JPS5937819B2 - Method for producing a coupler having a thiolether group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing color image-forming couplers used in color photography.

More specifically, it relates to a novel manufacturing method in which a thioether group is linked to the active site of a color image-forming coupler. In color photography using silver halide light-sensitive materials, color image-forming couplers are contained in the developer, in the photographic emulsion layer, or in other hydrophilic colloid layers, and are used to develop the exposed silver halide emulsion layer. By reacting with the oxidized color developer thus formed, a non-diffusible color image is formed.

Most conventional couplers have been 4-equivalent couplers, ie, require stoichiometrically 4 moles of exposed silver halide as the oxidizing agent to form 1 mole of dye. Incorporating a large amount of silver halide into the photosensitive layer increases light scattering in the emulsion layer, reduces image sharpness, and has disadvantages such as decreasing photographic processing speed as the thickness of the emulsion layer increases. accompanied by. Furthermore, the formation of dyes by these couplers was not completed in the color developing bath, and it was necessary to use a strong oxidizing agent in subsequent processing steps. To remedy these drawbacks, two-equivalent couplers have been proposed, ie, couplers that require only two moles of exposed silver halide to form one mole of dye.

The 2-equivalent coupler has one of the hydrogen atoms at the coupling position (e.g., the para-position of a phenolic hydroxyl group, the active methylene group at the 4-position of 5-pyrazolone, the active methylene group of an acylacetanilide, etc.) substituted with a group that can be separated during coupling. It has a structure.

Known examples of such leaving groups include sulfonamide groups, imide groups, sulfonyl groups, aryloxy groups, thiocyano groups, carbamoyl groups, aminosulfonyloxy groups, and sulfinyloxy groups. However, many of these two-equivalent couplers having a leaving group are unsatisfactory in terms of coupling reactivity, dispersibility, color fog, difficulties in synthesis, and storage stability of color images. Among the two-equivalent type couplers, development inhibitor-releasing couplers, so-called DIR couplers, are known for the purpose of improving the sharpness of color images and improving graininess due to edge effects within layers, or color correction effects due to interlayer effects.

Among the two-equivalent type couplers, so-called BAR couplers are known that release a bleaching accelerator for the purpose of bleaching silver remaining in the layer.

From the above, it can be seen that couplers having detachable substituents at the coupling active positions of yellow, magenta, and cyan couplers are extremely important compounds in the production of color photographic materials.

Among them, there is a group of couplers that couple with the oxidation product of a phenylenediamine developing agent to release a mercaptan group. For example, U.S. Pat. The method described,
ResearchDisclOsurelO volume, boiled 13
8 (1975) is known. 0LS-
The method described in No. 2,343,378 uses a so-called dihalogen compound in which two halogen atoms are introduced into the coupling active position of a pyrazolone coupler as a starting material, and reacts it with a mercapto compound in an amount of twice as much or more in mole to form a mercapto compound at the 4-position of the pyrazolone. This is a method in which a thiol ether group is introduced into.

Disadvantages of this method include that the dihalogen used as a starting material is unstable to heat, that this method produces many by-products, and that the reaction does not proceed well when an alkyl mercaptan is used. . Furthermore, even if a group represented by -S-Z-B or -S-V-B (ZlB is defined later) is introduced into the active position by this method, the yield is extremely low and by-products that are difficult to separate are produced. It is inconvenient that there are many.

For example, if you synthesize 1,3-dimonosubstituted-4,4-dibromo-5-pyrazolone, dissolve it in acetonitrile or tetrahydrofuran, add more than twice the mole of thiophenol to the dibromo compound, and heat and stir, you will certainly get 1 ,3-
Di-monosubstituted-4-phenylthio-5-pyrazolone can be synthesized as the main product.

However, even in this case, it cannot be applied universally to all various mercapto compounds. 1,3
In the reaction of -dimonosubstituted-4,4-dibromo-5-pyrazolone with 3 times the mole of dodecyl mercaptan, the desired 4
-The reaction rate of alkylthio-5-pyrazolone is at most 20%
In addition, there are large amounts of 1,3-di-monosubstituted-5-pyrazolone (so-called active position unsubstituted-5-pyrazolone; 4-equivalent coupler) and 1,3-di-monosubstituted-4-monobromo-5-pyrazolone. It was a byproduct.

