JP4445761B2 - Azo dye - Google Patents

Description

  The present invention relates to a novel azo dye having a nitrogen-containing heterocyclic structure.

  Conventionally, since azo dyes often have various visible light absorptions, they are used as dyes in various fields. In recent years, azo dyes have been used in various fields such as coloring of synthetic resins, printing inks, dyes for sublimation thermal transfer materials, ink jet inks, and color filter dyes. As a large performance required for an azo dye as a dye, there is an absorption spectrum. The hue of the pigment greatly affects the color and texture of an object colored by the pigment, and has a great effect on vision. For this reason, research has been conducted on the absorption spectrum of dyes for a long time. Regarding the absorption spectrum and the like of azo dyes, there are various reviews and books, which are described in detail in the chapter on azo dyes or azo pigments (for example, see Non-Patent Documents 1 to 3).

In recent years, color images have become mainstream as image recording materials, and the usages of dyes have been diversified. Specifically, azo dyes are actively used in ink jet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, and the like. Azo dyes are also used for dyes and hair dyeing.
On the other hand, a color filter is used to record or reproduce a color image in an image pickup device such as a CCD in a photographing apparatus and in an LCD or PDP in a display, and an azo dye is also used in the color filter.

  In these color image recording materials and color filters, three primary colorants (dyes and pigments) in so-called additive color mixing and subtractive color mixing methods are used to reproduce or record full color images. However, at present, there is an absorption characteristic that can realize a preferable color gamut, it can withstand various use conditions and environmental conditions, and there is no colorant that is robust and there is no strong colorant. Yes.

  On the other hand, it is known that yellow dyes are used for the green and red filter arrays of color filters (see, for example, Patent Document 1 or 2). However, pyridone azo dyes conventionally used as the yellow dye are insufficient in fastness such as heat resistance and light resistance, and further improvement is desired. Similarly, in a color filter composed of a yellow filter layer, a magenta filter layer, and a cyan filter layer, further improvement in fastness of the yellow dye used in the yellow filter layer is desired.

Furthermore, the colorant used in each of these applications is required to have, in common, favorable absorption characteristics for color reproduction, fastness under the environmental conditions used, and a large molar extinction coefficient. .
However, many azo dyes having a nitrogen-containing 5-membered ring as an azo component have been disclosed so far, but none of them satisfies the hue, fastness, and molecular extinction coefficient (for example, see Patent Documents 3 to 6). .) Further, although a method for synthesizing a 5-membered heterocyclic azo dye has been disclosed, it did not satisfy hue, spectral absorption coefficient, and the like (for example, see Non-Patent Document 4).
JP-A-55-161856 JP-A-6-145543 JP 7-224230 A JP 9-234964 A JP-A-9-277703 Japanese Patent Laid-Open No. 2003-246942 "Light Absorption of Organic Colorants" by J. Fabian and H. Hartmann, Springer-Verlag, Berline, 1980 Heinrich Zollinger "Color Chemistry" Weinheim, New York, Basel, Cambridge Noguchi Hiroshi “Synthetic Dyes”, Sankyo Publishing Co., Ltd., 1970 "Journal of Heterocyclic Chemistry" Vol. 22, 813-816, 1985

  An object of the present invention is to provide an azo dye having a novel structure having a good hue and fastness and a high spectral extinction coefficient.

  As a result of intensive studies, the inventors have obtained knowledge that a specific nitrogen-containing heterocyclic azo dye has a good hue and exhibits good fastness to light and heat. . Specific means for solving the above problems will be described below.

<1> An azo dye represented by the following general formula ( 2 ).

[In General Formula ( 2 ), R ¹ represents an aryl group . R ² represents a hydrogen atom or an aliphatic group , R ³ represents an aliphatic oxycarbonyl group, an aliphatic sulfonyl group or a cyano group, R ⁴ represents an aliphatic group, and R ⁵ represents a hydrogen atom or a cyano group. Represents . G ¹ and G ² each independently represents an aliphatic oxy group, an aliphatic amino group, an arylamino group or an aliphatic thio group . ]

  According to the present invention, it is possible to provide a novel azo dye having excellent hue, sufficient fastness to active gas in light, heat, humidity and environment, and having a high spectral absorption coefficient. .

