JP2002338549A - Benzimidazole compound, azobenzimidazole compound and its chelate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new benzimidazole compound useful as an intermediate for synthesizing various kinds of coloring matters, a new azobenzimidazole compound synthesized by using the same and its metal chelate. SOLUTION: This azobenzimidazole compound is represented by general formula (2-a) or (2-b) (R1 and R2 are each a hydrogen atom, an alkyl group, an alkoxyalkyl group, a cyanoalkyl group, an arylalkyl group or an aryl group; R1 and R2 are not hydrogen atoms at the same time; R1 and R2 may be bonded to form a heterocycle; R3 is a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group which may contain a substituent group; R4 is a hydrogen atom, a substituted or nonsubstituted alkyl group, a substituted or nonsubstituted aryl group; R5 and R6 are each a hydrogen atom, an alkyl group, a fluorinated alkyl group, an alkoxy group or a halogen atom; X is a substituted or nonsubstituted aromatic group, a substituted or nonsubstituted heterocycle). Its metal chelate compound is provided. This benzimidazole compound is an intermediate for synthesizing these compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel benzimidazole compound, an azobenzimidazole compound and a metal chelate compound thereof. The benzimidazole compound of the present invention is useful as an intermediate in dye synthesis, and the azobenzimidazole compound and its metal chelate compound derived therefrom are dyes for fibers, dyes for plastics, dyes for optical recording, dyes for thermal transfer recording. Which can be used as colorants for color filters and the like.

[0002]

2. Description of the Related Art Azo compounds are used in various applications as dyes and have a large number of molecular structures. Among them, those soluble in organic solvents include disperse dyes and dyes for thermal transfer recording. Are used as dyes for optical recording. These dyes require high extinction coefficient, high stability to light, high temperature and high humidity, insolubility in water, and solubility in organic solvents. Furthermore, as a dye for optical recording, especially as a write-once type optical recording dye, in addition to their properties,
High thermal responsiveness, such as a structural change that occurs instantaneously due to heating, is also required. In fact, there are few existing dyes that satisfy such diverse requirements at the same time.

[0003]

SUMMARY OF THE INVENTION The inventors of the present invention have studied to develop a dye capable of meeting the above-mentioned various requirements, and as a result, have found that an azo dye derived from a specific intermediate and its metal It has been found that chelate complexes have such useful properties.

[0004]

That is, the present invention firstly provides:
It relates to a benzimidazole compound represented by the following general formula (1-a) or (1-b).

[0005]

Embedded image [Wherein, R1 and R2 represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, a cyanoalkyl group, an arylalkyl group, or an aryl group. R1 and R2 do not simultaneously become hydrogen atoms. R1 and R2 may form a heterocyclic ring with the nitrogen atom to which they are bonded. R3 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group. R4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R
5, R6 is a hydrogen atom, an alkyl group, a fluorinated alkyl group,
Represents an alkoxy group or a halogen atom].

The present invention secondly relates to an azobenzimidazole compound represented by the following general formula (2-a) or (2-b).

[0007]

Embedded image [Wherein, R1, R2, R3, R4, R5, and R6 are the same as described above, and X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring].

The present invention thirdly relates to a chelate compound of the above-mentioned azobenzimidazole compound with a divalent metal ion and a chelate compound of the above-mentioned azobenzimidazole compound with a trivalent metal ion. .

The above-mentioned compound of the present invention is characterized by having an alkylamino group at the 4- or 7-position of the benzimidazole skeleton. The compound having an azo group introduced at the para-position of the alkylamino group becomes a dye having a large absorption coefficient due to electron transfer from the alkylamino group to the azo group. Further, in the molecular structure, the nitrogen contained in the benzimidazole skeleton and the nitrogen constituting the azo group are in a convenient positional relationship for chelating a metal ion, so that a stable chelate complex can be formed. The metal-containing azo dye thus obtained has a high extinction coefficient and a high weather resistance characteristic of the metal-containing dye, and the metal component originally having low lipophilicity is surrounded by the organic dye component having high lipophilicity. The affinity is also high.

These general formulas (1-a) and (1-b)
And (2-a) and (2-b) represent isomers, respectively. When R4 is a hydrogen atom, they are each a tautomer, so that it is usual to separate them from each other. Impossible and treated as substantially the same. In the following description, one of the structures may be displayed to indicate both.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (1-a), (1-b),
Examples of R1 and R2 in the compounds of (2-a) and (2-b) include a lower alkyl group as shown in Examples described later, a nitrogen atom having R1 and R2 bonded thereto, and a pyrrolidine ring. Alternatively, those having a piperidine ring may be used. Similarly, examples of R3 include a hydrogen atom, a lower alkyl group which may be substituted with a fluorine atom, and an unsubstituted phenyl group. Examples of R4, R5 and R6 include a hydrogen atom, a lower alkyl group and the like. There is. Here, the lower alkyl group refers to a C1-C3 alkyl group. Examples of X include substituted and unsubstituted pyridine rings, substituted and unsubstituted pyrimidine rings, substituted and unsubstituted pyridazine rings, substituted and unsubstituted pyrazine rings, substituted and unsubstituted Substituted quinoline ring, substituted and unsubstituted pyrazole ring, substituted and unsubstituted thiazole ring,
A substituted and unsubstituted thiadiazole ring, a substituted and unsubstituted oxazole ring, a substituted and unsubstituted isoxazole ring, a substituted and unsubstituted triazole ring, and a heterocyclic ring selected from substituted and unsubstituted benzothiazole rings, When the heterocyclic ring has a substituent,
Some substituents are selected from the group consisting of a methyl group, a trifluoromethyl group, a chlorine atom and a phenyl group. Similarly, examples of metal ions include nickel, copper, zinc,
There are divalent metal ions such as manganese and trivalent metal ions such as aluminum, chromium, iron and cobalt.

Other examples of R1 and R2 other than the above include C
4-C12 linear or branched alkyl group, optionally substituted benzyl group, methoxyethyl group, ethoxyethyl group, methoxypropyl group, ethoxypropyl group, butoxyethyl group, 2-cyanoethyl group, 3 -Cyanopropyl group, 4-cyanobutyl group and the like. Also R
Examples of the heterocyclic ring formed by 1 and R2 together with the nitrogen atom bonded thereto include a morpholine ring. Similarly, examples of R3 other than the above include C4-C12 linear or branched alkyl, tolyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, chlorophenyl, bromophenyl, and fluorophenyl groups. , A trifluoromethylphenyl group, a nitrophenyl group, a naphthyl group, and the like.
A linear or branched alkyl group of 4 to C12 is represented by R
5, examples of R6 include a trifluoromethyl group, a methoxy group, an ethoxy group, a fluorine atom, a chlorine atom, a bromine atom,
And iodine atoms.

Examples of X other than the above include substituted and unsubstituted benzene rings, substituted and unsubstituted naphthalene rings, substituted and unsubstituted phenanthrene rings, substituted and unsubstituted triazine rings, substituted and unsubstituted triazine rings. Quinazoline ring, substituted and unsubstituted phthalazine ring, substituted and unsubstituted imidazole ring, substituted and unsubstituted oxazole ring, substituted and unsubstituted tetrazole ring, substituted and unsubstituted benzimidazole ring, substituted and unsubstituted indazole And substituted and unsubstituted benzotriazole rings. Examples of the substituent of X include, in addition to the above, an ethyl group, a propyl group, a butyl group, a nitro group, a cyano group, a phenyl group having a substituent, a pyridyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a trioxy group. Fluoroethoxy group, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a fluorine atom,
Examples include a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a carboxy group, and a sulfonic acid group.

