bis (8′-quinolyleturyl) benzene, , 3—Bis (8'_quinolylethur) benzene, 1,3,5-Tris (8'_quinolylethur) benzene, 8-ethynylquinoline, 8— (1'-Probyl) quinoline, 8— (2'-cyclohexyl) Kisilchech Nyl) quinoline, 8_ (3'_phenyl-1'_propynyl) quinoline, 8-trimethylsilylethynino olequinoline, bis (8'_quinolyl) acetylene, 8_ (4'_fluorophenylethynyl) quinoline, 8_ (3 '_Fluorophenylethyninole) quinoline, 8_ (2'
  • the present invention relates to alkynyl group-substituted condensed condensed compounds represented by the following formulas (2) and (4).
  • Terocyclic compounds are preferably used.
  • R 1 represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a hetero ring.
  • n 2 represents an integer of 23.
  • R 1 is an arylalkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, Or a heterocyclic group.
  • the specific embodiments of these substituents are the same as those described as A in the above formula (1).
  • alkynyl group-substituted condensed heterocyclic compound examples include 8- (1-propynyl) quinoline, 8- (2-cyclopropylethyl) quinoline, — (4'-me Tilfeneretinyl) quinoline, 8-trimethylsilylethynylquinoline, 8_ (4'-fluoro mouth phenylethinyl) quinoline, 8- (3,1-fluorophenylethynyl) quinoline, 8- (2,1-fluorophenylene) Chininole) quinoline, 8_ (4'-methoxyphenyletinole) quinoline, 8_ (3, -methoxyphenyletulle) quinoline, 8- (4, -fuyphenylphenyletul) quinoline, 8_ (2'_ (Pyridyl etur) quinoline, 8_ (3 '_ pyrid
  • n 2 represents an integer of 2-3.
  • 1,4-bis (8, _quinolyletul) benzene, 1,3-bis (8, _quinolyletul) benzene, 1,3,5-tris (8′_quinolyletul) benzene, and the like are listed. I can do it.
  • the compound represented by the formula (4) is a bis (8,1-quinolyl) acetylene represented by the formula (1), wherein A is a quinolyl group, X and Y are both CH, and n 1 is 1. It is.
  • the second invention relates to an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1 ') except that in the formula (1), A is a hydrogen atom.
  • II 1 , X and Y have the same meanings as in the above formula (1), and when n 1 is 1, R 1 is an anoalkyl group, a cycloalkyl group or an unsubstituted phenyl. Represents an aryl group, an aralkyl group, an alkylsilyl group or a heterocyclic group other than the group, and when n 1 is 2 or 3, R 1 represents a divalent or trivalent aryl group or a heterocyclic group.
  • R 1 has the same meaning as the alkyl group, cycloalkyl group, aryl group other than unsubstituted phenyl group, aralkyl group, alkylsilyl group, or heterocyclic group described in A of the above formula (1).
  • Specific examples of the compound include compounds excluding 8-phenylethynylquinoline described in the above formula (1).
  • Preferred examples of the alkynyl group-substituted fused heterocyclic compound represented by the formula (1 ′) include the compounds represented by the formulas (2) to (4).
  • the production method of the third invention uses a trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound (the above formula (5)) and a terminal acetylene compound using a zero-valent palladium compound as a catalyst.
  • An alkynyl group-substituted condensed heterocyclic compound (formula (1)) is produced by reacting the above formula (6) with a basic solvent.
  • the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound is described, for example, in Journal of the American Chemical Society, 1987, 109, p. 5478. (Synthesis method described in this specification (in the presence of an organic base such as triethylamine or triethylenamine) in a solvent such as methylene chloride and a solvent such as trifluoromethanesulfonic anhydride and the intended trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound It is produced by reacting a hydroxy-substituted condensed heterocyclic compound corresponding to the above.
  • zero-valent palladium compound used as a catalyst examples include zero-valent palladium phosphine complexes (palladium tetrakistriphenylphosphine complex, bisdiphenylphosphinoethanepalladium complex, bistricyclohexinolephosphine palladium complex, etc.) And zero-valent palladium olefin complex (such as trisdibenzylideneacetone dipalladium complex). Of these compounds, a zero-valent palladium phosphine complex is preferred, and tetrax (triphenylphosphine) palladium is more preferred.
  • the use amount of these zero-valent palladium compounds is 0.1 to 10 mol%, preferably 0.5 to 5 mol%, based on the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound. is there.
  • A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and n 1 represents 1 Represents an integer of 13.
  • terminal acetylene compound examples include phenylacetylene, 4_fluorophenylacetylene, 3_fluorophenylacetylene, 2_fluorophenylacetylene, 4-methoxyphenylacetylene, Ethines such as 3-methoxyphenylacetylene, 4-fuphenylphenylacetylene, 4-benzoylphenylacetylene, 1,4_jetinolebenzene, 1,3-jetulbenzene, 1,3,5-triethylbenzene Substituted aryl compounds, 8_ethynylquinoline, 8—ethyurquinazoline, 8—ethyruquinoxaline, 2′_pyridylacetylene, 3′_pyridylacetylene, 5—ethyur—1—methyl Nore 1_H Ethynyl-substituted heterocyclic compounds such as imidazole
  • the amount of the terminal acetylene compound (formula (6)) used is 1.0-2 with respect to 1 mole of the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (formula (5)). 0.0 mol, preferably 1.0-1.3 mol.
  • Examples of the basic solvent used in the production method of the third invention include piperidine or pyrrolidine.
  • the amount of the basic solvent to be used is 112 L (liter), preferably 1 mol, per 1 mol of the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (formula (5)). 5-5L.
  • the reaction temperature is 80-100 ° C, preferably 80-90 ° C.
  • the reaction time varies depending on the type of the terminal acetylene compound, the amount of the solvent used, the reaction temperature and the like, but is 115 hours.
  • This reaction is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or in a stream of these gases.
  • the reaction pressure used is usually normal pressure.
  • the alkynyl group-substituted condensed heterocyclic compound produced according to the above-mentioned production method is subjected to ordinary post-treatments such as extraction, concentration and extraction after the reaction, and if necessary, distillation and recrystallization. And can be appropriately purified by known means such as various types of chromatography.
  • the obtained alkynyl group-substituted condensed heterocyclic compound is suitably used for an organic electroluminescent device.
  • an ethynyl group-substituted condensed heterocyclic compound represented by the following formula (7) wherein A is a hydrogen atom and n 1 is 1 is prepared separately from the above-mentioned production method. It can also be manufactured by a manufacturing method.
  • a condensed heterocyclic compound substituted with a trifluoromethanesulfonyloxy group in a basic solvent using a zero-valent palladium compound as a catalyst in accordance with the above-mentioned production method (previously described)
  • the above formula (5)) is reacted with the above-mentioned alkylsilylacetylene compound as the terminal acetylene compound (formula (6)) to form an alkylsilylethynyl group-substituted condensed heterocyclic compound.
  • the condensed heterocyclic compound substituted with a silylethynyl group is hydrolyzed to form a condensed heterocyclic compound substituted with an ethur group (the following formula (7)):
  • an aqueous solution of an alkali metal hydroxide is used.
  • alkali metal hydroxide examples include sodium hydroxide and potassium hydroxide.
  • the concentration of the alkali metal hydroxide is 0.1 to 12.5 mol / L, preferably 0.5 to 5 mol / L.
  • the amount used is 115 moles, preferably 112 moles, per mole of the alkylsilyl ethr group-substituted condensed heterocyclic compound.
  • the temperature used in this hydrolysis is 550 ° C, preferably 1525 ° C.
  • the reaction time varies depending on the concentration and temperature, but is 0.12 hours.
  • This hydrolysis is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or in a stream of these gases.
  • the reaction pressure used is usually normal pressure.
  • the ethynyl group-substituted condensed heterocyclic compound (the above formula (7)) produced according to the above production method is subjected to ordinary post-treatments such as extraction, concentration, and filtration after completion of the reaction, and if necessary, It can be appropriately purified by known means such as distillation, recrystallization and various types of chromatography.
  • a purified ethynyl group-substituted condensed heterocyclic compound (the formula (7)) is used as the terminal acetylene compound.
  • a crude product which has been subjected to the above-mentioned post-treatments such as extraction and concentration after the production of the heterocyclic compound substituted with a petroleum group (formula (7)) can also be used as it is.
  • R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acyl group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group; May be the same or different, and n 3 represents an integer of 1 to 5, and X and Y are as defined above.
  • the phenylethyl group-substituted condensed heterocyclic compound represented by the following formula can also be produced by the following production method separately from the above production method.
  • the fifth invention provides an ethynyl group-substituted fused heterocyclic compound represented by the above formula (7) and the following formula (9):
  • X ′ represents a halogen atom
  • R and n 3 are as defined above,
  • the condensed heterocyclic compound substituted with an ethur group (the above formula (7)) is produced according to any of the production methods described above.
  • R represents a halogen atom, a dianolequinoleamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acinole group, a nitro group, a cyano group, It is an alkyl group, a cycloalkyl group or an aryl group, and a plurality of Rs may be the same or different, and n 3 is an integer of 1 to 5.
  • the zero-valent palladium compound used as the catalyst includes the above-mentioned zero-valent palladium compound. Things.
  • the amount of the zero-valent palladium compound, a halogenated aromatic compound (a Formula (9 this 0-1- 10 mole 0/0 for, preferably is 0, 5-5 mol 0/0 .
  • Examples of the basic solvent used in the above reaction include piperidine and pyrrolidine.
  • the amount of the basic solvent to be used is 112 L (liter), preferably 1.5-5 L, per 1 mol of the ethynyl group-substituted condensed heterocyclic compound (the formula (7)). .
  • reaction temperature is 80 100 ° C, preferably 80 90 ° C.
  • the reaction time varies depending on the type of the halogenated aromatic ring compound (formula (9)), the amount of the solvent used, the reaction temperature and the like, but is 115 hours.
  • This reaction is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or under a stream of these gases.
  • the reaction pressure used is usually normal pressure.
  • the phenylethynyl group-substituted condensed heterocyclic compound (the formula (9)) produced according to the above-mentioned production method is subjected to ordinary post-treatments such as extraction, concentration and extraction after completion of the reaction. If necessary, it can be appropriately purified by known means such as distillation, recrystallization, and various types of chromatography.
  • the obtained phenylethynyl group-substituted condensed heterocyclic compound (the above formula (9)) is suitably used for an organic electroluminescence device.
  • the organic electroluminescent device of the present invention is an organic electroluminescent device having an organic compound layer between a pair of electrodes, wherein the organic compound layer is substituted with an alkynyl group represented by the formula (1). It is characterized by containing at least one of the fused heterocyclic compounds.
  • the organic compound layer is preferably a light emitting layer, an electron injection layer (or a hole blocking layer), or a hole transport layer.
  • the organic electroluminescent device is a device in which a single or multilayer organic compound layer is formed between an anode and a cathode.
  • the single-layer organic electroluminescent device has a light-emitting layer between an anode and a cathode.
  • the light emitting layer contains a light emitting material, and further contains a hole injection material or an electron injection material (or a hole blocking material) for transporting holes injected from an anode or electrons injected from a cathode to the light emitting material. Even good ,.
  • the multilayer type organic electroluminescent device includes, for example, (anode Z hole injection layer Z light emitting layer / cathode), (anode / light emitting layer / electron injection layer (or hole block layer) / cathode), ( Examples thereof include those laminated in a multilayer structure such as a positive electrode / a hole injection layer / a light emitting layer / an electron injection layer (or a hole blocking layer) / a cathode.
  • the alkynyl group-substituted condensed heterocyclic compound in addition to the alkynyl group-substituted condensed heterocyclic compound (formula (1)), known light emitting materials, doping materials, and hole injection materials (phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, Oxazole, oxaziazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxaziazole, hydrazone, isylhydrazone, polyarylanolecane, stilbene, butadiene, benzidine triphenylamine.
  • phthalocyanine derivatives naphthalocyanine derivatives, porphyrin derivatives
  • Oxazole, oxaziazole triazole, imidazole, imidazolone, imidazolethione
  • Materials) fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazonole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives, etc.
  • the alkynyl group-substituted condensed heterocyclic compound (the above formula (1)) has a concentration of 0 in any of a light emitting layer, an electron injection layer (or a hole block layer), a hole transport layer, and a hole injection layer. .5—100% by weight.
  • the organic electroluminescent device can also be used in combination with a light emitting material, another doping material, a hole injection material or an electron injection material (or a hole blocking material). Further, each of the hole injection layer, the light emitting layer, and the electron injection layer (or the hole blocking layer) may be formed in a layer structure of two or more layers. In this case, in the case of a hole injection layer, a layer that injects holes from the electrode is a hole injection layer, and a layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call.
  • an electron injection layer electrons are The layer to be injected is called an electron injection layer, the layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer, and the layer that prevents holes from flowing from the light emitting layer is called a hole blocking layer.
  • electron injection layer the layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer, and the layer that prevents holes from flowing from the light emitting layer is called a hole blocking layer.
  • condensed polycyclic aromatic anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, , Coronene, tarisene, fuoresai rescein, perylene, rubrene and derivatives thereof
  • perylene phthalate, perylene, naphthalene, perinone, phthaline perinone, naphthalene perinone, diphenylbutadiene, tetraphenylbutadiene, Coumarin, oxazine diazone, anoredazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzo
  • a more effective hole injecting material is an aromatic tertiary amine derivative or a phthalocyanine derivative.
  • the aromatic tertiary amine derivative include triphenylamine, tritolylamine, tolyldiphenylamine, N, ⁇ ′-diphenylenolene N, ⁇ , — (3-methylphenyl) —1,1, —biphenyl—4 , 4,-Jiamin (hereinafter referred to as TPD), ⁇ , ⁇ , ⁇ ,, ⁇ ,-(4-methylenophenone) -1, 1, 1, 1 feninolee 4, 4, 1 diamine, ⁇ , ⁇ , ⁇ ,, ⁇ '— (4-Methylphenyl
  • phthalocyanine (Pc) derivative examples include HPc, CuPc, CoPc, NiPc, ZnPc, and Pd.
  • a more effective and well-known electron injection material or hole blocking material is a metal complex compound or a nitrogen-containing five-membered ring derivative.
  • the metal complex compound include 8-hydroxyquinolinatolithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, and tris ( 8-Hydroxyquinolinato) aluminum (hereinafter referred to as Alq), tri
  • the nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxaziazole, thiaziazole or triazole derivative.
  • 2,5-bis (1-pheninole) -1,3,4-oxazole, dimethyl-1,4_bis (5'_phenyloxazolyl) benzene 2,5_ Bis (1-pheninole) _1,3,4-thiazole, 2,5_Bis (1-pheninole) _1,3,4oxaziazole, 2_ (4'_tert_butylphenyl) -5_ (4, 1,2-bis (1naphthyl 3,4_oxadiazole, 1,4_bis [2— (5-phenyloxadiazolyl)] benzene, 1,4_ Bis [2- (5-phenyl oxaziazolyl) _4_tert-butylbenzene], 2_ (4 '_tert-butylphenyl)
  • an inorganic compound layer may be provided between the light emitting layer and the electrode for improving the charge injection property.
  • the inorganic compound layer is made of an alkali compound such as LiF, Li0, RaO, Sr ⁇ , BaF, and SrF.
  • Examples include fluorides and oxides of metals or alkaline earth metals.
  • the conductive material used for the anode of the organic electroluminescent device of the present invention those having a work function larger than 4 eV are suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten , Silver, gold, platinum, palladium and their alloys, ITO (indium oxide and tin oxide 5-10. /. Added substances) substrates, metal oxides such as tin oxide and indium oxide used for NESA substrates, Further, organic conductive resins such as polythiophene and polypyrrole can be used.
  • the conductive material used for the cathode those having a work function of less than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and the like can be used.
  • those alloys are used.
  • the alloy includes magnesium Z silver, magnesium Z indium, lithium Z aluminum and the like.
  • the ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, etc. of the evaporation source, and is not particularly limited.
  • the anode and the cathode may be formed by two or more layers if necessary.
  • the organic electroluminescent device of the present invention it is preferable that at least one surface is transparent in the emission wavelength region of the device. Further, it is desirable that the substrate is also transparent.
  • the transparent electrode is obtained by using the above-mentioned conductive material and by setting such that a predetermined translucency is secured by a method such as vapor deposition or sputtering.
  • the electrode on the light emitting surface has a light transmittance of 10% or more.
  • the substrate is not particularly limited as long as it has mechanical and thermal strength and has transparency, but examples thereof include a glass substrate and a transparent resin film.
  • Examples of the transparent resin film include polyethylene, ethylene monobutyl acetate copolymer, ethylene monobutyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polychlorinated vinyl, polyvinyl alcohol, and polyvinyl alcohol.
  • the entire device in order to improve stability against temperature, humidity, atmosphere, and the like, the entire device is protected by a force for providing a protective layer on the surface of the device, or by using a silicon oil, a resin, or the like. It can also be protected.
  • Each layer of the organic electroluminescent device may be formed by a dry film forming method such as vacuum evaporation, sputtering, plasma, or ion plating, or a wet film forming method such as spin coating, diving or flow coating. Or can be applied.
  • a dry film forming method such as vacuum evaporation, sputtering, plasma, or ion plating
  • a wet film forming method such as spin coating, diving or flow coating.
  • the film thickness is not particularly limited, the usual film thickness is in the range of 5 nm ⁇ 10 ⁇ m, and more preferably in the range of 10 nm ⁇ 0.0.
  • a material such as an alkynyl group-substituted condensed heterocyclic compound (formula (1)) forming each layer is dissolved or dissolved in a solvent such as ethanol, chloroform, tetrahydrofuran, or dioxane.
  • the thin film can be prepared by dispersing.
  • the dry film forming method using the preferred tool vacuum deposition apparatus vacuum deposition, the vacuum degree 2 X 10- 3 Pa or less, the substrate temperature is set to room temperature, the present invention placed in an alumina deposition cell 8 — The ability to prepare thin films by heating materials such as alkynquinoline derivatives with tungsten filaments and evaporating the materials.
  • Co-evaporation of TPD and bis (8'-quinolyl) acetylene or the like can be performed by using respective evaporation sources and controlling the temperature independently.
  • any of the organic thin-film layers may be formed of polystyrene, polycarbonate, polyatalylate, polyester, polyamide, polyurethane, polysulfone, polymethylmetharylate, or the like in order to improve film forming properties and prevent pinholes in the film.
  • Insulating resins such as polymethyl acrylate, cellulose and their copolymers, photoconductive resins such as poly_N_bulcarbazole, polysilane, resins such as conductive resins such as polythiophene and polypyrrole, or antioxidants, ultraviolet rays Additives such as absorbents and plasticizers can be used.
  • the organic electroluminescent device of the present invention can be used, for example, in a flat panel of a wall-mounted television. It can be used as a flat light-emitting body such as a display, a copier, a printer, a backlight of a liquid crystal display, a light source such as an instrument, a display board, a sign lamp and the like.
  • the maximum ultraviolet absorption wavelength and maximum fluorescence wavelength of the alkynyl group-substituted condensed heterocyclic compound of the present invention were measured by the following methods.
  • the ultraviolet absorption maximum wavelength was determined by dissolving an alkynyl group-substituted condensed heterocyclic compound in chloroform (at a concentration of 0.1 Olmg / ml) and using an ultraviolet spectrophotometer at room temperature (20 ° C). The measurement was performed.
  • the maximum fluorescence wavelength was measured at room temperature (20 ° C) using a fluorescence spectrophotometer, using the above-described form-form solution.
  • the alkynyl group-substituted condensed heterocyclic compound of the present invention showed blue fluorescence having a fluorescence maximum at 380 to 400 nm when irradiated with ultraviolet light having a wavelength of about 240 nm in a chloroform solution.
  • the organic electroluminescent device containing the same realized blue fluorescence (see Examples 16 to 22 below).
  • the resulting organic layer was concentrated in the order of lmol / L hydrochloric acid (125 ml x 2) and water (125 ml x 1). After washing, drying over anhydrous magnesium sulfate and filtration, the ethyl ether is distilled off, the residue is dissolved in 250 ml of hexane at a temperature of 70 ° C, the insoluble matter is filtered off, and the filtrate is cooled to obtain a tea. The target compound was obtained as white crystals. (12.6 g, 91% yield)
  • the desired compound was obtained. (310 mg, 86% yield)
  • the target compound was obtained as a yellow-orange powder. (300 mg, 83% yield)
  • the target compound was obtained as an orange powder. (280 mg, 86% yield)
  • Total yield of the first to third steps is 71%.
  • the compound was obtained. (422 mg, yield 92%)
  • the physical properties are shown below.
  • the target compound was obtained as an oil. (188 mg, 41% yield)
  • the compound was obtained. (375 mg, 81% yield)
  • the compound was obtained. (605 mg, 60% yield)
  • the hole transport layer 3 made of TPD has a thickness of 40 nm
  • the light emitting layer 4 containing 1.4% by weight of bis (8,1-quinolyl) acetylene in TPD has a thickness of 40 nm
  • the electron transport layer 5 having Alq force has a thickness of 20 ⁇ .
  • the temperature of the source of bis (8,1-quinolyl) acetylene was controlled so as not to exceed 280 ° C.
  • the device When +30 V was applied between the electrodes with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode, the device emitted light at 16 cdZm 2 .
