JPS59121331A - Manufacture of phenol type cyan coupler - Google Patents

Abstract

PURPOSE:To manufacture a phenol type cyan coupler of high purity in a high yield by reacting 2-ureido-5-aminophenol with carboxylic acid chloride in water - an org. phase. CONSTITUTION:100pts.wt. of 2-ureido-5-aminophenol (a) represented by formula I (where Ar is aryl, and X is H or a group which can be eliminated by the coupling reaction of the oxidized product of aromatic primary amine as a color developing agent with a phenol type cyan coupler represented by formula III) are dissolved in 200-10,000pts.wt. aqueous soln. contg. an acid in amounts equimolar with the component (a). 100pts.wt. by weight of carboxylic acid chloride represented by formula II (where R is a group providing diffusion resistance to said phenol type cyan coupler) are dissolved in 200-10,000pts.wt. org. solvent immiscible with water. The solns. are mixed so that the component (b) is contained by 0.9-1.5mol per 1mol component (a), and they are reacted at 0-100 deg.C for 30min-1hr in the presence of an inorg. base in amounts equimolar with the component (b) to obtain a phenol type cyan coupler represented by the formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION ■ Background Technical Field of the Invention The present invention relates to a method for producing phenolic cyankaplani used for photography.
By the reaction of aminophenol and carboxylic acid chloride, 2
- A method for producing a ureido-5-acylaminophenol cyan coupler.

Methods for acylating an amine compound include a method in which an amino compound and a carboxylic acid chloride are reacted, and a method in which an amine compound and a carboxylic acid are reacted in the presence of N,N''-dicyclohexylcarbodiimide (D, C, C, J, etc.). method of condensation with,
Examples include a method of reacting an amine compound and an acid anhydride, and a method of condensing an amine compound and a carboxylic acid ester.

Among these acylation reactions, when producing an acylaminophenol cyan coupler used as a cyan coupler for photography such as silver halide color photosensitive dyes, the reaction between aminophenol and carboxylic acid chloride is carried out. It is common to use, for example, Japanese Patent Application Laid-Open No. 56-65
Publication No. 134, etc. 2-7E=R:) Reid-5-amine phenol, reaction with 5-carboxylic acid chloride 2
A method for preparing a cyan coupler based on -ureido-5-acylaminophenol is described.

However, the production method described in JP-A-56-65134 is inappropriate as a production method suitable for general and mass production of 2-ureido-5-acylaminophenol cyan couplers. This is because, depending on the substituent of the phenyl group introduced into the 2-position ureido group, it is poorly soluble in organic solvents, and is only possible in solvents such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (!). Therefore, when the reaction is carried out using a normal solvent, a compound in which the phenolic hydroxyl group is also acylated will be produced. This is thought to be due to the large excess of base added to remove hydrogen chloride, a by-product of the acylation reaction.For this reason, a large amount of solvent is used, and D
It is possible to use a solvent with strong dissolving power such as MF or DMSO, but if a large amount of solvent is used, a large reactor will be required. Since they are harmful to living organisms, they pose problems in the working environment and in wastewater treatment, so none of them can be said to be preferable.

Furthermore, if a base is used to remove by-product hydrogen chloride, the amine compound will be further oxidized and the yield of the desired acyl compound will decrease, and crab gas must be introduced into the reaction solution to prevent oxidation. Such complicated operations are essential.

+1 Object of the invention The object of the present invention is to produce 2-ureido-5-aminophenol by the reaction of 2-ureido-5-aminophenol with a carboxylic acid chloride.
It is an object of the present invention to provide a general method for producing a 2-ureido-5-acylaminophenol cyan coupler which can obtain an acylaminophenol cyan coupler at a high sieve yield and is suitable for mass production.

The present inventors, when producing a phenolic cyan coupler represented by the following general formula [Otori], used the following general formula [1].
The present inventors have discovered that the above object can be achieved by reacting the compound represented by the following general formula with the compound represented by the following general formula in a two-phase system of an aqueous phase and an organic phase, and have completed the present invention.