The benzimidazole compounds of the general formulas (1-a) and (1-b) of the present invention can be synthesized by the steps shown in the following scheme.

[0015]

Embedded image [Wherein L represents an acyl group or a sulfonyl group].

[0016]

Embedded image [Wherein L represents the same substituent as in Scheme 1].

[0017]

Embedded image Scheme 3

In the scheme 1, r1 is a reaction for introducing a substituent L as a protecting group for an amino group, and a carboxylic anhydride, an acyl halide, a sulfonic anhydride, a sulfonyl halide or the like is used as a reactant. Can be.
For the nitration reaction of r2, nitric acid, fuming nitric acid, mixed acid and the like can be used. At this time, it is a problem whether nitration occurs selectively at a target position.
(Journal of the American
Chemical Society), vol. 63,
p. 3276-3278 (1941), JCS (Jou
rnal of the Chemical Society
ty), p. By using a method similar to the synthesis method described in 1897-1899 (1955) and the like, a target nitro compound can be obtained as a main component. In the reaction for substituting a nitro group with an alkylamino group in r3, a primary or secondary amino compound can be used. A common base or acid such as sodium hydroxide, potassium hydroxide, hydrochloric acid, and sulfuric acid can be used for elimination of the protecting group L at r4.
However, even if this step is not particularly provided, it is possible to simultaneously remove the protecting group in the next reaction of r5 or r6. The reduction reaction of r5 is carried out by catalytic hydrogenation using a metal catalyst or a reducing agent such as sodium sulfide, zinc, iron, stannous chloride and the like. For the cyclization reaction of r6, carboxylic acid, carboxylic anhydride, carboxylic acid halide and the like can be used. The reaction of r4 to r6 can be performed in one bath without isolating the intermediate.

S1 and s2 in Scheme 2 are the same as r1 and r2 in Scheme 1, and the same reagents as r1 can be used for the reaction of s1, and the same reagents as r2 for the reaction of s2. Reactants can be used. The reaction of s3 in Scheme 2 corresponds to r in Scheme 1.
The reaction is the same as that of r4, and the same reactant as r4 is used. s4 is an alkylation or arylation reaction, in which an alkyl halide, an aryl halide, a sulfate, a sulfonate, or the like is used. By using a plurality of alkylating agents and arylating agents at the time of this alkylation and arylation, it is possible to obtain a compound in which R1 and R2 are different from each other. It is also possible to leave it as it is. S5 and s6 in Scheme 2 are the same reactions as r5 and r6 in Scheme 1, and the same reactants as r5 and r6 can be used.

In Scheme 3, nitric acid, mixed acid, fuming nitric acid and the like can be used for the nitration reaction at t1. t
2 reduction reaction is catalytic hydrogenation and sodium sulfide, zinc,
Performed with iron, stannous chloride, etc. For alkylation or arylation of t3, an alkyl halide, an aryl halide, a sulfate, a sulfonate, or the like is used. When alkylating or arylating t3,
By using a plurality of alkylating agents and arylating agents, R
It is also possible to obtain one in which 1, R2 and R4 are different from each other, and it is also possible to leave any one of R1, R2 and R4 as a hydrogen atom.

The resulting compounds of the general formulas (1-a) and (1-b) can be easily subjected to a coupling reaction with an amino compound or a hydrazino compound to easily form the compound of the general formula (2-a).
a) and (2-b) azo compounds. At this time, the amino compound is diazotized and then coupled. As the diazotizing agent, sodium nitrite, nitrosylsulfuric acid, alkyl nitrite and the like can be used.
The hydrazino compound is oxidized and then coupled, and as the oxidizing agent, hydrogen peroxide, acetic acid, iodine, iron sulfate, potassium ferricyanide, or the like can be used.
Although the solvent used for the coupling reaction is not particularly limited, water, methanol, ethanol, propanol, acetic acid, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-methylformanilide, diethyl ether, tetrahydrofuran, dioxane, Polar solvents such as ethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, and pyridine are suitable, and these may be used as a mixture. Hydrochloric acid for pH adjustment during the reaction,
Use acidic or basic substances such as sulfuric acid, formic acid, sodium hydroxide, sodium acetate, sodium carbonate, sodium bicarbonate, sodium ethylate, sodium methylate, potassium butoxide, triethylamine, or blow carbon dioxide or ammonia gas. May be.

The thus obtained general formulas (2-a) and (2)
The azo compound of -b) can be used as a dye as it is. By changing the type of substituent, orange, red, blue,
Dyes of various hues such as purple and green can be obtained. Since they are easily soluble in organic solvents, they are suitable as disperse dyes, dyes for thermal transfer recording, and the like. It is also possible to use it after further forming a metal complex, and the metal complex is formed by mixing the compounds of the general formulas (2-a) and (2-b) with a metal salt in an organic solvent or an aqueous solvent. This can be easily performed. As the metal ion, a divalent to tetravalent metal ion can be used, and a chelate compound in which the charge is neutralized only by the ligand and the metal ion can be produced. Complex salt type chelate compounds can be prepared. Since these metal-containing dyes are also well soluble in various organic solvents, they can be easily used as recording materials and the like.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the following description, in the case of a compound in which a hydrogen atom is attached to N of the benzimidazole skeleton, a tautomeric structure exists as described above, but for simplicity, one of the structures is described and both structures are described. Shall be represented. That is, the position of the substituent NR1R2 is the position of 4 of benzimidazole.
Even if only the structure at the 7th position is described, it also indicates the structure at the 7th position.

A. Synthesis of Compounds of General Formulas (1-a) and (1-b) Example A-1

Synthesis of 2-methyl-4- (dimethylamino) benzimidazole 1) 2,3-dinitroacetanilide A reaction flask was charged with 176 ml of 98% sulfuric acid and cooled to -2 ° C. A solution obtained by dissolving 50 g of 3-nitroacetanilide in 176 ml of fuming nitric acid was added dropwise thereto at a temperature of -2 ° C to 3 ° C over 2 hours. After stirring for 40 minutes after dropping, the mixture was discharged into 600 ml of ice water, stirred for a while, and the precipitated crystals were collected by filtration and washed with water. The obtained crystal was recrystallized from ethanol to obtain 18.3 g of the target crystal. GC / M
The molecular weight (225) was confirmed by S. The melting point of this crystal was 190 ° C. The results of 1H-NMR were as follows. 1H-NMR (DMSO-d6,300
MHz): δ (from TMS) = 2.08 (3H,
s), 7.85 (1H, t, J = 8.2 Hz), 7.9
7 (1H, dd, J = 1.3 Hz, 8.2 Hz) 8.0
4 (1H, dd, J = 1.3 Hz, 8.2 Hz), 1
0.25 (1H, s).

2) 3- (Dimethylamino) -2-nitroacetanilide In a reaction flask, 18.3 g of 2,3-dinitroacetanilide obtained in 1) was suspended in 81 ml of ethanol and stirred. There 50% dimethylamine aqueous solution 81
After heating and stirring at 65 ° C for 40 minutes, 70 ° C
Of warm water was added and the mixture was allowed to cool while stirring. The precipitated crystals were collected by filtration and washed with a mixed solvent of toluene and hexane. The yield was 9.2 g. Molecular weight (223) by GC / MS
It was confirmed. The melting point of the crystal was 126 ° C.

