JP2002371079A - Azo compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new dye having absorption characteristics with excellent color reproducibility as coloring matters of three primary colors and sufficient fastness, to provide a method for producing the dye, and to obtain a coloring composition capable of affording a colored image or a colored material having excellent hue and fastness. SOLUTION: The compound is represented by formula (1). The method for producing the compound is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel azo compound and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, as an image recording material, a material mainly for forming a color image has been mainly used. Specifically, an ink jet recording material, a thermal transfer type image recording material, and an electrophotographic recording material are used. Materials, transfer-type silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Color filters are used in LCDs and PDPs for displays, and in imaging devices such as CCDs for photographing equipment. In these color image recording materials and color filters, in order to reproduce or record a full-color image, colorants (dyes and pigments) of three primary colors of a so-called additive color mixture method or a subtractive color mixture method are used.
The fact is that there is no robust colorant that has absorption characteristics capable of realizing a preferable color reproduction range and can withstand various use conditions, and improvement is strongly desired.

[0003] The ink jet recording method is rapidly spreading and developing due to its low material cost, high speed recording, low noise during recording, and easy color recording. is there. Ink jet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in response to an image information signal. , A method in which bubbles are generated in ink by heat to discharge droplets, a method using ultrasonic waves, and a method in which droplets are sucked and discharged by electrostatic force. In addition, as ink for inkjet recording,
Water-based ink, oil-based ink, or solid (melt-type) ink is used.

With respect to the colorant used in such an ink for ink jet recording, good solubility or dispersibility in a solvent, high density recording is possible, good hue, light, It is robust against heat and active gases in the environment (oxidizing gases such as NOx and ozone as well as SOx, etc.), has excellent fastness to water and chemicals, and has good fixability to image receiving materials. It is required that the ink does not easily bleed, has excellent storage stability as an ink, has no toxicity, has high purity, and is available at a low cost. However, it is extremely difficult to search for dyes that meet these requirements at a high level. In particular, there is a strong demand for a colorant that has a good magenta hue and is robust against light and active gases in the environment, especially oxidizing gases such as ozone.

Hitherto, phenol, naphthol, aniline, and the like have been widely used as azo dye couplers. As azo dyes having good hue obtained by these couplers, dyes disclosed in JP-A-11-209673, JP-A-320660 / etc. Are known, but have a problem that light fastness is poor. . To improve this, a dye having a good hue and improved light fastness has recently been disclosed in Japanese Patent Application No. 2000-220649. However, any of the coloring agents known in these publications and the like has extremely poor fastness to oxidizing gases such as ozone.

In order to develop a dye that is robust against oxidizing gases such as ozone, the inventors of the present application have departed from conventional couplers such as phenol, naphthol, and aniline, and converted the nitrogen-containing heterocyclic compound into a coupler. I came to the idea of using it. So far, an azo dye system comprising an aminopyrazole diazo component and an aniline coupler has been disclosed in
Nos. 5-161856, 61-36362, 61-
No. 152768, JP-A-6-145543, JP-A-7
-224230, U.S. Patent Nos. 4,650,861 and 4,
Although disclosed in JP-A-301070 and JP-T-11-504958, as described above, none of them has achieved both hue and various fastnesses. An azo dye system having a pyridine coupler is disclosed in JP-A-51-8363.
No. 1, No. 49-74718, No. 58-101158
No. 52-46230, European Patent No. 23309.
, German Patent Nos. 2719079 and 2307444
Nos. 2513949, 2525505, 28
Although known as the azo dye described in No. 32020, an azo dye composed of a pyrazole diazo component and a pyridine coupler was not known at all.

On the other hand, an azo dye comprising a pyrazolediazo component and an aniline coupler has been conventionally disclosed in US Pat.
6,285,3,639,384 and British Patent 1,
No. 566,985 and the like. The method described in the above-mentioned U.S. Pat.
A 1-alkyl-4-cyano-pyrazol-5-ylazo dye is synthesized by diazotizing 1-alkyl-4-cyano-5-aminopyrazole and coupling. However, since the diazonium salt in this step is very unstable, it is difficult to obtain a dye in high yield and high purity by diazotization and coupling [Weaver and Shuttleworth, Dyes and
Pigments 3, 81 (1982)]. In addition, Japanese Patent Publication No. 6-19036
The 1-alkyl-3- (secondary or tertiary alkyl) -4-cyanopyrazol-5-ylazo dyes obtained by the synthesis method described in JP-A No. 6-222,1992 have a short wave hue and are not satisfactory as magenta dyes.

The process described in GB 1,566,985 discloses the use of 1-alkyl-3-alkyl or aryl-4-cyanopyrazol-5-ylazo dyes.
It is synthesized by diazotizing and coupling 1-alkyl-3-alkyl or aryl-4-halogeno-5-aminopyrazole with an aromatic coupling component, and then substituting the halogen at the 4-position with cyanide. However, the use of a heavy metal cyanide such as CuCN or Zn (CN) ₂ causes problems such as waste treatment after use and a method for purifying the generated dye. Furthermore, there has been no known method for producing an azo dye comprising a pyrazolediazo component and a pyridine coupler in a simple and high yield. As described above, the synthetic method applicable to the synthesis of the compound of the present invention also has many disadvantages. Furthermore, when an arbitrary substituent is introduced into the amino group of the pyridine coupler portion of the compound represented by the general formula (1-H1) of the present invention, the reaction temperature becomes high, the reaction system becomes complicated, and the isolation becomes difficult. Was often difficult. Moreover,
There has been no known method for making an azo dye composed of a pyrazole diazo component and a pyridine coupler simple and easy in high yield in water-solubility.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide (1) a novel compound derivative having a specific structure which can be a useful chemical / pharmaceutical / agrochemical organic compound intermediate; and (2) excellent color reproducibility as a three primary color pigment. To provide a novel dye having absorption properties and sufficient fastness to light, heat, humidity and an active gas in the environment, and a method for producing the same. (3) Coloring excellent in hue and fastness An ink composition for printing such as inkjet, which gives images and coloring materials, an ink sheet for thermal transfer image forming materials, a toner for electrophotography, a color filter used for displays such as LCD and PDP and an image pickup device such as CCD. To provide various coloring compositions such as a coloring composition for use, a dyeing solution for dyeing various fibers, and (4) having a good hue by using the dye, and an active gas in light and environment, particularly To provide a ink jet recording ink can form a high fastness image to Zongasu.

[0010]

Means for Solving the Problems The present inventors have studied in detail a dye derivative having a good hue and high fastness. It has been found that the above object can be achieved by the azo compound. That is, according to the present invention, an azo compound having the following constitution, a method for producing the same, and a coloring composition are provided, and the above object of the present invention is achieved. 1. A compound represented by the following general formula (1).

[0011]

Embedded image

In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or an acyl group. Each substituent may be further substituted. R ₂ represents a hydrogen atom, a halogen atom, or a cyano group. R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted. R ₄ , R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfonyl group,
Represents an acyl group, a carboxyl group, a sulfo group, or a carbamoyl group. Each substituent may be further substituted.
However, R ₄ and R ₅ are not both hydrogen atoms.
₆ and R ₇ are not both hydrogen atoms. A ₁ and A
₂ is an optionally substituted carbon atom, or one of these is an optionally substituted carbon atom, and the other is a nitrogen atom. 2. In the general formula (1), R ₃ is represented by the following general formula (1-R1), which is an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Item 7. The compound according to Item 1.

