JPH04252271A - Azomethine based compound - Google Patents

Abstract

PURPOSE:To obtain a new azomethine based compound useful for dye for dyeing photographic layer, dye for filter, etc., as yellow dye having excellent specter absorption characteristics, reduced in decomposition to moist heat, light, etc., and having excellent stability. CONSTITUTION:A compound expressed by formula I (R<1> and R<2> are aliphatic group or aromatic group; R<3> is aromatic group; Ar ms aromatic group having aliphatic amino group at para position) e.g. a compound expressed by formula II. The above-mentioned compound is obtained by reacting a compound expressed by formula III with a halogenating agent such as chlorine to give a compound expressed by formula IV (X is halogen), and then reacting the resultant compound with a compound expressed by the formula H2N-Ar in the presence of a base such as triethylamine and oxidizing agent such as ammonium persulfate.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azomethine compound, and more particularly to an azomethine compound useful as a yellow pigment, which has excellent spectral absorption characteristics, is resistant to decomposition against moist heat and light, and has excellent stability.

0002

BACKGROUND OF THE INVENTION Yellow dyes have been conventionally used in a wide range of fields, such as photographic dyes, inkjet dyes, printing dyes, and optical filter dyes. Although the required performance differs in detail, in most cases, the basic performance required is excellent spectral absorption characteristics and robustness against moist heat, light, etc.

Conventionally, a dye synthesized by an oxidative coupling reaction between malondianilide and paraphenylenediamine has been known as one of the azomethine-based yellow dyes (for example, British Patent No. 1,204,680 and (See Publication No. 55-47379).

0004

[Problems to be Solved by the Invention] However, azomethine dyes obtained from conventionally known malondianilide have a problem of low stability against moist heat and light. In addition, its spectral absorption had poor edges at the long wavelength end, making it look orange to brownish, and was not practically satisfactory as a yellow dye. Therefore, an object of the present invention is to overcome the above-mentioned drawbacks and provide an azomethine compound useful as a yellow dye, which has excellent spectral absorption characteristics, is less decomposed against moist heat, light, etc., and has excellent stability.

[0005]

[Means for Solving the Problems] As a result of extensive research in order to overcome the drawbacks of the above-mentioned azomethine dyes, the present inventors have developed an imino group in which an aliphatic amino group is substituted with an aromatic group having the para position. It was discovered that a specific azomethine compound in the structure is suitable for this purpose, and based on this knowledge, the present invention was accomplished. That is, the present invention provides an azomethine compound represented by the following general formula (I).

General formula (I)

[Formula 2] (In the formula, R1 and R2 each represent an aliphatic group or an aromatic group, R3 represents an aromatic group, and Ar represents an aromatic group having an aliphatic amino group at the para position.)

000
7] The compound represented by the general formula (I) will be described in detail below. When R1 and R2 represent an aliphatic group, preferably a group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
5 alkyl group, examples of which include methyl and ethyl. When R1 and R2 represent an aromatic group, the aromatic group represented by R3 is preferably a phenyl group.

The aromatic group represented by Ar is preferably a phenyl group substituted at the para position with an aliphatic amino group. This aliphatic amino group preferably has 1 carbon number.
It is an aliphatic amino group having at least one, more preferably two, alkyl groups of 1 to 10, more preferably 1 to 5. Such substituents include, for example, diethylamino group,
Dimethylamino group is mentioned.

The aliphatic group, aromatic group or aliphatic amino group explained above may further have a substituent. When it has a substituent, the following are representative examples of the substituent. Halogen atoms (e.g. fluorine, chlorine, bromine), alkoxycarbonyl groups (2 to 3 carbon atoms)
0, preferably 2 to 20 groups. For example, methoxycarbonyl, dodecyloxycarbonyl), acylamino group (group with 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, e.g. acetamide, tetradecanamide), sulfonamide group (group with 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, e.g. methanesulfonamide, dodecanesulfonamide), carbamoyl group (group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; for example, N-dodecylcarbamoyl), sulfamoyl group (group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms). For example, N-phenylsulfamoyl, N-dodecylsulfamoyl),
N-sulfonylsulfamoyl group (group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; for example, N-mesylsulfamoyl, N-dodecanesulfonylsulfamoyl), alkoxy group (having 1 to 30 carbon atoms, preferably 1 to 20 groups, e.g. methoxy, ethoxy), sulfonyl groups (1 to 20 carbon atoms)
30, preferably 1 to 20 groups. For example, methanesulfonyl, benzenesulfonyl, dodecanesulfonyl), phenoxy group, cyano group, carboxyl group, hydroxyl group, sulfo group, N-acylsulfamoyl group (carbon number 2 to
30, preferably 2 to 20 groups. For example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl) or an alkyl group (1 to 30 carbon atoms, preferably 1
~20 straight chain, branched, saturated, unsaturated groups. Examples include methyl, ethyl, t-pentyl, t-butyl). The above substituents may further have a substituent. Examples of the substituent include the substituents listed above.