3) 3- (Dimethylamino) -2-nitroaniline 3- (dimethylamino) obtained in 2) in a reaction flask
7.4 g of 2-nitroacetanilide in ethanol 83
and stirred. 41 ml of a 48% sodium hydroxide aqueous solution was put therein and heated. After stirring at 70 ° C for 4 hours, the mixture was allowed to cool, 170 ml of water was added, and chloroform 5 was added.
Extracted with 00 ml. The chloroform layer was washed twice with water, dried over anhydrous sodium sulfate, filtered off sodium sulfate, and distilled off chloroform. The yield was 7.6 g.

4) 2-Methyl-4- (dimethylamino)
3- (dimethylamino) obtained in 3) in a benzimidazole reaction flask
1.25 g of 2-nitroaniline in 20 ml of ethanol
Was dissolved. There 10% palladium-carbon 0.12
5 g were suspended and stirred for 2.5 hours while cooling in a water bath under a hydrogen atmosphere. After removing the insoluble matter by filtration, the filtrate was concentrated by an evaporator, and 16 ml of acetic acid was added to the residue.
For 3.5 hours. After cooling, the reaction solution was neutralized with an aqueous sodium hydroxide solution and extracted with chloroform. The chloroform layer was dehydrated using anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (elution solvent: chloroform: methanol = 93:
7), 1.1 g of a compound represented by the following formula (3) was obtained.
The molecular weight (175) was confirmed by LC / MS. Also one
H-NMR analysis results were as follows. 1H-NM
R (CDCl3): [delta] = 2.48 (3H, s), 2.9
9 (6H, s), 6.60 (1H, d, J = 7.3H)
z), 7.00-7.10 (2H, m), 10.44
(1H, br).

[0028]

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Example A-2 Synthesis of 2-trifluoromethyl-4- (dimethylamino) benzimidazole 26 g of 3- (dimethylamino) -2-nitroaniline obtained in the same manner as in 3) of Example A-1 To ethanol 400
Then, 2.6 g of 10% palladium-carbon was added thereto, suspended, and stirred for 3 hours while cooling in a water bath under a hydrogen atmosphere. After removing the insoluble matter by filtration, the filtrate was concentrated, and 300 ml of trifluoroacetic acid was added to the obtained oil.
Stir for 5 hours. Stop heating and allow to cool.
Then, the mixture was neutralized to pH 8 with an aqueous sodium hydroxide solution. After liquid separation, the organic layer was washed with water, dehydrated using anhydrous sodium sulfate, and then the organic layer was concentrated. The obtained crystals were recrystallized with a hexane-toluene mixed solvent to obtain 14 g of a compound represented by the following formula (4). The melting point of the crystals was 96 ° C. LC / MS confirmed a molecular weight of 229. FIG. 1 shows the infrared absorption spectrum (KBr) of this compound. The NMR analysis results were as follows. 1H-NMR
(DMSO-d6): 隆 = 3.17 (6H, s), 6.
46 (1H, d, J = 7.8 Hz), 6.98 (1H, d, J = 7.8 Hz)
d, J = 7.8 Hz), 7.21 (1H, t, J = 8.
1 Hz), 13.72 (1H, br).

[0030]

Embedded image

Example A-3 Synthesis of 4- (dimethylamino) benzimidazole 500 mg of 3- (dimethylamino) -2-nitroaniline obtained in the same manner as in 3) of Example A-1 was added to ethanol 8
was dissolved in ml. There 10% palladium-carbon 0.1%.
The suspension was stirred for 2 hours while cooling in a water bath under a hydrogen atmosphere. After removing the insoluble matter by filtration, the filtrate was concentrated, and 8 ml of formic acid was added to the obtained oil, followed by stirring at 95 ° C for 2.5 hours. The heating was stopped, the mixture was allowed to cool, water was added, and the reaction solution was made alkaline with a 48% aqueous sodium hydroxide solution. Thereto were added tetrahydrofuran and ethyl acetate, and the mixture was stirred. The organic layer was separated, washed with water and concentrated, and 0.37 g of a compound represented by the following formula (5) was obtained.
I got LC / MS confirmed a molecular weight of 161.

[0032]

Embedded image

Example A-4 Synthesis of 2-isopropyl-4- (dimethylamino) benzimidazole 1.2 g of 3- (dimethylamino) -2-nitroaniline obtained in the same manner as in 3) of Example A-1. To ethanol 20
was dissolved in ml. There 10% palladium-carbon 0.1%.
12 g were suspended and stirred for 2 hours while cooling in a water bath under a hydrogen atmosphere. After filtering off the insoluble matter, the filtrate was concentrated, and 20 ml of isobutyric acid was added to the obtained oil, followed by stirring at 110 ° C. for 4 hours. The heating was stopped, the mixture was allowed to cool, and the reaction solution was made alkaline with a 48% aqueous sodium hydroxide solution. Water was added thereto, and the precipitated insolubles were removed by filtration, and the filtrate was extracted with chloroform.
The chloroform layer was washed with water, dehydrated with anhydrous sodium sulfate, and concentrated to obtain a tar substance. This was purified by silica gel column chromatography (elution solvent: toluene to toluene: ethyl acetate = 9: 1) to obtain 0.3 g of a compound represented by the following formula (6). The melting point of the crystals was 124 ° C. LC / MS confirmed a molecular weight of 203.

[0034]

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Example A-5 Synthesis of 2-phenyl-4- (dimethylamino) benzimidazole 3- (dimethylamino) -2-nitroaniline 1.56
g was dissolved in 30 ml of ethanol, 0.20 g of 10% palladium-carbon was added, and the mixture was stirred under a hydrogen atmosphere for 4.8 hours. The catalyst was removed by filtration, and the filtrate was concentrated to give compound 1.70.
to 30 g of polyphosphoric acid and 1.62 g of benzoic acid
After the temperature was raised to 70 ° C. and the mixture was stirred for 35 minutes, 0.19 g of benzoic acid was added at this temperature, and the mixture was further stirred for 1.3 hours. The reaction solution was discharged into water and neutralized with an aqueous sodium hydroxide solution. After stirring for a while, the crystals were filtered, the crystals were washed with water, and recrystallized with methanol to obtain 1.1 g of the desired product represented by the formula (7). The melting point of the crystals was 165 ° C. LC / MS confirmed a molecular weight of 237. The NMR analysis results were as follows. 1H-NMR (CDCl
3): δ = 3.21 (6H, s), 6.38 (d, 1
H, J = 7.7 Hz), 6.93 (d, 1H, J = 7.
7 Hz), 7.04 (t, 1H, J = 7.9 Hz),
7.42-7.55 (m, 3H), 8.15 (d, 2
H, J = 7.2 Hz), 12, 61 (s, 1H). 13
C-NMR (CDCl 3): δ = 41.69, 101.
48, 105.05, 123.30, 125.91, 1
28.59, 128.99, 130.34, 134.4
6,136.16, 143.32, 147.37.

