JP2000327939A - Pyrrolo[1,2-a]-1,3,5-triazin-4-on-based azomethine pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new pigment of a specified azomethine pigment, excellent in color absorption property and color fastness and useful for image formation, solid-state camera tubes, filters for color liquid crystal displays and silver halide photosensitive materials. SOLUTION: This pyrrolo[1,2-a]-1,3,5-triazin-4-one-based azomethine pigment is represented by formula I [R1 is H or a substituent except cyano; R2 is an alkyl, an aryl or the like; R3 to R7 are each H or a substituent; M is a OY group or N(R8)(R9) (Y is H or a cationic species; R8 and R9 are each an alkyl, an aryl or the like); R8 or R9 may form a 5 to 7-membered ring with R6 or R3, R4 may form a ring with R5 and R6 may form a ring with R7] e.g. a pigment of formula II. The pigment of formula II is obtained by following steps; an aminopyrrole form of formula III is reacted with hydrochloride of methylimidic acid methyl ester, the product is reacted with chloride of paranitrophenoxy formic acid and the resultant product is reacted with a developing agent of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color electrophotography,
Pyrrolo [1,2-a] -1,3,3 useful as dyes for image formation such as ink-jet method and thermal transfer method, dyes for filters for solid-state imaging tubes and color liquid crystals, and dyes for silver halide photographic materials. It relates to a 5-triazin-4-one azomethine dye.

[0002]

2. Description of the Related Art Azomethine dyes have been widely used as dyes and dyes for image formation in silver halide color photographic materials. On the other hand, in recent years, new color image forming methods such as color electrophotography, an ink jet system, and a thermal transfer system have been put to practical use. Further, with the development of electronic imaging, the demand for solid-state image pickup tubes and filters for color liquid crystals is increasing. For these reasons, azomethine dyes have been applied and studied in various systems or products. Particularly, the usefulness of an azomethine dye obtained from a pyrrolo [1,2-a] -1,3,5-triazin-4-one compound is described in European Patent Application No. 0556700A and JP-A-8-122994.
The development of azomethine dyes with higher performance in practical use is demanded.

[0003] As described above, azomethine dyes have been energetically studied to improve the absorption characteristics and the fastness of the dyes. For example, JP-A-5-232648.
Japanese Patent Application Laid-Open No. H11-163873 discloses that an azomethine dye obtained from a coupler obtained by condensing a nitrogen-containing 6-membered ring containing two or three nitrogen atoms on a pyrrole ring makes a color image robust to light, heat, humidity, etc. It is disclosed that a photographic light-sensitive material having a high dye formation speed and a maximum color density in a liquid can be obtained. This publication also discloses pyrrolo [1,2-a] -1,
Some compounds belonging to the 3,5-triazin-4-one compound are also shown. However, this publication does not mention that an azomethine dye having excellent absorption properties, that is, having little unnecessary absorption in the blue light region and having excellent fastness can be obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyrrolo [1,2-a]-having excellent absorption characteristics and fastness.
An object of the present invention is to provide 1,3,5-triazin-4-one azomethine dyes.

[0005]

The above object of the present invention is attained by the following means. That is, the present invention provides: <1> a pyrrolo [1,2-) represented by the following general formula (1).
a] -1,3,5-Triazin-4-one azomethine dyes.

[0006]

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Where R₁Represents a hydrogen atom or a substituent (provided that
And a cyano group is excluded), R_TwoIs an alkyl group, aryl
Group, heterocyclic group, alkoxycarbonyl group, arylo
Xycarbonyl group, carbamoyl group, alkylsulfoni
Group, arylsulfonyl group, alkylsulfinyl
Group, arylsulfinyl group, sulfamoyl group, phos
A honyl group, a phosphinoylamino group, or an imide group
I forgot. R_ThreeRepresents a hydrogen atom or a substituent. R_Four, R_Five,
R₆And R₇Represents a hydrogen atom or a substituent
In addition, M is -OY group or -N (R₈) (R₉)
Y is a hydrogen atom or a cation required to neutralize the charge
Represents a seed. R₈And R₉Are each independently an alkyl
Group, aryl group, heterocyclic group, acyl group, or sulfoni
Represents a radical. R ₈Or R₉And R₆Or R_ThreeAnd each other 5
Or a 6- or 7-membered ring; _FourAnd R_Fiveas well as
/ Or R₆And R₇And may form a ring with each other.