[0010] In the general formula (I), it is particularly preferable that one of R1 and R2 is an alkyl group and the other is an aryl group. In general formula (I), R3 has at least one substituent, and a particularly preferred example is when the substituent is in the ortho position. As the substituent for the ortho group, a halogen atom or an alkoxy group is particularly preferred. In general formula (I), Ar is particularly preferably a phenyl group substituted with an aliphatic amino group at the para position and an aliphatic group (having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms) at the ortho position.

The compounds of the invention are preferably used as photographic compounds. That is, it is used as a dye for dyeing photographic layers, a dye for filters, a dye for image formation, a dye for masking, a dye for improving printer suitability, and the like. When the dye of the present invention is used for photography, it is particularly preferable that the dye has a diffusion-resistant group. A diffusion-resistant group is a group for immobilizing a compound in a photographic layer, and is generally used as a group in the field of photographic chemistry, particularly in coupler compounds. As the diffusion-resistant group, an organic group having a sufficiently large molecular weight is usually used, and preferred examples include an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20, or an aryl group having a substituent having a total carbon number of 4 to 20. It is. These diffusion-resistant groups may be substituted anywhere in the molecule,
Moreover, you may have multiple pieces.

Specific examples of the compounds of the present invention are shown below. However, it is not limited to these.

[0013]

[Chemical formula 3]

[0014]

[C4]

[0015]

[C5]

[0016]

[C6]

[0017]

[C7]

Next, a method for synthesizing the compound of the present invention will be described. For example, it can be synthesized by the following synthetic route.

[0019]

embedded image In the formula, R1, R2, R3 and Ar represent the general formula (I
), and X represents a halogen atom (preferably a bromine atom or a chlorine atom).

In the above, the halogenating agent used is, for example, bromine, chlorine, sulfuryl chloride, N-bromosuccinimide or N-chlorosuccinimide. As the oxidizing agent, for example, ammonium persulfate, potassium persulfate, ferric chloride, hydrogen peroxide, silver halide, perbenzoic acid or peracetic acid are used.

[0021] Generally, the above second step reaction is carried out in the presence of a base. The base may be either an inorganic base or an organic base. For example, sodium carbonate, potassium carbonate,
Sodium hydroxide, potassium hydroxide, triethylamine, sodium acetate, sodium methoxide, ammonia water, etc. are used.

As the reaction solvent, a halogenated hydrocarbon solvent (for example, methylene chloride, chloroform, methyl chloroform) is used in the first step. In the second step, an amide solvent (e.g. N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone), a nitrile solvent (e.g. acetonitrile),
Ether solvents (e.g. tetrahydrofuran, ethylene glycol diethyl ether, propylene glycol monomethyl ether), sulfonic solvents (e.g. dimethylsulfone, sulfolane), alcohol solvents (e.g. ethanol, methanol, isopropanol), water or ester solvents (e.g. ethyl acetate). , butyl acetate) are used. These reaction solvents may be used in combination of two or more, or may be reacted in a two-layer system.