[0036]

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Example A-6 Synthesis of 2-trifluoromethyl-4- (piperidino) benzimidazole 1) 2-Nitro-3-piperidinoacetanilide Obtained by the same procedure as in 1) of Example A-1. 4.7 g of 2,3-dinitroacetanilide and 50 ml of ethanol were mixed, and 23 ml of piperidine was added dropwise over 0.3 hours while stirring, and the mixture was heated to 70 to 75 ° C. and stirred for 2 hours. The heating was stopped, the reaction solution was allowed to cool and discharged into water. The obtained crystals were collected by filtration, washed with water, and recrystallized with ethanol. GC / MS confirmed a molecular weight of 263.

2) 2-Nitro-3-piperidinoaniline 3.4 g of 2-nitro-3-piperidinoacetanilide obtained in 1) and 30 ml of ethanol were mixed, and 16 ml of a 48% aqueous sodium hydroxide solution was slightly added thereto. And heated. After stirring at the reflux temperature of the solvent for 2.5 hours, the reaction solution was allowed to cool, discharged into water and extracted with chloroform. The chloroform layer was washed with water and concentrated to obtain 3.3 g of the desired product. GC
/ MS confirmed molecular weight 221.

3) 4-Piperidino-2-trifluoromethylbenzimidazole 2-nitro-3-piperidinoaniline obtained in 2) 2.8
g, ethanol 38 ml, 10% palladium-carbon 0.
28 g were mixed and stirred at room temperature under a hydrogen atmosphere for 2 hours. Thereafter, the inside of the system was replaced with nitrogen, the reaction solution was filtered, and the filtrate was concentrated. To this was added 38 ml of trifluoroacetic acid little by little, and after the exotherm had subsided, the temperature was raised and the mixture was stirred at the reflux temperature for 1.5 hours. The reaction solution was allowed to cool, discharged into water, neutralized with sodium hydroxide, and the obtained crystals were collected by filtration and recrystallized from ethanol to obtain 2.3 g of the desired product represented by the following formula (8). LC / MS confirmed a molecular weight of 269.

[0040]

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Example A-7 Synthesis of 2-methyl-4- (diethylamino) benzimidazole 1) 3- (Diethylamino) -2-nitroacetanilide 2, a compound obtained by a method similar to 1) of Example A-1 Dissolve 1.0 g of 3-dinitroacetanilide in 6 ml of DMF and add
After the temperature was raised to 0 ° C, 0.65 g of diethylamine was added little by little, and the mixture was stirred at 50 to 60 ° C for 2 hours. The heating was stopped, the reaction solution was allowed to cool, discharged into water, and the precipitated insolubles were separated by filtration. The filtrate was extracted with ethyl acetate. The ethyl acetate layer was washed with water and concentrated to obtain 1.4 g of the desired product. GC / MS confirmed a molecular weight of 251.

3) 2-Methyl-4- (diethylamino)
1.4 g of 3- (diethylamino) -2-nitroacetanilide obtained in benzimidazole 2) was dissolved in 20 ml of ethanol.
There, 0.14 g of 10% palladium-carbon was suspended,
The mixture was stirred for 3 hours while cooling in a water bath under a hydrogen atmosphere. After removing the insoluble matter by filtration, the filtrate was concentrated with an evaporator, 16 ml of acetic acid was added to the residue, and the mixture was stirred at 90 ° C for 4 hours. After cooling, the reaction solution was neutralized with an aqueous sodium hydroxide solution and extracted with chloroform. The chloroform layer was dehydrated using anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 1.2 g of a compound represented by the following formula (9). Molecular weight 203 by LC / MS
It was confirmed.

[0043]

Example A-8 Synthesis of 1-ethyl-2-trifluoromethyl-4 (7)-(diethylamino) -5,6-dimethylbenzimidazole 1) 5,6-dimethyl-4-nitro-2-nitro While cooling 10 ml of trifluoromethylbenzimidazole 98% sulfuric acid to 5 ° C. or less and stirring,
A solution obtained by dissolving 3.2 g of 2-trifluoromethyl-5,6-dimethylbenzimidazole in 10 ml of fuming nitric acid was added dropwise thereto over 30 minutes. Then, after stirring for 40 minutes, the reaction solution was poured into ice water and filtered, and the obtained solid was washed with alkali water and then with water, and dried to obtain 2.7 g of crystals. A molecular weight of 259 was confirmed by GC / MS.

2) 4-amino-5,6-dimethyl-2-
Trifluoromethylbenzimidazole 2.7 g of the nitro compound obtained in 1) above was added to ethanol 70
While stirring and charging to 1.0 ml, 10% palladium-carbon (1.0 g) was charged and hydrogen gas was introduced and stirred for 3 hours.
The reaction solution was filtered, and the filtrate was concentrated and dried to obtain 1.0 g of crystals. A molecular weight of 229 was confirmed by GC / MS.

3) 1-ethyl-4 (7)-(diethylamino) -5,6-dimethyl-2-trifluoromethylbenzimidazole 0.23 g of the amino compound obtained in the above 2), DMF2m
and 0.30 g of anhydrous potassium carbonate were mixed and stirred, and 0.34 g of ethyl iodide was added dropwise over 1 hour, followed by stirring for 4 hours. Thereafter, 0.3 g of anhydrous potassium carbonate and 0.69 g of ethyl iodide were added, and the mixture was stirred at 70 ° C. for 3 hours. The heating was stopped, toluene and water were added to the reaction solution, and the mixture was stirred. The toluene layer was separated and concentrated to obtain 0.36 g of a compound represented by the following formula (10). GC / MS confirmed a molecular weight of 313.

[0047]

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Example A-9 1) 4-Methyl-3-nitroacetanilide A reaction flask was charged with 4-methyl-3-nitroaniline 9.1.
g and 60 ml of toluene were added and 6.7 g of acetic anhydride was added dropwise thereto over 2 hours while stirring. After stirring at room temperature for 4 hours, the reaction solution was filtered, and the obtained crystals were washed with toluene and dried to obtain 11.2 g of crystals.

2) 4-Methyl-2,3-dinitroacetanilide 16 ml of fuming nitric acid was charged into a reaction flask, and 3.9 g of 4-methyl-3-nitroacetanilide was charged at 10 to 15 ° C. over 1 hour with stirring. Thereafter, the mixture was stirred for 1 hour. The reaction solution was poured into 150 ml of ice water, stirred for a while, and then filtered. The crystals were washed with toluene, recrystallized with acetic acid and dried to obtain 2.2 g of crystals. The melting point of the crystals was 124 ° C. GC / MS confirmed a molecular weight of 239.

3) 4-Methyl-2-nitro-3- (butylamino) acetanilide A reaction flask was charged with 2.2 g of 4-methyl-2,3-dinitroacetanilide obtained in 2), 16 ml of ethanol and 8 ml of butylamine and stirred. After heating to 60 ° C. and stirring for 6 hours, the reaction solution was concentrated to obtain 2.6 g of a crude product of the target product. GC / MS confirmed a molecular weight of 265.

4) 4-Methyl-2-nitro-3- (N-
Butyl-N-hexylamino) acetanilide 4-Methyl-2-nitro-3 obtained in 3) was placed in a reaction flask.
2.6 g of-(butylamino) acetanilide, 10 ml of dimethylformamide, 1.8 g of potassium carbonate and 2.2 g of 1-bromohexane were charged and reacted at 70 to 80 ° C for 20 hours. The reaction solution was discharged into water, extracted with toluene, and the extract was washed with water, dried and concentrated to obtain 2.9 g of a crude product of the desired product.

