WO2010008065A1 - Method for manufacturing substituted ethynyl gold-nitrogen containing heterocyclic carbene complex - Google Patents

Abstract

Disclosed is a method for manufacturing substituted ethynyl gold-nitrogen containing heterocyclic carbene complexes represented by general formula (3) that is characterized in that substituted ethylene represented by general formula (1) and a halogenated gold (I)-nitrogen containing heterocyclic carbene complex represented by general formula (2) are reacted in the presence of a base.  A substituted ethynyl gold-nitrogen containing heterocyclic carbene complex can be obtained easily without requiring multiple steps.

Description

Process for the preparation of substituted ethynylgold-nitrogen-containing heterocyclic carbene complexes

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.

Conventionally, as a method for producing a substituted ethynylgold-nitrogen-containing heterocyclic carbene complex, for example, as shown in the following reaction process formula (1), a substituted ethynylgold-phosphine complex and a nitrogen-containing heterocyclic carbene ligand are used. A method of producing by reacting with (L) has been known (see Patent Document 1). However, in this method, it is necessary to produce a substituted ethynylgold phosphine complex as a raw material through a plurality of steps, and further improvement of the production method has been demanded.

Where
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, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto group, aryl mercapto group, alkyl Optionally substituted with a sulfonyl group or an arylsulfonyl group, and a plurality of hydrogen atoms on the carbon atom of R are an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a dialkylamino group, When substituted by a formyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkyl mercapto group, an aryl mercapto group, an alkylsulfonyl group, or an arylsulfonyl group, adjacent groups may be bonded to form a ring. Often,
P represents a monodentate phosphine ligand.

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:

Where
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):

Where
X represents a halogen atom,
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):

In the formula, 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.

The present invention also provides that 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, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto group, Rumercapto group, alkylsulfonyl group, arylsulfonyl group, formyl group, alkylaminocarbonyl group, arylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylmercaptocarbonyl group or arylmercaptocarbonyl group may be substituted. 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 When substituted with a bonyl group, an alkyl mercaptocarbonyl group or an aryl mercaptocarbonyl 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. For example, 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, alkylsulfonyl group or arylsulfonyl group, adjacent substitution Base Judges may combine with each other to form a ring.

According to the present invention, it is possible 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.

In the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the general formula (3) produced by the present invention, 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. A group, an arylmercaptocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a formyl group, an alkylcarbonyl group or an arylcarbonyl group;

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. In particular, 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. For example, 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. For example, 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.

Note that one or more hydrogen atoms on the carbon atom of R may be substituted. When a plurality of hydrogen atoms are 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. . When a plurality of hydrogen atoms on the R carbon atom are substituted, adjacent substituents may be bonded to form a ring, for example, a plurality of hydrogen atoms on the R carbon atom. Is an alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, formyl group, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto group, aryl mercapto group, alkylsulfonyl Group, arylsulfonyl group, formyl group, alkylaminocarbonyl group, arylaminocarbonyl group, alkoxycarbonyl group, arylcarbonyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylmercaptocarbonyl group or arylmercaptocarbonyl group. If, by bonding a substituent each other adjacent may form a ring.

Examples of the halogen atom 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. For example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group. Group, undecenyl group, dodecenyl group and the like. These substituents include isomers thereof.

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.

As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is particularly preferable. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentanoxy group, a hexanoxy group, a heptanoxy group, an octanoxy group, a nonanoxy group, a decanoxy group Etc. These 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 When substituted with a mercapto group, an aryl mercapto group, an alkylsulfonyl group, an arylsulfonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyl mercaptocarbonyl group or an aryl mercaptocarbonyl group, 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.

Among them, 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.

The nitrogen-containing heterocyclic carbene ligand L is, for example, the general formula (1) or (2):

Where
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;
When 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.

Here, 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. Synonymous with

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.

Among these, as 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. As R ³ , R ⁴ , R ⁵ and R ⁶ Is preferably a hydrogen atom or a halogen atom, particularly a chlorine atom.

Specific examples of the nitrogen-containing heterocyclic carbene ligand (L) in the present invention include, for example, formulas (6) to (15)

The ligand shown by these is mentioned.

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.

Commercially available products can be used as they are for the substituted ethyne of the general formula (1).

In the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention, 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.

In the synthesis of the substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex of the present invention, a solvent can be used. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. For example, 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. In addition, an isomer may be used for these solvents, and they may be used alone or in combination of two or more.

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)

Etc.

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.

Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 (Synthesis of Au (IPr) (PE) [(phenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
In a 15 mL Schlenk tube under an argon atmosphere, 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene gold chloride (I) [IPrAuCl: 93.2 mg, 0.15 mmol], phenylethyne (16 mg,. 158 mmol) and ethanol (3 mL) were added, and then sodium ethoxide (62 μL, 0.158 mmol: ethanol solution having a concentration of 2.55 mol / L (liter)) was added dropwise. After stirring at room temperature for 19 hours, ethanol was distilled off under reduced pressure, methylene chloride was added and the mixture was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure using an evaporator. The obtained solid was recrystallized from an n-hexane-methylene chloride system to obtain 0.093 g of the desired product as a white solid (yield 90%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.49 (dd, 2H), 7.31-7.28 (m, 6H), 7.12 (s, 2H), 7.10- 7.00 (m, 3H), 2.61 (sept, 4H), 1.38 (d, 12H), 1.21 (d, 12H)
FAB-MS (M / Z): 687 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 250 nm) λ (nm): 414 (max), 434, 454
Elemental analysis Observation C: 60.95, H: 5.92, N: 4.02
Theoretical value C: 61.22, H: 6.02, N: 4.08

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.35-7.32 (m, 2H) 7.15-7.07 (m, 3H), 7.06 (s, 2H), 6 .99 (s, 4H) 2.35 (s, 6H), 2.12 (s, 12H)
FAB-MS (M / Z): 603 (M + H) ⁺
Luminescent analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 414 (max), 434, 453
Elemental analysis Observation C: 57.65, H: 4.74, N: 4.48
Theoretical value C: 57.81, H: 4.85, N: 4.65

Example 3 Synthesis of Au (IAd) (PE) [(phenylethynyl) [1,3-diadamantylimidazol-2-ylidene] gold]
1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene gold chloride (I) instead of 1,3-diadamantylimidazol-2-ylidene gold chloride (I) [IAdAuCl: 85.3 mg, 0 .15 mmol] was used in the same manner as in Example 1 to obtain 0.080 g of the target product as a white solid (yield 84%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.53-7.49 (m, 2H), 7.25-7.08 (m, 3H), 7.07 (s, 2H), 2.58-1.56 (m, 12H), 2.34-2.28 (m, 6H), 1.85-1.72 (m, 12H)
FAB-MS (M / Z): 635 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 415 (max), 435, 455
Elemental analysis Observation C: 58.71, H: 5.76, N: 4.44
Theoretical value C: 58.67, H: 5.88, N: 4.41

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.53-7.49 (m, 2H), 7.29-7.06 (m, 3H), 7.03 (s, 2H), 1.89 (s, 18H)
FAB-MS (M / Z): 479 (M + H) ⁺
Emission analysis _{(CHCl 3, 77K, Ex240nm)} λ (nm): 414 (max) 434,454
Elemental analysis Observation C: 47.30, H: 5.11, N: 5.76
Theoretical value C: 47.70, H: 5.27, N: 5.86

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.49 (dd, 2H), 7.30-7.22 (m, 8H), 7.12 (s, 2H), 6.82- 6.75 (m, 2H), 2.60 (sept, 4H), 1.38 (d, 12H), 1.21 (d, 12H)
FAB-MS (M / Z): 705 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 250 nm) λ (nm): 412 (max), 430, 451
Elemental analysis Observation C: 59.32, H: 5.68, N: 3.95
Theoretical value C: 59.66, H: 5.72, N: 3.98

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.32-7.26 (m, 2H) 7.06 (s, 2H), 6.99 (s, 4H) 6.81-6. 78 (m, 2H), 2.35 (s, 6H), 2.12 (s, 12H)
FAB-MS (M / Z): 621 (M + H) ⁺
Emission analysis _{(CHCl 3, 77K, Ex240nm)} λ (nm): 411 (max), 430,450
Elemental analysis Observation C: 55.85, H: 4.52, N: 4.60
Theoretical value C: 56.13, H: 4.55, N: 4.51

Example 7 (Synthesis of Au (IPr) (4MeO-PE) [(4-methoxyphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 4-methoxyphenylethyne (21 mg, 0.158 mmol) was used in place of phenylethine, 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.49 (dd, 2H), 7.30-7.22 (m, 6H), 7.11 (s, 2H), 6.67- 6.62 (m, 2H), 3.71 (s, 3H), 2.61 (sept, 4H), 1.38 (d, 12H), 1.21 (d, 12H)
FAB-MS (M / Z): 716 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 250 nm) λ (nm): 420 (max), 440
Elemental analysis Observation C: 59.98, H: 6.01, N: 3.87
Theoretical value C: 60.33, H: 6.05, N: 3.91

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.31-7.25 (m, 2H) 7.05 (s, 2H), 6.99 (s, 4H) 6.69-6. 64 (m, 2H), 3.72 (s, 3H), 2.34 (s, 6H), 2.12 (s, 12H)
FAB-MS (M / Z): 633 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 419 (max), 440, 459
Elemental analysis Observation C: 55.75, H: 4.92, N: 4.29
Theoretical value C: 56.96, H: 4.94, N: 4.43

Example 9 (Synthesis of Au (IPr) (2PyE) [(2-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.38-8.36 (m, 1H), 7.52-7.37 (m, 3H), 7.30-7.20 (m , 5H), 7.12 (s, 2H), 6.96-6.91 (m, 1H), 2.63-2.54 (sept, 4H), 1.37 (d, 12H), 1. 21 (d, 12H)
FAB-MS (M / Z): 688 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 417, 445, 457
Elemental analysis Observation C: 59.32, H: 5.82, N: 6.05
Theoretical value C: 59.38, H: 5.86, N: 6.11