Detailed description of the azo dye represented by a general formula (1) below.

[In General Formula (1), R ¹ represents an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, or Represents a sulfamoyl group. R ² represents a hydrogen atom or a substituent, and X ¹ represents —CR ³ ═ or a nitrogen atom. B ¹ represents -CR ⁴ = or a nitrogen atom, and B ² represents -CR ⁵ = or a nitrogen atom. However, B ¹ and B ² do not represent a nitrogen atom at the same time. R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent . ]

In the general formula (1), R ¹ represents an aliphatic group, aryl group, heterocyclic group, acyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, or sulfamoyl. Represents a group.
In the aliphatic group represented by R ¹ , the aliphatic moiety may be linear, branched, or cyclic, and may be saturated or unsaturated. Examples of the aliphatic group include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group, which may be unsubstituted or have a substituent. The aliphatic group preferably has 1 to 15 carbon atoms in total, for example, methyl, ethyl, vinyl, allyl, ethynyl, isopropenyl and 2-ethylhexyl are preferable.

  The aryl group may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. The aryl group preferably has 6 to 16 carbon atoms which may have a substituent, such as phenyl, 4-nitrophenyl, 2-nitrophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. 2,4-dimethylphenyl, 2-methylphenyl, 4-methoxyphenyl, 2-methoxyphenyl and 2-methoxycarbonyl-4-nitrophenyl are preferred.

The heterocyclic group has a hetero atom (for example, nitrogen atom, sulfur atom, oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. The heterocycle may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. The heterocyclic group is preferably a heterocyclic group having 3 to 15 carbon atoms which may be saturated or unsaturated. For example, 3-pyridyl, 2-pyridyl, 2-pyrimidinyl, 2 -Pyrazinyl is preferred.
The acyl group may be aromatic or aliphatic, and is preferably an acyl group having 2 to 15 carbon atoms in total. As the acyl group, for example, acetyl, pivaloyl, and benzoyl are preferable.

The aliphatic oxycarbonyl group may have a substituent and may be saturated or unsaturated. The aliphatic oxycarbonyl group preferably has 1 to 16 carbon atoms in total, for example, methoxycarbonyl and butoxycarbonyl are preferable.
The aryloxycarbonyl group may have a substituent and preferably has 7 to 17 carbon atoms in total. As the aryloxycarbonyl group, for example, phenoxycarbonyl is preferable.
The carbamoyl group may have a substituent and preferably has 1 to 12 carbon atoms in total. As the carbamoyl group, for example, carbamoyl and dimethylcarbamoyl are preferable.

The aliphatic sulfonyl group may have a substituent and may be saturated or unsaturated. The aliphatic sulfonyl group preferably has 1 to 15 carbon atoms in total, and for example, methanesulfonyl, butanesulfonyl, and methoxyethanesulfonyl are preferable.
The arylsulfonyl group preferably has 6 to 16 carbon atoms which may have a substituent. For example, phenylsulfonyl, 4-tbutylphenyl, 4-toluenesulfonyl and 2-toluenesulfonyl are preferable.

  The sulfamoyl group may have a substituent and preferably has 0 to 12 carbon atoms. As the sulfamoyl group, for example, sulfamoyl and dimethylsulfamoyl are preferable.

In view of the effect of the present invention, R ¹ is preferably an aliphatic group, an aryl group, or a heterocyclic group, more preferably an aryl group or a heterocyclic group, and most preferably an aryl group. preferable. Moreover, as a substituent which each group represented by R < ¹ > has, the thing similar to the substituent in R < ² > mentioned later can be mentioned.

In the general formula (1), R ² represents a hydrogen atom or a substituent. The substituent represented by R ² may be any group that can be substituted. For example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a hetero group Ring oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, hetero Ring sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryl Oxycarbonylamino group, heterocyclic oxyca Bonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoyl Examples thereof include an amino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

From the viewpoint of the effect of the present invention, R ² is a hydrogen atom, aliphatic group, aryl group, acyloxy group, acylamino group, aliphatic oxy group, aliphatic sulfonyloxy group, arylsulfonyloxy group, aliphatic sulfonamide group. , Arylsulfonamido group, amino group, aliphatic amino group, arylamino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group, hydroxy group, cyano group, sulfo group, carbamoylamino group And preferably a sulfamoylamino group, more preferably a hydrogen atom, an aliphatic group, an aryl group, an acyloxy group, an aliphatic oxy group, or an aliphatic sulfonyloxy group, and a hydrogen atom or an aliphatic group. Most preferred.