5) 4-Methyl-2-amino-3- (N-
Butyl-N-hexylamino) aniline 4-methyl-2-nitro-3 obtained in 4) was placed in a reaction flask.
2.9 g of-(N-butyl-N-hexylamino) acetanilide, 10 ml of acetic acid, and 3.2 g of zinc dust were charged, and the mixture was gradually heated and stirred at 50 ° C for 2 hours. After allowing the reaction solution to cool,
After filtration and neutralization of the filtrate with aqueous sodium hydroxide,
Extracted with toluene. The extract was washed with water, dried and concentrated to obtain 2.5 g of a crude product of the desired product.

6) 5-Methyl-4- (N-butyl-N-
Hexylamino) -2- (trifluoromethyl) benzimidazole 4-methyl-2-amino-3 obtained in 5) in a reaction flask
-(N-butyl-N-hexylamino) aniline 2.5
g, and 30 ml of trifluoroacetic acid was added thereto.
Stirred for hours. The heating was stopped, the mixture was allowed to cool, water and chloroform were added, and the mixture was neutralized with an aqueous sodium hydroxide solution. After liquid separation, the organic layer was washed with water, dried and concentrated. The obtained crude product of the target product was purified by column chromatography to obtain 0.12 g of the target product represented by the following formula (11). Molecular weight 355 by LC / MS
It was confirmed.

[0054]

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Example A-10 Synthesis of 4- (pyrrolidino) -2- (trifluoromethyl) benzimidazole 1) 2,3-dinitroaniline Obtained in a reaction flask in the same manner as in 1) of Example A-1. 4.3 g of 2,3-dinitroacetanilide, 87 ml of methanol and 3.7 g of a 28% sodium methylate-methanol solution were stirred at the reflux temperature of the charged solvent for 90 minutes.
Thereafter, the reaction solution was discharged into water, stirred, filtered, and the obtained crystals were washed with water and dried to obtain 3.4 g of the desired product. GC / MS confirmed a molecular weight of 183.

2) 1,2-Dinitro-3-pyrrolidinobenzene In a reaction flask, 3.7 g of 2,3-dinitroaniline obtained in 1), 20 ml of dimethylformamide, 6.6 g of anhydrous potassium carbonate, 1,4-dibromo After charging butane (5.2 g) and stirring at 60 to 70 ° C. for 4 hours, anhydrous potassium carbonate (2.0 g) and 1,4-dibromobutane (1.0 g) were added.
Stir at 0-70 ° C for 3 hours. The reaction solution was discharged into 500 ml of water and extracted with 50 ml of ethyl acetate. The extract was washed with water, concentrated, and the obtained crystals were loosened with methanol, filtered and dried to obtain 1.5 g of crystals of the desired product. Molecular weight 23 by GC / MS
7 was confirmed. The melting point of the crystals was 96 ° C.

3) 1.2-Diamino-3-pyrrolidinobenzene A reaction flask was charged with 1.5 g of 2,3-dinitropyrrolidinobenzene obtained in 2), 30 ml of ethanol and 0.15 g of 10% palladium-carbon, and charged with hydrogen. The reaction was performed for 5 hours under an atmosphere. After filtering off the insoluble matter, the filtrate was concentrated to obtain 1.1 g of a crude product of the desired product.

4) 4- (Pyrrolidino) -2- (trifluoromethyl) benzimidazole A reaction flask was charged with 1.1 g of 1,2-diamino-3-pyrrolidinobenzene obtained in 3), and trifluoroacetic acid 15
Then, the mixture was stirred at 70 ° C. for 3 hours. The heating was stopped, the mixture was allowed to cool, water and chloroform were added, and the mixture was neutralized with an aqueous sodium hydroxide solution. After liquid separation, the organic layer was washed with water, dried and concentrated. The obtained crude product of the target was purified by column chromatography to obtain 0.46 g of a compound represented by the following formula (12). LC
/ MS confirmed a molecular weight of 255.

[0059]

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B. Synthesis of compounds of general formulas (2-a) and (2-b) (the structures of these products are shown in Tables 1 to 3 below)

Example B-1 The reaction vessel was charged with 2-methyl-4- obtained in Example A-1.
0.25 g of (dimethylamino) benzimidazole was charged and dissolved in 2.2 ml of methanol and 0.7 ml of acetic acid, followed by stirring at room temperature. After charging and dissolving 0.0036 g of iodine therein, 0.34 g of 2-hydrazino-5-trifluoromethylpyridine was added little by little, and 0.35 g of 30% hydrogen peroxide solution was added dropwise little by little. After stirring for 30 minutes,
The crystals obtained by filtration are placed in a methanol-acetone mixed solvent, stirred, filtered, and dried to obtain the desired 7- (5-
Trifluoromethyl-2-pyridylazo) -2-methyl-4- (dimethylamino) benzimidazole 0.21
g was obtained. LC / MS confirmed a molecular weight of 348. This compound was dissolved in any solvent of chloroform, acetone, ethyl acetate, tetrahydrofuran and dimethylformamide in an amount of 1% or more.

Example B-2 0.25 g of 2-methyl-4- (dimethylamino) benzimidazole obtained in Example A-1 was added to methanol 2.2.
and 0.7 ml of acetic acid and stirred at room temperature. After charging and dissolving 0.0036 g of iodine therein, 0.34 g of 2-hydrazino-4,6-dimethylpyrimidine was added little by little, and 0.3 g of 30% hydrogen peroxide solution was added dropwise little by little. After stirring for 1 hour, the crystals obtained by filtration are washed with methanol, collected by filtration, and filtered to give 7- (4,6-dimethyl-2-pyrimidinylazo) -2-methyl-4- (dimethylamino) benzimidazole. 21 g were obtained. This compound is 1% in any solvent such as chloroform, acetone, ethyl acetate, tetrahydrofuran and dimethylformamide.
The above was dissolved.

Example B-3 The 2-methyl-4- obtained in Example A-1 was placed in a reaction flask.
(Dimethylamino) benzimidazole (250 mg), methanol (2.2 ml), and acetic acid (0.7 ml) were charged, and while stirring at room temperature, iodine (3.6 mg) was charged.
Hydrazino-6-methyl-2-phenylpyrimidine 34
3 mg was added little by little, and further 0.35 g of 30% aqueous hydrogen peroxide was added dropwise. After stirring for 10 minutes, the mixture was filtered. The obtained crystals were washed with a methanol-acetone mixed solvent and dried to obtain 0.21 g of 7- (6-methyl-2-phenyl-4-pyrimidinylazo) -2-methyl-4- (dimethylamino) benzimidazole. Obtained. LC / MS confirmed molecular weight 372.

