JP2012144455A - Method for producing imidazole compound, and imidazole compound - Google Patents

Method for producing imidazole compound, and imidazole compound Download PDF

Info

Publication number
JP2012144455A
JP2012144455A JP2011002084A JP2011002084A JP2012144455A JP 2012144455 A JP2012144455 A JP 2012144455A JP 2011002084 A JP2011002084 A JP 2011002084A JP 2011002084 A JP2011002084 A JP 2011002084A JP 2012144455 A JP2012144455 A JP 2012144455A
Authority
JP
Japan
Prior art keywords
group
imidazole compound
compound
solvent
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2011002084A
Other languages
Japanese (ja)
Inventor
Maki Numata
真樹 沼田
Original Assignee
Idemitsu Kosan Co Ltd
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd, 出光興産株式会社 filed Critical Idemitsu Kosan Co Ltd
Priority to JP2011002084A priority Critical patent/JP2012144455A/en
Priority claimed from US13/978,406 external-priority patent/US20130270541A1/en
Publication of JP2012144455A publication Critical patent/JP2012144455A/en
Application status is Pending legal-status Critical

Links

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an imidazole compound useful for obtaining a light-emitting material which is sharp in light-emitting spectrum and can emit light on a short wavelength side.SOLUTION: There is provided the method for producing the imidazole compound represented by general formula (1), by reacting a 1-arylimidazole with a halogen atom-substituted compound, characterized in that the mole number N[mole] of the halogen atom-substituted compound and the total volume V[liter] of ≤5C ether solvents satisfy the relation of V/N≤3, (wherein, Rand Rare each a substituent or the like; Zis a hydrocarbon ring group, or the like; Rand Rare each a direct bond, hydrogen atom or the like; Zis a five-membered hydrocarbon ring or the like together with C-C; m is an integer of 1-5).

Description

  The present invention relates to a method for producing an imidazole compound and an imidazole compound produced by the production method.

Conventionally, imidazole compounds have been used in various applications, but in recent years, they have also been used as materials for organic electroluminescence devices. For example, an imidazole compound is used as a ligand of a metal complex.
Patent Document 1 and Patent Document 2 describe N-phenyl-2-phenylimidazole derivatives in which substituents are introduced at the 2-position and 6-position of the N-position phenyl group. Examples of this substituent include a methyl group, an isopropyl group, a phenyl group, a 4-isopropylphenyl group, and a 3,5-dimethylphenyl group. In Patent Document 2, the bulkiness of the substituent is defined by a steric parameter (Es value).
In Patent Document 1 and Patent Document 2, a metal complex having a ligand of an imidazole compound into which a bulky substituent is introduced at the 2-position and 6-position of the N-position phenyl group has an emission wavelength on the short wavelength side. And the emission spectrum becomes sharper, and is said to be useful as a blue light-emitting material with excellent color purity.

Special table 2008-542203 gazette JP 2008-303150 A

However, in the synthesis methods disclosed in Patent Document 1 and Patent Document 2, the yield decreases as the bulk of the substituent of the imidazole compound increases (as the Es value decreases), and further, the synthesis cannot be performed. For example, if the substituent is a methyl group, it can be synthesized, but the yield of an imidazole compound having an isopropyl group or a phenyl group is very low, not at a practical level, and a carbazole group that is a bulky substituent. It is not possible to synthesize imidazole compounds having Patent Documents 1 and 2 disclose synthesis examples of imidazole compounds having an isopropyl group or a phenyl group, but do not disclose synthesis examples of imidazole compounds having a bulky substituent. Therefore, it can be said that it cannot be provided at a practical level.
Therefore, in order to obtain a light emitting material having a sharper emission spectrum and capable of emitting light on the short wavelength side, a production method capable of producing an imidazole compound having substituents introduced at the 2nd and 6th positions of the N-position phenyl group in a high yield is provided. It is desired.

  An object of the present invention is to provide an imidazole compound production method capable of producing an imidazole compound useful in obtaining a light-emitting material having a sharp emission spectrum and capable of emitting light on a short wavelength side, and an imidazole compound produced by the production method. Is to provide.

In the method for producing an imidazole compound of the present invention, an imidazole compound represented by the following general formula (1) is reacted with a compound represented by the following general formula (2) and a compound represented by the following general formula (3). A method for producing an imidazole compound,
In reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), the number of moles of the compound represented by the general formula (2) in the reaction system N f2 [ Mol] and the total volume V A [liter] of the ether solvent having 5 or less carbon atoms satisfy the relationship of the following mathematical formula (1).

(In the formula (1),
R 1 represents a hydrogen atom or a substituent,
Z 1 represents an atomic group necessary to form a hydrocarbon ring group or a heterocyclic group, wherein the hydrocarbon ring group or the heterocyclic group formed by said Z 1 is, the R 1 1 or more Have
R 2 and R 3 each represent a bond, a hydrogen atom or an aromatic hydrocarbon group, and are bonded to each other to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Further, these rings may have a substituent,
Z 2 represents an atomic group necessary to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with C—C;
R 4 represents a hydrogen atom or a substituent,
m represents an integer of 1 to 5. )


(In the formula (2),
X represents a halogen atom,
Z 2 , R 4 , and m have the same meanings as those in the general formula (1). )


(In formula (3),
M represents a boron atom, a magnesium atom, a silicon atom, a tin atom, or a zinc atom, and may further have a substituent,
Z 1 , R 1 , R 2 , and R 3 are respectively synonymous with the general formula (1). )

[Equation 1]
V A / N f2 ≦ 3 (1)

In the method for producing an imidazole compound of the present invention,
It is preferable that the number of moles N f2 of the compound represented by the general formula (2) and the total volume V A satisfy the relationship of the following mathematical formula (2).

[Equation 2]
V A / N f2 ≦ 2 (2)

In the method for producing an imidazole compound of the present invention,
It is preferable that the number of moles N f2 of the compound represented by the general formula (2) and the total volume V A satisfy the relationship of the following mathematical formula (3).

[Equation 3]
V A / N f2 ≦ 1 (3)

In the method for producing an imidazole compound of the present invention,
The ether solvent having 5 or less carbon atoms is at least one ether solvent selected from tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, diethyl ether, and 1,2-dimethoxyethane. Is preferred.

In the method for producing an imidazole compound of the present invention,
It is preferable to adjust the relationship between the number of moles N f2 and the total volume V A by performing a solvent removal process for removing the solvent in the reaction system.

In the method for producing an imidazole compound of the present invention,
In the reaction system, the second solvent includes at least one solvent selected from an aliphatic hydrocarbon solvent having 7 or more carbon atoms, an aromatic hydrocarbon solvent, and an ether solvent having 6 or more carbon atoms,
In reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), the number of moles N f2 of the compound represented by the general formula (2) in the reaction system. And the total volume V B of the second solvent preferably satisfy the relationship of the following mathematical formula (4).

[Equation 4]
0.1 ≦ V B / N f2 (4)

In the method for producing an imidazole compound of the present invention,
It is preferable that the number of moles N f2 of the compound represented by the general formula (2) in the reaction system and the total volume V B of the second solvent satisfy the relationship of the following formula (5).

[Equation 5]
0.1 ≦ V B / N f2 ≦ 10 (5)

In the method for producing an imidazole compound of the present invention,
The ether solvent having 6 or more carbon atoms is at least one selected from dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methoxybenzene, ethoxybenzene, methylanisole, ethylanisole, dimethoxybenzene, and methoxyethoxybenzene. Preferably there are two solvents.

In the method for producing an imidazole compound of the present invention,
The carbon number of the aliphatic hydrocarbon solvent having 7 or more carbon atoms is 7 or more and 50 or less,
It is preferable that the aromatic hydrocarbon solvent has 6 to 20 carbon atoms.

In the method for producing an imidazole compound of the present invention,
The aromatic hydrocarbon solvent is preferably at least one solvent selected from benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and tetramethylbenzene.

In the method for producing an imidazole compound of the present invention,
M in the general formula (3) is preferably a zinc atom which may have a substituent.