  • the emission spectrum had a shoulder at 435 nm and a peak at 497 nm, and the chromaticity coordinates of the emission color according to JIS Z8701 were (0.25, 0.36).
  • Ietchishi made of indium tin oxide (hereinafter, abbreviated as ITO) using a coated glass as the transparent electrodes substrate, using a vacuum evaporation apparatus (ULVAC machine manufactured by E), 2 X 1 0- 3 Pa or less on the same substrate
  • the hole transport layer 3 made of N, N'-bis (3-methylphenyl) -N, N, -bis (phenyl) -benzidine (hereinafter abbreviated as TPD) was formed at a vacuum degree of 40 nm
  • TPD N, N'-bis (3-methylphenyl) -N, N, -bis (phenyl) -benzidine
  • TPD N, N'-bis (phenyl) -benzidine
  • the light-emitting layer 4 containing 9% by weight of 8_ (4, _phenylphenylethynyl) quinoline in 4,4'_bis (carbazole-9-inole) biphenyl (hereinafter abbreviated
  • the device When a current was passed between the ITO electrode 2 of the device as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at 4 cd / m 2 at +22 V.
  • the emission spectrum had a peak at 418 nm, and the chromaticity coordinates of the emission color were (0.18, 0.14).
  • An organic electroluminescent device was manufactured in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8- (2′-methyl-2′-H-imidazolyl-etur) quinoline in CBP was used. .
  • the device When current was applied to the device with the ITO electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at +21 V at 14 cd / m 2 .
  • the maximum current efficiency at this time was 0.10 cd / A.
  • the emission spectrum had a peak at 427 nm, and the chromaticity coordinates of the emission color were (0.1, 0.12).
  • An organic electroluminescent device was produced in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8_ (4′-fluorophenylethul) quinoline in CBP was used.
  • the device was energized with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode. When the voltage between the electrodes was increased, the device emitted light at 5 cd / m 2 at +21 V. The maximum current efficiency at this time was 0.059 cd / A.
  • the emission spectrum had a peak at 420 nm, and the chromaticity coordinates of the emission color were (0.21, 0.19).
  • An organic electroluminescent device was prepared in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8-phenylethynylquinoline in CBP was used.
  • the device When a current was passed between the ITO electrode 2 of the device as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at +21 V at 4 cd / m 2 .
  • the maximum current efficiency at this time was 0.052 cd / A.
  • the emission spectrum had a peak at 415 nm, and the chromaticity coordinates of the emission color were (0.1, 0.11).
  • An organic electroluminescent device was prepared in the same manner as in Example 17, except that the light-emitting layer 4 containing 9% by weight of 1,3_bis (8'-quinolylethur) benzene in CBP was used. Energize the above-mentioned device with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode to increase the voltage between the electrodes. In particular, it emitted light at 0.4 cd / m 2 at +20 V. The maximum current efficiency at this time was 0.032 cd / A. The emission spectrum had a peak at 451 nm, and the chromaticity coordinates of the emission color were (0.18, 0.17).
  • An organic electroluminescent device was prepared in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8- (2′-fluorophenylethyl) quinoline in CBP was used.
  • the device was energized with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode. When the voltage between the electrodes was raised and increased, the device emitted light at 3 cd / m 2 at +18 V. The maximum current efficiency at this time was 0.018 cd / A.
  • the emission spectrum had a peak at 421 nm, and the chromaticity coordinates of the emission color were (0.19, 0.18).
  • an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1), which emits strong blue light under ultraviolet irradiation, in an organic compound layer.
  • an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1), which emits strong blue light under ultraviolet irradiation, in an organic compound layer.
  • the alkynyl group-substituted condensation represented by the above formula (1 ′), which shows strong blue light emission by ultraviolet irradiation in a black form solution and is extremely useful as an organic electroluminescent device material can provide a heterocyclic compound and a novel alkynyl group-substituted condensed heterocyclic compound represented by the formulas (2) and (4) included therein.
  • a novel alkynyl-substituted condensed heterocycle represented by the above formula (1) which exhibits strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescence device
  • a method for synthesizing a compound with high yield can be provided.

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Abstract

Disclosed is an alkynyl group-substituted condensed heterocyclic compound which is represented by the following formula (1): wherein n1 is an integer of 1-3, and when n1 is 1, A represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkylsilyl group or heterocyclic group, while n1 is 2 or 3, A represents a divalent or trivalent alkyl group or heterocyclic group; and X and Y respectively represent CH or N. Also disclosed are a method for producing such a compound and an organic electroluminescent device using such a compound.

Description

明 細 書  Specification
アルキニル基置換縮合へテロ環化合物及びその製法並びにそれを使用 する有機エレクト口ルミネッセンス素子  Alkynyl-substituted condensed heterocyclic compound, process for producing the same, and organic electroluminescent device using the same
技術分野  Technical field
[0001] 本発明は電界発光素子（有機エレクト口ルミネッセンス素子）用青色発光材料など に有用な次式 (1) :  [0001] The present invention provides the following formula (1) useful for a blue light-emitting material for an electroluminescent device (organic electroluminescent device):
Figure imgf000003_0001
式中、 n1は 1一 3の整数を表わし、 n1が 1の場合、 Aは水素原子、アルキル基、シク 口アルキル基、ァリーノレ基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わ し、 n1が 2又は 3の場合、 Aは 2価又は 3価のァリール基又はへテロ環基を表わし、 X 及び Yはそれぞれ CH又は Nを表わす、
Figure imgf000003_0001
In the formula, n 1 represents an integer of 13; and when n 1 is 1, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylene group, an aralkyl group, an alkylsilyl group, or a heterocyclic group. And when n 1 is 2 or 3, A represents a divalent or trivalent aryl or heterocyclic group, and X and Y represent CH or N, respectively.
で示されるアルキニル基置換縮合へテロ環化合物を含有する有機エレクト口ルミネッ センス素子、この素子に使用される前記式（1)で示されるアルキニル基置換縮合へ テロ環化合物及びその製法に関する。  The present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1), an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) used in the device, and a method for producing the same.
背景技術  Background art
[0002] 前記式（1)で示されるアルキニル基置換縮合へテロ環化合物及びその製造法とし て ίま、 列え ίま、ケミツシェ 'ベリヒテ（Chemische Berichte, 1960, 93, p. 593)に 、 8-ァセチルキノリンと五塩化リンを反応させることによる 8-ェチニルキノリンの製造 法が記載されている力 その収率は 14%と低収率であった。また、オーストラリアン* ジャーナノレ 'ォブ 'ケミストリー (Australian Journal of Chemistry, 1989, 42, p. 279)には、 8_トリフルォロメタンスルホ二口キシキノリンとトリブチルスタユルフェ二 ルアセチレンとを反応させることによる 8_フエ二ルェチ二ルキノリンの製造法が記載さ れているが、収率は 43%と低収率であった。  [0002] As an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1) and a method for producing the same, see, for example, Chemische Berichte (Chemische Berichte, 1960, 93, p. 593). A method for producing 8-ethynylquinoline by reacting 8-acetylquinoline with phosphorus pentachloride was described. Its yield was as low as 14%. Also, the Australian Journal of Chemistry, 1989, 42, p. 279 states that 8_ trifluoromethanesulfo-two-port xyquinoline can be reacted with tributylstanylphenylacetylene. Describes a method for producing 8_phenylenequinoline by the above method, but the yield was as low as 43%.
[0003] 更に、これらの化合物については、有機エレクト口ルミネッセンス素子用材料として の使用につレ、ては何ら知られてレ、なかった。 [0003] Further, these compounds are used as materials for organic electroluminescent devices. I didn't know anything about using it.
発明の開示  Disclosure of the invention
[0004] 本発明は、紫外線照射下で強い青色の発光を示す前記式（1)で示されるアルキニ ル基置換縮合へテロ環化合物を含有する有機エレクト口ルミネッセンス素子及び前 記式（1)で示されるアルキニル基置換縮合へテロ環化合物に包含される新規なアル キニル基置換縮合へテロ環化合物を提供する。  [0004] The present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1), which emits strong blue light under ultraviolet irradiation, and the above formula (1) The present invention provides a novel alkynyl group-substituted condensed heterocyclic compound which is included in the alkynyl group-substituted condensed heterocyclic compound.
[0005] 本発明は、また、紫外線照射下で強い青色の発光を示し、有機エレクト口ルミネッセ ンス素子用材料として有用である前記式（1)で示されるアルキニル基置換縮合へテ 口環化合物を収率良く合成する方法を提供する。  [0005] The present invention also relates to an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1), which shows strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescent device. A method for synthesizing with good yield is provided.
[0006] 本発明者らは鋭意検討した結果、前記式（1)で示されるアルキニル基置換縮合へ テロ環化合物を含有する有機エレクト口ルミネッセンス素子が、電圧印加により青白 色の発光を示すことを見出すと共に、前記式（1)で示されるアルキニル基置換縮合 ヘテロ環化合物がクロ口ホルム溶液中で紫外線照射により強い青色発光を示し、有 機エレクト口ルミネッセンス素子材料として極めて有用であることを見出して本発明に 至った。  The present inventors have conducted intensive studies and as a result, have found that an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) emits blue-white light when a voltage is applied. In addition, they found that the alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) showed strong blue light emission by ultraviolet irradiation in a chloroform solution, and was extremely useful as an organic electroluminescent device material. The present invention has been achieved.
[0007] また、本発明者らは、ヒドロキシ基置換縮合へテロ環化合物を対応するトリフルォロ メタンスルホン酸エステル (以下に示す式（5) )に誘導した後、 0価パラジウム触媒に より種々の末端アセチレンィ匕合物と反応させることにより、前記式（1)で示されるアル キニル基置換縮合へテロ環化合物を収率良く製造できることを見出した。  [0007] Further, the present inventors have derived a hydroxy-substituted condensed heterocyclic compound into the corresponding trifluoromethanesulfonic acid ester (formula (5) shown below), and then used a zero-valent palladium catalyst to prepare various terminal groups. It has been found that the alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1) can be produced in good yield by reacting with the acetylene conjugate.
[0008] 即ち、本発明は以下の通りである。  [0008] That is, the present invention is as follows.
第 1の発明は、 1対の電極間に有機化合物薄層を有する有機エレクト口ルミネッセ ンス素子であって、該有機化合物層が次式（1)：  The first invention is an organic electroluminescent device having an organic compound thin layer between a pair of electrodes, wherein the organic compound layer has the following formula (1):
Figure imgf000004_0001
式中、 n1は 1一 3の整数を表わし、 n1が 1の場合、 Aは水素原子、アルキル基、シク 口アルキル基、ァリーノレ基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わ し、 n1が 2又は 3の場合、 Aは 2価又は 3価のァリール基又はへテロ環基を表わし、 X 及び Yはそれぞれ CH又は Nを表わす、
Figure imgf000004_0001
In the formula, n 1 represents an integer of 13; when n 1 is 1, A represents a hydrogen atom, an alkyl group, Represents an alkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n 1 is 2 or 3, A represents a divalent or trivalent aryl group or a heterocyclic group. , X and Y each represent CH or N;
で示されるアルキニル基置換縮合へテロ環化合物を含有することを特徴とする有機 エレクト口ルミネッセンス素子に関するものである。  The present invention relates to an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula:
[0009] 第 2の発明は、次式（1 ' )：  [0009] A second invention provides the following formula (1 '):
Figure imgf000005_0001
Figure imgf000005_0001
式中、 η1は前記と同義であり、 η1が 1の場合、 R1は、アルキル基、シクロアルキル基 、無置換のフヱニル基以外のァリール基、ァラルキル基、アルキルシリル基、又はへ テロ環基を表わし、 η1が 2又は 3の場合、 R1は 2価又は 3価のァリール基又はへテロ 環基を表わし、 X及び Υは前記と同義である、 In the formula, η 1 is as defined above, and when η 1 is 1, R 1 is an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a hetero group. When η 1 is 2 or 3, R 1 represents a divalent or trivalent aryl group or a heterocyclic group, and X and Υ are as defined above;
で示されるアルキニル基置換縮合へテロ環化合物に関するものである。  The present invention relates to an alkynyl group-substituted fused heterocyclic compound represented by the formula:
[0010] 第 3の発明は、触媒として 0価パラジウム化合物を用いて、次式（5)：  [0010] The third invention uses a zero-valent palladium compound as a catalyst and uses the following formula (5):
Figure imgf000005_0002
Figure imgf000005_0002
式中、 X及び Υは前記と同義である、  In the formula, X and Υ are as defined above,
で示されるトリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物と、次式（ And a trifluoromethanesulfonyloxy group-substituted fused heterocyclic compound represented by the following formula:
6) :
Figure imgf000005_0003
6):
Figure imgf000005_0003
式中、 A及び n1は前記と同義である、 Wherein A and n 1 are as defined above,
で示される末端アセチレン化合物とを、塩基性溶媒中で反応させることを特徴とする 前記式（1)で示されるアルキニル基置換縮合へテロ環化合物の製造法に関するもの である。 Characterized by reacting with a terminal acetylene compound represented by in a basic solvent The present invention relates to a method for producing the alkynyl group-substituted fused heterocyclic compound represented by the formula (1).
[0011] 第 4の発明は、触媒として 0価パラジウム化合物を用いて、塩基性溶媒中、前記式（ 5)で示されるトリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物とアル キルシリルアセチレンィヒ合物とを反応させてアルキルシリルェチュル基置換縮合へ テロ環化合物（前記式（1)において n1が 1、 Aがアルキルシリル基である化合物）とし た後、加水分解することを特徴とする次式（7)： [0011] A fourth invention uses a zero-valent palladium compound as a catalyst and a trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound represented by the formula (5) and an alkylsilylacetylene in a basic solvent. Reacting with a compound of formula (I) to form an alkylsilyl-etul group-substituted condensed heterocyclic compound (compound wherein n 1 is 1 and A is an alkylsilyl group in the above formula (1)), and then hydrolyzes. The following equation (7) to be characterized:
Figure imgf000006_0001
Figure imgf000006_0001
式中、 X及び Yは前記と同義である、  Wherein X and Y are as defined above,
で示されるェチュル基置換縮合へテロ環化合物（前記式（1)において n1が 1、 Aが水 素原子である化合物）の製造法に関するものである。 The present invention relates to a process for producing a condensed heterocyclic compound substituted with an ethur group represented by the formula (compound wherein n 1 is 1 and A is a hydrogen atom in the formula (1)).
[0012] 第 5の発明は、前記式（7)で示されるェチニル基置換縮合へテロ環化合物と次式（ 9) :
Figure imgf000006_0002
式中、 X'はハロゲン原子を表し、 Rはハロゲン原子、ジアルキルアミノ基、ァリール ォキシ基、アルコキシ基、アルケニル基、アシノレ基、ニトロ基、シァノ基、アルキル基、 シクロアルキル基、又はァリール基を表し、複数の Rは、それぞれ同一でも異なって レ、てもよく、 n3は 1一 5の整数を表す、 A fifth invention relates to an ethynyl group-substituted fused heterocyclic compound represented by the above formula (7) and the following formula (9):
Figure imgf000006_0002
In the formula, X ′ represents a halogen atom, and R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acinole group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group. represents, a plurality of R, respectively be the same or different, at best, n 3 is an integer of 1 one 5,
で示されるハロゲン化芳香族環化合物とを、触媒として 0価パラジウム化合物を用い て、塩基性溶媒中で反応させることにより、前記式（1)において、 Aがァリール基であ り、 n1が 1である次式（8)：
Figure imgf000007_0001
Is reacted with a halogenated aromatic ring compound represented by the formula (1) in a basic solvent using a zero-valent palladium compound as a catalyst, whereby in the above formula (1), A is an aryl group, and n 1 is The following equation (8) which is 1:
Figure imgf000007_0001
式中、 X、 Y、 R及び η3は前記と同義である、 Wherein X, Y, R and η 3 are as defined above,
で示されるフヱニルェチュル基置換縮合へテロ環化合物の製造法に関するものであ る。  The present invention relates to a process for producing a fused heterocyclic compound substituted with a phenylethur group represented by the formula:
図面の簡単な説明  Brief Description of Drawings
[0013] [図 1]図 1は、実施例 16における有機 EL素子の断面図であり、図中、参照番号 1は ガラス基板を示し、 2は ΙΤΟを、 3はホール注入層を、 4は発光層を、 5は電子注入層 又はホールブロック層を、 6は A1電極をそれぞれ示す。  [FIG. 1] FIG. 1 is a cross-sectional view of an organic EL device in Example 16, in which reference numeral 1 indicates a glass substrate, 2 indicates a square, 3 indicates a hole injection layer, and 4 indicates a hole injection layer. A light emitting layer, 5 indicates an electron injection layer or a hole blocking layer, and 6 indicates an A1 electrode.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 第 1の発明の有機エレクト口ルミネッセンス素子に使用されるアルキニル基置換縮 合へテロ環化合物（前記式（1) )において、 η1は 1一 3の整数を表わし、 η1が 1の場合 、 Αは水素原子、アルキル基、シクロアルキル基、ァリール基、ァラルキル基、アルキ ルシリル基、又はへテロ環基を表わし、 n1が 2又は 3の場合、 Aは 2価又は 3価のァリ ール基又はへテロ環基を表わし、 X及び Yはそれぞれ CH又は Nを表わす。 [0014] The first organic-elect opening alkynyl heterocyclic compounds substituted condensed for use in luminescent element of the present invention in (Formula (1)), eta 1 represents an integer of 1 one 3, eta 1 1 In the formula, Α represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n 1 is 2 or 3, A is divalent or trivalent. Represents an aryl group or a heterocyclic group; X and Y each represent CH or N;
[0015] アルキル基としては、メチル基、ェチル基、プロピル基、ブチル基、ペンチル基、へ キシル基、ヘプチル基、ォクチル基、ノニル基、デシル基等の炭素原子数 1一 10の アルキル基が挙げられる。なお、これらの置換基は、その異性体も含む。  [0015] Examples of the alkyl group include a C11-C10 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. No. These substituents include isomers thereof.
[0016] シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、 シクロへキシル基、シクロペンチル基、シクロへキシル基、シクロへプチル基等の炭素 原子数 3— 7のシクロアルキル基が挙げられる。  Examples of the cycloalkyl group include a cycloalkyl group having 3 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Can be
[0017] ァリール基としては、フエニル基、トリル基、キシリル基、ナフチル基、ジメチルナフ チル基等が挙げられる。なお、これらの置換基は、その異性体も含む。  [0017] Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a dimethylnaphthyl group. These substituents include isomers thereof.
[0018] ァラルキル基としては、ベンジル基、フエネチル基、フエニルプロピル基、フエニル ブチル基、ナフチルメチル基、ナフチルェチル基、ナフチルプロピル基、ナフチルメ チル基、ジフエニルメチル基等が挙げられる。 [0019] アルキルシリル基としては、トリメチルシリル基、トリェチルシリル基、トリイソプロピル シリル基、トリブチルシリル基、メチルジイソプロビルシリル基、 t-ブチルジメチルシリノレ 基、メチルジ t-ブチルシリル基等が挙げられる。 Examples of the aralkyl group include a benzyl group, a phenyl group, a phenylpropyl group, a phenylbutyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylmethyl group, a diphenylmethyl group, and the like. [0019] Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a methyldiisopropylsilyl group, a t-butyldimethylsilinole group, a methyldi-t-butylsilyl group, and the like.
[0020] ヘテロ環基としては、キノリノレ基、キナゾリニル基、キノキサリニル基、イミダゾリル基[0020] Examples of the heterocyclic group include a quinolinole group, a quinazolinyl group, a quinoxalinyl group, an imidazolyl group
、イミダゾリジニル基、イミダゾリニル基、ピラゾリル基、ピリジノレ基、ピペリジル基等が 挙げられる。 , An imidazolidinyl group, an imidazolinyl group, a pyrazolyl group, a pyridinole group, a piperidyl group and the like.
[0021] n1が 2である場合、 Aは 2価のァリール基又は 2価のへテロ環基であり、 n1が 3である 場合、 Aは 3価のァリール基又は 3価のへテロ環基である。これらの基としては、上記 したァリール基又はへテロ環基の 2価又は 3価のものが挙げられる。 When n 1 is 2, A is a divalent aryl group or a divalent heterocyclic group, and when n 1 is 3, A is a trivalent aryl group or a trivalent hetero ring group. It is a ring group. These groups include the divalent or trivalent groups of the above aryl groups or heterocyclic groups.
