JPH0252657B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for producing oxonol dyes. In general, oxonol dyes are one of the dyes that are used particularly in silver halide photographic light-sensitive materials and are useful for preventing halation, preventing irradiation, and for filter layers. Regarding the manufacturing method of this oxonol dye,
For example, British Patent No. 506385, Special Publication No. 39-22069,
No. 54-38129, No. 54-20967, Japanese Unexamined Patent Publication No. 1973-
It is well known and is described in various specifications and publications such as No. 91627. That is, an α-ketomethylene compound and a methine chain donor such as orthoformate, diphenylformamidine, tetraalkoxypropane, malondialdehyde dianyl, 2,4-dinitrobenzenepyridinium chloride, or glutacondialdehyde dianyl are combined with a base. It can be produced by condensation in the presence of. When producing the oxonol dye industrially, as a supplier of the methine chain,
Traditionally, diphenylformamidine, malondialdehyde dianyl and glutacondialdehyde anil are used to prepare monomethine, trimethine and pentamethine oxonol dyes. However, it has been recognized that in the method for producing oxonol dyes as described above, by-products are produced during the reaction, reducing the purity and yield of the target product. Particularly in the case of pentamethine oxonol dye, it is unstable to heat, acidity, basicity, etc., and magenta-colored by-products are produced during the manufacturing process, so it is difficult to purify it.
Isolation requires many man-hours and is often difficult. Therefore, an object of the present invention is to provide a method for producing highly pure oxonol dyes in a high yield and for general purposes, with extremely little generation of by-products as described above. As a result of various studies carried out by the present inventors, the above object was achieved by condensing an α-ketomethylene compound represented by the following general formula [] with a compound represented by the following general formula []. We have discovered that this can be achieved by a method for producing an oxonol dye, which produces the oxonol dye shown below. General formula [] General formula [] General formula [A] In the formula, Q represents a nonmetallic atom group necessary to form a 5-pyrazolone ring or a barbituric acid residue, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each a hydrogen atom,
It represents a halogen atom, trifluoromethyl group, cyano group, alkoxycarbonyl group, nitro group, acyl group, methylsulfonyl group, carbamoyl group, or sulfamoyl group, but R ₁ to _{R 5} are not all hydrogen atoms. Further, L represents a methine group, and n represents an integer of 0, 1 or 2. The present invention will be explained in more detail below. The production method of the present invention is characterized by condensing the ketomethylene compound represented by the above general formula [] and the compound represented by the general formula [] in the presence of a base, where Q in the general formula [] is 5-
Examples include a pyrazolone ring and barbituric acid, but a 5-pyrazolone ring is preferred, and can be represented by the following general formula []. General formula [] In the formula, R ₆ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an amino group, an acylamino group, a carbamoyl group, a carboxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ₇ represents an alkyl group. represents a group, an aryl group and a heterocyclic group. More specifically, the alkyl group represented by R ₆ above is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, octyl, hydroxyethyl, methoxyethyl, Examples include ethoxycarbonylmethyl, trifluoroethyl, pentafluoroethyl, 1,1,2,2,3,3-hexafluoropropyl and the like. Furthermore, the aryl group represented by R ₆ above is as follows:
Examples include phenyl, tolyl, cyanophenyl, nitrophenyl, hydroxyphenyl, methoxyphenyl, chlorophenyl, 3,5-disulfophenyl, naphthyl, and the like. Next, as the alkoxy group represented by R ₆ above,
Examples of the aryloxy group include methoxy, ethoxy, propoxy, and the like, and examples of the aryloxy group include phenoxy, chlorophenoxy, and nitrophenoxy. Furthermore, examples of the acylamino group include acetamide, propionamide, succiimide, benzamide, chlorobenzamide, and nitrobenzamide. Subsequent carbamoyl groups include, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, hydroxycarbamoyl, phenylcarbamoyl, chlorophenylcarbamoyl, hydroxyphenylcarbamoyl, nitrophenylcarbamoyl, cyanophenylcarbamoyl, and the like. Further, examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, hydroxyethoxycarbonyl, and methoxyethoxycarbonyl, and examples of the aryloxycarbonyl group include phenoxycarbonyl and chlorophenoxycarbonyl. Examples include groups such as carbonyl. Next, the alkyl group represented by R ₇ in the above general formula [] is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-butyl, 2-hydroxyethyl, 2-methoxyethyl, 2-sulfoethyl. , 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, 2-