  The imidazole compound of the present invention is an imidazole compound produced by the method for producing an imidazole compound of the present invention.

  According to the present invention, an imidazole compound useful for obtaining a light emitting material having a sharp emission spectrum and capable of emitting light on the short wavelength side can be produced in high yield.

It shows a 1 H-NMR spectrum of the imidazole compound. 1 H-NMR enlarged view of a part of the spectrum of FIG. The figure which shows a high performance liquid chromatography analysis result.

[Imidazole compound]
The imidazole compound manufactured by the manufacturing method of the imidazole compound of this invention is represented by the said General formula (1).
In the general formula (1), Z 1 represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group. These hydrocarbon ring groups or heterocyclic groups have one or more substituents represented by R 1 described below. The number is preferably one of 1, 2, 3, 4, and 5. When the number of R 1 is plural, each R 1 may be the same or different. Of the imidazole compounds represented by the general formula (1), imidazole compounds each having R 1 at the ortho position of the hydrocarbon ring group or heterocyclic group are preferred.

R 1 represents a hydrogen atom or a substituent.
Examples of the substituent represented by R 1 include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, Tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aromatic Hydrocarbon group (also called aromatic hydrocarbon ring group, aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group , Acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl Group), aromatic heterocyclic groups (for example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole- 1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) ), Quinoxalinyl group, pyridazinyl group, triazinyl group, Nazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group) Octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy group (eg, phenoxy group, naphthyloxy group etc.), alkylthio group (eg, methylthio group, etc.) Ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthyl) Group), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, Naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group) Phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, pro A pyrcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group, a phenylcarbonyl group, a naphthylcarbonyl group, a pyridylcarbonyl group, etc.), an acyloxy group (for example, an acetyloxy group, an ethyl group) Carbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group) , Pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonyl Amino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octyl) Aminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group) Cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulf Nyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (For example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2 -Ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group) , Trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethyl) Silyl group and the like), phosphono group and the like.

In the general formula (1), R 1 is preferably a substituent having a steric parameter (Es) value of −1.70 or less. More preferably, it is a substituent having an Es value of −2.0 or less, more preferably a substituent having an Es value of −2.5 or less, and even more preferably, an Es value of −3.0 or less. It is a substituent, and a substituent of −5.0 or less is particularly preferable.
The Es value is a steric parameter derived from chemical reactivity, and it can be said that the smaller this value is, the sterically bulky substituent. Therefore, the smaller the Es value, the better.
Regarding the Es value, for example, “Structure Activity Relationship of Drugs, Guidelines for Drug Design and Action Mechanism Research (Chemistry Domain Extra Number 122)” (Nanedo 1979) p124-126, Unger, S. H. Hansch, C .; , Prog. Phys. Org. Chem. 12, 91 (1976), “American Chemical Society Reference Book, 'Exploring QSAR' p. 81 Table 3-3”.

The Es value in the present invention is a value represented by assuming that the Es value of a hydrogen atom is 0.
Examples of the substituent having an Es value of −2.0 or less include —CF 3 (trifluoromethyl group), 9-H-fluorene group (Es value = −2.34), and a carbazolyl group. Examples of the substituent having a value of −2.5 or less include —tC 4 H 9 (tert-butyl group), and examples of the substituent having an Es value of −3.0 or less include —CH ( C 2 H 5 ) 2 (3- (n-pentyl) group), —CHBr 2 (dibromomethyl group), —CCl 3 (trichloromethyl group), —CBr 3 (tribromomethyl group), and Es value Examples of the substituent having a value of −5.0 or less include —C (C 6 H 5 ) 3 (triphenylmethyl group). The substituent R 1 may be further substituted with respect to these substituents.

In the general formula (1), R 1 satisfies the range of the Es value and is preferably a substituent having a molecular weight of 43 or more, more preferably a substituent having a molecular weight of 77 or more, and a molecular weight of 116. The above substituents are more preferable, the molecular weight is more preferably 127 or more, and the molecular weight is more preferably 166 or more. Examples of the substituent having a molecular weight of 43 include an isopropyl group (molecular weight: 43), and examples of the substituent having a molecular weight of 77 or more include a phenyl group (molecular weight: 77), and a molecular weight of 116 or more. Examples of the substituent include an indole group (molecular weight: 116), examples of the substituent having a molecular weight of 127 or more include a naphthyl group (molecular weight: 127), and examples of the substituent having a molecular weight of 166 or more. , For example, a carbazole group (molecular weight: 166).

· As hydrocarbon ring group mentioned above, in the general formula (1), Z 1 is representative of the atomic group necessary to form a hydrocarbon ring group, As the hydrocarbon ring group, a cycloalkyl group Or an aryl group (aromatic ring group) is mentioned.

-Cycloalkyl group Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group, and a norbornyl group. The cycloalkyl group preferably has 5 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms.

Aryl group As the aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, biphenyl-2-yl group, biphenyl- 3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl Group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl group P- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenyl-4-yl group, Examples thereof include a 4 ″ -t-butyl-p-terphenyl-4-yl group, a fluorenyl group, etc. The aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. It is as follows.

· As heterocyclic groups described above, in the general formula (1), Z 1 is representative of even atomic group necessary to form a heterocyclic group, the heterocyclic group, aliphatic heterocyclic group, an aromatic Group heterocyclic group and the like.

Aliphatic heterocyclic group As the aliphatic heterocyclic group, epoxy ring, aziridine ring, thiirane ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring , Tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring , 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine ring, thiomorpholine-1, 1-dioxide ring, pyranose ring, diazabicyclo [2,2,2] -octane ring Name the origin It is possible. The aliphatic heterocyclic group preferably has 5 to 10 ring atoms, and more preferably 5 to 7 ring atoms.

Aromatic heterocyclic group As the aromatic heterocyclic group, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazole) -1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group Dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (one in which one of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazini Group, quinazolinyl group, phthalazinyl group and the like. The aromatic heterocyclic group preferably has 5 to 18 ring atoms, and more preferably 5 to 13 ring atoms.

In the general formula (1), R 2 and R 3 represent a bond, a hydrogen atom or an aromatic hydrocarbon group, and are bonded to each other to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered hydrocarbon ring, A heterocycle or a 6-membered heterocycle may be formed. Furthermore, these rings may have the substituent R 1 .
Examples of the 5-membered or 6-membered hydrocarbon ring include a cyclopentane ring, a cyclopentadiene ring, a cyclohexane ring, a cyclohexadiene ring, and a benzene ring.
As the 5-membered or 6-membered heterocyclic ring, a 5-membered or 6-membered aromatic heterocyclic ring (for example, oxazole ring, oxadiazole ring, oxatriazole ring, isoxazole ring, tetrazole ring, thiadiazole ring, thiatriazole) Ring, isothiazole ring, thiophene ring, furan ring, pyrrole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, pyrazole ring, triazole ring), 5-membered to 6-membered non-aromatic heterocycle Ring (for example, pyrrolidine ring, piperazine ring, pyrazolidine ring, imidazolidine ring, isoxazolidine ring, isothiazolidine ring).

In the general formula (1), Z 2 represents an atomic group necessary for forming a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with C—C. To express.
The 5-membered hydrocarbon ring, 6-membered hydrocarbon ring, 5-membered heterocycle or 6-membered heterocycle is the same as described for R 2 and R 3 above.

In the general formula (1), R 4 represents a hydrogen atom or a substituent. Examples of the substituent include the substituent R 1 described above.
In general formula (1), m represents an integer of 1 to 5. When the number of R 4 is 2 or more, each R 4 may be the same or different.

In the general formula (1), the hydrocarbon ring group formed by Z 1 is preferably an aryl group, more preferably a phenyl group.
Furthermore, the substituent R 1 is preferably substituted at the 2-position and 6-position of the phenyl group.

  Specific examples of the structure of the imidazole compound produced by the method for producing an imidazole compound of the present invention include the following. However, the compound manufactured by this invention is not limited to the imidazole compound of these structures.