[0013]

Embedded image

In the general formula (1-R1), R ₁ , R ₂ , R ₄ ,
R ₅ , R ₆ , R ₇ , A ₁ and A ₂ have the same meanings as in the general formula (1). 3. R _{4 in the} general formula (1) is an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group which may be substituted. The compound according to claim 2, which is represented by 1-R2).

[0015]

Embedded image

In the general formula (1-R2), R ₁ , R ₂ , R ₃ ,
R ₅ , R ₆ , R ₇ , A ₁ and A ₂ have the same meanings as in formula (1-R1). 4. R ₄ is A compound according to claim 2, characterized by being represented by the following general formula is a hydrogen atom (1-R3) of the general formula (1).

[0017]

Embedded image In the general formula (1-R3), R ₁ , R ₂ , R ₃ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1-R1). 5. R ₄ , R ₅ , R ₆ and R ₇ in the general formula (1) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group,
The compound according to claim 2, which is represented by the following general formula (1-R4), which is an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, or a carbamoyl group.

[0018]

Embedded image In the general formula (1-R4), R ₁ , R ₂ , R ₃ , A ₁ and A
₂ has the same meaning as in formula (1-R1). 6. The compound according to claim 1, wherein R _{3 in the} general formula (1) is a hydrogen atom and is represented by the following general formula (1-H1).

[0019]

Embedded image In the general formula (1-H1), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1). 7. R _{4 in the} general formula (1-H1) is a hydrogen atom, and R ₅
7. The compound according to claim 6, wherein R < ₇ > and R < ₇ > are not a hydrogen atom and are represented by the following general formula (1-H2).

[0020]

Embedded image In the general formula (1-H2), R ₁ , R ₂ , R ₆ , A ₁ and A
₂ has the same meaning as in formula (1-H1). 8. A method for producing a compound, characterized by obtaining the compound of the general formula (1-R1) according to claim 2, by any one of the following methods (1) and (2). Method (1): (a) a step of reacting an aminopyrazole represented by the following general formula (2) with a diazotizing agent to form a diazonium salt, (b) a diazonium formed in the above step (a) Reacting the salt with a coupling agent represented by the following general formula (3) to form a compound represented by the general formula (1-H1); and (c) in the presence of a base,
A method comprising a step of reacting the compound formed in the above step (b) with an alkylating agent, an arylating agent or a heterylating agent to form a compound represented by the general formula (1-R1).

[0021]

Embedded image

Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R
₈ , A ₁ and A ₂ have the same meanings as in the case of the above general formula (1). Method (2): a method including a step of introducing a water-soluble group into a compound represented by the general formula (1-R4) by an electrophilic reaction. 9. The method for producing a compound according to claim 8, wherein in the method (2) according to claim 8, the electrophilic reaction is sulfonation. 10. A method for producing a compound, characterized by obtaining the compound of the general formula (1-R2) according to claim 3, by any one of the following methods (3) and (4). Method (3): A method of reacting the compound of the general formula (1-H1) with the alkylating agent, the arylating agent, or the heterylating agent under deoxygenation conditions. Method (4): a step of reacting the compound of the general formula (1-H2) with the alkylating agent, the arylating agent, or the heterylating agent to produce a compound of the following general formula (1-R3); Reacting the compound of the general formula (1-R3) with the alkylating agent, the arylating agent, or the heterylating agent under deoxygenation conditions.

[0023]

Embodiments of the present invention will be described below in detail. (Azo compound) The compound of the present invention is a compound represented by the general formula (1). The general formula (1) is preferably the general formula (1)
-R1) and general formula (1-H1). Further, the general formula (1-R1) is preferably the general formula (1-R2), the general formula (1-R3), and the general formula (1-R4). Similarly, the general formula (1-H1) is preferably the general formula (1-H2).

Hereinafter, the compound represented by formula (1) of the present invention will be described in detail. R ₁ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group,
Represents a heterocyclic group or an acyl group, and each substituent may be further substituted. The alkyl group includes an alkyl group having a substituent and an unsubstituted alkyl group. The alkyl group has 1 to 1 carbon atoms excluding the carbon atom of the substituent.
An alkyl group of 2 is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom,
And ionic hydrophilic groups. Examples of alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-
Includes sulfobutyl. The cycloalkyl group includes a substituted cycloalkyl group and an unsubstituted cycloalkyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the cycloalkyl group include a cyclohexyl group.

The aralkyl group includes a substituted aralkyl group and an unsubstituted aralkyl group. As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the aralkyl group include a benzyl group and a 2-phenethyl group. The aryl group includes an aryl group having a substituent and an unsubstituted aryl group. As the aryl group,
An aryl group having 6 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of aryl groups include phenyl, p-tolyl, p
-Methoxyphenyl, o-chlorophenyl and m- (3
-Sulfopropylamino) phenyl.

The heterocyclic group includes a substituted heterocyclic group and an unsubstituted heterocyclic group. As the heterocyclic group, a 5- or 6-membered heterocyclic group is preferable. Examples of the substituent include an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxyl group, an ester group, and an ionic hydrophilic group. Examples of the heterocyclic group include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, and a 2-furyl group. The acyl group includes a substituted acyl group and an unsubstituted acyl group. As the acyl group, an acyl group having 1 to 12 carbon atoms excluding the carbon atom of the substituent is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

R ₂ represents a hydrogen atom, a halogen atom or a cyano group. R ₄ , R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfonyl group, an acyl group, a carboxyl group, Represents a carbamoyl group, and each substituent may be further substituted. Alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, with respect to the acyl group as defined in the above R _1. The alkenyl group includes a substituted alkenyl group and an unsubstituted alkenyl group. The alkenyl group has 5 to 5 carbon atoms excluding the carbon atom of the substituent.
Twelve alkenyl groups are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkenyl group include a vinyl group, an allyl group and the like. As the sulfonyl group,
It includes an alkylsulfonyl group such as a methanesulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group. However, R ₄ and R ₅ are not both hydrogen atoms, and R ₆ and R ₇ are not both hydrogen atoms.

R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group,
Represents a heterocyclic group, a carboxyl group, or a sulfo group, and each of these substituents may be further substituted. The details of these substituents are the same as those for R ₄ , R ₅ , R ₆ and R ₇ . A ₁ and A ₂ are each a carbon atom which may be substituted, or one of them is a carbon atom which may be substituted, and the other is a nitrogen atom.
The substituent of the carbon atom which may have a substituent is the above-mentioned R
₄ , R ₅ , R ₆ and R ₇ are the same.

With respect to the general formula (1), examples of preferred substituents represented by R _{1 to} R ₇ , A ₁ and A ₂ are shown below. R ₁ is
Alkyl and aryl groups are preferred. Further, among the alkyl groups, an isopropyl group and a t-butyl group are most preferred. As the aryl group, a phenyl group and a phenyl group having a further substituent at any of the 2-, 4- and 6-positions when viewed from the pyrazole mother nucleus side are preferred. R ₂ is most preferably a cyano group.

R ₃ is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group. Here, the Hammett's substituent constant [sigma] p value used in this specification will be briefly described. Hammett's rule is 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
Year L. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, "Lange's
Handbook of Chemistry "No. 12
Edition, 1979 (McGraw-Hill) and "Region of Chemistry" special edition, No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, each substituent is defined or described by Hammett's substituent constant σp, which means that it is limited to only those substituents having a value known in the literature, which can be found in the above-mentioned textbook. However, it goes without saying that even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett rule.