[0023] In addition to the synthetic route shown above,
For example, after converting X in compound (b) into Y as described below in the second step, a third step (in this case, the third step is the same reaction as the second step) is carried out to form a compound represented by the general formula (I). It may also be induced into a compound. As the group represented by Y here, commonly used coupling-off groups are useful. Y
Specific examples of the group represented by include, for example, benzotriazolyl group, 2,4-dioxo-1,3-imidazolidin-3-yl group, 2,4-dioxo-1,3-oxazolidine-3- yl group or phenoxy group. X
The reaction of converting Y into Y is generally carried out in the presence of a base in addition to H-Y. Specific examples of the base include the same bases listed above. Preferred bases used here include triethylamine, diisopropylethylamine, tetramethylguanidine, potassium hydroxide, potassium carbonate, t-butoxypotassium, sodium hydroxide, sodium methoxide, and pyridine. As the reaction solvent, the reaction solvents listed above are appropriately selected and used. As mentioned above, the azomethine compound of the present invention represented by the general formula (I) oxidizes the compound (b) and an aromatic primary amine, for example, an aromatic primary amine represented by the following general formula (II). It can be manufactured by coupling.

[0024]

embedded image In the formula, R11 and R12 represent a hydrogen atom or an alkyl group which may have a substituent, at least one of which is an alkyl group, and these may be the same or different from each other. R13 represents a halogen atom or an optionally substituted alkyl group. n is the number of substitutions of R13, and is 0,
It represents 1 or 2, and when it is 2, R13 may be the same or different.

When the amine represented by the general formula (II) is used as a salt with a mineral acid or an organic acid, air oxidation can be easily prevented and the dissolution rate can be improved. R11 and R12 in general formula (II) preferably represent an alkyl group or a substituted alkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkoxyalkyl group or an alkylsulfonamidoalkyl group.

R11 and R12 are both preferably selected from lower alkyl groups or lower substituted alkyl groups,
Particularly preferred is an ethyl group or a substituted ethyl group. Furthermore, R13 is preferably at the ortho position to the amino group, and is particularly preferably a methyl group.

Furthermore, paraphenylenediamine derivative (I
Examples of the alkyl groups, alkoxy groups, and substituted alkyl groups related to I) and the alkyl groups of the alkoxy groups include methyl, ethyl, n-propyl, iso-propyl,
Lower alkyl groups having 1 to 4 carbon atoms such as n-butyl, iso-butyl, sec-butyl, t-butyl, and n-
amyl, dl-2-methyl-1-butyl, iso-amyl, sec-amyl, t-amyl, n-hexyl, methylamyl, 2-ethylbutyl, n-heptyl, 2-heptyl, 3-heptyl, n-octyl, 2-octyl, 2
-ethylhexyl, n-dodecyl, n-octadecyl,
Any higher alkyl group having 5 to 18 carbon atoms such as cyclohexyl may be used, including linear, branched and cyclic ones. Examples of halogens include chlorine,
Contains bromine and iodine.

