WO2010008065A1 - Procédé de fabrication de complexe de carbène hétérocyclique à teneur en or-azote éthynyle substitué - Google Patents

Procédé de fabrication de complexe de carbène hétérocyclique à teneur en or-azote éthynyle substitué Download PDF

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WO2010008065A1
WO2010008065A1 PCT/JP2009/062951 JP2009062951W WO2010008065A1 WO 2010008065 A1 WO2010008065 A1 WO 2010008065A1 JP 2009062951 W JP2009062951 W JP 2009062951W WO 2010008065 A1 WO2010008065 A1 WO 2010008065A1
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group
gold
substituted
alkyl
containing heterocyclic
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PCT/JP2009/062951
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整 藤村
貴志 本間
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宇部興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table

Definitions

  • the present invention relates to a method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex useful as a material for an electroluminescent element (organic electroluminescence element) or the like.
  • L represents a nitrogen-containing heterocyclic carbene ligand
  • R is an alkyl group, cycloalkyl group, aryl group, aralkyl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, arylalkylaminocarbonyl group, alkyl mercaptocarbonyl group, An arylmercaptocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a formyl group, an alkylcarbonyl group or an arylcarbonyl group, wherein one or more hydrogen atoms on the carbon atom of R are a halogen atom, an alkyl group, a cycloalkyl group, Alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkylcarbon
  • Patent Document 1 International Publication No. 2006/080515 Pamphlet
  • An object of the present invention is to provide a production method in which a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex can be easily obtained without requiring a plurality of steps.
  • the subject of the present invention is general formula (1) in the presence of a base:
  • R is an alkyl group, cycloalkyl group, aryl group, aralkyl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, arylalkylaminocarbonyl group, alkyl mercaptocarbonyl group, An arylmercaptocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a formyl group, an alkylcarbonyl group or an arylcarbonyl group, wherein one or more hydrogen atoms on the carbon atom of R may be substituted, When the atom is substituted, adjacent substituents may be bonded to form a ring, and substituted ethyne represented by the general formula (2):
  • L represents a nitrogen-containing heterocyclic carbene ligand, and is represented by reacting a gold (I) halide-nitrogen-containing heterocyclic carbene complex represented by the general formula (3):
  • R and L are solved by the method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex represented by the same meaning as described above.
  • R is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an arylalkylaminocarbonyl group, An alkylmercaptocarbonyl group, an arylmercaptocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a formyl group, an alkylcarbonyl group or an arylcarbonyl group, wherein one or more hydrogen atoms on the carbon atom of R are a halogen atom or a nitro group Alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkyl
  • a plurality of hydrogen atoms on the carbon atom of R are alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto Group, aryl mercapto group, alkylsulfonyl group, arylsulfonyl group, formyl group, alkylaminocarbonyl group, arylaminocarbonyl group, alkoxycarbonyl group, aryloxy group
  • the above-mentioned substituted ethynyl gold-nitrogen-containing heterocyclic carbene may be bonded to each other to form a ring.
  • the present invention relates to a method for producing a complex.
  • one or more hydrogen atoms on the carbon atom of R are a halogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkylcarbonyl group, An arylcarbonyl group, an alkylmercapto group, an arylmercapto group, an alkylsulfonyl group or an arylsulfonyl group, wherein a plurality of hydrogen atoms on the carbon atom of R are an alkyl group, an alkenyl group, an aryl group, an aralkyl group When substituted with an alkoxy group, aryloxy group, dialkylamino group, formyl group, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto group, aryl mercapto group
  • L represents a nitrogen-containing heterocyclic carbene ligand (details will be described later).
  • R is an alkyl group, cycloalkyl group, aryl group, aralkyl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, arylaminocarbonyl group, arylalkylaminocarbonyl group, alkylmercaptocarbonyl.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Is mentioned.
  • alkyl having 1 to 6 carbon atoms is preferable. These groups include isomers thereof.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms.
  • a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclodecyl group, An undecyl group, a cyclododecyl group, etc. are mentioned.