<2> The pyrrolo [1,2-a] according to <1>, wherein R _{3 in the} general formula (1) is an alkyl group, an aryl group, an alkylthio group, or an arylthio group. ] -1,3,5-triazin-4-one azomethine dyes.

<3> The pyrrolo [1,2-a] -1,3,3 described in the above <1>, wherein R _{3 in the} general formula (1) is an alkylthio group or an arylthio group. 5
-Triazin-4-one azomethine dyes.

[0010] <4> wherein R ₁ in the general formula (1) is an alkyl group or an aryl group,, R ₂ is an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or arylsulfonyl group, and R ₃ Is a pyrrolo [1,2-a] -1,3,5-triazin-4-one azomethine dye described in the above <1>, wherein is an alkylthio group or an arylthio group.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Pyrrolo [1,2-a] -1,3,5-triazin-4-one azomethine dyes represented by the general formula (1) (hereinafter referred to as "dyes of the present invention"). Will be described in detail. First, R _{1 to} R ₇ and M in the dye of the present invention will be described in detail below.

[0012] will be described in detail R _1. R ₁ represents a hydrogen atom or a substituent (however, excluding a cyano group); specifically, R ₁ represents a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), and an alkyl group (preferably having 1-32 linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl,
Cyclopropyl, cyclopentyl, cyclohexyl, 1
-Norbornyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 32 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 32 carbon atoms) For example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably a 5- to 8-membered heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2
-Benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), a silyl group (preferably a silyl group having 3 to 32 carbon atoms, for example, trimethylsilyl, triethylsilyl, tocibutylsilyl, t-
Butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 32 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t -Butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably aryloxy groups having 6 to 32 carbon atoms, for example, phenoxy, 2-naphthoxy), heterocyclic oxy Group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably 1 to 32 carbon atoms) A silyloxy group such as trimethylsilyl Shi, t- butyl-dimethyl-silyloxy, diphenylmethyl silyloxy group), acyloxy groups (preferably acyloxy groups having 2 to 32 carbon atoms, e.g., acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy),

An alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 32 carbon atoms,
For example, ethoxycarbonyloxy, t-butoxycarbonyloxy, a cycloalkyloxycarbonyloxy group such as cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, for example, , Phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 32 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably having 1 to 32 sulfamoyloxy groups, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably having 1 to 32 carbon atoms)
Alkylsulfonyloxy group, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy), arylsulfonyloxy (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, for example, phenylsulfonyloxy), acyl group (Preferably an acyl group having 1 to 32 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexylcarbonyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, Methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, If, phenoxycarbonyl), carbamoyl groups (preferably carbamoyl group having 1 to 32 carbon atoms, e.g., carbamoyl, N, N- dibutylcarbamoyl, N- ethyl -N- octylcarbamoyl, N
-Propylcarbamoyl, N, N-dicyclohexylcarbamoyl), an amino group (preferably an amino group having 32 or less carbon atoms, for example, amino, methylamino, N, N-
Dioctylamino, tetradecylamino, octadecylamino, cyclohexylamino), anilino group (preferably anilino group having 6 to 32 carbon atoms, for example, anilino,
N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, for example, 4-pyridylamino),

A carbonamide group (preferably having 2 to 2 carbon atoms)
32 carbonamide groups such as acetamido, benzamide and tetradecaneamide), ureido groups (preferably ureido groups having 1 to 32 carbon atoms such as ureido, N, N-dimethylureido, N-phenylureido), imide Group (preferably an imide group having 10 or less carbon atoms, for example, N-succinimide, N-phthalimido), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxy Carbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, for example, phenoxy) Carbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 32 carbon atoms, for example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexylsulfonylamino), sulfamoylamino group ( It is preferably a sulfamoylamino group having 1 to 32 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably 1 to 3 carbon atoms).
2 azo groups such as phenylazo), alkylthio groups (preferably alkylthio groups having 1 to 32 carbon atoms, such as ethylthio, octylthio, cyclohexylthio), and arylthio groups (preferably arylthio groups having 6 to 32 carbon atoms). For example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms,
For example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl), an arylsulfinyl (preferably carbon An arylsulfinyl group of the number 6 to 32, for example, phenylsulfinyl),
An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 32 carbon atoms, for example, methylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 32 carbon atoms, for example, phenylsulfonyl , 1-
Naphthylsulfonyl),

A sulfamoyl group (preferably having 32 carbon atoms)
In the following sulfamoyl groups, for example, sulfamoyl,
N, N-dipropylsulfamoyl, N-ethyl-N-
Dodecylsulfamoyl), a sulfo group, a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a phosphinoylamino group (diethoxyphosphino) Ylamino, dioctyloxyphosphinoylamino group).

