JPH0639573B2 - Pyrrole compound and dyeing or coloring method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pyrrole compound suitable for dyeing hydrophobic synthetic fibers and coloring synthetic resins, and a dyeing and coloring method using the same.

Conventional technology Conventionally, monoazo disperse dyes have been used to obtain deep color tone of blue to blue green in dyeing hydrophobic synthetic fibers and coloring synthetic resins.
Anthraquinone-based disperse dyes Naphthoquinone-based disperse dyes, phthalocyanine-based pigments, polycyclic condensation-based pigments, etc. are used, but their coloring power, affinity for fibers, compatibility with resins,
There is nothing that can sufficiently meet various requirements such as light resistance, wet resistance and solvent resistance, and a synthetic dye / pigment having characteristics suitable for each individual use is used.

Problems to be Solved by the Invention In view of the above situation, the color value is high as compared with known dyes and pigments,
It is desired to develop a coloring agent that is clear and has a high affinity for fibers and resins and is robust.

Means for Solving Problems As a result of earnest research in order to obtain a coloring agent that is clear and has high coloring power, the following structural formula (I) (In the formula (I), X is an ethoxycarbonyl group, a methoxycarbonyl group or a phenylsulfone group, Y is an ethoxycarbonyl group, a methoxycarbonyl group, a phenylsulfone group or a cyano group, and R ₁ is hydrogen, a methyl group, An ethyl group, an allyl group or a benzyl group, R ₂ is hydrogen, a methyl group, a methoxy group or an ethoxy group, and W ₁ and W ₂ are C _1-4 alkyl groups, cyanoethyl groups, β-methoxyethyl groups, β- An ethoxyethyl group, a benzyl group, a phenylethyl group or a phenylpropyl group, respectively, provided that R ₁ and R ₂ are hydrogen, X and Y are phenyl sulfone groups, and W ₁
And W ₂ is a butyl group. The present invention has led to the discovery of a method for synthesizing a pyrrole-based compound represented by the formula (1), and the development of a method for coloring fibers and resins into vivid red-blue to blue-green by using the method.

Thus, the pyrrole compound (I) in the present invention is produced, for example, as shown in the following steps.

(In the formulas (I) to (IV), X, Y, R ₁ , R ₂ , W ₁ and W ₂ have the same meanings as described above.) That is, ethyl cyanoacetate and methyl cyanoacetate represented by CNCH ₂ X. , Cyanomethylphenyl sulfone 2 mol, or CN
Compounds of the formulas (II) and (II) ′ obtained by reacting 1 mol of CH ₂ X and 1 mol of malononitrile with a slight excess of 1 mol of sodium methylate or sodium ethylate are condensed with diethyl oxalate to form the formula (III ) Compound is synthesized. Further formula
The compound of (III) is reacted with a chlorinating agent to form the formula (IV) and condensed with the aniline of the formula (V) to form (I), or the alkylating agent R ₁ -Z (IV) is further added. By acting, (I) 'is synthesized.

(II) and (II) 'are easily obtained by refluxing CNCH ₂ X alone or CNCH ₂ X and malononitrile in ethanol in the presence of sodium alcoholate. Formula (II) or (I
Condensation of the compound of I) 'with diethyl oxalate is 2 in ethanol.
Refluxing in the presence of a molar ratio of sodium methylate for 2 to 3 hours facilitates the progress, and after cooling, the precipitate can be isolated as the sodium salt of formula (III). When the sodium salt of formula (III) is dissolved in dimethylformamide and 2 to 4 mol of a chlorinating agent such as phosphorus oxychlorothionyl chloride is added and reacted at room temperature for 2 to 3 hours, formula (IV) is formed, which is ice water. The compound of formula (IV) can be isolated by medium pouring and salting out, but the condensation of the next step can also be carried out without isolation.

Specific examples of the aniline derivative of the formula (V) include N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, N-ethyl-N-benzylaniline and N-methyl-N-phenyl. Phenylpropylaniline, 3-methyl-N, N
-Diethylaniline, 3-ethoxy-N, N-diethylaniline, 2-methoxy-N, N-diethylaniline, N-
Ethyl-N-cyanoethyl-aniline, N, N-bis-β
-Ethoxyethylaniline and the like are exemplified, but the condensation of these with the compound of the formula (IV) can be carried out in an inert solvent such as dimethylformamide, acetonitrile, tetrahydrofuran, etc.
It is achieved by heating and stirring at 100 ° C, preferably 20 to 40 ° C.

