JPS59116656A - Preparation of magenta coupler - Google Patents

Abstract

PURPOSE:To speed up development and to sharpen an image by reacting a specified compd. with a 4-equiv. magenta coupler, and introducing a thioether group into the active site of said coupler in one step to obtain a 2-equiv. coupler. CONSTITUTION:A sulfur contg. compd. represented by formula I or II is reacted at normal temp. with the active site of a 4-equiv. magenta coupler to obtain a thioether type 2-equiv. magenta coupler of formula III. In formula I -III, R, R2, R5 are each alkyl, alkenyl, aryl, or the like; R1, R3, R4 are each H, alkyl, alkenyl, or the like, or a cation; and Coup is a magenta coupler residue free of H at the coupling active site. The 2-equiv. coupler thus obtained is better in coupling reactivity than the 4-equiv. coupler, and more suitable for rapid color development. An amt, of silver halide to be used is halved because of the 2- equiv. coupler, reduced in cost, thinned in an emulsion layer, and further, improved in resolution of a color image and its sharpness.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a magenta dye-forming coupler (hereinafter simply referred to as magenta coupler) used in color photography. More specifically, it relates to a one-step synthesis method for introducing a thioether group into the active site of a magenta coupler.

Generally, in subtractive color photography, as is well known, the oxidation product of an aromatic primary amine color developer FM agent produced by reducing exposed silver halide grains and a dye-forming coupler are combined into a silver halide emulsion. A color image is formed by oxidative coupling therein. Most conventional couplers are 4
It was an equivalent coupler, ie one requiring reduction of 4 moles of silver halide to form 1 mole of dye. On the other hand, two-equivalent couplers are known in which the active site of the puller is substituted with a group capable of leaving on coupling, requiring the reduction of two moles of silver halide for the formation of one mole of dye. Since the 2-equivalent coupler has a higher turning reactivity than the 4-equivalent coupler, it is possible to provide a color photographic material suitable for rapid color development processing without requiring a long time for development.

In addition, color photographic light-sensitive materials containing a 2-equivalent coupler in a silver halide photographic emulsion require only half as much silver halide to obtain a certain amount of dye as compared to a 4-equivalent coupler, reducing costs. The layer can be made thinner, improving the resolution and sharpness of color images. Thus, 2-equivalent couplers have many advantages over 4-equivalent couplers.

Among 2-equivalent couplers, couplers that couple with oxidation products of color developers to release mercaptans are known. Certain thioether derivatives mentioned above are known as DIR (current inhibitor releasing) couplers, DIR (bleach inhibitor releasing) couplers or BAR (bleach accelerator releasing) couplers.

Until now, the method for producing a 2-equivalent magenta coupler that releases a mercaptan is U.S. Pat. No. 3,227.354.
No. 3,701,783,
A method of reacting a sulfenyl chloride with a 4-equivalent magenta coupler, as described in JP-A-49-62゜464, a method of dibrominating the 4-position of a magenta coupler and reacting it with about 3 times the mole of mercaptan. , Research Disclosure
1380f3 (1975), a method of dropping bromine in the presence of a 4-equivalent magenta coupler and a mercaptan, JP-A-5
5-25.056, a method for reacting a 4-equivalent magenta coupler with S-alkylthioisothiourea, JP-A-55-29. As described in the SOS issue, a method is known in which a magenta coupler having a mercapto group at its active site is reacted with a halogen compound.

The present invention relates to a novel method for producing 2-equivalent magenta kaglar which is not described in the above-mentioned known literature. The method described in U.S. Pat. No. 3,227,554, U.S. Pat. There are restrictions on the types, and although it is effective for heterocyclic mercaptans and aryl mercaptans, it produces many by-products for alkyl mercaptans, so it cannot be said to be a general method.

Furthermore, in these methods, the 4-position dibrome compound of sulfenyl chloride and pyrazolone is chemically unstable, causing a decrease in yield. In the method described in JP-A-55-25.056, the mercaptans that can be introduced into the active site of the magenta coupler are limited to alkylthio groups, acylthio groups, and thioacylthio groups, and the introduction of arylthio groups and heteromonkey thio groups is based on this method. This method is not possible, and it cannot be said to be a general method.