When the group represented by R ₁ is a group that can be further substituted, the group represented by R ₁ may further have a substituent. In this case, preferred substituents are those described above for R ₁ . It is a group and / or cyano group having the same meaning as the substituent. When substituted by two or more substituents, those substituents may be the same or different.

Next, R ₂ will be described in detail. R ₂ represents an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, an alkylsulfinyl group, or an arylsulfinyl group; It represents a group having the same meaning as the alkyl group and aryl described for R ₁ .

The alkyl group of the alkoxycarbonyl group is
The above R₁Represents the same meaning as the alkyl group described in
You. The aryl group of the arylcarbonyloxy group is as defined above.
R ₁Represents a group having the same meaning as the aryl group described in.
The carbamoyl group is preferably a C-C
Alkylcarbamoyl group, N-arylcarbamoyl group,
N, N-dialkylcarbamoyl group or N, N-dia
Represents a carbamoyl group,
And the aryl group are represented by R₁The alkyl group and a
Represents a group having the same meaning as the reel group. Alkylsulfonyl
The alkyl group of the group is a group represented by R₁Same as the alkyl group described in
Represents the same meaning group. Aryl of arylsulfonyl group
The group is R₁Group having the same meaning as the aryl group described in
Represents

The sulfamoyl group is preferably from 0 to 38.
A sulfamoyl, an N-alkylsulfamoyl group, N
-Arylsulfamoyl, N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl or N-alkyl-N-arylsulfamoyl. These alkyl groups and aryl groups represent groups having the same meaning as the alkyl groups and aryl groups described for R ₁ above.

The alkyl group of the alkylsulfinyl group is
It preferably represents 1 to 38 alkylsulfinyl groups, wherein the alkyl group of the alkylsulfinyl group is
Represents a group having the same meaning as the alkyl group described in ₁ .

The aryl group of the arylsulfinyl group is
Preferably an aryl group of 6 to 38, the aryl group has the same meaning groups and aryl group described for the R _1.

When these groups of R ₂ can be further substituted, they may be substituted with the substituents and / or cyano groups described above for R ₁ and may be substituted with two or more substituents. When present, those substituents may be the same or different.

Next, R ₃ will be described in detail. R ₃ is
Represents a hydrogen atom or a substituent, In detail, the substituent represents a group or a cyano group having the same meaning as the substituent described in the explanation of the above R _1. When the group represented by R ₃ is additionally displaceable group, the group represented by R ₃ may further have a substituent group, preferred substituents that case the substituents described for R ₁ Groups and / or cyano groups having the same meaning. 2
When substituted with two or more substituents, those substituents may be the same or different.

Next, R _{4 to} R ₇ will be described in detail below.

R_Four, R_Five, R₆And R₇Are independent of each other
R represents a hydrogen atom or a substituent; _Four, R_Five, R₆And R₇
Is a group represented by R₁Group having the same meaning as the substituent described in
Or a cyano group.

Next, M will be described in detail below.
M represents a -OY group or -N (R₈) (R₉), Y is water
Displays the cation species required to neutralize elemental atoms or charges.
I forgot. R₈And R₉Are each independently an alkyl group, an ant
Group, a heterocyclic group, an acyl group, or a sulfonyl group.
I forgot. R₈Or R₉And R₆Or R_ThreeHave 5 members, 6 members or
May form a 7-membered ring,_FourAnd R _FiveAnd / or R₆
And R₇And may form a ring with each other.

Next, Y will be described in detail. Y represents a hydrogen atom or a cation species necessary for neutralizing the charge, and the cation species is a metal cation species (eg, lithium, sodium, potassium, magnesium, calcium, aluminum, iron, zinc), an organic cation species ( For example, quaternary ammonium, guanidinium cation, and trialkylammonium cation). These cationic species are not limited to the formation of a 1: 1 salt with the dye,
A salt with a plurality of dyes may be formed.

Next, R ₈ and R ₉ will be described in detail.
The alkyl group, aryl group, heterocyclic group, acyl group, and sulfonyl group of R ₈ and R ₉ are the same as those of the alkyl group, aryl group, heterocyclic group, acyl group, and sulfonyl group described for R ₁ above. Represents a group of meaning.