[0022] Aとして挙げられる上記の置換基は、その炭素原子に結合している水素原子が更 にハロゲン原子、好ましくは、フッ素原子、塩素原子、臭素原子、又はヨウ素原子;ジ ァノレキノレアミノ基、好ましくは、ジメチノレアミノ基、ジェチルァミノ基、ジプロピルアミノ 基等の炭素数 2— 10のジアルキルアミノ基；ァリールォキシ基、好ましくは、フエノキ シ基、トリロキシ基、キシリロキシ基、ナフトキシ基、ジメチルナフトキシ基等の炭素数 6 一 14のァリールォキシ基；アルコキシ基、好ましくは、メトキシ基、エトキシ基、プロボ キシ基、ブトキシ基、ペンタノキシ基、へキサノキシ基、ヘプタノキシ基、オタタノキシ 基、ノナノキシ基、デカノキシ基等の炭素数 1一 10のアルコキシ基；アルケニル基、好 ましくは、ビニノレ基、プロぺニル基、ブテュル基、ペンテュル基、へキセニル基、ヘプ テニル基、オタテニル基、ノネニル基、デセニル基、ゥンデセニル基、ドデセ二ル基等 の炭素数 2— 20、特に 2— 12のアルケニル基；ァシル基、好ましくは、ホルミル基、ァ セチル基、プロピオニル基、プチリル基、バレリル基、ビバロイル基等の炭素数 1一 7 の脂肪族酸のァシル基若しくはベンゾィル基等の芳香族ァシル基；ニトロ基、シァノ 基、或いは、上記と同義であるアルキル基、シクロアルキル基、又はァリール基等で 置換されていても良レ、。なお、これらの置換基は、その異性体も含む。  [0022] In the above-mentioned substituents exemplified as A, the hydrogen atom bonded to the carbon atom may further be a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; An amino group, preferably a dialkylamino group having 2 to 10 carbon atoms such as a dimethinoleamino group, a getylamino group, a dipropylamino group; an aryloxy group, preferably a phenoxy group, a trioxy group, a xyloxy group, a naphthoxy group, or a dimethylnaphthoxy group; An aryloxy group having 614 carbon atoms such as a group; an alkoxy group, preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentaoxy group, a hexoxy group, a heptanoxy group, an otatanoxy group, a nonanoxy group, a decanoloxy group, and the like. An alkoxy group having 1 to 10 carbon atoms; an alkenyl group, preferably a vinylinole group, Alkenyl groups having 2 to 20, especially 2 to 12 carbon atoms such as benzyl, butyr, pentenyl, hexenyl, heptenyl, otathenyl, nonenyl, decenyl, pendecenyl and dodecenyl; Acetyl group, preferably aromatic group such as formyl group, acetyl group, propionyl group, butyryl group, valeryl group, aromatic group such as benzoyl group or benzoyl group of C 17 aliphatic acid such as valiroyl group; , A cyano group, or an alkyl group, a cycloalkyl group, or an aryl group as defined above. These substituents include isomers thereof.
[0023] 上記のアルキニル基置換縮合へテロ環化合物（前記式（1) )の具体的な態様として は、 8—フエ二ルェチ二ルキノリン、 1， 4—ビス（8 '―キノリルェチュル）ベンゼン、 1， 3— ビス（8 ' _キノリルェチュル）ベンゼン、 1 , 3， 5—トリス（8' _キノリルェチュル）ベンゼ ン、 8—ェチニルキノリン、 8— (1 '—プロビュル）キノリン、 8— (2 '―シクロへキシルェチ ニル）キノリン、 8_(3'_フェニルー1'_プロピニル）キノリン、 8—トリメチルシリルェチニ ノレキノリン、ビス（8' _キノリル）アセチレン、 8_(4'_フルオロフェニルェチニル）キノリ ン、 8_ (3' _フルオロフェニルェチニノレ）キノリン、 8_ (2' _フルオロフェニルェチェル )キノリン、 8— (4 '—メトキシフエニルェチュル）キノリン、 8— (3 '—メトキシフエ二ルェチ ニル）キノリン、 8_(4'_フヱニルフヱニルェチュル)キノリン、 8_(2'_ピリジルェチュル )キノリン、 8_ (3' _ピリジルェチュル）キノリン、 8_ (2， _メチル—2'—H—イミダゾリルェ チニノレ）キノリン、 8_(4'_ベンゾィルフエ二ルェチ二ノレ）キノリンなどのアルキニル基 置換キノリン化合物、 8_フエニルェチュルキナゾリン、 1， 4_ビス（8'—キナゾリニルェ チュル）ベンゼン、 1， 3_ビス（8'—キナゾリ二ルェチ二ノレ）ベンゼン、 1， 3， 5_トリス（ 8'—キナゾリ二ルェチ二ノレ）ベンゼン、 8—ェチュルキナゾリン、 8_(1'_プロビュル） キナゾリン、 8_ (2 '—シクロへキシルェチニノレ）キナゾリン、 8_(3'_フェニノレ_1'_プ ロビニル）キナゾリン、 8—トリメチルシリルェチュルキナゾリン、ビス（8'—キナゾリニル） アセチレン、 8_ (4' _フルオロフェニルェチニノレ）キナゾリン、 8_(3'_フルオロフェニ ノレェチニノレ）キナゾリン、 8_(2'_フルオロフェニルェチニノレ）キナゾリン、 8_(4'-メト キシフエニルェチェル）キナゾリン、 8_ (3 '—メトキシフエ二ルェチ二ノレ）キナゾリン、 8 一 (4'—フエニルフエ二ルェチニル)キナゾリン、 8— (2'—ピリジルェチニル)キナゾリン、 8- (3 '—ピリジルェチェル）キナゾリン、 8_ (2，—メチルー 2 '—H—イミダゾリルェチェル )キナゾリン、 8_ (4' _ベンゾィルフエ二ルェチニル）キナゾリンなどのアルキニル基置 換キナゾリン化合物、 8_フエ二ルェチ二ルキノキサリン、 1, 4_ビス（8，一キノキサリニ ノレェチニル）ベンゼン、 1, 3—ビス（8，一キノキサリニルェチ二ノレ）ベンゼン、 1, 3, 5— トリス（8'_キノキサリニルェチェル）ベンゼン、 8_ェチニルキノキサリン、 8_(1'_プロ ピニル）キノキサリン、 8_ (2 '—シクロへキシルェチュル）キノキサリン、 8_(3'_フエ二 ノレ— 1'—プロビュル）キノキサリン、 8—トリメチルシリルェチニルキノキサリン、ビス（8'— キノキサリニル）アセチレン、 8_ (4' _フルオロフェニルェチュル）キノキサリン、 8_(3 ，—フルオロフェニルェチニノレ）キノキサリン、 8-(2'—フルオロフェニルェチニノレ）キノ キサリン、 8_(4 '—メトキシフエニルェチュル）キノキサリン、 8_ (3 '—メトキシフエ二ル ェチュル）キノキサリン、 8— (4' _フエユルフェニルェチュル)キノキサリン、 8— (2'_ピリ ジルェチュル)キノキサリン、 8_ (3' _ピリジルェチュル）キノキサリン、 8_(2 '—メチル -2 ' _H—イミダゾリルェチニル）キノキサリン、 8- (4，—ベンゾィルフエ二ルェチニル） キノキサリンなどのアルキニル基置換 8—キノキサリン化合物等が挙げられる。 Specific examples of the above-mentioned alkynyl group-substituted condensed heterocyclic compound (the formula (1)) include 8-phenylethynylquinoline, 1,4-bis (8′-quinolyleturyl) benzene, , 3—Bis (8'_quinolylethur) benzene, 1,3,5-Tris (8'_quinolylethur) benzene, 8-ethynylquinoline, 8— (1'-Probyl) quinoline, 8— (2'-cyclohexyl) Kisilchech Nyl) quinoline, 8_ (3'_phenyl-1'_propynyl) quinoline, 8-trimethylsilylethynino olequinoline, bis (8'_quinolyl) acetylene, 8_ (4'_fluorophenylethynyl) quinoline, 8_ (3 '_Fluorophenylethyninole) quinoline, 8_ (2'_Fluorophenylethyl) quinoline, 8- (4'-methoxyphenylethynyl) quinoline, 8- (3'-methoxyphenylethyl) quinoline, 8_ (4'_Phenylpenyletul) quinoline, 8_ (2'_Pyridyletul) quinoline, 8_ (3'_Pyridyletul) quinoline, 8_ (2, _Methyl-2'-H-imidazolyl Alkynyl group-substituted quinoline compounds such as ethyninole) quinoline and 8_ (4'_benzoylphenylethyninole) quinoline, 8_phenylenyl quinazoline, 1,4_bis (8'-quinazolinyl ethyl) benzene, 1,3 _Bis (8'-quinazolinyletininole) benzene, 1,3,5_tris (8'-quinazolinyletininole) benzene, 8-ethuchlquinazoline, 8_ (1'_probyl) quinazoline, 8_ ( 2'-cyclohexylethininole) quinazoline, 8_ (3'_phenylinole_1'_vinyl) quinazoline, 8-trimethylsilyllechurquinazoline, bis (8'-quinazolinyl) acetylene, 8_ (4'_fluorophenylethininole) ) Quinazoline, 8_ (3'_fluorophenylenotininole) quinazoline, 8_ (2'_fluorophenylethininole) quinazoline, 8_ (4'-methoxyphenylenyl) quinazoline, 8_ (3'-methoxyphenylenetin) Nore) quinazoline, 8 1- (4'-phenylphenylethynyl) quinazoline, 8- (2'-pyridylethynyl) quinazoline, 8- (3'-pyridylethyl) quinazoline, 8_ (2 —Methyl-2′—H—Imidazolylchel) quinazoline, alkynyl-substituted quinazoline compounds such as 8_ (4′_benzoylphenyletinyl) quinazoline, 8_phenylenechirquinoxaline, 1,4_bis (8,1 Quinoxalinini (norethynyl) benzene, 1,3-bis (8,1-quinoxalinylethyninole) benzene, 1,3,5-tris (8'_quinoxalinylethyl) benzene, 8_ethynylquinoxaline, 8_ (1'_propynyl) quinoxaline, 8_ (2'-cyclohexyl etul) quinoxaline, 8_ (3'_phenynole-1'-provyl) quinoxaline, 8-trimethylsilylethynylquinoxaline, bis (8'- Quinoxalinyl) acetylene, 8_ (4'-fluorophenylethul) quinoxaline, 8_ (3, -fluorophenylethininole) quinoxaline, 8- (2'-fluorophen Luetininole) quinoxaline, 8_ (4'-methoxyphenylethyl) quinoxaline, 8_ (3'-methoxyphenylethyl) quinoxaline, 8- (4'_fuyphenylphenyletur) quinoxaline, 8— (2'_ Pyridyl-etul) quinoxaline, 8_ (3'_pyridyl-etur) quinoxaline, 8_ (2'-methyl Alkynyl group-substituted 8-quinoxaline compounds such as -2'_H-imidazolylethynyl) quinoxaline and 8- (4, -benzoylphenylethynyl) quinoxaline.
[0024] 本発明の式（1)で示されるアルキニル基置換縮合へテロ環化合物の中でも、本発 明におレ、ては、次式（2) (4)で示されるアルキニル基置換縮合へテロ環化合物が 好ましく使用される。 [0024] Among the alkynyl group-substituted condensed heterocyclic compounds represented by the formula (1) of the present invention, the present invention relates to alkynyl group-substituted condensed condensed compounds represented by the following formulas (2) and (4). Terocyclic compounds are preferably used.
Figure imgf000010_0001
Figure imgf000010_0001
式中、 R1は、アルキル基、シクロアルキル基、無置換のフヱニル基以外のァリール 基、ァラルキル基、アルキルシリル基、又はへテロ環を表わす。 In the formula, R 1 represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a hetero ring.
Figure imgf000010_0002
Figure imgf000010_0002
式中、 n2は 2 3の整数を表す。 In the formula, n 2 represents an integer of 23.
Figure imgf000010_0003
Figure imgf000010_0003
[0025] 前記式（2)で示されるアルキニル基置換縮合へテロ環化合物において、 R1は、了 ノレキル基、シクロアルキル基、無置換のフエニル基以外のァリール基、ァラルキル基 、アルキルシリル基、又はへテロ環基を表わす。なお、これら置換基の具体的な態様 は、前記式（1)において Aとして挙げたものと同様である。 In the alkynyl group-substituted condensed heterocyclic compound represented by the formula (2), R 1 is an arylalkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, Or a heterocyclic group. The specific embodiments of these substituents are the same as those described as A in the above formula (1).
[0026] 上記、アルキニル基置換縮合へテロ環化合物（前記式（2) )の具体的な態様として は、 8— (1—プロピニル）キノリン、 8— (2—シクロプロピルェチュル）キノリン、 8— (4 '—メ チルフエ二ルェチニル）キノリン、 8—トリメチルシリルェチニルキノリン、 8_(4'—フルォ 口フエ二ルェチニル）キノリン、 8— (3，一フルオロフェニルェチニル）キノリン、 8— (2，一 フルオロフェニルェチニノレ）キノリン、 8_ (4 '—メトキシフエ二ルェチ二ノレ）キノリン、 8_ ( 3，—メトキシフエニルェチュル）キノリン、 8-(4，—フエユルフェニルェチュル)キノリン 、 8_(2' _ピリジルェチュル)キノリン、 8_ (3' _ピリジルェチュル）キノリン、 8_ (2 '—メ チノレ— 2'—H—イミダゾリルェチニノレ）キノリン、 8_ (4' _ベンゾィルフエニルェチュル） キノリン等が挙げられる。 Specific examples of the above-mentioned alkynyl group-substituted condensed heterocyclic compound (the formula (2)) include 8- (1-propynyl) quinoline, 8- (2-cyclopropylethyl) quinoline, — (4'-me Tilfeneretinyl) quinoline, 8-trimethylsilylethynylquinoline, 8_ (4'-fluoro mouth phenylethinyl) quinoline, 8- (3,1-fluorophenylethynyl) quinoline, 8- (2,1-fluorophenylene) Chininole) quinoline, 8_ (4'-methoxyphenyletinole) quinoline, 8_ (3, -methoxyphenyletulle) quinoline, 8- (4, -fuyphenylphenyletul) quinoline, 8_ (2'_ (Pyridyl etur) quinoline, 8_ (3 '_ pyridyl etur) quinoline, 8_ (2'-methinole-2 '-H-imidazolyllechininole) quinoline, 8_ (4' _ benzoyl phenyl etur) quinoline And the like.
[0027] 前記式（3)で示されるアルキニル基置換縮合へテロ環化合物において、 n2は 2— 3 の整数を表わす。 In the alkynyl group-substituted fused heterocyclic compound represented by the formula (3), n 2 represents an integer of 2-3.
具体的な態様としては、 1 , 4—ビス（8， _キノリルェチュル）ベンゼン、 1 , 3—ビス（8， —キノリルェチュル）ベンゼン、 1， 3, 5—トリス（8 ' _キノリルェチュル）ベンゼン等が挙 げられる。  As specific embodiments, 1,4-bis (8, _quinolyletul) benzene, 1,3-bis (8, _quinolyletul) benzene, 1,3,5-tris (8′_quinolyletul) benzene, and the like are listed. I can do it.
[0028] 前記式 (4)で示される化合物は、式（1)において、 Aがキノリル基であり、 X及び Y が共に CHであり、 n1が 1であるビス（8，一キノリル）アセチレンである。 The compound represented by the formula (4) is a bis (8,1-quinolyl) acetylene represented by the formula (1), wherein A is a quinolyl group, X and Y are both CH, and n 1 is 1. It is.
[0029] 第 2の発明は、前記式（1)において、 Aが水素原子である場合を除ぐ式（1 ' )で示 されるアルキニル基置換縮合へテロ環化合物に関するものである。  [0029] The second invention relates to an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1 ') except that in the formula (1), A is a hydrogen atom.
[0030] 式（1 ' )において、 II1、 X及び Yは前記式（1)と同義であり、 n1が 1の場合、 R1は、ァ ノレキル基、シクロアルキル基、無置換のフエニル基以外のァリール基、ァラルキル基 、アルキルシリル基、又はへテロ環基を表わし、 n1が 2又は 3の場合、 R1は 2価又は 3 価のァリール基又はへテロ環基を表わす。上記 R1としては、前記式（1)の Aにおいて 記載したアルキル基、シクロアルキル基、無置換のフエニル基以外のァリール基、ァ ラルキル基、アルキルシリル基、又はへテロ環基と同義のものが挙げられ、具体的化 合物としては、前記式（1)において記載した 8—フエ二ルェチ二ルキノリンを除く化合 物が挙げられる。 In the formula (1 ′), II 1 , X and Y have the same meanings as in the above formula (1), and when n 1 is 1, R 1 is an anoalkyl group, a cycloalkyl group or an unsubstituted phenyl. Represents an aryl group, an aralkyl group, an alkylsilyl group or a heterocyclic group other than the group, and when n 1 is 2 or 3, R 1 represents a divalent or trivalent aryl group or a heterocyclic group. R 1 has the same meaning as the alkyl group, cycloalkyl group, aryl group other than unsubstituted phenyl group, aralkyl group, alkylsilyl group, or heterocyclic group described in A of the above formula (1). Specific examples of the compound include compounds excluding 8-phenylethynylquinoline described in the above formula (1).
[0031] 式（1 ' )で示されるアルキニル基置換縮合へテロ環化合物の好ましレ、ものとしては、 前記式（2)— (4)で示される化合物が挙げられる。  Preferred examples of the alkynyl group-substituted fused heterocyclic compound represented by the formula (1 ′) include the compounds represented by the formulas (2) to (4).
[0032] 第 3の発明の製造法は、触媒として 0価パラジウム化合物を用いて、トリフルォロメタ ンスルホニルォキシ置換縮合へテロ環化合物（前記式（5) )と末端アセチレン化合物 (前記式（6) )とを塩基性溶媒中で反応させることによってアルキニル基置換縮合へ テロ環化合物（前記式（1 ) )を製造するものである。 [0032] The production method of the third invention uses a trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound (the above formula (5)) and a terminal acetylene compound using a zero-valent palladium compound as a catalyst. An alkynyl group-substituted condensed heterocyclic compound (formula (1)) is produced by reacting the above formula (6) with a basic solvent.
[0033] ここでトリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物は、例えば、 ジャーナノレ'ォブ'ザ'アメリカン'ケミカノレ'ソサエティ（Journal of the American Chemical Society, 1987, 109， p. 5478) (こ記載の合成法 (こ従レヽ、トリェチノレ ァミン等の有機塩基の存在下、塩化メチレン等の溶媒中にトリフルォロメタンスルホン 酸無水物と目的のトリフルォロメタンスルホニルォキシ置換縮合へテロ環化合物に対 応するヒドロキシ基置換縮合へテロ環化合物とを反応させることによって製造される。 [0033] Here, the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound is described, for example, in Journal of the American Chemical Society, 1987, 109, p. 5478. (Synthesis method described in this specification (in the presence of an organic base such as triethylamine or triethylenamine) in a solvent such as methylene chloride and a solvent such as trifluoromethanesulfonic anhydride and the intended trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound It is produced by reacting a hydroxy-substituted condensed heterocyclic compound corresponding to the above.
[0034] 触媒として用いられる 0価パラジウム化合物としては、例えば、 0価パラジウムホスフ イン錯体（パラジウムテトラキストリフエニルホスフィン錯体、ビスジフエニルホスフイノェ タンパラジウム錯体、ビストリシクロへキシノレホスフィンパラジウム錯体など）、 0価パラ ジゥムォレフイン錯体（トリスジベンジリデンアセトンジパラジウム錯体など）などが挙げ られる。これら化合物の内、 0価パラジウムホスフィン錯体が好ましぐ更には、テトラキ ス（トリフエニルホスフィン）パラジウムが好ましレ、。  Examples of the zero-valent palladium compound used as a catalyst include zero-valent palladium phosphine complexes (palladium tetrakistriphenylphosphine complex, bisdiphenylphosphinoethanepalladium complex, bistricyclohexinolephosphine palladium complex, etc.) And zero-valent palladium olefin complex (such as trisdibenzylideneacetone dipalladium complex). Of these compounds, a zero-valent palladium phosphine complex is preferred, and tetrax (triphenylphosphine) palladium is more preferred.
[0035] これらの 0価パラジウム化合物の使用量は、トリフルォロメタンスルホニルォキシ基 置換縮合へテロ環化合物に対して 0. 1— 10モル％であり、好ましくは 0. 5— 5モル %である。  [0035] The use amount of these zero-valent palladium compounds is 0.1 to 10 mol%, preferably 0.5 to 5 mol%, based on the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound. is there.
[0036] 前記式（6)で示される末端アセチレン化合物において、 Aは水素原子、アルキル基 、シクロアルキル基、ァリール基、ァラルキル基、アルキルシリル基、又はへテロ環基 を表わし、 n1は 1一 3の整数を表わす。 In the terminal acetylene compound represented by the formula (6), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and n 1 represents 1 Represents an integer of 13.
Aで表わされるこれら置換基は、前記式（1)の Aと同義である。  These substituents represented by A have the same meaning as A in the above formula (1).
