JPH11130969A - Production of azo dye with solfo group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-purity azo dye having a sulfo group easily in a simple manner by condensing a specific azo dye with a specific amine deriv. SOLUTION: An azo dye of formula I is condensed with an amine deriv. of formula II to give an azo dye of formula III having a sulfo group. In those formulas, 'Dye' is an azo dye; R is H, alkyl, or aryl; L is a divalent linking group provided L may combine with R to form a ring; and M1 and M2 are each H, an alkali metal, or ammonium. 'Dye' in the formulas is represented by formula IV, wherein either Cp or A has a carboxyl group. Generally, an azo dye is prepd. by the coupling reaction of a coupler component CpH with a diazonium salt derived from an amine deriv. ANH2 , wherein A is an aryl or heterocyclic group. L in formula II is pref. a m<-> or p-phenylene group. A high-purity azo dye having a sulfo group is obtd. at a high productivity by condensing an azo dye of formula I with an amine deriv. of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an azo dye having a sulfo group.

[0002]

2. Description of the Related Art An azo dye having a sulfo group is used as a water-soluble azo dye used in ink jet or micro color filters, or as a synthetic intermediate of a dye releasing compound used in a color transfer photosensitive material of a diffusion transfer system. Useful. Above all, dye-releasing compounds of the type described in U.S. Pat.No. 4,135,929 and JP-A-56-71061, which are oxidized and cleaved by development to release a diffusible dye, are generally used. After acid chloride of an azo dye having a sulfo group into a sulfonyl chloride,
The compound is produced by reacting this sulfonyl chloride with an aniline derivative as exemplified below.

[0003]

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[0004] Therefore, in order to synthesize such a dye-releasing compound at low cost, it is important to produce an azo dye having a sulfo group, which is a synthetic intermediate thereof, easily and with high purity and high productivity. is there.

An azo dye having a sulfo group can be produced by either a coupling reaction between a coupler component having a sulfo group and a diazonium salt or a coupling reaction between a coupler component and a diazonium salt having a sulfo group. is there. However, as described in, for example, Maruzen Co., Ltd., edited by The Chemical Society of Japan, New Experimental Chemistry, Vol. 14, “Synthesis and Reaction of Organic Compounds (III)”, page 1525, this coupling reaction is generally performed. Since the reaction is performed in an aqueous solution, the azo dye having a sulfo group obtained as a result of the coupling reaction is at least partially dissolved in the aqueous reaction solvent system. As a method for extracting the target azo dye having a sulfo group from the reaction system, salting out is generally performed, and the precipitated crystals are collected by filtration, but the volume of the solution increases during salting out. In addition, the filterability is poor, and it often takes time for filtration. Further, since the obtained azo dye having a sulfo group contains a large amount of water, it takes time to dry. (In the case of producing a dye-releasing compound as described above, the next step is acid chloride, so drying of the obtained azo dye having a sulfo group is indispensable.) It means deterioration (decrease in production volume per batch) and an increase in the number of working days, which causes an increase in manufacturing costs. Furthermore, in the above-mentioned method, it is difficult to produce an azo dye having a sulfo group with high purity because the salt used for salting out cannot be avoided. Therefore,
It has been strongly desired to develop a method for producing an azo dye having a sulfo group simply, with high purity, and with high productivity.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an azo dye having a sulfo group simply, with high purity, and with high productivity.

[0007]

The object of the present invention has been attained by the following (1) and (2). (1) Azo dye represented by general formula (I) and general formula (II)
A method for producing an azo dye having a sulfo group represented by the general formula (III) by condensing with an amine derivative represented by the following formula: In the general formula (I) Dye-COOH Formula (II) HN (R) -L -SO 3 M 1 formula (III) Dye-CON (R ) -L-SO 3 M 2 above formula, Dye azo Represents a dye, R represents a hydrogen atom, an alkyl group or an aryl group, and L represents a divalent linking group. R may be linked to L to form a ring. M ₁ and M ₂ each independently represent a hydrogen atom, an alkali metal atom, or an ammonium compound.