Examples of the alkylating agent represented by R ₁ -Z include diethyl sulfate, methyl toluenesulfonate, allyl bromide,
Examples include benzyl chloride and the like.
The conversion to (I) ′ is carried out by reacting the compound of formula (I) in dimethylformamide in the presence of magnesium oxide, potassium carbonate or the like as an acid neutralizing agent at 60 to 100 ° C. Can be implemented.

Thus, these pyrrole compounds are novel, have a vivid red-blue to blue-green color, and are suitable for dyeing hydrophobic synthetic fibers such as polyester fibers, triacetate fibers, and polyamide fibers, and synthetic resins such as It is also useful for coloring polystyrene type, polyolefin type, polyacrylate type, polyamide type, acrylonitrile-styrene copolymer type, acrylonitrile-butadiene-styrene copolymer type resins and the like.

As a method for dyeing the hydrophobic synthetic fiber, the compound of the formula (I) is dispersed by a conventional method. For example, in a sand mill, wet microparticulation is carried out in the presence of a small amount of water together with an anionic dispersant such as naphthalene sulfonic acid, formalin condensate and lignin sulfonic acid, and a nonionic dispersant such as polyoxyalkyl ethers to form a liquid state. Alternatively, it is provided as a spray-dried powder for dyeing. As the dyeing method, high temperature or carrier dip dyeing by a conventional method, continuous dyeing by a thermosol method,
Printing and transfer printing can be applied. As a method for coloring synthetic resins, the required amount of the pyrrole compound of the present invention is blended in the synthetic resin and kneaded, followed by molding at a temperature corresponding to each synthetic resin by compression molding, injection molding or calender molding. Can be implemented easily.

The pyrrole-based compound of the formula (I) shows high dyeability or colorability with respect to the hydrophobic synthetic fiber or the synthetic resin, and the obtained dyed product or colored product showing a vivid blue color has excellent fastness (especially sunlight). Fastness).

EXAMPLES The present invention will be described in more detail by way of examples.

In the examples, "part" represents part by weight.

Example 1. Known β-imino-α-cyano-glutaric acid diethyl ester obtained by dimerizing ethyl cyanoacetate 5.6
And 3.7 parts of diethyl oxalate were stirred in 20 parts of ethanol and added with 9.6 parts of 28% sodium methylate solution to obtain 7 parts.
The mixture was heated and stirred at 5 ± 2 ° C for 2 hours. Cool to room temperature, separate the precipitate and wash with some ethanol. When dried, 7.5 parts of a sodium salt of a compound represented by the following structural formula (a) was obtained. This compound (a) was dissolved in 50 parts of dimethylformamide, 7.7 parts of phosphorus oxychloride was added dropwise over 30 minutes under stirring at 15 ° C. or lower, and then the temperature was raised by heating at 20 ± 2 ° C. for 1 hour 3
Stir for 0 minutes. Pour the reaction solution into 500 parts of ice water and add salt.
Add 0 part, stir, and salt out. The precipitate was separated, washed with water and dried to obtain 5.5 parts of the compound of the following structural formula (II). mp
128-131 ° C. 1.6 parts of the compound of structural formula (b) was added to dimethylformamide 20.
1.0 part of N, N-diethylaniline was added, and the mixture was stirred at room temperature for 2 hours and 40 ± 2 ° C. for 2 hours. The reaction solution is poured into 300 parts of ice water and 10 parts of common salt is added for salting out. The precipitate was separated, washed with water, and dried to obtain 1.5 parts of a pyrrole compound represented by the following structural formula (C).

Example 2. Cyanomethyl-phenyl-sulfone 13.2 parts, ethanol 35 parts, 28% sodium methylate methanol solution
7.8 parts are refluxed and stirred for 3 hours. 28% in this reaction solution
Add 2.8 parts of sodium methylate methanol solution and stir under reflux for 2 hours. The reaction solution is poured into 500 parts of ice water, hydrochloric acid is added with stirring to adjust the pH to 3, and 10 parts of sodium chloride is added to carry out acid precipitation. Separate the precipitate, wash with water and dry. Recrystallization from ethanol gave 9.2 parts of the compound of the following structural formula (d). mp211-213 ° C. 9.0 parts of the above compound (d) and 3.7 parts of diethyl oxalate are stirred in 30 parts of ethanol, then 9.7 parts of 28% sodium methylate solution are added and the mixture is stirred under reflux for 2 hours. The mixture was cooled to room temperature, the precipitate was separated, washed with a small amount of ethanol and then dried to obtain 10.8 parts of a sodium salt of a compound represented by the following structural formula (e).