Example 10 (Synthesis of Au (IPr) (3PyE) [(3-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 9 except that 3-ethynylpyridine (16 mg, 0.158 mmol) was used in place of 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.52-8.51 (m, 1H), 8.27-8.25 (m, 1H), 7.58-7.48 (m 3H), 7.31-7.27 (m, 4H), 7.14 (s, 2H), 7.04-7.00 (m, 1H), 2.65-2.56 (sept, 4H) , 1.38 (d, 12H), 1.22 (d, 12H)
FAB-MS (M / Z): 688 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 443, 450, 462
Elemental analysis Observation C: 59.44, H: 5.82, N: 6.16
Theoretical value C: 59.38, H: 5.86, N: 6.11

Example 11 (Synthesis of Au (IPr) (5F-2PyE) [(5-Fluoro-2-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 2-ethynyl-5-fluoropyridine (19 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography using silica gel (Hexane / Purification by AcOEt = 3/1) yielded 0.094 g of the desired product as a yellow solid (89% yield).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.22 (d, 1H), 7.49 (t, 2H), 7.19-7.29 (m, 6H), 7.12 ( s, 2H), 2.54-2.63 (sept, 4H), 1.36 (d, 12H), 1.22 (d, 12H)
FAB-MS (M / Z): 706 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 419, 436, 448, 460
Elemental analysis Observation C: 57.62, H: 5.30, N: 5.91
Theoretical value C: 57.87, H: 5.57, N: 5.95

Example 12 (Synthesis of Au (IPr) (6F-3PyE) [(6-Fluoro-3-pyridylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 3-ethynyl-6-fluoropyridine (19 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography (Hexane / Purified by AcOEt = 3/1), the obtained solid was dissolved in ethyl acetate and reprecipitated with hexane. The resulting precipitate was filtered to obtain 0.098 g of the target product as a yellow solid (yield 93%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.11 (s, 1H), 7.61-7.67 (m, 1H), 7.48-7.53 (m, 2H), 7.26-7.31 (m, 4H), 7.14 (s, 1H), 6.64-6.68 (m, 1H), 2.55-2.64 (sept, 4H), 36 (d, 12H), 1.22 (d, 12H)
FAB-MS (M / Z): 706 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 410, 428, 438, 449
Elemental analysis Observation C: 57.11, H: 5.48, N: 5.87
Theoretical value C: 57.87, H: 5.57, N: 5.95

Example 13 (Synthesis of Au (IPr) (4Ph-PE) [(4-phenylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 4-phenylphenylethine (28 mg, 0.158 mmol) was used in place of phenylethine, 0.11 g of the target product as a white solid was obtained (yield 96%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.54-7.47 (m, 1H), 7.39-7.23 (m, 11H), 7.13 (s, 2H), 6.96-6.91 (m, 1H), 2.67-2.57 (sept, 4H), 1.39 (d, 12H), 1.22 (d, 12H)
FAB-MS (M / Z): 763 (M + H) ⁺
Luminescent analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 485, 517
Elemental analysis Observation C: 64.26, H: 5.76, N: 3.62
Theoretical value C: 64.56, H: 5.95, N: 3.67

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.9-7.96 (m, 2H), 7.53-7.48 (m, 2H), 7.39-7.29 (m , 6H), 7.15 (s, 2H), 6.96-6.91 (m, 1H), 2.62-2.57 (sept, 4H), 1.38 (d, 12H), 23 (d, 12H)
FAB-MS (M / Z): 730 (M−H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 494, 523
Elemental analysis Observation C: 64.35, H: 5.46, N: 5.74
Theoretical value C: 57.45, H: 5.51, N: 5.74

Example 15 Synthesis of (Au (IPr) (2,4F ₂ -PE) [(2,4-difluorophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold) )
After the same operation as in Example 1 except that 2,4-difluoro-phenylethyne (22 mg, 0.158 mmol) was used in place of phenylethine, 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.52-7.47 (m, 2H), 7.34-7.22 (m, 5H), 7.12 (s, 2H), 6.67-6.58 (m, 2H), 2.65-2.56 (sept, 4H), 1.37 (d, 12H), 1.21 (d, 12H)
FAB-MS (M / Z): 723 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 414, 426, 442, 454, 468
Elemental analysis Observation C: 57.93, H: 5.25, N: 3.91
Theoretical value C: 58.17, H: 5.44, N: 3.88

Example 16 (Synthesis of Au (IPr) (1NpE) [(1-naphthylethynyl) [1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 1-ethynylnaphthalene (24 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 100 / (0 → 1/4) to obtain 0.11 g of the target compound as a white solid (yield 98%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.40-8.37 (m, 1H), 7.71-7.68 (m, 1H), 7.57-7.46 (m 5H), 7.40-7.30 (m, 6H), 7.16 (s, 2H), 2.65 (sept, 4H), 1.44 (d, 12H), 1.23 (d, 12H)
MS EI (m / z): 736 (M +), CI (m / z): 737 (MH +)
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 530 nm
Elemental analysis Observation C: 63.40, H: 6.05, N: 3.63
Theoretical value C: 63.58, H: 5.88, N: 3.80