(2) After converting the azo dye represented by the general formula (I) into an acid halide (IV), the acid halide (IV) is reacted with an amine derivative represented by the general formula (II). To produce an azo dye having a sulfo group represented by the general formula (III). General formula (IV) Dye-COX Here, Dye has the same meaning as in the above general formulas (II) and (III), and X represents a halogen atom.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the general formulas (I), (III) and (IV), Dye
Is an azo dye represented by the general formula Cp-N = NA, wherein Cp in the formula
Alternatively, one of A is linked to a carboxyl group. This azo dye can be generally synthesized by a coupling reaction between a coupler component (CpH) and a diazonium salt derived from an amine derivative (A-NH ₂ ). Also,
It can also be synthesized without relying on the coupling reaction.

As the coupler component (CpH), any known coupler capable of performing a coupling reaction with a diazonium salt can be used. Preferred coupler components are aromatic amine compounds, phenol and naphthol compounds, and heterocyclic compounds.

More specifically, the aromatic amine compounds include N, N-dimethylaniline, N, N-diethylaniline,
2-methoxy-N, N-diethylaniline, 2-methoxy-5-acetylamino-N, N-bis (2-cyanoethyl) aniline,
An aniline derivative such as 3-methyl-N-ethyl-N- (2,3-dihydroxypropyl) aniline and a naphthylamine derivative such as 1-N, N-diethylnaphthylamine and 2-N, N-dimethylnaphthylamine.

As the phenol compound, phenol, 2-
Chlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 2-acetylaminophenol, 2,5-
Phenol derivatives such as diacetylaminophenol, 2,6-diacetylaminophenol, and 2-acetylamino-6-chlorophenol; naphthol compounds include 1-naphthol, 2-naphthol, and 5-acetylamino-1
-Naphthol derivatives such as -naphthol, 5-methylsulfonylamino-1-naphthol and 5-phenylsulfonylamino-1-naphthol.

Heterocyclic compounds include azole compounds such as pyrazolone derivatives and pyridine derivatives, for example, 1-N-phenyl-3-methyl-5-pyrazolone,
1-N-phenyl-3-cyano-5-pyrazolone, N, N-dimethylaminopyridine, 6-hydroxypyridone, 1-N-phenyl-3
-Cyano-4-methyl-2,6-dioxo-1,2,5,6-tetrahydropyridine, 2-phenyl-6-tert-butyl-1H-pyrazolo [1,5
-b] [1,2,4] triazole, 2-phenyl-6-cyano-7-methoxycarbonyl-1H-pyrrolo [1,2-b] [1,2,4] triazole) and the like. .

A represents an aryl group or a heterocyclic group.
The aryl group represented by A is preferably a phenyl group or a naphthyl group having an electron-withdrawing group as a substituent.
A more preferred aryl group has a total of Hammett's substituent constant [sigma] _p of the substituent on the aryl group of 0.3 to 2.0. Examples of preferred aryl groups include, for example, 2-cyano-4-nitrophenyl group, 2-methylsulfonyl-4-nitrophenyl group, 2,4-dinitro-6-chlorophenyl group, 2,6-dicyano-4-nitro Phenyl group, 2,4,5-tricyanophenyl group, 2-cyano-4-methylsulfonylphenyl group, 2,4-bis (methylsulfonyl) phenyl group, 2-chloro-4-nitrophenyl group, 2-fluoro -4-nitrophenyl group, 2-fluoro-4-methylsulfonylphenyl group, 4-methylsulfonylphenyl group, 3-methylsulfonyl-4- (2-methoxyethoxy) phenyl group, 3-methylsulfonyl-4-morpholinophenyl And a 3-methylsulfonyl-4-chlorophenyl group.