  • the aryl group is preferably an aryl group having 6 to 18 carbon atoms, such as a phenyl group, tolyl group, xylyl group, naphthyl group, dimethylnaphthyl group, anthracenyl group, phenanthrenyl group, chrycenyl group, tetraphenyl group, naphthacenyl. Group, biphenyl group and the like. In particular, aryl having 6 to 14 carbon atoms is preferred. These groups include isomers thereof.
  • the aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a naphthylmethyl group, an indenylmethyl group, and a biphenylmethyl group.
  • the heterocyclic group is preferably a saturated or unsaturated cyclic group consisting of 3 to 10 ring members containing at least one heteroatom selected from N, O or S.
  • a pyrrolyl group examples include a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, a benzothiophenyl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a pyridazyl group, a quinolyl group, an isoquinolyl group, a quinazolyl group, and a quinoxalyl group.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentoxycarbonyl group, an isopropoxycarbonyl group, an isobutoxy group. Examples thereof include a carbonyl group and a tert-butoxycarbonyl group.
  • the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 11 carbon atoms, and examples thereof include a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group.
  • the alkylaminocarbonyl group is preferably an alkylaminocarbonyl group having 2 to 10 carbon atoms, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, and a dipropylaminocarbonyl group.
  • the amino moiety in the alkylaminocarbonyl group may be mono-substituted or di-substituted with an alkyl group (same as the above alkyl group).
  • the arylaminocarbonyl group is preferably an arylaminocarbonyl group having 7 to 18 carbon atoms, and examples thereof include a phenylaminocarbonyl group, a diphenylaminocarbonyl group, a ditolylaminocarbonyl group, and a naphthylaminocarbonyl group.
  • the amino moiety in the arylaminocarbonyl group may be mono-substituted or di-substituted with an aryl group (same as the aryl group).
  • the arylalkylaminocarbonyl group is preferably an arylalkylaminocarbonyl group having 8 to 18 carbon atoms, such as a phenylmethylaminocarbonyl group, a phenylethylaminocarbonyl group, a tolylmethylaminocarbonyl group, a tolylethylaminocarbonyl group, A naphthylmethylaminocarbonyl group, a naphthylethylaminocarbonyl group, etc. are mentioned.
  • the alkyl mercaptocarbonyl group is preferably an alkyl mercaptocarbonyl group having 2 to 18 carbon atoms, and examples thereof include a methyl mercaptocarbonyl group, an ethyl mercaptocarbonyl group, and a propyl mercaptocarbonyl group.
  • the arylmercaptocarbonyl group is preferably an arylmercaptocarbonyl group having 2 to 18 carbon atoms, and examples thereof include a phenylmercaptocarbonyl group, a tolylmercaptocarbonyl group, and a naphthyl mercaptocarbonyl group.
  • the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 12 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group.
  • the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 18 carbon atoms, and examples thereof include a phenylsulfonyl group, a tolylsulfonyl group, and a naphthylsulfonyl group.
  • the alkylcarbonyl group is particularly preferably an alkylcarbonyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, and a butanoyl group. These groups include isomers thereof.
  • the arylcarbonyl group is particularly preferably an arylcarbonyl group having 7 to 11 carbon atoms, and examples thereof include a benzoyl group, a fluorobenzoyl group, and a naphthoyl group. These groups include isomers thereof.
  • one or more hydrogen atoms on the carbon atom of R may be substituted.
  • the substituents may be the same or different.
  • Substituents include halogen atoms, nitro groups, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, dialkylamino groups, alkylcarbonyl groups, arylcarbonyl groups, alkyl mercapto groups, An arylmercapto group, alkylsulfonyl group, arylsulfonyl group, formyl group, alkylaminocarbonyl group, arylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylmercaptocarbonyl group or arylmercaptocarbonyl group may be substituted.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl. Group, decyl group, undecyl group, dodecyl group and the like. These substituents include isomers thereof.