[0037] 上記末端アセチレン化合物（前記式（6) )の具体的な態様としては、フエニルァセチ レン、 4_フルオロフェニルアセチレン、 3_フルオロフェニルアセチレン、 2_フルォロ フエニルアセチレン、 4ーメトキシフエ二ルアセチレン、 3—メトキシフエ二ルアセチレン、 4—フエユルフェニルアセチレン、 4—ベンゾィルフエニルアセチレン、 1 , 4_ジェチ二 ノレベンゼン、 1 , 3—ジェチュルベンゼン、 1， 3， 5—トリエチュルベンゼン等のェチニ ル基置換ァリール化合物、 8_ェチニルキノリン、 8—ェチュルキナゾリン、 8—ェチュル キノキサリン、 2 '_ピリジルアセチレン、 3 '_ピリジルアセチレン、 5—ェチュル— 1—メチ ノレ 1_H イミダゾール等のェチニル基置換へテロ環化合物、トリメチルシリルァセチ レン等のアルキルシリルアセチレン化合物、 1 プロピン、 1ーブチン等のアルキル基 置換アセチレン化合物、シクロへキシルアセチレン等のシクロアルキル基置換ァセチ レン化合物、 3_フヱニルー 1_プロピン等のァラルキル基置換アセチレン化合物等が 挙げられる。 [0037] Specific examples of the terminal acetylene compound (formula (6)) include phenylacetylene, 4_fluorophenylacetylene, 3_fluorophenylacetylene, 2_fluorophenylacetylene, 4-methoxyphenylacetylene, Ethines such as 3-methoxyphenylacetylene, 4-fuphenylphenylacetylene, 4-benzoylphenylacetylene, 1,4_jetinolebenzene, 1,3-jetulbenzene, 1,3,5-triethylbenzene Substituted aryl compounds, 8_ethynylquinoline, 8—ethyurquinazoline, 8—ethyruquinoxaline, 2′_pyridylacetylene, 3′_pyridylacetylene, 5—ethyur—1—methyl Nore 1_H Ethynyl-substituted heterocyclic compounds such as imidazole, alkylsilylacetylene compounds such as trimethylsilylacetylene, alkyl-substituted acetylene compounds such as 1-propyne, 1-butyne, and cycloalkyl-substituted acetylene compounds such as cyclohexylacetylene And aralkyl group-substituted acetylene compounds such as 3,3-phenyl-1-propyne and the like.
[0038] 末端アセチレン化合物（前記式（6) )の使用量は、トリフルォロメタンスルホ二ルォキ シ基置換縮合へテロ環化合物（前記式（5) ) 1モルに対して、 1. 0-2. 0モルであり、 好ましくは 1. 0—1. 3モルである。  [0038] The amount of the terminal acetylene compound (formula (6)) used is 1.0-2 with respect to 1 mole of the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (formula (5)). 0.0 mol, preferably 1.0-1.3 mol.
[0039] 第 3の発明の製造法において使用される塩基性溶媒としては、ピぺリジン又はピロリ ジンが挙げられる。  [0039] Examples of the basic solvent used in the production method of the third invention include piperidine or pyrrolidine.
[0040] 塩基性溶媒の使用量は、トリフルォロメタンスルホニルォキシ基置換縮合へテロ環 化合物（前記式（5) ) 1モルに対して、 1一 20L (リットル）であり、好ましくは 1. 5-5L である。  [0040] The amount of the basic solvent to be used is 112 L (liter), preferably 1 mol, per 1 mol of the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (formula (5)). 5-5L.
また、反応温度は 80— 100°Cであり、好ましくは 80— 90°Cである。  The reaction temperature is 80-100 ° C, preferably 80-90 ° C.
反応時間は、前記の末端アセチレン化合物の種類、溶媒の使用量、及び反応温度 等によって変化するが 1一 5時間である。  The reaction time varies depending on the type of the terminal acetylene compound, the amount of the solvent used, the reaction temperature and the like, but is 115 hours.
[0041] この反応は、通常、アルゴン、窒素などの不活性ガス雰囲気、或はこれらガス気流 下で行われる。また、用いられる反応圧は通常、常圧である。 This reaction is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or in a stream of these gases. The reaction pressure used is usually normal pressure.
[0042] 上記の製造方法に従って製造されたアルキニル基置換縮合へテロ環化合物は、反 応終了後、抽出、濃縮、口過などの通常の後処理を行い、必要に応じて蒸留、再結 晶、各種クロマトグラフィーなどの公知の手段で適宣精製することができる。 [0042] The alkynyl group-substituted condensed heterocyclic compound produced according to the above-mentioned production method is subjected to ordinary post-treatments such as extraction, concentration and extraction after the reaction, and if necessary, distillation and recrystallization. And can be appropriately purified by known means such as various types of chromatography.
[0043] 得られたアルキニル基置換縮合へテロ環化合物は、有機エレクト口ルミネッセンス 素子に好適に用いられる。 [0043] The obtained alkynyl group-substituted condensed heterocyclic compound is suitably used for an organic electroluminescent device.
[0044] 前記式（1)において、 Aが水素原子であり、 n1が 1である次式（7)で示されるェチニ ル基置換縮合へテロ環化合物は、上記の製法とは別に下記の製法でも製造すること ができる。 In the above formula (1), an ethynyl group-substituted condensed heterocyclic compound represented by the following formula (7) wherein A is a hydrogen atom and n 1 is 1 is prepared separately from the above-mentioned production method. It can also be manufactured by a manufacturing method.
[0045] 即ち、第 4の発明は、前記製法に従って、触媒として 0価パラジウム化合物を用いて 、塩基性溶媒中、トリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物（前 記式（5) )と末端アセチレン化合物（前記式 (6) )として上記のアルキルシリルァセチ レン化合物とを反応させて、アルキルシリルェチニル基置換縮合へテロ環化合物とし た後、このアルキルシリルェチニル基置換縮合へテロ環化合物を加水分解すること によりェチュル基置換縮合へテロ環化合物（次式（7) )： That is, according to the fourth invention, a condensed heterocyclic compound substituted with a trifluoromethanesulfonyloxy group in a basic solvent using a zero-valent palladium compound as a catalyst in accordance with the above-mentioned production method (previously described) The above formula (5)) is reacted with the above-mentioned alkylsilylacetylene compound as the terminal acetylene compound (formula (6)) to form an alkylsilylethynyl group-substituted condensed heterocyclic compound. The condensed heterocyclic compound substituted with a silylethynyl group is hydrolyzed to form a condensed heterocyclic compound substituted with an ethur group (the following formula (7)):
Figure imgf000014_0001
Figure imgf000014_0001
式中、 X及び Yは前記と同義である、  Wherein X and Y are as defined above,
を製造すること力 Sできる。  Can manufacture power S.
[0046] この加水分解は、例えば、アルカリ金属の水酸化物の水溶液が用いられる。 For the hydrolysis, for example, an aqueous solution of an alkali metal hydroxide is used.
アルカリ金属の水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられ る。  Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.
[0047] アルカリ金属の水酸化物の水溶液において、アルカリ金属の水酸化物の濃度は、 0 . 1一 12. 5mol/Lであり、好ましくは 0· 5— 5mol/Lである。また、その使用量は、 アルキルシリルェチュル基置換縮合へテロ環化合物 1モルに対して 1一 5モルであり 、好ましくは 1一 2モルである。  [0047] In the aqueous solution of the alkali metal hydroxide, the concentration of the alkali metal hydroxide is 0.1 to 12.5 mol / L, preferably 0.5 to 5 mol / L. The amount used is 115 moles, preferably 112 moles, per mole of the alkylsilyl ethr group-substituted condensed heterocyclic compound.
[0048] この加水分解で使用される温度は、 5 50°Cであり、好ましくは 15 25°Cである。  [0048] The temperature used in this hydrolysis is 550 ° C, preferably 1525 ° C.
また、反応時間は、前記の濃度、温度によって変化するが 0. 1 2時間である。  The reaction time varies depending on the concentration and temperature, but is 0.12 hours.
[0049] この加水分解は、通常、アルゴン、窒素などの不活性ガス雰囲気、或はこれらガス 気流下で行われる。また、用いられる反応圧は通常、常圧である。  [0049] This hydrolysis is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or in a stream of these gases. The reaction pressure used is usually normal pressure.
[0050] 上記の製造法に従って製造されたェチニル基置換縮合へテロ環化合物（前記式 ( 7) )は、反応終了後、抽出、濃縮、ろ過などの通常の後処理を行い、必要に応じて蒸 留、再結晶、各種クロマトグラフィーなどの公知の手段で適宣精製することができる。  The ethynyl group-substituted condensed heterocyclic compound (the above formula (7)) produced according to the above production method is subjected to ordinary post-treatments such as extraction, concentration, and filtration after completion of the reaction, and if necessary, It can be appropriately purified by known means such as distillation, recrystallization and various types of chromatography.
[0051] 第 4の発明のアルキニル基置換縮合へテロ環化合物の製造法には、末端ァセチレ ン化合物として、精製されたェチュル基置換縮合へテロ環化合物 (前記式 (7) )を用 いることも出来る力 ェチュル基置換縮合へテロ環化合物（前記式（7) )の製造後、口 過、濃縮などの上記後処理を施したのみの粗精製物を、そのまま用いることも出来る [0052] また、前記式（1)において、 Aがァリール基であり、 n1が 1である次式（8)： [0051] In the method for producing the alkynyl group-substituted condensed heterocyclic compound of the fourth invention, a purified ethynyl group-substituted condensed heterocyclic compound (the formula (7)) is used as the terminal acetylene compound. A crude product which has been subjected to the above-mentioned post-treatments such as extraction and concentration after the production of the heterocyclic compound substituted with a petroleum group (formula (7)) can also be used as it is. In the above formula (1), the following formula (8) in which A is an aryl group and n 1 is 1:
Figure imgf000015_0001
式中、 Rはハロゲン原子、ジアルキルアミノ基、ァリールォキシ基、アルコキシ基、ァ ルケニル基、ァシル基、ニトロ基、シァノ基、アルキル基、シクロアルキル基、又はァリ 一ル基を表し、複数の Rは、それぞれ同一でも異なっていてもよぐ n3は 1一 5の整数 を表し、 X及び Yは前記と同義である、
Figure imgf000015_0001
In the formula, R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acyl group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group; May be the same or different, and n 3 represents an integer of 1 to 5, and X and Y are as defined above.
で示されるフエニルェチュル基置換縮合へテロ環化合物も、上記の製法とは別に下 記の製法で製造することができる。  The phenylethyl group-substituted condensed heterocyclic compound represented by the following formula can also be produced by the following production method separately from the above production method.
[0053] 即ち、第 5の発明は、前記式 (7)で示されるェチニル基置換縮合へテロ環化合物と 次式 (9) :
Figure imgf000015_0002
式中、 X'はハロゲン原子を表し、 R及び n3は前記と同義である、 That is, the fifth invention provides an ethynyl group-substituted fused heterocyclic compound represented by the above formula (7) and the following formula (9):
Figure imgf000015_0002
In the formula, X ′ represents a halogen atom, R and n 3 are as defined above,
で示されるハロゲン化芳香族環化合物とを、触媒として 0価パラジウム化合物を用い て、塩基性溶媒中で反応させることによりフエ二ルェチニル基置換縮合へテロ環化合 物 (前記式 (8) )を製造すること力 Sできる。  Is reacted with a halogenated aromatic ring compound represented by the formula (1) in a basic solvent using a zero-valent palladium compound as a catalyst to give a phenylethynyl group-substituted condensed heterocyclic compound (formula (8)). Can manufacture power S.
[0054] ここでェチュル基置換縮合へテロ環化合物（前記式（7) )は、上記いずれかの製法 に従って製造される。  [0054] Here, the condensed heterocyclic compound substituted with an ethur group (the above formula (7)) is produced according to any of the production methods described above.
[0055] 前記式（9)で示されるハロゲン化芳香族環化合物において、 Rはハロゲン原子、ジ ァノレキノレアミノ基、ァリールォキシ基、アルコキシ基、アルケニル基、アシノレ基、ニトロ 基、シァノ基、アルキル基、シクロアルキル基、又はァリール基であり、複数の Rは、そ れぞれ同一でも異なっていてもよぐ n3は 1から 5の整数である。 In the halogenated aromatic ring compound represented by the formula (9), R represents a halogen atom, a dianolequinoleamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acinole group, a nitro group, a cyano group, It is an alkyl group, a cycloalkyl group or an aryl group, and a plurality of Rs may be the same or different, and n 3 is an integer of 1 to 5.
[0056] 触媒として用いられる 0価パラジウム化合物としては、前記した 0価パラジウム化合 物が挙げられる。 [0056] The zero-valent palladium compound used as the catalyst includes the above-mentioned zero-valent palladium compound. Things.
これらの 0価パラジウム化合物の使用量は、ハロゲン化芳香族環化合物（前記式（9 こ対して 0· 1— 10モル0 /0であり、好ましくは 0· 5— 5モル0 /0である。 The amount of the zero-valent palladium compound, a halogenated aromatic compound (a Formula (9 this 0-1- 10 mole 0/0 for, preferably is 0, 5-5 mol 0/0 .
[0057] の反応で使用される塩基性溶媒としては、ピぺリジン又はピロリジンが挙げられる  Examples of the basic solvent used in the above reaction include piperidine and pyrrolidine.
[0058] 塩基性溶媒の使用量は、ェチニル基置換縮合へテロ環化合物 (前記式 (7) ) 1モル に対して、 1一 20L (リットル）であり、好ましくは 1. 5— 5Lである。 [0058] The amount of the basic solvent to be used is 112 L (liter), preferably 1.5-5 L, per 1 mol of the ethynyl group-substituted condensed heterocyclic compound (the formula (7)). .
また、反応温度は 80 100°Cであり、好ましくは 80 90°Cである。  Further, the reaction temperature is 80 100 ° C, preferably 80 90 ° C.
反応時間は、前記のハロゲン化芳香族環化合物 (前記式 (9) )の種類、溶媒の使 用量、及び反応温度等によって変化するが 1一 5時間である。  The reaction time varies depending on the type of the halogenated aromatic ring compound (formula (9)), the amount of the solvent used, the reaction temperature and the like, but is 115 hours.
この反応は、通常、アルゴン、窒素などの不活性ガス雰囲気、或はこれらガス気流 下で行われる。また、用いられる反応圧は通常、常圧である。  This reaction is usually performed in an atmosphere of an inert gas such as argon or nitrogen, or under a stream of these gases. The reaction pressure used is usually normal pressure.
[0059] 上記の製造方法に従って製造されたフエ二ルェチニル基置換縮合へテロ環化合 物（前記式（9) )は、反応終了後、抽出、濃縮、口過などの通常の後処理を行い、必 要に応じて蒸留、再結晶、各種クロマトグラフィーなどの公知の手段で適宣精製する こと力 Sできる。  [0059] The phenylethynyl group-substituted condensed heterocyclic compound (the formula (9)) produced according to the above-mentioned production method is subjected to ordinary post-treatments such as extraction, concentration and extraction after completion of the reaction. If necessary, it can be appropriately purified by known means such as distillation, recrystallization, and various types of chromatography.
[0060] 得られたフエ二ルェチニル基置換縮合へテロ環化合物（前記式（9) )は、有機エレ タトロルミネッセンス素子に好適に用いられる。  [0060] The obtained phenylethynyl group-substituted condensed heterocyclic compound (the above formula (9)) is suitably used for an organic electroluminescence device.
[0061] 以下、第 1の発明である、同有機エレクト口ルミネッセンス素子について、その実施 形態を示す。  [0061] Hereinafter, embodiments of the organic electroluminescent device of the first invention, which is the same, will be described.
[0062] 第ェの発明の有機エレクト口ルミネッセンス素子は、一対の電極間に有機化合物層 を有する有機エレクト口ルミネッセンス素子であって、該有機化合物層が前記式（1) で示されるアルキニル基置換縮合へテロ環化合物の内、少なくとも 1種を含有するこ とを特徴とする。ここで有機化合物層は、発光層、電子注入層（又はホールブロック 層）、もしくは正孔輸送層であることが好ましい。  [0062] The organic electroluminescent device of the present invention is an organic electroluminescent device having an organic compound layer between a pair of electrodes, wherein the organic compound layer is substituted with an alkynyl group represented by the formula (1). It is characterized by containing at least one of the fused heterocyclic compounds. Here, the organic compound layer is preferably a light emitting layer, an electron injection layer (or a hole blocking layer), or a hole transport layer.
[0063] 更に、この有機エレクト口ルミネッセンス素子は、陽極と陰極間に単層もしくは多層 の有機化合物層を形成した素子である。  [0063] Further, the organic electroluminescent device is a device in which a single or multilayer organic compound layer is formed between an anode and a cathode.
[0064] 単層型の有機エレクト口ルミネッセンス素子は、陽極と陰極との間に発光層を有する 。発光層は、発光材料を含有し、更に、陽極から注入した正孔、もしくは陰極から注 入した電子を発光材料まで輸送させるための正孔注入材料もしくは電子注入材料（ 又はホールブロック材料）を含有しても良レ、。 [0064] The single-layer organic electroluminescent device has a light-emitting layer between an anode and a cathode. . The light emitting layer contains a light emitting material, and further contains a hole injection material or an electron injection material (or a hole blocking material) for transporting holes injected from an anode or electrons injected from a cathode to the light emitting material. Even good ,.
[0065] 多層型の有機エレクト口ルミネッセンス素子は、例えば、（陽極 Z正孔注入層 Z発 光層/陰極）、（陽極/発光層/電子注入層（又はホールブロック層）/陰極）、（陽 極/正孔注入層/発光層/電子注入層（又はホールブロック層）/陰極）等の多層 構成で積層したものが挙げられる。  The multilayer type organic electroluminescent device includes, for example, (anode Z hole injection layer Z light emitting layer / cathode), (anode / light emitting layer / electron injection layer (or hole block layer) / cathode), ( Examples thereof include those laminated in a multilayer structure such as a positive electrode / a hole injection layer / a light emitting layer / an electron injection layer (or a hole blocking layer) / a cathode.
[0066] 発光層には、アルキニル基置換縮合へテロ環化合物（前記式（1) )の他に、公知の 発光材料、ドーピング材料、正孔注入材料 (フタロシアニン誘導体、ナフタロシアニン 誘導体、ポルフィリン誘導体、ォキサゾール、ォキサジァゾール、トリァゾール、イミダ ゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾ ール、ォキサゾール、ォキサジァゾール、ヒドラゾン、ァシルヒドラゾン、ポリアリールァ ノレカン、スチルベン、ブタジエン、ベンジジン型トリフエニルァミン、スチリルアミン型ト リフエニノレアミン、ジァミン型トリフエニルァミン等と、それらの誘導体、およびポリビニ ルカルバゾール、ポリシラン、導電性高分子等の高分子材料等）や電子注入材料（ 又はホールブロック材料）（フルォレノン、アントラキノジメタン、ジフエノキノン、チォピ ランジオキシド、ォキサゾール、ォキサジァゾール、トリァゾーノレ、イミダゾール、ペリレ ンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれ らの誘導体等）を使用しても良レ、。  In the light emitting layer, in addition to the alkynyl group-substituted condensed heterocyclic compound (formula (1)), known light emitting materials, doping materials, and hole injection materials (phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, Oxazole, oxaziazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxaziazole, hydrazone, isylhydrazone, polyarylanolecane, stilbene, butadiene, benzidine triphenylamine. Triphenylenoleamine, diamine-type triphenylamine, and derivatives thereof, and polymer materials such as polyvinyl carbazole, polysilane, and conductive polymers, etc., and electron injection materials (or hole block materials). Materials) (fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazonole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives, etc.) Good to use.
[0067] アルキニル基置換縮合へテロ環化合物（前記式（1) )は、発光層、電子注入層（又 はホールブロック層）、正孔輸送層又は正孔注入層のいずれかに、濃度 0. 5— 100 重量％で添加される。  [0067] The alkynyl group-substituted condensed heterocyclic compound (the above formula (1)) has a concentration of 0 in any of a light emitting layer, an electron injection layer (or a hole block layer), a hole transport layer, and a hole injection layer. .5—100% by weight.
[0068] この有機エレクト口ルミネッセンス素子は、発光材料、他のドーピング材料、正孔注 入材料や電子注入材料 (又はホールブロック材料）を組み合わせて使用することもで きる。更に、正孔注入層、発光層、電子注入層（又はホールブロック層）は、それぞれ 二層以上の層構成により形成されても良い。その際には、正孔注入層の場合、電極 から正孔を注入する層を正孔注入層、正孔注入層から正孔を受け取り発光層まで正 孔を輸送する層を正孔輸送層と呼ぶ。同様に、電子注入層の場合、電極から電子を 注入する層を電子注入層、電子注入層から電子を受け取り発光層まで電子を輸送 する層を電子輸送層、発光層からの正孔の流入を防止する層をホールブロック層と 呼ぶ。これらの各層は、材料のエネルギー準位、耐熱性、有機化合物層もしくは金属 電極との密着性等の各要因により選択されて使用される。 [0068] The organic electroluminescent device can also be used in combination with a light emitting material, another doping material, a hole injection material or an electron injection material (or a hole blocking material). Further, each of the hole injection layer, the light emitting layer, and the electron injection layer (or the hole blocking layer) may be formed in a layer structure of two or more layers. In this case, in the case of a hole injection layer, a layer that injects holes from the electrode is a hole injection layer, and a layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, electrons are The layer to be injected is called an electron injection layer, the layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer, and the layer that prevents holes from flowing from the light emitting layer is called a hole blocking layer. These layers are selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic compound layer or the metal electrode.