The heterocyclic group represented by A is a 5- or 6-membered ring containing at least a nitrogen, oxygen or sulfur atom in the ring, and the ring may be a condensed ring. Preferred heterocyclic groups include azole, oxazole, thiazole, pyrazole, imidal, oxazoline, thiazoline, isothiazoline, furyl, thienyl, and pyridyl groups. Preferred specific heterocyclic groups include 2- [1,3,4] thiadiazolyl, 2- [1,3,4] oxadiazolyl, 4,5-dicyano-2-imidazolyl, 3
-Phenyl-5- [1,2,4] thiadiazolyl group, 2-N-phenyl-
4-cyano-3-pyrazolyl group, 2-N- (4-chlorophenyl)-
3-methyl-4-cyano-3-pyrazolyl group, 2-N-phenyl-4,5
-Dicyano-3-pyrazolyl group, 2-benzoxazolyl group,
2-benzothiazolyl group, 3-methyl-4-cyano-5-isothiazolyl group, 4-methyl-5-cyano-2-thiazolyl group, 5-nitro-2-thiazolyl group, 3,5-dicyano-4-methyl- 2-thienyl group, 3-ethoxycarbonyl-4-methyl-5-cyano-2-thienyl group, 3-benzoisothiazolyl group, 5-methylsulfonyl-3-benzoisothiazolyl group, 5-nitro-3- Benzoisothiazolyl group and the like can be mentioned.

In the present invention, a preferred embodiment of the azo dye represented by the general formula (I) is an azo dye derivative represented by the general formula (I-1), and particularly preferably the general formula (I-2) Is an azo dye derivative represented by

[0017]

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In the general formulas (I-1) and (I-2), R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. R ₁ and R ₂ may be linked together to form a naphthalene ring or other condensed ring system. Preferred examples of the substituent represented by R ₁ , R ₂ and R ₃ include a halogen atom, an amino group which may have a substituent and which may be ring-closed including an N atom, Cyano group, nitro group, alkyl group, aryl group, alkoxy group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, acylamino group, alkyl and arylsulfonylamino group, alkoxycarbonylamino group, aminocarbonyl And an amino group.

Examples of the preferred substituents represented by R ₁ , R ₂ and R ₃ include fluorine, chlorine, bromine, iodine, dimethylamino, 1-pyrrolidinyl, 1-morpholino, cyano, Nitro group, methyl group, ethyl group, n-butyl group, isopropyl group, phenyl group, 1-naphthyl group,
2-naphthyl group, methoxy group, ethoxy group, isopropoxy group, 2-methoxyethoxy group, methanesulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, benzenesulfonyl group, p-tolylsulfonyl group, sulfamoyl group, methylsulfur Famoyl, diethylsulfamoyl, carbamoyl, dimethylcarbamoyl, methoxycarbonyl, ethoxycarbonyl, acetylamino, benzoylamino, methanesulfonylamino, benzenesulfonylamino, methoxycarbonylamino, ethoxycarbonyl Examples include an amino group, an ethylaminocarbonylamino group, and a diethylaminocarbonylamino group. Among these substituents, those that can be further substituted may be further substituted with the above-mentioned substituents.

[0020] R ₄ represents an alkyl group, an aryl group, an alkoxy group, or _{-NR 11 R 12 (R 11,} R 1 2 are each independently a hydrogen atom,. An alkyl group or an aryl group) a. The alkyl group represented by R ₄ is an alkyl group having 1 to 18, preferably 1 to 8, and more preferably 1 to 4 carbon atoms, and may be unsubstituted or substituted with the above-described substituent. Preferred alkyl groups represented by R ₄ are, for example, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. The aryl group represented by R ₄ has 6 to 12 carbon atoms.
And may be unsubstituted or substituted with the substituents described above, and represents, for example, phenyl, 1-naphthyl, or 2-naphthyl. The aryl group represented by R ₄ is preferably a substituted or unsubstituted phenyl group.
The alkoxy group represented by R ₄ is an alkoxy group having 1 to 18, preferably 1 to 8, and more preferably 1 to 4 carbon atoms, and may be unsubstituted or substituted with the above-described substituent; Preferred alkoxy groups are, for example, methoxy,
Ethoxy, n-propoxy and 2-methylpropoxy. The alkyl group and the aryl group represented by R ₁₁ and R ₁₂ have the same meaning as the alkyl group and the aryl group represented by R ₄ . W represents -C (= O)-or -S (= O) _2- , and A has the same meaning as described above.

