JP2001328980A - 2-substituted imidazole compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of producing a 2-substituted imidazole compound useful as a coupler for recording materials in high yield. SOLUTION: This method for producing a 2-substituted imidazole compound is to prepare a 2-aminoimidazole derivative by using an α-haloketone derivative expressed by the following general formula (A) and acetylguanidine as starting materials, and produce the 2-susbstituted imidazole compound expressed by the following general formula (F) by position-selectively introducing a dimethylcarbamoyl group into the 2-aminoimidazole derivative and hydrolyzing the resulting compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel imidazole compound and a novel method for producing the same, and more particularly, to a novel 1-position-unsubstituted-2-position-substituted imidazole compound and the conversion of the compound into a 2-aminoimidazole derivative. A regioselective introduction of a dimethylcarbamoyl group and hydrolysis by hydrolysis.

[0002]

2. Description of the Related Art Compounds having an imidazole skeleton are known as color-forming components in light-sensitive materials, heat-sensitive materials and color-forming materials.
And it is known that it is useful as a precursor of a physiologically active substance, and various derivatives have been synthesized.

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel 2-substituted imidazole compound which exhibits good hue and is useful as a coupler for recording materials, and a process for producing the compound in high yield. The purpose is to:

[0004]

Means for solving the above problems are as follows. That is, <1> a first step of reacting an α-haloketone derivative represented by the following general formula (A) with acetylguanidine to produce a substituted imidazole represented by the following general formula (B): A second step of hydrolyzing a substituted imidazole represented by the following general formula (B) to produce a 2-amino-imidazole compound represented by the following general formula (C); Reacting the represented 2-amino-imidazole compound with dimethyl carbamic acid chloride,
A third step of producing an adduct represented by the following general formula (D), an adduct represented by the following general formula (D), an electrophile having R ² as a substituent and / or R ³ (Wherein R ² and R ³ are other than a hydrogen atom among those shown below) to form an adduct represented by the following general formula (E). A fourth step and a fifth step of hydrolyzing an adduct represented by the following general formula (E) to produce a 2-substituted imidazole compound represented by the following general formula (F). A method for producing a 2-substituted imidazole compound represented by the following general formula (F):

Formula (A)

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General formula (B)

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General formula (C)

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Formula (D)

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Formula (E)

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General formula (F)

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In the formula, R ¹ represents a hydrogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group. R ² and R ³ each independently represent a hydrogen atom, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a phosphate group, Represents an acid amide group. However, R ² and R ³ are not simultaneously hydrogen atoms. X represents a halogen atom.

<2> A 2-substituted imidazole compound represented by the following general formula (F).

General formula (F)

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In the formula, R ¹ represents a hydrogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group. R ² and R ³ each independently represent a hydrogen atom, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a phosphate group, Represents an acid amide group. However, R ² and R ³ are not simultaneously hydrogen atoms.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION [2-substituted imidazole compound]
The 2-substituted imidazole compound of the present invention is represented by the above general formula (F). In the general formula (F), R ¹ represents a hydrogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl. Represents a group.

The aryl group represented by R ¹ includes a substituted aryl group and an unsubstituted aryl group. Examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group,
Substituted oxycarbomoyl group, substituted oxysulfonyl group,
Examples include an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, a hydroxy group, an acyl group, an acyloxy group, a substituted sulfonyloxy group, a substituted aminocarbonyloxy group, and a substituted phosphoryloxy group.

The aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms, for example, a phenyl group, a 2-methylphenyl group, a 2-chlorophenyl group,
-Methoxyphenyl group, 2-ethoxyphenyl group, 2-
Propoxyphenyl group, 2-isopropoxyphenyl group, 2-butoxyphenyl group, 2- (2-ethylhexyloxy) phenyl group, 2-octyloxyphenyl group, 2-undecyloxyphenyl group, 2-trifluoromethylphenyl group , 2- (2-ethylhexyloxy) -5-chlorophenyl group, 2,2'-hexyloxy-3,5-dichlorophenyl group, 3- (2,4-di-
t-pentylphenoxyethoxy) phenyl group, 2-
(Dibutylaminocarbonylethoxy) phenyl group,
2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4,6-trimethylphenyl group, 3-chlorophenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3-trifluoromethylphenyl group, 3 -Methoxyphenyl group, 3-ethoxyphenyl group, 3-butoxyphenyl group, 3- (2'-ethylhexyloxy) phenyl group, 3,4-cyclophenyl group, 3,5-dichlorophenyl group, 3,4-dimethoxyphenyl Group, 3,5
-A dibutoxyphenyl group, a 3-octyloxyphenyl group, a 3- (dibutylaminocarbonylmethoxy) phenyl group,

