JPH07331105A - Preparation of azo dye - Google Patents

Abstract

PURPOSE:To provide a process for preparing an azo dye which has excellent light resistance, solvent resistance and other properties and is useful as a dye and a pigment by using a phthalimide deriv., having an amino group, as a base of an azo dye. CONSTITUTION:A diazonium salt of a phthalimide deriv. represented by the formula (wherein X is H, a halogen, a lower alkyl, a lower alkoxy, nitro, amino, a substd. amino, or an alkoxycarbonyl; and Y is H, a halogen, a lower alkyl, a lower alkoxy, nitro, an alkoxycarbonyl, carboxyl, sulfamide, or sulfo) is coupled with an acetoacetanilide coupling component, a naphthol coupling component, or a barbituric acid coupling component. The phthalimide deriv. is prepd. by dehydration condensation of an aniline deriv. with an N-hydroxymethyl phthalimide deriv., e.g. in a conc. sulfuric acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an azo dye, and more particularly to a method for producing an azo dye such as a dye or a pigment using a phthalimide derivative having an amino group as the base of the azo dye.

[0002]

2. Description of the Related Art Conventionally, various aniline derivatives have been known as raw materials for dyes, pigments and the like. For example, as an aniline derivative which is an intermediate for dyes and pigments, it is required that the resulting pigment has high weather resistance, solvent resistance, etc., but no aniline derivative that is sufficiently satisfactory at present is known. . Therefore, an object of the present invention is to provide azo dyes such as dyes and pigments having excellent various physical properties.

[0003]

The above object can be achieved by the present invention described below. That is, the present invention is characterized by coupling a diazonium salt of a phthalimide derivative represented by the following general formula (I) with an acetoacetanilide coupling component, a naphthol coupling component or a barbituric acid coupling component. And a method for producing an azo dye.

[Chemical 2] (Wherein X represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, a nitro group, a halogen atom, an amino group, a substituted amino group or a substituent such as an alkoxycarbonyl group, and Y represents hydrogen. Atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, a carboxyl group, a sulfonamide group, a sulfonic acid group or the like.

[0004]

When the phthalimide derivative of the above general formula (I) is diazotized and coupled with the above coupling component, an azo dye useful as a dye or pigment having excellent weather resistance and solvent resistance can be obtained.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. The phthalimide derivative used in the present invention is obtained by subjecting an aniline derivative and an N-hydroxymethylphthalimide derivative to dehydration condensation in concentrated sulfuric acid, for example.

The aniline derivative which can be used as a raw material includes aniline, o, m or p-chloroaniline, o, m or p-methylaniline, o, m or p-
Ethylaniline, o, m or p-methoxyaniline,
o, m or p-ethoxyaniline, o, m or p-nitroaniline, o, m or p-aminoacetanilide,
2-methyl-4-chloroaniline, 2-methyl-5-chloroaniline, 2,6-xylidine, 2,4-xylidine, 2,5-xylidine, 2-methoxy-5-chloroaniline, 2-methoxy-5 -Bromoaniline, 2-methyl-4-methoxyaniline, 2,5-dimethoxyaniline, 2,4-dimethoxyaniline, 2-methoxy-5-
Methyl aniline, anthranilic acid methyl ester, anthranilic acid ethyl ester, etc. are mentioned.

The N-hydroxymethylphthalimides include N-hydroxymethylphthalimide, N-hydroxymethyl-4-nitrophthalimide, N-hydroxymethyl-3-nitrophthalimide, N-hydroxymethyl-3-hydroxyphthalimide, N-hydroxymethyl-3-chlorophthalimide, N-hydroxymethyl-4-chlorophthalimide, N-hydroxymethyl-
3,6-dichlorophthalimide, N-hydroxymethyl-3,4,5,6-tetrachlorophthalimide, N-hydroxymethyl-3,4,5,6-tetrabromophthalimide, N-hydroxymethyl-4-amino Phthalimide, N-hydroxymethyl-3-methoxyphthalimide, N-hydroxymethyl-3-methylphthalimide,
N-hydroxymethyl-4-methylphthalimide, N-
Examples thereof include hydroxymethyl-4,5-dibromophthalimide.