[Method for producing imidazole compound]
In the method for producing an imidazole compound of the present invention, the compound represented by the general formula (2) and the compound represented by the general formula (3) are reacted (hereinafter, this reaction is referred to as reaction 1). The imidazole compound represented by the general formula (1) that satisfies the relationship of the mathematical formula (1) is manufactured. In carrying out the reaction 1, the total volume V A [liter] of the number of moles N f (2) [mol] of the compound represented by the general formula (2) in the reaction system and the ether solvent having 5 or less carbon atoms. Satisfies the relationship of the above formula (1).

  In General formula (3), it is preferable that M is a zinc atom which may have a substituent. In this case, the synthesis reaction of the compound represented by the general formula (3), which is the synthesis reaction in the previous stage of the reaction 1, and the reaction 1 are continuously performed in terms of the reaction mechanism. (Also referred to as “one-pot synthesis”), and the manufacturing process can be simplified.

V A is the sum of these when a plurality of types of ether solvents having 5 or less carbon atoms are contained in the reaction system.

  The method for producing an imidazole compound of the present invention is preferably performed in a state satisfying the relationship of the mathematical formula (2), and more preferably performed in a state satisfying the relationship of the mathematical formula (3).

  Examples of the ether solvent having 5 or less carbon atoms include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, diethyl ether, and 1,2-dimethoxyethane. The solvent can be said to be an ether solvent having 2 to 5 carbon atoms.

  In order to satisfy any one of the formulas (1) to (3), the amount of the ether solvent having 5 or less carbon atoms added when the reaction 1 is charged can be adjusted. In addition, when the relationship of the following mathematical formula (6) is established before the reaction 1 due to the solubility of the reagent used in the reaction 1 or the convenience of the process before the reaction 1, the reaction system includes On the other hand, a solvent removal process is performed, and the amount of the ether solvent having 5 or less carbon atoms is adjusted so as to satisfy any one of the formulas (1) to (3).

[Equation 6]
V A / N f2 > 3 (6)

  Solvent removal methods include a vacuum distillation method in which the solvent is removed under reduced pressure using a solvent trap container and various vacuum pumps cooled by various cooling systems, and a solvent is removed under normal pressure using a Dean-Stark trap. The atmospheric distillation method to remove can be used.

In the method for producing an imidazole compound of the present invention, an ether solvent having a carbon number of 6 or more and an aliphatic hydrocarbon solvent having a carbon number of 7 or more are satisfied in the reaction system while satisfying any one of the formulas (1) to (3). It is preferable that at least one solvent selected from aromatic hydrocarbon solvents is contained.
In this case, in carrying out the reaction 1, the total volume V B [liter] of at least one solvent selected from an ether solvent having 6 or more carbon atoms, an aliphatic hydrocarbon solvent having 7 or more carbon atoms, and an aromatic hydrocarbon solvent and the above-mentioned It is preferable that the number of moles N f2 [mol] of the compound represented by the general formula (2) satisfies the relationship of the mathematical formula (4), and it is more preferable to satisfy the relationship of the mathematical formula (5).

Preferred examples of the ether solvent having 6 or more carbon atoms include dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methoxybenzene, ethoxybenzene, methylanisole, ethylanisole, dimethoxybenzene, and methoxyethoxybenzene. The ether solvent having 6 or more carbon atoms is preferably an ether solvent having 6 to 30 carbon atoms, and more preferably an ether solvent having 8 to 15 carbon atoms.
The aliphatic hydrocarbon solvent having 7 or more carbon atoms is preferably selected from aliphatic hydrocarbon solvents having 7 to 50 carbon atoms, and n-heptane, n-octane, n-nonane and n-decane are preferred examples. As mentioned. More preferably, the aliphatic hydrocarbon solvent is an aliphatic hydrocarbon solvent having 8 to 30 carbon atoms.
The aromatic hydrocarbon solvent is preferably selected from aromatic hydrocarbon solvents having 6 to 20 carbon atoms, and preferred examples include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and tetramethylbenzene. More preferably, the aromatic hydrocarbon solvent is an aromatic hydrocarbon solvent having 7 to 10 carbon atoms.

In the method for producing an imidazole compound of the present invention, the organic compound in the presence of a metal catalyst in the presence of a metal catalyst in the presence of an inorganic basic compound and / or an organic basic compound as necessary during the reaction 1. It is preferable to react in a solvent.
Examples of the inorganic basic compound used as necessary during the reaction 1 include sodium carbonate, potassium carbonate, cesium carbonate, and potassium phosphate.
Examples of the organic basic compound used as necessary in the reaction 1 include sodium acetate, potassium acetate, sodium tert-butoxide, potassium tert-butoxide and the like.

As the metal catalyst used in the reaction 1, a palladium catalyst, a nickel catalyst, or the like is preferably used.
As the palladium catalyst, a palladium compound having a phosphine ligand is preferably used, and examples thereof include Pd (PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 and the like. Pd (OAc) 2 , Pd (dba) 2 , Pd 2 (dba) 3 and other palladium compounds not containing a phosphine ligand, and PPh 3 , tricyclohexylphosphine, tri-tert-butylphosphine, dppe, dppp, dppf and other phosphine ligands in the reaction system The palladium compound which has a phosphine ligand can also be prepared in the said reaction system by mixing by.
In addition to these, palladium catalysts used for carbon-carbon (CC) bond formation known to those skilled in the art are suitably used.
As the nickel catalyst, a nickel compound having a phosphine ligand is preferably used, and examples thereof include NiCl 2 (dppe), NiCl 2 (dppf), and NiCl 2 (PPh 3 ) 2 . In addition to these, nickel catalysts used for CC bond formation known to those skilled in the art are preferably used.

According to the method for producing an imidazole compound of the present invention described above, an imidazole compound that is low in yield or impossible to synthesize can be produced in a high yield by the synthesis method disclosed in the prior art.
The reason is presumed as follows.
The ether solvent is a molecule composed of an oxygen atom and a hydrocarbon group, and the hydrophobicity of the solvent increases as the carbon number of the hydrocarbon group increases. In this regard, for example, “Surfactants—Physical Properties / Applications / Chemical Ecology—” (Kodansha (1979, 1st print)) and “New Surfactants” (Sankyo Publishing (1986, 4th print)) Are listed.
As shown in the examples described later, the reaction 1 is performed in a state where a large amount of tetrahydrofuran having 4 carbon atoms is present in the reaction system as a reaction solvent (a state in which the relationship represented by the formula (1) is not satisfied). In this case, the synthesis reaction yield of the imidazole compound represented by the general formula (1) is low or cannot be synthesized. On the other hand, by reducing the amount of tetrahydrofuran present in the reaction system, or by adding toluene to the reaction system to reduce the proportion of tetrahydrofuran in the reaction solvent, that is, the relationship represented by the above formula (1) is satisfied. The yield is dramatically improved by performing the reaction in a state or satisfying the relationship represented by the mathematical formula (1) and performing the reaction in a state satisfying the mathematical formula (4). From this, it is considered that the hydrophobicity of the solvent present in the reaction system has a great influence.
That is, when there are many ether solvents having 5 or less carbon atoms present in the reaction system, the yield is low, but the amount of the ether solvent having 5 or less carbon atoms present in the reaction system can be reduced, By adding at least one solvent selected from an ether solvent, an aliphatic hydrocarbon solvent having 7 or more carbon atoms, and an aromatic hydrocarbon solvent to the reaction system to reduce the proportion of tetrahydrofuran in the reaction solvent, the general formula The imidazole compound represented by (1) can be synthesized in high yield.

[Imidazole compounds]
By using the imidazole compound produced by the method for producing an imidazole compound of the present invention, an imidazole compound having the imidazole compound as a partial structure can be obtained.
The imidazole compound of the present invention has an imidazole compound represented by the general formula (1) as a partial structure. In other words, even if the compound has a structure represented by the general formula (1) even if partially, it corresponds to the imidazole compound of the present invention. Therefore, for example, polysubstituted compounds such as L-104 to L-119 exemplified as imidazole compounds also correspond to the imidazole compounds of the present invention.
Specific examples of the imidazole compound of the present invention will be further described below.

