JP2001039980A - Arylidene compound and silver halide photographic photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as e.g. a dyestuff for dyeing various materials, dyestuff for coating materials and silver halide color-photosensitive materials, and having hardly any load in its synthesis and longer wavelengths in absorption region. SOLUTION: This compound is a compound of formula I (A is an acidic nucleus of formula II; R1 to R4 are each H or a substituent, R5 and R6 are each H, an alkyl, aryl or the like, and R1 and R2, R2 and R5, R5 and R6, R4 and R6, and R3 and R4 can each form a ring by binding to each other; (n) is 0-3; R7 to R9 are each H or a substituent; M is oxygen or sulfur; and *indicates a bound position with methine on the right side of the nucleus A in formula I), for instance, a compound of formula III. The compound of formula I is obtained, for instance, in the case of the above illustrated compound, by reacting a compound of formula IV obtained through e.g. reaction between an aminopyrrole form and ethoxycarbonyl thioisocyanate with a compound of formula V in acetic acid in the presence of acetic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
a] The present invention relates to a novel arylidene compound having a -1,3,5-triazine skeleton, and further relates to a silver halide photosensitive material containing the novel arylidene compound as a dye.

[0002]

2. Description of the Related Art An arylidene compound is a compound useful as a dye, and is used for dyeing a fiber, or added to a paint or a silver halide photographic material. For example, in the use of a silver halide photographic light-sensitive material, a dye is added to a silver halide emulsion layer and / or a non-photosensitive hydrophilic colloid layer in order to absorb light in a specific wavelength range. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the silver halide emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of silver halide emulsion layers, the filter layer may be located between them. Light scattered when passing through or after passing through the silver halide emulsion layer is reflected at the interface between the emulsion layer and the support or on the surface of the photosensitive material on the opposite side of the silver halide emulsion layer and again. An antihalation layer is provided on the surface opposite to the silver halide emulsion layer between the silver halide emulsion layer and the support or between the support for the purpose of preventing the image from being blurred due to the incident light, i.e., the halation. Is provided.
When there are a plurality of silver halide emulsion layers, an antihalation layer may be provided between the layers. Coloring of the silver halide emulsion layer has also been performed to prevent a reduction in image sharpness due to light scattering in the silver halide emulsion layer (this is called irradiation prevention). These hydrophilic colloid layers to be colored usually contain a dye. Dyes used for these must satisfy the following conditions.

(1) To have appropriate spectral absorption. The specific absorption wavelength range is determined according to the purpose of use of the dye. (2) Photochemically inert. Chemical adverse effects on the performance of the silver halide emulsion layer, for example,
Changes in sensitivity, effects on the storage stability of the latent image, and fogging must not occur. (3) Decolorization or removal performance in photographic processing. The dye functions in principle at the time of exposing the image, and after exhibiting the function, the image is contaminated by the dye unless it is quickly decolorized or removed from the silver halide photographic material. Accordingly, the dye is used in a photographic processing solution (a developing solution or /
And bleaching solution) or heating or the like. (4) Diffusion resistance Since the dye functions in a specific layer of the silver halide photographic material, a problem arises when the dye is diffused into another layer. For example,
When the dye added to the non-photosensitive hydrophilic colloid layer for the purpose of preventing halation diffuses into the silver halide emulsion layer, the sensitivity of the silver halide is reduced. (5) Stability During storage of the dye, for example, during storage as a solution of the dye or a silver halide photographic light-sensitive material, no discoloration or fading should occur.

On the other hand, in recent years, dyes having long-wave absorption which can be used for photographic light-sensitive materials sensitive to near-infrared light have been demanded, and a dye having a pyrazolopyridone skeleton in an acidic nucleus is disclosed in JP-A-3-7931. Have been. However, in order to further increase the absorption wavelength of the dyes described above, it is necessary to increase the number of vinyl groups to increase the number of conjugated systems, which increases the load on synthesis. Had. In addition, benzylidene dyes have high nucleophilic reactivity and deteriorate the storage stability of the dye, making it difficult to achieve both storage stability and decolorization.

[0005]

SUMMARY OF THE INVENTION
An object of the present invention is to provide an arylidene compound useful as a dye for dyeing various materials, a paint or a dye for a silver halide color light-sensitive material. Another object of the present invention is to provide a novel arylidene compound which has a small load on synthesis and has a longer absorption range. Another object of the present invention is to provide a dye for a silver halide photographic light-sensitive material which is advantageous from the viewpoint of cost and is excellent in photographic properties such as preservability and decolorization.