Specific examples of the primary amine (II) used to synthesize the compound of the present invention are: 1) 4-amino-N-ethylaniline 2) 4-amino-N,N-diethylaniline 3 4) 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline 5) 4-amino- 3-Methyl-N-ethyl-N-(β-
Those having an N-hydroxyalkyl group such as hydroxyethyl)aniline, 6) 4-
Amino-3-methyl-N-ethyl-(β-methoxyethyl)aniline 7) 4-Amino-3-methyl-N-ethyl-N-methoxybutylaniline 8) 4-Amino-3-methyl-N-ethyl- N-(β-
ethoxyethyl)aniline9) 4-Amino-3-propyl-N-ethyl-N-(β
-methoxyethyl)aniline 10) 4-amino-3-propyl-N-ethyl-N-(
β-ethoxyethyl)aniline 11) 4-amino-3-methoxy-N-ethyl-N-(
12) 4-Amino-3-methyl-N-ethyl-N-(β-methoxyethyl)aniline
-Butoxyethyl)aniline and other N-alkoxyalkyl groups, 13)4
-amino-3-methyl-N-ethyl-N-(β-(β-
methoxyethoxy)ethyl)aniline 14) 4-Amino-3-methyl-N-ethyl-N-(β-(β-ethoxyethoxy)ethyl)aniline 15) 4-amino-3-methyl-N-ethyl-N- (β-(β-butoxyethoxy)ethyl)aniline16)4-amino-3-methyl-N
-Methyl-N-(β-(β-ethoxyethoxy)ethyl)aniline 17) 4-Amino-N-ethyl-N-(β-
(β-methoxyethoxy)ethyl)aniline 18) Those having an N-alkoxyalkoxyalkyl group such as 4-amino-N-ethyl-N-(β-(β-ethoxyethoxy)ethyl)aniline, 19) 4-amino -N-ethyl-N-(β-methylsulfonamidoethyl)aniline 20) 4-amino-3-methyl-N-ethyl-N-(β
-Methylsulfonamidoethyl)aniline 21) 4-Amino-3-chloro-N-ethyl-N-(β-methylsulfonamidoethyl)aniline 22) 4-Amino-N-ethyl-(β-methylsulfonamidoethyl) -3,5-
These include those having an N-alkylsulfonamide alkyl group such as xylidine. Examples of these salts include mineral acid salts of the above-mentioned phenylenediamine derivatives, such as hydrohalides such as hydrochlorides, hydrobromides, and hydroiodides, sulfates,
inorganic acid salts or formates such as nitrates, phosphates, carbonates,
acetate, aliphatic carboxylate such as propionic acid, benzoate, naphthalene-α-carboxylate, naphthalene-
Aromatic carboxylates such as β-carboxylate, aliphatic sulfonates such as methanesulfonate, naphthalene-α-
These include organic acid salts such as sulfonate, naphthalene-β-sulfonate, p-toluenesulfonate, etc., and are preferably selected appropriately depending on the manufacturing conditions of the compound of the present invention. When used as such, it is preferable to use one that does not adversely affect photographic properties. For this purpose, mineral salts such as sulfates or aromatic sulfonates such as p-toluenesulfonic acid are usually used. As paraphenylenediamines used in the present invention,
The compounds of Specific Examples 3), 5), 6), 19) and 20) above are particularly preferred in that they provide particularly good hues. Additionally, substituents at the 3-position are useful for adjusting the coupling rate; electron-withdrawing groups such as chlorine atoms improve the coupling rate, and electron-donating substituents such as the methyl group increase the coupling rate. It has a slowing effect.

[0029]

EXAMPLES Next, the present invention will be explained in more detail based on examples. Example 1 Synthesis of Exemplified Compound (1) Synthesis was carried out by the following synthetic route.

[0030]

[Chemical formula 10]

First step: Synthesis of intermediate compound (B-1) 20 g of compound (A-1) was mixed with 150 ml of dichloromethane. Dichloromethane solution containing 4.8 g of bromine 10
ml was added dropwise under ice cooling (5°C to 10°C). After reacting for 10 minutes, the mixture was transferred to a separatory funnel and washed with water. Oil layer (compound (
The solution containing B) was taken and used as it was in the next step.

Second Step: Synthesis of Intermediate Compound (C-1) 15 g of phenoxycarbonylbenzotriazole and 8.8 ml of triethylamine were added to 160 ml of N,N-dimethylformamide. This solution was added to the solution obtained in the previous step (
A dichloromethane solution containing B) was added dropwise at room temperature while stirring. After reacting for 1 hour, 500 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. After neutralizing with dilute hydrochloric acid, wash again with water,
The oil layer was separated. The solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography. Silica gel was used as a packing agent, and ethyl acetate/hexane (1/1) was used as an eluent. By collecting the fractions containing intermediate compound (C) and distilling off the solvent, 21.2 g of waxy intermediate compound (C) was obtained.

Third step: Synthesis of exemplified compound (1) 4.7 g of (C) obtained in the previous step was dissolved in a mixed solvent of 40 ml of ethanol and 50 ml of ethyl acetate. To this solution was added 30 ml of water in which 4.1 g of sodium carbonate had been dissolved while stirring at room temperature. Add 4-{N-ethyl (2
-hydroxyethyl)amino}-2-methylaniline sulfate (referred to as D-1) was added. To this solution, 30 ml of water in which 1.7 g of ammonium persulfate was dissolved was added dropwise. After dropping, the mixture was stirred for 1 hour, 200 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. After making it acidic with dilute hydrochloric acid, it was further washed with water twice. The oil layer was taken and the solvent was distilled off under reduced pressure. The residue was separated and purified by column chromatography. Silica gel was used as a packing agent, and ethyl acetate/hexane (1/1) was used as an eluent. Fractions containing Exemplified Compound (1) were collected and the solvent was distilled off under reduced pressure to obtain 2.1 g of Exemplified Compound (1) having a melting point of 111 to 113°C.