Example 17 (Synthesis of 3-benzoylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3BzPE)])
After the same operation as in Example 1 except that 3-benzoylphenylethine (33 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5). / 1 to 3/1), and the obtained solid was washed with hexane and filtered to obtain 0.10 g of the desired product as a white solid (yield 88%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.74-7.12 (m, 17H), 2.64-2.55 (sept, 4H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 790 (M) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 446 (max)
Thermal analysis: Melting point: 224 ° C
Elemental analysis Observation C: 63.74, H: 5.58, N: 3.68
Theoretical value C: 63.79, H: 5.74, N: 3.54

Example 18 (3- (4′-fluorobenzoyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) [3 (4′FBz) PE] ]
After the same operation as in Example 1 except that 3- (4′-fluorobenzoyl) phenylethyne (35 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel. The product was purified by (Hexane / AcOEt = 5/1), and the obtained solid was washed and filtered with hexane to obtain 0.10 g of the desired product as a white solid (yield 85%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.76-7.07 (m, 16H), 2.62-2.56 (sept, 4H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 808 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 442 (max)
Thermal analysis: Melting point: 224 ° C
Elemental analysis Observation C: 62.35, H: 5.44, N: 3.44
Theoretical value C: 62.37, H: 5.48, N: 3.46

Example 19 (Synthesis of 3-acetylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3AcPE)])
After the same operation as in Example 1 except that 3-acetylphenylethine (23 mg, 0.158 mmol) was used instead of phenylethine, the white solid obtained was subjected to column chromatography using silica gel (Hexane / AcOEt = 5). / 1 to 3/1), and the resulting solid was washed with hexane and filtered to obtain 0.10 g of the desired product as a white solid (yield 95%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.88-7.13 (m, 12H), 2.65-2.49 (sept, 4H), 2.49 (s, 3H), 1.44 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 728 (M) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 440 (max)
Thermal analysis: Melting point: 224 ° C
Elemental analysis Observation C: 60.73, H: 5.95, N: 3.97
Theoretical value C: 60.98, H: 5.95, N: 3.84

Example 20 (Synthesis of 3- (diethylaminocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3DEACPE)])
After the same operation as in Example 1 except that 3- (diethylaminocarbonyl) phenylethyne (32 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography (Hexane / AcOEt = 5/1 to 1/1), and the obtained solid was washed and filtered with hexane to obtain 0.11 g of the desired product as a white solid (yield 93%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.52-7.03 (m, 12H), 3.31 (m, 4H), 2.65-2.54 (sept, 4H), 1.44 (d, 12H), 1.21 (d, 12H), 1.09 (m, 6H)
EI-MS (M / Z): 785 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 421 (max)
Thermal analysis: Melting point: 218 ° C
Elemental analysis Observation C: 61.02, H: 6.30, N: 5.32
Theoretical value C: 61.14, H: 6.41, N: 5.35

Example 21 (Synthesis of 3- (diphenylaminocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3DPACPE)])
After the same operation as in Example 1 except that 3- (diphenylaminocarbonyl) phenylethyne (47 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography (Hexane / AcOEt = 5/1), and the obtained solid was washed with hexane and filtered to obtain 0.13 g of the desired product as a white solid (yield 95%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.54-6.83 (m, 22H), 2.62-2.55 (sept, 4H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 881 (M) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 427 (max)
Thermal analysis: Melting point: 260 ° C
Elemental analysis Observation C: 65.23, H: 5.62, N: 4.87
Theoretical value C: 65.37, H: 5.71, N: 4.76

Example 22 (Synthesis of 3- (methoxycarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3MCPE)])
After the same operation as in Example 1 except that 3- (methoxycarbonyl) phenylethyne (25 mg, 0.158 mmol) was used in place of phenylethine, the white solid obtained was subjected to column chromatography (Hexane / AcOEt = 5/1) and the obtained solid was washed with hexane and filtered to obtain 0.098 g of the desired product as a white solid (yield 88%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.98-7.12 (m, 12H), 3.83 (s, 3H), 2.67-2.54 (sept, 4H), 1.38 (d, 12H), 1.23 (d, 12H)
EI-MS (M / Z): 744 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 426 (max)
Thermal analysis: Melting point: 205 ° C
Elemental analysis Observation C: 59.75, H: 5.69, N: 3.77
Theoretical value C: 59.67, H: 5.82, N: 3.76

Example 23 (Synthesis of 3- (phenoxycarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3PCPE)])
After the same operation as in Example 1 except that 3- (phenoxycarbonyl) phenylethyne (35 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography (Hexane / AcOEt = 5/1) and the obtained solid was washed with hexane and filtered to obtain 0.11 g of the desired product as a white solid (yield 92%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.16-7.13 (m, 17H), 2.63-2.56 (sept, 4H), 1.38 (d, 12H), 1.22 (d, 12H)
EI-MS (M / Z): 806 (M) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 427 (max)
Thermal analysis: Melting point: 224 ° C
Elemental analysis Observation C: 62.17, H: 5.52, N: 3.48
Theoretical value C: 62.53, H: 5.62, N: 3.47