[0006]

The object of the present invention has been attained by the following means. [1] An arylidene compound represented by the following general formula (1). General formula (1)

[0007]

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In the formula, A represents an acidic nucleus represented by the following general formula (2), and R _{1 to} R ₄ represent a hydrogen atom or a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; R ₁ and R ₂ , R ₂ and R ₅ , R ₅ and R ₆ , R ₄ and R ₆ , or / and R ₃ and R ₄ can be bonded to each other to form a ring. n represents an integer of 0 to 3. General formula (2)

[0009]

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R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom or a substituent, and M represents an oxygen atom or a sulfur atom.
* Represents a bonding position to the methine group on the right side of A in the general formula (1). [2] A silver halide photosensitive material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support,
A silver halide light-sensitive material, wherein the silver halide emulsion layer and / or the non-light-sensitive hydrophilic colloid layer contains the arylidene compound described in 1 above. [3] The arylidene compound according to the above item 1, wherein R _{9 of the} acidic nucleus represented by the general formula (2) is an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group. A silver halide light-sensitive material containing said compound. [4] R ₁ represented by the general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, or a carbamoylamino group, and R ₂ , R ₃ , and R ₄ Is a hydrogen atom, R ₅ and R ₆ are alkyl groups, and R _{9 of the} acidic nucleus represented by the general formula (2) is an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group. 3. An arylidene compound as described in the above item 1 and a silver halide photosensitive material containing the compound as described in the above item 2. [5] R ₁ represented by the general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, or a carbamoylamino group, and R ₂ , R ₃ , and R ₄ Is a hydrogen atom, R ₅ and R ₆ are alkyl groups, R _{7 of the} acidic nucleus represented by the general formula (2) is an alkyl group or an aryl group, R ₈ is an alkoxycarbonyl group, a carbamoyl group,
The arylidene compound according to the above 1, wherein the arylidene compound is a cyano group, an alkylsulfonyl group, or an arylsulfonyl group, and R ₉ is an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group. 2. A silver halide light-sensitive material containing the compound described in 2. [6] R ₁ represented by the general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group,
R ₂ , R ₃ , and R ₄ are hydrogen atoms, R ₅ and R ₆ are alkyl groups, and R 2 of the acidic nucleus represented by the general formula (2)
₇ is an alkyl group or an aryl group, R ₈ is an alkoxycarbonyl group, a carbamoyl group, a cyano group, an alkylsulfonyl group, or an arylsulfonyl group;
_9. The arylidene compound according to the above item 1, wherein ₉ is an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group, and a silver halide photosensitive material containing the compound as described in the above item 2. Achieved by

The arylidene compound represented by the general formula (1) will be described in detail below. A represents an acidic nucleus represented by the general formula (2). The acidic nucleus represented by the general formula (2) will be described in more detail. R ₇ , R ₈ and R ₉ in the general formula (2) each independently represent a hydrogen atom or a substituent, and the substituent is a halogen atom (for example,
Fluorine, chlorine, bromine, iodine), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, dodecyl, hexadecyl, octadecyl, Isopropyl, 2-ethylhexyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, adamantyl,
Trifluoromethyl),

An alkenyl group (preferably having 2 to 48 carbon atoms)
Alkenyl group of, for example, vinyl, hexadecenyl,
Octadecenyl, cyclohexenyl), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, for example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably having 1 to 32 carbon atoms, 5 to 5 carbon atoms) 8-membered heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl) , A cyano group, a silyl group (preferably a silyl group having 3 to 36 carbon atoms, for example, trimethylsilyl, triethylsilyl, toshibutylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl),
Hydroxyl group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 38 carbon atoms, for example, methoxy,
Ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 38 carbon atoms, for example, phenoxy, 2- Naphthoxy), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 38 carbon atoms, for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably Is a silyloxy group having 1 to 38 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 38 carbon atoms, for example, acetoxy, pivaloyloxy, Benzoyloxy, Decanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 38 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably An aryloxycarbonyloxy group having 7 to 38 carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 38 carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy),

A sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 38 carbon atoms;
N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy ),
Arylsulfonyloxy (preferably having 6 to 38 carbon atoms)
An arylsulfonyloxy group, for example, phenylsulfonyloxy), a carboxyl group, an acyl group (preferably an acyl group having 1 to 38 carbon atoms, for example, formyl,
Acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexylcarbonyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 38 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxy A carbonyl group (preferably an aryloxycarbonyl group having 7 to 38 carbon atoms such as phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 38 carbon atoms such as carbamoyl, N, N-dibutylcarbamoyl,
-Ethyl-N-octylcarbamoyl, N-propylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having a carbon number of 38 or less, for example, amino, methylamino, N, N-dioctylamino, tetra Decylamino, octadecylamino,
Cyclohexylamino), anilino group (preferably anilino group having 6 to 38 carbon atoms, for example, anilino, N-methylanilino), and heterocyclic amino group (preferably having 1 carbon atom)
-38 heterocyclic amino groups, for example, 4-pyridylamino), carbonamido group (preferably having 2 to 38 carbon atoms)
And a ureido group (preferably a ureido group having 1 to 38 carbon atoms, such as ureido,
N, N-dimethylureido, N-phenylureido),
An imide group (preferably an imide group having 24 or less carbon atoms, for example, N-succinimide and N-phthalimido), an alkoxycarbonylamino group (preferably having 2 to 38 carbon atoms)
And for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino)

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 38 carbon atoms, for example, phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 38 carbon atoms, for example, Methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexylsulfonylamino), sulfamoylamino group (preferably a sulfamoylamino group having 1 to 38 carbon atoms, for example, N, N-dipropyls) Rufamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1 to 3 carbon atoms)
8 azo groups, for example, phenylazo), alkylthio groups (preferably alkylthio groups having 1 to 38 carbon atoms, such as ethylthio, octylthio, cyclohexylthio), and arylthio groups (preferably arylthio groups having 6 to 38 carbon atoms). For example, phenylthio) heterocyclic thio group (preferably a heterocyclic thio group having 1 to 38 carbon atoms, for example, 2-benzothiazolylthio, 2-pyridylthio,
1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 38 carbon atoms, for example, dodecanesulfinyl), and an arylsulfinyl (preferably an arylsulfinyl group having 6 to 38 carbon atoms, for example, phenyl Sulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 38 carbon atoms, for example, methylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 38 carbon atoms, for example, Phenylsulfonyl, 1-naphthylsulfonyl), sulfamoyl group (preferably a sulfamoyl group having a carbon number of 38 or less, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecyls) Famoyl), a sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 38 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (diethoxyphosphinoylamino, Dioctyloxyphosphinoylamino group).

These substituents may further have the substituents described above, if further substitution is possible,
When substituted by two or more substituents, those substituents may be the same or different. M in the general formula (2) represents an oxygen atom or a sulfur atom.

Next, R _{1 to} R ₆ in the general formula (1) and n will be described in detail. R _{1 to} R ₄ represent a hydrogen atom or a substituent, and the substituents of R _{1 to} R ₄ are the same as those described above for R ₇ ,
It represents a group having the same meaning as the groups described for the substituents of R ₈ and R ₉ . When these substituents of R _{1 to} R ₄ are further substitutable groups, they may be substituted with groups having the same meanings as the substituents of R ₇ , R ₈ and R ₉ described above. And when substituted with two or more substituents, those substituents may be the same or different.

[0017] R ₅ and R ₆ represent each independently a hydrogen atom or an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, R ₁
And R ₂ , R ₂ and R ₅ , R ₅ and R ₆ , R ₄ and R ₆ , and / or R ₃
And R ₄ can combine with each other to form a ring. The alkyl group, the aryl group, the heterocyclic group, the acyl group, the alkylsulfonyl group, and the arylsulfonyl group of R ₅ and R ₆ are the same as the alkyl group, the aryl group, and the hetero ring described for R ₇ , R _8, and R ₉ above. Represents a group having the same meaning as the group, acyl group, alkylsulfonyl group, and arylsulfonyl group. R ₅
And when these groups of R ₆ are further substitutable groups, they may be substituted with groups having the same meanings as the substituents of R ₇ , R ₈ and R ₉ described above. When substituted by the substituents, these substituents may be the same or different. n represents an integer of 0 to 3.