[0069] アルキニル基置換縮合へテロ環化合物（前記式（1) )と共に有機化合物層に使用 できる発光材料又はホスト材料としては、縮合多環芳香族（アントラセン、ナフタレン、 フエナントレン、ピレン、テトラセン、ペンタセン、コロネン、タリセン、フノレ才レセイン、 ペリレン、ルブレン及びそれらの誘導体等）、フタ口ペリレン、ナフタ口ペリレン、ぺリノ ン、フタ口ペリノン、ナフタ口ペリノン、ジフヱニルブタジエン、テトラフヱニルブタジエン 、クマリン、ォキサジァゾ一ノレ、ァノレダジン、ビスベンゾキサゾリン、ビススチリル、ピラ ジン、シクロペンタジェン、キノリン金属錯体、ァミノキノリン金属錯体、ベンゾキノリン 金属錯体、ィミン、ジフエニルエチレン、ビュルアントラセン、ジァミノカルバゾール、ピ ラン、チォピラン、ポリメチン、メロシアニン、イミダゾールキレートィ匕ォキシノイド化合 物、キナクリドン、ルブレン、スチルベン系誘導体及び蛍光色素等が挙げられる。  [0069] As a light emitting material or a host material that can be used in the organic compound layer together with the alkynyl group-substituted condensed heterocyclic compound (the above formula (1)), condensed polycyclic aromatic (anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, , Coronene, tarisene, fuoresai rescein, perylene, rubrene and derivatives thereof), perylene, phthalate, perylene, naphthalene, perinone, phthaline perinone, naphthalene perinone, diphenylbutadiene, tetraphenylbutadiene, Coumarin, oxazine diazone, anoredazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, buluanthracene, diaminocarbazole, run Thiopyran, polymethine, merocyanine, imidazole chelate dioxinoid compounds, quinacridone, rubrene, stilbene derivatives, and fluorescent dyes.
[0070] 本発明の有機エレクト口ルミネッセンス素子において使用できる公知の正孔注入材 料の中で、更に効果的な正孔注入材料は、芳香族三級アミン誘導体もしくはフタロシ ァニン誘導体である。芳香族三級アミン誘導体の具体例は、トリフエニルァミン、トリト リルァミン、トリルジフエニルァミン、 N, Ν '—ジフエニノレー N, Ν，—（3—メチルフエニル） —1 , 1，—ビフエニル— 4, 4，—ジァミン（以下、 TPDと記載）、 Ν, Ν, Ν，， Ν，—（4—メチ ノレフエ二ノレ）一 1 , 1，一フエニノレー 4, 4，一ジァミン、 Ν, Ν, Ν，， Ν'— (4—メチルフエニル  [0070] Among the known hole injecting materials that can be used in the organic electroluminescent device of the present invention, a more effective hole injecting material is an aromatic tertiary amine derivative or a phthalocyanine derivative. Specific examples of the aromatic tertiary amine derivative include triphenylamine, tritolylamine, tolyldiphenylamine, N, Ν′-diphenylenolene N, Ν, — (3-methylphenyl) —1,1, —biphenyl—4 , 4,-Jiamin (hereinafter referred to as TPD), Ν, Ν, Ν,, Ν,-(4-methylenophenone) -1, 1, 1, 1 feninolee 4, 4, 1 diamine, Ν, Ν, Ν ,, Ν'— (4-Methylphenyl
1 '—ビフエ二ルー 4, 4，—ジァミン、 Ν, N '—ジフエ二ルー Ν, N'—ジナフチルー 1 , 1，—ビフエ二ル _4， 4 '—ジァミン、 Ν, Ν，—（メチルフエ二ル）— Ν, Ν，—（4_η—ブチ ルフエニル）—フエナントレン— 9, 10—ジァミン、 Ν, Ν—ビス（4—ジ— 4—トリルァミノフエ ニル)一 4—フエ二ルーシクロへキサン等、もしくはこれらの芳香族三級アミン骨格を有し たオリゴマーもしくはポリマーであるが、これらに限定されるものではない。  1'-biphenyl 4,4, -diamine, Ν, N'-diphenyl, N'-dinaphthyl 1,1, -biphenyl_4,4'-diamine, Ν, Ν, — (methylphen -), Ν, Ν,-(4_η-butylphenyl) -phenanthrene-9,10-diamine, Ν, Ν-bis (4-di-4-tolylaminophenyl) -14-phenylcyclohexane, etc. Oligomer or polymer having an aromatic tertiary amine skeleton, but is not limited thereto.
[0071] フタロシアニン（Pc)誘導体の具体例は、 H Pc、 CuPc、 CoPc、 NiPc、 ZnPc、 Pd  [0071] Specific examples of the phthalocyanine (Pc) derivative include HPc, CuPc, CoPc, NiPc, ZnPc, and Pd.
2  2
Pc、 FePc、 MnPc、 ClAlPc、 ClGaPc、 ClInPc、 ClSnPc、 CI SiPc、 （H〇）AlPc、  Pc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, CI SiPc, (H〇) AlPc,
2  2
(HO) GaPc、 VOPc、 TiOPc、 MoOPc、 GaPc—〇— GaPc等のフタロシアニン誘導 体およびナフタロシアニン誘導体であるが、これらに限定されるものではない。 (HO) Phthalocyanine derived from GaPc, VOPc, TiOPc, MoOPc, GaPc—〇—GaPc Body and naphthalocyanine derivatives, but are not limited thereto.
[0072] 本発明の有機エレクト口ルミネッセンス素子において、更に効果的な公知の電子注 入材料又はホールブロック材料は、金属錯体化合物もしくは含窒素五員環誘導体で ある。金属錯体化合物の具体例は、 8—ヒドロキシキノリナ一トリチウム、ビス（8—ヒドロ キシキノリナート）亜鉛、ビス（8—ヒドロキシキノリナート）銅、ビス（8—ヒドロキシキノリナ ート）マンガン、トリス（8—ヒドロキシキノリナート）アルミニウム（以下、 Alqと記載）、トリ  In the organic electroluminescent device of the present invention, a more effective and well-known electron injection material or hole blocking material is a metal complex compound or a nitrogen-containing five-membered ring derivative. Specific examples of the metal complex compound include 8-hydroxyquinolinatolithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, and tris ( 8-Hydroxyquinolinato) aluminum (hereinafter referred to as Alq), tri
3  Three
ス（2—メチノレ一 8—ヒドロキシキノリナート）ァノレミニゥム、トリス（8—ヒドロキシキノリナート )ガリウム、ビス（10—ヒドロキシベンゾ [h]キノリナート）ベリリウム、ビス（10—ヒドロキシ ベンゾ [h]キノリナート）亜鉛、ビス（2—メチル _8_キノリナート）クロ口ガリウム、ビス（2 —メチノレ _8_キノリナート）（o_クレゾラート）ガリウム、ビス（2—メチノレ _8_キノリナート） (1—ナフトラート）アルミニウム、ビス（2—メチル _8_キノリナート）（2—ナフトラート）ガリ ゥム等が挙げられる力 S、これらに限定されるものではない。  (2-Methynole-1-hydroxyquinolinato) anoreminidium, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinate) beryllium, bis (10-hydroxybenzo [h] quinolinate) Zinc, bis (2-methyl _8_quinolinato) chromium gallium, bis (2-methinolate _8_quinolinato) (o_cresolate) gallium, bis (2-methinolle _8_quinolinato) (1-naphtholate) aluminum, bis (2 —Methyl _8_quinolinato) (2-naphtholate) gallium, etc., but not limited thereto.
[0073] また、含窒素五員誘導体は、ォキサゾール、チアゾール、ォキサジァゾール、チア ジァゾールもしくはトリァゾール誘導体が好ましレ、。具体的には、 2, 5-ビス（1-フエ 二ノレ）— 1 , 3, 4—ォキサゾール、ジメチルー 1 , 4_ビス（5 ' _フエニルォキサゾリル）ベ ンゼン、 2, 5_ビス（1—フエ二ノレ）_1 , 3, 4—チアゾール、 2, 5_ビス（1—フエ二ノレ）_1 , 3, 4 ォキサジァゾール、 2_ (4 ' _tert_ブチルフエ二ル）— 5_ (4，しビフエニル）_1 , 3, 4 ォキサジァゾール、 2, 5 ビス（1 ナフチル 3, 4_ォキサジァゾール、 1 , 4_ビス [2— (5—フエニルォキサジァゾリル）]ベンゼン、 1 , 4_ビス [2— (5—フエニル ォキサジァゾリル） _4_tert ブチルベンゼン]、 2_ (4 ' _tert ブチルフエニル） _5_( 4"ービフエニル) 1 , 3, 4—チアジアゾール、 2, 5—ビス（1 ナフチル) _1 , 3, 4—チア ジァゾール、 1， 4_ビス [2_(5_フエ二ルチアジァゾリル)]ベンゼン、 2_ (4 ' _tert—ブ チルフエニル） _5_(4 "—ビフエ二ル)— 1 , 3， 4_トリァゾーノレ、 2， 5_ビス（1—ナフチル ) _1， 3， 4_トリァゾーノレ、 1， 4—ビス [2— (5—フエニルトリァゾリル)]ベンゼン、 3— (4— ビフエ二ルイル）_4_フエニル _5_t_ブチルフエニル— 1， 2, 4—トリアゾール等が挙 げられる力 これらに限定されるものではない。  [0073] The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxaziazole, thiaziazole or triazole derivative. Specifically, 2,5-bis (1-pheninole) -1,3,4-oxazole, dimethyl-1,4_bis (5'_phenyloxazolyl) benzene, 2,5_ Bis (1-pheninole) _1,3,4-thiazole, 2,5_Bis (1-pheninole) _1,3,4oxaziazole, 2_ (4'_tert_butylphenyl) -5_ (4, 1,2-bis (1naphthyl 3,4_oxadiazole, 1,4_bis [2— (5-phenyloxadiazolyl)] benzene, 1,4_ Bis [2- (5-phenyl oxaziazolyl) _4_tert-butylbenzene], 2_ (4 '_tert-butylphenyl) _5_ (4 "-biphenyl) 1,3,4-thiadiazole, 2,5-bis (1naphthyl) _1,3,4 —Thiadiazole, 1,4_bis [2_ (5_phenylthiaziazolyl)] benzene, 2_ (4'_tert-butylphenyl) _5_ (4 "—biphenyl) —1,3,4_tri Zonore, 2,5_bis (1-naphthyl) _1,3,4_triazonole, 1,4-bis [2- (5-phenyltriazolyl)] benzene, 3- (4-biphenylyl) _4 _Phenyl _5_t_Butylphenyl-1,2,4-triazole, etc. Forces to be listed are not limited to these.
[0074] 本発明の有機エレクト口ルミネッセンス素子は、電荷注入性向上のために発光層と 電極との間に無機化合物層を設けることもできる。 [0075] この無機化合物層としては、 LiF、 Li 0、 RaO、 Sr〇、 BaF、 SrFなどの、アルカリ [0074] In the organic electroluminescent device of the present invention, an inorganic compound layer may be provided between the light emitting layer and the electrode for improving the charge injection property. [0075] The inorganic compound layer is made of an alkali compound such as LiF, Li0, RaO, Sr〇, BaF, and SrF.
2 2 2  2 2 2
金属又はアルカリ土類金属のフッ化物、酸化物などを挙げられる。  Examples include fluorides and oxides of metals or alkaline earth metals.
[0076] 本発明の有機エレクト口ルミネッセンス素子の陽極に使用される導電性材料として は、 4eVより大きな仕事関数を持つものが適しており、炭素、アルミニウム、バナジゥ ム、鉄、コバルト、ニッケル、タングステン、銀、金、白金、パラジウム及びそれらの合 金、 ITO (酸化インジウムに酸化スズを 5— 10。 /。添加した物質）基板、 NESA基板に 使用される酸化スズ、酸化インジウム等の酸化金属、更にポリチォフェンやポリピロ一 ル等の有機導電性樹脂を用いることができる。  As the conductive material used for the anode of the organic electroluminescent device of the present invention, those having a work function larger than 4 eV are suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten , Silver, gold, platinum, palladium and their alloys, ITO (indium oxide and tin oxide 5-10. /. Added substances) substrates, metal oxides such as tin oxide and indium oxide used for NESA substrates, Further, organic conductive resins such as polythiophene and polypyrrole can be used.
[0077] 陰極に使用される導電性物質としては、 4eVより小さな仕事関数を持つものが適し ており、マグネシウム、カルシウム、錫、鉛、チタニウム、イットリウム、リチウム、ルテニ ゥム、マンガン、アルミニウム等およびそれらの合金を用いられる。ここで合金とは、マ グネシゥム Z銀、マグネシウム Zインジウム、リチウム Zアルミニウム等が挙げられる。 合金の比率は、蒸着源の温度、雰囲気、真空度等により制御され、特に限定されな レ、。  [0077] As the conductive material used for the cathode, those having a work function of less than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, and the like can be used. Those alloys are used. Here, the alloy includes magnesium Z silver, magnesium Z indium, lithium Z aluminum and the like. The ratio of the alloy is controlled by the temperature, atmosphere, degree of vacuum, etc. of the evaporation source, and is not particularly limited.
陽極および陰極は、必要があれば二層以上の層構成により形成されていても良い  The anode and the cathode may be formed by two or more layers if necessary.
[0078] 本発明の有機エレクト口ルミネッセンス素子は、少なくとも一方の面は素子の発光波 長領域において透明であることが望ましい。また、基板も透明であることが望ましい。 [0078] In the organic electroluminescent device of the present invention, it is preferable that at least one surface is transparent in the emission wavelength region of the device. Further, it is desirable that the substrate is also transparent.
[0079] 透明電極は、前記の導電性材料を使用して、蒸着あるいはスパッタリング等の方法 で所定の透光性が確保するように設定して得られる。  [0079] The transparent electrode is obtained by using the above-mentioned conductive material and by setting such that a predetermined translucency is secured by a method such as vapor deposition or sputtering.
[0080] 発光面の電極は、光透過率を 10%以上にすることが望ましい。  It is desirable that the electrode on the light emitting surface has a light transmittance of 10% or more.
基板は、機械的、熱的強度を有し、透明性を有するものであれば特に限定されるも のではなレ、が、ガラス基板あるいは透明性樹脂フィルムが挙げられる。  The substrate is not particularly limited as long as it has mechanical and thermal strength and has transparency, but examples thereof include a glass substrate and a transparent resin film.
[0081] 透明性樹脂フィルムとしては、ポリエチレン、エチレン一酢酸ビュル共重合体、ェチ レン一ビュルアルコール共重合体、ポリプロピレン、ポリスチレン、ポリメチルメタアタリ レート、ポリ塩化ビュル、ポリビュルアルコール、ポリビュルブチラール、ナイロン、ポリ エーテルエーテルケトン、ポリサルホン、ポリエーテルサルフォン、テトラフルォロェチ レン一パーフルォロアルキルビュルエーテル共重合体、ポリビュルフルオライド、テト ラフルォロエチレン一エチレン共重合体、テトラフルォロエチレン一へキサフルォロプ ロピレン共重合体、ポリクロ口トリフルォロエチレン、ポリビニリデンフルオライド、ポリエ ステル、ポリカーボネート、ポリウレタン、ポリイミド、ポリエーテルイミド、ポリイミド、ポリ プロピレン等が挙げられる。 [0081] Examples of the transparent resin film include polyethylene, ethylene monobutyl acetate copolymer, ethylene monobutyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polychlorinated vinyl, polyvinyl alcohol, and polyvinyl alcohol. Butyral, nylon, polyetheretherketone, polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkylbutylether copolymer, polybutylfluoride, tet Lafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorinated trifluoroethylene, polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, Polypropylene and the like can be mentioned.
[0082] 本発明の有機エレクト口ルミネッセンス素子は、温度、湿度、雰囲気等に対する安 定性の向上のために、素子の表面に保護層を設ける力 \或いは、シリコンオイル、樹 脂等により素子全体を保護することもできる。  [0082] In the organic electroluminescent device of the present invention, in order to improve stability against temperature, humidity, atmosphere, and the like, the entire device is protected by a force for providing a protective layer on the surface of the device, or by using a silicon oil, a resin, or the like. It can also be protected.
[0083] また、有機エレクト口ルミネッセンス素子の各層の形成は、真空蒸着、スパッタリング 、プラズマ、イオンプレーティング等の乾式成膜法、あるいはスピンコーティング、ディ ッビング、フローコーティング等の湿式成膜法のいずれかを適用することができる。膜 厚は特に限定されるものではなレ、が、通常の膜厚は 5nm 10 x mの範囲であり、更 には 10nm— 0. の範囲が好ましい。  [0083] Each layer of the organic electroluminescent device may be formed by a dry film forming method such as vacuum evaporation, sputtering, plasma, or ion plating, or a wet film forming method such as spin coating, diving or flow coating. Or can be applied. Although the film thickness is not particularly limited, the usual film thickness is in the range of 5 nm × 10 × m, and more preferably in the range of 10 nm−0.0.
[0084] 湿式成膜法の場合、各層を形成するアルキニル基置換縮合へテロ環化合物（前記 式（1) )等の材料を、エタノール、クロ口ホルム、テトラヒドロフラン、ジォキサン等の溶 媒に溶解又は分散させて薄膜を調製することができる。  [0084] In the case of the wet film formation method, a material such as an alkynyl group-substituted condensed heterocyclic compound (formula (1)) forming each layer is dissolved or dissolved in a solvent such as ethanol, chloroform, tetrahydrofuran, or dioxane. The thin film can be prepared by dispersing.
[0085] 乾式成膜法としては、真空蒸着が好ましぐ真空蒸着装置を用い、真空度 2 X 10— 3 Pa以下、基板温度を室温にして、アルミナ製蒸着セルに入れた本発明の 8—アルキ 二ルキノリン誘導体等の材料をタングステンフィラメントで加熱し、該材料を蒸発させ ることにより薄膜を調製すること力 Sできる。 [0085] The dry film forming method, using the preferred tool vacuum deposition apparatus vacuum deposition, the vacuum degree 2 X 10- 3 Pa or less, the substrate temperature is set to room temperature, the present invention placed in an alumina deposition cell 8 — The ability to prepare thin films by heating materials such as alkynquinoline derivatives with tungsten filaments and evaporating the materials.
[0086] TPDとビス（8 ' -キノリル)アセチレンなどの共蒸着は、それぞれに蒸着源を用い、 且つ温度をそれぞれ独立に制御することによって行うことができる。  [0086] Co-evaporation of TPD and bis (8'-quinolyl) acetylene or the like can be performed by using respective evaporation sources and controlling the temperature independently.
[0087] ここで、いずれの有機薄膜層も、成膜性向上、膜のピンホール防止等のためポリス チレン、ポリカーボネート、ポリアタリレート、ポリエステル、ポリアミド、ポリウレタン、ポリ スルフォン、ポリメチルメタタリレート、ポリメチルアタリレート、セルロース等の絶縁性 樹脂およびそれらの共重合体、ポリ _N_ビュルカルバゾール、ポリシラン等の光導電 性樹脂、ポリチォフェン、ポリピロール等の導電性樹脂等の樹脂、あるいは酸化防止 剤、紫外線吸収剤、可塑剤等の添加剤を使用することができる。  [0087] Here, any of the organic thin-film layers may be formed of polystyrene, polycarbonate, polyatalylate, polyester, polyamide, polyurethane, polysulfone, polymethylmetharylate, or the like in order to improve film forming properties and prevent pinholes in the film. Insulating resins such as polymethyl acrylate, cellulose and their copolymers, photoconductive resins such as poly_N_bulcarbazole, polysilane, resins such as conductive resins such as polythiophene and polypyrrole, or antioxidants, ultraviolet rays Additives such as absorbents and plasticizers can be used.
[0088] 本発明の有機エレクト口ルミネッセンス素子は、例えば壁掛けテレビのフラットパネ ルディスプレイ等の平面発光体、複写機、プリンター、液晶ディスプレイのバックライト 又は計器類等の光源、表示板、標識灯等に利用できる。 The organic electroluminescent device of the present invention can be used, for example, in a flat panel of a wall-mounted television. It can be used as a flat light-emitting body such as a display, a copier, a printer, a backlight of a liquid crystal display, a light source such as an instrument, a display board, a sign lamp and the like.
[0089] 本発明のアルキニル基置換縮合へテロ環化合物の紫外線吸収極大及び蛍光極大 波長は、以下の方法によって測定した。  [0089] The maximum ultraviolet absorption wavelength and maximum fluorescence wavelength of the alkynyl group-substituted condensed heterocyclic compound of the present invention were measured by the following methods.
[0090] 紫外線吸収極大波長は、アルキニル基置換縮合へテロ環化合物をクロ口ホルム中 に溶解し (濃度 0. Olmg/ml)、紫外分光光度計を用いて、室温 (20°C)にて測定を 行った。 [0090] The ultraviolet absorption maximum wavelength was determined by dissolving an alkynyl group-substituted condensed heterocyclic compound in chloroform (at a concentration of 0.1 Olmg / ml) and using an ultraviolet spectrophotometer at room temperature (20 ° C). The measurement was performed.
[0091] また、蛍光極大波長は、上記のクロ口ホルム溶液を用いて、蛍光分光光度計を用い て、室温（20°C)にて測定を行った。  [0091] The maximum fluorescence wavelength was measured at room temperature (20 ° C) using a fluorescence spectrophotometer, using the above-described form-form solution.
[0092] 本発明のアルキニル基置換縮合へテロ環化合物はクロ口ホルム溶液中、波長 240 nm前後の紫外線照射により、 380— 400nmを蛍光極大とする青色の蛍光を示した[0092] The alkynyl group-substituted condensed heterocyclic compound of the present invention showed blue fluorescence having a fluorescence maximum at 380 to 400 nm when irradiated with ultraviolet light having a wavelength of about 240 nm in a chloroform solution.