Example B-4 0.143 g of 2-aminothiazole, 0.5% of 62% sulfuric acid
7 g and 1.57 g of water were mixed and cooled to 0 ° C. in an ice bath with stirring (component A). On the other hand, 0.20 g of 2-methyl-4- (dimethylamino) benzimidazole, 6.2 ml of methanol, 0.26 g of sodium acetate, 0.02 g of urea
26 g were mixed and cooled to 0 ° C. in an ice bath with stirring (component B). Next, a mixture of 0.1 g of sodium nitrite, 0.11 g of 62% sulfuric acid, and 2.0 g of water was dropped into the component A, and the reaction solution stirred for 5 minutes was dropped into the component B, followed by stirring for 30 minutes. The crystals obtained by filtering the reaction mixture are dissolved in water, neutralized with a saturated aqueous solution of sodium hydrogen carbonate, and the precipitated crystals are collected by filtration, dried and dried to give 7- (2-thiazolylazo) -2-methyl-4. 56 mg of-(dimethylamino) benzimidazole were obtained.

Example B-5 1.5 g of 2-trifluoromethyl-4- (dimethylamino) benzimidazole obtained in Example A-2 was dissolved in 10 ml of methanol and 3 ml of acetic acid and stirred at room temperature. 0.03 g of iodine was added thereto, and after dissolution, 1.4 g of 2-hydrazino-5-trifluoromethylpyridine was added little by little, and 2.0 g of 30% hydrogen peroxide solution was further added dropwise. After stirring for 1 hour, the reaction solution was filtered, and the resulting crystals were washed with hot water and recrystallized with a mixed solvent of methanol and ethyl acetate to give 7- (5-trifluoromethyl-2-pyridylazo) -2-trifluoro. 1.4 g of methyl-4- (dimethylamino) benzimidazole were obtained. LC / MS confirmed molecular weight 402. The results of NMR analysis were as follows. 1H-NMR (CDCl3): δ = 3.77
(6H, s), 6.66 (1H, d, J = 9.5H)
z), 7.51 (1H, d, J = 9.5 Hz), 7.7
4 (1H, d, J = 8.7 Hz), 7.94 (1H, d
dd, J = 0.5 Hz), 8.71-8.72 (1H,
m). Elemental analysis: H = 2.90%, C = 47.85.
%, N = 20.88%, F = 28.18% (theoretical values H = 3.01%, C = 47.77%, N = 20.8
9%, F = 28.34%). The infrared absorption spectrum (KBr) and the visible absorption spectrum (chloroform) of this compound are shown in FIGS. 2 and 3, respectively.

Example B-6 The same moles of 4-hydrazino-6-methyl-2-phenylpyrimidine were used in place of 2-hydrazino-5-trifluoromethylpyridine in Example B-5, except that B-
No. 5 in Table 1 below by operating in the same manner as No. 5. Thus, 6 azo dyes were obtained.

Example B-7 The same molar number of 2-hydrazino-4,6 was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-5.
-Dimethylpyrimidine was used, and the other procedures were the same as in Example B-5. 7 azo dyes were obtained.

Example B-8 The same molar number of 3-hydrazino-6-phenylpyridazine was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-5, and the others were the same as Example B-5. The same operation was performed in the same manner as in Table 1 below. Thus, 8 azo dyes were obtained.

Example B-9 The same molar number of 4-hydrazino-6-trifluoromethylpyrimidine was used in place of 2-hydrazino-5-trifluoromethylpyridine in Example B-5, except that 5
No. in Table 1 described below. 9 azo dyes were obtained.

Example B-10 In place of 2-aminothiazole of Example B-4, the same molar number of 2-aminothiadiazole was used instead of 2-methyl-4-
The same molar number of 2-trifluoromethyl-4- (dimethylamino) benzimidazole was used in place of (dimethylamino) benzimidazole, and the others were operated in the same manner as in Example B-4. 10 azo dyes were obtained.

Example B-11 0.03 g of 3-aminoisoxazole, 0.2% of 62% sulfuric acid.
04 ml, acetic acid 0.39 ml, propionic acid 0.2 ml
And stirred and cooled to 0 ° C. in an ice bath. Thereto, 0.04 ml of 44% nitrosylsulfuric acid was added and stirred (component A). On the other hand, 2-methyl-4- (dimethylamino) benzimidazole 90 mg, methanol 1.2 ml, urea 0.00
9 g and 0.09 g of sodium acetate were mixed, stirred, and cooled to 0 ° C. in an ice bath (component (B)). A component is dropped on B component,
Stirred. The precipitated crystals were collected by filtration, washed with water, washed with methanol, and dried. 90 mg of 11 were obtained.

Example B-12 The same procedure as in Example B-5 was repeated, except that the same molar number of 2-hydrazinoquinoline was used instead of 2-hydrazino-5-trifluoromethylpyridine in Example B-5. No. in Table 1 below. Twelve azo dyes were obtained.

Example B-13 The same procedure as in Example B-5 was followed, except that the same molar number of 2-hydrazinopyrimidine was used instead of 2-hydrazino-5-trifluoromethylpyridine in Example B-5. Table 2 below
No. 13 azo dyes were obtained.

Example B-14 The same procedure as in Example B-5 was repeated except that 2-hydrazino-5-trifluoromethylpyridine was replaced with the same molar number of 4-hydrazino-2-methyl-6-phenylpyrimidine. B-
No. 5 in Table 2 described below by operating in the same manner as No. 5. 14 azo dyes were obtained.

Example B-15 2-amino-3,5-dichloropyridine 83 mg, 20 mg
% Sodium ethylate-ethanol solution 173 mg,
After 1 ml of ethanol was charged and 60 mg of isopentyl nitrite was added dropwise with stirring, the mixture was heated and stirred at the reflux temperature for 1 hour. There, 2-trifluoromethyl-4- (dimethylamino) benzimidazole 6 obtained in Example A-2 was used.
0 mg was added and the mixture was stirred for 2 hours. The heating was stopped, the mixture was allowed to cool, water was added, and the precipitated crystals were collected by filtration, washed with methanol, and dried. No. of Table 2 below. 32 mg of 15 azo dyes were obtained.

Example B-16 The same procedure as in Example B-10 was repeated, except that the same molar number of 3-amino-1,2,4-triazole was used instead of 2-aminothiazole in Example B-10. No. in Table 1 below. 1
Thus, 6 azo dyes were obtained.

Example B-17 50 mg of the azo dye obtained in Example B-16, 1 ml of N, N-dimethylformamide, 15 mg of anhydrous potassium carbonate,
After mixing 16 mg of propyl iodide and stirring at 30 to 40 ° C. for 5 hours, heating was stopped and the mixture was allowed to cool. Water was added, and the precipitated crystals were collected by filtration, dried, and dried. 17 azo dyes were obtained.

Example B-18 The same procedure as in Example B-4 was followed except that the same molar number of 3-amino-5-methylpyrazole was used in place of 2-aminothiazole in Example B-4, and the following description was used. No. of Table 2 18 azo dyes were obtained.

Example B-19 50 mg of the azo dye obtained in Example B-18, 1 ml of N, N-dimethylformamide, 15 mg of anhydrous potassium carbonate,
After mixing 17 mg of propyl iodide and stirring at 30 to 40 ° C. for 5 hours, heating was stopped and the mixture was allowed to cool. Water was added, and the precipitated crystals were collected by filtration, dried, and dried. 19 azo dyes were obtained.

Example B-20 The same molar number of 2-hydrazino-3,6 was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-5.
-Dimethylpyrazine was used, and otherwise operated in the same manner as in Example B-5. 20 azo dyes were obtained.