Next, a preferred range of the arylidene compound represented by the general formula (1) will be described. General formula (1)
A preferred range of the acidic nucleus represented by A will be described. M is preferably an oxygen atom. R ₇ is an alkyl group,
An aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group are preferable, and an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxycarbonyl group, and a carbamoyl group are more preferable. Most preferred R ₇ includes an alkyl group and an aryl group.

R ₈ represents an alkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfinyl group, an arylsulfinyl, an alkylsulfonyl group, an aryl group. Sulfonyl group,
Sulfamoyl, sulfo and phosphonyl groups are preferred. More preferred R ₈ is a trifluoromethyl group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfinyl group, an arylsulfinyl, an alkylsulfonyl group, Examples include an arylsulfonyl group, a sulfamoyl group, and a phosphonyl group. Most preferred R ₈ is an alkoxycarbonyl group,
Examples include a cyano group, a carbamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

R ₉ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, a carbonamide group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an alkylthio group, an arylthio group. , A heterocyclic thio group, an alkylsulfinyl group,
Alkylsulfonyl, arylsulfonyl, and phosphinoylamino groups are preferred. More preferably, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamide group, a ureido group, an alkoxycarbonylamino group,
Sulfonamide group, alkylthio group, arylthio group,
Heterocyclic thio, alkylsulfonyl and arylsulfonyl groups are preferred. Most preferred R ₉ includes an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group.

Specific examples of the acidic nucleus represented by A are shown below, but the present invention is not limited thereto.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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Next, preferred ranges of R ₁ to R ₆ of the arylidene compound represented by the general formula (1) will be described. R ₁ and R ₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carboxyl group, an alkoxycarbonyl Group, a carbamoyl group, a carbonamide group, a ureido group, an alkoxycarbonylamino group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, more preferably, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, and a hetero group. Examples include a ring group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamide group, a ureido group, and an alkoxycarbonylamino group. Most preferably, R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carbonamido group, an alkoxycarbonylamino group, or a carbamoylamino group, and R ₃ is a hydrogen atom.

R ₂ and R ₄ each independently represent a hydrogen atom,
Halogen atom, alkyl group, aryl group, cyano group, alkoxy group, carboxyl group, alkoxycarbonyl group, carbamoyl group, carbonamide group, ureido group,
An alkoxycarbonylamino group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, a ureido group, and an alkoxycarbonylamino group are more preferable. Most preferably, it is a hydrogen atom.

R ₅ and R ₆ are preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group. Most preferably, an alkyl group is mentioned.

R ₁ and R ₂ , R ₂ and R ₅ , R ₅ and R ₆ , R ₄ and R ₆ , or / and R ₃ and R ₄ may be bonded to each other to form a ring. When R ₁ and R ₂ or R ₃ and R ₄ are bonded, preferably an aromatic ring such as a 5- or 6-membered benzene ring or a pyridine ring, an imidazole ring, a thiazole ring, a pyrimidine ring or the like is used. Aromatic heterocycles are preferred.

R ₂ and R ₅ or / and R ₄ and R ₆ may combine to form a ring. R ₂ and R ₅ or / and R ₄ and R ₆
Is preferably bonded to form a 5-, 6- or 7-membered saturated ring, more preferably a 5- or 6-membered saturated ring. R ₅ and R ₆ may combine to form a ring, and when R ₅ and R ₆ combine to form a ring, 5
A 6-membered, 6-membered or 7-membered saturated ring is preferred, and a pyrrolidine ring, a piperidine ring or a morpholine ring is particularly preferred.

N represents an integer of 0 to 3, preferably 0, 1, or 2, and most preferably 0 or 1.

Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited by these.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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Next, specific synthesis examples of the compound of the present invention will be described. (Synthesis Example 1) (Synthesis of Exemplified Compound B-1) Reaction Scheme A is shown below. Reaction Scheme A

[0045]

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(Synthesis of Intermediate C) To 15.6 g (0.0.38 mol) of the aminopyrrole derivative (Intermediate C), 50 ml of dimethylacetamide was added, and the mixture was cooled to 10 ° C. or lower and stirred. To this solution was added dropwise 5.0 g (0.038 mol) of ethoxycarbonylthioisocyanate (intermediate B). After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. Water and ethyl acetate were added to the reaction solution for extraction. This ethyl acetate solution was washed with water, and ethyl acetate was distilled off under reduced pressure. The residue was separated and purified by silica gel column chromatography (eluent: n-hexane / chloroform = 1/2). The eluate was concentrated to dryness. 13.5 g of intermediate C
(66.9%).