3- (di-2-ethylhexylaminocarbonylmethoxy) phenyl, 3-dodecyloxyphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-nitrophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-isopropoxyphenyl group, 4-butoxyphenyl group, 4- (2-ethylhexyloxy) phenyl group, 4-isopentyloxyphenyl group, 4- (octadecyloxy) Phenyl group, 4-benzylphenyl group, 4-aminosulfonylphenyl group, 4-N, N-dibutylsulfonylphenyl group, 4-ethoxycarbonylphenyl group, 4- (2-ethylhexyloxycarbonyl) phenyl group, 4-t- Octylphenyl group, 4-fluorophenyl group, 3 Acetylphenyl group, 2-acetylaminophenyl group, 2,4-di-t-pentylphenyl group, 4- (2-ethylhexyloxy) carbonylphenyl group, 4-methylthiophenyl group, 4- (4-chlorophenylthio) phenyl And a hydroxyphenyl group, a phenylsulfonylphenyl group, a phenylsulfonyloxyphenyl group, a phenylcarbonyloxyphenyl group, a dimethylaminocarbonyloxyphenyl group, a butylcarbonyloxyphenyl group, and the like.

The alkyl group represented by R ¹ includes an alkyl group having a substituent and an unsubstituted alkyl group. Further, the alkyl group may be linear or branched, and may have an unsaturated bond. Examples of the substituent include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, and a halogen atom. Further, an aryl group as a substituent further includes an alkyl group,
It may be substituted with an alkoxy group, a nitro group, a cyano group, a hydroxy group or a halogen atom.

The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, a trifluoromethyl group, an ethyl group, a butyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. , Decyl, dodecyl, octadecyl, propyl, isopropyl, isobutyl, sec-butyl, t-butyl, pentyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, isopentyl, heptyl, Nonyl group, undecyl group, propenyl group, heptadecenyl group, t-octyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, 1- (ethoxycarbonyl) ethyl group, 2 ′, 4′- Diisopentylphenyloxymethyl group, 2 ', 4'-di t-butylphenyloxymethyl group, ethoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, butyldecyloxycarbonylethyl group, dibutylaminocarbonylmethyl group, dibenzylaminocarbonylethyl group, ethyloxycarbonylpropyl group, 2-ethylhexyl Oxycarbonylpropyl group, 2,4-di-t-amylphenyloxypropyl group, 1- (2 ′, 4′-di-t-amylphenyloxy) propyl group, 2,4-di-t-butylphenyloxy Propyl group, acetylaminoethyl group, N, N-dihexylaminocarbonylethyl group,
2,4-di-t-amyloxyethyloxycarbonylpropyl group, isostearyloxycarbonylpropyl, 1- (2,4-di-t-pentylphenyloxy)
Propyl group, 2,4-di-t-pentylphenyloxyethyloxycarbonylpropyl group, naphthyloxyethyloxycarbonylethyl group, N-methyl-N-phenylethyloxycarbonylethyl group, methanesulfonylaminopropyl group, and the like. Can be

The acyl group represented by R ¹ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group represented by R ¹ is preferably an acyl group having 2 to 20 carbon atoms, for example, an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, an octanoyl group, a 2-ethylhexanoyl group, a decanoyl group, and a dodecanoyl group ,
Octadecanoyl group, 2-cyanopropanoyl group, 1,
And a 1-dimethylpropanoyl group.