In General formula (1), X < ¹ > represents -CR < ³ > = or a nitrogen atom. R ³ represents a hydrogen atom or a substituent. The substituent represented by R ³ may be any group that can be substituted, and examples thereof include the same substituents as those described above for R ² .

From the standpoint of the effects of the present invention, X ¹ represents that R ³ is an aliphatic group, aryl group, acyl group, acylamino group, aliphatic oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group. group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an arylsulfonyloxy group, an aliphatic sulfonamido group, an aryl sulfonamide group, -CR ³ = when a cyano group, a carboxyl group, and it is a nitrogen atom It is more preferable that R ³ is an acyl group, an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a cyano group, a carboxyl group, -CR ³ =, and a nitrogen atom, R ³ is an aliphatic oxycarbonyl group, an aliphatic sulfonyl group, -CR ³ of a cyano group , And, most preferably a nitrogen atom.

In the general formula ^(1), B 1 represents -CR ⁴ = or a nitrogen atom, B ² represents -CR ⁵ = or a nitrogen atom. However, B ¹ and B ² do not represent a nitrogen atom at the same time. R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent.

The substituent represented by R ⁴ and R ⁵ may be any group that can be substituted, and examples thereof include the same substituents as those described above for R ² .
In terms of the effects of the present invention, R ⁴ and R ⁵ are each independently a hydrogen atom, aliphatic group, aryl group, heterocyclic group, acyl group, acylamino group, aliphatic oxy group, aliphatic oxycarbonyl group. Carbamoyl group, sulfamoyl group, aliphatic sulfonamido group, arylsulfonamido group, amino group, aliphatic amino group, hydroxy group, cyano group, sulfo group, carboxyl group, hydrogen atom, aliphatic group, More preferred is a cyano group.

B ¹ and B ² are preferably such that B ¹ is —CR ⁴ ═ and B ² is —CR ⁵ ═ or a nitrogen atom. In B ¹ and B ² , it is more preferable that B ¹ is —CR ⁴ ═ and B ² is —CR ⁵ ═. When B ¹ is —CR ⁴ ═ and B ² is —CR ⁵ ═, it is most preferred that R ⁴ is an aliphatic group and R ⁵ is a hydrogen atom or a cyano group. .

In the general formula (1), G ¹ and G ² each independently represent a hydrogen atom or a substituent. The substituent represented by G ¹ and G ^{2 only} needs to be a substitutable group, and examples thereof include the same substituents as those described above for R ² .
From the viewpoint of the effect of the present invention, G ¹ and G ² are each independently a hydrogen atom, aliphatic group, aryl group, heterocyclic group, acyloxy group, acylamino group, aliphatic oxy group, aryloxy group, hetero Ring oxy group, aliphatic sulfonamido group, aryl sulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group A heterocyclic oxycarbonylamino group, an aliphatic thio group, an arylthio group, a hydroxy group, a cyano group, a sulfo group, a carboxyl group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a hydrogen atom, an aliphatic group Group, heterocyclic group, acylamino group, aliphatic oxy group, aryloxy group, fat It is more preferably an aliphatic sulfonamido group, an arylsulfonamido group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic thio group, an arylthio group, or a halogen atom, an aliphatic oxy group, an aliphatic amino group Particularly preferred are a group, an arylamino group and an aliphatic thio group. Furthermore, it is most preferable that at least one of G ^{1 and} G ² is an aliphatic amino group or an aromatic amino group.

The azo dye of the present invention is represented by the following general formula (2) .

[In General Formula (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , G ¹ and G ² have the same meanings as in General Formula (1). ]

Furthermore, as the azo dye represented by the general formula (2), R ¹ is an aryl group, R ² is a hydrogen atom or an aliphatic group, and R ³ is an aliphatic oxycarbonyl group, an aliphatic sulfonyl group or A cyano group, R ⁴ is an aliphatic group, R ⁵ is a hydrogen atom or a cyano group, and G ¹ and G ² are an aliphatic oxy group, an aliphatic amino group, an arylamino group, or an aliphatic thio group. Most preferably, at least one of G ¹ or G ² is an aliphatic amino group or an arylamino group.