  • the cycloalkyl group is particularly preferably a cycloalkyl group having 3 to 7 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms.
  • alkenyl group having 2 to 20 carbon atoms, particularly 2 to 12 carbon atoms.
  • vinyl group propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, particularly 6 to 16 carbon atoms, such as phenyl group, tolyl group, xylyl group, naphthyl group, dimethylnaphthyl group, anthryl group, phenanthryl group, fluorenyl group, Examples include a pyrenyl group and a biphenyl group. These substituents include isomers thereof.
  • the aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a naphthylmethyl group, an indenylmethyl group, and a biphenylmethyl group.
  • an alkoxy group having 1 to 10 carbon atoms is particularly preferable.
  • substituents include isomers thereof.
  • the aryloxy group is particularly preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group, a triloxy group, a xylyloxy group, a naphthoxy group, and a dimethylnaphthoxy group. These substituents include isomers thereof.
  • the dialkylamino group is particularly preferably a dialkylamino group having 2 to 10 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group, and a dipropylamino group. These substituents include isomers thereof.
  • the alkylcarbonyl group is particularly preferably an alkylcarbonyl group having 2 to 10 carbon atoms, and examples thereof include an acetyl group, a propanoyl group, and a butanoyl group. These substituents include isomers thereof.
  • the arylcarbonyl group is particularly preferably an arylcarbonyl group having 7 to 11 carbon atoms, and examples thereof include a benzoyl group, a fluorobenzoyl group, and a naphthoyl group. These substituents include isomers thereof.
  • the alkyl mercapto group is preferably an alkyl mercapto group having 1 to 6 carbon atoms, and examples thereof include a methyl mercapto group, an ethyl mercapto group, a propyl mercapto group, a butyl mercapto group, a pentyl mercapto group, and a hexyl mercapto group. These substituents include isomers thereof.
  • the aryl mercapto group is preferably an aryl mercapto group having 6 to 14 carbon atoms, and examples thereof include a phenyl mercapto group, a tolyl mercapto group, a xylyl mercapto group, and a naphthyl mercapto group. These substituents include isomers thereof.
  • the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 12 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group.
  • the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 18 carbon atoms, and examples thereof include a phenylsulfonyl group, a tolylsulfonyl group, and a naphthylsulfonyl group.
  • the alkylaminocarbonyl group is preferably an alkylaminocarbonyl group having 2 to 10 carbon atoms, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, and a dipropylaminocarbonyl group.
  • the amino moiety in the alkylaminocarbonyl group may be mono-substituted or di-substituted with an alkyl group (same as the above alkyl group).
  • the arylaminocarbonyl group is preferably an arylaminocarbonyl group having 7 to 18 carbon atoms, and examples thereof include a phenylaminocarbonyl group, a diphenylaminocarbonyl group, a ditolylaminocarbonyl group, and a naphthylaminocarbonyl group.
  • the amino moiety in the arylaminocarbonyl group may be mono-substituted or di-substituted with an aryl group (same as the aryl group).
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentoxycarbonyl group, an isopropoxycarbonyl group, an isobutoxy group. Examples thereof include a carbonyl group and a tert-butoxycarbonyl group.
  • the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 11 carbon atoms, and examples thereof include a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group.
  • the alkyl mercaptocarbonyl group is preferably an alkyl mercaptocarbonyl group having 2 to 18 carbon atoms, and examples thereof include a methyl mercaptocarbonyl group, an ethyl mercaptocarbonyl group, and a propyl mercaptocarbonyl group.
  • the arylmercaptocarbonyl group is preferably an arylmercaptocarbonyl group having 2 to 18 carbon atoms, and examples thereof include a phenylmercaptocarbonyl group, a tolylmercaptocarbonyl group, and a naphthyl mercaptocarbonyl group.
  • the substituent may be further substituted with a halogen atom, a nitro group, or the like.
  • a plurality of hydrogen atoms on the carbon atom of R are, for example, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkylcarbonyl group, arylcarbonyl group, alkyl
  • Adjacent substituents may be bonded to form a ring.