Furthermore, many of the S-alkylthioisothiourea salts used in this method are difficult to purify, causing a decrease in yield. The method described in JP-A-55-29805 involves introducing a mercapto group into the active site of the coupler in advance, and then reacting with a halide to introduce a thioether group into the active site. is limited to alkylthio groups and others, and it is impossible to introduce arylthio groups and heteroarthio groups using this method. Also, since a synthetic step is added to introduce a mercapto group into the coupler in advance, the synthetic route becomes long and the overall However, this method has the disadvantage that the yield is low, so it cannot be called a general method.

Therefore, the first objective of the present invention is to provide a new manufacturing method that can introduce a thioether group into the active site of a magenta coupler in one step, and the twentieth objective is to provide a new production method that can introduce a thioether group into the active site of a magenta coupler in a simple operation and in a high yield. The purpose is to provide a one-stage manufacturing method that can be introduced into the active site of a magenta coupler.
The purpose of the above is to provide a 2-equivalent magenta coupler having a thioether group as a leaving group obtained by such a production method.

As a result of various studies by the present inventors, the above purpose was achieved by adding the following general formula (I) or (If
It has been found that this can be achieved by a method for producing a magenta coupler, in which a 2-equivalent thio-type maze/ta coupler represented by the following general formula (I[) is obtained by reacting a compound represented by the following formula (I[)].

General formula (I) R-8-8o-0-R.

General formula (III) Coup -8-R5 In the formula, R'% R2 and R6 each represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, and R1R8 and R4 are Each represents a hydrogen atom, an alkyl group, a cycloaltyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, or a cation, and 0oup represents a magenta coupler residue from which one hydrogen atom of the coupling active site has been removed.

That is, in the production method of the present invention, the above general formula (I) t is directly applied to the coupling active site of the 4-equivalent magenta coupler.
or (II), to obtain a thioether type two-equivalent magenta coupler represented by the general formula (III),
According to the present invention, the above production method not only has the advantage that a thioether group can be introduced into the active site of the magenta coupler in one step, but also the mercaptans that can be introduced are not limited to alkylthio groups, but also alkenylthio groups and arylthio groups. This is a highly versatile method for producing 2-equivalent magenta kaglar, which allows the introduction of a heterozygotic thio group.

The invention will now be described in more detail.

In the general formulas (I), (n) and (m), R%
The alkyl groups to be used in R2 and R3 may be either linear or branched, such as methyl, ethyl, 1-propyl, n-butyl, t-
Examples include butyl, n-dodecyl, n-octadecyl, cyclohexylmethyl, etc. cycloalkyl groups include cyclohexfur, etc., and alkenyl groups include allyl, oleyl, etc., and cycloalkenyl groups include Examples include cyclohexenyl.

The above alkyl groups, cycloargyl groups, alkenyl groups and cycloalkenyl groups further include haloken atoms, nitro, cyan, hydroxy, alkoxy, aryloxy, heterocyclooxy, acyloxy, sulfonyloxy, carboxy, carboxylic acid ester, carbamoyl, sulfo, Sulfonic acid ester, sulfamoyl, alkylthio, arylthio, heterocyclothio, sulfonyl, acyl, amine, acylamino, sulfonamide,
It may be substituted with substituents such as ureido, urethane, sulfinyl, mercapto, aryl, and -heterocycle.

Further, in each of the above general formulas, typical examples of the aryl group represented by R, R, and R5 are a phenyl group and a naphthyl group, and these groups may further include a halogen atom, nitro, cyan, alkyl, Hydroxy,
Alkoxy, aryloxy, heterocyclothioxy, acyloxy, sulfonyloxy, carboxy, carboxylic acid ester, carbamoyl, sulfo, sulfonic acid ester, sulfamoyl, alkylthio, arylthio, sulfonyl, acyl, amine, acylamino, sulfonamide, ureido, urethane, It may be substituted with substituents such as sulfinyl, mercapto, aryl, and heterocycle.

Furthermore, specific examples of the heterocyclic group represented by R, R, and R6 include, for example, tetrazolyl, benzoxasilyl, penduthiazolyl, benzimidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, furanyl, benzofuranyl, oxasilyl, pyranyl, oxazinyl, hyridyl. , pyrimidinyl, chenyl, tetrahydrochenyl, tetrahydrofuranyl, tetrahydropyranyl, pyrrolyl, imidazolyl, pyrazolyl, morpholinyl, etc., and these groups further include norogen atoms, nitro, cyano, alkyl, hydroxy, alkoxy, aryloxy, Heterocyclooxy, acyloxy, sulfonyloxy, carboxy, carboxylic acid ester, carno(moyl, sulfo, sulfonic acid ester, sulfamoyl, alkylthioarylthio, sulfonyl,
It may be substituted with substituents such as acyl, amine, acylamino, sulfonamide, ureido, urethane, sulfinyl, mercapto, aryl, and heterocycle.