The carbamoyl group represented by R ¹ includes carbamoyl, N-alkylcarbamoyl, N-arylcarbamoyl, N, N-dialkylcarbamoyl,
N, N-diarylcarbamoyl group, N-alkyl-N
-Arylcarbamoyl groups and the like.

The carbamoyl group represented by R ¹ is preferably a substituted carbamoyl group having 1 to 30 carbon atoms, for example, N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-butylcarbamoyl. , N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group,
N-2-ethylhexylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-
Phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group,
N-2-methoxyphenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-
Ethylhexyloxy) phenylcarbamoyl group, N-
3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxycarbamoyl group, N-4-
(2′-ethylhexyloxy) phenylcarbamoyl, N-4-cyanophenylcarbamoyl, N-methyl-N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N, N-dibutylcarbamoyl,
And N-diphenylcarbamoyl group.

The alkoxycarbonyl group represented by R ¹ includes
It includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group represented by R ¹ is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, 2-ethylhexyloxy Carbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, phenyloxyethyloxycarbonyl, phenyloxypropyloxycarbonyl, 2,4-di-t-amylphenyloxyethylcarbonyl, 2,6 -Di-t-butyl-4-methylcyclohexyloxycarbonyl group, isostearyloxycarbonyl group and the like.

The aryloxycarbonyl group represented by R ¹ includes a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. R ¹
The aryloxycarbonyl group represented by is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms,
For example, a 2-methylphenyloxycarbonyl group, 2-
Chlorophenyloxycarbonyl group, 2,6-dimethylphenyloxycarbonyl group, 2,4,6-trimethylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-
Nitrophenyloxycarbonyl group, 2,2-ethylhexylphenyloxycarbonyl group, 3- (2-ethylhexyloxy) phenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-chlorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl Group, 4-butoxyphenyloxycarbonyl group and the like.

The amino group represented by R ¹ includes a substituted amino group and an unsubstituted amino group. Examples of the amino group having a substituent include an N-alkylamino group and an N-
Arylamino group, N-acylamino group, N-sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group, etc. Is mentioned.

The amino group represented by R ¹ has 0 to 0 carbon atoms.
50 amino groups are preferred, for example, N-methylamino group, N-ethylamino group, N-propylamino group, N-
Isopropylamino group, N-tertbutylamino group,
N-hexylamino group, N-cyclohexylamino group,
N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group,
N-benzylamino group, N-phenylamino group, N-2
-Methylphenylamino group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-
An isopropoxyphenylamino group, an N-2- (2-ethylhexyloxy) phenylamino group, an N-3-chlorophenylamino group, an N-3-nitrophenylamino group,
N-3-cyanophenylamino group, N-4-methoxyamino group, N-4- (2'-ethylhexyloxy) phenylamino group, N-4-cyanophenylamino group, N-
Methyl-N-phenylamino group, N, N-dimethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N , N- (dibutylcarbonyl) amino group, N, N- (di-2-ethylhexylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N
-(Dibutylsulfonyl) amino group, N, N- (2-ethylhexylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like.

The alkylsulfonyl group represented by R ¹ includes an alkylsulfonyl group having a substituent and an unsubstituted alkylsulfonyl group. The alkylsulfonyl group represented by R ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl Group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group and the like.

The arylsulfonyl group represented by R ¹ includes a substituted arylsulfonyl group and an unsubstituted arylsulfonyl group. The arylsulfonyl group represented by R ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, for example, a phenylsulfonyl group,
1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethyl Phenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-
A (2-ethylhexyloxy) phenylsulfonyl group,
3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4
-Butoxyphenylsulfonyl group, 4- (2-ethylhexyloxy) phenylsulfonyl group, 4-octadecylphenylsulfonyl group and the like.

The sulfamoyl group represented by R ¹ includes sulfamoyl, N-alkylsulfamoyl, N-arylsulfamoyl, N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl And N
-Alkyl-N-arylsulfamoyl groups are included.

The sulfamoyl group represented by R ¹ is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N
-Cyclohexylsulfamoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N −
2-methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-2- (2-ethylhexyl Oxy) phenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group,
N-4-methoxysulfamoyl group, N-4- (2'-
Ethylhexyloxy) phenylsulfamoyl group, N
-4-cyanophenylsulfamoyl group, N-methyl-
N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group,
N, N-diphenylsulfamoyl group, N, N-di (2-ethylhexyl) sulfamoyl group and the like can be mentioned.