Example B-21 2-trifluoromethyl-4- (dimethylamino) benz obtained in Example A-2 in place of 2-methyl-4- (dimethylamino) benzimidazole of Example B-4 The same molar number of imidazole was used, and the other procedures were the same as in Example B-4, and the results were as shown in Table 2 below. 21 azo dyes were obtained.

Example B-22 The same molar number of 2-hydrazino-4-methylpyridine was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-5, except that Example B-5 was the same as Example B-5. By operating in the same manner as in No. 2 in Table 2 below. Thus, 22 azo dyes were obtained.

Example B-23 The same procedure as in Example B-5 was followed, except that the same molar number of 2-hydrazinopyridine was used instead of 2-hydrazino-5-trifluoromethylpyridine in Example B-5. No. in Table 2 below. 23 azo dyes were obtained.

Example B-24 The same molar number of 2-hydrazino-4,6 was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-5.
-Diphenylpyrimidine was used, and the other procedures were the same as in Example B-5. 24 azo dyes were obtained.

Example B-25 The same procedure as in Example B-5 was repeated, except that the same molar number of 2-hydrazinobenzothiazole was used in place of the 2-hydrazino-5-trifluoromethylpyridine of Example B-5. Operate No. 3 in Table 3 below. 25 azo dyes were obtained.

Example B-26 2-isopropyl-4- (dimethylamino) benzimidazole obtained in Example A-4 was replaced with 2-methyl-4- (dimethylamino) benzimidazole in Example B-1. The same molar number was used, and the other procedures were the same as in Example B-1. 26 azo dyes were obtained.

Example B-27 The same molar number of 4-hydrazino-6 was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-26.
Example B using methyl-2-phenylpyrimidine and others
No. 26 in Table 3 described below. 27 azo dyes were obtained.

Example B-28 The same molar number of 4- (dimethylamino) benzimidazole obtained in Example A-3 was used instead of 2-isopropyl-4- (dimethylamino) benzimidazole in Example B-27. And the others were operated in the same manner as in Example B-27. 28 azo dyes were obtained.

Example B-29 Instead of 2-trifluoromethyl-4- (dimethylamino) benzimidazole of Example B-5, 4- (dimethylamino) benzimidazole obtained in Example A-3 was equimolar. Using the same numbers as in Example B-5, operate as in Example B-5.
No. 29 azo dyes were obtained.

Example B-30 2-trifluoromethyl-4-piperidino obtained in Example A-6 in place of 2-trifluoromethyl-4- (dimethylamino) benzimidazole of Example B-5 The same molar number of benzimidazole was used, except that the operation was the same as in Example B-5. 30 azo dyes were obtained.

Example B-31 2-trifluoromethyl-4- (diethylamino) obtained in Example A-7 in place of 2-trifluoromethyl-4- (dimethylamino) benzimidazole of Example B-5
The same moles of benzimidazole were used and the others were as in Example B-5.
No. in Table 3 described below. 31 azo dyes were obtained.

Example B-32 The same molar number of 4-hydrazino-6 was used in place of 2-hydrazino-5-trifluoromethylpyridine of Example B-30.
Example B using methyl-2-phenylpyrimidine and others
No. -30 in Table 3 below by operating in the same manner as No.-30. 32 azo dyes were obtained.

Example B-33 2-phenyl-4- (dimethylamino) benz obtained in Example A-5 in place of 2-trifluoromethyl-4- (dimethylamino) benzimidazole in Example B-5 The same molar number of imidazole was used, and the other procedures were the same as in Example B-5, and the results were as shown in Table 3 below. 33 azo dyes were obtained.

Example B-34 The same molar number of 4-hydrazino-6-methoxy-2-methyl-5-trifluoromethylpyrimidine was used in place of 2-hydrazino-5-trifluoromethylpyridine in Example B-5. Using the same procedures as in Example B-5 but following Table 3
No. 34 azo dyes were obtained.

Example B-35 Instead of 2-aminothiazole of Example B-4, the same molar number of 4-amino-5-cyano-1-phenylimidazole was used instead of 2-methyl-4- (dimethylamino) benz. Using the same molar number of 2-trifluoromethyl-4- (dimethylamino) benzimidazole instead of imidazole,
Others were operated in the same manner as in Example B-4, and No. 3 in Table 3 below. 3
Thus, 5 azo dyes were obtained.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

Table 4 below shows the maximum absorption wavelength (λmax) in the solution for the representative examples of the compounds shown in Tables 1 to 3 above.

[0100]

[Table 4]

C. Synthesis of metal chelate compound Example C-1 7- (5-trifluoromethyl-2) obtained in Example B-5
-Pyridylazo) -2-trifluoromethyl-4- (dimethylamino) benzimidazole (1.1 g) was suspended in methanol (15 ml) and heated to 50 ° C. while stirring, and nickel acetate tetrahydrate (0.33 g) was added thereto. Added little by little. After heating and stirring for 2 hours as it was, the mixture was allowed to cool and filtered. The obtained crystals are washed with hot water and dried to obtain the following (13)
1.0 g of a nickel complex represented by the formula was obtained. LC / MS
The molecular weight of 861 was confirmed. Elemental analysis: H = 2.49.
%, C = 44.70%, N = 19.62%, F = 26.
78% (theoretical values H = 2.57%, C = 44.
63%, N = 19.52%, F = 26.47%). The infrared absorption spectrum (KBr) and the visible absorption spectrum (chloroform) of this compound are shown in FIGS. 4 and 5, respectively.

[0102]

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This compound was dissolved in a solvent of 1% or more in any of chloroform, acetone, ethyl acetate, tetrahydrofuran and dimethylformamide. In addition, 2,2,3,3 which is often used as a coating solvent for dyes
-Tetrafluoropropanol, 2,2,3,3,4
1% or more was dissolved in any of 4,5,5-octafluoropentanol. The maximum absorption wavelength (λmax) in chloroform was 612 nm, and the molar extinction coefficient ε at the same wavelength was 130,000. The extrapolated heat generation temperature of this crystal in differential thermal scanning calorimetry (DSC) was 3
16 ° C, exothermic peak temperature 322 ° C, calorific value 94 J /
g. The starting temperature of extrapolation weight loss by thermogravimetric analysis (TGA) was 335 ° C, and the weight loss rate up to 500 ° C was 44%. Note that these DSC and TGA analyzes were performed at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and the same applies to the following examples.

Example C-2 7- (2-Phenyl-6-methyl) obtained in Example B-3
100 mg of 4-pyrimidinylazo) -2-methyl-4- (dimethylamino) benzimidazole was suspended in 1.5 ml of methanol and heated to 50 ° C with stirring. 34 mg of nickel acetate tetrahydrate was added thereto little by little. After heating and stirring as such for 30 minutes, the mixture was allowed to cool and filtered. The obtained crystals were washed with hot water and methanol and then dried to obtain 83 mg of the desired nickel complex. LC / M
S confirmed the molecular weight of 800. The extrapolated heat generation temperature by DSC of this crystal was 349 ° C., and the heat generation peak temperature was 35.
2 ° C., calorific value is 107 J / g, extrapolation weight loss starting temperature in TGA is 368 ° C., weight loss rate up to 500 ° C. is 53
%Met.