Next, in each of the above general formulas, the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and heterofiller represented by R1, R3, and R4, respectively, are the above-mentioned RXR2 and R.

an alkyl group, a cycloalkyl group, respectively represented by
The cations represented by the above R1, R3 and R, which are synonymous with alkenyl group, cycloalkenyl group, aryl group and double violet ring group, include sodium ion, potassium ion, magnesium ion, Ions containing calcium ions, silver ions, and nitrogen atoms (
Examples include ammonium ion, pyridinium ion, triethylammonium ion and diethylammonium ion).

Next, in the general formula (III), the magenta coupler residue represented by Coup is 5-oxo-2
-pyrazoline nucleus, pyrazolo-[1.5-albenzimitazole nucleus, 1H pyrazolo[5.1-c][1,2
．． 4]) Riazole nucleus, indacylon nucleus, benzyl cyanide nucleus, pyrazolidine-3.

There are 5-dione nuclei, etc., such as 5-oxo-2-pyrazoline nucleus, pyrazolo-[1,5-a'll benzimidazole nucleus, and 1H pyrazolo[5.1-c][1.

A 2,4'J triazole nucleus is preferred.

The magenta coupler residues represented by Ooup useful in the present invention have the following general formulas (IV), (V) and ('V
I).

General formula (IV) General formula (V) 9 General formula (VI) In the above general formula (IV), R6 (d, alkyl group, cycloalkyl group, alkenyl group, /chloroalkenyl group, aryl group or ring group) represents.

The alkyl group represented by R6 above is a straight chain one,
Any of the branched ones are acceptable, such as methyl, ethyl, 1-propyl, n-butyl, 1-butyl, n-
Examples include dodecyl, n-octadecyl, cyclohexylmethyl, and cycloalkyl groups such as cyclohexyl. As an alkenyl group, 1] is allyl,
There is Oreille, 17 mag.

Examples of the cycloalkenyl group include cyclohexenyl. These groups further include halogen atoms, nitro, cyan,
Hydroxy, alkoxy, aryloxy, acyloxy, sulfonyloxy, carboxy, carboxylic acid ester, carbamoyl, sulfo, sulfonic acid ester, sulfamoyl, alkylthio, arylthio, sulfonyl, acyl, amine, acylamino, sulponamide, ureido, urethane, sulfenyl, mercapto may be substituted with a substituent such as , aryl, or heterocycle.

Further, the aryl group represented by R6 includes a phenyl group and a naphthyl group, and these groups represented by the above-mentioned aryl group may have one or more substituents, and the substituents include, for example, alkyl, Halogen atom, nitro, cyano, hydroxy, alkoxy, aryloxy, acyloxy, sulfonyloxy, carboxy, carboxylic acid ester, carbamoyl, sulfo, sulfonic acid ester, sulfamoyl, alkylthio, arylthio, sulfonyl, acyl, amine, acylamino, sulfonamide, ureide, urethane, flufinil, mercapto,
May have aryl, heterocycle, etc.

Furthermore, the heterocyclic group represented by R6 includes pyridyl,
Quinolyl, furyl, benzothiazolyl, be/dioxazolyl, benzimidazo, ryl, piperidinyl, etc.
These groups may be substituted with the substituents listed for the aryl groups above.

Next, R7 is a hydrogen atom, an alkyl group (a group with the same meaning as the argyl group in R0 above), a cycloalkyl group (a group with the same meaning as the cycloalkyl group in R6 above), an alkenyl group (a group with the same meaning as the alkenyl group in R6 above) , cycloalkenyl group (the above R
6), an aryl group (a group synonymous with the aryl group of R6), a heterocyclic group (a group synonymous with the heterocyclic group of R6), a carboxylic acid ester (e.g. carbonyl, phenoxycarbonyl, etc.), alkoxy groups (e.g. mer-coconut, n-dodecyloxy, etc.)
, aryloxy group ([1klJ is phenoxy), alkylthio group (e.g. methylthio, benzylthio, etc.),
Arylthio groups (e.g. phenylthio), carboxy groups, carbamoyl groups (ethylcarbamoyl, N-
phenylcarbamoyl, etc.), acylamino groups (e.g. acetylamino, n-tetradecanoylamine, α-(2
, 4-di-t-amylphenoxy7)butyramide, 32[α-(2,4-di-t-amylphenoxy)acetamide]benzamide, etc.), amino groups (for example, methylamino, anilino, 2-chloro- 5-n-tetradecanamide anilino, 2-chloro-5-(3-occudecenylsuccinimide)anilino, etc.), ureido groups (such as n-tetradecylureido, phenylureido, N-
dodecyl-N-phenylureido, etc.), sulfonamide groups (for example, n-butanesulfonamide, p-n-dodecyloxybenzenesulfonamide, etc.), sulfamoyl groups (for example, n-dodecylsulfamoyl, phenylsulfa) moyl, etc.), carbamoyl groups (e.g. ethylcarbamoyl, dienylcarbamoyl, etc.), acyl groups (
(eg, acetyl, benzoyl, etc.), a urethane group, a cyano group, a hydroxy group, a mercapto group, a sulfo group, and a halogen atom.