Example 24 (Synthesis of 3- (methylmercaptocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3MMCPE)])
After the same operation as in Example 1 except that 3- (methylmercaptocarbonyl) phenylethyne (28 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1), and the obtained solid was washed with hexane and filtered to obtain 0.11 g of the desired product as a white solid (yield 93%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.91-7.13 (m, 12H), 2.67-2.54 (sept, 4H), 2.40 (s, 3H), 1.38 (d, 12H), 1.22 (d, 12H)
EI-MS (M / Z): 760 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 434 (max)
Thermal analysis: Melting point: 212 ° C
Elemental analysis Observation C: 58.15, H: 5.70, N: 3.80
Theoretical value C: 58.41, H: 5.70, N: 3.68

Example 25 (Synthesis of 3- (phenylmercaptocarbonyl) phenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (3PMCPE)])
After the same operation as in Example 1 except that 3- (phenylmercaptocarbonyl) phenylethyne (27 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1), and the obtained solid was washed with hexane and filtered to obtain 0.11 g of the desired product as a white solid (yield 86%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.9-7.13 (m, 17H), 2.63-2.56 (sept, 4H), 1.39 (d, 12H), 1.22 (d, 12H)
EI-MS (M / Z): 822 (M) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 435 (max)
Thermal analysis: Melting point: 223 ° C
Elemental analysis Observation C: 60.94, H: 5.49, N: 3.50
Theoretical value C: 61.30, H: 5.51, N: 3.40

Example 26 (Synthesis of 2-benzoylphenylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (2BzPE)])
After the same operation as in Example 1 except that 2-benzoylphenylethyne (33 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5). / 1), and the obtained solid was washed with hexane and filtered to obtain 0.11 g of the desired product as a white solid (yield 93%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.67-7.06 (m, 17H), 2.53-2.44 (sept, 4H), 1.23 (d, 12H), 1.18 (d, 12H)
EI-MS (M / Z): 790 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 457 (max)
Thermal analysis: Melting point: 242 ° C
Elemental analysis Observation C: 63.77, H: 5.51, N: 3.54
Theoretical value C: 63.79, H: 5.74, N: 3.54

Example 27 (Synthesis of Au (IPr) (3MMPE) [(3-Methylmercaptophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 3-methylmercaptophenylethine (23 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5/1) and the resulting solid was washed with hexane and filtered to obtain 0.089 g of the desired product as a white solid (yield 81%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.47-7.52 (m, 2H), 7.19-7.31 (m, 4H), 6.91-7.12 (m , 6H), 2.54-2.68 (sept, 4H), 2.38 (s, 3H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 732 (M +), CI (m / z): 733 (MH +)
Luminescence analysis (CHCl ₃ , 77K, Ex 250 nm) λ (nm): 431 (max)
Thermal analysis: Melting point: 330 ° C
Elemental analysis Observation C: 58.76, H: 5.88, N: 3.75
Theoretical value C: 59.01, H: 5.91, N: 3.82

Example 28 (Synthesis of Au (IPr) (4MMPE) [(4-methylmercaptophenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 4-methylmercaptophenylethine (23 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5/1), and the obtained solid was washed with hexane and filtered to obtain 0.095 g of the desired product as a white solid (yield 86%).

^{1 H-NMR (300MHz, CDCl} 3) δ (ppm): 7.44-7.52 (m, 2H), 7.19-7.30 (m, 8H), 6.99 (d, 2H), 2.56-2.67 (sept, 4H), 2.39 (s, 3H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 732 (M +), CI (m / z): 733 (MH +)
Luminescence analysis (CHCl ₃ , 77K, Ex 250 nm) λ (nm): 450 (max)
Thermal analysis: Melting point: 355 ° C
Elemental analysis Observation C: 58.65, H: 5.81, N: 3.76
Theoretical value C: 59.01, H: 5.91, N: 3.82

Example 29 (Synthesis of cyclohexylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (CyE)])
After the same operation as in Example 1 except that ethynylcyclohexane (17 mg, 0.158 mmol) was used instead of 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%).