Various groups such as carboxyethyl and 3-carboxyethyl can be mentioned. Examples of the aryl group represented by R ₇ above include phenyl, 4-chlorophenyl, 4-sulfenyl, 3-sulfophenyl, 2-methyl-4
-Sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-methoxy-4-sulfophenyl, 2-hydroxy-
4-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 3,5-disulfophenyl, 2,
5-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-hydroxy-3-sulfophenyl, 4-carboxyphenyl, Examples of the heterocyclic group represented by R7 include 3-carboxyphenyl, 3,6-disulfo-α-naphthyl, 6,8-disulfo-β-naphthyl, and examples of the heterocyclic group represented by R ₇ include, for example, 4-pyridyl. , 5 (or 6)
There are various groups such as -sulfo-2-benzthiazolyl. Next, R ₁ , R ₂ , R ₃ in the above general formula [],
R ₄ and R ₅ are halogen atoms (fluorine, chlorine,
bromine, etc.), trifluoromethyl group, cyano group, alkoxycarbonyl group (ethoxycarbonyl group, etc.), nitro group, acyl group (acetyl group, propionyl group, pivalyl group, etc.), methylsulfonyl group,
Examples include carbamoyl group and sulfamoyl group. In the present invention, the general formula []
Particularly preferred are compounds in which the meta position of the phenyl group, ie, R ₂ or R ₄ or the para position, ie, R _3, is an electron-withdrawing group. Further, the methine group represented by L in the general formula [] may be substituted with, for example, an alkyl group (methyl group, ethyl group, etc.) or an aryl group (phenyl group, etc.). Furthermore, the compound represented by the general formula [] may form a salt with various acids, examples of which include hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid,
Examples include p-toluenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid. In the production method of the present invention, a method for producing a pentamethine oxonol dye by condensation of the pyrazolone derivative represented by the general formula [] with a compound represented by the general formula [] is preferred, and furthermore, a method in which pentamethine oxonol dyes are produced by fluorinated at the 3-position is preferred. The most preferred method is to produce a pentamethine oxonol dye using the above pyrazolone derivative having an alkyl group. In the production method of the present invention described above, a base is used during the condensation reaction. Examples of the bases used in the present invention include pyridine, piperidine, triethylamine, diethanolamine, triethanolamine, and ammonia. Further, an organic solvent is used during the above condensation reaction. Examples of organic solvents include alcohols (methanol, ethanol, etc.), ethylene glycol,
Although ethylene glycol monoalkyl ethers (ethylene glycol monotyl ether, ethylene glycol monoethyl ether, etc.), acetonitrile, dimethyl sulfoxide, amides (dimethylformamide, dimethylacetamide, acetamide, etc.) are commonly used, In the method for producing methine oxonol dyes, solvents having a dielectric constant in the range of 35 to 40 (20 DEG to 25 DEG C.), such as dimethylformamide, dimethylacetamide, acetonitrile, and ethylene glycol, are preferably used. The above condensation reaction in the present invention can be carried out at a temperature ranging from 0° C. to the boiling point of the solvent used. Particularly, since pentamethine oxonol dye is unstable to heat, it is preferable to carry out the reaction in the range of 0° to room temperature. Further, in the above reaction, it is appropriate to use the pyrazolone derivative represented by the general formula [], which is a reaction reagent, in a molar amount approximately twice that of the compound represented by the general formula []. Next, typical examples of the phenyl group having an electron-withdrawing group in the compound represented by the general formula [] will be described, but the present invention is not limited thereto. Specific examples (1) 4-fluorophenyl group (2) 3,5-difluorophenyl group (3) 2,4,6-trifluorophenyl group (4) 4-chlorophenyl group (5) 3-chlorophenyl group ( 6) 2-chlorophenyl group (7) 3,4-dichlorophenyl group (8) 3,5-dichlorophenyl group (9) 2,4,6-trichlorophenyl group (10) 4-bromophenyl group (11) ) 3-bromophenyl group (12) 3,5-dibromophenyl group (13) 2,4,6-tribromophenyl group (14) 3-trifluoromethylphenyl group (15) 4-trifluoromethylphenyl group enyl group (16) 2-cyanophenyl group (17) 3-cyanophenyl group (18) 4-cyanophenyl group (19) 2-ethoxycarbonylphenyl group (20) 4-ethoxycarbonylphenyl group (21) 4-methoxycarbonyl Phenyl group (22) 2-nitrophenyl group (23) 3-nitrophenyl group (24) 4-nitrophenyl group (25) 3-acetylphenyl group (26) 4-acetoxyphenyl group (27) 4-sulfonamidophenyl group enyl group (28) 4-carbamoylphenyl group (29) 2-chloro-5-trifluoromethylphenyl group (30) 4-bromo-3-chlorophenyl group General groups having groups as described in the above specific examples The compound represented by formula [] is described in Chemical Abstracts, Vol. 58, p. 4141, (1957), Beilstein Handbook der Organik Chemie, Vol. 12, p. 604, p. 610, p. 611, 634. page,
pp. 691, 703, 718, and Berichte der Deutschchen Hemitschen Geselschaft, no.