In the general formula (F), R ² and R ³ each independently represent a hydrogen atom, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, Represents a sulfamoyl group, a phosphoric ester group or a phosphoric amide group. However, R ² and R ³ are not simultaneously hydrogen atoms. The acyl group, carbamoyl group, alkoxycarbonyl group, aryl group, oxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, and sulfamoyl group represented by R ² and R ³ are the same as those described above for R ¹ . The same applies to preferred examples.

The phosphate groups represented by R ² and R ³ each include a dialkyl phosphate group, a diaryl phosphate group, and an alkyl / aryl phosphate group. For example, the following phosphate ester groups and the like can be mentioned.

[0034]

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The phosphoric amide groups represented by R ² and R ³ include a monoalkyl phosphoric amide group, a dialkyl phosphoric amide group, a trialkyl phosphoric amide group, a tetraalkyl phosphoric amide group, and a monoaryl phosphoric amide group. Groups, diarylphosphoramide groups, triarylphosphamide groups, tetraarylphosphamide groups, and alkylarylphosphamide groups (including di, tri, and tetra substitutions). For example, the following phosphoric amide groups and the like can be mentioned.

[0036]

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Specific examples of the 2-substituted imidazole compound represented by formula (F) (exemplary compounds K-1 to 97) are shown below, but the present invention is not limited by the following specific examples. Absent.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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The 2-substituted imidazole compound represented by the general formula (F) is useful as a color-forming component in a light-sensitive material, a heat-sensitive material and a color-forming material, and as a precursor of a physiologically active substance. In particular, the 2-substituted imidazole compound is useful as a coloring component for recording materials because it can form a dye exhibiting a good hue by coupling with a diazo compound.

[Production Method of 2-Substituted Imidazole Compound] The 2-substituted imidazole compound represented by the above general formula (F) can be synthesized by the following first to fifth steps. Hereinafter, each step will be described.

-First Step- In the first step, an α-haloketone derivative represented by the following general formula (A) is reacted with acetylguanidine to give a substituted compound represented by the following general formula (B). This is a cyclization step for producing imidazole.

[0053]

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[0054] In the general formula (A) and (B), R ¹ has the same meaning as R ¹ in the general formula (F). In the general formula (A), X represents a halogen atom such as a chlorine atom, bromine and iodine. The same applies to the following general formulas (C) to (E).

In the first step, the amount (mol) of acetylguanidine used is preferably 2 to 3 times the amount (mol) of the α-haloketone derivative represented by the general formula (A).

In the first step, the reaction can be advanced by dissolving or suspending the acetylguanidine and the α-haloketone derivative in a solvent and, if desired, heating. The solvent is preferably an organic solvent, for example, dimethylformamide (DM
F), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), tetrahydrofuran (T
HF), N-methylpyrrolidone (NMP), N, N-dimethylimidazolidinone (DMI), acetic acid, chloroform and the like.

The reaction temperature may be appropriately determined according to the reactivity of the α-haloketone derivative.
C. to 80.degree. C., preferably room temperature to 60.degree.

-Second step- In the second step, the compound represented by the general formula (B) obtained in the first step is used.
Is a hydrolysis step of hydrolyzing a substituted imidazole represented by the following formula to produce a 2-amino-imidazole compound represented by the following general formula (C).

Formula (C)

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In the second step, the substituted imidazole represented by the general formula (B) is dissolved or suspended in a solvent, a hydrolysis catalyst is added as required, and the reaction is allowed to proceed by heating. . As the hydrolysis catalyst, an acid and a base can be used, but it is preferable to use an acid because the generated 2-amino-imidazole compound can be easily isolated. Proton acids and Lewis acids can be used as the acid catalyst.
Above all, it is preferable to use a protonic acid from the viewpoint of easy isolation of the 2-amino-imidazole compound and handling. For the protonic acid, a catalytic amount or a stoichiometric amount may be used, but it is preferable to use a stoichiometric amount because the reaction time can be shortened.