Further, in the general formula (V), R8 represents the same group as the group represented by R7 above. and Ro is a hydrogen atom, an alkyl group (the same group as the alkyl group of R6 above), a cycloalkyl group (a group with the same meaning as the cycloalkyl group of R6 above)
, alkenyl group (group synonymous with the alkenyl group of F6 above)
, a cycloalkenyl group (a group with the same meaning as the cycloalkenyl group in R6 above), an aryl group (a group with the same meaning as the aryl group in R6 above), a heterocyclic group (a group with the same meaning as the heterocyclic group in R6 above)
, halogen atom, nitro, cyano, hydroxy, alkoxy, aryloxy, alkoxy group sulfonyloxy, carboquine, carboxylic acid ester, carbamoyl, sulfo, sulfonic acid ester, sulfamoyl, alkylthio, arylthio, sulfonyl, acyl, amine, acylamino, sulfonamide , ureido, urethane, sulfinyl and mercapto.

In the general formula (VI), "10 and R1□ are
It represents a group of the same type as the group represented by R7 above. And Isamu.

and R11 may be the same or different from each other.

In the present invention, the magenta coupler residue represented by Coup is preferably a group represented by the general formula (IV) above.

Typical specific examples of the compounds represented by the general formulas (I) and (II>) are listed below, but the present invention is not limited thereto.

(Exemplary Compound) (1,) C! H, -S -5o2-00 Na■(2
) c2H, -S -5o2- oOK■(3) n-
0,2H,-8-SO2-OH(131HOOH20H
2-S -So, 0H(2o) (27) (28) (29) (30) (311 (Ea a) Among the compounds related to the present invention, the compound represented by the general formula (I) is a conventionally known compound. That is, the above production method is described in Angewand Haemi International Edition, Vol. 6 (1967), pp. 544-553, and the literature listed on the same page. has been done.

Compound 2 represented by the general formula (n) can be obtained by, for example, a method of reacting a sulfinic acid or a metal salt thereof with a sulfenyl chloride, a method of reacting a thiosulfonate with a halogen compound, or a method of reacting a mercaptan with a sulfonyl chloride. It can be produced using conventionally known methods such as a reaction method.

Next, the production method of the present invention, ie, the reaction of the 4-equivalent magenta coupler with the compounds represented by the general formulas (I) and (II), will be described in detail.

During the production, the molar ratio of the compound represented by the general formulas (I) and (n) of the present invention to the coupler used in the reaction with respect to the 4-equivalent dollar is in the range of 1 to 10, preferably 1 to 2 times the amount is appropriate. Reaction solvents that can be used during production include alcohol solvents (methanol, ethanol, ituburobanol, etc.), ether solvents (tetrahydrofuran, dioxane, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), and ketone solvents (acetone, etc.). , methyl ethyl ketone, etc.), hydrogen halide solvents (chloroform, dichloroethane, etc.), aromatic hydrocarbon solvents (benzene, toluene, xylene, etc.), aprotic polar solvents (dimethylbormamide, dimethylsulfoquine, hexamethylphosphotrifluoride, etc.) amide etc.), organic acid supermediates (acetic acid etc.), petroleum solvents, acetonitrile, water, etc., and alcohol solvents are particularly preferred.

Furthermore, as a base catalyst used for the reaction, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, DBU, sodium ethylate, sodium methylate, sodium metal, etc. may be used. sodium ethylate and sodium methylate are particularly preferred. The amount of catalyst is 1 to 4 equivalent couplers.
Although it can be used in a 20-fold molar amount, a 1- to 4-fold molar amount is particularly preferred. The reaction temperature can be carried out at 10 to 150°C, but is preferably in the range of 10 to 50°C.