General formula (1) General formula […] 0CI General formula [厘] I (In general formula (1), general formula mouth opening, and general formula (1), Ar represents an aryl group. λ )
The phenolic cyan coupler represented by t represents a group that imparts diffusion resistance. X represents a hydrogen atom or a group that can be separated by a coupling reaction between an oxidation product of an aromatic primary amine color developing agent and a phenolic cyan coupler represented by formula (1). ) ■ Detailed Description of the Invention As mentioned above, the characteristics of the present invention are as follows.
The compound represented by (1) and the compound represented by general formula (I) are reacted in a two-phase system of an aqueous phase and an organic phase. acylation, that is, a compound represented by the general formula El) according to the following reaction formula 1 is reacted with a compound represented by the general formula [1] at the aqueous phase-organic phase interface.

()1( λ [11(II) ()IT (f) Sehotten-Bnu
mqnn ) method (mainly alkaline aqueous J is available, and this method was applied in the present invention.

In this 5chotten-Baumann method, organic solvents are not normally used, but in the present invention (,
11 In order to carry out the reaction according to the above reaction formula efficiently, an organic phase, that is, an organic solvent is used.

For example, the compound represented by the general formula (1) is preliminarily treated with hydrochloric acid,
As a salt of an inorganic acid such as sulfuric acid or perchloric acid, or an organic acid such as a carboxylic acid or a sulfonic acid, the salt may be dissolved in water to form an aqueous phase, or A compound of general formula [1] is dissolved in an aqueous solution of formula [1] to form an aqueous phase.

In this way, by subjecting the compound of general formula (1) to the reaction in an aqueous phase, preferably in the form of an acidic aqueous solution, the compound of general formula (1)
Among the compounds of formula [1], the reaction according to the above reaction formula proceeds satisfactorily even in compounds that are soluble in organic solvents.
Air oxidation of the compound is well prevented. The acid used in the present invention is preferably hydrochloric acid. In addition, it is preferable to form an organic phase by dissolving the compound (j) of the general formula [11] in an organic solvent. It is preferable to use an organic solvent that is immiscible with water such as
The compound of general formula (1) and the compound of general formula (It) are caused to react by bringing the aqueous phase and the organic phase into contact, usually by mechanical stirring or the like.

In this case, in the two-phase system reaction of aqueous phase and organic phase, the reaction of the above reaction formula proceeds by intervening a base, and the desired phenolic cyan coupler of the general formula [IJ] is produced in high yield. This will be obtained. The bases used in the present invention include organic bases such as pyridine, quinoline, and triethylamine, and inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate. When using an inorganic base, It is preferable to add this inorganic base to the reaction system as an aqueous solution.

According to a preferred embodiment of the present invention, the reaction in the two-phase system of aqueous phase and organic phase is carried out by dissolving a compound represented by the general formula (+1) in an acidic aqueous solution as the aqueous phase, This is carried out by dissolving the compound shown in the organic phase in an organic solvent, mixing them, and then adding an aqueous solution of an inorganic base or an organic base to the mixed solution.

In the present invention, when the compound of general formula (1) is previously converted into the above-mentioned salt and this salt is dissolved in water to form an aqueous phase,
The amount of water used is usually 200 to io, ooo parts by weight, preferably C4200 to 2000 parts by weight, per 100 parts by weight of the salt of the compound of general formula [1]. In addition, when dissolving the compound of general formula [1] in an acidic aqueous solution, the general formula (11
It is preferable that the acid is contained in an equimolar amount to the compound, and in this case as well, the amount of acidic aqueous solution used is usually
0-10.000 parts by weight, preferably 200-2
,000 parts by weight.

In the present invention, the amount of the compound of the general formula 〇] used is:
Usually 6409 to 1 mole of the compound of general formula (1)
15 mol, preferably 1.0 to 1.2 mol, and the amount of organic solvent used in the organic phase is usually 200 to 1 O,0 per ioo parts by weight of the compound of general formula [II].
00 parts by weight of C, preferably 200 to 2,000 parts by weight.

In the present invention, the reaction temperature in the two-phase system of aqueous phase and organic phase is usually 0-100°C, preferably 15-40°C.
℃ or may be carried out under cooling.

When the base used in the present invention is an organic base (・J, it may be added as is to the two-phase reaction system, or it may be added after diluting with water. Also, in the case of an inorganic base It is preferable to use an equimolar amount of the compound of the general formula [[1], and the amount of water used to dissolve it is:
It is preferable to use 500 to 2,000 parts by weight based on 100 parts by weight of base. The addition time of the base to the two-phase reaction system is usually 30 minutes to 1 hour, and after this addition of the base,
The two-phase reaction is almost complete.