Volume 102, page 2609 (1969) or Journal of the Photographic Society of Japan,
Volume 33, page 33 (1970), etc., and generally include aniline derivatives, orthoformate, tetraalkoxypropane, 2,4-
It can be easily synthesized by reacting with dinitrobenzenepyridinium chloride. Further, typical examples of the pyrazolone derivative represented by the general formula [] are shown below, but the present invention is not limited thereto. Concrete example

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[Formula] In the oxonol dye produced by the production method of the present invention, the sulfo group may form a salt with an alkali metal such as sodium or potassium, an organic base such as triethylamine or pyridine, or a base such as ammonia. , generally the sodium or potassium salts are suitable. Typical specific examples of oxonol dyes produced as described above are described below, but the present invention is not limited thereto. The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Example 1 [Synthesis of compound represented by general formula []] (1) Synthesis of glutacondialdehyde bis(m-chloroanyl) hydrochloride 17.7 g of 2,4-dinitrobenzenepyridinium chloride was added to 100 ml of ethanol, and m - Add 23.0 g of chloroaniline and stir at room temperature for 5 hours. The contents will dissolve once, but as the reaction progresses, red crystals will precipitate. Take this, wash it with 50ml of ethanol, and then wash it with 150ml of acetone.
ml and dried to obtain 17.0 g of the desired product (red crystals). (2) Synthesis of malondialdehyde bis(m-chloroanyl) hydrochloride m-
Add 28.1g of chloroaniline and then add concentrated hydrochloric acid.
Add 40ml and stir. The contents will be uniform,
To this was added 16.4 g of tetramethoxypropane, stirred at room temperature for 5 hours, and then left overnight. As the reaction progresses, brown crystals precipitate. Add 150ml of water to the reaction solution, remove the precipitated crystals, and add water.
After washing with 100 ml, washing with 300 ml of acetone and drying, 20.5 g of the target product (yellow-orange crystals) was obtained. (3) Synthesis of bis(m-chlorophenyl)formamidine 14.8 g of orthoformic acid ester and 25.5 g of m-chloroaniline are mixed and reacted for 4 hours while ethanol produced at 100°C is distilled off at atmospheric pressure. Cool the contents to approximately 50℃ and add methanol to this.
Add 120ml. White crystals precipitate, but they are dissolved by further heating and allowed to cool. Remove the crystals, wash them with 50ml of methanol, and dry them.