The preferred range of the dye of the present invention will be described. The preferred range of R ₁ will be described. R ₁ preferably represents an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group, and more preferably represents an alkyl group, an aryl group, an alkoxycarbonyl group, or a carbamoyl group. . Most preferred R ₁ is an alkyl or aryl group.

The preferred range of R ₂ will be described. R ₂
Is preferably an alkyl group, an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, more preferably an alkoxycarbonyl group,
Examples include an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.
Most preferred R ₂ includes an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

The preferred range of R ₃ will be described. R ₃
Is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a carbonamide group, a ureido group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, and more preferably, alkyl group, aryl group, alkoxy group, alkylthio group, arylthio group, heterocyclic thio group, carbonamido group, ureido group, alkoxycarbonylamino group No.
More preferred R ₃ includes an alkyl group, an aryl group, an alkylthio group, an arylthio group, a carbonamido group, a ureido group, and an alkoxycarbonylamino group. More preferred R ₃ includes an alkyl group, an aryl group, an alkylthio group, and an arylthio group. Most preferred R ₃ includes an alkylthio group and an arylthio group.

Next, the preferred ranges of M and R _{4 to} R ₉ will be described. When M is a -OY group, Y is preferably a cationic species necessary for neutralizing the charge. Further, as the cationic species, lithium, sodium, potassium, magnesium, zinc, quaternary ammonium, guanidinium cation, and trialkylammonium cation are preferable, and most preferably, sodium, potassium, quaternary ammonium, guanidinium cation, and trialkylammonium cation. Alkyl ammonium cations.

When M is --OY, R _{4 to} R ₇ represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonamide group, an alkane sulfonamide group, an arene sulfonamide group, an alkoxy group, an aryloxy group. Group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, hydroxy group, carboxy group, sulfo group, nitro group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, or An acyloxy group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, a carbonamide group, an alkane sulfonamide group, an arenesulfonamide group, an alkoxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group is more preferable.
Examples include a carbamoyl group, a cyano group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. Particularly preferably, in R _{4 to} R ₇ , one of R _{4 and} R ₆ is a hydrogen atom.

When M is -N (R ₈ ) (R ₉ ), R ₈
And R ₉ are preferably an alkyl group, an aryl group or a heterocyclic group, and R ₈ or R ₉ and R ₆ or R ₃ may form a 5-, 6- or 7-membered ring with each other. , R ₄ and R ₅ and / or R ₆ and R ₇ may form a ring with each other.

When M is —N (R ₈ ) (R ₉ ), preferred R _{4 to} R ₇ and particularly preferred R _{4 to} R ₇ are those wherein M is —
Examples include groups having the same meanings as R _{4 to} R ₇ described in connection with the OY group.

M is preferably -N (R ₈ ) (R ₉ ).

When M is -OY, the dye of the present invention is obtained by oxidizing pyrrolo [1,2-a] -1,3,5-triazin-4-one and paraaminophenol or parasulfonamidophenol. Specific examples of para-aminophenols and parasulfonamidophenols are easily obtained from coupling with a compound, for example, see JP-A-9-14624.
No. 8 is mentioned.

When M is -N (R ₈ ) (R ₉ ), the dye of the present invention comprises pyrrolo [1,2-a] -1,3,5-triazin-4-one and paraphenylene It can be easily obtained from an oxidized form of a diamine, and specific examples of paraphenylenediamines are described, for example, in JP-A-5-257248 and JP-A-6-257248.
No. 161061, No. 7-36162, Japanese Patent Application No. 9-32
8129, Japanese Patent Application No. 9-328130, and Japanese Patent Application No. 9
-329998 and the like.

Hereinafter, specific illustrative dyes (P-1 to P-86) of the dye of the present invention are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The following are specific examples of the synthesis of the dye of the present invention. (Synthesis Example 1) -Synthesis of P-1- Synthesized according to Synthesis Scheme A shown below. Reaction Scheme A

[0056]

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(Synthesis of Intermediate C) To 4.40 g (0.04 mol) of methyl imido acid methyl ester hydrochloride was added 40 ml of acetonitrile, followed by stirring at room temperature. To this solution, 4.04 g (0.04 mol) of triethylamine was added dropwise to liberate the hydrochloric acid, and then 11.0 gg (0.027 mol) of the aminopyrrole compound (intermediate A) and 2.28 m 2 of acetic acid.
1 was added. The solution was stirred at room temperature for 24 hours. After completion of the reaction, the precipitated crystals were filtered, washed with acetonitrile, then washed with water, and dried. 7.8 g (yield 63.9%) of Intermediate C was obtained.