As described above, the selectivity decreases significantly depending on the type of mercaptan compound, so it cannot be said that it is an excellent synthesis method. R
esearchDisclOsurelO volume, boiled 138
In the method described in , bromine is added dropwise in the presence of a so-called 4-equivalent coupler which is unsubstituted at the coupling active position of the coupler and a heterocyclic mercapto compound to introduce a mercapto group into the coupling active position of the coupler. There are limitations on mercapto compounds for this method to proceed effectively;
Although it is effective for heterocyclic mercaptans and aryl mercaptans, it is difficult to say that it is a general method for alkyl mercaptans because it produces many by-products. Even with this method-
Mu D with S-C-B and -S-P-B
Even if the group shown is introduced into the active position, the yield is extremely low and many by-products which are difficult to separate are produced, which is disadvantageous.

For example, 3-acylamino-5-pyrazolone or 3-anilino-5-pyrazolone and 1-phenyl-2-mercaptotetrazole are dissolved in dimethylformamide, bromine is added, and 3-acylamino-4-(1-phenyltetrazole-2 -thio)-5-pyrazolone is obtained, but in addition to the target product, some by-products are present and purification is not easy.

When 1-phenyl-2-mercaptotetrazole and bromine are added to 3-cycloamino-5-pyrazolone in the same manner, the desired product can be synthesized relatively easily.

As described above, in this method, the behavior of the product differs depending on the type of the unsubstituted coupler at the active site of the mother nucleus, and the reaction does not proceed in the same way with solvents other than dimethylformamide. For example, carbon tetrachloride, ethanol,
It has the disadvantage that it does not proceed well in acetic acid. In particular, even if an alkylmercaptan is present in 1,3-di-monosubstituted-5-oxo-12-pyrazoline and bromine is added dropwise, only a small amount of the desired compound is produced, and a large amount of disulfide of the alkylmercaptan is produced. . Again, it can be concluded that this method is not suitable for introducing an alkylthio group into the coupling active position of the coupler. The first object of the present invention is to provide a novel synthetic method for introducing a thioether group into the coupling activity of color image-forming couplers.

The second object is to provide a method for producing 2-equivalent couplers having a thioether group in a simple manner and in high yield.

A third object is to provide a novel method for producing a 2-equivalent coupler in which a substituent that can be separated upon oxidative coupling with a paraphenylene diamine color developing agent is introduced into the coupling position of the color image-forming coupler.

The fourth object is to provide a practical method for producing color image-forming two-equivalent couplers.

The purpose of the present invention is to prepare a compound represented by the following general formula [] which has a -SH group introduced into the active site of a 4-equivalent yellow, magenta or cyan coupler, and to combine this compound with the following general formula []. By reacting with a compound, the following general formula [1]
This was achieved by obtaining a 2-equivalent coupler shown as

, where A represents a residue obtained by removing one hydrogen atom from the coupling active position of a yellow coupler, magenta coupler or cyan coupler.

R is an alkyl group, =C-B group, -N<o1 group, -
Represents either SO2Yl-P-B.

B is Y, -D-Y or -N. -, , represents the residue Q.

D represents an oxygen atom or -NR, one group, R1 represents a hydrogen atom, an alkyl group or an aryl group, or Y represents an alkyl, aryl or heterocyclic group, 1), QO)Q
represents a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle.

Z represents an oxygen atom or a sulfur atom. D1 represents a hydrogen atom, alkyl, aryl, acyl, or sulfonyl group, and D2 represents an alkyl, aryl, acyl group, or sulfonyl group. Further, Dl and D2 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle containing a nitrogen atom. X represents a halogen atom (for example, a chlorine atom or a bromine atom). The alkyl group represented by R represents a linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, a cyclic alkenyl group, or an aralkyl group.

Examples of straight-chain or branched alkyl groups include methyl, ethyl, isopropyl, n-butyl, t-butyl, hexyl, hepetadecyl, and the like. Specific examples of alkenyl groups are allyl and oleyl; examples of cyclic alkyl groups are cyclohexyl and cyclohexylmethyl; examples of cyclic alkenyl groups are cyclohexenyl; and examples of aralkyl groups are benzyl, p-nitrobenzyl, and β-phenylethyl. Of course, it is not limited to these. These groups include halogen atoms, nitro, cyano, alkoxy, aryloxy,
Carboxy, alkylcarbonyl, alkylthiocarbonyl, arylcarbonyl, -arylthiocarbonyl, alkoxycarbonyl, aryloxycarbonyl,
Sulfo, acyloxy, sulfamoyl, carbamoyl, thiocarbamoyl, acylamino, diacylamino,
Ureido, thioureido, urethane, thiourethane, sulfonamide, heterocycle, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialkylamino, anilino , N-arylanilino, N-alkylanilino, N-acylanilino, hydroxy, mercapto, etc. (the number of carbon atoms in the alkyl part of these substituents is preferably 1 to 2).
2). Y is preferably an alkyl, aryl, or heterocyclic group having 1 to 40 carbon atoms.