Formula (1) and the following shows a specific example of the represented luer zone dye (2) (exemplified compounds (1) to (54)). However, the present invention is not limited to the following examples.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
[Example 1]
-Synthesis of Exemplified Compound (1)-
The exemplified compound (1) was synthesized according to the following scheme 1.

  In Scheme 1, first, 98.7 g (0.50 mol) of 3- (2-ethylhexyloxy) propylamine was gradually added to 18.7 g (0.10 mol) of compound (A) while stirring with water cooling, Stir at 120 ° C. for 4 hours. Next, the temperature of the reaction solution was lowered to room temperature, and 300 ml of ethyl acetate and 300 ml of water were added. Thereafter, the mixture was separated, and the ethyl acetate layer of the reaction solution was washed twice with 200 ml of saturated brine. After washing, ethyl acetate was distilled off under reduced pressure, and the resulting viscous liquid was purified by silica gel column chromatography to obtain 45.5 g of a colorless viscous liquid compound (B). The yield of compound (B) was 93.2%.

  Next, 1.5 g (0.022 mol) of sodium nitrite was added while stirring a solution of 2.16 g (0.02 mol) of compound (C) in 25 ml of phosphoric acid at 0 ° C., and the mixture was stirred for 30 minutes. . After stirring, 9.7 g (0.02 mol) of the above compound (B) was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Furthermore, 300 ml of water was added to the reaction solution and stirred for 1 hour, and the precipitated crystals were filtered and thoroughly washed with water. After washing, the resulting crystals were dried to obtain 11.0 g of compound (D). The yield of compound (D) was 90.1%.

Furthermore, 30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 2.0 g (0.014 mol) of p-fluoronitrobenzene were added to 6.1 g (0.01 mol) of the obtained compound (D), Stir for hours. The obtained reaction solution was poured into 100 ml of water and 100 ml of ethyl acetate, and the mixture was separated to saturate the ethyl acetate layer and washed twice with 100 ml of brine. After washing, ethyl acetate was distilled off under reduced pressure and purified by silica gel column chromatography. After purification, it was crystallized with 40 ml of acetonitrile, filtered, washed with 20 ml of cold acetonitrile, and dried to obtain 4.8 g of the exemplified compound (1) of the present invention as yellow crystals. The obtained exemplary compound (1) had a yield of 65.9%, a melting point of 157 to 158 ° C., an absorption λmax of 466.9 nm in ethyl acetate, and ε49,300.
The NMR data of the obtained exemplary compound (1) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 0.70-1.95 (m, 34H), 2.55 (s, 3H), 3.18-3.38 (m, 4H), 3.38-3 .60 (m, 6H), 3.65 (m, 2H), 8.32-7.78 (t, 1H), 8.12 (d, 2H), 8.32 (d, 2H), 9. 50 (s, 1H), 10.72 (t, 1H)

[Example 2]
-Synthesis of Exemplified Compound (2)-
In Example 1, “p-fluoronitrobenzene 2.0 g (0.014 mol)” was changed to “o-fluoronitrobenzene 2.0 g (0.014 mol)”, and “potassium carbonate 3.0 g” was further changed. Exemplified compound (2) was synthesized in the same manner as in Example 1 except that was changed to “5.0 g of sodium bicarbonate”. The obtained exemplary compound (2) had a yield of 4.6 g, a yield of 63.1%, a melting point of 132 to 135 ° C., an absorption λmax of 457.3 nm in ethyl acetate, and ε39,800.

The NMR data of the obtained exemplary compound (2) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 0.65-1.93 (m, 34H), 2.65 (s, 3H), 3.23 (t, 4H), 3.42 (t, 4H), 3.47-3.75 (m, 4H), 7.75-8.05 (m, 4H), 8.20 (d, 1H), 9.20 (s, 1H), 10.67 (t, 1H)

[Example 3]
-Synthesis of Exemplified Compound (5)-
Exemplary compound (5) was synthesized according to the following scheme 2.