In the general formula (II), R represents a hydrogen atom, an alkyl group or an aryl group. Alkyl group or aryl group represented by R has the same meaning as alkyl or aryl group represented by the above R _4. L represents a divalent linking group, for example, a substituted or unsubstituted ortho, meta or paraphenylene group, a substituted or unsubstituted alkylene group, or a direct or -O-, -S-
, -N (R ₅ ) CO-, -N (R ₅ ) SO _2- , -CON (R ₅ )-, -SO ₂ N (R ₅ )-
And a linking group linked via. Here, R ₅ has the same meaning as R described above. L is preferably a substituted or unsubstituted meta or paraphenylene group. M ₁ represents a hydrogen atom, an alkali metal atom (for example, sodium, potassium, rubidium, cesium), or an ammonium group (for example, ammonium group, trimethylammonium group, triethylammonium group, pyridinium group, picolinium group, coridinium group).

In the general formula (III), Dye, R and L
Is as defined above. Although the selection of M ₂ are the same as M _1, M ₁ and M ₂ may be different even in the same. In the general formula (IV), Dye has the same meaning as described above, and X represents a halogen atom (eg, chlorine, bromine, iodine). X is preferably a chlorine atom. Specific examples of the azo dye having a sulfo group represented by the general formula (III) suitable for production by the production method of the present invention are shown below, but are not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

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Next, a method for condensing the azo dye represented by the general formula (I) with the amine derivative represented by the general formula (II) will be described. The feature of the present invention is that the azo dye having a carboxyl group represented by the general formula (I) and the amine derivative having a sulfo group represented by the general formula (II) are condensed in a non-aqueous solvent to form a sulfo group. Azo dyes having the general formula (I) can be produced more easily, with higher purity and higher productivity than conventional methods (synthesis method by azo coupling in an aqueous solution). Formula (II)
For the condensation process with the amine derivative represented by
For example, Maruzen Co., Ltd., edited by The Chemical Society of Japan, New Experimental Chemistry Lecture Vol. 14, "Synthesis and Reaction of Organic Compounds (II)", 1136-11
The method described on page 47 (for example, via an acid halide of the general formula (I), via a mixed acid anhydride of the general formula (I), dicyclohexylcarbodiimide (D
CC) or a method using a condensing agent such as carbonyldiimidazole). Among them, a method of converting the general formula (I) into an acid halide to obtain a general formula (IV), and reacting the general formula (IV) with an amine derivative represented by the general formula (II) in the presence of a suitable base, is generally used. It has been found that this is a more preferable method in that the azo dye having a sulfo group represented by the formula (III) can be easily produced with high purity and high productivity.

Next, a method for producing an azo dye having a sulfo group represented by the general formula (III) via an acid halide represented by the general formula (IV) will be described in detail. The reaction route can be shown as follows.

[0029]

In the reaction for synthesizing the acid halide of the corresponding azo dye represented by the general formula (IV) from the azo dye represented by the general formula (I), preferred acid halide agents include thionyl chloride, phosphoryl chloride and Phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, dichloromethyl methyl ether, triphenylphosphine / carbon tetrachloride, phosphorus tribromide, selenium tetrafluoride, cyanuric fluoride, and the like, more preferably thionyl chloride, Phosphoryl chloride,
Phosphorus trichloride, phosphorus pentachloride, oxalyl chloride,
Particularly preferred is thionyl chloride. The molar ratio of the acid halide agent to the compound of the formula (I) is from 0.1 to 100, preferably from 0.5 to 50, more preferably from 1 to 10. Preferred solvents for the acid halide are acetonitrile, ethyl acetate, tetrahydrofuran, diethyl ether, dichloromethane, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane,
Examples thereof include dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylimidazolidone, and a mixed solvent system thereof, and acetonitrile is particularly preferred. The preferred reaction temperature for acid halide formation is -20 to 150 ° C.
And more preferably -10 to 100 ° C. The obtained acid halide may be used in the next step after isolation and purification, but is preferably used in the next step without isolation and purification. The amine derivative represented by the general formula (II) can be synthesized, for example, by sulfonating aniline or its N-substituted product by a general method.