These alkyl groups in Y can be straight chain or branched alkyl (e.g. methyl, ethyl, isopropyl, butyl, isobutyl, dodecyl, stearyl, etc.), alkenyl (e.g. allyl, oleyl, etc.), cyclic alkyl (e.g. cyclopentyl, cyclohexyl group, etc.), aralkyl (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl (e.g., cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro, cyano, aryl, alkoxy, aryloxy, Carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido,
Sulfonamide, urethane, thiourethane, heterocycle (e.g. pyridyl, quinolyl, furyl, piperdyl group, etc.)
, arylsulfonyl, alkylsulfonyl, arylsulfonyloxy, alkylsulfonyloxy, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, optionally substituted with a substituted amino group (for example, N,N-diethylamino group, etc.) .

These aryl groups in Y include phenyl, naphthyl (α- or β-), substituted phenyl, substituted naphthyl (
It represents a polycyclic aryl group such as α- or β-), and these represent one or more than one alkyl, aralkyl, alkenyl, cyclic alkyl, cyclic alkenyl, halogen atom, nitro, cyano, aryl, alkoxy, aryloxy, Carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxysulfamoyl, N,N
-dialkylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-alkylsulfamoyl, N
-Arylsulfamoyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N
-Alkyl-N-arylcarbamoyl, N-arylcarbamoyl, acylamino, diacylaminoureido, thiouretodosulfonamide, urethane, thiourethane heterocycle (e.g. pyridyl, quinolyl, furyl, piperidyl group, etc.), alkylsulfonyl, arylsulfonyl, Alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, substituted amino groups (e.g. N,
represents a substituted aryl group which may be substituted with (N-dialkylamino, anilino, N-acylanilino, N-arylanilino group, etc.).

Furthermore, these heterocyclic groups in Y include nitrogen-containing heterocycles such as pyridyl, quinolyl, pyrrolidyl, etc.
Examples of heterocycles containing 1 or more nitrogen atoms include benzimidazolyl groups, which may be substituted with substituents for the above aryl groups, and oxygen-containing heterocycles (eg, tetrahydrofurfuryl, benzofuryl groups, etc.); These may be substituted with the above substituent for the aryl group.
8-containing sulfur heterocycle (for example, thienyl, benzothienyl group, etc., which may be substituted with a substituent for the above aryl group), or a heterocycle containing two or more heteroatoms of different types in the heterocycle Represents a cyclic group (eg, benzoxazolyl, benzothiazolyl group, etc.).

More preferably, Y represents the above-mentioned alkyl and aryl groups.

R1 represents an alkyl group, an aryl group, or a hydrogen atom having the same meaning as Y above.

On the other hand, -? ? :? Preferred heterocycles represented by include pyrrolidine, piperidine, morpholine, imidazole, benzimidazole, phthalimide, succinimide, glutarimide, hydantoin, oxazolidinedione, benzotriazole, α-pyridone, γ-pyridone, oxazolidone, valerolactam, butyrolactam,
Examples include thiohydantoin, naphthotriazole, tetrazole, pyrazole, indole, imidazoline, pyrazoline, piperazine, indoline, isoindoline, and the like.

D1 represents a hydrogen atom, an alkyl or aryl group having the same meaning as Y above, an acyl group such as acetyl, benzoyl, (2,4-di-t-amylphenoxy)acetyl group, etc., and a sulfonyl group such as methane, Sulfonyl, benzenesulfonyl, n-butanesulfonyl, p
-Represents a toluenesulfonyl group, etc.