。また、これを含有する有機エレクト口ルミネッセンス素子は青色蛍光を実現した（下 記実施例 16— 22参照）。 . Further, the organic electroluminescent device containing the same realized blue fluorescence (see Examples 16 to 22 below).
実施例  Example
[0093] 以下に実施例、および比較例を挙げて、本発明を具体的に説明する。  [0093] Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples.
[0094] 参考例 1 8_トリフルォロメタンスルホキシキノリンの合成  Reference Example 1 Synthesis of 8_trifluoromethanesulfoxyquinoline
8—キノリノ一ノレ 7. 26g (50mmol)、塩化メチレン 50ml及びトリェチルァミン 9. lml (65mmol)の黄色溶液を氷浴で 0°Cにした後、トリフルォロメタンスルホン酸無水物 9 . 3ml (55mmol)を滴下した。滴下後、ほぼ黒色に変化した反応溶液を反応温度を 0°Cに維持して 1時間攪拌した。反応終了後、反応溶液に水 200ml及びジェチルェ 一テル 250mlを加えて分液し、得られた有機層を濃度 lmol/Lの塩酸（125ml X 2 回）、水（125ml X 1回）の順で洗浄し、無水硫酸マグネシウムで乾燥、ろ過後、ジェ チルエーテルを留去し、残滓をへキサン 250mlに温度 70°Cにて溶解し、不溶物をろ 過した後、ろ液を冷却することにより茶白色結晶である目的化合物を得た。 (12. 6g 、収率 91 %)  A yellow solution of 8.26 g (50 mmol) of 8-quinolino, 50 ml of methylene chloride and 9.1 ml (65 mmol) of triethylamine was brought to 0 ° C. in an ice bath, and then 9.3 ml (55 mmol) of trifluoromethanesulfonic anhydride. Was dropped. After the dropwise addition, the reaction solution, which turned almost black, was stirred for 1 hour while maintaining the reaction temperature at 0 ° C. After the completion of the reaction, 200 ml of water and 250 ml of Jethyl ether were added to the reaction solution, and the mixture was separated. The resulting organic layer was concentrated in the order of lmol / L hydrochloric acid (125 ml x 2) and water (125 ml x 1). After washing, drying over anhydrous magnesium sulfate and filtration, the ethyl ether is distilled off, the residue is dissolved in 250 ml of hexane at a temperature of 70 ° C, the insoluble matter is filtered off, and the filtrate is cooled to obtain a tea. The target compound was obtained as white crystals. (12.6 g, 91% yield)
以下に、その物性を示す。  The physical properties are shown below.
[0095] 'H-NMR (300MHz, CDC1 ) δ : 9. 11-9. 03 (m、 1Η)、 8. 30-8. 19 (m [0095] 'H-NMR (300MHz, CDC1) δ: 9.11-9.03 (m, 1Η), 8.30-8.19 (m
3 、 1Η 3, 1Η
)、 7. 89-7. 81 (m、 1H)、 7. 65-7. 50 (m、 3H) EI-MS (m/e)： 277 (M+)、 CI—MS (m/z)： 278 (MH+) ), 7.89-7.81 (m, 1H), 7.65-7.50 (m, 3H) EI-MS (m / e): 277 (M +), CI—MS (m / z): 278 (MH +)
[0096] 実施例 1 [0096] Example 1
1 , 4一ビス（8 '—キノリルェチュル）ベンゼン（次式 10)の合成  Synthesis of 1,4-monobis (8'-quinolyletul) benzene (Formula 10)
Figure imgf000023_0001
Figure imgf000023_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、テ トラキス（トリフエニルホスフィン）パラジウム 27mg (2. 4 X 10— 5mol)、ピぺリジン 6ml を加えて攪拌した。この黄色溶液に 1， 4—ジェチュルベンゼン 120mg (0. 95mmol )をカ卩えて、 80°Cで 3時間攪拌した。反応終了後、反応混合物に塩化メチレンを加え て希釈して、飽和塩化アンモニゥム水溶液で洗浄し、次いで無水硫酸マグネシウム で乾燥して、ろ過後、得られたろ液を減圧乾固した。得られた反応粗生成物をシリカ ゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢酸ェチル = 100/0 力 1/1に徐々に変えて展開した。 )によって精製することにより黄橙色粉末である 目的化合物を得た。 （310mg、収率 86%) 20ml Schlenk, 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), Te tetrakis (triphenyl phosphine) palladium 27mg (2. 4 X 10- 5 mol ), was added and stirred piperidine 6 ml. To this yellow solution was added 120 mg (0.95 mmol) of 1,4-diethylbenzene, and the mixture was stirred at 80 ° C. for 3 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, filtered, and the filtrate obtained was dried under reduced pressure. The resulting crude reaction product was purified by column chromatography using silica gel (developing solvent while gradually changing the developing solvent to hexane / ethyl acetate = 100/0 force 1/1) to obtain a yellow-orange powder. The desired compound was obtained. (310 mg, 86% yield)
以下に、その物性を示す。  The physical properties are shown below.
'H-NMR (300MHz, CDC1 ) δ : 9. 09-9. 05 (m、 2Η)、 8. 25-8. 14 (m、 2H  'H-NMR (300MHz, CDC1) δ: 9.09-9.05 (m, 2Η), 8.25-8.14 (m, 2H
3  Three
)、 8. 06-8. 00 (m、 2H)、 7. 87—7. 80 (m、 2H)、 7. 69(s, 4H)、 7. 60—7. 40 ( m, 4H)  ), 8.06-8.00 (m, 2H), 7.87—7.80 (m, 2H), 7.69 (s, 4H), 7.60—7.40 (m, 4H)
EI-MS (m/e)： 380 (M+) , CI— MS (m/z) : 381 (MH+) EI-MS (m / e): 380 (M + ), CI—MS (m / z): 381 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm  [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 393nm  [Fluorescence maximum wavelength: black form solution] 393nm
[0097] 実施例 2 [0097] Example 2
1 , 3_ビス（8 '—キノリルェチュル）ベンゼン（次式 11 )の合成
Figure imgf000024_0001
Synthesis of 1,3_bis (8'-quinolyletul) benzene (Formula 11)
Figure imgf000024_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 27mg (2. 4 X 10— 5mol)、ピぺリジン 6m 1を加え攪拌した。この黄色溶液に 1 , 3—ジェチニルベンゼン 120mg (0. 95mmol) を加えて、 80°Cで 4時間攪拌した。反応終了後、反応混合物に塩化メチレンを加え て希釈した後、飽和塩ィ匕アンモニゥム水溶液で洗浄し、次いで無水硫酸マグネシゥ ムで乾燥し、ろ過後、ろ液を減圧乾固した。得られた橙色の反応粗生成物をシリカゲ ルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢酸ェチル = 100/0か ら 1/1に徐々に変えて展開した。 )によって精製することで黄橙色粉末である目的化 合物を得た。 （300mg、収率 83%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 27mg (2. 4 X 10- 5 mol ), was added and stirred piperidine 6 m 1. To this yellow solution was added 120 mg (0.95 mmol) of 1,3-getynylbenzene, and the mixture was stirred at 80 ° C for 4 hours. After completion of the reaction, the reaction mixture was diluted by adding methylene chloride, washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, filtered, and the filtrate was dried under reduced pressure. The resulting orange reaction crude product was purified by column chromatography using silica gel (developed by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 1/1). The target compound was obtained as a yellow-orange powder. (300 mg, 83% yield)
以下に、その物性を示す。 The physical properties are shown below.
'H-NMR (300MHz, CDCl ) δ : 9. 09-9. 06 (m, 2Η) , 8. 23-8. 15 (m, 2Η  'H-NMR (300MHz, CDCl) δ: 9.09-9.06 (m, 2Η), 8.23-8.15 (m, 2Η
3  Three
) , 8. 06-7. 98 (m、 3H)、 7. 86—7. 78 (m、 2H)、 7. 70—7. 65 (m、 2H)、 7. 59 -7. 35 (m、 5H)  ), 8.06-7.98 (m, 3H), 7.86-7.78 (m, 2H), 7.70-7.65 (m, 2H), 7.59-7.35 (m , 5H)
EI_MS (m/e) : 380 (M+)、 CI— MS (m/z) : 381 (MH+) EI_MS (m / e): 380 (M +), CI—MS (m / z): 381 (MH + )
[吸収極大：クロ口ホルム溶液] 242nm [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 386nm [Fluorescence maximum wavelength: black form solution] 386nm
実施例 3 Example 3
1 , 3， 5—トリス（8' _キノリルェチュル）ベンゼン（次式 12)の合成
Figure imgf000025_0001
Synthesis of 1,3,5-tris (8'_quinolyletul) benzene (Formula 12)
Figure imgf000025_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 800mg (2. 9mmol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2. 0 X 10— 5mol)、ピぺリジン 6m 1を加え攪拌した。この黄色溶液に 1 , 3, 5—トリエチニルベンゼン 91mg (0. 61mmol )を加え、 80°Cで 3時間攪拌した。反応終了後、反応混合物に塩化メチレンを加えて 希釈した後、飽和塩化アンモニゥム水溶液で洗浄し、次いで無水硫酸マグネシウム で乾燥、減圧乾固した。得られた橙色の反応粗生成物をシリカゲルを用いたカラムク 口マトグラフィー（展開溶媒をへキサン/酢酸ェチル = 100/0から 1/1に徐々に変 えて展開した。）によって精製することで黄橙色粉末である目的化合物を得た。 (280 mg、収率 86%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 800 mg (2. 9 mmol), tetrakis (triphenyl phosphine) palladium 23mg (2. 0 X 10- 5 mol ), was added and stirred piperidine 6 m 1. To this yellow solution was added 91 mg (0.61 mmol) of 1,3,5-triethynylbenzene, and the mixture was stirred at 80 ° C for 3 hours. After completion of the reaction, the reaction mixture was diluted by adding methylene chloride, washed with a saturated aqueous solution of ammonium chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting crude orange reaction product was purified by column chromatography using silica gel (developed with the developing solvent gradually changed from hexane / ethyl acetate = 100/0 to 1/1) to develop a yellow color. The target compound was obtained as an orange powder. (280 mg, 86% yield)
以下に、その物性を示す。 The physical properties are shown below.
'H-NMR (300MHz, CDCl ) δ : 9. 10-9. 05 (m、 3Η)、 8. 21-8. 17 (m、 3H  'H-NMR (300MHz, CDCl) δ: 9.10-9.05 (m, 3Η), 8.21-8.17 (m, 3H
3  Three
)、 8. 08-8. 01 (m、 6H)、 7. 86—7. 82 (m, 3H)、 7. 60—7. 53 (m, 3H)、 7. 50 -7. 45 (m、 3H)  ), 8.08-8.01 (m, 6H), 7.86-7.82 (m, 3H), 7.60-7.53 (m, 3H), 7.50 -7.45 (m , 3H)
EI-MS (m/e) : 403 (M_C H N)  EI-MS (m / e): 403 (M_C H N)
9 6  9 6
[吸収極大：クロ口ホルム溶液] 242nm  [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 386nm [Fluorescence maximum wavelength: black form solution] 386nm
実施例 4 Example 4
ビス（8 '—キノリル）アセチレン（次式 4)の合成
Figure imgf000026_0001
Synthesis of bis (8'-quinolyl) acetylene (Formula 4)
Figure imgf000026_0001
[0100] (第 1工程）  [0100] (First step)
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 1 1. 6mg (l . 0 X 10— 5mol)、ピペリジン 6mlを加え攪拌した。この黄色溶液にトリメチルシリルアセチレン 290 /i 1 (2. lmmol )をカ卩えて、 90°Cで 3時間攪拌した。反応終了後、反応混合物に塩化メチレンを加え て希釈した後、飽和塩ィ匕アンモニゥム水溶液で洗浄し、減圧乾固することで 8-トリメ チルシリルェチニルキノリンを得た。 （360mg、本工程の収率 80%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 1 1. 6mg (l. 0 X 10- 5 mol), was added and stirred piperidine 6 ml. Trimethylsilylacetylene 290 / i 1 (2.lmmol) was added to the yellow solution, and the mixture was stirred at 90 ° C for 3 hours. After completion of the reaction, the reaction mixture was diluted by adding methylene chloride, washed with a saturated aqueous solution of ammonium chloride, and dried under reduced pressure to obtain 8-trimethylsilylethynylquinoline. (360 mg, yield of this process 80%)
[0101] (第 2工程） [0101] (Second step)
上記反応で得られた 8—トリメチルシリルェチニルキノリンをメタノール 6mlに溶解さ せ、 NaOH水溶液 (濃度 lmol/1. 3ml)を滴下した後、室温で 15分攪拌した。反応 混合物に水 20mlをカ卩えた後、塩化メチレンで抽出（10ml X 3回）し、得られた有機 層を減圧下にて溶媒を留去することで 8—ェチニルキノリンを得た。 （245mg、本工程 の収率 99%)  8-Trimethylsilylethynylquinoline obtained in the above reaction was dissolved in 6 ml of methanol, and an aqueous NaOH solution (concentration: lmol / 1.3 ml) was added dropwise, followed by stirring at room temperature for 15 minutes. After 20 ml of water was added to the reaction mixture, the mixture was extracted with methylene chloride (10 ml × 3 times), and the obtained organic layer was evaporated under reduced pressure to obtain 8-ethynylquinoline. (245 mg, yield of this process 99%)
[0102] (第 3工程） [0102] (3rd step)
上記反応で得られた 8_ェチニルキノリンに 8_トリフルォロメタンスルホキシキノリン 5 27mg (l . 9mmol)、テトラキス（トリフエニルホスフィン）パラジウム 11. 6mg (l . 0 X 1 0_5mol)、ピペリジン 6mlをカ卩えて 90°Cで 2時間攪拌した。反応終了後、反応系中に 沈殿した黄色固体をろ取し、得られた個体を、水（5ml)、へキサン（5ml)の順で洗浄 し、次いで乾燥することで淡黄色粉末である目的化合物を得た。 （400mg、本工程 の収率 90%) 8_ to 8_ Echinirukinorin obtained in the above reaction triflate Ruo b methane sulfoxylate quinoline 5 27mg (l. 9mmol), tetrakis (triphenyl phosphine) palladium 11. 6mg (l. 0 X 1 0_ 5 mol), piperidine 6ml The mixture was stirred at 90 ° C for 2 hours. After completion of the reaction, the yellow solid precipitated in the reaction system is collected by filtration, and the obtained solid is washed with water (5 ml) and hexane (5 ml) in that order, and then dried to obtain a light yellow powder. The compound was obtained. (400 mg, yield of this process 90%)
第 1工程から第 3工程の、トータル収率 71 %。  Total yield of the first to third steps is 71%.
以下に、その物性を示す。 'H-NMR (300MHz, CDC1 ) δ : 9. 11-9. 05 (m、 2H)、 8. 22-8. 15 (m、 4H The physical properties are shown below. 'H-NMR (300MHz, CDC1) δ: 9.11-9.05 (m, 2H), 8.22-8.15 (m, 4H
3  Three
)、 7. 84-7. 80 (m、 2H)、 7. 60-7. 51 (m、 2H)、 7. 49-7. 39 (m、 2H) EI_MS (m/e) : 280 (M+)、 CI— MS (m/z) : 281 (MH+) ), 7.84-7.80 (m, 2H), 7.60-7.51 (m, 2H), 7.49-7.39 (m, 2H) EI_MS (m / e): 280 (M + ), CI—MS (m / z): 281 (MH + )
[吸収極大：クロ口ホルム溶液] 240nm  [Maximum absorption: black mouth form solution] 240nm
[蛍光極大波長：クロ口ホルム溶液] 397nm  [Fluorescence maximum wavelength: black-mouthed form solution] 397nm
[0103] 実施例 5 [0103] Example 5
8_フヱニルェチ二ルキノリン（次式 13)の合成  Synthesis of 8_phenylethynylquinoline (Formula 13)
Figure imgf000027_0001
Figure imgf000027_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピペリジン 6mlを 加え攪拌した。この黄色反応溶液にフエニルアセチレン 231 μ 1 (2. lmmol)を加え て、 80°Cで 2. 5時間攪拌した。反応終了後、反応混合液に飽和塩ィ匕アンモニゥム水 溶液をカ卩えた後、塩化メチレンで抽出し、有機層を無水硫酸マグネシウムで乾燥し、 減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー (展開溶媒をへキサン Z酢酸ェチル = 100/0から 5Z1に徐々に変えて展開した。 ) によって精製することで、黄色固体である目的化合物を得た。 （422mg、収率 92%) 以下に、その物性を示す。 In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. Phenylacetylene (231 μl, 2.1 mmol) was added to the yellow reaction solution, and the mixture was stirred at 80 ° C for 2.5 hours. After completion of the reaction, a saturated aqueous sodium chloride solution was added to the reaction mixture, extracted with methylene chloride, and the organic layer was dried over anhydrous magnesium sulfate and dried under reduced pressure. The resulting crude reaction product was purified by column chromatography on silica gel (developing the solvent by gradually changing the developing solvent from hexane Z to ethyl acetate = 100/0 to 5Z1) to obtain a yellow solid. The compound was obtained. (422 mg, yield 92%) The physical properties are shown below.