[Organic metal complex]
Moreover, the organometallic complex which has the said imidazole compound as a partial structure can be obtained using the imidazole compound manufactured with the manufacturing method of the imidazole compound of this invention.
This organometallic complex preferably contains at least one metal selected from the metal elements from Group 8 to Group 11 of the Periodic Table. The metal is preferably platinum or iridium.
As this organometallic complex, for example, a compound in which the imidazole compound represented by the general formula (1) is used as a ligand for the metal elements from Group 8 to Group 11 of the Periodic Table can be given.
This organometallic complex has an imidazole compound represented by the general formula (1) as a ligand, and thus can be used as a light emitting material having a sharp emission spectrum and capable of emitting light on the short wavelength side. Therefore, it is particularly useful as a blue light emitting organic EL device material.
Specific examples of such organometallic complexes are shown below, but are not limited thereto.

[Materials for organic electroluminescence elements]
An organic electroluminescent element material can be provided using at least one of the imidazole compound produced by the method for producing an imidazole compound of the present invention, the imidazole compound, and the organometallic complex. Hereinafter, the organic electroluminescence element is referred to as an organic EL element, and the organic electroluminescence element material is referred to as an organic EL element material.

[Organic EL elements, displays, lighting devices]
Further, the following organic EL element can also be regarded as one of other embodiments of the present invention. That is, the imidazole compound production method of the present invention makes it possible to produce an imidazole compound that is useful as a material for an organic EL device, which was difficult to produce by a conventional production method. The following organic EL device containing an imidazole compound, which has been difficult, can be efficiently produced.

This organic EL element is
An organic EL device comprising an organic compound layer having one or more layers between an anode and a cathode,
The organic compound layer includes a light emitting layer,
Any one of the organic compound layers includes an organometallic complex,
The organometallic complex has an imidazole compound represented by the following general formula (4) as a partial structure.

(However, in the general formula (4),
R 1 is a substituent having a steric parameter (Es) value of −1.70 or less,
Z 1 represents an atomic group necessary for forming a hydrocarbon ring group or a heterocyclic group, and the hydrocarbon ring group or the heterocyclic group formed in Z 1 represents one or more of R 1 Have
R 2 and R 3 represent a bond, a hydrogen atom or an aromatic hydrocarbon group, and are bonded to each other to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocycle or a 6-membered heterocycle. A ring may be formed, and these rings may have a substituent,
Z 2 represents an atomic group necessary to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with C—C;
R 4 represents a hydrogen atom or a substituent,
m represents an integer of 1 to 5. )

The preferred examples of Z 1 , Z 2 , R 1 , R 2 , R 3 , and R 4 are the same as those described in the general formula (1), and thus detailed description thereof is omitted.

In general formula (4), R 1 is a three-dimensional parameter (Es) value is at -1.70 or less, may be greater than -2.0. R 1 is preferably a substituent having an Es value of −2.0 or less, more preferably a substituent having an Es value of −2.5 or less, and even more preferably an Es value of −3. The substituent is 0 or less, and particularly preferably -5.0 or less.

The R 1 substituent preferably has a molecular weight of 43 or more, more preferably 77 or more, more preferably 116 or more, still more preferably 127 or more, and particularly preferably. Is 165 or more.
In addition, the organometallic complex having the imidazole compound represented by the general formula (4) as a partial structure is preferably a metal element selected from the group 8 to group 11 metal elements of the periodic table More preferably, the metal element is either iridium or platinum.
Specific examples of the organometallic complex include, but are not limited to, (C-1) to (C-12).

  The organometallic complex is preferably included in the light emitting layer, and particularly preferably included as a light emitting dopant material. This organic EL element preferably emits phosphorescence.

  As another embodiment, the present invention also provides a display device or a lighting device including the organic EL element.

The organic EL element will be described in more detail below.
The organic EL element has an organic compound layer between a cathode and an anode, and the organic compound layer includes at least one layer composed of an organic compound. The organic compound layer may contain an inorganic compound.
In this organic EL element, at least one of the organic compound layers includes the material for the organic EL element. The organic compound layer has at least one light emitting layer. Therefore, the organic compound layer may be composed of, for example, a single light emitting layer, and is used in known organic EL elements such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer. The layers to be stacked may be laminated via the light emitting layer.
As the structure of the multilayer organic EL element, for example,
(A) Anode / hole injection / transport layer / light emitting layer / cathode,
(B) Anode / light emitting layer / electron injection / transport layer / cathode,
(C) Anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode,
(D) Anode / hole injection / transport layer / light emitting layer / hole barrier layer / electron injection / transport layer / cathode,
The thing laminated | stacked by the multilayer structure of these is mentioned.
The “hole injection / transport layer” means “at least one of a hole injection layer and a hole transport layer”, and “electron injection / transport layer” means “electron injection layer and electron transport layer”. It means “at least one of the layers”.

An organic EL device material containing the imidazole compound or the imidazole compound can be used as a host of the light emitting layer, or an organic EL device material containing the organometallic complex can be used as a dopant of the light emitting layer.
In the latter case, the organometallic complex is particularly useful for forming a blue light-emitting layer because it has a sharp emission spectrum as described above and emits light on the short wavelength side.
Not only an organic EL element having a blue light emitting layer but also an organic EL element having a red light emitting layer and an organic EL element having a green light emitting layer can be arranged side by side to constitute a display device or a lighting device capable of color display.
Alternatively, a red light emitting layer and a green light emitting layer may be separately laminated on the blue light emitting layer to constitute a white light emitting organic EL element. In this case, a so-called tandem element structure is preferable. An organic EL element that emits white light can also be suitably used for a display device and a lighting device.

  In the organic EL element, in addition to the material for the organic EL element, an arbitrary material can be selected from known materials used in conventional organic EL elements.

  Hereinafter, examples according to the present invention will be described, but the present invention is not limited to these examples.

Example 1 Synthesis of Imidazole Compound (Compound 3) (Synthesis Example 1) Synthesis of Compound 1

Methanol (100 ml), glyoxal aqueous solution (40% by mass) (11.4 ml, 100 mmol), and 2,6-diisopropylaniline (17.73 g, 100 mmol) were placed in a three-necked flask and stirred at room temperature for 16 hours. Thereafter, methanol (400 ml), ammonium chloride (6.42 g, 120 mmol), and an aqueous formaldehyde solution (37% by mass) (16.2 ml, 200 mmol) were added and refluxed for 8 hours.
After completion of the reaction, the mixture was concentrated with an evaporator and adjusted to pH 10 with an aqueous sodium hydroxide solution. The sample was transferred to a separatory funnel, extracted with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (dichloromethane: ethyl acetate = 9: 1 (volume ratio)), and recrystallized from hexane to obtain a white solid (compound 1).
Compound 1 was identified by 1 H-NMR and FD-MS.
Yield 9.2g
Yield 40%

Synthesis Example 2 Synthesis of Compound 2

Under a nitrogen atmosphere, Compound 1 (27.4 g, 60 mmol) and tetrahydrofuran (60 ml) were placed in a three-necked flask and dissolved. The solution was cooled to 0 ° C., and n-BuLi hexane solution (35.9 ml, mole number of n-BuLi in the solution: 60 mmol, mole concentration (number of moles of n-BuLi / amount of solution): 1.67 M) over 10 minutes The mixture was further stirred at 0 ° C. for 30 minutes. Next, a solution of zinc chloride (13.6 g, 100 mmol) dissolved in tetrahydrofuran (100 ml) was added over 10 minutes. The solution was then returned to room temperature. n-Hexane was used as a solvent for the n-BuLi hexane solution. The same applies to other examples and comparative examples described later.
Compound 2 was directly used in the next reaction without purification.