The electron-withdrawing group for R _{3 is} an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less. Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, and a diarylphospho group. , Diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy, acylthio, sulfamoyl, thiocyanate, thiocarbonyl, halogenated alkyl, halogenated alkoxy Substituted with a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, a heterocyclic group, a halogen atom, an azo group, a selenocyanate group and another electron-withdrawing group having a σp value of 0.20 or more. Aryl group And
Preferred are a cyano group, a nitro group and a halogen atom.
The heterocyclic group may or may not be substituted with an electron-withdrawing group.

As described above, A ₁ and A ₂ are each a carbon atom which may be substituted, or one of them may be a carbon atom which may be substituted.
The other is a nitrogen atom. It is preferred that both A ₁ and A ₂ are carbon atoms, since more excellent performance can be exhibited. As the further substituent of the carbon atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group, a carbamoyl group, and a cyano group are preferable. R ₄ , R ₅ , R ₆ and R ₇ are each independently preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, a sulfonyl group, an acyl group, or a heterocyclic group,
Further, a sulfonyl group, an acyl group, an aryl group, and a heterocyclic group are most preferable. As already mentioned,
R ₄ and R ₅ are not both hydrogen atoms, and R ₆ and R ₇ are not both hydrogen atoms.

When the compound represented by the general formula (1) of the present invention is used as a water-soluble compound, R ₃ , R ₄ , R ₅ , R ₆ and R 3
₇ is preferably substituted with at least two or more sulfo groups or carboxyl groups, and more preferably substituted with three or more sulfo groups or carboxyl groups.

(Method for Producing Azo Compound) A method for producing the compound represented by (1-R1) will be described. The general formula (1-) is obtained by any one of the following methods (1) and (2).
The compound of R1) is obtained. The method (1) comprises: (a) reacting an aminopyrazole represented by the following general formula (2) with a diazotizing agent to form a diazonium salt;
(B) reacting the diazonium salt formed in the above step (a) with a coupling agent represented by the following general formula (3) to form a compound represented by the general formula (1-H1) And (c) reacting the compound formed in the above step (b) with an alkylating agent, an arylating agent or a heterylating agent in the presence of a base to give a compound represented by the above general formula (1-R1) A method comprising the step of:

The method (2) according to the present invention comprises a compound represented by the general formula (1-R)
This is a method including a step of introducing a water-soluble group into the compound represented by 4) by an electrophilic reaction. Further, for the electrophilic reaction, a method described in detail below is preferable.

In the method (1) of the present invention, the step (a)
As the diazotizing agent used in the above, it is preferable to use a dilute hydrochloric acid aqueous solution of sodium nitrite. Further, isopentyl nitrite, nitrosyl sulfuric acid and the like can also be used as the diazotizing agent.

In the method (1) of the present invention, the step (b)
As the coupling agent used in the above, it is most preferable to use a nitrogen-containing 6-membered heterocyclic coupler represented by the general formula (3). A ₁ , A ₂ , R ₄ , R ₅ in the general formula (3)
Preferred examples of R ₆ and R ₇ are the same as in the case of the general formula (1).

In the method (1) of the present invention, the step (c)
The alkylating agent, arylating agent or heterylating agent used in the above is represented by the following general formulas (4), (5) and (6).

[0039]

Embedded image

In the above formula (4), R represents an alkyl group which may be substituted, and X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group. In the general formula (5), Ar represents a phenyl group substituted with an electron-withdrawing group, and is preferably substituted with a substituent having a total Hammett σp value of 0.2 or more. In the general formula (6), Het represents a hetero ring, and is preferably a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a triazyl group, or a 2-furyl group. As the base used in the step (c), an organic base such as diisopropylethylamine and an inorganic base such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like can be used. .

The electrophilic reaction in the above method (2) includes sulfonation, Mannich reaction, and Friedel-Crafts reaction, with sulfonation being preferred. The general formula (1-
As a method for sulfonating R4), concentrated sulfuric acid, 10%
To 60% of a sulfonating agent such as fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, amidosulfuric acid and the like. Further, a solvent may be used, and as the solvent, acetic acid, acetic anhydride, ethyl acetate, ether, carbon tetrachloride, acetonitrile, or the like may be used. In the general formula (1-R4), R ₃ , R ₄ , R ₅ , R ₆ , and R ₇
Is preferably sulfonated, and R ₃ , R ₄ , R ₅ ,
When the substituents of R ₆ and R ₇ have a plurality of reactive sites that can be sulfonated, sulfonated dyes having different substitution positions may be mixed. In this case, the sulfonated dye having a different substitution position may be mixed in the range of 0.1% to 20% by HPLC area% with respect to the main sulfonated dye. The reaction temperature (Celsius) is preferably from -20 to 50 degrees, more preferably from -5 to 30 degrees. The reaction time is preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.

As a method for producing the compound of the present invention, the compound of the general formula (1-R2) can be obtained by any of the following methods (3) and (4). Method (3)
Is a method of reacting the compound of the general formula (1-H1) with the alkylating agent, the arylating agent, or the heterylating agent under deoxygenation conditions.

The method (4) according to the present invention is characterized by the general formula (1-
H2), the alkylating agent, the arylating agent,
Or reacting with a heterylating agent to react with the following general formula (1-R3)
A compound of the general formula (1-R
Reacting the compound of 3) with the above-mentioned alkylating agent, arylating agent or heterylating agent under deoxygenation conditions. The above-mentioned alkylating agent, arylating agent or heterylating agent can be used.

In the production method of the general formula (1-R2),
As the deoxidizing conditions, it is preferable to manufacture the reaction system by filling the inside of the reaction system with an inert gas such as nitrogen or argon, and it is preferable to bubble the inside of the reaction solution with these inert gases.

The aminopyrazole represented by the general formula (2), which is a starting material used in the step (a) of the method (1), is
It can be synthesized by the methods described in U.S. Pat. No. 3,336,285 and Heterocycles, 20,519 (1983) and Japanese Patent Publication No. 6-19036.

The pyridine coupler (coupling agent represented by the general formula (3)) used in the step (b) of the method (1) is described in JP-A-51-83631, JP-A-49-83631.
The compound can be synthesized by a method described in JP-A-74718, JP-B-52-46230, or the like.

The azo compound (azo dye) represented by the general formula (1) can be synthesized by the above-mentioned production method of the present invention. Specific examples (exemplary compounds 1-1 to 8-3) of the azo compound of the present invention are shown below, but are not limited to the following examples.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

[Table 8]

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

[Table 12]

[0060]

[Table 13]

[0061]

[Table 14]

[0062]

[Table 15]

[0063]

[Table 16]

[Applications of Azo Compound, etc.] Examples of the application of the compound of the present invention as a dye include an image recording material for forming an image, in particular, a color image. Starting with the method recording materials, heat-sensitive transfer type image recording materials, pressure-sensitive recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials,
There are a printing ink, a recording pen and the like, preferably an ink jet recording material, a thermal transfer image recording material, a recording material using an electrophotographic method, and more preferably an ink jet recording material. Also, U.S. Patent 4,808,501
Specification, L described in JP-A-6-35182
It can also be applied to color filters used in solid-state imaging devices such as CDs and CCDs, and dyeing solutions for dyeing various fibers. The azo compound of the present invention is used after adjusting physical properties such as solubility and heat transferability suitable for the application by a substituent. Further, the azo compound of the present invention can be used in a uniform dissolved state, a dispersed dissolved state such as emulsified dispersion, or a solid dispersed state according to the system used.