(Synthesis of Intermediate E) Acetonitrile 7 was added to 7.5 g (0.0166 mol) of Intermediate C obtained by the above method.
5 ml and 10 ml of dimethylacetamide were added, and the mixture was stirred at room temperature. To this solution, 4.0 g (0.02 mol) of paranitrophenoxyformic chloride was slowly added. After the addition was completed, 5.6 ml of triethylamine was added to the reaction mixture.
(0.04 mol) was added dropwise under water cooling. After stirring at room temperature for 2 hours, 2.0 g (0.01 mol) of paranitrophenoxyformate chloride and 2.8 m of triethylamine were further added.
1 was added.

After completion of the addition, the reaction was carried out at room temperature for 4 hours.
After completion of the reaction, the reaction solution was neutralized by adding concentrated hydrochloric acid dropwise.
Was. Then, 100 ml of water is dropped to precipitate crystals.
Was. After being washed with the filtered water, it was dried. The resulting crystal
Was dispersed in 30 ml of chloroform, washed and purified.
5.25 g (66.2%) of intermediate E were obtained. Of intermediate E
¹H NMR (CDCl_Three) Is δ (ppm), 9.83
(S, 1H), 7.50-6.95 (m, 6H), 5.
92 (s, 1H), 2.55 (br, 3H), 1.70
０．５0.50 (m, 28H).

(Synthesis of Exemplified Dye P-1) 4.78 (0.01 mol) of coupler (intermediate E) obtained by the above method, 3.51 g (0.012 mol) of developing agent, 15 g of sodium hydrogen carbonate To the mixture were added 50 ml of ethyl acetate and 150 ml of water, and the mixture was stirred at room temperature. Ammonium persulfate crystals were added in small portions to this solution until intermediate E disappeared. After the reaction, the aqueous layer was removed. The ethyl acetate solution was acidified by adding acetic acid, and further washed with water. The ethyl acetate solution was concentrated under reduced pressure and dried. The residue was separated and purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 1/1). 4.15 g (62.1%) of exemplified dye P-1 was obtained.

-Synthesis of Exemplified Dye P-20- Synthesized according to the following synthesis scheme B.

Synthesis Scheme B

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(Synthesis of Intermediate G) To 15.6 g (OO381 mol) of the aminopyrrole derivative (Intermediate A), 50 ml of dimethylacetamide was added, and the mixture was cooled to 10 ° C. or lower and stirred. To this solution, 5.0 g (0.0381 mol) of ethoxycarbonylthioisocyanate was added dropwise. 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 (66.9%) of intermediate G
Obtained.

(Synthesis of Intermediate H) 13.5 g (0.025 mol) of the thiourea compound (intermediate G) 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 H was obtained.

(Synthesis of Intermediate I) 10.0 g of potassium carbonate and 50 ml of dimethylacetamide were added to 12.0 g (0.024 mol) of the thione compound (intermediate H) obtained by the above method.
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,
It was dried 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 I
(82.9%). ¹ H NMR of the obtained intermediate I
(CDCl ₃ ) is δ (ppm) 7.55 (s, 1).
H), 7.40-7.20 (m, 5H), 7.00
(S, 1H), 5.85 (s, 1H), 3.45 to 3.45.
25 (m, 2H), 1.78-0.60 (m, 43H)
Met.

(Synthesis of Exemplified Dye P-20) 6.08 g (0.01 mol) of coupler (intermediate I) obtained by the above method, 5.24 g (0.012 mol) of developing agent B, 20 g of sodium hydrogen carbonate 200 ml of water and 10 ethyl acetate
0 ml was added and the mixture was stirred at room temperature. Ammonium persulfate crystals were added to the solution in small portions until the intermediate I disappeared. After completion of the reaction, the aqueous layer was removed, and the ethyl acetate layer was neutralized by adding acetic acid. This ethyl acetate solution was washed with water, concentrated under reduced pressure and dried. The residue was subjected to silica gel column chromatography (eluent: ethyl acetate /
(n-hexane = 1/1). Illustrative dye P
6.13 g (70.1%) of -20 were obtained.

-Synthesis of Illustrative Dye P-67- Synthesized according to Synthesis Scheme C shown below.