  In Scheme 2, first, 18.7 g (0.10 mol) of the compound (A) in Scheme 1 was gradually added while stirring 45.0 g (0.60 mol) of 1-amino-2-propanol with water cooling, Stir at 130 ° C. for 3 hours. The temperature of the reaction solution was lowered to room temperature, and 500 ml of ethyl acetate and 300 ml of water were added. Thereafter, the mixture was separated, and the ethyl acetate layer of the reaction solution was washed twice with 200 ml of saturated brine. After washing, ethyl acetate was distilled off under reduced pressure to obtain a solid. To this solid, 100 ml of acetonitrile was added and dissolved by heating, and then further cooled with water. The precipitated crystals were filtered and washed with 50 ml of cold acetonitrile. After washing, the obtained crystals were dried to obtain 19.7 g of compound (E). The yield of compound (E) was 74.5%.

  Next, 0.73 g (0.011 mol) of sodium nitrite was added and stirred for 30 minutes while stirring a solution of 1.4 g (0.01 mol) of compound (F) in 20 ml of phosphoric acid at 0 ° C. . 2.6 g of the compound (E) was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. After stirring, 150 ml of water was added to the reaction solution, and the mixture was further stirred for 1 hour, and the precipitated crystals were filtered. The obtained crystal was sufficiently washed with water and dried to obtain 3.5 g of Compound (G). The yield of compound (G) was 85.0%.

  Furthermore, 30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 1.5 g (0.011 mol) of p-fluoronitrobenzene were added to 3.4 g (0.08 mol) of compound (G), and the mixture was stirred at 75 ° C. for 2 hours. After stirring, the reaction solution was poured into 100 ml of water, and the precipitated crystals were filtered and washed thoroughly with water. The crystals were dried and recrystallized with 15 ml of ethyl acetate and 5 ml of methanol. The precipitated crystals were filtered and washed with 10 ml of cold ethyl acetate. After washing, the crystals were dried to obtain 3.2 g of the exemplified compound (5) of the present invention as yellow crystals. The obtained exemplary compound (5) had a yield of 60.5%, a melting point of 250 ° C. or higher, an absorption λmax of 456.6 nm in ethyl acetate, and ε40,900.

The NMR data of the obtained exemplary compound (5) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 1.00-1.15 (m, 6H), 1.20 (t, 3H), 2.67 (s, 3H), 2.94 (q, 2H), 3.20-3.55 (m, 4H), 3.75-4.00 (m, 2H), 4.82 (d, 1H), 4.90 (d, 1H), 7.65 (t, 1H), 7.97 (d, 2H), 8.47 (d, 2H), 10.73 (t, 1H)

[Example 4]
-Synthesis of Exemplified Compound (6)-
In Example 3, “p-fluoronitrobenzene 1.5 g (0.011 mol)” was changed to “o-fluoronitrobenzene 1.5 g (0.011 mol)”, and “potassium carbonate 3.0 g” was further changed. A yellow crystal was obtained by reacting in the same manner as in Example 3 except that it was changed to “Baking soda 5.0 g”. The obtained yellow crystals were purified by silica gel column chromatography, crystallized with 15 ml of methanol, and the precipitated crystals were filtered and washed with 10 ml of cold methanol. After washing, the crystals were dried to obtain 2.6 g of the exemplified compound (6) of the present invention as yellow crystals. The exemplified compound (6) had a yield of 48.8%, a melting point of 242 to 245 ° C., an absorption λmax of 452.9 nm in ethyl acetate, and ε36,600.

The NMR data of the obtained exemplary compound (6) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 1.00-1.22 (m, 9H), 2.67 (s, 3H), 2.78 (q, 2H), 3.20-3.55 (m , 4H), 3.75-4.00 (m, 2H), 4.83 (d, 2H), 7.66 (t, 1H), 7.82-8.12 (m, 3H), 8. 30 (d, 1H), 10.63 (t, 1H)

[ Reference Example 5]
-Synthesis of Exemplified Compound (8)-
The exemplified compound (8) was synthesized according to the following scheme 3.