^{1 H-NMR (300MHz, CDCl} 3) δ (ppm): 7.49-7.44 (m, 2H), 7.28-7.25 (m, 4H), 7.06 (d, 2H), 2.65-2.60 (sept, 4H), 2.32-2.25 (m, 1H), 1.79-1.10 (m, 34H)
EI-MS (M / Z): 692 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 214 ° C
Elemental analysis Observation C: 61.21, H: 6.95, N: 3.98
Theoretical value C: 60.68, H: 6.84, N: 4.04

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.49-7.44 (m, 2H), 7.28-7.25 (m, 4H), 7.07 (d, 2H), 2.66-2.52 (sept, 4H), 2.21-2.16 (m, 2H), 1.45-1.13 (m, 28H), 0.82-0.77 (m, 3H) )
EI-MS (M / Z): 666 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 215 ° C
Elemental analysis Observation C: 59.18, H: 6.59, N: 3.21
Theoretical value C: 59.45, H: 6.80, N: 4.20

Example 31 (Synthesis of cyclopentylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (CpE)])
After the same operation as in Example 1 except that ethynylcyclopentane (15 mg, 0.158 mmol) was used instead of phenylethine, 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).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.50-7.45 (m, 2H), 7.28-7.26 (m, 4H), 7.06 (d, 2H), 2.65-2.60 (m, 5H), 1.84-1.81 (m, 2H), 1.60-1.16 (m, 28H), 0.90-0.86 (m, 2H) )
EI-MS (M / Z): 678 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 244 ° C
Elemental analysis Observation C: 60.22, H: 6.47, N: 4.19
Theoretical value C: 60.17, H: 6.68, N: 4.13

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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.50-7.45 (m, 2H), 7.29-7.25 (m, 4H), 7.06 (d, 2H), 2.67-2.55 (sept, 4H), 1.34 (d, 12H), 1.18 (d, 12H), 1.11 (s, 9H)
EI-MS (M / Z): 666 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 201 ° C
Elemental analysis Observation C: 59.16, H: 6.72, N: 4.18
Theoretical value C: 59.45, H: 6.80, N: 4.20

Example 33 (Synthesis of cyclopropylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (cPrE)])
After the same operation as in Example 1 except that ethynylcyclopropane (10 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1) using silica gel. The product was washed with hexane and filtered to obtain 0.087 g of the desired product as a white solid (yield 89%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.49-7.44 (m, 2H), 7.27-7.25 (m, 4H), 7.06 (d, 2H), 2.65-2.51 (sept, 4H), 1.34 (d, 12H), 1.20-1.18 (m, 13H), 0.54-0.51 (m, 4H)
EI-MS (M / Z): 650 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 265 ° C
Elemental analysis Observation C: 58.79, H: 6.12, N: 4.35
Theoretical value C: 59.07, H: 6.35, N: 4.31

Example 34 (Synthesis of methoxycarbonylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (MCE)])
After the same operation as in Example 1 except that methoxycarbonylethine (27 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5/1). The product was washed with hexane and filtered to obtain 0.096 g of the desired product as a white solid (yield 96%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.61-7.47 (m, 2H), 7.29-7.26 (m, 4H), 7.13 (d, 2H), 3.59 (s, 3H), 2.57-2.45 (sept, 4H), 1.42 (d, 12H), 1.20 (d, 12H)
EI-MS (M / Z): 668 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 374 (max)
Thermal analysis: Melting point: 303 ° C
Elemental analysis Observation C: 55.02, H: 5.63, N: 4.14
Theoretical value C: 55.69, H: 5.88, N: 4.19

Example 35 (Synthesis of p-tolylsulfonylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (pTsE)])
After the same operation as in Example 1 except that p-tolylsulfonylethine (28 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography (Hexane / AcOEt = 5/1 to 3). After purification by 1), the product was washed with hexane and filtered to obtain 0.095 g of the desired product as a white solid (yield 83%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.80-7.76 (m, 2H), 7.54-7.48 (m, 2H), 7.30-7.19 (m 6H), 7.13 (d, 2H), 2.54-2.42 (sept, 4H), 2.37 (s, 3H), 1.30-1.28 (m, 12H), 1. 21-1.19 (m, 12H)
EI-MS (M / Z): 764 (M) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 364 (max)
Thermal analysis: Melting point: 268 ° C
Elemental analysis Observation C: 56.55, H: 5.56, N: 3.59
Theoretical value C: 56.54, H: 5.67, N: 3.66

Example 36 (Synthesis of acetylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (AcE)])
The obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1 to 3/1) after the same operation as in Example 1 except that acetylethine (11 mg, 0.158 mmol) was used instead of phenylethine. After purification by filtration, the product was washed with hexane and filtered to obtain 0.093 g of the target product as a white solid (yield 95%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.53-7.45 (m, 2H), 7.30-7.26 (m, 4H), 7.14 (s, 2H), 2.61-2.47 (sept, 4H), 2.15 (s, 3H), 1.33 (d, 12H), 1.21 (d, 12H)
CI-MS (M / Z): 653 (MH) ⁺
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 424 (max)
Thermal analysis: Melting point: 269 ° C
Elemental analysis Observation C: 56.63, H: 5.90, N: 4.20
Theoretical value C: 57.05, H: 6.02, N: 4.29