[Ink for Inkjet Recording] The ink for inkjet recording can be prepared by dissolving and / or dispersing the azo compound dye of the present invention in a lipophilic medium or an aqueous medium. Preferably, an aqueous medium is used. If necessary, other additives are contained within a range that does not impair the effects of the present invention. As other additives, for example, an anti-drying agent (wetting agent),
Anti-fading agent, emulsion stabilizer, penetration enhancer, ultraviolet absorber,
Known additives such as preservatives, fungicides, pH adjusters, surface tension adjusters, defoamers, viscosity adjusters, dispersants, dispersion stabilizers, rust preventives, chelating agents and the like can be mentioned. These various additives are added directly to the ink liquid in the case of a water-soluble ink. When the oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but may be added to the oil phase or the aqueous phase during the preparation.

The anti-drying agent is suitably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet opening of the nozzle used in the ink-jet recording system.

As a drying inhibitor, a water-soluble organic solvent having a lower vapor pressure than water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol,
Polyhydric alcohols represented by dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane, etc., ethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-
Heterocycles such as 2-imidazolidinone and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-mentioned drying inhibitors may be used alone or in combination of two or more. These anti-drying agents are preferably contained in the ink in an amount of 10 to 50% by mass.

The penetration enhancer is suitably used for the purpose of better penetrating the ink-jet ink into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, and 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and a nonionic surfactant can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect,
It is preferable to use it in the range of the amount of addition which does not cause bleeding of printing and paper missing (print-through).

An ultraviolet absorber is used for the purpose of improving the storability of an image. JP-A-5858 as an ultraviolet absorber
No. 185677, No. 61-90537,
JP-A-2-782, JP-A-5-1970075,
Benzotriazole compounds described in JP-A-9-34057 and the like; JP-A-46-2784;
No. 194483, U.S. Pat. No. 3,214,463, and the like.
Nos. 0492 and 56-21141,
0-88106, cinnamic acid-based compounds, and the like;
JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621
Compounds disclosed in Japanese Unexamined Patent Application Publication No. Hei 8-501291, Research Disclosure N
o. No. 24239, stilbene compounds,
A compound that absorbs ultraviolet light and emits fluorescence, typically a benzoxazole-based compound, that is, a so-called fluorescent whitening agent, can also be used.

The anti-fading agent is used for the purpose of improving the storability of an image. As an anti-fading agent, various organic and metal complex-based anti-fading agents can be used.
Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans, alkoxyanilines, heterocycles, and the like. Complexes and zinc complexes. More specifically, Research Disclosure No. 176
No. 43, Nos. VII, I through J; 15162; No. 18716, page 650, left column, ibid. 36544
No. 527, ibid. Page 872 of 307105, N
o. Compounds described in the patent cited in US Pat. No. 15,162, and the compounds represented by the general formulas and compound examples of typical compounds described on pages 127 to 137 of JP-A-62-215272 can be used.

As a fungicide, sodium dehydroacetate,
Sodium benzoate, sodium pyridinethione-1-
Oxides, p-hydroxybenzoic acid ethyl ester,
Examples thereof include 1,2-benzisothiazolin-3-one and a salt thereof. These are contained in the ink at 0.02 to 1.00.
It is preferable to use it by mass%.

As the pH adjusting agent, the above-mentioned neutralizing agents (organic bases, inorganic alkalis) can be used. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added to the inkjet ink at a pH of 6 to 10 for summer use, and more preferably added to a pH of 7 to 10 for the summer.

Examples of the surface tension modifier include nonionic, cationic and anionic surfactants. In addition, the surface tension of the inkjet ink is preferably 20 to 60 mN / m. Furthermore, 25 to 45 mN / m is preferable. The viscosity of the inkjet ink is preferably 30 mN / m or less. More preferably, it is adjusted to 20 mN / m or less. Examples of surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester,
Nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, and oxyethylene oxypropylene block copolymer are preferred. In addition, SURFYNOLS (Air, which is an acetylene-based polyoxyethylene oxide surfactant)
Products & Chemicals) are also preferably used. Further, amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide are also preferable. Further, Research Disclosure N, pages 37-38 of JP-A-59-157636.
o. 308119 (1989) may be used as the surfactant.

As the defoaming agent, a fluorine-based or silicone-based compound, a chelating agent represented by EDTA, or the like can be used as required.

When the azo dye compound of the present invention is dispersed in an aqueous medium, JP-A-11-286637, Japanese Patent Application No. 2000-78491
Nos. 2000-80259, 2000-62370 and the like, and disperse colored fine particles containing a dye and an oil-soluble polymer in an aqueous medium as described in JP-A Nos. 2000-62370 and 2000-78454. -7
As described in JP-A-8491, JP-A-2000-203856 and JP-A-2000-203857, it is preferable to disperse the dye of the present invention dissolved in a high-boiling organic solvent in an aqueous medium. The specific method for dispersing the dye of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additives, and the amounts used thereof can be appropriately selected with reference to the description in the above publication. it can. Alternatively, the azo dye may be dispersed as fine particles in a solid state. At the time of dispersion, a dispersant or a surfactant can be used. Examples of the dispersing device include a simple stirrer or impeller stirring method, an in-line stirring method, a mill method (for example, a colloid mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, etc.), an ultrasonic method, a high-pressure emulsifying dispersion method (a high-pressure homogenizer). Specific examples of commercially available devices include a Gorin homogenizer, a microfluidizer, and DeBEE2000)
Can be used. Regarding the method of preparing the above ink for inkjet recording, besides the above-mentioned patents, JP-A-5-148436, JP-A-5-295512, and JP-A-5-295512
97541, 7-82515, 7-11858
No. 4, JP-A-11-286637, Japanese Patent Application No. 2000-8
The details are described in each of the publications of No. 7539 and can also be used for preparing the ink for inkjet recording of the present invention.

As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec.
-Butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol),
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether Ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine) , N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide,
N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, Acetone). Incidentally, two or more of these water-miscible organic solvents may be used in combination.

The azo compound of the present invention is preferably contained in an amount of 0.2 to 10 parts by mass in 100 parts by mass of the ink for ink jet recording. Further, other colorants may be used in combination with the azo compound in the inkjet ink of the present invention. When two or more colorants are used in combination, the total content of all the colorants is preferably within the above range.

The ink-jet recording ink of the present invention comprises:
It can be used not only for monochromatic image formation but also for full-color image formation. To form a full-color image,
Magenta color ink, cyan color ink, and yellow color ink can be used, and further black color ink may be used to adjust the color. Any applicable yellow dye can be used. For example, aryl or hetarylazo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds as coupling components (hereinafter referred to as coupler components); Azomethine dyes having open-chain active methylene compounds; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

Any applicable cyan dye can be used. For example, aryl or hetarylazo dyes having phenols, naphthols, and anilines as coupler components; azomethine dyes having phenols, naphthols, heterocycles such as pyrrolotriazole as coupler components;
Polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo and thioindigo dyes. Each of the above-mentioned dyes may be one that exhibits each color of yellow and cyan only after a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium. Alternatively, organic cations such as pyridinium and quaternary ammonium salts may be used, and further, polymer cations having these in a partial structure may be used. Examples of applicable black materials include disazo, trisazo, and tetraazo dyes as well as carbon black dispersions.

[Ink-jet recording method] The ink-jet recording method of the present invention provides a known image-receiving material, that is, plain paper or resin-coated paper, for example, by applying energy to the ink for ink-jet recording described in JP-A-8-169172. JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238873, JP-A-10-
No. 153989, No. 10-217473, No. 10-235995, No. 10-337947, No. 10-217597, No. 10-33794
An image is formed on ink-jet dedicated paper, film, electrophotographic common paper, fabric, glass, metal, porcelain, and the like described in Japanese Patent Publication No. 7 and the like.