'H-NMR (300MHz, CDC1 ) δ : 9. 08—9. 05 (m、 1Η)、 8. 22-8. 17 (m, 1Η  'H-NMR (300MHz, CDC1) δ: 9.08-9.05 (m, 1Η), 8.22-8.17 (m, 1Η)
3  Three
)、 8. 30-7. 90 (m、 1H)、 7. 83—7. 79 (m、 1H)、 7. 71—7. 67 (m、 2H)、 7. 56 -7. 50(m, 1H)、 7. 48—7. 43 (m, 1H)、 7. 40—7. 30 (m, 3H)  ), 8.30-7.90 (m, 1H), 7.83-7.79 (m, 1H), 7.71-7.67 (m, 2H), 7.56-7.50 (m , 1H), 7.48-7.43 (m, 1H), 7.40-7.30 (m, 3H)
EI-MS (m/e)： 229 (M+)、 CI—MS (m/z)： 230 (MH+)  EI-MS (m / e): 229 (M +), CI—MS (m / z): 230 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm  [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 391nm  [Fluorescence maximum wavelength: black form solution] 391nm
[0104] 実施例 6 8- (4 '一フルオロフヱ二ルェチニル）キノリン（次式 14)の合成 [0104] Example 6 Synthesis of 8- (4'monofluorophenylethynyl) quinoline (Formula 14)
Figure imgf000028_0001
Figure imgf000028_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 4_フルオロフヱニルアセチレン 241 μ 1 (2. lmmol) を加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加え た後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。 得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへ キサン/酢酸ェチル = 100Z0から 5/1に徐々に変えて展開した。 )によって精製 することで黄色固体である目的化合物を得た。 （403mg、収率 82%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 241 μl (2.1 mmol) of 4_fluorophenylacetylene, and the mixture was stirred at 80 ° C for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting crude reaction product was purified by column chromatography on silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100Z0 to 5/1) to yield the target compound as a yellow solid. Got. (403 mg, 82% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 06—9. 04 (m、 1Η)、 8. 20—8. 17 (m, 1Η 'H-NMR (300MHz, CDC1) δ: 9.06-9.04 (m, 1Η), 8.20-8.17 (m, 1Η
3  Three
)、 8. 01-7. 98 (m、 1H)、 7. 84-7. 81 (m、 1H)、 7. 70-7. 63 (m、 2H)、 7. 56 -7. 51 (m, 1H)、 7. 48-7. 44 (m, 1H)、 7. 22-7. 02 (m、 2H)  ), 8.01-7.98 (m, 1H), 7.84-7.81 (m, 1H), 7.70-7.63 (m, 2H), 7.56 -7.51 (m , 1H), 7.48-7.44 (m, 1H), 7.22-7.02 (m, 2H)
CI-MS (m/z) ： 248 (MH + ) CI-MS (m / z): 248 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 392nm [Fluorescence maximum wavelength: black form solution] 392nm
実施例 7 Example 7
8- (3 '一フルオロフェニルェチニル）キノリン（次式 15)の合成  Synthesis of 8- (3'-fluorophenylethynyl) quinoline (Formula 15)
Figure imgf000028_0002
Figure imgf000028_0002
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピペリジン 6mlを 加え攪拌した。この黄色溶液に 3—フルオロフェニルアセチレン 243 μ 1 (2. lmmol) を加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加え た後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。 得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへ キサン/酢酸ェチル = 100Z0から 5/1に徐々に変えて展開した。 )によって精製 することで黄色固体である目的化合物を得た。 （353mg、収率 71%) 554mg (2.Ommol) of 8-trifluoromethanesulfoxyquinoline in 20ml Schlenk, Tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 243 μl (2.1 mmol) of 3-fluorophenylacetylene, and the mixture was stirred at 80 ° C. for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting crude reaction product was purified by column chromatography on silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100Z0 to 5/1) to yield the target compound as a yellow solid. Got. (353mg, 71% yield)
'H-NMR (300MHz, CDC1 ) : 5 9. 07—9. 05 (m、 1H)、 8. 21—8. 18 (m, 1H 'H-NMR (300MHz, CDC1): 5 9.07-9.05 (m, 1H), 8.21-8.18 (m, 1H
3  Three
)、 8. 02-7. 99 (m, 1H)、 7. 86—7. 82 (m, 1H)、 7. 57-7. 52 (m, 1H)、 7. 50 -7. 44(m， 2H)、 7. 39—7. 28 (m, 2H)、 7. 09—7. 04 (m, 1H)  ), 8.02-7.99 (m, 1H), 7.86-7.82 (m, 1H), 7.57-7.52 (m, 1H), 7.50 -7.44 (m , 2H), 7.39-7.28 (m, 2H), 7.09-7.04 (m, 1H)
CI-MS (m/z)： 248 (MH + ) CI-MS (m / z): 248 (MH +)
[吸収極大：クロ口ホルム溶液] 241nm [Maximum absorption: Black mouth form solution] 241nm
[蛍光極大波長：クロ口ホルム溶液] 386nm [Fluorescence maximum wavelength: black form solution] 386nm
実施例 8 Example 8
8- (2 '—フルオロフヱ二ルェチニル）キノリン（次式 16)の合成  Synthesis of 8- (2'-fluorophenylethynyl) quinoline (Formula 16)
Figure imgf000029_0001
Figure imgf000029_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピペリジン 6mlを 加え攪拌した。この黄色溶液に 2—フルオロフェニルアセチレン 238 μ 1 (2. lmmol) を加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加え た後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。 得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへ キサン/酢酸ェチル = 100/0から 5/1に徐々に変えて展開した。 )によって精製 することで黄色固体である目的化合物を得た。 （357mg、収率 72%) 'H-NMR (300MHz, CDC1 ) δ : 9. 08-9. 06 (m、 1H)、 8. 20-8. 17 (m, 1HIn 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 238 μl (2.1 mmol) of 2-fluorophenylacetylene, and the mixture was stirred at 80 ° C for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting crude reaction product was purified by column chromatography using silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 5/1) to yield a yellow solid. The desired compound was obtained. (357 mg, yield 72%) 'H-NMR (300MHz, CDC1) δ: 9.08-9.06 (m, 1H), 8.20-8.17 (m, 1H
3 Three
)、 8. 06-8. 03 (m, 1H)、 7. 85-7. 82 (m, 1H)、 7. 72-7. 67 (m, 1H)、 7. 57 -7. 52(m, 1H)、 7. 49-7. 44 (m, 1H)、 7. 35-7. 30(m, 1H)、 7. 18-7. 09 ( m， 2H)  ), 8.06-8.03 (m, 1H), 7.85-7.82 (m, 1H), 7.72-7.67 (m, 1H), 7.57 -7.52 (m , 1H), 7.49-7.44 (m, 1H), 7.35-7.30 (m, 1H), 7.18-7.09 (m, 2H)
CI-MS (m/z)： 248 (MH + )  CI-MS (m / z): 248 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 387nm [Fluorescence maximum wavelength: black form solution] 387nm
実施例 9 Example 9
8- (4 'ーメトキシフヱニルェチュル）キノリン（次式 17)の合成  Synthesis of 8- (4'-methoxyphenyluetur) quinoline (Formula 17)
Figure imgf000030_0001
Figure imgf000030_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 4ーメトキシフエニルアセチレン 272 μ 1 (2. Immol)を 加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加えた 後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反 応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢 酸ェチル = 100/0から 4/1に徐々に変えて展開した。 )によって精製することで黄 色油状物である目的化合物を得た。 （253mg、収率 49%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 272 μl (2.1 mmol) of 4-methoxyphenylacetylene, and the mixture was stirred at 80 ° C for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The crude reaction product was purified by column chromatography on silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 4/1) to yield a yellow oil. A certain target compound was obtained. (253mg, 49% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 04-9. 02 (m, 1Η)、 8. 18-8. 15 (m, 1Η  'H-NMR (300MHz, CDC1) δ: 9.04-9.02 (m, 1Η), 8.18-8.15 (m, 1Η
3  Three
)、 8. 00-7. 97 (m, 1H)、 7. 80-7. 77 (m, 1H)、 7. 73-7. 58 (m, 2H)、 7. 55 -7. 52(m, 1H)、 7. 49-7. 43 (m, 1H)、 6. 90-6. 86 (m, 2H)、 3. 86(s, 3H) CI-MS (m/z) : 260 (MH + )  ), 8.00-7.97 (m, 1H), 7.80-7.77 (m, 1H), 7.73-7.58 (m, 2H), 7.55 -7.52 (m , 1H), 7.49-7.43 (m, 1H), 6.90-6.86 (m, 2H), 3.86 (s, 3H) CI-MS (m / z): 260 (MH +)
[吸収極大：クロ口ホルム溶液] 247nm [Absorption maximum: black-mouthed form solution] 247 nm
[蛍光極大波長：クロ口ホルム溶液] 420nm [0108] 実施例 10 [Fluorescence maximum wavelength: black mouth form solution] 420 nm [0108] Example 10
8- (3 'ーメトキシフヱニルェチュル）キノリン（次式 18)の合成  Synthesis of 8- (3'-methoxyphenyl etul) quinoline (Formula 18)
Figure imgf000031_0001
Figure imgf000031_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 3—メトキシフエニルアセチレン 267 μ 1 (2. Immol)を 加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加えた 後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反 応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢 酸ェチル = 100/0から 3/1に徐々に変えて展開した。 )によって精製することで黄 色油状物である目的化合物を得た。 （364mg、収率 70%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 267 μl of 3-methoxyphenylacetylene (2. Immol), and the mixture was stirred at 80 ° C for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The crude reaction product was purified by column chromatography on silica gel (developing solvent while gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 3/1) to yield a yellow oil. A certain target compound was obtained. (364mg, 70% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 07—9. 05 (m、 1Η)、 8. 20—8. 17 (m, IH  'H-NMR (300MHz, CDC1) δ: 9.07-9.05 (m, 1Η), 8.20-8.17 (m, IH
3  Three
)、 8. 03-8. 00 (m, IH)、 7. 84-7. 81 (m, IH)、 7. 57-7. 52 (m, IH)、 7. 48 -7. 44(m, 1H)、 7. 36-7. 22 (m, 3H)、 6. 95-6. 89 (m, 1H)、 3. 84(s , 3H) CI-MS (m/z) : 260 (MH + )  ), 8.03-8.00 (m, IH), 7.84-7.81 (m, IH), 7.57-7.52 (m, IH), 7.48 -7.44 (m , 1H), 7.36-7.22 (m, 3H), 6.95-6.89 (m, 1H), 3.84 (s, 3H) CI-MS (m / z): 260 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm  [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 398nm  [Fluorescence maximum wavelength: black form solution] 398nm
[0109] 実施例 11 [0109] Example 11
8-(4 '—フエ二ルフヱ二ルェチニル)キノリン（次式 19)の合成  Synthesis of 8- (4'-phenyl-2-ethyninyl) quinoline (Formula 19)
(19)
Figure imgf000031_0002
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピペリジン 6mlを 加え攪拌した。この黄色溶液に 4_フエエルフェニルアセチレン 374mg (2· lmmol) を加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加え た後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。 反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/ 酢酸ェチル = 100Z0から 4/1に徐々に変えて展開した。 )によって精製することで 黄色固体である目的化合物を得た。 （297mg、収率 49%) (19)
Figure imgf000031_0002
In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 374 mg (2 l mmol) of 4-phenylphenylacetylene, and the mixture was stirred at 80 ° C for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The crude reaction product was purified by column chromatography using silica gel (developing solvent while gradually changing the developing solvent from hexane / ethyl acetate = 100Z0 to 4/1) to obtain the target compound as a yellow solid. . (297 mg, 49% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 07—9. 05 (m, 1Η)、 8. 19—8. 15 (m, 1Η  'H-NMR (300MHz, CDC1) δ: 9.07-9.05 (m, 1Η), 8.19-8.15 (m, 1Η
3  Three
)、 8. 03-8. 00 (m, 1H)、 7. 82—7. 73 (m, 3H)、 7. 64—7. 59 (m, 4H)、 7. 56 -7. 5 l(m, 1H)、 7. 48—7. 42 (m, 3H)、 7. 38—7. 25 (m, 1H)  ), 8.03-8.00 (m, 1H), 7.82-7.73 (m, 3H), 7.64-7.59 (m, 4H), 7.56-7.5 l ( m, 1H), 7.48-7.42 (m, 3H), 7.38-7.25 (m, 1H)
CI-MS (m/z) : 306 (MH + ) CI-MS (m / z): 306 (MH +)
[吸収極大：クロ口ホルム溶液] 242nm [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 402nm [Fluorescence maximum wavelength: black form solution] 402nm
実施例 12 Example 12
8— (2'—ピリジルェチニル)キノリン（次式 20)の合成  Synthesis of 8- (2'-pyridylethynyl) quinoline (Formula 20)
Figure imgf000032_0001
Figure imgf000032_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 2'—ピリジルアセチレン 262 μ 1 (2. 6mmol)を加え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加えた後、有 機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗 生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢酸ェ チル = 100/0から 0/100に徐々に変えて展開した。 )によって精製することで黄色 油状物である目的化合物を得た。 （188mg、収率 41 %) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. 262 μl (2.6 mmol) of 2′-pyridylacetylene was added to this yellow solution, and the mixture was stirred at 80 ° C. for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and dried under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 0/100). The target compound was obtained as an oil. (188 mg, 41% yield)
'H-NMR (300MHz, CDCl ) δ : 9. 08-9. 06 (m, 1Η)、 8. 68-8. 65 (m, 1Η  'H-NMR (300MHz, CDCl) δ: 9.08-9.06 (m, 1Η), 8.68-8.65 (m, 1Η)
3  Three
)、8. 21-8. 18 (m, 1H)、 8. 10-8. 07 (m, 1H)、 7. 87-7. 84 (m, 1H)、 7. 74 -7. 70 (m, 2H)、 7. 58—7. 55 (m, 1H)、 7. 53—7. 47 (m, 1H)、 7. 28-7. 24 ( m， 1H)  ), 8.21-8.18 (m, 1H), 8.10-8.07 (m, 1H), 7.87-7.84 (m, 1H), 7.74 -7.70 (m , 2H), 7.58-7.55 (m, 1H), 7.53-7.47 (m, 1H), 7.28-7.24 (m, 1H)
CI-MS (m/z) : 231 (MH + )  CI-MS (m / z): 231 (MH +)
[吸収極大：クロ口ホルム溶液] 241nm [Maximum absorption: Black mouth form solution] 241nm
[蛍光極大波長：クロ口ホルム溶液] 377nm [Fluorescence maximum wavelength: black form solution] 377nm
実施例 13 Example 13
8_ (3，一ピリジルェチュル）キノリン（次式 21)の合成  8_ Synthesis of (3,1-pyridyl-etur) quinoline (Formula 21)
Figure imgf000033_0001
Figure imgf000033_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 3 ' _ピリジルアセチレン 244mg (2. 37mmol)を加え 、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水溶液を加えた後、 有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応 粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢酸 ェチル = 100/0から 0/100に徐々に変えて展開した。 )によって精製することで黄 色油状物である目的化合物を得た。 （375mg、収率 81 %) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution, 244 mg (2.37 mmol) of 3′-pyridylacetylene was added, and the mixture was stirred at 80 ° C. for 2 hours. After adding a saturated aqueous solution of ammonium chloride to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and dried under reduced pressure. The reaction crude product was purified by column chromatography on silica gel (developing solvent while gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 0/100) to obtain a yellow oil. The compound was obtained. (375 mg, 81% yield)
'H-NMR (300MHz, CDCl ) δ : 9. 08-9. 06 (m, 1Η)、 8. 92-8. 91 (m, 1Η  'H-NMR (300MHz, CDCl) δ: 9.08-9.06 (m, 1Η), 8.92-8.91 (m, 1Η)
3  Three
)、 8. 58-8. 56 (m, 1H)、 8. 22—8. 19 (m, 1H)、 8. 04—8. 02 (m, 1H)、 7. 99 -7. 95 (m, 1H)、 7. 87-7. 84 (m, 1H)、 7. 56-7. 53(m, 1H)、 7. 50-7. 46 ( m， 1H)、 7. 33-7. 29 (m, 1H)  ), 8.58-8.56 (m, 1H), 8.22-8.19 (m, 1H), 8.04-8.02 (m, 1H), 7.99-7.95 (m , 1H), 7.87-7.84 (m, 1H), 7.56-7.53 (m, 1H), 7.50-7.46 (m, 1H), 7.33-7.29 (m, 1H)
CI-MS (m/z) : 231 (MH + ) [吸収極大：クロ口ホルム溶液] 241nm CI-MS (m / z): 231 (MH +) [Maximum absorption: Black mouth form solution] 241nm
[蛍光極大波長：クロ口ホルム溶液] 378nm  [Fluorescence maximum wavelength: black-mouthed form solution] 378 nm
[0112] 実施例 14 Example 14
8- (2'ーメチルー 2，—H—イミダゾリルェチュル）キノリン（次式 22)の合成  Synthesis of 8- (2'-methyl-2, -H-imidazolyl-chur) quinoline (Formula 22)
Figure imgf000034_0001
Figure imgf000034_0001
20mlシュレンクに 8—トリフルォロメタンスルホキシキノリン 554mg (2. Ommol)、 テトラキス（トリフエニルホスフィン）パラジウム 23mg (2 X 10— 5mol)、ピぺリジン 6mlを 加え攪拌した。この黄色溶液に 5—ェチュル— 1—メチル _1—H—イミダゾール 244 μ 1 ( 2. 4mmol)をカ卩え、 80°Cで 2時間攪拌した。反応混合液に飽和塩化アンモニゥム水 溶液をカ卩えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減 圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒 をへキサン Z酢酸ェチル =ιοο/οから oZiooに徐々に変えて展開し、更に、メタ ノール/酢酸ェチル = 1/10で展開した。 )によって精製することで黄色固体である 目的化合物を得た。 （418mg、収率 90%) In 20ml Schlenk 8 triflate Ruo b methane sulfoxylate quinoline 554mg (2. Ommol), tetrakis (triphenyl phosphine) palladium 23mg (2 X 10- 5 mol) , was added and stirred piperidine 6 ml. To this yellow solution was added 244 μl (2.4 mmol) of 5-ethyl-1-methyl_1-H-imidazole, and the mixture was stirred at 80 ° C. for 2 hours. After a saturated aqueous ammonium chloride solution was added to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and dried under reduced pressure to dryness. The reaction crude product was developed by column chromatography using silica gel (developing solvent was gradually changed from hexane Z ethyl acetate = ιοο / ο to oZioo, and further developed with methanol / ethyl acetate = 1/10). ) To give the target compound as a yellow solid. (418 mg, 90% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 05-9. 03 (m, 1Η)、 8. 21-8. 18 (m, 1Η  'H-NMR (300MHz, CDC1) δ: 9.05-9.03 (m, 1Η), 8.21-8.18 (m, 1Η
3  Three
)、 7. 98-7. 95 (m, 1H)、 7. 85-7. 82 (m, 1H)、 7. 57-7. 44 (m, 4H)、 3. 88 ), 7.98-7.95 (m, 1H), 7.85-7.82 (m, 1H), 7.57-7.44 (m, 4H), 3.88
(s, 3H) (s, 3H)
CI-MS (m/z) : 234 (MH + )  CI-MS (m / z): 234 (MH +)
[吸収極大：クロ口ホルム溶液] 246nm  [Absorption maximum: black mouth form solution] 246 nm
[蛍光極大波長：クロ口ホルム溶液] 416nm  [Fluorescence maximum wavelength: black form solution] 416nm
[0113] 実施例 15 [0113] Example 15
8- (4 '一ベンゾィルフエニルェチュル）キノリン（次式 23)の合成
Figure imgf000035_0001
Synthesis of 8- (4'-Benzylphenyl etul) quinoline (Formula 23)
Figure imgf000035_0001
20mlシュレンクに 8_ェチニルキノリン 460mg (3. Ommol)、テトラキス（トリフエ二 ルホスフィン）パラジウム 69mg (6 X 10— 5mol)、ピペリジン 9mlを加え攪拌した。この 黄色溶液に 4_ブロモベンゾフエノン 783mg (3. Ommol)を加え、 80°Cで 32時間攪 拌した。反応混合液に飽和塩ィ匕アンモニゥム水溶液をカ卩えた後、有機物は塩化メチ レンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲ ルを用いたカラムクロマトグラフィー（展開溶媒をへキサン/酢酸ェチル = 100/0か ら 3/1に徐々に変えて展開した。 )によって精製することで黄色固体である目的化合 物を得た。 （605mg、収率 60%) 20ml Schlenk to 8_ Echinirukinorin 460mg (3. Ommol), tetrakis (bird whistle two Le phosphine) palladium 69mg (6 X 10- 5 mol) , was added and stirred piperidine 9 ml. To this yellow solution was added 783 mg (3.0 mmol) of 4-bromobenzophenone, and the mixture was stirred at 80 ° C for 32 hours. After a saturated aqueous sodium chloride solution was added to the reaction mixture, the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and dried under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (developing the solvent by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 3/1) to yield a yellow solid. The compound was obtained. (605 mg, 60% yield)
'H-NMR (300MHz, CDC1 ) δ : 9. 09—9. 07 (m, 1Η)、 8. 22-8. 19 (m, 1Η  'H-NMR (300MHz, CDC1) δ: 9.09-9.07 (m, 1Η), 8.22-8.19 (m, 1Η)
3  Three
) 8. 06-8. 03 (m， 1H)、 7. 88—7. 79 (m, 7H)、 7. 64—7. 47 (m, 5H) CI-MS (m/z) : 334 (MH + )  ) 8.06-8.03 (m, 1H), 7.88-7.79 (m, 7H), 7.64-7.47 (m, 5H) CI-MS (m / z): 334 ( MH +)
[吸収極大：クロ口ホルム溶液] 242nm [Absorption maximum: black form solution] 242nm
[蛍光極大波長：クロ口ホルム溶液] 473nm [Fluorescence maximum wavelength: black form solution] 473nm
実施例 16 Example 16
ビス（8 '—キノリル)アセチレン (前記式 (4)の化合物）を有機発光層に含む有機エレ タトロルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing bis (8′-quinolyl) acetylene (compound of the formula (4)) in an organic light emitting layer.
真空蒸着装置（アルバック機ェ製）を使用して、ソーダガラス上に透明電極として IT Oを真空蒸着したものを基板として用い、同基板上に 2 X 10— 3Pa以下の真空度にて 、 TPDからなるホール輸送層 3を膜厚 40nm、 TPD中にビス（8，一キノリル）ァセチレ ンを 1. 4重量％含む発光層 4を膜厚 40nm、 Alq力 なる電子輸送層 5を膜厚 20η Using a vacuum evaporation apparatus (ULVAC machine manufactured by E), used after vacuum evaporation IT O as a transparent electrode on a soda glass as the substrate, at 2 X 10- 3 Pa or less in vacuum degree on the same substrate, The hole transport layer 3 made of TPD has a thickness of 40 nm, the light emitting layer 4 containing 1.4% by weight of bis (8,1-quinolyl) acetylene in TPD has a thickness of 40 nm, and the electron transport layer 5 having Alq force has a thickness of 20η.
3  Three
m、電極 6としてアルミニウム (A1)を膜厚 100nm、順次蒸着させて形成し有機エレク トロルミネッセンス素子を作製した。 m, aluminum (A1) as electrode 6 was formed by sequentially depositing A luminescence device was manufactured.
なお、ビス（8，一キノリル）アセチレンの蒸着源の温度は、 280°Cを超えない範囲に 制御した。  The temperature of the source of bis (8,1-quinolyl) acetylene was controlled so as not to exceed 280 ° C.
前記素子の IT〇電極 2を正極、 A1電極 6を負極として電極間に + 30Vを印加したと ころ、前記素子は 16cdZm2で発光した。発光スペクトルは 435nmにショルダーと、 4 97nmにピークを持つものであり、発光色の JIS Z8701による色度座標は（0. 25, 0 . 36)であった。 When +30 V was applied between the electrodes with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode, the device emitted light at 16 cdZm 2 . The emission spectrum had a shoulder at 435 nm and a peak at 497 nm, and the chromaticity coordinates of the emission color according to JIS Z8701 were (0.25, 0.36).
[0115] 実施例 17 [0115] Example 17
8- (4 '—フエユルフェニルェチュル)キノリン (前記式（19)の化合物）を有機発光層 に含む有機エレクト口ルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing 8- (4′-fuyerphenyl ethr) quinoline (compound of the above formula (19)) in an organic light emitting layer.