(Synthesis of Intermediate D) 13.5 g (0.025 mol) of the thiourea compound (intermediate C) obtained by the above method.
3.75 ml of triethylamine and 65 ml of tetrahydrofuran were added to the mixture, and the mixture was heated to 60 ° C. and stirred for 3 hours.
After the reaction solution was cooled to room temperature, it was neutralized with concentrated hydrochloric acid and extracted with water and ethyl acetate. The ethyl acetate solution was washed with water and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. 50 ml of toluene in the residue
Was added to precipitate crystals. The crystals were filtered and dried. 12.0 g (96.8%) of intermediate D was obtained.

(Synthesis of Intermediate E) To 12.0 g (0.024 mol) of the thione compound (intermediate D) obtained by the above method, 10.0 g of potassium carbonate and 50 ml of dimethylacetamide were added.
Was added and heated to 60 ° C. and stirred. 4.87 g (0.0252 mol) of 2-ethylhexyl bromide was added to this solution.
Was added dropwise. After completion of the dropwise addition, the mixture was heated and stirred at 55 ° C to 60 ° C for 6 hours to complete the reaction. After the reaction solution was filtered to remove inorganic substances, water and ethyl acetate were added to the filtrate for extraction.
This ethyl acetate solution was acidified with diluted hydrochloric acid and then washed with water,
Dry over anhydrous sodium sulfate. This ethyl acetate solution was concentrated under reduced pressure. The residue was purified by recrystallization from a mixed solvent of hexane / ethyl acetate. 12.1 g of intermediate E
(82.9%). ¹ H NMR (CDCl ₃ ) δ (ppm) 7.55 (s, 1H), 7.40 to 7.20 (m, 5H), 7.00 (s, 1H), 5.8
5 (s, 1H), 3.45-3.25 (m, 2H), 1.78-0.60 (m, 43H)

(Synthesis of Exemplified Compound B-1) 6.08 g (0.01 mol) of the coupler (intermediate E) obtained by the above method and 4.2 g (0.012) of the aldehyde compound (intermediate F).
Mol) was added, and the mixture was stirred at room temperature. 15 ml of acetic anhydride was added to this solution, heated to 80 ° C. to 90 ° C., and stirred for about 3 hours. After completion of the reaction, the reaction solution is
Poured into 0 ml and extracted with ethyl acetate. After washing the ethyl acetate solution with water and drying over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: n-hexane /
Purification was performed using ethyl acetate (10/1). Exemplified compound B-1
6.68 g (71.6%) of powder was obtained. The maximum absorption wavelength (visible) in methanol was 622 nm.

(Synthesis Example 2) (Synthesis of Exemplified Compound B-57) The compound was synthesized according to the following reaction scheme B.

[0051]

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6.07 g of a coupler (intermediate E) (0.0
1 mol) and 50 ml of acetic acid to the aldehyde compound (intermediate G) and stirred at room temperature. 15 ml of acetic anhydride was added to this solution, heated to 80 to 90 ° C., and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 400 ml of water and extracted with ethyl acetate. The ethyl acetate solution was washed with water and dried over anhydrous magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. A mixed solvent of n-hexane / ethyl acetate = 1/1 was added to the residue, and the mixture was stirred at room temperature to precipitate crystals.
The crystals were filtered and dried. 5.83 g (76.2%) of crystals of the exemplary compound B-57 were obtained. The maximum absorption wavelength (visible) in methanol was 670 nm.

[0053]

Example 1 (Comparison of maximum absorption wavelength) Compound 37 (Comparative Compound A) and Compound 42 (Comparative Compound B) described in JP-A-3-7931 and exemplified compounds B-1 and B- of the present invention. 57 and the maximum absorption wavelength in a dimethyl sulfoxide solution.
The results are shown in Table 1.

[0054]

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[0055]

[Table 1]

The compound of the present invention has a maximum absorption wavelength of about 45 n.
It has been revealed that the dye has a long wavelength and is useful for photographic light-sensitive materials sensitive to near-infrared light, which has been desired in recent years.