In the reaction for producing an azo dye represented by the general formula (III) by reacting an acid halide represented by the general formula (IV) with an amine derivative represented by the general formula (II) in the presence of a base, The preferred solvent is the same as the solvent exemplified in the synthesis of the acid halide represented by the general formula (IV), but may not necessarily be the same as the solvent used in the above-mentioned acid halide reaction step. Preferred bases include pyridine, α,
β or γ-picoline, lutidine, collidine, triethylamine, diisopropylethylamine, N-methylmorpholine and the like. The molar ratio of the base to the acid halide represented by the general formula (IV) is 0.1 to 100, preferably 0.5 to 50, more preferably 1 to 10. Further, the amine derivative represented by the general formula (II)
The molar ratio to the acid halide represented by V) is from 0.1 to 100, preferably from 0.5 to 30, and more preferably from 0.8 to 5. A preferred reaction temperature is from -20 to 100C, more preferably from 0 to 80C. As a reaction procedure, the amine derivative represented by the general formula (II) and the base may be added (or dropped) in this order to the solution of the acid halide represented by the general formula (IV) prepared by the above method. Good or
A solution of the acid halide represented by the general formula (IV) may be added (or dropped) to a solution in which the amine derivative represented by the general formula (II) and a base are dissolved.

Next, the production method of the present invention will be described with reference to specific synthetic examples. [Synthesis Example 1] The compound of compound example (III-1) was prepared by the following route a (synthesis method of the present invention) and route b (conventional synthesis method).
Synthesized.

[0033]

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<Synthesis of Compound (III-1) by Route a> (i) Synthesis of Compound 3 To 73.6 g of concentrated sulfuric acid, 4.9 g of sodium nitrite was added at 30 ° C. or less, followed by stirring at 60 ° C. for 1 hour. Nitrosyl sulfate was prepared. After cooling this nitrosyl sulfate solution to 40 ° C., 14.9 g of 2-methylsulfonyl-4-nitroaniline was added over 1 hour, and the mixture was further stirred at 45 ° C. for 3 hours to prepare diazonium salt 2. 20 g of the compound 1, 180 ml of N, N-dimethylacetamide, 90 ml of methanol and 90 ml of water were added to the above diazonium salt 2 cooled to 10 ° C. while maintaining the temperature at 10 ° C. or lower.
It was added over time and stirred for another 5 hours. 270 ml of water was poured into the reaction solution, and the crystals were collected by filtration (diameter of 110).
The solution was subjected to suction filtration at a reduced pressure of about 1 mmHg using a Nutsche of mm. The time required for suction filtration was about 90 seconds. ), Dried. 200 ml of methanol and 9.1 g of triethylamine were added to the obtained crude crystals, and the mixture was stirred under reflux for 30 minutes, and then filtered at 50 ° C. under reduced pressure to remove insoluble components. 15 g of concentrated hydrochloric acid was added to the filtrate, and the mixture was stirred at 5 ° C. for 1 hour. The crystals were collected by filtration (a suction filtration was performed using a Nutsche having a diameter of 110 mm at a reduced pressure of about 1 mmHg. The time required for the suction filtration was about 130 seconds), and dried to obtain 24 g (7 g).
Compound 3 (9%) was obtained.

(Ii) Synthesis of Compound (III-1) To a solution of 15.6 g of compound 3 and 80 ml of acetonitrile was added dropwise a solution of 5.2 ml of thionyl chloride in 10 ml of acetonitrile at 70 ° C., and the mixture was refluxed for 1 hour at a reflux temperature. After stirring, the mixture was cooled to 25 ° C. to prepare an acid solution of Compound 3. Aniline (II-1) 4.7 g, pyridine
To a solution of 11.4 ml and 60 ml of acetonitrile was added dropwise the acid chloride solution of the above compound 3 at 25 ° C. The reaction solution was stirred at 60 ° C for 4 hours and then cooled to 20 ° C. The precipitated crystals were collected by filtration (with a Nutsche having a diameter of 110 mm and suction-filtered at a reduced pressure of about 1 mmHg. The time required for suction-filtration was about 65 seconds), and the compound (III-1) was dried. ) 17.5 g (88%, purity 99%, mp = 240-243
° C, M = pyridinium). The structure of the compound (III-1) was confirmed by NMR and Mass spectrum. Also,
The purity was confirmed by HPLC (relative area ratio at a detection wavelength of 254 nm).