4.2 parts of the compound represented by the structural formula (e) was added to dimethylformamide 40
Then, 3.2 parts of phosphorus oxychloride was added dropwise with stirring at 10 ° C. or lower over about 20 minutes, and the mixture was stirred at room temperature for 1 hour. Then N,
3.6 parts of N-diethyl-aniline was added at 10 ° C or lower, and the mixture was stirred for 15 minutes. The obtained reaction solution was added to 300 parts of ice water,
The mixture was poured under stirring, the precipitate was separated, washed with water and dried to obtain 4.2 parts of a pyrrole compound represented by the following structural formula (f).

Example 3. 4.6 parts of cyanomethyl-phenyl sulfone and 1.7 parts of malononitrile were stirred in 10 parts of ethanol, 4.8 parts of 28% sodium methylate was added thereto, and the mixture was stirred at room temperature for 1 hour. After stirring under reflux for 3 hours, the mixture is poured into 150 parts of ice water and hydrochloric acid is added to adjust the pH to 4. Separate the precipitate, wash with water,
When dried, 5.1 parts of a compound having the structural formula (g) as a main component was obtained.

5.0 parts of the above compound (g) and 2.9 parts of diethyl oxalate were stirred in 25 parts of ethanol, and then 7.8 parts of 28% sodium methylate was added thereto, followed by heating at 75 ± 2 ° C. for 2 hours. . After cooling, the precipitate was separated, washed with a small amount of ethanol, and then dried to obtain the sodium salt of the compound of structural formula (H) 6.
5 copies were obtained.

2.9 parts of the compound of structural formula (H) was added to dimethylformamide 30
Then, 3.1 parts of phosphorus oxychloride was added dropwise at 10 ° C or lower with stirring and the mixture was stirred at room temperature for 1 hour. Further, 3.8 parts of N-ethyl-N-β-ethoxyethyl-aniline was added at 10 ° C or lower, and the mixture was stirred for 15 minutes. The reaction solution was poured into 250 parts of ice water, the precipitate was separated, washed with water and dried to obtain 2.3 parts of a pyrrole compound of the following structural formula (i).

Example 4. Ethyl cyanoacetate (22.6 parts) and malononitrile (13.2 parts) were stirred in 60 parts of ethanol, 28% sodium methylate (38.5 parts) was added thereto, and the mixture was refluxed for 5 hours. Ice water 600
PH to 4 by adding hydrochloric acid with stirring, and salt 2
Add 0 parts and salt out. The precipitate was separated and dried to obtain 15 parts of a compound having the following structural formula (e) as a main component.
9.6 parts of the compound of the structural formula (nu) and 7.3 parts of diethyl oxalate are added to 50 parts of ethanol, 19.5 parts of 28% sodium methylate is added with stirring, and the mixture is heated under reflux for 2 hours. After cooling, the precipitate was separated, washed with a small amount of ethanol and dried to obtain 14.0 parts of a compound represented by the following structural formula (l). 2.7 parts of the compound of structural formula (l) was dissolved in 30 parts of dimethylformamide to obtain 10 parts.
4.6 parts of phosphorus oxychloride is added dropwise with stirring at a temperature below ℃. After stirring at room temperature for 2 hours, 4.5 parts of N-methyl-N-phenylpropyl-aniline was added at 10 ° C or lower, and the mixture was stirred for 15 minutes. Ice water 2
The mixture was poured into 50 parts, the precipitate was separated, washed with water and dried to obtain 3.7 parts of the pyrrole compound represented by the following structural formula (e).

This dye dyed polyester fibers in a bright blue color.

Examples 5-19. Pyrrole compounds of formula (I) were synthesized from compounds of formula (III) and formula (V) as described in Examples 1-4. Their λmax
(85% in acetone) and the hues of polyester fibers dyed with them are shown.