  • Examples of the ring when the adjacent substituents are bonded to form a ring include, for example, a cyclopentene ring, cyclohexene ring, cycloheptene ring, benzene ring, naphthalene ring, tetrahydrofuran ring, benzopyran ring, and N-methylpyrrolidine ring. And N-methylpiperidine ring. These rings may be further substituted with a halogen atom, a nitro group or the like.
  • R is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a heterocyclic group containing an N atom as a hetero atom, a carbon atom
  • An alkoxycarbonyl group having 2 to 7 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, or an arylsulfonyl group having 6 to 10 carbon atoms is preferable.
  • One or more hydrogen atoms on the atom are a halogen atom (especially a fluorine atom), nitro group, methoxy group, benzoyl group, fluorobenzoyl group, acetyl group, diethylaminocarbonyl group, diphenylaminocarbonyl group, methyl mercapto group, methyl Sulfonyl group, methoxycarbonyl group, methyl mercaptocarbonyl group or phenyl merca It may be substituted by preparative carbonyl group.
  • a halogen atom especially a fluorine atom
  • the nitrogen-containing heterocyclic carbene ligand L is, for example, the general formula (1) or (2):
  • R 1 and R 2 may be the same or different and each represents an alkyl group, a cycloalkyl group, a polycycloalkyl group, or an aryl group;
  • R 3 , R 4 , R 5 and R 6 may be the same or different and each is a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, nitro group, A cyano group or a dialkylamino group, and adjacent groups may be bonded to form a ring;
  • R 1 to R 6 represent a group containing a carbon atom, one or more hydrogen atoms on the carbon atom are a halogen atom, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group or aryl It may be substituted with an oxy group.
  • R 1 and R 2 represent an alkyl group, a cycloalkyl group, a polycycloalkyl group or an aryl group, and the alkyl group, the cycloalkyl group and the aryl group are defined as substituents on the carbon atom of R.
  • the polycycloalkyl group is preferably a polycycloalkyl group having 6 to 10 carbon atoms, and includes a bicyclo- [2.1.1] -hexyl group, a bicyclo- [2.2.1] -heptyl group, and a bicyclo- [ 2.2.2] -octyl group, bicyclo- [3.3.0] -octyl group, bicyclo- [4.3.0] -nonyl group, bicyclo- [4.4.0] -octyl group, adamantyl Groups and the like.
  • R 3 , R 4 , R 5 and R 6 represent a halogen atom, alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, nitro group, cyano group or dialkylamino group, , Are the same as those defined as the substituent on the carbon atom of R.
  • One or more hydrogen atoms on the carbon atoms of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group.
  • An alkoxy group or an aryloxy group may be substituted, and these groups are also synonymous with those defined as the substituent on the carbon atom of R.
  • R 1 and R 2 a tert-butyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group or an adamantyl group is preferable.
  • R 3 , R 4 , R 5 and R 6 Is preferably a hydrogen atom or a halogen atom, particularly a chlorine atom.
  • nitrogen-containing heterocyclic carbene ligand (L) in the present invention include, for example, formulas (6) to (15)
  • the gold halide (I) -nitrogen-containing heterocyclic carbene complex of the general formula (2) used in the present invention may be a commercially available product, or can be synthesized by a known method (for example, Organometallics, 2005, 24, 2411).
  • X in General formula (2) shows a halogen atom, and a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • the amount of the substituted ethyne is preferably 1 to 3 with respect to 1 mol of the gold (I) halide-nitrogen-containing heterocyclic carbene complex. Mol, more preferably 1 to 1.5 mol.
  • a solvent can be used.
  • the solvent to be used is not particularly limited as long as it does not inhibit the reaction.
  • alcohols such as methanol, ethanol, propanol and butanol; tetrahydrofuran, furan, dioxane, tetrahydropyran, diethyl ether, diisopropyl ether, dibutyl ether and the like Ethers; aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane and dichloropropane; chlorobenzene and the like The halogenated aromatic hydrocarbons are used.