Example C-3 The same procedure as in Example C-1 was repeated, except that the same molar number of zinc acetate dihydrate was used in place of the nickel acetate tetrahydrate of Example C-1. Was obtained. A molecular weight of 867 was confirmed by LC / MS. The results of NMR analysis were as follows. 1H-NMR (CDCl3): δ = 3.79
(12H, br), 6.69 (2H, d, J = 9.5H)
z), 7.75 (2H, d, J = 9.5 Hz), 7.7
8 (2H, dd, J = 9.0 Hz), 7.93 (2H,
d, J = 9.0 Hz), 8.02-8.03 (1H,
m)

Example C-4 The same procedure as in Example C-1 was repeated, except that the same moles of copper acetate anhydride were used in place of the nickel acetate tetrahydrate of Example C-1. A copper complex was obtained. The extrapolated heat generation start temperature in DSC of this crystal was 239 ° C., and the heat generation peak temperature was 26.
0 ° C., calorific value is 404 J / g, extrapolation weight loss starting temperature in TGA is 268 ° C., and weight loss rate up to 500 ° C. is 39
%Met.

Example C-5 The same procedure as in Example C-1 was repeated, except that the same molar number of manganese acetate tetrahydrate was used in place of the nickel acetate tetrahydrate of Example C-1. Was obtained.

Example C-6 The same moles of aluminum chloride hexahydrate and sodium methylate were used in place of the nickel acetate tetrahydrate of Example C-1, and the other conditions were the same as in Example C-1. The desired aluminum complex was obtained by operation.

Examples C-7 to C-39 In the same manner as in Example C-1, azo compounds shown in Tables 5 and 6 below were reacted with metal ions to obtain metal chelate complexes. The compound numbers of the azo compounds shown in Tables 5 and 6 are common to the compound numbers in Tables 1 to 4. Tables 5 and 6 also show λmax in solution of the produced metal complex dye.

[0110]

[Table 5]

[0111]

[Table 6]

D. Light fastness test The compounds obtained in the above examples were subjected to a light fastness test by the following method. Example D-1 0.5 g of the metal-containing azo dye obtained in Example C-1
10 g of a 10% aqueous solution of polyvinyl alcohol and 7.0 g of water were mixed, and 20 g of glass beads were added. This dispersion was applied onto neutral paper using a wire bar and air-dried to obtain a coated paper having a dye coating amount of 0.6 g / m2. The hue of the coated surface was purple.

Comparative Example In place of the metal-containing azo dye in Example D-1, the same amount of the dye represented by the following formula (14) was used.
-1 to obtain a dye-coated paper. The hue of the coated surface was bluish purple.

[0114]

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The dye-coated papers obtained in Example D-1 and Comparative Example were exposed for 24 hours with a fade tester using a carbon arc as a light source, and the absorbance before and after the exposure was measured. The results are shown in Table 7 below.

[0116]

[Table 7]

From the above examples, the azo compounds and metal-containing azo compounds derived from the benzimidazole compounds of the present invention are dyes having a high absorption coefficient that can have various absorption wavelengths, have good solubility in organic solvents, and have good light resistance. Was also confirmed to be good. In analyzing the compounds of the above examples, the following analyzer was used. GC / MS: GCMS-QP20 manufactured by Shimadzu Corporation
00GF LC / MS: Company's LCMS-QP8000 IR: Company's FTIR-8000PC DSC: Company's DSC-50 TGA: Company's TGA-50 NMR: JEOL FT-NMR spectrometer # 300 Visible absorption spectrum (solution) : UV-2500PC made by Shimadzu Corporation Visible absorption spectrum (solid film): UV-365 made by Shimadzu Corporation

[0118]

The present invention provides a benzimidazole compound useful as an intermediate in the synthesis of various dyes. An azo dye and a metal chelate dye synthesized using the benzimidazole compound have high solubility and high solubility. It has excellent properties such as light resistance, and is of high industrial value.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of the compound obtained in Example A-2.

FIG. 2 is an infrared absorption spectrum of the compound obtained in Example B-5.

FIG. 3 is a visible absorption spectrum of the compound obtained in Example B-5.

FIG. 4 is an infrared absorption spectrum of the compound obtained in Example C-1.

FIG. 5 is a visible absorption spectrum of the compound obtained in Example C-1.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 29/09 C09B 29/09 BC Z 45/00 45/00 (72) Inventor Masatoshi Taniguchi Minami Kyoto City 1F, Kamidaba-Kamichocho-ku, Yamada F-term in Yamada Chemical Industry Co., Ltd. 4C063 AA01 BB09 CC26 CC29 CC34 CC43 CC51 CC62 DD12 DD14 DD22 DD26

Claims (7)

[Claims] 1. A benzimidazole compound represented by the following general formula (1-a) or (1-b). Embedded image [Wherein, R1 and R2 represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, a cyanoalkyl group, an arylalkyl group, or an aryl group. R1 and R2 do not simultaneously become hydrogen atoms. R1 and R2 may form a heterocyclic ring with the nitrogen atom to which they are bonded. R3 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a substituted or unsubstituted aryl group. R4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R
5, R6 is a hydrogen atom, an alkyl group, a fluorinated alkyl group,
Represents an alkoxy group or a halogen atom]. 2. R1 and R2 are alkyl groups, or R1 and R2
2 forms a pyrrolidine ring or a piperidine ring with the nitrogen atom bonded thereto, and R3 is a hydrogen atom, a lower alkyl group which may be substituted with a fluorine atom, or an unsubstituted phenyl group; The benzimidazole compound according to claim 1, wherein R4, R5, and R6 are a hydrogen atom or a lower alkyl group. 3. An azobenzimidazole compound represented by the following general formula (2-a) or (2-b). Embedded image [Wherein, R1 and R2 represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, a cyanoalkyl group, an arylalkyl group, or an aryl group. R1 and R2 do not simultaneously become hydrogen atoms. R1 and R2 may combine to form a heterocyclic ring. R3 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, or an optionally substituted aryl group. R4
Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R5 and R6 are hydrogen atoms,
Represents an alkyl group, a fluorinated alkyl group, an alkoxy group, or a halogen atom. X represents a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring]. 4. R1 and R2 are lower alkyl groups, or R1
And R2 form a pyrrolidine ring with the nitrogen atom bonded thereto, and R3 is a hydrogen atom, a lower alkyl group which may be substituted by a fluorine atom, an unsubstituted phenyl group, and R4, R5 and R6 each represent a hydrogen atom or a lower alkyl group, and X represents a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted pyridazine ring, a substituted or unsubstituted pyrazine ring, a substituted or unsubstituted pyrazine ring. Substituted quinoline ring, substituted and unsubstituted imidazole ring, substituted and unsubstituted pyrazole ring, substituted and unsubstituted thiazole ring, substituted and unsubstituted thiadiazole ring, substituted and unsubstituted oxazole ring, substituted and unsubstituted A heterocyclic ring selected from an isoxazole ring, a substituted and unsubstituted triazole ring, and a substituted and unsubstituted benzothiazole ring The azobenz according to claim 3, wherein, when the heterocyclic ring has a substituent, the substituent is selected from the group consisting of a methyl group, a trifluoromethyl group, a chlorine atom and a phenyl group. Imidazole compounds. 5. A chelate compound of the azobenzimidazole compound according to claim 3 and a divalent metal ion. 6. A chelate compound of the azobenzimidazole compound according to claim 3 and a trivalent metal ion. 7. The chelate compound according to claim 5, wherein the divalent metal ion is any of nickel, copper, zinc and manganese.