That is, according to the present invention, a basic catalyst is first dissolved in the reaction medium, a 4-equivalent magenta coupler is added to the solution, and then a compound of the general formula (I) or (n ) at room temperature after adding the compound represented by 4.
Let it react for about an hour. The reaction mixture was then dissolved in water.
For example, when poured into a dilute acid water bath, the product precipitates out. If necessary, this product was recrystallized from an appropriate solvent to obtain the desired 2-equivalent maze/ta coupler with good purity.

In some cases, the above-mentioned product may be extracted using an appropriate organic solvent, washed with water, dried and concentrated to obtain the desired product.

According to the production method of the present invention, it is possible to synthesize a two-equivalent magenta coupler having an arylthio group or a petrosalthio group as a leaving group, which could not be easily synthesized by methods known in the literature. The production method of the present invention has the advantage that various thioether groups can be introduced into the active site of the coupler in a high yield in one step from a 4-equivalent coupler without substitution at the active site under mild reaction conditions at room temperature. have.

Specific examples of 2-equivalent magenta couplers that can be obtained according to the present invention are as follows.

(Shi0 indicating coupler) (1) I2 Oh.

CH (9) Shi1 (10) (jl) B (14) Cβ :15) GiCH3 (17) (18) (19) (20) (21) t=d (22) (24) (25) ( 27) (30) (31) (32) (35) Synthesis examples of typical couplers by the production method of the present invention are described below as examples, but the present invention is not limited thereby.

Example 1 (Synthesis of Exemplary Coupler (4)) 1-(2,4,
6-dolychlorphenyl)-3-(2-chloro-5-n
-tetradecanamide anilino)-4-benzylthio-
Synthesis of 5-oxo-2-pyrazoline Add 1-(2,4,6-dolychlorphenyl) to a solution of 3 g of sodium metal dissolved in 5 QmJ of absolute ethanol.
--Add 6.1 g of --3-(2-chloro-5-n-tetradecanamidoanilino)-5-oxo-2-pyrazoline, and then add benzyldimethylaminethiosulfone) 3.
0 g was added and reacted at room temperature for 4 hours. When the reaction mixture was poured into dilute hydrochloric acid, a white solid precipitated. This solid was collected by filtration and then recrystallized from ethanol to obtain 5.9 g of white crystals of the target product. The melting point is 181-182℃ and the yield is 80
It was Chi.

Example 2 (Synthesis of Exemplary Coupler (6)) 1-', 2.4
．． 6-)lichlorphenyl)-3-(2-chloro-5-
Synthesis of n-tetradecanamide anilino)-4-7enylthio-5-oxo-2-pyrazoline Add 1-(2,4,6-dolychlorphenyl) to a solution of 3 g of sodium metal in 50 ml of absolute ethanol. −
3-(2-chloro-5-n-tetradecanamideanilino)-5-oxo-2-viraso IJ 76.1.9 was added, and then phenyldiphenylamine thiosulfonate 4
．． 4 g was added and reacted at room temperature for 5 hours. This solid was collected by filtration, and then recrystallized from ethanol to obtain 5.71 of the target substance as white crystals.

The melting point was 214.5-216°C and the yield was 79%.

Implementation ipu3 (synthesis of mt-indicating coupler (1)) 1-(2
,4,6-dolychlorophenyl)-3-C2-chloro-
Synthesis of 5-(3-octadecenylsuccinimide)anilinoyo4-ethylthio-5-oxo-2-pyrazoline Add 1-(2,4,6- ) Lichlorphenyl)
7.4 g of '-3-[2-chloro-5-(3-octadecenylsuccinimide)anilinoyo5-oxo-2-pyrazoline was added, and further 2.21 g of ethyldimethylaminethiosulfonate was added, and the Allowed time to react. The reaction mixture was poured into dilute hydrochloric acid, extracted with ethyl acetate, dried,
Concentrated.

A pale yellow caramel-like target product 6.8# was obtained. Yield is 8
It was 6%.

Comparative Example 1 Synthesis example 1-(2, 4, 6 -)lychlorphenyl)-3-(2-
Chlor-5-n-tetragucanamide anilino)-5-
6.1 g of oxo-2-pyrazoline to 1 part of 80% ethanol
The mixture was heated to 25 mJ, 0.9 I of potassium carbonate was added, and a solution of 3.1 g of S-benzylthioisothiourea hydrochloride dissolved in 30 TL of 90% ethanol was added dropwise over 1 hour while heating and stirring under reflux.