In the present invention, Ar of the general formulas [1) and El)
The aryl group represented by is, for example, a phenyl group, a naphthyl group, etc., preferably a (4 phenyl group). When these aryl groups have a substituent, this substituent is preferably , chlorine, fluorine, bromine, etc.), nitro group, cyano group, alkyl group (e.g. methyl group, trifluoromethyl group, ethyl group, l-propyl group, t-butyl group, n-pentyl group, t-pentyl group, octyl group, dodecyl group, octadecyl group, benzyl group, etc.], alkoxy group (e.g., methoxy group, ethoxy group, butoxy group, etc.), hydroxycarbonyl group, alkylcarbonyl group (e.g., methylcarbonyl group, ethylcarbonyl group, etc.), aryl Carbonyl groups (e.g., phenylcarbonyl group, naphthylcarbonyl group, tolylcarbonyl group, etc.), alkyloxycarbonyl groups (e.g., ethoxycarbonyl group, t-butoxycarbonyl group, etc.), bearyloxycarbonyl groups (e.g., phenoxycarbonyl group, etc.), alkylsulfonyl groups groups (e.g. trifluoromethylsulfonyl group, methylsulfonyl group, propylsulfonyl group, butyl-sulfonyl group, benzylsulfonyl group, phenethylsulfonyl group, etc.), arylsulfonyl groups (e.g. phenylsulfonyl group, naphthylsulfonyl group, trisulfonyl group, etc.), alkylthio group (moyl group (eg N-methylcarba7yl group, N-ethylcarbamoyl group, etc.), arylthio group (moyl group (
For example, N-phenylcarbamoyl group, etc.).

One or more of these substituents may be introduced into the aryl group. For example, the number of substituents introduced into the phenyl group is 1 to 5, preferably 1 to 3.

Furthermore, different types of substituent groups may be introduced into the same aryl group.

In the present invention, as a group (hereinafter referred to as a diffusion-resistant group) that imparts diffusion resistance to the phenolic cyan coupler represented by the general formula [Otori], which is represented by R in the general formula [11] and E-Rin], , preferably a straight chain or branched alkyl group having 4 to 30 carbon atoms (e.g. t-butyl group, n-octyl group, t-octyl group, n-dodecyl group, n-octyloxyethyl group, n-dodecyl group) oxymethyl group, pen-zyl group, etc.), alkenyl group (e.g. n-dodecenyl group, n-octadecenyl group, phenylpropenyl group, etc.)
, aryl groups (phenyl group, tolyl group, etc.), cycloalkyl groups (e.g. cyclohexyl group, etc.), and 5-membered or c-J6-membered heterocyclic groups.More preferable diffusion-resistant groups include the following general groups. It is a group represented by formula [1v].

General formula [1v] In the formula, R24 is a hydrogen atom, a hydrogen atom, an alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, hydroxy group, acyloxy group, carboxy' group,
Represents an alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfonamide group, carbamoyl group or (sulfamoyl group), where m is 2 or more When representing an integer, R26 may be the same or different.
It represents a sulfur atom or a sulfonyl group, l represents 0 or t, and m represents an integer of 1 to 4.

In the general formula LIV)I, the halogen atom represented by R2 is preferably chlorine or bromine, and the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms,
Particularly preferred are methyl group, t-butyl group, pentyl group, octyl group, dotecyl group, pentadecyl group, etc., aryl group is preferably 6-J phenyl group, and heterocyclic group is preferably 6-J phenyl group. It is a heterocyclic group. The alkoxy group represented by R2 is preferably an iα chain or a branched alkyloxy group having 1 to 20 carbon atoms, particularly preferably a methoxy group, an ethoxy group, a t-butyloxy group, an octyloxy group, a decyloxy group, or a dodecyloxy group. The aryloxy group is preferably a phenoxy group, the acyloxy group is preferably an alkylcarbonyloxy group, an arylcarbonyloxy group, particularly preferably an acetoxy group, a benzoyloxy group, and an alkoxy The carbonyl group preferably has a straight chain of 1 to 20 carbon atoms or (j branched alkyloxycarbonyl group, preferably an aryloxycarbonyl group)
It is a phenoxycarbonyl group. Furthermore, the alkylthio group represented by R2 preferably has 1 carbon atom.
~20 straight chain or branched alkylthio groups, the acyl group is preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms, and the acylamino group is preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms. a straight-chain or branched alkylcarboxamide group, a benzenecarboxamide group, and a sulfonamide group (preferably one carbon atom
~20 linear or branched alkylsulfonamide groups, benzenesulfonamide groups, and the carbamoyl group is preferably an IK chain having 1 to 20 carbon atoms or ? −
In each of the four-branched alkylaminocarbonyl group and the phenylaminocarbonyl group, the sulfamoyl group preferably has a carbon atom number of 1 to 20, and each of the straight chain or C'-branched alkylaminosulfonyl group and phenylaminesulfonyl group. Each of these groups may have a substituent.