As the solvent, alcohol-based, ether-based, and halogen-based solvents can be used. When an alcohol-based solvent is used, the solvent can be used alone or as a mixed solvent with water. When a system solvent is used, it is preferably used as a mixed solvent with water. Among them, a single solvent of alcohol is preferable in that the isolation of the 2-amino-imidazole compound becomes easy.

The reaction temperature is preferably from room temperature to 100 ° C.
40 ° C to 80 ° C is more preferred.

After completion of the reaction, for example, the reaction solution is concentrated to precipitate the 2-amino-imidazole compound as a salt of the protonic acid or the like used in the hydrolysis and can be easily isolated.

-Third Step- The third step is to carry out the above-mentioned general formula (C) produced in the second step.
Is an addition step in which a 2-amino-imidazole compound represented by the following formula is reacted with dimethylcarbamic acid chloride to produce an adduct represented by the following general formula (D).

[0065]

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In the third step, the amount of the dimethyl carbamic chloride used is preferably 1 to 2 equivalents to the amount of the 2-amino-imidazole compound represented by the general formula (C).

In the third step, the 2-amino-imidazole compound is dissolved or suspended in a solvent, dimethylcarbamic acid chloride is added to a system to which a base is added as required, and the mixture is optionally heated. By
The reaction can proceed. The solvent is preferably an organic solvent, for example, DMF, DMAc, DMS
O, THF, NMP, DMI, chloroform and the like.

The presence of a base in the reaction system is preferable because the reaction can be promoted. Examples of the base include triethylamine, pyridine, 1,8-diazobicyclo [5.4.
0] undec-7-ene (DBU), N, N-dimethylaminopyridine (DMAP), K ₂ CO ₃ , NaHC
O ₃ , Na ₂ CO ₃ , KHCO _{3 and the} like can be mentioned. When a base is used, its use amount (mol) is preferably 1 to 3 times the use amount (mol) of the 2-amino-imidazole compound represented by the general formula (C). In the second step, 2 represented by the general formula (C) is used.
-When the amino-imidazole compound is obtained as a salt of a protonic acid, the salt can be subjected to the third step as it is, but in that case, the amount of the base used is only the amount necessary for neutralization with the protonic acid. It is preferable to add a large amount.

The reaction temperature may be appropriately determined depending on the reactivity of the 2-amino-imidazole compound, and is generally 0 ° C. to 100 ° C., preferably room temperature to 70 ° C.
° C. The reaction time can be appropriately adjusted according to the reactivity of the reagent.

-Fourth Step- The fourth step comprises the step of adding the adduct represented by the general formula (D) obtained in the third step and an electrophile having R ² and / or R ³ (Provided that R ² and R ³
Is a hydrogen atom other than those described above) to produce an adduct represented by the following general formula (E).

Formula (E)

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[0072] In the general formula (E), R ² and R ³ have the same meanings as R ² and R ³ in the general formula (F).

In the general formula (E), when an adduct in which both R ² and R ³ are substituents (other than a hydrogen atom) is formed, an electrophile having R ² as a substituent and R ³ Both the electrophile having a substituent and the adduct represented by the general formula (D) are sequentially reacted (when R ² and R ³ are the same substituent, R ² (= R ³ ) As a substituent is used in an amount about twice as large as the amount used when R ² and R ³ are different from each other). On the other hand, when an adduct in which either of R ² and R ^{3 in} the general formula (E) is a hydrogen atom is generated (for example, when a substituent is introduced as R ³ while R ² is a hydrogen atom) ) Reacts an electrophile having R ² as a substituent or an electrophile having R ³ as a substituent with the adduct represented by the general formula (D).