The alkyl, aryl, acyl, and sulfonyl groups in D2 have the same meanings as in D1 above. Preferred examples of the 5- or 6-membered nitrogen-containing heterocycle containing a nitrogen atom formed by bonding Dl and D2 to each other include pyrrolidine, piperidine,
Morpholine, imidazole, benzimidazole, phthalimide, succinimide, glutarimide, hydantoin, oxazolidinedione, benzotriazole, alpha
- pyridone, γ-pyridone, oxazolidone, valerolactam, butyrolactam, thiohydantoin, naphthotriazole, tetrazole, pyrazole, indole,
imidazoline, pyrazoline, piperazine, indoline,
Examples include isoindoline. The yellow one-color image forming coupler residue represented by A includes pivaloylacetanilide type, benzoylacetanilide type, malondiamide type, benzothiazolylacetamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxa Preferred are zolylacetate-type, benzimidazolylacetamide-type, benzimidazolylacetate-type coupler residues, and residues derived from heterocycle-substituted acetamides and hexerocycle-substituted acetates contained in US Pat. No. 3,841,880.

Masenku 已 1 Bj Takuhira Rikito Nora One residue is 5-oxo-12-pyrazoline nucleus or pyrazolo-1 [1,5-a]
Coupler residues with a benzimidazole core are preferred.

Further, as the cyan image forming coupler residue, a coupler residue having a phenol nucleus or an α-naphthol nucleus is preferable.

The present invention is particularly effective when the residue represented by A is represented by the following general formula [IV], [, [VD, CV[), [or []].

In the ceremony υIL)i 18? S group group or heterocyclic group, 3
It represents a heterocyclic group. In the formula, R2
The aliphatic group represented by preferably has 1 to 22 carbon atoms,
It may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, and an acylamino group, which may themselves have further substituents. R2
Specific examples of aliphatic groups useful as are: isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-
dimethylbutyl group, 1,1-dimethylhexyl group, 1,
1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p
-Tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-
(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, etc. R2 or R
When 3 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted.

Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbohalamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamido groups, and alkylureido groups. group, an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl group of these substituents In addition, the total number of carbon atoms in the part is 1 to 22.
may be substituted with one or more alkyl groups. The phenyl group represented by R2 or R3 further has 1 to 1 carbon atoms.
Amino groups including those substituted with lower alkyl groups of 6,
It may be substituted with a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or a halogen atom.

R2 or R3 may also represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like.

These substituents may themselves have further substituents. When R2 or R3 is a heterocyclic group, each heterocyclic group is bonded to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group through one of the carbon atoms forming the ring. do.

Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, and oxazine. These may further have a substituent on the ring. In the general formula [v], R5 has 1 to 40 carbon atoms.
1, preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl,
hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aralkyl groups (e.g. benzyl, β-phenylethyl group, etc.)
, represents a cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl group, etc.), and these represent a halogen atom,
Nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacyl Amino group, ureido group, urethane group, thiourethane group,
Sulfonamide group, heterocyclic group, arylsulfonyl group,
Substituted with alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialsalamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. You can leave it there.

Furthermore, R5 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.).

The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. You may do so. More preferably, R is at least one ortho position.
Phenyl in which each group is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is useful because the coupler remaining in the film exhibits less coloring due to light or heat. Furthermore, R5 is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), heterocyclic group substituted with the substituents listed for the above aryl group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group, alkyl It may also represent a carbamoyl group, arylcarbamoyl group, alkylthiocarbamoyl group or arylthiocarbamoyl group.

In the formula, R4 is a hydrogen atom, having 1 to 40 carbon atoms, preferably 1
to 22 straight-chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have substituents listed for R5 above), aryl groups and heterocyclic groups (these are may have the substituents listed above for R), alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), carbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group,
heptadecyloxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), alkylthio group (e.g., ethylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino groups (e.g., acetylamino group, 3-[(2,4-di-Tert-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g. N-phenylacetamide group, etc.)
, ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (e.g. phenylamino,
N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5-tetradecanamideanilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.) , cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g. 4-pyridylamino group, 2-benzoxazolamino group, etc.), alkylcarbonyl group (e.g. methylcarbonyl group, etc.),
Arylcarbonyl group (e.g., phenylcarbonyl group), sulfonamide group (e.g., alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N -phenylcarbamoyl, etc.), sulfamoyl groups (e.g.,
N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), cyano represents any one of a group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group.

In the formula, R7 represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these represent the above-mentioned R5 may have the substituents listed above. Furthermore, R7 may represent an aryl group or a heterocyclic group, and these may represent the above-mentioned R5
may have the substituents listed above.