In the following general formula (ffH), R1 represents a U chain or a branched alkylene group preferably having 1 to 1 carbon atoms.
20 alkylene groups. These alkylene groups may have a substituent.

In addition, in the general formula N) and general formula (1)t, the group represented by Alternatively, examples thereof include an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group, a succinimide group, etc., in which a nitrogen atom is directly bonded to the coupling position.

Furthermore, as specific examples of these groups, for example,
[Specification No. 3476563, Japanese Unexamined Patent Publication No. 47-37425
No., Special Publication No. 48-36894, Japanese Patent Publication No. 1977-101
No. 35, No. 50-117422, No. 50-13044
No. 1, No. 51-108841, No. 50-120334
No. 52-18315, No. 53-52423, No. 53-105226, No. 54-14736, No. 5
No. 4-48237, No. 53-32071, No. 55-
No. 65957, No. 56-1938, No. 56-1264
It is described in various publications such as No. 3 and No. 56-27147.

X is preferably a hydrogen atom or )/rogen atom (chlorine atom, etc.) Specific compound compounds of the phenolic cyan coupler according to the present invention represented by the formula (1) are listed below. Not limited.

(Rin-l) Eye-2) +1-31 (Yu-4) (Rin-7) 1 Rin-8) +1-91 (Rin-10) 1 (Otori-111 +1-161 l (Yaku-17) OH l-181 (Quantity-191 (1-203 shi4119 1 rin-21) (Otori-22) +1-231 +1-251 (Otori-26) Low 27) +1-2RI L;2116 (■-29) (rin -30) +1-311 (1-321 (Yo-33) fl-341 (1-351 (1-361 II +1-381 +1-391 +1-40) CR3 (Yaku-411 0-42) l-431 ( I-441 (1-451) Specific Applications of the Invention Process for producing the phenolic cyan coupler of the present invention The phenolic cyan coupler produced from this invention can be produced using the same methods and techniques as those used for ordinary cyan dye-forming couplers. (Typically a cyan coupler)
- Blend I7 into a silver halide emulsion, and coat this emulsion onto a support to form a silver halide photographic light-sensitive material. The silver halide photosensitive material A is a silver halide photosensitive material for single color or multicolor use. Although it is contained in the red-sensitive silver halide emulsion layer, it may also be contained in the non-sensitized emulsion layer, and silver halide photographic JIc photosensitive materials are sensitive to each of the three primary color regions of the spectrum. , for example, a red-sensitive silver halide emulsion layer containing at least L cyan dye-forming couplers (at least one of the cyan dye-forming couplers (4 being a phenolic cyan coupler according to the invention), at least one magenta A multi-halogenated compound comprising a single layer or a combination of layers, each of a green-sensitive silver halide emulsion layer containing a dye-forming dye and a blue-sensitive silver halide emulsion layer containing at least one yellow dye-forming dye. It can be a silver color photographic A photosensitive material.

In order to incorporate the cyan coupler according to the present invention into an emulsion, a conventionally known method may be followed. For example, the rJit point of tricresyl phosphate, dibutyl 7-talate, etc. is 17.
High boiling point organic solvent at 5°C or higher or h'1': butyl acid,
The cyan coupler according to the present invention is dissolved in a low boiling point solvent such as butyl globionate alone or in a mixture thereof as necessary, and then mixed with an aqueous gelatin solution containing a surfactant, Next, after emulsifying with a high-speed rotary mixer or a colloid mill, silver halide can be added to prepare the silver halide emulsion used in the present invention. When added to a silver halide emulsion used for the invention, the amount is usually 0.07 to 0.00% per mole of silver halide.
It is preferably added in an amount of 0.1 mol to 0.4 mol.

■Specific effects of the invention According to the method for producing a 7-enol cyan coupler of the present invention, a compound represented by the general formula [J] and a compound represented by the general formula [1] are mixed in a two-phase system of an aqueous phase and an organic phase. The phenolic cyan coupler represented by the general formula (1) can be obtained in high yield by the reaction. Moreover, when the addition of the base is finished, the reaction is completed, and the reaction time can be shortened.