The reaction between the aniline derivative and the N-hydroxymethylphthalimides is not particularly limited, but both are in equimolar ratio in concentrated sulfuric acid of 80 to 100% at a temperature of about -10 to 100 ° C. The reaction is carried out for a period of time to several tens of hours, then the reaction mixture is poured into water or ice water, and the deposited precipitate is filtered to obtain the compound of the general formula (I). In the present invention, various azo dyes can be obtained by diazotizing the compound of the general formula (I) by a conventional method and coupling it to the following coupling component by a conventional method. The conditions for the diazotization and the coupling are not special as described in the examples below, and may be ordinary conditions.

As the acetanilide coupling component to be coupled with the compound represented by the general formula (I), acetoacetanilide and its benzene ring have halogen atoms such as chlorine; lower alkyl groups such as methyl group; A lower alkoxy group such as a methoxy group and an ethoxy group; a nitro group; a carbamoyl group; an acetanilide derivative having at least one substituent such as a substituted amino group such as an acetylamino group and a benzoylamino group, for example, o-chloroacetate Acetanilide, p-chloroacetoacetanilide, 4-chloro-2,5-dimethoxyacetoacetanilide, 2,4-dimethoxyacetoacetanilide, o-acetoacetanisidide, o-acetoacetanisidide, o-acetoacetotoluidide, p-acetoacetotoluidide , 2,4-acetoacetoxylide, 4-chloro-2-methylacetoacetanilide, p-ethoxyacetoacetanilide, 4-nitro-2-methylacetoacetanilide, 2,5-diethoxy-4- Phenylcarbamoyl-acetoacetanilide, 4-benzoylamino-2,5-diethoxyacetoacetanilide, 4-acetylamino-acetoacetanilide, 4-acetoacetaminophthalimide,
5-acetoacetylamino-benzimidazolone and the like can be mentioned.

Examples of the naphthol type coupling component to be coupled with the compound represented by the general formula (I) include β-naphthol, its derivatives, 3-hydroxy-2-naphthanilide and 2-hydroxy-3. -Naphthoanilide and the like and halogen atoms such as chlorine in these benzene rings; lower alkyl groups such as methyl group; lower alkoxy groups such as methoxy group, ethoxy group; nitro group; substituted amino such as acetylamino group, benzoylamino group A derivative having at least one substituent such as a group, for example,
4'-chloro-3-hydroxy-2-naphthanilide, 3'-chloro-3-hydroxy-2-naphthanilide, 3-hydroxy-3'-nitro-2-naphthanilide, 3-hydroxy-4 ′ -Nitro-2-naphthanilide, 3-hydroxy-2-naphtho-o-toluidide, 3-hydroxy-2-naphtho-p-toluidide, 4′-chloro-3-hydroxy-2-naphtho-o-
Toluidide, 5'-chloro-3-hydroxy-2-naphtho-o-toluidide, 3-hydroxy-2-naphtho-2,4-xylidide, 5'-chloro-3-hydroxy-2-naphtho-o-anisidide, 5'-bromo-3
-Hydroxy-2-naphtho-o-anisidide, 3-hydroxy-2-naphtho-p-anisidide, 3-hydroxy-2'-methyl-2-naphtho-p-anisidide,
3-hydroxy-2 ', 5'-dimethoxy-2-naphthanilide, 5'-chloro-3-hydroxy-2',
4'-dimethoxy-2-naphthanilide, 4'-chloro-3-hydroxy-2 ', 4'-dimethoxy-2-naphthanilide, 4'-chloro-3-hydroxy-
2 ', 5'-dimethoxy-2-naphthanilide, 3-
Hydroxy-2-naphtho-o-phenetide, 3-hydroxy-2-naphtho-p-phenetide, 3-hydroxy-2-o-anthrotoluide, 2-hydroxy-naphthalene-3-carboyl-5'-chloro-
2 ', 4'-dimethoxyanilide, 3-hydroxy-
2-naphthamide, 2-hydroxy-3-naphthamide and the like and 3-hydroxy- substituted with these amide groups
N-1-naphthyl-2-naphthamide, 3-hydroxy-N-2-naphthyl-2-naphthamide, 5- (2 ′,
3'-oxynaphthoylamino) benzimidazolone, etc., other 4'-chloro-2-hydroxy-3-carbazole carboxanilide, 2-hydroxy-
2 ', 5'-dimethoxy-3-dibenzofurancarboxyanilide and the like can be mentioned. Other coupling components include barbituric acid, barbital, phenobarbital and the like.