In forming an image, a polymer latex compound may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. Regarding the time of applying the latex compound to the image receiving material, before, after, or simultaneously with the application of the colorant, it may be performed at the same time. It may be in the ink, or may be used as a liquid of the polymer latex alone. Specifically, Japanese Patent Application No. 2000-363090,
2000-315231, 2000-354380, 2000-343944, 200
0-268952, 2000-299465 and 2000-297365 can be preferably used.

The recording paper and recording film used for ink-jet printing using the ink of the present invention will be described below. The support in recording paper and recording film is made of chemical pulp such as LBKP, NBKP, G
P, PGW, RMP, TMP, CTMP, CMP, CG
It consists of mechanical pulp such as P, waste paper pulp such as DIP,
If necessary, conventionally known pigments, binders, sizing agents,
Mix additives such as fixing agent, cationic agent, paper strength agent,
Those manufactured by various apparatuses such as a fourdrinier paper machine and a round paper machine can be used. In addition to these supports, any of synthetic paper and plastic film sheet may be used. The support has a thickness of 10 to 250 μm and a basis weight of 10 to 250 g.
/ M ² is desirable. The support may be provided with an ink receiving layer and a back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol or the like, and then providing an ink receiving layer and a back coat layer. Further, the support may be subjected to a flattening treatment using a calender such as a machine calender, a TG calender, and a soft calender. In the present invention, as the support,
Paper and plastic films laminated on both sides with a polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene, and copolymers thereof) are more preferably used. It is preferable to add a white pigment (for example, titanium oxide, zinc oxide) or a coloring dye (for example, cobalt blue, ultramarine, neodymium oxide) to the polyolefin.

The ink receiving layer provided on the support includes:
Contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin, and melamine resin. As the white pigment contained in the ink receiving layer, a porous inorganic pigment is preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, both silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, and it is particularly preferable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivative. Such as water-soluble polymers, styrene butadiene latex,
A water-dispersible polymer such as an acrylic emulsion can be used. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer. The ink receiving layer may contain a mordant, a water-proofing agent, a lightfastness improving agent, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For this purpose, a polymer mordant is preferably used. Polymer mordants are described in JP-A-48-28325 and JP-A-54-74430.
No. 54-124726, No. 55-22766,
No. 55-142339, No. 60-23850, No. 6
Nos. 0-23851, 60-23852, 60-2
No. 3853, No. 60-57836, No. 60-6064
No. 3, No. 60-118834, No. 60-122940
No. 60-122941, No. 60-122942
No. 60-235134, JP-A-1-161236
Nos. 2,484,430 and 25,485.
Nos. 64, 3148061, 3309690, 4115124, 4124386, 41938
No. 00, No. 4,273,853, No. 4,282,305, and No. 4,450,224. JP 1
An image receiving material containing a polymer mordant described on pages 212 to 215 of 161236 is particularly preferred. When the polymer mordant described in the publication is used, an image having excellent image quality is obtained, and the light fastness of the image is improved.

The water-proofing agent is effective for making the image water-resistant,
As these waterproofing agents, cationic resins are particularly desirable. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethylene imine, polyamine sulfone, dimethyl diallyl ammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably from 1 to 15% by mass, more preferably from 3 to 15% by mass, based on the total solid content of the ink receiving layer.
It is preferably 10% by mass.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzophenone and benzotriazole ultraviolet absorbers. Of these, zinc sulfate is particularly preferred.

Surfactants include coating aids, release improvers,
It functions as a slipperiness improver or an antistatic agent. The surfactants are described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used instead of the surfactant. Preferably, the organic fluoro compound is hydrophobic. Examples of the organic fluoro compound include a fluorinated surfactant, an oily fluorinated compound (for example, fluorinated oil), and a solid fluorinated compound resin (for example, ethylene tetrafluoride resin). About the organic fluoro compound, Japanese Patent Publication No. 57-9
No. 053 (columns 8 to 17), JP-A-61-20994.
And JP-A-62-135826. Other additives added to the ink receiving layer include a pigment dispersant, a thickener, a defoamer, a dye, a fluorescent whitening agent, a preservative,
pH adjusters, matting agents, hardeners and the like can be mentioned. The ink receiving layer may be a single layer or two layers.

The recording paper and the recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of the white pigment contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. , Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite,
Examples include white inorganic pigments such as hydrohaloysite, magnesium carbonate, and magnesium hydroxide, and organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin.

The aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin And water-soluble polymers such as carboxymethylcellulose, hydroxyethylcellulose and polyvinylpyrrolidone, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent.

A polymer latex may be added to the constituent layers (including the back coat layer) of the ink jet recording paper and the recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, and film crack prevention. Polymer latex is described in JP-A-62-245258 and JP-A-62-1.
Nos. 36648 and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or less) is added to the layer containing a mordant, cracking and curling of the layer can be prevented. Curling can also be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink of the present invention is not limited to an ink jet recording method, and is a known method, for example, a charge control method in which ink is ejected by using electrostatic attraction, a drop-on-demand method in which vibration pressure of a piezo element is used. (Pressure pulse method), an acoustic ink jet method in which an electric signal is converted into an acoustic beam to irradiate the ink, and the ink is ejected using a radiation pressure, and a pressure is generated by heating the ink to form bubbles. Used in thermal ink jet systems and the like. The ink jet recording method uses a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality by using a plurality of inks having substantially the same hue and different densities, or a colorless transparent ink. The method is included.

[0093]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the examples, temperatures represent degrees Celsius. (Synthesis Example 1) Synthesis of Compound (1-1) (1) Synthesis of Compound (1-1a) 8-amino-3-tert-butyl-4-cyanopyrazole (1) 8 g (48.7 mmol), concentrated hydrochloric acid 15 ml of water and 50 ml of water were stirred at an internal temperature of 5 degrees, and sodium nitrite 3.3 parts
6 g (48.7 mmol) were added in portions over 10 minutes.
After stirring for 10 minutes as is, coupler component (2) 21.3
g (40.6 mmol) to 50 g of sodium acetate, DMF
50 ml and 50 ml of ethyl acetate were added and stirred.
The above diazonium salt was added to the three-necked flask which had been cooled frequently for 10 minutes. After the addition of the diazonium salt, the reaction solution was further stirred as it was for 30 minutes.
0 ml was added, and the precipitated compound (1-1a) was isolated by suction filtration. Yield 24.2 g, 85%.

(2) Synthesis of Compound 1-1 To 28.0 g (40 mmol) of the dye (1-1a), 8.8 g (52 mmol) of the heterylating agent (3), 5.5 g of potassium carbonate, and 100 ml of DMAc were added. For 1 hour. After completion of the reaction, the mixture was cooled to room temperature, 400 ml of saturated saline was added, and the precipitated dye (1-1) was isolated by suction filtration. Further, the crude crystals were recrystallized with an acetonitrile solvent. Yield 33.3 g, 80%. λmax
= 545 nm (DMF solution). m / Z (POSI) = 834.

[0095]

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The following compounds were synthesized in the same manner as in Synthesis Example 1. The results are shown in the table below.