In the case where an adduct in which either R ² or R ³ is a hydrogen atom in the general formula (E) is obtained, the electrophile as a reaction reagent is represented by the general formula (D). It is preferable to use a molar amount of 1 to 1.5 times the used amount (mole) of the adduct. In the general formula (E), when obtaining an adduct in which R ² and R ³ are the same substituents other than a hydrogen atom, the electrophile as a reaction reagent is represented by the general formula (D). To the used amount (mol) of the adduct
It is preferred to use up to 5 times the molar amount. In the general formula (E), when an adduct in which R ² and R ³ are different substituents other than a hydrogen atom is obtained, the amount (mol) of the adduct represented by the general formula (D) is used. Te, the molar amount of 1 to 1.1 times the electrophile having as a substituent R ^2, and R ³
Is preferably used in an amount of 1 to 1.1 times the molar amount of an electrophile having the above formula as a substituent.

In the fourth step, the adduct represented by the general formula (D) and the electrophile are dissolved or suspended in a solvent, a base is added if necessary, and the mixture is heated if necessary. The reaction can proceed. As the solvent, an organic solvent is preferable, and a solvent that does not react with the electrophile (and a base optionally added) can be used. For example, DMF, DM
Ac, DMSO, THF, NMP, DMI, chloroform and the like.

The presence of a base in the reaction system is preferable because the reaction can be promoted. Examples of the base include NaH, K
H, triethylamine, pyridine, DBU, DMAP,
K ₂ CO ₃ , NaHCO ₃ , Na ₂ CO ₃ , KHCO _{3 and the} like. When a base is used, it is preferably used in an amount of 1 to 5 equivalents based on the amount of the adduct represented by the general formula (D).

The reaction temperature may be appropriately determined according to the reactivity of the reagents and the like, and is generally 0 ° C. to 100 ° C.
It is preferably room temperature to 60 ° C.

-Fifth Step- In the fifth step, the adduct represented by the general formula (E) is hydrolyzed to produce a 2-substituted imidazole compound represented by the general formula (F). This is a hydrolysis step.

In the fifth step, the reaction can proceed by dissolving or suspending the adduct represented by the general formula (E) in a solvent, adding a hydrolysis catalyst as required, and heating. . Although both an acid and a base can be used as the hydrolysis catalyst, it is preferable to use a base from the viewpoint of hydrolyzability. Examples of the base catalyst include NaOH, KOH, NaOMe, and KOMe. The amount (mole) of the base catalyst used is the same as in the general formula (E)
Is preferably 1 to 3 times the amount (mol) of the adduct represented by

As the solvent, alcohol-based, ether-based, and halogen-based solvents can be used. When an alcohol-based solvent is used, the solvent can be used alone or as a mixed solvent with water. When a system solvent is used, it is preferably used as a mixed solvent with water. Among them, a single solvent of alcohol is preferable in that the isolation of the 2-amino-imidazole compound becomes easy.

The reaction temperature is preferably from room temperature to 100 ° C.
Room temperature to 60 ° C is more preferred.

[0082]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Compound (1) was obtained according to the following scheme.

[0083]

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P-chlorophenacyl bromide (160
g, 0.69 mol) and acylguanidine (173)
g, 1.71 mol) was dissolved in 1.5 L of DMF, and the mixture was stirred at 50 ° C. while heating for 6.5 hours. After confirming the completion of the reaction by TLC, the reaction solution was poured into 3 liters of 1 mol / l HCl (aq) to obtain crude crystals. The crude crystals obtained are filtered and acetonitrile
The compound (1) was obtained by washing with 500 ml (yield 110 g, 57%). ¹ H-NMR of the obtained compound (solvent: DMSO d ₆ ; TM
S standard; 300 Hz) data (δ ppm) are shown below. 2.1 (S, 3H), 2.2 (S, 3H), 7.5
(D, 2H), 7.8 (S, 1H), 7.9 (d, 2
H)

Next, the compound (2) was obtained according to the following scheme.

[0086]

Embedded image

The obtained compound (1) (210 g, 0.8
9 mol) was suspended in 1 liter of a 1: 1 (volume ratio) mixed solvent of methanol and ethanol, and sulfuric acid (87 g,
0.89 mol). The mixture was stirred for 16 hours while heating under reflux. After confirming that the raw materials were consumed by TLC, the reaction solution was concentrated using a rotary evaporator to obtain a sulfate of compound (2) (145 g, yield 54).
%). If purification is necessary, the product may be washed with acetonitrile. ¹ H-NMR of the obtained compound (solvent: D
MSO d ₆ ; TMS standard; 300 Hz) data (δ
ppm) are shown below. 4.6 (S, 3H), 7.5-7.8 (m, 5H)

Next, the compound (3) was obtained according to the following scheme.