Thus, the method 1 for producing a phenolic cyan coupler of the present invention can be said to be a general method for producing a phenolic cyan coupler and suitable for mass production.

(2) Specific Examples of the Invention The present invention will be explained in more detail with reference to specific examples below, but the embodiments of the present invention are not limited to these examples.

2-(3,4-cyclophenylncreito-5-aminophenol N)3121! was dissolved in 1/1 water containing 88 me concentrated hydrochloric acid. Add 2-(2,4-di-
t-Pentylphenoxy)butanoyl chloride 373f
of ethyl acetate 1.51! A solution of H dissolved in was added and stirred with a stirrer. Next, add 44f of sodium hydroxide to 55f of water.
00 me and this solution was added to the reaction solution over 1 hour. During this time, the reaction temperature was 25 to 30C. After continued stirring for 30 minutes, the aqueous layer was separated from the reaction solution, the 41-layer was washed with water, dried over MgSO4, the solvent was distilled off, and the residue was crystallized from acetonitrile.

Further, recrystallization was performed with acetonitrile to obtain colorless solid 593F, which is the target compound Ell. Yield 86%, melting point 221-2
22℃.

As described above, according to the method for producing a phenolic cyan coupler of the present invention, a desired phenolic cyan coupler can be synthesized in a short reaction time and in high yield.

2-(4-cyanophenyl)ureido-5-aminophenol (1) 268F was added to lI water containing 88 ml of concentrated hydrochloric acid.
! dissolved in it. Add 2-(2゜4-di-t) to this solution.
-Pentylphenoxy)hexanoyl chloride 404g
Toluene 1.51! A solution dissolved in was added and stirred with a stirrer. Next, 629 parts of potassium hydroxide was added to 500 parts of water.
-, and this solution was added to the reaction solution over 1 hour. At this time, the reaction temperature was 25 to 30°C. After stirring for 30 minutes, the aqueous layer was separated from the reaction solution, the organic layer was washed with water, dried with MgSO4, and the solvent was distilled off.
The residue was crystallized from acetonitrile. Further, the mixture was recrystallized with acetonate IJ to obtain colorless solid 495F, which is the target compound [1]. Yield: 83 cm. Melting point: 179-180°C.

As described above, according to the method for producing a phenolic cyan coupler of the present invention, the desired phenolic cyan coupler can be synthesized in a short reaction time and in high yield.

2-(4-ethylsulfonylphenyl)ureido-5-aminephenol (1) instead of 2-(3,4-dichlorophenyl)ureido-5-aminephenol El)
287F and 373 g of 2-(2,4-di-t-pentylphenoxybutyroyl chloride) were carried out in the same manner as in Example to obtain 495f of the target compound [1] as a colorless solid. Yield 84%. Melting point 130-132℃
.

As described above, according to the method for producing a phenolic cyan coupler of the present invention, nitro compounds that are sparingly soluble in organic solvents such as 2-(4-ethylsulponylphenylonureido-5-aminephenol) can be used. , the reaction can be carried out in the same manner, and the desired cyan coupler can be obtained in high yield without any by-products.

The structures of each of the phenolic cyan couplers obtained in Examples 1 to 3 were confirmed by IR spectra, NMR spectra/I/, and FD-MASS spectra.

[Comparison]

2-(4-methylsulfonylphenyl)ureido-5-
Aminophenol 3.211 to tetrahydrofuran 30
1.42F of quinoline was added to the suspended mixture. While introducing nitrogen gas, 2-(2,4-di-t-
Pentylphenoxy)hexanoyl chloride 4.041
was added dropwise over 30 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours. Insoluble matter was removed by filtration. This was the starting amino compound (1,0Of). The P solution was poured into hydrochloric acid diluted with water, and the precipitated oily base was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried with MgSO4. What remains after distilling off ethyl acetate? When toluene was added to U and left to stand, a solid precipitated. [Solid A, colorless solid, yield 1:1.5011, yield 23, melting point 220-222°C]. The filtrate was dried under reduced pressure, and the residue was crystallized from acetone trile and collected by suction filtration. [Solid B1 colorless solid, yield '+g, '3
．． 83F, yield 39%, melting point 250C or higher]. Fl)
-MASS and NMR spectra showed that Compound A (J was the target compound) and Compound B (4 had the following structure).