[0097]

[Table 17]

(Synthesis Example 2) Synthesis of Compound (2-1) (1) Synthesis of Compound (2-1a) 8 g (48.7 mmol) of 5-amino-3-tert-butyl-4-cyanopyrazole (1) , Concentrated hydrochloric acid 15 ml, acetic acid 8 ml, and propionic acid 12 ml were stirred at an internal temperature of 5 ° C., and sodium nitrite 3.36 g (48.7 mmol)
Was dissolved in 10 ml of water and added dropwise over 10 minutes. After stirring for 30 minutes as it is, 18.5 g of the coupler component (2) (4
(0.6 mmol), pyridine (100 ml) was added, the mixture was stirred, cooled to an internal temperature of 5 ° C., and the above diazonium salt was added over 30 minutes. After the addition of the diazonium salt, the reaction solution was further treated for 30 minutes.
After stirring for 300 minutes, 300 ml of a saturated saline solution was added, and the precipitated compound (4-5) was isolated by suction filtration. Yield 17.
6 g, yield 75%.

(2) Synthesis of Compound 2-1 To 214 g (40 mmol) of compound (4-5) were added 17 g (100 mmol) of a heterylating agent (3), 5.5 g of potassium carbonate, and 100 ml of DMAc. The mixture was heated and stirred for hours. After completion of the reaction, the mixture was cooled to room temperature, 400 ml of a saturated saline solution was added, and the precipitated compound (2-1) was isolated by suction filtration. Further, the crude crystals were recrystallized with an acetonitrile solvent. Yield 15.4 g, 48%. λma
x = 558 nm (DMF solution). m / Z (POSI) = 802.

[0100]

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The following compounds were synthesized in the same manner as in Synthesis Example 2. The results are shown in the table below.

[0102]

[Table 18]

Synthesis Example 3 Synthesis of Compound (2-1) To 37.3 g (56 mmol) of compound (2-4) were added 18.9 g (112 mmol) of a heterylating agent (3), 20 g of potassium carbonate, and 210 ml of DMSO. The mixture was heated and stirred at 100 ° C. for 4 hours while bubbling with nitrogen. After completion of the reaction, the resultant was cooled to room temperature, and the precipitated compound (2-1) was precipitated.
Was isolated by suction filtration, and the obtained crystals were separated into DMSO200
Washed with ml. The crystals were dispersed in 1500 ml of water, and subjected to suction filtration and water washing to obtain a compound (2-1). 29 g, 65% yield. λmax = 558 nm (DMF solution). m / Z (POSI) = 802.

[0104]

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(Synthesis Example 4) Synthesis of Compound (6-4) In a three-necked flask containing 90% of 30% fuming sulfuric acid, the internal temperature was 1
While maintaining about 5 degrees, 30 g of the dye (2-1) (3
7.5 mmol) was added in portions over 30 minutes. After the addition was completed, the reaction solution was reacted at an internal temperature of 20 ° C. for 5 hours while being vigorously stirred. The reaction solution was cooled to 5 degrees, and 10 ml of pure water was carefully added dropwise. The reaction temperature was kept below 30 degrees. After completion of the dropping, the solution was gradually dropped into 800 ml of cold saturated saline to crystallize a crude pigment. At this time, the concentrated NaOH
An aqueous solution (70 g of NaOH dissolved in 200 ml of pure water) was simultaneously dropped. The internal temperature during crystallization was kept below 40 degrees. After the completion of the dropwise addition, the precipitated dye was separated by filtration.
The filtrate was washed with 300 ml of saturated saline. The obtained crude dye (6-4) was treated with methanol / ethanol = 1/1 (v /
v) After dissolving in 600 ml and filtering while hot, a potassium acetate solution dissolved in 120 ml of methanol / ethanol = 1/1 (v / v) was added dropwise to the filtrate, and a recrystallization operation was performed. The obtained dye was desalted with a desalting membrane to obtain 35 g of a highly pure dye (6-4). Yield 72.3%. λma
x = 560 nm (DMSO).

[0106]

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(Synthesis Example 5) The following compound was synthesized by the same synthesis method as in the above Synthesis Example. The results are shown in the table below.

[0108]

[Table 19]

[0109]

[Table 20]

Synthesis Example 6 Synthesis of Compound (2-1) (1) Synthesis of Compound (4-5) 7.55 g (46 mmol) of 5-amino-3-tert-butyl-4-cyanopyrazole (1) 15 ml of concentrated hydrochloric acid,
20 ml of acetic acid / propionic acid = 2/3 (v / v) was stirred at an internal temperature of 5 ° C., and 3.36 g of sodium nitrite (48 m
mol) was dissolved in 10 ml of water and added in 10 min portions. After stirring for 10 minutes, coupler component (2) 2
100 g of pyridine was added to 0.0 g (44 mmol), and the mixture was stirred. The diazonium salt was added to the three-necked flask cooled to 5 ° C. for 10 minutes. After the diazonium salt was added, the reaction solution was further stirred for 30 minutes as it was, then dropped into a mixture of 110 ml of a 1N aqueous HCl solution and 600 g of ice, and the precipitated compound (4-5) was isolated by suction filtration. Yield 26.2 g, 88%.

(2) Synthesis of Compound (2-1) 30.0 g (56 mmol) of the compound (4-5) was added to a heterylating agent (2-chlorobenzothiazole) (3) 5.
8.4 ml (224 mmol), potassium carbonate 62 g,
210 ml of DMSO was added, and the mixture was heated and stirred at 100 ° C. for 4 hours while bubbling with nitrogen. After completion of the reaction, the resultant was cooled to room temperature, the precipitated compound (2-1) was isolated by suction filtration, and the obtained crystals were washed with 200 ml of DMSO. The crystals were dispersed in 1500 ml of water, and subjected to suction filtration and water washing to obtain a compound (2-1). Yield 63
g, 80% yield. λmax = 558 nm (DMF solution). m / Z
(POSI) = 802.

In Example 6, when the compound (2-1) was produced in the same manner as described above except that only nitrogen bubbling was not performed, the yield was 45%.

(Synthesis Example 7) Synthesis of Compound (2-1) 37.3 g (56 mmol) of compound (2-4) was added to a heterylating agent (2-chlorobenzothiazole) (3) 18.9.
g (112 mmol), potassium carbonate 20 g, DMSO
Add 210 ml and add 10 g while bubbling nitrogen.
The mixture was heated and stirred at 0 degrees for 4 hours. After completion of the reaction, the resultant was cooled to room temperature, the precipitated compound (2-1) was isolated by suction filtration, and the obtained crystals were washed with 200 ml of DMSO. The crystals were dispersed in 1500 ml of water, and subjected to suction filtration and water washing to obtain a compound (2-1). 29 g, 65% yield. λmax = 558 nm (DMF solution). m / Z (POSI)
= 802.

When the compound (2-1) was produced in the same manner as in Synthesis Example 7 except that only nitrogen bubbling was performed, and the subsequent operation was exactly the same, the yield was 50%.

From the above synthesis examples, it is clear that in any case, it is effective in terms of yield to carry out the reaction by cutting off oxygen from the reaction system.

Example 1 (Preparation of Aqueous Ink) After stirring the following components for 1 hour while heating at 30 to 40 ° C., the average pore diameter was 0.8 μm and the average diameter was 4 μm.
Ink liquid A was prepared by pressure filtration using a 7 mm microfilter. -Composition of Ink Liquid A-5 parts by mass of compound (specific compound example 2-14) 9 parts by mass of diethylene glycol 9 parts by mass of tetraethylene glycol monobutyl ether 7 parts by mass of glycerin 2 parts by mass of diethanolamine 70 parts by mass of water Department

Ink liquids B to H were prepared in the same manner as in preparation of ink liquid A, except that the azo compound was changed as shown in Table 10 below.