The coupling of the diazonium salt of the phthalimide derivative represented by the general formula (I) with the above compound may be carried out according to a known coupling method and is not particularly limited.

[0012]

The present invention will be described in more detail with reference to the following examples. Unless otherwise specified,% and parts in the examples are by weight. Example 1 6.3 parts of 2,5-dimethoxyaniline was added to 90% sulfuric acid 3
It was added to 9.5 parts with stirring at 20 to 25 ° C. and dissolved therein, and at the same temperature, N-hydroxymethylphthalimide 7.6 was added.
And the mixture was stirred for 48 hours. The reaction product was gradually added to 400 parts of ice water so that the temperature was kept at 10 ° C or lower, and the precipitated crystals were filtered. The isolated crystals were washed with water until the washing liquid became neutral. After drying at 80 ° C, pale yellow 4-phthalimidomethyl-2,5-dimethoxyaniline (mp 168 to 170 ° C) was obtained with a yield of 80%.

The obtained 4-phthalimidomethyl-2,5
-Suspending 4.8 parts of dimethoxyaniline in 100 parts of water,
To this, 5.9 parts of concentrated hydrochloric acid was added and stirred, and the temperature was adjusted to 0 to 5 ° C.
The temperature was maintained at 3.0 and 3.0 parts of a 40% aqueous sodium nitrite solution was added, followed by stirring at the same temperature for about 30 minutes to obtain a pale yellow diazonium salt solution. On the other hand, 5-acetoacetylamino-
After adding 3.5 parts of benzimidazolone to a solution consisting of 150 parts of water and 0.9 parts of caustic soda, stirring and dissolving,
5.6 parts of sodium acetate trihydrate and 1.5 parts of acetic acid were further added to obtain an acetic acid acidic suspension. To this suspension, a solution of the above diazonium salt was added dropwise for coupling,
8.0 parts of a reddish yellow azo pigment represented by the following structural formula (maximum absorption wavelength 420 nm) was obtained.

[0014]

[Chemical 3]

Example 2 7.7 parts of o-toluidine in 20 parts in 150 parts of 95% sulfuric acid.
Add and dissolve at ~ 25 ° C with stirring and N-at the same temperature.
After adding 22 parts of hydroxymethyl-3,4,5,6-tetrachlorophthalimide and stirring for 48 hours, the reaction product was gradually added to 1500 parts of ice water so that the temperature became 10 ° C or lower. The precipitated crystals were filtered and washed with water until the washing liquid became neutral. After drying at 80 ° C, pale yellow 4- (3,4,5,6-tetrachlorophthalimidomethyl) -2-methylaniline was obtained with a yield of 95%.

The resulting 4- (3,4,5,6-tetrachlorophthalimidomethyl) -2-methylaniline 4.0
A part was subjected to diazotization in the same manner as in Example 1 to obtain a solution of diazonium salt. This solution was added dropwise to an acetic acid acidic suspension of 2.2 parts of acetoaceto-o-chloroanilide to carry out a coupling reaction. As a result, 6.5 parts of a bright yellow azo pigment (maximum absorption wavelength 415 nm) represented by the following structural formula was obtained.