  In scheme 3, 1.5 g (0.022 mol) of sodium nitrite was added while stirring a solution of 2.16 g (0.02 mol) of compound (C) in scheme 1 above in 25 ml of phosphoric acid at 0 ° C. And stirred for 30 minutes. After stirring, 5.2 g (0.02 mol) of the compound (E) in Scheme 2 was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Furthermore, 200 ml of water was added to the reaction solution and stirred for 1 hour, and the precipitated crystals were filtered and washed thoroughly with water. After washing, the obtained crystals were dried to obtain 6.9 g of compound (H). The yield of compound (H) was 90.0%.

  Next, 30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 2.2 g (0.011 mol) of 2-ethylhexyl bromide were added to 3.8 g (0.01 mol) of compound (H), and the mixture was stirred at 75 ° C. for 2 hours. The reaction solution was poured into 100 ml of water and 100 ml of ethyl acetate, and the phases were separated. The ethyl acetate layer was washed twice with 100 ml of saturated brine. After washing, ethyl acetate was distilled off under reduced pressure, crystallized with 50 ml of methanol and 50 ml of chloroform, and filtered. After filtration, the obtained crystals were washed with 50 ml of cold methanol and dried to obtain 2.9 g of exemplary compound (8) of the present invention as yellow crystals. The obtained exemplary compound (8) had a yield of 58.5%, a melting point of 223 to 224 ° C., an absorption λmax of 450.7 nm in ethyl acetate, and ε31,100.

The NMR data of the obtained exemplary compound (8) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 0.88 (t, 6H), 1.00-1.35 (m, 14H), 1.92 (m, 1H), 2.64 (s, 3H), 3.25-3.50 (m, 4H), 3.75-3.90 (m, 2H), 4.10 (d, 2H), 4.78-4.90 (m, 2H), 7. 67 (t, 1H), 8.65 (t, 1H), 10.60 (t, 1H)

[ Reference Example 6]
Exemplary compound (40) was synthesized according to scheme 4 below.

  In Scheme 4, first, 9.2 g (0.05 mol) of compound (I) was gradually added while stirring with water-cooling 23 g (0.31 mol) of 1-amino-2-propanol, and the mixture was stirred at 50 ° C. for 1 hour. Stir. Thereafter, the temperature of the reaction solution was lowered to room temperature, 300 ml of water was added, and the mixture was stirred for 1 hour under ice cooling. After stirring, the precipitated crystals were filtered, washed with cold water and dried to obtain 7.5 g of white crystals (J). The yield of white crystals (J) was 50.0%.

  Next, 1.5 g (0.022 mol) of sodium nitrite was added while stirring a solution of 2.16 g (0.02 mol) of compound (C) in Scheme 1 in 25 ml of phosphoric acid at 0 ° C. Stir for minutes. After stirring, 6.0 g (0.02 mol) of compound (J) was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Furthermore, 200 ml of saturated brine was added to the reaction solution and stirred for 1 hour. The precipitated crystals were filtered and washed with 50 ml of saturated brine. The obtained crystals were dried to obtain crude crystals of compound (K).

  30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 4.0 g (0.028 mol) of o-fluoronitrobenzene were added to the total amount of the obtained compound (K), and the mixture was stirred at 75 ° C. for 2 hours. After stirring, the reaction solution was poured into 150 ml of water and 150 ml of ethyl acetate and separated, and the ethyl acetate layer was washed twice with 150 ml of saturated brine. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography, crystallized from 100 ml of acetonitrile, and filtered. Next, the obtained crystals were washed with 50 ml of cold acetonitrile and dried to obtain 2.8 g of the exemplified compound (40) of the present invention as yellow crystals. The exemplary compound (40) had a yield of 51.9%, a melting point of 190 to 192 ° C., an absorption λmax of 429.1 nm in ethyl acetate, and ε34,400.

The NMR data of the obtained exemplary compound (40) are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 1.06-1.15 (m, 9H), 3.15-3.50 (m, 6H), 3.70-3.90 (m, 2H), 4 .70-4.86 (m, 3H), 6.97 (m, 1H), 7.50 (m, 1H), 7.75-8.00 (m, 3H), 8.20 (d, 1H) ), 9.12 (s, 1H), 10.33 (m, 1H)

[ Reference Example 7]
The exemplified compound (44) was synthesized according to the following scheme 5.