(Image recording and evaluation) Using ink liquids A to H, an ink-jet printer (PM-700C, manufactured by Seiko Epson Corporation) was used to produce photo glossy paper (ink-jet paper manufactured by Fuji Photo Film Co., Ltd.) (Grade). The resulting image was evaluated for hue and light fastness. The hue was visually evaluated in three stages of best, good and poor. The evaluation results are shown in Table 21 below. In Table 21 below, Δ represents the best hue;
Δ indicates good, and x indicates poor hue. Regarding the light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165), and then the image was re-imaged. The density Cf was measured, and the residual dye ratio ({(Ci−Cf) / Ci} × 100%) was calculated from the difference in image density before and after irradiation with xenon light, and evaluated. The image density was measured using a reflection densitometer (X-Rite310T).
R). The dye residual ratio is such that the reflection density is 1,
The measurement was performed at three points of 1.5 and 2.0. The evaluation results are shown in the following table. In the following table, the case where the dye remaining ratio is 80% or more at any concentration is indicated by Δ, the case where two points are less than 80% is indicated by Δ, and the case where the concentration is less than 80% at all concentrations is indicated by X. Regarding the ozone gas resistance, the image immediately after recording was left in a box in which the ozone gas concentration was set to 0.5 ppm for 24 hours, and the image density before and after the ozone gas was left under ozone gas was measured using a reflection densitometer (X-Rite310TR). It was measured and evaluated as the residual dye ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. At any concentration, the residual dye ratio was 70% or more, ○: 1 or 2 points less than 70%, Δ: 70% at all concentrations
The case of less than was evaluated as x, and evaluated in three steps.

[0119]

[Table 21]

[0120]

[Table 22]

[0121]

Embedded image

[0122]

Embedded image

As shown in the above table, the magenta images obtained from the ink liquids A to D were clearer than the magenta images obtained from the ink liquids E to H. In addition, ink liquids A to
The image obtained using D had excellent light fastness.

Further, using the ink liquids A to D, an ink jet printer (PM-700C, manufactured by Seiko Epson Corporation) was used to make a glossy paper (MJ
A4S3P, manufactured by Seiko Epson Corporation). When the hue and the light fastness of the obtained image were evaluated, the same results as those in the above table were obtained.

Example 2 (Preparation of Ink Sample 101) 5.63 g of an azo compound (Specific Compound Example 2-8; oil-soluble compound) and 7.04 g of sodium dioctylsulfosuccinate were mixed with the following high boiling organic solvent (S -2) 4.22 g, the following high boiling organic solvent (S-1)
1) It was dissolved in 5.63 g and 50 ml of ethyl acetate at 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion. Next, this coarse particle dispersion is used as a microfluidizer (MICROFLUIDEX I).
(NC) for 5 passes at a pressure of 600 bar to obtain fine particles. The resulting emulsion was desolvated with a rotary evaporator until the odor of ethyl acetate disappeared. 140 g of diethylene glycol and glycerin 5 were added to the fine emulsion of the hydrophobic dye thus obtained.
0g, SURFYNOL465 (AirProduct)
s & Chemicals) 7g, 900m of deionized water
1 was added to prepare Ink Sample 101.

[0126]

Embedded image

(Preparation of Ink Samples 102 to 105) Sample 101 was prepared in the same manner as in ink sample 101 except that the azo compound (specific compound example 2-8; oil-soluble compound) in the ink sample 101 was changed to an azo compound (oil-soluble compound) shown in the following table. Samples 102 to 10 as in
5 was produced. The volume average particle sizes of the emulsified dispersion inks of Samples 101 to 105 thus obtained were measured using Microtrac UPA (Nikkiso Co., Ltd.). The results are shown in Table 23 below.

(Image Recording and Evaluation) Ink Samples 101 to 101
The following evaluations were performed on 105 and comparative samples (the ink liquids E to H). The results are shown in Table 24 below. In Table 24, "color tone", "paper dependence", "waterfastness" and "lightfastness" indicate that each inkjet ink is an inkjet printer (manufactured by EPSON Corp .; PM-7).
00C) and photo glossy paper (Fuji Photo Film Co., Ltd .;
(E.g., inkjet paper, photo grade).

<Tone> 390-730n of recorded image
The reflection spectrum at an interval of 10 nm in the m region was measured, and a * and b * were calculated based on the reflection spectrum based on the CIE L * a * b * color space system. The preferred color tone for magenta was defined as follows.

Preferred a *: 76 or more, Preferred b *: -30 or more and 0 or less A: Preferred area for both a * and b * B: Preferred area for only one of a * and b * C: Any of a * and b * Also outside the preferred area

<Paper Dependency> The color tone of the image formed on the photo glossy paper and the image separately formed on plain paper for PPC were compared. The case where the difference between the images was large was evaluated as B (poor) and evaluated in two steps.

<Water Resistance> The photo glossy paper on which the image was formed was dried for 1 hour at room temperature, immersed in water for 30 seconds, allowed to dry naturally at room temperature, and observed for bleeding. A sample without bleeding was evaluated as A, a sample with slight bleeding as B, and a sample with much bleeding as C.

<Light resistance> The photo glossy paper on which the image was formed was irradiated with xenon light (85000 lx) for 3 days using a weather meter (Atlas CI65), and the image density before and after the xenon irradiation was measured using a reflection densitometer. (X-Rite
310TR) and evaluated as the residual dye ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. In any of the concentrations, the case where the dye residual ratio was 70% or more was evaluated as A, and 1 or 2 points were evaluated as B when it was less than 70%, and when all the concentrations were lower than 70% as C.

<Ozone resistance> The photo glossy paper on which the image was formed was left in a box having an ozone gas concentration of 0.5 ppm for 24 hours. (Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. In any of the concentrations, if the residual ratio of the dye is 70% or more, A indicates that 1 or 2 points have less than 70% B, and
%, C was evaluated in three steps.

[0135]

[Table 23]

[0136]

[Table 24]

As is evident from the above table, the ink-jet ink of the present invention was excellent in color development and color tone, had low dependence on paper, and was excellent in water resistance and light resistance.

(Example 3) The same ink prepared in Example 2 was used in an ink jet printer BJ-F850 (CA
Example 1) An image was printed on the photo glossy paper GP-301 of the company using the same machine.
The same evaluation as in Example 2 was performed, and the same result as in Example 2 was obtained.

(Example 4) (Preparation of water-based ink)
Then, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, if necessary, the pH was adjusted to 9 with KOH 10 mol / L, and the mixture was filtered under reduced pressure using a microfilter having an average pore diameter of 0.25 μ to prepare a magenta ink liquid A. 8.5 g / L of the azo compound of the present invention (exemplified compound 2-17) 150 g / L of diethylene glycol 37 g / L of urea 130 g / L of glycerin 130 g / L of triethylene glycol monobutyl ether 130 g / L of triethanolamine 6.9 g / L Benzotriazole 0.08g / L ・ Surfinol 465 10g / L ・ PROXEL XL2 3.5g / L

Ink liquids B to D were prepared in the same manner as in the preparation of ink liquid A, except that the azo dye was changed as shown in the following table.