R7 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group , N-
It may also represent an arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group or a mercapto group.

R8, R, and RlO represent groups used in ordinary 4-equivalent phenol or α-naphthol couplers; specifically, R8 represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino group -0- Rll
or -S-Rll (where Rl is an aliphatic hydrocarbon residue), and when two or more R8s exist in the same molecule, the two or more R8s may be different groups, Aliphatic hydrocarbon residues include those having substituents.

R and RIO can be a group selected from an aliphatic hydrocarbon residue, an aryl group, or a heterocyclic residue, or one of these groups may be a hydrogen atom, and these groups may be substituted with a hydrogen atom. Including those with groups.
Further, R and RlO may jointly form a nitrogen-containing heterocyclic nucleus. ' is an integer of 1 to 4, m is an integer of 1 to 3, and n is an integer of 1 to 5. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). . Typical aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include groups such as aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. R2, R3, R4, R5, R6, R8 of the substituents of the coupler represented by the general formula [] to [],
R9, RlO integrate with each other, or either one is 2
The valence groups may form symmetrical or asymmetrical complex couplers.

The effect of the present invention is particularly large because A is a general formula [] or []
The present invention is applied to a 4-equivalent coupler represented by A-H.

The compound represented by the general formula () can be synthesized from the 4-equivalent coupler A1H by a well-known method. For example, an alkaline solution of a coupler with no substitution at the coupling active site (for example, 1
, a coupler anion solution prepared by adding sodium hydride to a tetrahydrofuran solution of 3-di-monosubstituted-5-oxo-2-pyrazoline, etc.) at -100 to 100°C.
By dropping a solution of elemental sulfur dissolved in a suitable solvent in a temperature range of 100 to 100 ml and continuing stirring, it is possible to synthesize a compound in which a mercapto group is substituted at the coupling active position of the desired coupler. However, since this method produces a small amount of by-products, the following method is preferable. Yellow one,
A monohalogen compound in which one of the hydrogen atoms in the coupling active position of magenta and cyan couplers is replaced with a halogen atom (
For example, monochlor, monopro, etc.; these halogens can be synthesized by known methods, such as the method described in US Pat. No. 3,006,759.

) is used as a starting material, 1 to 10 times the molar amount of thiourea is added to convert it into a thiuronium salt, and this is hydrolyzed with an alkali to produce a mercapto compound represented by the general formula [ ], which is the starting material of the present invention. Obtainable. intermediates in the middle,
The synthesis of the thiuronium salt is not limited to thiourea, and for example, N-alkylthiourea, N,N'-dialkylthiourea, 5-membered ring, and 6-membered cyclic thiourea derivatives can also be used. Here, we will discuss the general synthesis method for thiourea, but solvents used for thiouronium salt synthesis include alcoholic solvents (e.g., methanol, ethanol, etc.), aromatic solvents (e.g., benzene, toluene, etc.), and organic solvents. Carboxylic acid solvents (e.g., formic acid, acetic acid, etc.), halogenated hydrocarbon solvents (e.g., chloroform, ethylene chloride, etc.), aprotic basic solvents (e.g.,
Examples include dimethylformamide, dimethyl sulfoxide), other ester solvents, acetonitrile, etc., but alcoholic solvents are preferred. The reaction temperature can be in the range of -10 to 200°C, but -52 to 80°C is particularly preferred. Regarding the following hydrolysis conditions, the thiuronium salt can be isolated and dissolved or suspended in the above solvent, or the thiuronium salt can be isolated without being isolated. As a base,
Examples include alkali hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), alkali metal alkoxides (e.g., sodium, methoxide, etc.), organic bases (e.g., triethylamine, DBUL, sodium acetate, etc.), and alcohols of alkali hydroxides. A solution is preferred. The amount added can range from 1 to 20 times the molar amount of the thiuronium salt, but an appropriate amount is 1 to 5 times the molar amount. The reaction temperature is -101 ~
It can be carried out in the range of 100℃, but -51 to 50℃
C is particularly preferred. In this way, mercapto compounds represented by the general formula 1 can be synthesized in substantially pure form. Next, the reaction between the mercapto compound represented by the general formula [] and the halogen compound represented by the general formula [], which is the object of the present invention, will be described in detail. The halogen compound represented by the general formula [] can be used in an amount of 1 to 10 times the molar amount of the mercapto compound, preferably 1 to 2 times the molar amount.