ィーエッチシー製インジウム錫酸化物（以下、 ITOと略す)被膜付きガラスを透明電 極基板として用い、真空蒸着装置 (アルバック機ェ製）を使用して、同基板上に 2 X 1 0— 3Pa以下の真空度で、 N, N'—ビス（3—メチルフエ二ル）— N, N，—ビス（フエ二ル）— ベンジジン（以下、 TPDと略す）からなるホール輸送層 3を膜厚 40nm、 4, 4'_ビス（ カルバゾールー 9ーィノレ）ビフエ二ル（以下、 CBPと略す）中に 8_ (4，_フエニルフエ二 ルェチニル）キノリンを 9重量％含む発光層 4を膜厚 20nm、 3—（4ービフエ二ルイル） _4_フエ二ルー 5_t_ブチルフエ二ルー 1 , 2, 4—トリアゾール（以下、 TAZと略す）から なるホールブロック層（電子輸送層） 5を膜厚 20nm、電極 6としてアルミニウム（A1)を 膜厚 100nm、順次蒸着させて形成し有機エレクト口ルミネッセンス素子を作製した。 前記素子の ITO電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 22Vにおいて 4cd/m2で発光した。発光スペクトルは 418nmにピークを持 つものであり、発光色の色度座標は（0. 18， 0. 14)であった。 Ietchishi made of indium tin oxide (hereinafter, abbreviated as ITO) using a coated glass as the transparent electrodes substrate, using a vacuum evaporation apparatus (ULVAC machine manufactured by E), 2 X 1 0- 3 Pa or less on the same substrate The hole transport layer 3 made of N, N'-bis (3-methylphenyl) -N, N, -bis (phenyl) -benzidine (hereinafter abbreviated as TPD) was formed at a vacuum degree of 40 nm, The light-emitting layer 4 containing 9% by weight of 8_ (4, _phenylphenylethynyl) quinoline in 4,4'_bis (carbazole-9-inole) biphenyl (hereinafter abbreviated as CBP) has a thickness of 20 nm, 3— (4 -Biphenyl) _4_phenyl-5_t_butylphenyl 1,2,4-triazole (hereinafter abbreviated as TAZ), a hole block layer (electron transport layer) 5 with a film thickness of 20 nm and an electrode 6 made of aluminum (A1 ) To a thickness of 100 nm to form an organic A device was fabricated. When a current was passed between the ITO electrode 2 of the device as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at 4 cd / m 2 at +22 V. The emission spectrum had a peak at 418 nm, and the chromaticity coordinates of the emission color were (0.18, 0.14).
[0116] 実施例 18 Example 18
8- (2'ーメチノレー 2，—H—イミダゾリルェチュル）キノリン（前記式（22)の化合物）を 有機発光層に含む有機エレクト口ルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing 8- (2′-methinolay 2, -H-imidazolyl-etul) quinoline (compound of the formula (22)) in an organic light-emitting layer.
CBP中に 8—（2 '—メチルー 2 '—H—イミダゾリルェチュル）キノリンを 9重量％含む発 光層 4を用いた以外は実施例 17と同様にして有機エレクト口ルミネッセンス素子を作 製した。 前記素子の ITO電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 21Vにおいて 14cd/m2で発光した。この時の最大電流効率は 0. 10cd/ Aであった。発光スぺクトノレは 427nmにピークを持つものであり、発光色の色度座標 は（0. 17, 0. 12)であった。 An organic electroluminescent device was manufactured in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8- (2′-methyl-2′-H-imidazolyl-etur) quinoline in CBP was used. . When current was applied to the device with the ITO electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at +21 V at 14 cd / m 2 . The maximum current efficiency at this time was 0.10 cd / A. The emission spectrum had a peak at 427 nm, and the chromaticity coordinates of the emission color were (0.1, 0.12).
[0117] 実施例 19 Example 19
8- (4 '一フルオロフェニルェチュル)キノリン (前記式（14)の化合物）を有機発光層 に含む有機エレクト口ルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing 8- (4′-fluorophenylethyl) quinoline (compound of the formula (14)) in an organic light emitting layer.
CBP中に 8_ (4 '—フルオロフェニルェチュル）キノリンを 9重量％含む発光層 4を用 レ、た以外は実施例 17と同様にして有機エレクト口ルミネッセンス素子を作製した。 前記素子の IT〇電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 21Vにおいて 5cd/m2で発光した。この時の最大電流効率は 0. 059cd/ Aであった。発光スペクトルは 420nmにピークを持つものであり、発光色の色度座標 は（0. 21, 0. 19)であった。 An organic electroluminescent device was produced in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8_ (4′-fluorophenylethul) quinoline in CBP was used. The device was energized with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode. When the voltage between the electrodes was increased, the device emitted light at 5 cd / m 2 at +21 V. The maximum current efficiency at this time was 0.059 cd / A. The emission spectrum had a peak at 420 nm, and the chromaticity coordinates of the emission color were (0.21, 0.19).
[0118] 実施例 20 [0118] Example 20
8—フエ二ルェチ二ルキノリン (前記式（13)の化合物）を有機発光層に含む有機ェ レクト口ルミネッセンス素子の作製。  Preparation of an organic EL device containing 8-phenylenequinoline (compound of the formula (13)) in an organic light emitting layer.
CBP中に 8—フエ二ルェチ二ルキノリンを 9重量％含む発光層 4を用いた以外は実 施例 17と同様にして有機エレクト口ルミネッセンス素子を作製した。  An organic electroluminescent device was prepared in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8-phenylethynylquinoline in CBP was used.
前記素子の ITO電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 21Vにおいて 4cd/m2で発光した。この時の最大電流効率は 0. 052cd/ Aであった。発光スぺクトノレは 415nmにピークを持つものであり、発光色の色度座標 は（0. 17, 0. 11)であった。 When a current was passed between the ITO electrode 2 of the device as the positive electrode and the A1 electrode 6 as the negative electrode, and the voltage between the electrodes was increased, the device emitted light at +21 V at 4 cd / m 2 . The maximum current efficiency at this time was 0.052 cd / A. The emission spectrum had a peak at 415 nm, and the chromaticity coordinates of the emission color were (0.1, 0.11).
[0119] 実施例 21 [0119] Example 21
1 , 3_ビス（8 '一キノリルェチニル)ベンゼン (前記式（11)の化合物）を有機発光層 に含む有機エレクト口ルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing 1,3_bis (8′-quinolylethynyl) benzene (compound of the formula (11)) in an organic light emitting layer.
CBP中に 1， 3_ビス（8 '—キノリルェチュル）ベンゼンを 9重量％含む発光層 4を用 レ、た以外は実施例 17と同様にして有機エレクト口ルミネッセンス素子を作製した。 前記素子の IT〇電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 20Vにおいて 0. 4cd/m2で発光した。この時の最大電流効率は 0. 032c d/ Aであった。発光スぺクトノレは 451nmにピークを持つものであり、発光色の色度 座標は（0. 18, 0. 17)であった。 An organic electroluminescent device was prepared in the same manner as in Example 17, except that the light-emitting layer 4 containing 9% by weight of 1,3_bis (8'-quinolylethur) benzene in CBP was used. Energize the above-mentioned device with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode to increase the voltage between the electrodes. In particular, it emitted light at 0.4 cd / m 2 at +20 V. The maximum current efficiency at this time was 0.032 cd / A. The emission spectrum had a peak at 451 nm, and the chromaticity coordinates of the emission color were (0.18, 0.17).
[0120] 実施例 22 Example 22
8- (2'—フルオロフェニルェチニル)キノリン (前記式（16)の化合物）を有機発光層 に含む有機エレクト口ルミネッセンス素子の作製。  Preparation of an organic electroluminescent device containing 8- (2'-fluorophenylethynyl) quinoline (compound of the formula (16)) in an organic light emitting layer.
CBP中に 8—（2 '—フルオロフェニルェチュル）キノリンを 9重量％含む発光層 4を用 レ、た以外は実施例 17と同様にして有機エレクト口ルミネッセンス素子を作製した。 前記素子の IT〇電極 2を正極、 A1電極 6を負極として通電し、電極間電圧を上げて レヽくと、 + 18Vにおいて 3cd/m2で発光した。この時の最大電流効率は 0. 018cd/ Aであった。発光スペクトルは 421nmにピークを持つものであり、発光色の色度座標 は（0. 19， 0. 18)であった。 An organic electroluminescent device was prepared in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8- (2′-fluorophenylethyl) quinoline in CBP was used. The device was energized with the IT electrode 2 as the positive electrode and the A1 electrode 6 as the negative electrode. When the voltage between the electrodes was raised and increased, the device emitted light at 3 cd / m 2 at +18 V. The maximum current efficiency at this time was 0.018 cd / A. The emission spectrum had a peak at 421 nm, and the chromaticity coordinates of the emission color were (0.19, 0.18).
産業上の利用可能性  Industrial applicability
[0121] 本発明によれば、紫外線照射下で強い青色の発光を示す前記式（1)で示されるァ ルキニル基置換縮合へテロ環化合物を有機化合物層に含有する有機エレクト口ルミ ネッセンス素子を提供することができる。  According to the present invention, there is provided an organic electroluminescent device containing an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1), which emits strong blue light under ultraviolet irradiation, in an organic compound layer. Can be provided.
[0122] 本発明によれば、また、クロ口ホルム溶液中で紫外線照射により強い青色発光を示 し、有機エレクト口ルミネッセンス素子材料として極めて有用な前記式（1 ' )で示される アルキニル基置換縮合へテロ環化合物及びそれに包含される前記式（2) (4)で示 される新規なアルキニル基置換縮合へテロ環化合物を提供することができる。  According to the present invention, the alkynyl group-substituted condensation represented by the above formula (1 ′), which shows strong blue light emission by ultraviolet irradiation in a black form solution and is extremely useful as an organic electroluminescent device material, The present invention can provide a heterocyclic compound and a novel alkynyl group-substituted condensed heterocyclic compound represented by the formulas (2) and (4) included therein.
[0123] 本発明によれば、更に、紫外線照射下で強い青色の発光を示し、有機エレクトロル ミネッセンス素子用材料として有用である前記式（1)で示される新規なアルキニル基 置換縮合へテロ環化合物を収率良く合成する方法を提供することができる。  According to the present invention, further, a novel alkynyl-substituted condensed heterocycle represented by the above formula (1), which exhibits strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescence device A method for synthesizing a compound with high yield can be provided.

Claims

請求の範囲  The scope of the claims
[1] 1対の電極間に有機化合物薄層を有する有機エレクト口ルミネッセンス素子であつ て、その有機化合物層が次式（1)：  [1] An organic electroluminescent device having an organic compound thin layer between a pair of electrodes, wherein the organic compound layer has the following formula (1):
Figure imgf000039_0001
式中、 n1は 1一 3の整数を表わし、 n1が 1の場合、 Aは水素原子、アルキル基、シク 口アルキル基、ァリーノレ基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わ し、 n1が 2又は 3の場合、 Aは 2価又は 3価のァリール基又はへテロ環基を表わし、 X 及び Yはそれぞれ CH又は Nを表わす、
Figure imgf000039_0001
In the formula, n 1 represents an integer of 13; and when n 1 is 1, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an arylene group, an aralkyl group, an alkylsilyl group, or a heterocyclic group. And when n 1 is 2 or 3, A represents a divalent or trivalent aryl or heterocyclic group, and X and Y represent CH or N, respectively.
で示されるアルキニル基置換縮合へテロ環化合物を含有することを特徴とする有機 エレクトロノレミネッセンス素子。  An organic electroluminescence device comprising an alkynyl group-substituted condensed heterocyclic compound represented by the formula:
[2] 式（1)で示される化合物が、次式（2)：  [2] The compound represented by the formula (1) is represented by the following formula (2):
Figure imgf000039_0002
Figure imgf000039_0002
式中、 R1は、アルキル基、シクロアルキル基、無置換のフヱニル基以外のァリール 基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わす、 In the formula, R 1 represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group;
で示されるものである請求の範囲第 1項に記載の有機エレクト口ルミネッセンス素子。  2. The organic electroluminescent device according to claim 1, wherein the device is represented by:
[3] 式（1)で示される化合物が、次式 (3)：  [3] The compound represented by the formula (1) is represented by the following formula (3):
Figure imgf000039_0003
Figure imgf000039_0003
式中、 n2は 2 3の整数を表す。 In the formula, n 2 represents an integer of 23.
で示されるものである請求の範囲第 1項に記載の有機エレクト口ルミネッセンス素子。 [4] 式（1)で示される化合物が、次式 (4)： 2. The organic electroluminescent device according to claim 1, wherein the device is represented by: [4] A compound represented by the formula (1) is represented by the following formula (4):
Figure imgf000040_0001
Figure imgf000040_0001
で示されるものである請求の範囲第 1項に記載の有機エレクト口ルミネッセンス素子。  2. The organic electroluminescent device according to claim 1, wherein the device is represented by:
[5] 次式 (1 ' )：  [5] The following equation (1 '):
Figure imgf000040_0002
Figure imgf000040_0002
式中、 n1は 1一 3の整数を表わし、 n1が 1の場合、 R1は、アルキル基、シクロアルキ ル基、無置換のフエニル基以外のァリール基、ァラルキル基、アルキルシリル基、又 はへテロ環基を表わし、 n1が 2又は 3の場合、 R1は 2価又は 3価のァリール基又はへ テロ環基を表わし、 X及び Yは前記と同義である、 In the formula, n 1 represents an integer of 13; when n 1 is 1, R 1 is an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or Represents a heterocyclic group, and when n 1 is 2 or 3, R 1 represents a divalent or trivalent aryl group or a heterocyclic group, and X and Y are as defined above.
で示されるアルキニル基置換縮合へテロ環化合物。  An alkynyl group-substituted fused heterocyclic compound represented by the formula:
[6] 式（1 ' )で示される化合物が、次式 (2)：  [6] The compound represented by the formula (1 ′) is represented by the following formula (2):
Figure imgf000040_0003
Figure imgf000040_0003
式中、 R1は、アルキル基、シクロアルキル基、無置換のフヱニル基以外のァリール 基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わす、 In the formula, R 1 represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group;
で示されるものである請求の範囲第 5項に記載のアルキニル基置換縮合へテロ環化 合物。  6. The alkynyl group-substituted condensed heterocyclic compound according to claim 5, which is represented by the formula:
[7] 式（1 ' )で示される化合物が、次式 (3)：
Figure imgf000041_0001
[7] The compound represented by the formula (1 ′) is represented by the following formula (3):
Figure imgf000041_0001
式中、 n2は 2 3の整数を表す。 In the formula, n 2 represents an integer of 23.
で示されるものである請求の範囲第 5項に記載のアルキニル基置換縮合へテロ環化 合物。  6. The alkynyl group-substituted condensed heterocyclic compound according to claim 5, which is represented by the formula:
[8] 式（1 ' )で示される化合物が、次式 (4)：  [8] The compound represented by the formula (1 ′) is represented by the following formula (4):
Figure imgf000041_0002
Figure imgf000041_0002
で示されるものである請求の範囲第 5項に記載のアルキニル基置換縮合へテロ環化 合物。  6. The alkynyl group-substituted condensed heterocyclic compound according to claim 5, which is represented by the formula:
[9] 触媒として 0価パラジウム化合物を用いて、次式（5)：  [9] Using a zero-valent palladium compound as a catalyst, the following formula (5):
Figure imgf000041_0003
Figure imgf000041_0003
式中、 X及び Yはそれぞれ CH又は Nを表わす、  Wherein X and Y each represent CH or N;
で示されるトリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物と、次式（ 6) :
Figure imgf000041_0004
A trifluoromethanesulfonyloxy group-substituted fused heterocyclic compound represented by the following formula (6):
Figure imgf000041_0004
式中、 n1は 1一 3の整数を表わし、 n1が 1の場合、 Aは水素原子、アルキル基、シク 口アルキル基、ァリーノレ基、ァラルキル基、アルキルシリル基、又はへテロ環基を表わ し、 n1が 2又は 3の場合、 Aは 2価又は 3価のァリール基又はへテロ環基を表わす、 で示される末端アセチレン化合物とを、塩基性溶媒中で反応させることを特徴とする 次式 (1) : In the formula, n 1 represents an integer of 13; when n 1 is 1, A represents a hydrogen atom, an alkyl group, Represents an alkyl group, an arylene group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n 1 is 2 or 3, A represents a divalent or trivalent aryl group or a heterocyclic group Wherein a terminal acetylene compound represented by the following formula is reacted in a basic solvent:
(り
Figure imgf000042_0001
式中、
Figure imgf000042_0002
A、 X及び Yは前記と同義である。 (R
Figure imgf000042_0001
Where
Figure imgf000042_0002
A, X and Y are as defined above.
で示されるアルキニル基置換縮合へテロ環化合物の製造法。  A method for producing an alkynyl group-substituted fused heterocyclic compound represented by the formula:
[10] 0価パラジウム化合物力 0価パラジウムホスフィン錯体又は 0価パラジウムォレフィ ン錯体であることを特徴とする請求の範囲第 9項記載のアルキニル基置換縮合へテ 口環化合物の製造法。 [10] The method for producing an alkynyl group-substituted condensed heterocyclic compound according to claim 9, wherein the compound is a zero-valent palladium phosphine complex or a zero-valent palladium olefin complex.
[11] 塩基性溶媒がピぺリジン又はピロリジンであることを特徴とする請求の範囲第 9項又 は第 10項記載のアルキニル基置換縮合へテロ環化合物の製造法。  [11] The method for producing an alkynyl group-substituted condensed heterocyclic compound according to claim 9 or 10, wherein the basic solvent is piperidine or pyrrolidine.
[12] 触媒として 0価パラジウム化合物を用いて、塩基性溶媒中、次式 (5)： [12] Using a zero-valent palladium compound as a catalyst in a basic solvent, the following formula (5):
Figure imgf000042_0003
Figure imgf000042_0003
式中、 X及び Υはそれぞれ CH又は Νを表わす、  Wherein X and Υ represent CH or そ れ ぞ れ, respectively.
で示されるトリフルォロメタンスルホニルォキシ基置換縮合へテロ環化合物とアルキ ルシリルアセチレン化合物とを反応させてアルキルシリルェチュル基置換縮合へテロ 環化合物とした後、このアルキルシリルェチニル基置換縮合へテロ環化合物を加水 分解することを特徴とする次式 (7)：
Figure imgf000043_0001
The trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound shown in the above is reacted with an alkylsilyl acetylene compound to form an alkylsilyl eturyl group-substituted condensed heterocyclic compound. The following formula (7) characterized in that the condensed heterocyclic compound is hydrolyzed:
Figure imgf000043_0001
式中、 X及び Yは前記と同義である、  Wherein X and Y are as defined above,
で示されるェチニル基置換縮合へテロ環化合物の製造法。  A method for producing an ethynyl group-substituted fused heterocyclic compound represented by the formula:
[13] 0価パラジウム化合物力 0価パラジウムホスフィン錯体又は 0価パラジウムォレフィ ン錯体であることを特徴とする請求の範囲第 12項記載のェチュル基置換縮合へテロ 環化合物の製造法。 13. The process for producing a condensed heterocyclic compound substituted with an ethur group according to claim 12, wherein the compound is a zero-valent palladium phosphine complex or a zero-valent palladium olefin complex.
[14] 塩基性溶媒がピぺリジン又はピロリジンであることを特徴とする請求の範囲第 12項 又は第 13項記載のェチニル基置換縮合へテロ環化合物の製造法。 第 12項記載のェチュル基置換縮合へテロ環化合物の製造法。  14. The method for producing a condensed ethynyl group-substituted heterocyclic compound according to claim 12 or 13, wherein the basic solvent is piperidine or pyrrolidine. 13. The process for producing a condensed heterocyclic compound substituted with an ethur group according to claim 12.
[16] 次式（7) : [16] The following equation (7):
Figure imgf000043_0002
Figure imgf000043_0002
式中、 X及び Υはそれぞれ CH又は Νを表わす、  Wherein X and Υ represent CH or そ れ ぞ れ, respectively.
で示されるェチュル基置換縮合へテロ環化合物と次式（9)
Figure imgf000043_0003
式中、 X'はハロゲン原子を表し、 Rは、ハロゲン原子、ジアルキルアミノ基、ァリール ォキシ基、アルコキシ基、アルケニル基、アシノレ基、ニトロ基、シァノ基、アルキル基、 シクロアルキル基、又はァリール基を表し、複数の Rは、それぞれ同一でも異なって いてもよぐ η3は 1一 5の整数を表す、 And a heterocyclic compound substituted with an ethur group represented by the following formula (9)
Figure imgf000043_0003
In the formula, X ′ represents a halogen atom, and R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acylone group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group. And a plurality of Rs may be the same or different, and η 3 represents an integer of 1 to 5.
で示されるハロゲン化芳香族環化合物とを、触媒として 0価パラジウム化合物を用い て、塩基性溶媒中で反応させることを特徴とする、前記式（1)において、 Aがァリーノレ 基であり、 n1が 1である次式（8)：Using a halogenated aromatic ring compound represented by Wherein, in the above formula (1), A is an arylene group, and n 1 is 1 in the following formula (8):
Figure imgf000044_0001
Figure imgf000044_0001
式中、 X、 Y、 R及び η3は前記と同義である、 Wherein X, Y, R and η 3 are as defined above,
で示されるフヱニルェチュル基置換縮合へテロ環化合物の製造法。  The method for producing a fused heterocyclic compound substituted with a phenylethur group represented by the formula:
[17] 0価パラジウム化合物力 0価パラジウムホスフィン錯体又は 0価パラジウムォレフィ ン錯体であることを特徴とする請求の範囲第 16項記載のフヱニルェチュル基置換縮 合へテロ環化合物の製造法。  17. The method for producing a heterocyclic compound substituted with a phenylethur group according to claim 16, wherein the compound is a zero-valent palladium phosphine complex or a zero-valent palladium olefin complex.
[18] 塩基性溶媒がピぺリジン又はピロリジンであることを特徴とする請求の範囲第 16項 又は第 17項記載のフエ二ルェチニル基置換縮合へテロ環化合物の製造法。  [18] The method for producing a phenylethynyl group-substituted condensed heterocyclic compound according to claim 16 or 17, wherein the basic solvent is piperidine or pyrrolidine.
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