Then, the mixture was further heated and stirred for 2 hours. After confirming the completion of the reaction using thin layer chromatography, the reaction vessel was cooled with ice. The produced solid was collected by filtration and crystallized from ethanol to obtain 3.5 g of white crystals of the desired product. Melting point is 181°C to 182°C
The yield was 47%.

Comparative Example 2 The following coupler was synthesized by the method described in U.S. Pat. No. 3,227,554.

1-(2,4,6-dolychlorophenyl)-3-(5-
[γ-(2,4-di-t-amylphenoxy)butanamido-2-chloroanilino)-4-phenylthio-5
-Synthesis of oxo-2-pyrazoline Thiophenol 1.2I was dissolved in carbon tetrachloride at 30 mA' [to an orange solution obtained by introducing chlorine gas at room temperature for 13 minutes.
m to obtain benzenesulfenyl chloride as an orange oil. 1-(2,4,6-dolychlorfeol)-3-
(5-[γ-(2,4-di-t-amylphenoxy)butanamide]-2-chloroanilino)-5-oxo-2
- 30 ml of the toluic acid solution of benzenesulfenyl chloride was added dropwise to a solution of pyrazoline 7, O, li' acidified in 100 ml of toluene and heated to about 80° C. and stirred. After heating and stirring for 3 hours, the reaction solution was concentrated and the residue was subjected to column chromatography (developed with benzene and ethyl acetate using silica gel as a packing material) to isolate the desired product, which was further recrystallized from benzene to give white crystals. 3
, OI was obtained.

The melting point was 127-130'C and the yield was 37 inches. Comparative Example 1 and Comparative Example 2 are conventionally known methods for introducing an alkylthio group and an arylthio group into the active site of a magenta coupler, and compared to the production method of the present invention, both yields are lower and by-products are produced. It can be seen that many appear.

The present method for producing a magenta coupler having an F3Ao thioether group has an advantage over these conventionally known methods in that the reaction temperature can be carried out at room temperature, and moreover, it is possible to introduce either an arylthio or a heterothio group. It is characterized by its versatility.

Agent Yoshi Kuwahara Beautiful procedural amendment January 14, 1980 Mr. Kazuo Wakasugi, Commissioner of the Japan Patent Office 2 Name of the invention Method for manufacturing magenta couplers 3 Relationship to the supplementary case Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name (+27) Konishiroku Photo Industry Co., Ltd. Representative Director Kawa
Nobuhiko Lives: 1 Sakuracho, E1no City, Tokyo Roku Konishi Photography
Column 7 of "Detailed Description of the Invention" in the Specification of the Nigyo Corporation, Contents of Amendment (1) The detailed description of the invention will be amended as follows.

Procedural amendment January 27, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the case 1982 Patent Application No. 213127-Li.2 Name of the invention Process for manufacturing magenta coupler 3, Supplementary case Relationship Patent applicant address: 1-26-27 Nishi-Shinjuku, Shinjuku-ku, Tokyo, Japan
Name (1271 Konishiroku Photo Industry Co., Ltd.)
乎道μ 4, Agent Address: 191 Address: 1 Sakura-cho, Hino-shi, Tokyo Vol. 6 Column 7 of “Detailed Description of the Invention” of the Specification Subject to Amendment Contents of the Amendment (1) Detailed Description of the Invention The explanation has been amended as follows.

Claims (1)

[Claims] (1) The following general formula □(I) is applied to the 4-equivalent magenta coupler.
A method for producing a magenta coupler, characterized in that a two-equivalent thio-type magenta coupler represented by the following general formula (1) is obtained by reacting a compound represented by (n). General formula (I) R-El-8o2-0-R. General formula (I[I) C! oup -S -R6 (wherein R% R2 and R7 each represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, and R1, R3 and h are each a hydrogen atom , represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an allinol group, a heterocyclic group, or a cation, and 0oup represents all magenta coupler residues from which one hydrogen atom of the coupling active site has been removed.) (2) The 4-equivalent maze/ta coupler is a 5-oxo-2-pyrazoline derivative, a pyrazolo-(1,5-a)benzimidazole derivative or]H
Claim No. (1) characterized in that it is a pyrazolo-[5,1-Cl1,2,4-1-riazole derivative.
A method for producing a magenta coupler as described in Section 1.