As reaction solvents, the alcoholic solvents, aromatic solvents, organic carboxylic acid solvents mentioned in the above thiuronium salt synthesis,
Although aprotic basic solvents, ester solvents, acetonitrile, etc. can be used, alcoholic solvents and halogenated hydrocarbon solvents are preferred. The reaction temperature is -10°~20°
It can be carried out at a temperature in the range of 0°C, but a range of -5°C to 100°C is particularly preferable. As the base catalyst, alkali hydroxide (e.g., sodium hydroxide, potassium hydroxide, etc.),
Alkali metal alkoxides (e.g., sodium methoxide, sodium ethoxide, etc.), organic bases (e.g., triethylamine, DBU, pyridine, sodium acetate, etc.) are preferred, and the amount added can be 1 to 10 times the molar amount, but 1 to 2 times. Molar amounts are particularly preferred, and it is preferred to keep the reaction vessel filled with an inert gas (eg nitrogen, argon, etc.) during the reaction. After the reaction is complete, extract with a water-insoluble solvent (e.g., ether, chloroform, ethyl acetate, benzene, hexane, etc.) that has a high extraction power for organic compounds.
By concentrating, a compound of general formula [I] can be obtained. In addition, any starting material for obtaining the compound of the general formula [I] is not required to proceed by isolating the former mercapto compound, but it is necessary to carry out the process from the thiuronium compound in the previous step consistently in the reaction vessel. Hydrolysis and thioetherification may be performed, or thiuroniumization, hydrolysis, and thioetherification may be performed consistently from a monohalogen compound in which one halogen atom is substituted at the coupling active position of the coupler one step before the thiuronium compound. You may do so.

Furthermore, if the monohalogen compound is unstable and cannot be successfully isolated, the desired product can be obtained by consistently carrying out halogenation, thiuronation, hydrolysis, and thioetherification from a 4-equivalent coupler. For example, in the case of 3-anilino-5-pyrazolones whose monohalogens are not easily isolated, a halogenating agent is added to a system in which a thiourea compound and a 4-equivalent coupler are simultaneously dissolved, and a thiuronium salt is synthesized in a consistent manner. It is preferable to do so. Next, the general formula [
Preferred halogen compounds represented by [□] are illustrated below, but the invention is not limited thereto.

According to the production method of the present invention, couplers having alkylthio, acylthio, and phosphorylthio groups, which could not be easily synthesized by methods known in the literature, can be synthesized.

Furthermore, according to the production method of the present invention, at the end of the reaction, the target compound is the main product, and it can be easily separated and produced simply by recrystallization, without using complicated separation methods such as column chromatography. can. Examples of two-equivalent couplers that can be synthesized according to the present invention include the following.

Specific examples of the present invention are shown below, but the present invention is not limited thereto.

Example (1) 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2,4,6-trichlorophenyl)-4-ethylthio-2-pyrazolin-5-one Synthesis step of [Coupler (22)] 1 S-{3-[3-(2,4-di-Tert-amylphenoxy)acetamide]benzamide 1-(2,4,6
-trichlorophenyl)-2-pyrazolin-5-one-
Synthesis of 4-yl}-isothiuronium hydrobromide 509 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-4-bromo-
1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-one and 559! of thiourea was dissolved in 250 ml of methanol.

This solution was stirred at room temperature (20°C) for 1 hour. The reaction mixture was gradually added to 500 d of water with stirring, and the precipitated solid was filtered and dried. 559 pieces of the desired product as a white solid were obtained. Step 2 Synthesis of 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1(2,4,6-trichloropheno(ha)-4-mercapto-2-pyrazolin-5-one) 16g of potassium hydroxide in 400m
1 in methanol.

After passing nitrogen gas into this reaction vessel and replacing it with nitrogen,
The isothiuronium salt obtained in Step 1 was added as 559 powder and stirred at room temperature for 1 hour. The reaction mixture was gradually added to 800 ml of 1N diluted hydrochloric acid with stirring, and the precipitated solid was filter-dried. The desired product, pale yellow solid 489, was obtained. This solid was used in the next step without purification. Step 3 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2,4,6-trichloropheno(ha)-4-ethylthio-2-pyrazolin-5-one) Synthesis of Coupler (22)] 12 g of potassium hydroxide was dissolved in 400 Tn1 of methanol.