Example 37 (Synthesis of benzoylethynyl [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold [Au (IPr) (BzE)])
The obtained white solid was subjected to column chromatography (Hexane / AcOEt = 5/1 to 3/1) after the same operations as in Example 1 except that benzoylethine (21 mg, 0.158 mmol) was used instead of phenylethine. Then, the product was washed with hexane and filtered to obtain 0.098 g of the desired product as a white solid (yield 91%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): δ 7.71-7.25 (m, 11H), 7.14 (s, 2H), 2.65-2.50 (sept, 4H), 1.33 (d, 12H), 1.22 (d, 12H)
CI-MS (M / Z): 715 (MH) ⁺
Emission analysis _{(CHCl 3, 77K, Ex240nm)} λ (nm): 474
Thermal analysis: Melting point: 280 ° C
Elemental analysis Observation C: 60.63, H: 5.80, N: 3.90
Theoretical value C: 60.50, H: 5.78, N: 3.92

Example 38 (Synthesis of Au (IPr) (4MSFPE) [(4-methylsulfonylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 4-methylsulfonylphenylethine (28 mg, 0.158 mmol) was used instead of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = The solid obtained was washed with hexane and filtered to obtain 0.10 g of the desired product as a white solid (yield 88%).

^{1 H-NMR (300MHz, CDCl} 3) δ (ppm): 7.67-7.60 (m, 4H), 7.53-7.40 (m, 4H), 7.32-7.23 (m , 2H), 7.14 (d, 2H), 2.95 (s, 3H), 2.67-2.53 (sept, 4H), 1.37 (d, 12H), 1.21 (d, 12H)
EI-MS (M / Z): 764 (M +), CI (m / z): 765 (MH +)
Luminescence analysis (CHCl ₃ , 77 K, Ex 250 nm) λ (nm): 435 (max)
Thermal analysis: Melting point: 295 ° C
Elemental analysis Observation C: 56.32, H: 5.41, N: 3.65
Theoretical value C: 56.54, H: 5.67, N: 3.66

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. After the same operation, the obtained white solid was purified by column chromatography (Hexane / AcOEt = 100/0 → 1/4) using silica gel to obtain 0.10 g of the target compound as a white solid. (Yield 89%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.32-8.29 (m, 1H), 7.97-7.94 (m, 1H), 7.44-6.92 (m , 9H), 6.92-6.86 (m, 1H), 4.03 (s, 4H), 3.13 (sept, 4H), 1.50 (d, 12H), 1.35 (d, 12H)
MS EI (m / z): 756 (M +), CI (m / z): 757 (MH +)
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 530 nm
Elemental analysis Observation C: 61.40, H: 5.91, N: 3.50
Theoretical value C: 61.90, H: 5.86, N: 3.70

Example 40 Synthesis of Au (IPr) (4F-1NpE) [(4-Fluoro-1-naphthylethynyl) [1,3-bis (2,6-diisopropylphenyl) -imidazol-2-ylidene] gold]
After the same operation as in Example 1 except that 4-fluoro-1-ethynylnaphthalene (27 mg, 0.158 mmol) was used instead of phenylethine, the resulting white solid was subjected to column chromatography using silica gel (Hexane / Purification by AcOEt = 100/0 → 1/4) gave 0.11 g of the target compound as a white solid (yield 95%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.37-8.36 (m, 1H), 7.98-7.95 (m, 1H), 7.52-7.30 (m , 10H), 7.16 (s, 2H), 2.64 (sept, 4H), 1.42 (d, 12H), 1.23 (d, 12H)
MS EI (m / z): 754 (M +), CI (m / z): 755 (MH +)
Luminescence analysis (CHCl ₃ , 77K, Ex 240 nm) λ (nm): 529 nm
Elemental analysis Observation C: 62.01, H: 5.44, N: 3.53
Theoretical value C: 62.06, H: 5.61, N: 3.71

Example 41 (Synthesis of Au (IPr) (9AntE) [(9-anthrylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 9-ethynylanthracene (32 mg, 0.158 mmol) was used instead of phenylethine, the obtained solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 3/1). 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.63-8.58 (m, 2H), 8.14 (s, 1H), 7.88-7.83 (m, 2H), 7.54-7.49 (m, 2H), 7.39-7.23 (m, 8H), 7.17 (s, 2H), 2.73-2.64 (sept, 4H), 48 (d, 12H), 1.24 (d, 12H)
FAB-MS (M / Z): 787 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 409, 432, 453, 481
Elemental analysis Observation C: 65.65, H: 5.66, N: 3.58
Theoretical value C: 65.64, H: 5.76, N: 3.56

Example 42 (Synthesis of Au (IPr) (9PhenE) [(9-phenanthrylylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 9-ethynylphenanthrene (32 mg, 0.158 mmol) was used instead of phenylethine, the obtained solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 3 / Purified by 1), the resulting solid 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 (89% yield).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.58-8.51 (m, 3H), 7.79 (s, 1H), 7.70-7.67 (m, 1H), 7.59-7.29 (m, 10H), 7.15 (s, 2H), 2.70-2.61 (sept, 4H), 1.43 (d, 12H), 1.25 (d, 12H)
FAB-MS (M / Z): 786 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 524, 534, 569
Elemental analysis Observation C: 65.55, H: 5.61, N: 3.55
Theoretical value C: 65.64, H: 5.76, N: 3.56