In this way, c-t, m-soluble amino compounds (
In the case of 1), a compound in which the phenolic hydroxyl group was also acylated was obtained as the main product.

[Present invention]

2-(4-methylsulfonylphenylneurido-5-
Aminophenol (1) 321F was dissolved in 1 liter of water containing 49f of concentrated sulfuric acid. 2-(2,4-di-t-pentylphenoxy)hexanoyl chloride El was added to this swamp liquid.
] A solution of 404 f dissolved in 1.51 g of total toluene was added and stirred with a stirrer. Then, 86.9 g of pyridine was added dropwise to the reaction solution over 81 hours. At this time, the reaction temperature is 25~
It was carried out at 30°C. After stirring for 30 minutes at the same temperature, the aqueous layer was separated from the reaction solution, the organic layer was washed with water, and Mg5
O.

After drying, the cyanide solution was concentrated, left in the refrigerator overnight, and the precipitated solid was collected by suction filtration. Further, recrystallization was prevented with acetonitrile (the target compound [1], colorless solid 521 F, was obtained. Yield: 80%, melting point: 220-222°C.
.

As described above, by following the method of the present invention, the target compound [I] can be obtained in high yield.

TSJ Thistle-Honeno-Nitsuichizuy-z≦-No A-7-
3-2, Mimitsu ni Tsukoshichi Jhiko - Sueno i Nino? -L Example 4 Yunoritomo 22-22 (j-311 (7) Shunchi 2-[3-2I:)xycarbonylphenyl)ureido-4-chloro-5-ditrophenol hydrochloride 386f
was dissolved in 1.5/ml of water. A solution of 2-(4-dodecylsulfonylaminophenoxy)phenylacetyl chloride 543f dissolved in benzene 2/2 was added to this solution,
The mixture was stirred using a stirrer.

Next, potassium hydroxide 62F was dissolved in 500-mL, and this solution was added to the reaction solution over 1 hour. At this time, the reaction temperature was 25 to 30°C. After stirring for 30 minutes, the aqueous layer was separated from the reaction solution, the organic layer was washed with water, and M
After drying with gSO4 and evaporating the solvent, the -C1 residue was purified by column chromatography (silica gel) to obtain the target compound [1
] Caramel 670f was obtained. As described above, according to the method for producing a phenolic cyan coupler of the present invention, it is possible to synthesize the desired phenolic cyan coupler in a short reaction time and in a high yield.

Commissioner of the Japan Patent Office Kazu Wakasugi Failure■, Small case indication 1982 Patent Application No. 2307522, Title of invention Phenolic cyan coupler 4 Toga. A name＞
(127) Konishiroku Photo Industry Co., Ltd. Director Fushiuchi
Nobuhiko Kawamoto89. Contents of the amendment (1) On page 17, line 13 of the specification, "...oxygen atom or nitrogen atom..." is changed to "...oxygen atom, sulfur atom, or nitrogen atom...".

(2) Add "tetrazolylthio group, triazolylthio group" after "no-phosphate imide group" on page 17, line 17 of the specification.

(3) Delete "X is preferably a hydrogen atom or a halogen atom (chlorine atom, etc.)" on page 18, lines 9-10 of the specification.

(4) C1l on page 26, lines 1-2 of the specification,
Let J be.

(5) Lines 1-2 of page 30 of the specification C41+, after J that's all

Claims (1)

[Scope of Claims] (11) When producing a phenolic cyan coupler represented by the following general formula [position], a compound represented by the following general formula (I) and a compound represented by the following general formula [1] are mixed in water. A method for producing a phenolic cyan coupler in which %* is a reaction in a two-phase system of phase and organic phase. , general formula [...], and general formula [■], represent an Ar ltJ aryl group.R represents a group that imparts diffusion resistance to the phenolic cyan coupler represented by general formula [1). X is a hydrogen atom or an oxidation product of an aromatic primary amine color developing agent and the general formula [1]
represents a group that can be separated by a coupling reaction with a phenolic cyan coupler shown in ) (2) After dissolving the compound represented by the general formula (1) in an acidic aqueous solution as the aqueous phase, dissolving the compound represented by the general formula (1) in an organic solvent as the organic phase, and mixing these. A method for producing a phenolic cyan coupler according to claim 11, characterized in that an aqueous solution of an inorganic base is added to the mixed liquid.