After passing nitrogen gas into this reaction vessel and replacing it with nitrogen,
3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2
,4,6-trichlorophenyl)-4-mercapto-2
-Pyrazolin-5-one was added as 489 powder and dissolved. Then 12.59 parts of ethyl iodide was added. This solution was stirred at room temperature for 1 hour. Ethyl acetate 11 was added, transferred to a separation load, and washed with 11 water. Separate the oil layer, 1
After washing with N diluted hydrochloric acid, it was further washed twice with water 11. After drying the oil layer over sulfuric acid (anhydrous), ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain the desired product 369. The melting point was 138-140°C. Example (2) 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-4-carbamoylmethylthio-1-(2,4,6-trichlorophenyl)-2
-Pyrazolin-5-one [Coupler (23) 7) Synthesis] In step 3 of Example (1), instead of ethyl iodide,
A similar procedure was carried out using chloroacetamide 119.

The desired coupler 329 was obtained by recrystallization from a mixed solvent of acetonitrile and ethyl acetate. Melting point is 157-159
It was warm at ℃. Example (3) 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2,4,6-trichlorophenyl)-4-(2-methanesulfonamido)ethylmercapto -2-
Pyrazolin-5-one [Synthesis of coupler (24)] S-{3-[3-(2,4-di-Tert-amylphenoxy) obtained in Step 1 of Example (1)] was placed in a reaction vessel purged with nitrogen. acetosamide]benzamide-1-(2,4,
22 g of 6-trichlorophenyl)-2-pyrazolin-5-one-4-yl}isothiuronium salt was added to 1 part of methanol.
It was dissolved in 00ml.

To this solution was added a solution of 7.49 ml of potassium hydroxide dissolved in 40 ml of methanol. After stirring for 1 hour at room temperature, 6.3 g of 2-methanesulfonamidoethyl chloride was added. Stirred at room temperature for 2 hours. Ethyl acetate 11 was added, transferred to a liquid separation load, and washed with water 12. The oil layer was separated, washed with 1N diluted hydrochloric acid and then with water, and dried over sodium sulfate (anhydrous). Ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain the desired product 159.
The melting point was 147-149°C. Example (4) 1-(2,4,6-trichlorophenyl)-3-(2,
4-dichloro-5-methoxy)anilino-4-dodecylthio-2-pyrazolin-5-one [Coupler (25
) Synthesis of 459 1-(2
,4,6-trichlorophenyl)-3-(2,4-dichloro-5-methoxy)-anilino-2-pyrazoline-5
-one and 7.6 g of thiourea were dissolved in 250 d of N,N-dimethylformamide.

Bromine 169 was added dropwise below 10°C.

A solution of 259 potassium hydroxide dissolved in 120 ml of methanol was added to this solution. The reaction temperature was gradually raised to room temperature and stirred for 1 hour. Next, 22f1 of dodecyl mercaptan was added and stirred for 2 hours. Ethyl acetate 11 was added, transferred to a separation load, and washed with 11 water. The oil layer was separated, washed with 1N diluted hydrochloric acid, and further washed twice with water 12. After drying the oil layer over sodium sulfate (anhydrous), ethyl acetate was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethyl acetate and acetonitrile to obtain the desired product 219. The melting point was 100-102°C. Example (5) 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2,4,6-trichlorophenyl)-4-(2-ethoxyethylthio)
-2-pyrazolin-5-one [Synthesis of coupler (33)] Synthesized in the same manner as in Example (1).

However, in place of the ethyl iodide used in Example (1), an equimolar amount of 2-ethoxyethyl bromide was used. The desired coupler was recrystallized from a mixed solvent of ethyl acetate and acetonitrile. Example (6) 4-Carbamoylmethylthio-1-(2,4,6-trichlorophenyl)-3-(2-chloro5-myristoylamino)anilino-2-pyrazolin-5-one [Coupler (35)] Synthesis] Synthesis was performed in the same manner as in Example (4).

However, 1-(2,4,6-trichloropheno(c)-3-(2,4-dichloro-5) used in Example (4)
-methoxy)anilino-2-pyrazolin-5-one instead of 1-(2,4,6-trichlorophenyl)-3-(
2-chloro-5-myristoylamino)-anilino-2
-Pyrazolin-5-one was used in place of dodecyl mercaptan by replacing each equimolar amount of chloroacetamide. Example (7) 2-Carbamoylmethylthio-2-pivaloyl Z-chloro-5'-{3-(2,4-di-Tert-amylphenoxy)butyramide}acetanilide [Synthesis of coupler (3)] Example It was synthesized by the same method as (2).