Example 2 Compounds B-26, B-42 and B-60 of the present invention were prepared according to the method described in Example 5 of JP-A-3-7931.
Were prepared respectively, and photosensitive materials 5-11, 5-12 and 5-13 were similarly prepared. Exposure and development are performed in the same manner as in the above embodiment, and sharpness (MTF) is determined.
And the residual color was evaluated. Table 2 shows the results.

[0058]

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[0059]

[Table 2]

From the results of the above evaluation, the relative sensitivity and MT
It was clear that F was excellent and there was no problem with residual color. Example 3 The cyan dyes described in Table 2 of Example 1 of JP-A-10-207027 were prepared using the compounds B-1, B-2, B-4 of the present invention.
B-10, B-13, B-15, B-17, B-18,
And B-39 were prepared in the same manner as in Example 1 of JP-A-10-207027, except that each was replaced by an equimolar amount.
As a result of evaluating the graininess, sharpness and the like by performing the same treatment, the compound A-7 described in JP-A-10-207027 was evaluated.
4, A-27, A-53, A-134, and A-144
Good images were obtained in the same manner as described above.

[0061]

The novel arylidene compound of the present invention is
Useful for dyes for dyeing various materials, paints and dyes for silver halide color light-sensitive materials, especially when used in silver halide color light-sensitive materials, the maximum absorption wavelength must be longer. As a dye for photographic light-sensitive materials sensitive to near-infrared light, the decrease in sensitivity obtained by exposure and development processing is smaller than that of conventionally known arylidene compounds, and the sharpness is more significantly improved. In addition, an excellent effect that there is no problem of residual color due to the dye after the treatment is obtained.

Claims (6)

[Claims] 1. An arylidene compound represented by the following general formula (1). General formula (1) In the formula, A represents an acidic nucleus represented by the following general formula (2), and R _{1 to} R ₄ represent a hydrogen atom or a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; R ₁ and R ₂ , R ₂ and R ₅ , R ₅ and R ₆ , R ₄ and R ₆ , or / and R ₃ and R ₄ can be bonded to each other to form a ring. n represents an integer of 0 to 3. General formula (2) R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom or a substituent, and M represents an oxygen atom or a sulfur atom. * Represents a bonding position to the methine group on the right side of A in the general formula (1). 2. A silver halide photosensitive material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on a support, wherein the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer comprises: A silver halide photosensitive material comprising the arylidene compound according to claim 1. 3. R _{9 of the} acidic nucleus represented by the general formula (2)
Is a alkyl group, an aryl group, a heterocyclic group, an alkylthio group, or an arylthio group. The silver halide photosensitive material containing the compound according to claim 2, wherein 4. R ₁ represented by the general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, or a carbamoylamino group, and R ₂ , R ₃ , and R ₄ is a hydrogen atom, R ₅ and R ₆ are alkyl groups, and a compound represented by the general formula (2)
R _{9 of the} acidic nucleus represented by an alkyl group, an aryl group,
3. The silver halide light-sensitive material containing the compound according to claim 2, which is a heterocyclic group, an alkylthio group, or an arylthio group. 5. R ₁ represented by the general formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonylamino group, or a carbamoylamino group, and R ₂ , R ₃ , and R ₄ is a hydrogen atom, R ₅ and R ₆ are alkyl groups, and a compound represented by the general formula (2)
R _{7 of the} acidic nucleus represented by is an alkyl group or an aryl group, R ₈ is an alkoxycarbonyl group, a carbamoyl group, a cyano group, an alkylsulfonyl group, or an arylsulfonyl group; and R ₉ is an alkyl group or an aryl group. 3. A silver halide photosensitive material containing the compound according to claim 2, which is a heterocyclic group, an alkylthio group or an arylthio group. 6. R represented by the general formula (1)₁Is a hydrogen source
Atom, halogen atom, alkyl group, or alkoxy group
R_Two, R_Three, And R_FourIs a hydrogen atom, and R_FiveAnd R₆
Is an alkyl group, and is an acidic nucleus represented by the general formula (2)
R₇Is an alkyl group or an aryl group;₈Is Arco
Xycarbonyl, carbamoyl, cyano, alkyl
A rusulfonyl group or an arylsulfonyl group;
One R ₉Is an alkyl group, an aryl group, a heterocyclic group,
Characterized by a luthio group or an arylthio group
A silver halide photosensitive material containing the compound according to claim 2.
Fees.