(Image Recording and Evaluation) The ink liquids A to D were packed in a cartridge of an ink jet printer (PM-670C, manufactured by Seiko Epson Corporation), and the same machine was used for ink jet paper photo glossy paper EX (Fuji Photo Film Co., Ltd.). Image). The resulting images were evaluated for hue, paper dependence, water resistance, light fastness, ozone gas resistance, and paper dependence. <Hue> The hue was visually evaluated in three stages of best, good and poor. The evaluation results are shown in the following table. In the table below, Δ indicates the best hue; Δ indicates that the color was good;
Indicates that the hue was poor. <Paper Dependency> The color tone of the image formed on the photo glossy paper and the image separately formed on the plain paper for PPC are compared. When the difference between the two images is small, A (good) is determined. The case where the difference was large was evaluated as B (poor) and evaluated in two steps.

<Water Resistance> A sample having an image formed on the photo glossy paper and having a reflection density of about 1.0 was dried at room temperature for 1 hour, immersed in ion-exchanged water for 3 minutes, and allowed to dry naturally at room temperature. Was evaluated based on the change in concentration. A sample having little change was evaluated as A, a sample showing a decrease in concentration as B, and a sample showing a large decrease in concentration as C, which was evaluated in three steps. A similar experiment was performed on an image formed on plain paper for PPC.

<Lightfastness> Xenon light (85,000 lux) was irradiated on the photo glossy paper on which the image was formed for 7 days using a weather meter (Atlas CI65).
Image densities before and after xenon irradiation are measured with a reflection densitometer (X-Rit
e310TR) and evaluated as the residual dye ratio. The reflection density is 3, 1.5 and 2.0.
Measured in points. At any of the concentrations, the case where the residual ratio of the dye was 80% or more was evaluated as A, and B was evaluated at 1 or 2 points of less than 80%, and C was evaluated at less than 80% at all concentrations.

<Ozone resistance> The photo glossy paper on which the image was formed was allowed to stand in a box having an ozone gas concentration of 0.5 ppm for 7 days. (Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. A: A case where the dye residual ratio is 80% or more at any concentration is B, B is a case where 1 or 2 points are less than 80%, and 70% at all concentrations.
The case of less than C was evaluated in three steps.

[0145]

[Table 25]

As shown in the above table, the magenta images obtained from the ink liquids A to D were clearer than the magenta images obtained from the ink liquids a to d. In addition, ink liquids A to
The image obtained using D was excellent in light fastness and ozone gas resistance.

(Example 5) Further, using the ink liquids A to D, an ink jet printer (PM-670C, manufactured by Seiko Epson Corporation) was used to print PM photographic paper <gloss>.
(KA420PSK, manufactured by Seiko Epson Corporation). When the hue, paper dependence, water fastness, light fastness, and ozone gas fastness of the obtained image were evaluated, the same results as in Example 4 were obtained.

(Example 6) The same ink prepared in Example 4 was applied to an ink jet printer BJ-F850 (CA
Example 4) An image was printed on the photo glossy paper GP-301 of the company using the same machine.
The same evaluation as in Examples 4 and 5 was obtained.

[0149]

According to the present invention, (1) a dye having three primary colors, having excellent absorption characteristics with excellent color reproducibility, and having sufficient fastness to light, heat, humidity and an active gas in the environment. (2) an ink composition for printing such as inkjet, which provides a colored image or a coloring material having excellent hue and fastness, an ink sheet for a thermal transfer type image forming material, Toner for electrophotography,
Coloring compositions for color filters used in LCDs and CCDs,
Various coloring compositions such as a dyeing solution for dyeing various fibers are provided, and (3) having a good hue by using the dye, and being fast to light and the active gas in the environment, particularly ozone. The present invention provides an inkjet recording ink capable of forming an image having a high density.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 29/036 C09B 29/036 29/42 29/42 B // C09D 11/00 C09D 11/00 (72 Inventor: Shigeaki Tanaka 210, Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. 210 Nakanuma Fuji Photo Film Co., Ltd.F-term (reference)

Claims (9)

[Claims] 1. A compound represented by the following general formula (1). Embedded image In the general formula (1), R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group or an acyl group. Each substituent may be further substituted. R ₂ represents a hydrogen atom, a halogen atom, or a cyano group. R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group,
Represents a heterocyclic group, a carboxyl group, or a sulfo group. Each substituent may be further substituted. R ₄ , R ₅ , R ₆
And R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfonyl group, an acyl group, a carboxyl group, a sulfo group, or a carbamoyl group. . Each substituent may be further substituted. However, R ₄ and R ₅ are not both hydrogen atoms, and R ₆ and R ₇ are not both hydrogen atoms. A ₁ and A ₂ are each a carbon atom which may be substituted, or one of them is a carbon atom which may be substituted, and the other is a nitrogen atom. 2. In the general formula (1), R ₃ is an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, a heterocyclic group, a carboxyl group, or a sulfo group. The compound according to claim 1, which is represented by the formula: Embedded image In the general formula (1-R1), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1). 3. The compound represented by the following general formula (1), wherein R _{4 in the} general formula (1) is an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic group which may be substituted. The compound according to claim 2, which is represented by -R2). Embedded image In the general formula (1-R2), R ₁ , R ₂ , R ₃ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1-R1). 4. The compound according to claim 2, wherein R _{4 in the} general formula (1) is a hydrogen atom and is represented by the following general formula (1-R3). Embedded image In the general formula (1-R3), R ₁ , R ₂ , R ₃ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1-R1). 5. R ₄ , R ₅ , R ₆ and R ₇ in the general formula (1) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, The compound according to claim 2, which is represented by the following general formula (1-R4), which is a ring group, an acyl group, or a carbamoyl group. Embedded image In the general formula (1-R4), R ₁ , R ₂ , R ₃ , A ₁ and A
₂ has the same meaning as in formula (1-R1). 6. The compound according to claim 1, wherein R _{3 in the} general formula (1) is a hydrogen atom and is represented by the following general formula (1-H1). Embedded image In the general formula (1-H1), R ₁ , R ₂ , R ₄ , R ₅ , R ₆ ,
R ₇ , A ₁ and A ₂ have the same meanings as in formula (1). 7. The following general formula (1-H1) wherein R ₄ is not a hydrogen atom and R ₅ and R ₇ are not hydrogen atoms.
The compound according to claim 6, which is represented by H2). Embedded image In the general formula (1-H2), R ₁ , R ₂ , R ₆ , A ₁ and A
₂ has the same meaning as in formula (1-H1). 8. A method for producing a compound, characterized in that the compound of the formula (1-R1) according to claim 2 is obtained by one of the following methods (1) and (2). Method (1): (a) a step of reacting an aminopyrazole represented by the following general formula (2) with a diazotizing agent to form a diazonium salt, and (b) a diazonium formed in the above step (a) Reacting the salt with a coupling agent represented by the following general formula (3) to form a compound represented by the general formula (1-H1); and (c) performing the above step in the presence of a base. The compound formed in (b) is reacted with an alkylating agent, an arylating agent or a heterylating agent to form the compound represented by the above general formula (1-R
A method comprising the step of forming the compound represented by 1). Embedded image Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , A ₁ and A
₂ has the same meaning as in the above formula (1). Method (2): a method including a step of introducing a water-soluble group into a compound represented by the general formula (1-R4) by an electrophilic reaction. 9. A method for producing a compound, wherein the compound of the general formula (1-R2) according to claim 3 is obtained by one of the following methods (3) and (4). Method (3): A method of reacting the compound of the general formula (1-H1) with the alkylating agent, the arylating agent, or the heterylating agent under deoxygenation conditions. Method (4): a step of reacting the compound of the general formula (1-H2) with the alkylating agent, the arylating agent, or the heterylating agent to produce a compound of the following general formula (1-R3); Reacting the compound of the general formula (1-R3) with the alkylating agent, the arylating agent, or the heterylating agent under deoxygenation conditions.