<Synthesis of Compound (III-1) by Route b> (i) Synthesis of Compound 4 A solution of 52.3 g of compound 1 and 28 g of phenyl ester of aniline (II-1) in 300 ml of N, N-dimethylacetamide was prepared. At 25 ° C., 17.5 ml of thionyl chloride was added dropwise. After the reaction solution was stirred at 25 ° C for 1 hour, ethyl acetate 500
The solution was poured into 500 ml of a milliliter / 0.5N hydrochloric acid aqueous solution. The organic layer was washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solution: ethyl acetate / hexane = 1/1) to obtain 34 g (49%) of compound 4.

(Ii) Synthesis of compound 5 36.6 g of compound 4, 33.6 g of potassium hydroxide and 240
The milliliter was stirred at 50 ° C. for 1 hour and cooled to 25 ° C. The reaction solution was poured into 1200 ml of ethyl acetate / 1200 ml of water / 120 ml of concentrated hydrochloric acid, and separated. The organic layer was concentrated under reduced pressure, and recrystallized from 12 ml of methanol / 600 ml of isopropyl alcohol to obtain 31.2 g (98%) of compound 5.

(Iii) Synthesis of Compound (III-1) To 73.6 g of concentrated sulfuric acid, 4.9 g of sodium nitrite was added at 30 ° C. or lower, and the mixture was stirred at 60 ° C. for 1 hour to prepare nitrosyl sulfuric acid. After cooling the nitrosyl sulfate solution to 40 ° C., 14.9 g of 2-methylsulfonyl-4-nitroaniline was added over 1 hour, and the mixture was further stirred at 45 ° C. for 3 hours to prepare diazonium salt 2. 27.7 g of the compound 5, 300 ml of methanol, 100 ml of N, N-dimethylacetamide and 300 ml of water were added with the diazonium salt 2 cooled to 10 ° C. over 5 hours while maintaining the temperature at 10 ° C. or less. The mixture was further stirred for 5 hours. Pour 2500 ml of saturated saline into the reaction solution,
Stirred at 35 ° C. for 1 hour. After cooling to 25 ° C., the crystals were collected by filtration (suction-filtered using a Nutsche with a diameter of 150 mm at a reduced pressure of about 1 mmHg. The time required for suction filtration was about 1 hour) and dried. Compound (III-1) 52 g [130
% (Containing NaCl), purity 70%, M = H). Purity is HPLC
(Relative area ratio at detection wavelength 254 nm and comparison with compound (III-1) synthesized by route a).

By comparing the synthesis examples of the compound example (III-3) by the above route a and route b, the production method of the present invention is simpler, higher in purity and more productive than the conventional method. It can be seen that an azo dye having a group can be synthesized.

[Synthesis Example 2] The compound of Compound Example (111-4) was synthesized by the following route.

[0041]

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(I) Synthesis of Compound 8 To 150 g of concentrated sulfuric acid, 6.3 g of sodium nitrite was added at 30 ° C. or less, followed by stirring at 60 ° C. for 1 hour to prepare nitrosyl sulfuric acid. After cooling the nitrosylsulfate solution to 5 ° C., 60 ml of acetic acid and 30 ml of propionic acid were added, followed by 2-cyano-4-nitroaniline 14.
2 g was added over 1 hour, and the mixture was further stirred at 10 ° C. or lower for 3 hours to prepare diazonium salt 7. 12.5g
The above diazonium salt 7 cooled to 10 ° C. was added to a solution of the compound (6), 120 ml of N, N-dimethylacetamide, 60 ml of methanol and 60 ml of water.
The mixture was added over 5 hours while maintaining the temperature at or below ℃, and further stirred for 5 hours. 150 ml of water was poured into the reaction solution, and the crystals were collected by filtration (suction filtration was performed using a Nutsche having a diameter of 110 mm at a reduced pressure of about 1 mmHg. The time required for suction filtration was about 100 seconds), and drying was performed. did. Methanol is added to the obtained crude crystals.
125 ml and 8.1 g of triethylamine were added, and the mixture was stirred under reflux for 30 minutes, and then filtered at 50 ° C. under reduced pressure to remove insoluble components. 13.3 g of concentrated hydrochloric acid was added to the filtrate, and 5
Stirred at C for 1 hour. The crystals were collected by filtration (a suction filtration was performed using a Nutsche having a diameter of 110 mm at a reduced pressure of about 1 mmHg. The time required for suction filtration was about 110 seconds), and 17.2 g (85%) of the compound was dried. 8 was obtained.