Examples 2 to 10 Exemplary compounds (2) to (
10) Synthesis was carried out in the same manner as in Synthesis Example 1. Table 1 shows the raw materials used.

[0035]

[Table 1] Note 1) Refers to the raw material used in place of (A-1) used in Example 1. The structural formula is shown below.

[0036]

[Chemical formula 11]

[0037]

[Chemical formula 12]

Note 2) Refers to the raw material used in place of (D-1) used in Example 1. The structural formula is shown below.

[0039]

[Chemical formula 13]

Examples 11 to 20 Measurement of λmax and ε In order to clarify the absorption characteristics of the compounds of the present invention as dyes, the absorption characteristics in an ethyl acetate solvent were measured. Table 2 shows the measured λmax and ε.

[0041]

[Table 2]

Example 21 Comparison of absorption forms as optical filters (solvents) In order to clarify the basic characteristics of the chemicals of the present invention as optical filters, absorption spectra in ethyl acetate solutions were compared. As a typical example of the compound of the present invention, (1
), (2), (3) and (4) were used. The following (R-1) was used as a comparative compound. The results (absorption spectra) are shown in FIGS. 1 and 2. It is clear that the compound of the present invention has extremely sharp long-wavelength absorption (sharp tail) and is excellent as an optical filter. In comparison, the comparative compound (R-1) has poor hem sharpness.

[0043]

[Chemical formula 14]

Example 22 Evaluation of stability against moist heat and light Sample 22
-1 was produced. (1) Yellow filter layer Exemplary compound (1)
0.22g/m2
tricresyl phosphate
1.00g/m2 gelatin
3.80g/m
2 (2) Protective layer 2,4-dichloro-6-hydroxy-S-
triazine sodium
0.10g/m2 gelatin
1.80g/m2

Samples 22-2 to 22-9 were prepared by replacing the exemplified compound (1) of Sample 22-1 with other compounds of the present invention and comparative compounds in equimolar amounts. When the yellow density was measured, it was in the range of 0.45 to 0.55. Next, each sample was divided into two, and one half was heated at 60°C and 70% relative humidity.
The yellow density was measured after leaving the other side under 20,000 lux fluorescent lamp irradiation for 7 days under these conditions for 14 days. The dye residual rate was calculated from each density as a percentage of the density before performing the fading test. The results are shown in Table 3.

[0046]

[Table 3]

As is clear from Table 3, the comparative sample showed a large decrease in yellow density due to moist heat and light, but the inventive sample showed almost no decrease, demonstrating that the stability of the compound was excellent. .

On the other hand, this example shows that the compound of the present invention having a diffusion-resistant group can be easily dissolved in a high boiling point organic solvent and dispersed in a gelatin matrix. This method is one method for dyeing a specific photographic layer in a coating film of a photographic light-sensitive material. That is, in the case of a compound having a diffusion-resistant group, it is advantageous because it does not leak into other layers or the processing solution during the development processing step.

[0049]

[Effects of the Invention] The compounds of the present invention exhibit excellent hue. In particular, it has good sharpness on the long wavelength side, which is important as a yellow dye, and is suitable for color photographic materials where color reproducibility is important, dyes for various optical filters, dyes for inkjet, printing dyes, etc. It is also robust against moisture, heat and light.
This is also the reason why it is suitable for the above-mentioned applications.

[Brief explanation of the drawing]

FIG. 1 shows absorption spectra of exemplary compounds (1) and (3).

FIG. 2: Exemplary compound (2) and comparative compound (R-1
) is the absorption spectrum of

Claims (1)

[Scope of Claims] [Claim 1] An azomethine compound represented by the following general formula (I). General formula (I) [Formula 1] (wherein, R1 and R2 each represent an aliphatic group or an aromatic group, R3 represents an aromatic group, and Ar is an aromatic group having an aliphatic amino group at the para position. 2. A dye comprising an azomethine compound represented by the general formula (I) according to claim 1. 3. The dye according to claim 2, which is used for photography. 4. The dye according to claim 2, wherein the compound represented by the general formula (I) has a diffusion-resistant group.