  • an isomer may be used.
  • the amount of the solvent used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 1 to 30 L, more preferably 1 mol per 1 mol of the gold halide (I) -nitrogen-containing heterocyclic carbene complex. 5 to 20 L.
  • the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention involves mixing a substituted ethyne, a gold halide (I) -nitrogen-containing heterocyclic carbene complex, a base and a solvent, and reacting with stirring. It can be done by the method.
  • the reaction temperature at that time is preferably 0 to 120 ° C., more preferably 20 to 100 ° C., and the reaction pressure is not particularly limited.
  • the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention is carried out in the presence of a base.
  • a metal alkoxide is preferable as the base.
  • Alkali metal alkoxides are particularly preferable. Specific examples include lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, and potassium butoxide. It is done. Regarding the alkali metal propoxide and butoxide, isomers of alkoxy groups are also included.
  • the amount of the base to be used is preferably 1 to 3 mol, more preferably 1 to 1.5 mol, per 1 mol of the gold (I) halide-nitrogen-containing heterocyclic carbene complex.
  • the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention is isolated and produced by a known method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, sublimation, and chromatography after completion of the reaction. .
  • the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex obtained by the production method of the present invention includes the following formulas (16) to (61)
  • the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex obtained by the production method of the present invention has CIE chromaticity coordinates (0.150, 0.060) to (0) in chloroform at a temperature of 77 K (Kelvin) under ultraviolet irradiation. .218, 0.385) blue light emission and (0.187, 0.452) to (0.324, 0.554) green light emission, and can be suitably used as an organic electroluminescence device. It was suggested.
  • Example 2 Synthesis of Au (IMes) (PE) [(phenylethynyl) [1,3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] gold]) 1,3-bis (1,3,5-trimethylphenyl) imidazole-2-ylidene gold chloride (I) instead of 1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene gold chloride (I) )
  • the same operation as in Example 1 was carried out except that [IMesAuCl: 80.5 mg, 0.15 mmol] was used to obtain 0.077 g of the desired product as a white solid (yield 85%).
  • Example 4 Synthesis of Au (ItBu) (PE) [(phenylethynyl) [1,3-di-tert-butylimidazol-2-ylidene] gold] Instead of 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene chloride (I), 1,3-di-tert-butylimidazol-2-ylidene chloride (I) [ItBuAuCl: 93. The same operation as in Example 1 was performed except that 5 mg, 0.15 mmol] was used, to obtain 0.064 g of the target product as a white solid (yield 89%).
  • Example 5 Synthesis of Au (IPr) (4F-PE) [(4-fluorophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • the white solid obtained was recrystallized from the n-hexane-diethyl ether-methylene chloride system after the same operation as in Example 1 except that 4-fluorophenylethine (19 mg, 0.158 mmol) was used instead of phenylethine. Operation was performed to obtain 0.093 g of the target product as a white solid (yield 88%).
  • Example 6 Synthesis of Au (IMes) (4F-PE) [(4-fluorophenylethynyl) [1,3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] gold]) 1,3-bis (1,3,5-trimethylphenyl) imidazole-2-ylidene gold chloride (I) instead of 1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene gold chloride (I) ) Except that [IMesAuCl: 80.5 mg, 0.15 mmol] was used, the same operation as in Example 5 was performed to obtain 0.086 g of the target product as a white solid (yield 92%).
  • Example 7 Synthesis of Au (IPr) (4MeO-PE) [(4-methoxyphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr 4MeO-PE
  • 4-methoxyphenylethyne 21 mg, 0.158 mmol
  • the obtained white solid was recrystallized in an n-hexane-diethyl ether-methylene chloride system. The operation was performed to obtain 0.087 g of the desired product as a white solid (yield 81%).