(Synthesis Example 3) Synthesis of Compound 3

After preparing Compound 2 in Synthesis Example 2, an oil rotary pump was connected to the three-necked flask containing Compound 2 as it was through a solvent trap cooled with a dry ice / acetone refrigerant under reduced pressure. The three-necked flask was heated to about 40 ° C. to remove the solvent (150 ml) from the reaction system (solvent removal step). Here, the removal amount of the solvent is the amount collected in the solvent trap.
Thereafter, nitrogen was introduced into the system to return to normal pressure, and 2-tert-butyl-5-Bromopyrimidine (10.8 g, 50 mmol) and Pd (PPh 3 ) 4 (2.89 g, 2.5 mmol) were added to the reaction system. In addition, the mixture was reacted at 90 ° C. for 16 hours under a nitrogen atmosphere.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 3.
In addition, n-butane was produced by changing n-BuLi (molecular weight MW = 64.06) by the reaction of Synthesis Example 2. Specifically, n-BuLi (60 mmol) was changed to n-butane (60 mmol, 5.8 ml). The volume of n-butane was calculated based on the molecular weight of n-butane (MW = 58.12) and the specific gravity of n-butane (0.60).
Moreover, the volume of n-hexane was calculated | required as follows. First, the solution mass (24.4 g) is calculated from the specific gravity (0.68) of the n-BuLi hexane solution, and then the mass of n-hexane (20.56 g) is subtracted from the mass of the solution by subtracting the mass of n-BuLi (3.84 g). It calculated and calculated | required by converting into the volume with the specific gravity (0.66) of n-hexane.
These calculations are the same in the following examples and comparative examples.

As shown in Table 1, since the total amount of the solvent remaining in the flask after the solvent removal step was 47.0 ml, the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, was 47.0 ml. It can be said that it was the following.
Therefore, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mol] of 2-tert-butyl-5-Bromopyrimidine is as shown in Table 1. ,
V A / N f2 ≦ 0.94
Thus, the relationship of the mathematical formula (3) was satisfied.

After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (200 ml), and an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (62.43 g, 150 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (dichloromethane: acetone = 95: 5 (volume ratio)), and then recrystallized from a hexane / ethyl acetate mixed solvent to obtain a white solid (compound 3).
Compound 3 was identified by 1 H-NMR and FD-MS.
Yield 15.2 g
Yield 84%

Example 2 Synthesis of Imidazole Compound (Compound 4) (Synthesis Example 4) Synthesis of Compound 4

In the same process as in Synthesis Example 2, compound 1 (28.5 g, 125 mmol), tetrahydrofuran (125 ml), n-BuLi hexane solution (74.9 ml, number of moles of n-BuLi in the solution: 125 mmol, molar concentration (n Compound 2 was prepared from a solution containing 1.67M) and zinc chloride (28.4 g, 208 mmol) dissolved in tetrahydrofuran (208 ml). After the preparation, an oil rotary pump is connected to the three-necked flask containing compound 2 through a solvent trap cooled with a dry ice / acetone refrigerant, and the three-necked flask is heated to about 40 ° C. under reduced pressure. The solvent (310 ml) was removed from the reaction system (solvent removal step). Here, the removal amount of the solvent is the amount collected in the solvent trap.
Thereafter, nitrogen was introduced into the system to return to normal pressure, toluene (104 ml) was added to the reaction system (toluene addition step), then iodobenzene (21.3 g, 104 mmol), and Pd (PPh 3 ) 4 (2.89 g, 2.5 mmol) was added, and the mixture was reacted at 120 ° C. for 16 hours under a nitrogen atmosphere.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 4.
At this time, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mole] of iodobenzene was calculated by the same calculation as in (Synthesis Example 3). As shown in 1,
V A / N f2 ≦ 0.96
Thus, the relationship of the mathematical formula (3) was satisfied.
Furthermore, the relationship between the volume V B [liter] of toluene, which is an aromatic hydrocarbon solvent having 7 carbon atoms, and the number of moles N f2 [mol] of iodobenzene is as shown in Table 1.
V B / N f2 = 1
Thus, the relationship of the mathematical formula (5) was satisfied.
Note that the reaction system in Synthesis Example 4 may contain n-hexane, which is an aliphatic hydrocarbon solvent having 6 carbon atoms, even after the solvent removal step. However, since the volume of n-hexane after the solvent removal step is smaller than the volume of toluene added thereafter, even if n-hexane is taken into account, the relationship of the formula (5) is still satisfied. This also applies to Example 3 and Example 4 described later.
Therefore, the reaction conditions of Synthesis Example 4 were performed under the conditions satisfying the relations of Equation (3) and Equation (5).

After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (300 ml), an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (129.9 g, 312 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (toluene: ethyl acetate = 95: 5 (volume ratio)), and then recrystallized from a mixed solvent of hexane / ethyl acetate to obtain a white solid.
Compound 4 was identified by 1 H-NMR and FD-MS.
Yield 24.7g
Yield 78%

Example 3 Synthesis of Imidazole Compound (Compound 5) (Synthesis Example 5) Synthesis of Compound 5

In the same process as in Synthesis Example 2, compound 1 (15.98 g, 70 mmol), tetrahydrofuran (140 ml) and n-BuLi hexane solution (41.9 ml, number of moles of n-BuLi in the solution: 70 mmol, molar concentration (n Compound 2 was prepared from a solution containing 1.67M) and zinc chloride (13.6 g, 100 mmol) dissolved in tetrahydrofuran (100 ml). After the preparation, an oil rotary pump is connected to the three-necked flask containing compound 2 through a solvent trap cooled with a dry ice / acetone refrigerant, and the three-necked flask is heated to about 40 ° C. under reduced pressure. The solvent (250 ml) was removed from the reaction system (solvent removal step). Here, the removal amount of the solvent is the amount collected in the solvent trap.
After this, nitrogen was introduced into the system to return to normal pressure, and toluene (50 ml) was added to the reaction system (toluene addition step), followed by 2-Bromodibenzofuran (12.35 g, 50 mmol), and Pd (PPh 3 ) 4 ( 2.89 g, 2.5 mmol) was added, and the mixture was reacted at 120 ° C. for 18 hours under a nitrogen atmosphere.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 5.
As shown in Table 1, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mol] of 2-Bromodibenzofuran is (Synthesis Example 3) With similar calculations,
V A / N f2 ≦ 0.66
Thus, the relationship of the mathematical formula (3) was satisfied.
Further, the relationship between the volume V B [liter] of toluene and the number of moles N f2 [mol] of 2-Bromodibenzofuran is as shown in Table 1.
V B / N f2 = 1
Thus, the relationship of the mathematical formula (5) was satisfied.
Therefore, the reaction conditions of Synthesis Example 5 were performed under the conditions satisfying the relations of Equation (3) and Equation (5).

After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (300 ml), to which is added an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (62.4 g, 150 mmol), shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (dichloromethane: ethyl acetate = 95: 5 (volume ratio)), and then recrystallized from a hexane / ethyl acetate mixed solvent to obtain a white solid (compound 5).
Compound 5 was identified by 1 H-NMR and FD-MS.
Yield 15.8g
Yield 80%

Example 4 Synthesis of Imidazole Compound (Compound 9) (Synthesis Example 6) Synthesis of Compound (2-Fluoro-1,3-diiodobenzene)

Under a nitrogen atmosphere, 2-Fluoroiodobenzene (75.0 g, 338 mmol) and tetrahydrofuran (676 ml) were added to a three-necked flask and cooled to −70 ° C., and diisopropylamine (41.0 g, 405.6 mmol) and an n-BuLi hexane solution were previously added thereto. (228.1 ml, number of moles of n-BuLi in solution: 371.8 mmol, mole concentration (number of moles of n-BuLi / volume of solution): 1.63 M), and 20 ml of lithium diisopropylamide / tetrahydrofuran solution prepared from tetrahydrofuran (300 ml) It was added dropwise over a period of minutes. After stirring at −70 ° C. for 1 hour, iodine (94.4 g, 371.8 mmol) was added, the temperature was slowly returned to room temperature, and the mixture was stirred for 12 hours.
After completion of the reaction, the reaction mixture was deactivated by adding a small amount of water, and then concentrated with an evaporator. Residual iodine was deactivated by adding sodium thiosulfate / sodium hydroxide aqueous solution, and the sample was transferred to a separatory funnel and extracted three times with dichloromethane. The extract was dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (hexane) and recrystallized from hexane (150 ml) at −10 ° C. to obtain a white solid (2-Fluoro-1,3-diiodobenzene).
This compound was identified by 1 H-NMR and FD-MS.
Yield 62.0g
Yield 53%