However, 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-4-bromo-1-(2,4,6-trichlorophenyl)-2-pyrazoline used in Example (2) -5-one in place of an equimolar amount of 2-chloro-2-pivaloyl-2-chloro-5-{3
-(2,4-di-Tert-amylphenoxy)-butyramide}acetanilide was used. Example (8) 4-ethoxycarbonylmethylthio-1-hydroxy-
2-Naphthoic acid-N-dodecylamide [coupler (44
)] was carried out in the same manner as in step 3 of Synthesis Example (1).

However, 3-{3-(2,4-di-Tert-amylphenoxy)acetamide}benzamide-1-(2,4,
6-Trichlorofenino(ha)-4-mercapto-2-
In place of pyrazolin-5-one, an equimolar amount of 1-hydroxy-4-mercapto-2-naphthoic acid-N-dodecylamide was used, and in place of ethyl iodide, an equimolar amount of ethyl bromoacetate was used. It was used. Comparative Example 1 3-{3-[α-(2,4-di-Tert-amylphenoxy)butanamide]}benzamide-4,4-dibromo-1-(2,4,6-trichlorophenyl)-2-
Reaction of pyrazolin-5-one and decanethiol 109 3-{3-[α-(2,4-di-Tert-amylphenoxy)butanamide]}benzamide-4,4-dibromo-1-(2,4,6 -trichlorophenyl)-2-
Pyrazolin-5-one was dissolved in 200 ml of tetrahydrofuran.

Claims (1)

[Scope of Claims] 1. A compound represented by general formula [II] and general formula [III] in a method for producing a coupler represented by general formula [I]
A method characterized by reacting with a halogen compound represented by the general formula [I] A-S-R General formula [II] A-SH General formula [III] X-R In the above general formula, R is an alkyl group , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, -SO_2-Y, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
represents. B represents a residue of -Y, -D-Y or ▲which has a mathematical formula, chemical formula, table, etc., where D is an oxygen atom or -
NR_1- group, R_1 represents a hydrogen atom, an alkyl group, or an aryl group, and Y represents an alkyl, aryl, or heterocyclic group; Represents a group of nonmetallic atoms necessary to form a nitrogen heterocycle. Z represents an oxygen atom or a sulfur atom. D_1 represents a hydrogen atom, alkyl, aryl, acyl or sulfonyl group, and D_2 represents an alkyl, aryl, acyl or sulfonyl group. Also D_1
, D_2 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle containing a nitrogen atom. X represents a halogen atom. In addition, in the above general formula, A is the following general formula [I
V], [V], [VI], [VII], [VIII] or [IX]
It is represented by. General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VIII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IX] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (General formulas (IV) to (IX) Wherein, R_2 represents an aliphatic group, aromatic group or heterocyclic group, R_3 represents an aromatic group or heterocyclic group, and R_4 represents a hydrogen atom, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group. group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carboxy group, acylamino group, diacylamino group, N-alkylacyl Amino group, N-arylacylamino group, ureido group, urethane group, thiourethane group, arylamino group, alkylamino group, cycloamino group, heterocyclic amino group, alkylcarbonyl group, arylcarbonyl group, sulfonamide group, carbamoyl group, sulfamoyl group, cyano group, hydroxy group, mercapto group, halogen atom, or sulfo group, and R_5 represents an alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, cyclic alkenyl group, aryl group, heterocyclic group, aliphatic group. R_7 represents a hydrogen atom, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, cyclic alkenyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, halogen atom, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfo group, sulfamoyl group, carbamoyl group,
Acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N -alkylanilino group,
N-acylanilino group, hydroxy group, or mercapto group, R_8 is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino group, -O-R_1_1 or -S-R_1_1 (however, R_1_1 is an aliphatic hydrocarbon residue ), R_9 and R_1_0 can represent a group selected from an aliphatic hydrocarbon residue, an aryl group or a heterocyclic residue, or one of them may be a hydrogen atom, and l is 1 to An integer of 4, m is 1~
An integer of 3, n is an integer of 1 to 5. )