Synthesis Scheme C

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(Synthesis of Exemplified Dye P-67) 0.3 g (0.5 mmol) of coupler (intermediate I) obtained by the above method, 0.20 g (0.5 mmol) of developing agent C, 0.1 g of potassium carbonate. 35 g (2.5 mmol) of ethyl acetate 1
0 ml and 10 ml of water were added and stirred at room temperature. To this solution, 0.43 g (5.0 mmol) of manganese dioxide was added. The reaction solution was stirred at room temperature for 5 hours, then 0.2 g of developing agent C and 0.43 g of manganese dioxide were added, and the mixture was further stirred for 5 hours. The solution was left overnight and filtered to remove insolubles. The ethyl acetate solution was washed with water, concentrated and dried. The residue was separated and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/5). 0.23 g (46.8%) of exemplified dye P-67 was obtained.

The pyrrolo [1, 1 represented by the above general formula (1)
2-a] -1,3,5-triazin-4-one-based azomethine dyes include color electrophotography, an ink-jet method,
It can be suitably used as a dye for image formation such as a thermal transfer method, a dye for a filter for a solid-state image pickup tube or a color liquid crystal, and a dye for a silver halide photographic material.

[0071]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these examples.

(Example 1) For the dyes of the present invention shown in Table 1, the maximum absorption wavelength in an ethyl acetate solvent (where P-67 is in dimethylformamide) was measured using UV-2 manufactured by Shimadzu.
It measured using the 60 type spectrometer. Table 1 shows the results.

[0073]

[Table 1]

(Example 2) The absorption spectra of the dyes of the present invention shown in Table 2 in an ethyl acetate solution were measured using a UV-260 spectrometer manufactured by Shimadzu, and the absorbance at 450 nm and the maximum absorption wavelength were measured. The ratio with the absorbance was determined. Table 2 shows the results.

(Comparative Example 1) Comparative dyes shown in Table 2 (Comparative Dyes A, B, and C described below) were treated with 450 n in the same manner as in Example 2.
The ratio of the absorbance at m to the absorbance at the maximum absorption wavelength was determined. Table 2 shows the results.

[0076]

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[0077]

[Table 2]

It can be seen that the dye of the present invention is a preferable dye having a low absorbance at 450 nm and a high color purity.

[0079]

As described above, the present invention provides a novel pyrrolo [1,2-a] -1,3,5 having excellent absorption properties and fastness.
-Triazin-4-one azomethine dyes can be provided.

Claims (4)

[Claims] 1. A pyrrolo represented by the following general formula (1):
[1,2-a] -1,3,5-triazin-4-one type
Azomethine dyes. Embedded imageWhere R₁Represents a hydrogen atom or a substituent (however, a cyano group
Excluding), R_TwoIs an alkyl group, an aryl group, a hetero ring
Group, alkoxycarbonyl group, aryloxy carbonyl
Group, carbamoyl group, alkylsulfonyl group, aryl
Rusulfonyl group, alkylsulfinyl group, aryls
Rufinyl group, sulfamoyl group, phosphonyl group, phos
Represents a inoylamino group or an imide group. R_ThreeIs water
Represents an atom or a substituent. R_Four, R_Five, R₆And R₇Haso
Each independently represents a hydrogen atom or a substituent, and M is -O
Y group or -N (R₈) (R₉), Y is a hydrogen atom or
Represents a cationic species necessary for neutralizing the charge. R
₈And R₉Are each independently an alkyl group, an aryl group,
Represents a heterocyclic group, an acyl group, or a sulfonyl group. R
₈Or R₉And R₆Or R_ThreeHave 5 members, 6 members or 7 members
May form a ring; _FourAnd R_FiveAnd / or R₆And R₇And
They may form a ring with each other. 2. The pyrrolo [1, 2] according to claim 1, wherein R _{3 in the} general formula (1) is an alkyl group, an aryl group, an alkylthio group, or an arylthio group.
2-a] -1,3,5-Triazin-4-one azomethine dyes. 3. The pyrrolo [1,2-a] -1,3,5- according to claim 1, wherein R _{3 in the} general formula (1) is an alkylthio group or an arylthio group. Triazin-4-one azomethine dyes. 4. In the above general formula (1), R ₁ is an alkyl group or an aryl group, R ₂ is an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and R ₃ is The pyrrolo [1,2-a] -1,3,5-triazin-4-one azomethine dyes according to claim 1, which is an alkylthio group or an arylthio group.