(Synthesis Example 7) Synthesis of Compound 6


Under a nitrogen atmosphere, in a three-necked flask, 2-Fluoro-1,3-diiodobenzene (61.9 g, 178 mmol), carbazole (71.4 g, 427.2 mmol), K 3 PO 4 (151.14 g, 712 mmol), CuI (6.78 g, 35.6 mmol) ), Trans-1,2-diaminocyclohexane (12.8 ml, 106.8 mmol) and 1,4-dioxane (178 ml) were added and refluxed for 16 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and then the sample was dissolved in toluene (500 ml) and filtered using Celite to separate inorganic salts, and the filtrate was concentrated. Methanol was added to the filtrate to precipitate a sample, dispersion washing was performed, the sample was collected by filtration and vacuum dried (50 ° C., 8 hours) to obtain a white solid (Compound 6).
Compound 6 was identified by 1 H-NMR and FD-MS.
Yield 42.57 g
Yield 56%

Synthesis Example 8 Synthesis of Compound 7

In a nitrogen atmosphere, put potassium hydride (3.0 g, 75 mmol) and N, N-dimethylformamide (50 ml) in a three-necked flask, cool to 0 ° C., and add N, N-dimethylformamide (50 ml) there. A solution of dissolved imidazole (6.81 g, 100 mmol) was added over 20 minutes while paying attention to the hydrogen gas evolution rate, and then stirred at room temperature for 1 hour. Compound 6 (21.32 g, 50 mmol) was then added and refluxed for 6 hours.
After completion of the reaction, water (200 ml) was added and the precipitated sample was collected by filtration. The sample was dissolved in dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (dichloromethane: ethyl acetate = 9: 1 (volume ratio)), then dispersed and washed with hexane, collected by filtration and dried in vacuo (50 ° C., 8 hours) to give a white solid (compound 7 )
Compound 7 was identified by 1 H-NMR and FD-MS.
Yield 17.79 g
Yield 75%

(Synthesis Example 9) Synthesis of Compound 8

In a nitrogen atmosphere, compound 7 (5.69 g, 12 mmol) and tetrahydrofuran (72 ml) were placed in a three-necked flask, and then n-BuLi hexane solution (7.2 ml, moles of n-BuLi in the solution: 12 mmol, mol) at room temperature. Concentration (number of moles of n-BuLi / amount of solution): 1.67M) was added and stirred for 30 minutes. Next, a solution of zinc chloride (2.04 g, 15 mmol) dissolved in tetrahydrofuran (15 ml) was added over 5 minutes.
Compound 8 was directly used in the next reaction without purification.

(Synthesis Example 10) Synthesis of Compound 9

After synthesizing compound 8 in Synthesis Example 9, an oil rotary pump was connected to the three-necked flask containing compound 8 as it was through a solvent trap cooled with a dry ice / acetone refrigerant, under reduced pressure. The three-necked flask was heated to about 40 ° C. to remove the solvent (90 ml) from the reaction system (solvent removal step). Here, the removal amount of the solvent is the amount collected in the solvent trap.
Then, after cooling to room temperature, nitrogen was introduced into the system to return to normal pressure, toluene (30 ml) was added (toluene addition step), then iodobenzene (2.04 g, 10 mmol), and Pd (PPh 3 ) 4 (231 mg, 0.2 mmol) was added, and the mixture was reacted at 120 ° C. for 16 hours under a nitrogen atmosphere.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 10.
As shown in Table 1, since the total amount of the solvent remaining in the flask after the solvent removal step was 4.4 ml, the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, was 4.4 ml. It can be said that it was the following.
Therefore, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mol] of iodobenzene is as shown in Table 1.
V A / N f2 ≦ 0.44
Thus, the relationship of the mathematical formula (3) was satisfied.
Furthermore, as shown in Table 1, the relationship between the toluene volume V B [liter] and the number of moles of iodobenzene N f2 [mol] is as follows.
V B / N f2 = 3.0
Thus, the relationship of the mathematical formula (5) was satisfied.
Therefore, the reaction conditions of Synthesis Example 10 were performed under the conditions satisfying the relations of Equation (3) and Equation (5).

After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (200 ml), and an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (8.32 g, 20 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was recovered, further extracted from the aqueous phase with dichloromethane several times, dried over anhydrous magnesium sulfate, filtered, concentrated and dried. This was purified by silica gel chromatography (toluene: ethyl acetate = 90: 10 (volume ratio)), and then dispersed and washed with methanol to obtain a white solid (compound 9).
The compound 9 was identified by 1 H-NMR and FD-MS. 1 and 2 show the 1 H-NMR spectrum of Compound 5.
Yield 2.3g
Yield 42%

Comparative Example 1 Synthesis of Imidazole Compound (Compound 3) (Synthesis Example 11)

In the same process as in Synthesis Example 2, compound 1 (27.4 g, 60 mmol), tetrahydrofuran (60 ml), n-BuLi hexane solution (35.9 ml, number of moles of n-BuLi in the solution: 60 mmol, molar concentration (n Compound 2 was prepared from a solution containing 1.67M) and zinc chloride (13.6 g, 100 mmol) dissolved in tetrahydrofuran (100 ml). After the preparation, add 2-tert-butyl-5-Bromopyrimidine (10.8 g, 50 mmol) and Pd (PPh 3 ) 4 (2.89 g, 2.5 mmol) to the three-necked flask containing Compound 2 as it is under a nitrogen atmosphere. And reacted at 90 ° C. for 16 hours. That is, in Comparative Example 1, the solvent removal step was not performed, and toluene was not added.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 11.
As shown in Table 1, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mol] of 2-tert-butyl-5-Bromopyrimidine is By the same calculation as in Example 3,
V A / N f2 = 3.2
Thus, the relationship of the mathematical formula (1) was not satisfied.

After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (200 ml), and an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (62.43 g, 150 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. This was purified by silica gel chromatography (dichloromethane: acetone = 95: 5 (volume ratio)) to obtain a white solid (compound 3).
Compound 3 was identified by 1 H-NMR and FD-MS.
Yield 0.72g
Yield 4%

Comparative Example 2 Synthesis of Imidazole Compound (Compound 4) (Synthesis Example 12)

In the same process as in Synthesis Example 2, compound 1 (28.5 g, 125 mmol), tetrahydrofuran (125 ml), and n-BuLi hexane solution (74.9 ml, number of moles of n-BuLi in the solution: 125 mmol, molar concentration (n Compound 2 was prepared from a solution containing 1.67 M) and zinc chloride (28.4 g, 208 mmol) dissolved in tetrahydrofuran (208 ml). After the preparation, iodobenzene (21.3 g, 104 mmol) and Pd (PPh 3 ) 4 (2.89 g, 2.5 mmol) were added to the three-necked flask containing Compound 2 as it was, and the mixture was refluxed for 16 hours under a nitrogen atmosphere. That is, in Comparative Example 2, the solvent removal step was not performed, and toluene was not added.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 12.
As shown in Table 1, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles of iodobenzene N f2 [mole] was calculated in the same manner as in Synthesis Example 3. ,
V A / N f2 = 3.2
Thus, the relationship of the mathematical formula (1) was not satisfied.

  After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (300 ml), an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (129.9 g, 312 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. However, the presence of the target product could not be confirmed by thin layer chromatography.