  • Example 8 Synthesis of Au (IMes) (4MeO-PE) [(4-methoxyphenylethynyl) [1,3-bis (2,4,6-trimethylphenyl) imidazol-2-ylidene] gold]) 1,3-bis (1,3,5-trimethylphenyl) imidazole-2-ylidene gold chloride (I) instead of 1,3-bis (2,6-diisopropylphenyl) imidazole-2-ylidene gold chloride (I) ) Except that [IMesAuCl: 80.5 mg, 0.15 mmol] was used, the same operation as in Example 7 was performed to obtain 0.081 g of the target product as a white solid (yield 85%).
  • Example 9 Synthesis of Au (IPr) (2PyE) [(2-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 2-ethynylpyridine (16 mg, 0.158 mmol) was used instead of phenylethine
  • the obtained white solid was recrystallized in an n-hexane-ethyl acetate system, 0.086 g of the target product was obtained as a white solid (yield 83%).
  • Example 10 Synthesis of Au (IPr) (3PyE) [(3-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr IPr
  • 3-ethynylpyridine 16 mg, 0.158 mmol
  • 2-ethynylpyridine the obtained white solid was recrystallized in an n-hexane-methylene chloride system. This yielded 0.094 g of the desired product as a white solid (yield 91%).
  • Example 11 Synthesis of Au (IPr) (5F-2PyE) [(5-Fluoro-2-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 2-ethynyl-5-fluoropyridine (19 mg, 0.158 mmol) was used instead of phenylethine
  • Example 12 Synthesis of Au (IPr) (6F-3PyE) [(6-Fluoro-3-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr IPr
  • 6F-3PyE 3-ethynyl-6-fluoropyridine (19 mg, 0.158 mmol) was used instead of phenylethine
  • the resulting precipitate was filtered to obtain 0.098 g of the target product as a yellow solid (yield 93%).
  • Example 13 Synthesis of Au (IPr) (4Ph-PE) [(4-phenylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr 4Ph-PE
  • 4-phenylphenylethine 28 mg, 0.158 mmol
  • 0.11 g of the target product as a white solid was obtained (yield 96%).
  • Example 14 (Au (IPr) (4NO 2 -PE) [(4- nitro-phenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold] Synthesis of) After the same operation as in Example 1 except that 4-nitrophenylethine (16 mg, 0.158 mmol) was used in place of phenylethine, the obtained white solid was recrystallized in an n-hexane-ethyl acetate system. As a result, 0.11 g of the target product was obtained as a white solid (yield 98%).
  • Example 15 Synthesis of (Au (IPr) (2,4F 2 -PE) [(2,4-difluorophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold) )
  • 2,4-difluoro-phenylethyne 22 mg, 0.158 mmol
  • the obtained white solid was recrystallized in an n-hexane-ethyl acetate system. Operation was performed to obtain 0.10 g of the desired product as a white solid (yield 94%).
  • Example 16 Synthesis of Au (IPr) (1NpE) [(1-naphthylethynyl) [1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene] gold]
  • IPr IPr
  • 1NpE 1-ethynylnaphthalene
  • phenylethine 1-ethynylnaphthalene
  • Example 17 (Synthesis of 3-benzoylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3BzPE)])
  • 3-benzoylphenylethine 33 mg, 0.158 mmol
  • Example 18 (3- (4′-fluorobenzoyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) [3 (4′FBz) PE] ]
  • 3- (4′-fluorobenzoyl) phenylethyne 35 mg, 0.158 mmol
  • the obtained white solid was subjected to column chromatography using silica gel.