  In scheme 5, first, 30.0 g (0.16 mol) of compound (A) in scheme 1 was gradually added while stirring 87.0 g (0.67 mol) of 2-ethylhexylamine with water. After stirring at 130 ° C. for 4 hours, the reaction solution was cooled to room temperature, 300 ml of ethyl acetate and 300 ml of water were added and separated, and the ethyl acetate layer was washed twice with 300 ml of saturated brine. After washing, ethyl acetate was distilled off under reduced pressure, and the resulting viscous liquid was purified by silica gel column chromatography to obtain 45.0 g of a colorless viscous liquid compound (L). The yield of the obtained compound (L) was 75.6%.

  Next, 0.73 g (0.011 mol) of sodium nitrite was added to a solution of 0.90 g (0.01 mol) of compound (M) in 25 ml of phosphoric acid while stirring at 0 ° C., and the mixture was stirred for 30 minutes. After stirring, 3.7 g (0.01 mol) of compound (L) was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Furthermore, 200 ml of water was added to the reaction solution and stirred for 1 hour, and the precipitated crystals were filtered and washed thoroughly with water. After washing, the obtained crystals were dried to obtain 4.4 g of compound (N). The yield of Compound N was 94.2%.

  Furthermore, 30 ml of dimethylacetamide, 3.0 g of potassium carbonate, and 2.0 g (0.014 mol) of p-fluoronitrobenzene were added to 4.4 g (0.0094 mol) of the obtained compound (N). Stir for hours. After stirring, the reaction solution was poured into 100 ml of water and 100 ml of ethyl acetate, and the phases were separated. The ethyl acetate layer was washed twice with 100 ml of saturated brine. After washing, ethyl acetate was distilled off under reduced pressure and purified by silica gel column chromatography. The obtained crystals were crystallized from 40 ml of acetonitrile, filtered, washed with 20 ml of cold acetonitrile and dried to obtain 2.3 g of the exemplified compound (44) of the present invention as yellow crystals. The exemplified compound (44) had a yield of 41.8%, a melting point of 172 to 173 ° C., an absorption λmax of 452.3 nm in ethyl acetate, and ε41,400.

The NMR data of the exemplified compound (44) obtained are shown below.
¹ H-NMR DMSO-d ₆ δ ppm: 0.80-1.00 (m, 12H), 1.25-1.50 (m, 16H), 1.55-1.70 (m, 1H), 1 70-1.85 (m, 1H), 2.64 (s, 3H), 3.25-3.50 (m, 2H), 3.50-3.75 (m, 2H), 7.80 (M, 1H), 8.22 (d, 2H), 8.45 (d, 2H), 9.92 (s, 1H), 11.07 (t, 1H)

The use of the azo dye of the present invention represented by the general formula (1) includes a color filter for recording and reproducing a color image used in a solid-state imaging device such as a CCD or CMOS, a display such as an LCD or PDP, or the like. Examples thereof include a curable composition for producing these color filters, a color image recording material for forming a color image, and dyeing. Specifically, color filters, curable compositions for producing these color filters, ink jet recording materials, heat sensitive recording materials, pressure sensitive recording materials, recording materials using electrophotographic methods, transfer type silver halide photosensitive materials , Printing inks, recording pens, fiber dyeing, hair dyeing, etc., preferably for use in cured compositions for preparing color filters, ink jet recording materials, heat sensitive recording materials, recording materials using electrophotographic methods, etc. It is done.
The azo dye of the present invention can be used by optimizing physical properties such as solubility and dispersibility suitable for the application by adjusting substituents. The dye of the present invention can be used in a dissolved state, an emulsified dispersion state, or a solid dispersion state depending on the system used.

Claims (3)

An azo dye represented by the following general formula ( 2 ):

[In General Formula ( 2 ), R ¹ represents an aryl group . R ² represents a hydrogen atom or an aliphatic group , R ³ represents an aliphatic oxycarbonyl group, an aliphatic sulfonyl group or a cyano group, R ⁴ represents an aliphatic group, and R ⁵ represents a hydrogen atom or a cyano group. Represents . G ¹ and G ² each independently represents an aliphatic oxy group, an aliphatic amino group, an arylamino group or an aliphatic thio group . ] R in the general formula (2) ² Is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. R in the general formula (2) ² Is a hydrogen atom, a methyl group, or an ethyl group, The azo dye according to claim 1, wherein