Comparative Example 3 Synthesis of Imidazole Compound (Compound 5) (Synthesis Example 13)

In the same process as in Synthesis Example 2, compound 1 (15.98 g, 70 mmol), tetrahydrofuran (140 ml) and n-BuLi hexane solution (41.9 ml, number of moles of n-BuLi in the solution: 70 mmol, molar concentration (n Compound 2 was prepared from a solution containing 1.67M) and zinc chloride (13.6 g, 100 mmol) dissolved in tetrahydrofuran (100 ml). After preparation, 2-Bromodibenzofuran (12.35 g, 50 mmol) and Pd (PPh 3 ) 4 (2.89 g, 2.5 mmol) were added to the three-necked flask containing compound 2 and refluxed for 18 hours under a nitrogen atmosphere. . That is, in Comparative Example 3, the solvent removal step was not performed, and toluene was not added.

The relationship of the amount of solvent in the reaction system in Synthesis Example 13 is summarized in Table 1.
As shown in Table 1, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles N f2 [mol] of 2-Bromodibenzofuran is the same calculation as in Synthesis Example 3. By
V A / N f2 = 4.8
Thus, the relationship of the mathematical formula (1) was not satisfied.

  After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (300 ml), to which is added an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (62.4 g, 150 mmol), shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. However, the presence of the target product could not be confirmed by thin layer chromatography.

Comparative Example 4 Synthesis of Imidazole Compound (Compound 9) (Synthesis Example 14)

In the same manner as in Synthesis Example 9, compound 7 (5.69 g, 12 mmol), tetrahydrofuran (72 ml), n-BuLi hexane solution (7.5 ml, number of moles of n-BuLi in the solution: 12.5 mmol, molar concentration (n -BuLi mole number / solution amount): 1.67 M) and compound 8 was prepared from a solution containing zinc chloride (2.04 g, 15 mmol) dissolved in tetrahydrofuran (15 ml). After the preparation, iodobenzene (2.04 g, 10 mmol) and Pd (PPh 3 ) 4 (231 mg, 0.2 mmol) were added to the three-necked flask containing Compound 8 as it was, and the mixture was refluxed for 16 hours under a nitrogen atmosphere. That is, in Comparative Example 4, the solvent removal step was not performed, and toluene was not added.

Table 1 summarizes the relationship of the amount of solvent in the reaction system in Synthesis Example 14.
As shown in Table 1, the relationship between the total volume V A [liter] of tetrahydrofuran, which is an ether solvent having 5 or less carbon atoms, and the number of moles of iodobenzene N f2 [mole] was calculated in the same manner as in Synthesis Example 3. ,
V A / N f2 = (72 + 15) × 10 −3 / 10 × 10 −3 = 8.7
Thus, the relationship of the mathematical formula (1) was not satisfied.

  After completion of the reaction, the reaction was deactivated by adding a small amount of water to the sample. This is diluted with dichloromethane (200 ml), and an aqueous solution of tetrasodium ethylenediaminetetraacetate dihydrate (8.32 g, 20 mmol) is added thereto, shaken well in a separatory funnel, and the pH of the aqueous phase becomes 10 or more. A sodium hydroxide aqueous solution was added to adjust. The dichloromethane phase was collected, extracted from the aqueous phase several times with dichloromethane, dried over anhydrous magnesium sulfate, filtered and concentrated. Compound 9 was not confirmed in Synthesis Example 14 from the results of high performance liquid chromatography analysis described below.

[Liquid chromatography analysis]
Prior to silica gel chromatography purification, samples obtained in the synthesis of Example 9 and Comparative Example 9 Compound 9 were each prepared in 100 ml tetrahydrofuran solution using a 100 ml graduated cylinder, and then 1 / 10th. The process of diluting to a concentration (specifically, extracting 1 ml of the solution and preparing it in a 10 ml tetrahydrofuran solution using a 10 ml graduated cylinder) is repeated three times, and the sample is substantially dissolved in 100 L of tetrahydrofuran. 10 ml of a solution having a concentration corresponding to the concentration of the solution was prepared.
The results of high performance liquid chromatography analysis using this solution are shown in FIG.
-High-performance liquid chromatography analysis conditions The high-performance liquid chromatography apparatus was measured under the following conditions using Agilent 1100 series (model: binary pump G1312A) manufactured by Agilent Technologies.
Column: Inertsil ODS3V (φ4.6mm × 250mm, 5μm)
Mobile phase: 0.1% by mass HCOOH + 0.1% by mass HCOONH 4 aqueous solution / acetonitrile = 30/70 (v / v) (volume ratio)
Flow rate: 1000μl / min
Injection volume: 5.0 μl
UV detection wavelength: 254nm

(Mass spectrometry)
In addition, mass spectrometry was also performed, and it was confirmed that each peak component on the chart was the compound 7 as the raw material and the target product 9.

  From the results of high performance liquid chromatography analysis and mass spectrometry, compound 9 can be synthesized in a relatively good yield in the present invention, and compound 9 cannot be synthesized by the conventional method as shown in the comparative example. I understand that.

  Table 2 compares the yields of the compounds 3, 4, 5, and 9 synthesized in Examples 1 to 4 and Comparative Examples 1 to 4.

As shown in Table 2, even with the same target compound, the synthesis method of the comparative example has a very low yield or cannot be synthesized, whereas the synthesis method of the examples can be synthesized with a high yield.
Therefore, it turns out that the manufacturing method of the imidazole compound which concerns on this invention is a very useful manufacturing method, when synthesize | combining the imidazole compound shown by General formula (1).

Claims (12)

  1. In the method for producing an imidazole compound, the imidazole compound represented by the following general formula (1) is produced by reacting the compound represented by the following general formula (2) with the compound represented by the following general formula (3). There,
    In reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), the number of moles of the compound represented by the general formula (2) in the reaction system N f2 [ Mole] and the total volume V A [liter] of the ether solvent having 5 or less carbon atoms satisfy the relationship of the following formula (1): A method for producing an imidazole compound.

    (In the formula (1),
    R 1 represents a hydrogen atom or a substituent,
    Z 1 represents an atomic group necessary to form a hydrocarbon ring group or a heterocyclic group, wherein the hydrocarbon ring group or the heterocyclic group formed by said Z 1 is, the R 1 1 or more Have
    R 2 and R 3 each represent a bond, a hydrogen atom or an aromatic hydrocarbon group, and are bonded to each other to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring. Further, these rings may have a substituent,
    Z 2 represents an atomic group necessary to form a 5-membered hydrocarbon ring, a 6-membered hydrocarbon ring, a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with C—C;
    R 4 represents a hydrogen atom or a substituent,
    m represents an integer of 1 to 5. )

    (In the formula (2),
    X represents a halogen atom,
    Z 2 , R 4 , and m have the same meanings as those in the general formula (1). )