[0017]

[Chemical 4]

Examples 3 to 41 In the same manner as in Examples 1 and 2, azo pigments were produced using the phthalimide derivatives of the general formula (I) shown in Tables 1 to 4 and the coupling component. The maximum absorption wavelengths of the obtained azo pigments are also shown in Tables 1 to 4.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4]

Example 42 9.0 parts of 2-methoxy-5-methylaniline was added to and dissolved in 185 parts of 95% sulfuric acid at 15 to 20 ° C. with stirring, and N-hydroxymethyl-3,4,4 was added at the same temperature. 5,6-
After adding 20.0 parts of tetrachlorophthalimide and stirring for 24 hours, the reaction product was gradually added to 1000 parts of ice water while maintaining the temperature at 5 ° C or lower. The precipitated crystals were filtered and washed with water until the washing liquid became neutral. After drying at 80 ° C, pale yellow 4- (3,4,5,6-tetrachlorophthalimidomethyl) -2-methoxy-5-methylaniline (mp 217 ° C) was obtained with a yield of 94%. This 4- (3,
4,5,6-Tetrachlorophthalimidomethyl) -2-
21.7 parts of methoxy-5-methylaniline was partially dissolved and dispersed in 434 parts of ice water and 63 parts of 2N hydrochloric acid, and diazotized with 25 parts of 2N sodium nitrite solution to obtain a solution of a diazonium salt.

On the other hand, 16.5 parts of 5- (2 ', 3'-oxynaphthoylamino) -benzimidazolone was added to 300 parts.
Part of water and 65 parts of 2N caustic soda solution were dissolved, and the above diazonium salt solution was added dropwise to this solution to cause a coupling reaction. After reaction, heat to 95 ° C for 1 hour,
The reaction product is filtered, washed with water, and dried to obtain a brown-red azo pigment represented by the following structural formula (maximum absorption wavelength 515 nm) 3
6.0 parts were obtained.

[0025]

[Chemical 5]

Example 43 8.0 parts of 2,5-dimethoxyaniline was added to 100% sulfuric acid 1
It is added to 24 parts with stirring at 15 to 20 ° C. and dissolved, and N-hydroxymethyl-3,4,5,6-
Tetrachlorophthalimide (16.0 parts) was added, and the mixture was stirred at 20 to 25 ° C. for 48 hours after the addition was completed.
It was added little by little to 0 part while keeping the temperature at 5 ° C or lower.
The precipitated crystals were filtered and washed with water until the washing liquid became neutral. After drying at 80 ° C., yellow 4- (3, 95% yield
4,5,6-tetrachlorophthalimidomethyl) -2,
5-dimethoxyaniline (mp 170-171 ° C.) was obtained. 11.3 parts of this 4- (3,4,5,6-tetrachlorophthalimidomethyl) -2,5-dimethoxyaniline was partially dissolved and dispersed in 220 parts of ice water and 32 parts of 2N hydrochloric acid to obtain 12.5 parts. 2N sodium nitrite solution was added for diazotization to obtain a diazonium salt solution.

On the other hand, 3.6 parts of β-naphthol was added to 150
Part of water and 33 parts of 2N caustic soda aqueous solution were dissolved, and the above-mentioned diazonium salt solution was added thereto to carry out a coupling reaction. After the reaction, the mixture was heated to 95 ° C. for 1 hour, the reaction product was filtered, washed with water and dried to give a red azo pigment represented by the following structural formula (maximum absorption wavelength 520 nm).
I got 4 parts.

[0028]

[Chemical 6]

Examples 44 to 71 In the same manner as in Examples 42 and 43, azo pigments were prepared using the phthalimide derivatives of the general formula (I) shown in Tables 5 to 7 and the coupling component. The maximum absorption wavelengths of the obtained azo pigments are also shown in Tables 5 to 7.

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Effect] When the phthalimide derivative of the general formula (I) is diazotized and coupled with a coupling component, an azo dye useful as a dye or pigment having excellent weather resistance and solvent resistance can be obtained.

Claims (1)

[Claims] 1. A diazonium salt of a phthalimide derivative represented by the following general formula (I) and an acetoacetanilide coupling component, a naphthol coupling component or a barbituric acid coupling component are coupled. A method for producing an azo dye. [Chemical 1] (Wherein X represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, a nitro group, a halogen atom, an amino group, a substituted amino group or a substituent such as an alkoxycarbonyl group, and Y represents hydrogen. Atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, a nitro group, an alkoxycarbonyl group, a carboxyl group, a sulfonamide group, a sulfonic acid group or the like.