(Ii) Synthesis of compound (III-4) To a solution of 15 g of compound 8 and 150 ml of acetonitrile was added dropwise a solution of 7.3 ml of thionyl chloride in 20 ml of acetonitrile at 70 ° C., and the mixture was stirred at reflux for 30 minutes. After cooling to 25 ° C., an acid chromatography solution of compound 8 was prepared. To a solution of 6.6 g of aniline (II-1), 16 ml of pyridine and 84 ml of acetonitrile was added dropwise an acid chloride solution of the above compound 8 at 25 ° C. Reaction solution 60
After stirring at 3 ° C. for 3 hours, the mixture was cooled to 10 ° C. The precipitated crystals are collected by filtration (about 1 m using a Nutsche with a diameter of 110 mm and filter paper).
Suction filtration was performed at a reduced pressure of mHg. The time required for suction filtration was about 45 seconds. ) And dried to give the compound (III-
4) 13.7 g (65%, purity 97%, mp 235-239 ° C) were obtained.
The structure of compound (III-4) was confirmed by NMR and mass spectrum analysis. The purity was confirmed by HPLC (relative area ratio at a detection wavelength of 254 nm).

Synthesis Example 3 The compound of Compound Example (III-5) was synthesized by the following route.

[0045]

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Synthesis of compound (III-5) To a solution of 15.6 g of compound 3 and 80 ml of acetonitrile was added dropwise a solution of 5.2 ml of thionyl chloride in 10 ml of acetonitrile at 70 ° C., and the mixture was stirred at reflux temperature for 1 hour and then stirred at 25 ° C. By cooling the solution, an acid chloride solution of Compound 3 was prepared. To a solution of 3.3 g of aniline (II-2), 12.0 ml of 2-methylpyridine and 60 ml of acetonitrile was added dropwise an acid chloride solution of the above compound 3 at 25 ° C. The reaction solution was stirred at 60 ° C for 4 hours and then cooled to 10 ° C. The precipitated crystals were collected by filtration (with a Nutsche having a diameter of 110 mm and suction-filtered at a reduced pressure of about 1 mmHg. The time required for suction-filtration was about 70 seconds), and the compound (III-5) was dried. 12 g (62%, purity 97%, mp = 228-23
1 ° C.). The structure of compound (III-5) was confirmed by NMR and mass spectrum analysis. The purity was confirmed by HPLC (relative area ratio at a detection wavelength of 254 nm). Synthesis Examples 2 and 3 show that the azo dye having a sulfo group can be easily synthesized with high purity and high productivity by the production method of the present invention.

The compound (II) synthesized by the production method of the present invention
I-1) could be easily derived to a cyan dye releasing compound A for a color photographic light-sensitive material of a diffusion transfer system by the following scheme. Further, this cyan dye releasing compound A
Showed a performance equal to or higher than that of Exemplified Compound 11 in the examples of use in JP-A-60-28651.

[0048]

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[0049]

The azo dye of the general formula (I) and the azo dye of the general formula (II)
The azo dye having a sulfo group can be obtained with high purity by the production method of the present invention in which the amine derivative is condensed directly or via an acid halide, the number of steps is small, the time is short, and the azo dye can be easily produced.

Claims (2)

[Claims] An azo dye having a sulfo group represented by the general formula (III) by condensing an azo dye represented by the general formula (I) with an amine derivative represented by the general formula (II). How to make. General formula (I) Dye-COOH Formula (II) HN (R) -L -SO 3 M 1 formula (III) Dye-CON (R ) -L-SO 3 M 2 (Dye represents an azo dye, R represents a hydrogen atom, an alkyl group or an aryl group, L represents a divalent linking group, R may be linked to L to form a ring, and M ₁ and M ₂ are each independently hydrogen. Atom, alkali metal atom or ammonium group.) 2. An azo dye represented by the general formula (I) is converted into an acid halide represented by the general formula (IV), and the acid halide (IV) and the amine derivative represented by the general formula (II) are used. To produce an azo dye having a sulfo group represented by the general formula (III). General formula (IV) Dye-COX (Dye has the same meaning as described above, and X represents a halogen atom.)