19.3g of the target product (white crystals) was obtained. Other compounds represented by the general formula [] can also be easily synthesized by using the corresponding aniline derivatives and carrying out the same reaction as above. Example 2 [Synthesis of Exemplified Compound 1] 30.8 g of 3-trifluoromethyl-1-(4'-sulfophenyl)-5-pyrazolone and 20.2 g of triethylamine are dissolved in 300 ml of dimethylformamide. Add 17.7 g of glutacondialdehyde bis(m-chloroanyl) hydrochloride to this, and
Stir with After reacting for 3 hours, add 60ml of distilled water,
After adding 19.6 g of potassium acetate and stirring for 20 minutes, 1200 ml of acetonitrile was added and left overnight. The precipitated crystals were collected, washed with 100 ml of ethanol, and then washed with 200 ml of acetone and dried to obtain 27.8 g of oxonol dye. This product did not require further purification and was a highly pure dye. The λmax of the aqueous solution of this dye was 627 nm. For comparison, when the same reaction was carried out using glutacondialdehyde dianyl hydrochloride instead of glutacondialdehyde bis(m-chloroanyl) hydrochloride, the resulting dye had a magenta color The dye was contaminated with living organisms, and in order to obtain a highly pure dye, salting-out purification had to be performed, resulting in a significant decrease in yield. Furthermore, glutacondialdehyde bis(m
-Chloroanyl) hydrochloride was used, and when the same reaction was carried out using methanol instead of dimethylformamide, a large amount of magenta-colored dye was produced, and the desired pentamethine oxonol dye was produced in purified form. I couldn't let go. When a similar reaction was carried out using glutacondialdehyde anil hydrochloride in methanol, a magenta dye was the main product, and the desired pentamethine dye was hardly obtained. Example 3 [Synthesis of Exemplified Compound 2] 3-carbamoyl-1-(4'-sulfophenyl)
-5-pyrazolone 28.3g and triethylamine 20.2g
Dissolve in 400 ml of dimethylformamide. To this was added 21.0 g of glutacondialdehyde bis(m-trifulmethylanyl) hydrochloride, and the mixture was stirred at room temperature. After reacting for 3 hours, 800 ml of methanol was added, followed by 19.6 g of potassium acetate, stirred for 30 minutes, and then left overnight. The precipitated crystals were collected, thoroughly washed with 200 ml of ethanol, and dried to obtain 28.5 g of oxonol dye. The aqueous solution of this dye had a λmax of 635 nm, indicating that it was a highly pure dye. For comparison, when the same reaction was carried out in methanol using glutacon dialdehyde dianyl hydrochloride instead of glutacon dialdehyde bis(m-trifluoromethylanyl) hydrochloride, a magenta colored by-product was produced. The dye produced in larger amounts was of lower purity. Example 4 [Synthesis of Exemplified Compound 3] 3-carboxy-1-(4'-sulfophenyl)-
28.4 g of 5-pyrazolone and 18.2 g of triethylamine are dissolved in 300 ml of dimethylformamide.
22.1 g of glutacondialdehyde bis(m-bromoanil) hydrochloride is added to this, and the mixture is stirred at room temperature.
After 2 hours of reaction, 180 ml of ethanol and 6.0 g of glacial acetic acid were added, followed by 14.7 g of potassium acetate, and the mixture was stirred for 2 hours. Collect the precipitated crystals and add ethanol
After washing with 150 ml and further washing with 200 ml of acetone, it was dried to obtain 30.2 g of oxonol dye. The aqueous solution of this dye had a λmax of 635 nm, indicating that it was a highly pure dye. For comparison, when the same reaction was carried out in methanol using glutacondialdehyde dianyl hydrochloride instead of glutacondialdehyde bis(m-bromoanil) hydrochloride, a larger amount of magenta-colored by-products were produced. However, the obtained dye had low purity. Example 5 [Synthesis of Exemplified Compound 4] 3-amino-1-(3'-sulfophenyl)-5-
25.5 g of pyrazolone and 20.2 g of triethylamine are placed in 300 ml of dimethylformamide, 19.4 g of glutacondialdehyde bis(3,4-dichloroanyl) hydrochloride is added thereto, and the mixture is stirred at room temperature. After reacting for 5 hours, 150 ml of methanol was added, followed by 16.4 g of sodium acetate, and after stirring for 1 hour, it was left to stand overnight. Collect the precipitated crystals and add ethanol
Wash twice with 100ml, dry and apply oxonol dye.
Obtained 30.8g. The λmax of this dye aqueous solution is
It had a wavelength of 602 nm and was a highly pure dye. For comparison, when a reaction was carried out using glutacon dialdehyde dianyl hydrochloride in addition to glutacon dialdehyde bis(3,4-dichloroanyl) hydrochloride in methanol, magenta dye was produced as a by-product. However, the obtained dye had low purity. Example 6 [Synthesis of Exemplified Compound 5] 30.8 g of 1-(4'-sulfophenyl)-3-trifluoromethyl-5-pyrazolone and 20.2 g of triethylamine were placed in 450 ml of ethanol, and malondialdehyde bis(m- bromoanil)
19.0 g was added, heated, and reacted under reflux for 1.5 hours. After the reaction, 30.0 g of potassium acetate was added and refluxed for 10 minutes, then cooled and the precipitated crystals were collected, thoroughly washed with 200 ml of ethanol, and dried to obtain 30.7 g of oxonol dye. λmax of the aqueous solution of this dye
The wavelength was 538 nm, indicating that the dye was highly pure. Example 7 [Synthesis of Exemplified Compound 6] 3-carbamoyl-1-(4'-sulfophenyl)
-5-pyrazolone 14.2g and triethylamine 15.2g
into 200ml of methanol, and add 8.2g of malondialdehyde bis(m-chloroanyl) hydrochloride.
was added, and the mixture was heated and reacted under reflux for 1 hour. After the reaction, 14.7 g of potassium acetate was added and refluxed for 10 minutes, then cooled, the precipitated crystals were collected, and ethanol was added.