[0089]

Embedded image

The obtained compound (2) (100 g, 333)
mmol) and triethylamine (135 g, 1.3 m
ol) was suspended in 350 ml of acetonitrile, and dimethylcarbamic acid chloride (43 g 400
Milliliters). The reaction mixture is heated under reflux,
After stirring for 3 hours, consumption of the raw materials was confirmed by TLC. 1 mol / L HCl (aq) 2
When 00 ml and 10 ml of ethyl acetate were added and stirred, crystals were precipitated. The crystals were collected by filtration to give compound (3) (yield 82 g, 94%).
I got ¹ H-NMR of the obtained compound (solvent: DMS
Od ₆ ; TMS standard; 300 Hz) data (δ pp
m) is shown below. 3.0 (S, 6H), 6.9 (S, 2H), 7.5
(D, 2H), 7.6 (S, 1H), 7.6 (d, 2
H)

According to the following scheme, compound (4)
(Compound represented by the general formula (F)) was obtained.

[0092]

Embedded image

The obtained compound (3) (5 g, 19 mmol)
l) and p-dodecylbenzenesulfonyl chloride (7.8 g, 23 mmol) were dissolved in 50 ml of THF, and NaH (2.3 g, 57 mm) was dissolved at room temperature.
ol) was added. After confirming by TLC that the raw materials were consumed, 1 mol / L of HCl 100 was added to the reaction solution.
Milliliter was added, and the precipitated crystals were collected by filtration. The obtained crystals were washed with acetonitrile to obtain compound (4) (yield 7.6 g, 70%). ¹ of the resulting compound
H-NMR (solvent: DMSO d ₆ ; TMS standard; 30)
0 Hz) data (δ ppm) is shown below. 0.6-2.0 (m, 2tH), 3.3 (S, 6H),
7.0-7.5 (m, 5H), 7.7 (d, 2H),
7.8 (d, 2H), 12.4 (S, 1H)

When the obtained compound (4) was reacted with a diazonium salt, a good magenta hue was formed.

[0095]

According to the present invention, there is provided a novel 2-substituted imidazole compound which exhibits good hue and is useful as a coupler for recording materials, and a process for producing the compound in high yield. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 417/04 C07D 417/04

Claims (2)

[Claims] 1. A first step of reacting an α-haloketone derivative represented by the following general formula (A) with acetylguanidine to produce a substituted imidazole represented by the following general formula (B): A second step of hydrolyzing a substituted imidazole represented by the following general formula (B) to produce a 2-amino-imidazole compound represented by the following general formula (C); A third step of reacting the represented 2-amino-imidazole compound with dimethyl carbamic acid chloride to produce an adduct represented by the following general formula (D); And an electrophile having R ² as a substituent and / or an electrophile having R ³ as a substituent (provided that R ² and R ³ are other than the hydrogen atoms shown below) With the following general formula ( A) a hydrolyzing the adduct represented by the following general formula (E) to produce a 2-substituted imidazole compound represented by the following general formula (F). A fifth step of generating, represented by the following general formula (F):
A method for producing a position-substituted imidazole compound. General formula (A) General formula (B) General formula (C) General formula (D) General formula (E) General formula (F) (Wherein, R ¹ represents a hydrogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R ² and R ³ are each independently a hydrogen atom, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group,
Represents a phosphoric ester group or a phosphoric amide group. However,
R ² and R ³ are not hydrogen atoms at the same time. X represents a halogen atom. ) 2. A 2-substituted imidazole compound represented by the following general formula (F). General formula (F) (Wherein, R ¹ represents a hydrogen atom, an aryl group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group; R ² and R ³ are each independently a hydrogen atom, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl group, an oxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group,
Represents a phosphoric ester group or a phosphoric amide group. However,
R ² and R ³ are not hydrogen atoms at the same time. )