  • Example 19 (Synthesis of 3-acetylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3AcPE)])
  • 3-acetylphenylethine 23 mg, 0.158 mmol
  • Example 20 (Synthesis of 3- (diethylaminocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3DEACPE)])
  • 3- (diethylaminocarbonyl) phenylethyne 32 mg, 0.158 mmol
  • Example 21 (Synthesis of 3- (diphenylaminocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3DPACPE)])
  • 3- (diphenylaminocarbonyl) phenylethyne 47 mg, 0.158 mmol
  • Example 22 (Synthesis of 3- (methoxycarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3MCPE)])
  • 3- (methoxycarbonyl) phenylethyne 25 mg, 0.158 mmol
  • Example 23 (Synthesis of 3- (phenoxycarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3PCPE)])
  • 3- (phenoxycarbonyl) phenylethyne 35 mg, 0.158 mmol
  • Example 24 (Synthesis of 3- (methylmercaptocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3MMCPE)])
  • 3- (methylmercaptocarbonyl) phenylethyne 28 mg, 0.158 mmol
  • Example 25 (Synthesis of 3- (phenylmercaptocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3PMCPE)])
  • 3- (phenylmercaptocarbonyl) phenylethyne 27 mg, 0.158 mmol
  • Example 26 (Synthesis of 2-benzoylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (2BzPE)])
  • 2-benzoylphenylethyne 33 mg, 0.158 mmol
  • Example 27 Synthesis of Au (IPr) (3MMPE) [(3-Methylmercaptophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 3-methylmercaptophenylethine 23 mg, 0.158 mmol
  • Example 28 Synthesis of Au (IPr) (4MMPE) [(4-methylmercaptophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr IPr
  • 4MMPE (4MMPE) [(4-methylmercaptophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold
  • 4-methylmercaptophenylethine 23 mg, 0.158 mmol
  • Example 29 Synthesis of cyclohexylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (CyE)]
  • ethynylcyclohexane 17.1 mg, 0.158 mmol
  • phenylethine the obtained white solid was dissolved in ethyl acetate and reprecipitated with hexane to obtain a white solid. 0.088 g of a certain target product was obtained (yield 85%).
  • Example 30 (Synthesis of n-butylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (n-BuE)]) After the same operation as in Example 1 except that 1-hexyne (13 mg, 0.158 mmol) was used in place of phenylethine, the obtained solid was washed with hexane to obtain the target product as a white solid in an amount of 0.00. 088 g was obtained (yield 88%).
  • Example 31 Synthesis of cyclopentylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (CpE)]
  • ethynylcyclopentane 15 mg, 0.158 mmol
  • the obtained white solid was dissolved in ethyl acetate and reprecipitated with hexane to obtain a white solid. 0.091 g of the target product was obtained (89% yield).
  • Example 32 (Synthesis of t-butylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (t-BuE)]) After the same operation as in Example 1 except that 3,3-dimethyl-1-butyne (13 mg, 0.158 mmol) was used instead of phenylethine, the obtained solid was washed with hexane to give a white solid. 0.086g of a certain target product was obtained (yield 86%).
  • Example 33 Synthesis of cyclopropylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (cPrE)]
  • ethynylcyclopropane 10 mg, 0.158 mmol
  • the product was washed with hexane and filtered to obtain 0.087 g of the desired product as a white solid (yield 89%).
  • Example 34 Synthesis of methoxycarbonylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (MCE)]
  • methoxycarbonylethine 27 mg, 0.158 mmol
  • Example 35 (Synthesis of p-tolylsulfonylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (pTsE)])
  • p-tolylsulfonylethine 28 mg, 0.158 mmol
  • Example 36 (Synthesis of acetylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (AcE)])
  • Example 37 Synthesis of benzoylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (BzE)]
  • the product was washed with hexane and filtered to obtain 0.098 g of the desired product as a white solid (yield 91%).
  • Example 38 Synthesis of Au (IPr) (4MSFPE) [(4-methylsulfonylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 4-methylsulfonylphenylethine 28 mg, 0.158 mmol
  • Example 39 (Au (H 2 -IPr) (4F-1NpE) [(4-Fluoro-1-naphthylethynyl) [1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazole-2 -Synthesis of iridene] gold] 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene Instead of gold (I) chloride, 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene Example 1 except that gold (I) chloride [H 2 -IPrAuCl: 93.4 mg, 0.15 mmol] was used and 4-fluoro-1-ethynylnaphthalene (27 mg, 0.158 mmol) was used instead of phenylethine.