Example 19. 1.7 parts of the pyrrole dye (c) described in Example 2 was dissolved in 20 parts of dimethylformamide, 0.4 parts of potassium carbonate and 0.6 parts of benzyl chloride were added, and the mixture was heated with stirring at 90 ± 2 ° C. for 2 hours. To do. After cooling, the mixture is poured into 300 parts of ice water, the precipitate is separated and recrystallized from methanol. Compound of the following structural formula (wa)
1.2 copies were obtained.

This dye dyed polyester fibers in purple blue.

Examples 20-23. Pyrrole compounds (c), (f) and (i) described in Examples 1 to 4
Alternatively, (e) was reacted with an alkylating agent for R ₁ -Z as described in Example 20 to obtain a pyrrole compound (Ic). The λ max values (85% acetone water) and the hues of the polyester dyed with them are shown.

Example 24. 20 parts of the pyrrole-based compound (i) of Example 3 and demol N
(Naphthalene formalin condensate made by Kao Atlas) 20
Part and 60 parts of water were treated in a sand mill for 5 hours to obtain a dispersion liquid. A dyebath is prepared with 8 parts of this dispersion and 3000 parts of water, and acetic acid is added to adjust the pH to 5. 100 parts of polyester fiber is dipped and dyed under pressure at 130 ° C. for 60 minutes. After that, reduction and washing gave a bright blue dyed product. The fastness (in particular, fastness to sunlight) of this dyed product was excellent.

Example 25. Using the pyrrole compound (C) of Example 1, a dispersion is prepared as in Example 25.

Using this dispersion, a mixture having the following composition is mixed with a homomixer to prepare a printing paste.

Polyester fibers are imprinted with this printing paste and intermediate drying is carried out at 80 ± 3 ° C. for 30 minutes. Then, steaming is performed at 130 ° C. for 30 minutes to develop a color. It was washed with water, washed with hot water, desized, and subjected to reduction washing to obtain a clear purple-blue printed fabric. The fastness (particularly fastness to sunlight) of this printing cloth was excellent.

Example 26. Fine powder 0.2 parts of the pyrrole compound (f) of Example 2 and 100 parts of powdered ABS resin were thoroughly mixed, heated and melted at 120 ° C., and pelletized through an extruder. Then, molded at 230 ° C. with an injection molding machine. Then, a clear greenish blue molded product was obtained. The fastness (particularly fastness to sunlight) of this colored molded article was excellent.

EFFECTS OF THE INVENTION A clear and fast blue to green-blue pyrrole compound having a high color value, which is useful for dyeing hydrophobic fibers and coloring synthetic resins, was obtained.

Claims (2)

[Claims] 1. A formula (I) (In the formula (I), X represents an ethoxycarbonyl group, a methoxycarbonyl group or a phenylsulfone group, Y represents an ethoxycarbonyl group, a methoxycarbonyl group, a phenylsulfone group or a cyano group, and R ₁ represents hydrogen, a methyl group or an ethyl group. ,
Allyl group or benzyl group, R ₂ is hydrogen, methyl group, methoxy group or ethoxy group, W ₁ and W ₂ are C _1-4 alkyl group, cyanoethyl group, β-methoxyethyl group, β
-Ethoxyethyl group, benzyl group, phenylethyl group or phenylpropyl group is shown. However, R ₁ and R
₂ is hydrogen, X and Y are phenyl sulfone groups, and W ₁ and W ₂ are butyl groups). 2. Formula (I) (In the formula (I), X represents an ethoxycarbonyl group, a methoxycarbonyl group or a phenylsulfone group, Y represents an ethoxycarbonyl group, a methoxycarbonyl group, a phenylsulfone group or a cyano group, and R ₁ represents hydrogen, a methyl group or an ethyl group. ,
Allyl group or benzyl group, R ₂ is hydrogen, methyl group, methoxy group or ethoxy group, W ₁ and W ₂ are C _1-4 alkyl group, cyanoethyl group, β-methoxyethyl group, β
-Ethoxyethyl group, benzyl group, phenylmethyl group or phenylpropyl group is shown. However, R ₁ and R
₂ is hydrogen, X and Y are phenyl sulfone groups, and W ₁ and W ₂ are butyl groups, except for the use of a pyrrole compound, and dyeing or synthesizing a hydrophobic fiber. Resin coloring method