Example 43 (Synthesis of Au (IPr) (1PyrenE) [(1-pyrenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 1-ethynyl-pyrene (36 mg, 0.158 mmol) was used in place of phenylethine, the obtained yellow solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 3). / 1), the solid obtained 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 pale yellow solid (yield 91%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.60-8.58 (d, 2H), 8.10-7.89 (m, 8H), 7.55-7.50 (m , 2H), 7.39-7.21 (m, 4H), 7.16 (s, 2H), 2.72-2.63 (sept, 4H), 1.48 (d, 12H), 24 (d, 12H)
FAB-MS (M / Z): 810 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 397, 413
Elemental analysis Observation C: 65.65, H: 5.66, N: 3.58
Theoretical value C: 66.39, H: 5.58, N: 3.38

Example 44 (Synthesis of Au (IPr) (2FluorE) [(2-fluorenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 2-ethynylfluorene (30 mg, 0.158 mmol) was used instead of phenylethine, the obtained yellow solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 5 / 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%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.67-7.64 (d, 2H), 7.54-7.44 (m, 5H), 7.34-7.18 (m 7H), 7.18 (s, 2H), 3.74 (s, 2H), 2.66-2.57 (sept, 4H), 1.39 (d, 12H), 1.24 (d, 12H)
FAB-MS (M / Z): 775 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 481, 500, 511, 520
Elemental analysis Observation C: 64.85, H: 5.87, N: 3.60
Theoretical value C: 65.11, H: 5.85, N: 3.62

Example 45 (Synthesis of Au (IPr) (4Bz-PE) [(4-benzoylphenylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 4-benzoylphenylethine (33 mg, 0.158 mmol) was used in place of phenylethine, the obtained white solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 3). / 1), 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 white solid (yield 93%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.71-7.26 (m, 15H), 7.14 (s, 2H), 2.65-2.56 (sept, 4H), 1.48 (d, 12H), 1.24 (d, 12H)
FAB-MS (M / Z): 791 (M + H) ⁺
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 474, 507
Elemental analysis Observation C: 63.56, H: 5.47, N: 3.47
Theoretical value C: 63.79, H: 5.74, N: 3.54

Example 46 (Synthesis of Au (IPr) (PzE) [(pyrazylethynyl) [1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene] gold])
After the same operation as in Example 1 except that 2-ethynylpyrazine (16 mg, 0.158 mmol) was used instead of phenylethine, the resulting yellow solid was subjected to column chromatography using silica gel (Hexane / AcOEt = 3 / Purified by 1), the resulting solid was dissolved in ethyl acetate and reprecipitated with hexane. The resulting precipitate was filtered to obtain 0.10 g of the desired product as a yellow solid (yield 99%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 8.45 (d, 1H), 8.30 (dd, 1H), 8.17 (d, 1H), 7.52-7.49 ( m, 2H), 7.31-7.29 (m, 4H), 2.61-2.55 (sept, 4H), 1.36 (d, 12H), 1.22 (d, 12H)
FAB-MS (M / Z): 689 (MH +)
Luminescence analysis (CHCl ₃ , 77 K, Ex 240 nm) λ (nm): 445, 463, 475, 491
Elemental analysis Observation C: 57.41, H: 5.49, N: 8.06
Theoretical value C: 57.55, H: 5.71, N: 8.14

The present invention relates to a method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex. According to the present invention, 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).

Claims (5)

1. In the presence of a base, general formula (1):
   

   

   Where
   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 or substituted. The adjacent substituents may be bonded to form a ring, and the substituted ethyne represented by the general formula (2):
   

   

   Where
   X represents a halogen atom,
   L represents a nitrogen-containing heterocyclic carbene ligand, and represents a reaction of a gold (I) halide-nitrogen-containing heterocyclic carbene complex represented by the general formula (3):
   

   

   Where
   A method for producing a substituted ethynylgold-nitrogen-containing heterocyclic carbene complex, wherein R and L are as defined above.
2. 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 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, a nitro group, an alkyl group, a cyclo Alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, dialkylamino group, alkylcarbonyl group, arylcarbonyl group, alkyl mercapto group, aryl mercapto group , An alkylsulfonyl group, an arylsulfonyl group, a formyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylmercaptocarbonyl group or an arylmercaptocarbonyl group, A plurality of hydrogen atoms on a carbon atom is an 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, formyl, alkylaminocarbonyl, arylaminocarbonyl, alkoxycarbonyl group, aryloxycarbonyl group, alkylme The substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 1, wherein when substituted with a captocarbonyl group or an arylmercaptocarbonyl group, adjacent substituents may be bonded to form a ring. Manufacturing method.
3. The process for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 1 or 2, wherein the base is an alkali metal alcoholate.
4. The process for producing a substituted ethynylgold-nitrogen-containing heterocyclic carbene complex according to any one of claims 1 to 3, wherein the reaction is carried out in an organic solvent.
5. The method for producing a substituted ethynyl gold-nitrogen-containing heterocyclic carbene complex according to claim 4, wherein the organic solvent is an alcohol.