    (In formula (3),
    M represents a boron atom, a magnesium atom, a silicon atom, a tin atom, or a zinc atom, and may further have a substituent,
    Z 1 , R 1 , R 2 , and R 3 are respectively synonymous with the general formula (1). )
    [Equation 1]
    V A / N f2 ≦ 3 (1)
  2. In the manufacturing method of the imidazole compound of Claim 1,
    The method for producing an imidazole compound, wherein the number of moles N f2 of the compound represented by the general formula (2) and the total volume VA satisfy the relationship of the following formula (2).
    [Equation 2]
    V A / N f2 ≦ 2 (2)
  3. In the manufacturing method of the imidazole compound of Claim 1,
    The method for producing an imidazole compound, wherein the number of moles N f2 of the compound represented by the general formula (2) and the total volume VA satisfy the relationship of the following formula (3).
    [Equation 3]
    V A / N f2 ≦ 1 (3)
  4. In the manufacturing method of the imidazole compound as described in any one of Claim 1- Claim 3,
    The ether solvent having 5 or less carbon atoms is at least one ether solvent selected from tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,3-dioxane, diethyl ether, and 1,2-dimethoxyethane. A method for producing an imidazole compound.
  5. In the manufacturing method of the imidazole compound as described in any one of Claim 1- Claim 4,
    A method for producing an imidazole compound, wherein a solvent removal treatment for removing the solvent of the reaction system is performed to adjust the relationship between the number of moles Nf2 and the total volume VA .
  6. In the manufacturing method of the imidazole compound as described in any one of Claim 1- Claim 5,
    In the reaction system, the second solvent includes at least one solvent selected from an aliphatic hydrocarbon solvent having 7 or more carbon atoms, an aromatic hydrocarbon solvent, and an ether solvent having 6 or more carbon atoms,
    In reacting the compound represented by the general formula (2) with the compound represented by the general formula (3), the number of moles N f2 of the compound represented by the general formula (2) in the reaction system. And the total volume V B of the second solvent satisfy the relationship of the following mathematical formula (4): A method for producing an imidazole compound.
    [Equation 4]
    0.1 ≦ V B / N f2 (4)
  7. In the manufacturing method of the imidazole compound of Claim 6,
    The number of moles N f2 of the compound represented by the general formula (2) in the reaction system and the total volume V B of the second solvent satisfy the relationship of the following mathematical formula (5). Compound production method.
    [Equation 5]
    0.1 ≦ V B / N f2 ≦ 10 (5)
  8. In the manufacturing method of the imidazole compound of Claim 6 or Claim 7,
    The ether solvent having 6 or more carbon atoms is at least one selected from dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methoxybenzene, ethoxybenzene, methylanisole, ethylanisole, dimethoxybenzene, and methoxyethoxybenzene. A method for producing an imidazole compound, characterized by comprising two solvents.
  9. In the manufacturing method of the imidazole compound as described in any one of Claim 6- Claim 8,
    The carbon number of the aliphatic hydrocarbon solvent having 7 or more carbon atoms is 7 or more and 50 or less,
    The method for producing an imidazole compound, wherein the aromatic hydrocarbon solvent has 6 to 20 carbon atoms.
  10. In the manufacturing method of the imidazole compound as described in any one of Claim 6- Claim 9,
    The method for producing an imidazole compound, wherein the aromatic hydrocarbon solvent is at least one solvent selected from benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and tetramethylbenzene.
  11. In the manufacturing method of the imidazole compound as described in any one of Claim 1- Claim 10,
    M in the said General formula (3) is a zinc atom which may have a substituent. The manufacturing method of the imidazole compound characterized by the above-mentioned.
  12.   The imidazole compound manufactured by the manufacturing method of the imidazole compound as described in any one of Claim 1- Claim 11.
JP2011002084A 2011-01-07 2011-01-07 Method for producing imidazole compound, and imidazole compound Pending JP2012144455A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011002084A JP2012144455A (en) 2011-01-07 2011-01-07 Method for producing imidazole compound, and imidazole compound

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP2011002084A JP2012144455A (en) 2011-01-07 2011-01-07 Method for producing imidazole compound, and imidazole compound
US13/978,406 US20130270541A1 (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
EP12732174.3A EP2662365A4 (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
TW101100395A TW201233675A (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
PCT/JP2012/050087 WO2012093688A1 (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
CN2012800046521A CN103443081A (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device
KR1020137017116A KR20130140810A (en) 2011-01-07 2012-01-05 Imidazole compound production method, imidazole compound, imidazole-based compound, organic metal complex, material for organic electroluminescent element, organic electroluminescent element, display device, and lighting device

Publications (1)

Publication Number Publication Date
JP2012144455A true JP2012144455A (en) 2012-08-02

Family

ID=46788422

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2011002084A Pending JP2012144455A (en) 2011-01-07 2011-01-07 Method for producing imidazole compound, and imidazole compound

Country Status (1)

Country Link
JP (1) JP2012144455A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014091722A (en) * 2012-11-06 2014-05-19 Konica Minolta Inc Imino chloride derivative production method and phenylimidazole derivative production method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03192366A (en) * 1989-12-22 1991-08-22 Mitsubishi Paper Mills Ltd Electrophotographic sensitive body
JP2005068110A (en) * 2003-08-27 2005-03-17 Mitsubishi Chemicals Corp Organometallic complex, luminescent material and organic electroluminescent element
JP2006509837A (en) * 2001-05-11 2006-03-23 テラセンス,インコーポレイテッド (Pyridyl) transition metal complex having an imidazole ligand
JP2008542203A (en) * 2005-05-06 2008-11-27 ユニバーサル ディスプレイ コーポレイション Devices with stable oled material and improved stability
JP2008303150A (en) * 2007-06-05 2008-12-18 Konica Minolta Holdings Inc Synthesis method of imidazole compound and organometal complex

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03192366A (en) * 1989-12-22 1991-08-22 Mitsubishi Paper Mills Ltd Electrophotographic sensitive body
JP2006509837A (en) * 2001-05-11 2006-03-23 テラセンス,インコーポレイテッド (Pyridyl) transition metal complex having an imidazole ligand
JP2005068110A (en) * 2003-08-27 2005-03-17 Mitsubishi Chemicals Corp Organometallic complex, luminescent material and organic electroluminescent element
JP2008542203A (en) * 2005-05-06 2008-11-27 ユニバーサル ディスプレイ コーポレイション Devices with stable oled material and improved stability
JP2008303150A (en) * 2007-06-05 2008-12-18 Konica Minolta Holdings Inc Synthesis method of imidazole compound and organometal complex

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JPN6014038772; BELLINA, Fabio et al: 'Regioselective Synthesis of 1,5-Diaryl-1H-imidazoles by Palladium-Catalyzed Direct Arylation of 1-Ar' The Journal of Organic Chemistry Vol.70, No.10, 2005, p.3997-4005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014091722A (en) * 2012-11-06 2014-05-19 Konica Minolta Inc Imino chloride derivative production method and phenylimidazole derivative production method

Similar Documents

Publication Publication Date Title
Tucker et al. Tin-free radical cyclization reactions initiated by visible light photoredox catalysis
Gujadhur et al. Formation of aryl nitrogen bonds using a soluble copper (I) catalyst
CN102292409B (en) Blue emitter with high efficiency based on imidazo [1,2-f] phenanthridine iridium complexes
JP4787259B2 (en) New organic light emitting device material and organic light emitting device using the same (8)
EP3046156A1 (en) Organic electroluminescent element, and illumination device and display device each comprising the element
US8142909B2 (en) Blue phosphorescent imidazophenanthridine materials
JP4595116B2 (en) Iridium complexes and luminescent materials using the same
TWI551606B (en) As the synthetic full color displays platinum narrow band of phosphorescent emitter, and palladium complexes of
JP5444715B2 (en) Organic electroluminescence element, lighting device and display device
EP2254173A1 (en) Organometallic complex and light emitting element, light emitting device, and electronic device using the organometallic complex
JP5765223B2 (en) Manufacturing method for organic electroluminescent element, and lighting device and display device provided with organic electroluminescent element
JP5055818B2 (en) Organic electroluminescent element material, organic electroluminescent element, display device and lighting device
Hart et al. Generalization of the triptycene concept. Use of diaryne equivalents in the synthesis of iptycenes
TWI624471B (en) Pyridyl carbene phosphorescent emitters
JP5194596B2 (en) Organic electroluminescence element, display device and lighting device
EP1904508B1 (en) Electro luminescent metal complexes
JP4496357B2 (en) Fluorinated iridium complex and light emitting material using the same
KR20120114030A (en) Novel organometallic compound and organic light-emitting diode using the same
JP5983648B2 (en) Organic electroluminescent element, compound for organic electroluminescent element, method for producing organic electroluminescent element, lighting device and display device
KR20110131201A (en) Light emitting material for use as-host dopant in emissive layer for oleds
WO2016129672A1 (en) Aromatic heterocyclic derivative, and organic electroluminescent element, illumination device, and display device using aromatic heterocyclic derivative
US9711742B2 (en) Four coordinated platinum and palladium complexes with geometrically distorted charge transfer state and their applications in light emitting devices
CN102892860B (en) Synthesis of four-coordinated gold complexes and their application in light emitting apparatus
JP5304010B2 (en) Organic electroluminescence element, display device and lighting device
CN101460515A (en) Heteroleptic transition metal-carbene complexes and their use in organic light-emitting diodes (OLEDs)

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20130918

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20140916

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20150217