  • Example 41 Synthesis of Au (IPr) (9AntE) [(9-anthrylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • IPr 9AntE
  • 9-ethynylanthracene 32 mg, 0.158 mmol
  • the solid obtained was dissolved in ethyl acetate and reprecipitated with hexane.
  • the resulting precipitate was filtered to obtain 0.11 g of the target product as a yellow solid (yield 92%).
  • Example 42 Synthesis of Au (IPr) (9PhenE) [(9-phenanthrylylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
  • 9-ethynylphenanthrene 32 mg, 0.158 mmol
  • Example 43 Synthesis of Au (IPr) (1PyrenE) [(1-pyrenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 1-ethynyl-pyrene 36 mg, 0.158 mmol
  • Example 44 Synthesis of Au (IPr) (2FluorE) [(2-fluorenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 2-ethynylfluorene 30 mg, 0.158 mmol
  • the resulting solid was dissolved in ethyl acetate and reprecipitated with hexane.
  • the resulting precipitate was filtered to obtain 0.11 g of the desired product as a yellow solid (yield 95%).
  • Example 45 Synthesis of Au (IPr) (4Bz-PE) [(4-benzoylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 4-benzoylphenylethine 33 mg, 0.158 mmol
  • Example 46 Synthesis of Au (IPr) (PzE) [(pyrazylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold]
  • 2-ethynylpyrazine (16 mg, 0.158 mmol
  • the present invention relates to a method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex.
  • a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex can be easily obtained without requiring a plurality of steps.
  • the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex obtained by the present invention is a useful compound as a material for an electroluminescence device (organic electroluminescence device).

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Abstract

L'invention porte sur un procédé de fabrication de complexes de carbène hétérocyclique à teneur en or-azote éthynyle substitué représentés par la formule générale (3), qui est caractérisé en ce que de l'éthylène substitué représenté par la formule générale (1) et un complexe de carbène hétérocyclique à teneur en or halogéné (I)-azote représenté par la formule générale (2) sont mis à réagir en présence d'une base. Un complexe de carbène hétérocyclique à teneur en or-azote éthynyle substitué peut être obtenu facilement sans nécessiter de multiples étapes.
PCT/JP2009/062951 2008-07-18 2009-07-17 Procédé de fabrication de complexe de carbène hétérocyclique à teneur en or-azote éthynyle substitué WO2010008065A1 (fr)

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* Cited by examiner, † Cited by third party
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WO2012046769A1 (fr) * 2010-10-08 2012-04-12 宇部興産株式会社 Complexe d'or et de carbène et éléments électroluminescents organiques

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WO2008050733A1 (fr) * 2006-10-24 2008-05-02 Ube Industries, Ltd. Complexe de l'or, procédé pour la production du complexe de l'or et élément électroluminescent ultraviolet organique utilisant le complexe de l'or

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WO2006080515A1 (fr) * 2005-01-31 2006-08-03 Ube Industries, Ltd. Complexe d’or a substitution ethynyle et de carbene heterocyclique azote et dispositif electroluminescent organique utilisant celui-ci

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WO2008050733A1 (fr) * 2006-10-24 2008-05-02 Ube Industries, Ltd. Complexe de l'or, procédé pour la production du complexe de l'or et élément électroluminescent ultraviolet organique utilisant le complexe de l'or

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SINGH, S. ET AL.: "A facile one-step synthesis of a lipophilic gold(I) carbene complex - X-ray crystal structures of LAuCl and LAuC=CH (L = 1,3-di-tert-butylimidazol-2-ylidene)", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, no. 15, 2005, pages 3057 - 3062 *
WANG, H.M. ET AL.: "Synthesis, Structure, and Spectroscopic Properties of Gold(I)-Carbene Complexes", ORGANOMETALLICS, vol. 18, no. 7, 1999, pages 1216 - 1223 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012046769A1 (fr) * 2010-10-08 2012-04-12 宇部興産株式会社 Complexe d'or et de carbène et éléments électroluminescents organiques

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