Wash thoroughly with 150ml, dry, and apply oxonol dye.
Obtained 14.5g. The λmax of the aqueous solution of this dye is 544nm
It was a highly pure dye. Example 8 [Synthesis of Exemplified Compound 7] 3-Methyl-1-(3'-sulfophenyl)-5-
15.3 g of pyrazolone and 12.1 g of triethylamine were placed in 150 ml of dimethyl formaldehyde, and 8.0 g of bis(m-chlorophenyl)formamidine was added thereto, heated, and reacted at 80° C. for 30 minutes. After the reaction, the mixture was cooled and 70 ml of methanol was added, followed by 11.8 g of potassium acetate and stirred for 1 hour. 200 ml of acetonitrile was added to collect the precipitated crystals and washed with 100 ml of methanol. Dissolve the crude crystals in 45ml of pure water, add 360ml of methanol,
The precipitated crystals were collected, washed with 100 ml of methanol, and dried to obtain 12.0 g of oxonol dye. The aqueous solution of this dye had a λmax of 420 nm, indicating that it was a highly pure dye. Example 9 [Synthesis of Exemplified Compound 8] 12.8 g of barbituric acid was dissolved in dimethylformamide.
Pour into 180ml and comb. Furthermore, 21.0 g of glutacondialdehyde bis(m-trifluoromethylanyl) hydrochloride is added and stirred. After the reaction became uniform, 15.2 g of triethylamine was added and stirred at room temperature. After reacting for 2 hours, 9.0 g of glacial acetic acid was added, followed by 180 ml of ethanol, and the mixture was stirred for 1 hour.
The precipitated crystals were collected, washed with 200 ml of ethanol, and dried to obtain 15.1 g of oxonol dye. The aqueous solution of this dye had a λmax of 582 nm, indicating that it was a highly pure dye. Example 10 [Synthesis of Exemplary Compound (2)] 28.3 g of 1-(p-sulfophenyl)-3-carbamoyl-5-pyrazolone (general formula []-13), 150 ml of dimethylformamide, and triethylamine.
30 g of glutacondialdehyde bis(o-ethoxycarbonylanyl) hydrochloride was added thereto and reacted at room temperature for 5 hours. After the reaction was completed, 300 ml of ethanol was added, followed by 20 g of potassium acetate, and the mixture was stirred at room temperature. The precipitated solid was filtered, washed with ethanol and acetone, and dried to obtain the desired product. Yield 29g Yield 82% λmax (H ₂ O) = 635mm Example 11 [Synthesis of Exemplary Compound (1)] 34.6g of 1-(p-sulfophenyl)-3-trifluoromethyl-5-pyrazolone and 200ml of dimethylformamide, 30 g of triethylamine was added, and glutacondialdehyde bis(p-methylsulfonylanyl) hydrochloride was further added, followed by reaction at room temperature for 4 hours. After the reaction was completed, 300 ml of ethanol was added, followed by 25 g of potassium acetate, and the mixture was stirred at room temperature. The precipitated solid was filtered, washed with ethanol and acetone, and dried to obtain the desired product. Yield 34g Yield 91% λmax (H ₂ O) = 627mm

Claims (1)

[Claims] 1. Obtaining an oxonol dye represented by the general formula [A] by condensing an α-ketomethylene compound represented by the following general formula [] with a compound represented by the following general formula [] Characteristic method for producing oxonol dyes. General formula [] General formula [] General formula [A] [In the formula, Q represents a nonmetallic atom group necessary to form a 5-pyrazolone ring or a barbituric acid residue, and R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each a hydrogen atom,
It represents a halogen atom, trifluoromethyl group, cyano group, alkoxycarbonyl group, nitro group, acyl group, methylsulfonyl group, carbamoyl group, or sulfamoyl group, but R ₁ to _{R 5} are not all hydrogen atoms. Further, L represents a methine group, and n represents an integer of 0, 1 or 2. ]