JPS6236071B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a water-insoluble pyridone azo dye. More specifically, 1,6-diaminoanthraquinone and/or 1,7-diaminoanthraquinone is diazotized, and the formula () 3-cyano-4-methyl-6 represented by {in formula (), R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group,}
Formula () characterized by coupling with -hydroxy-2-pyridones [In the formula (), R ₁ represents the same meaning as in the formula (), and the azo group and the amino group are present at the α and β′ positions with respect to the anthraquinone, respectively.] It is. The present invention provides a method for producing useful new azo dyes using 1,6- and 1,7-diaminoanthraquinones, which have rarely been used as dye intermediates. α・α′-disubstituted anthraquinone, which is an important intermediate in the production of various dyes, is conventionally obtained by disulfonating anthraquinone using mercury as a catalyst.
-The method using anthraquinone disulfonic acid as a starting material was the most common industrial method, but in recent years it has become nearly impossible to implement this method due to pollution problems caused by mercury, and instead anthraquinone is dinitrated. A method using the obtained dinitroanthraquinone as a starting material has attracted attention as an effective means. However, when anthraquinone is dinitrated, in addition to the target α・α′-dinitroanthraquinone, α・β′-dinitroanthraquinone is
It is well known that 30% of the product is produced as a by-product. In this sense, it is of great industrial significance to effectively utilize α·β′-diaminoanthraquinone obtained by reducing α·β′-dinitroanthraquinone. In addition to a hydrogen atom, R ₁ of the pyridones represented by the general formula (), which is the other raw material of the present invention, includes a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group,
sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-octyl group,
1 such as 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc.
Alkyl groups having ~12 carbon atoms; lower alkoxy lower alkyl groups such as methoxyethyl, methoxypropyl, ethoxypropyl and the like. These 3-cyano-4-methyl-6-hydroxy-2-pyridones have the following formula (), R ₁ -NH ₂ ...... () {In formula (), R ₁ is the above formula () } and methyl acetoacetate and methyl cyanoacetate according to the method of JMBobbitt & DAScola {J.Org.
Chem.Vol.25P.560 (1960)}. In the present invention, commonly used methods are used for diazotization and coupling reactions.
For example, 1,6- and/or 1,7-diaminoanthraquinone is diazotized by adding to nitrosyl sulfuric acid prepared from concentrated sulfuric acid and sodium nitrite, or dissolved or suspended in an aqueous hydrochloric acid solution, and then dissolved in an aqueous solution of sodium nitrite. This is carried out by adding to an alkaline aqueous solution of 3-cyano-4-methyl-6-hydroxy-2-pyridones containing sodium acetate, sodium carbonate, sodium hydroxide and the like. Although the coupling reaction can be carried out in neutral or alkaline conditions, it is preferably carried out in acidic conditions. The dyes obtained according to the invention are suitable for dyeing various synthetic fiber materials, especially polyester fibers. In addition, synthetic fibers made of synthetic or semi-synthetic polymer substances such as polyacrylonitrile fibers, triacetate fibers, diacetate fibers, polyamide fibers, polyurethane fibers, etc. can be dyed yellow with good fastness. I can do it. Many dyes similar to the dye of the present invention have been reported, but each of these known dyes has its own characteristics, and although they have been put into practical use, they all have various unsatisfactory points. ing. As a result of intensive research and consideration, the present inventors have found that when the dye of the present invention is used to dye and print the synthetic fiber materials, especially polyester fibers, various fastness properties are markedly excellent, especially sunlight fastness and sublimation fastness. The present invention was completed by discovering that a yellow dyed product with extremely high strength can be obtained. When used as a dye, it is dispersed in fine form with a dispersant and a wetting agent by a known method, preferably from an aqueous dispersion bath, and can be prepared by conventional methods such as high temperature dyeing, carrier dyeing, thermosol dyeing or printing. method is applied. In this way, a yellow dyed product with excellent fastness to sunlight, sublimation, washing, abrasion, etc., especially after silicone water repellent finishing and antistatic finishing, is obtained. In addition, the novel dye obtained by the present invention has features such as a high dyeing rate in real-temperature dyeing, low PH sensitivity, and little decomposition of the dye during dyeing. The contents of the present invention will be specifically explained below by giving Examples. Example 1 1,6-diaminoanthraquinone and 1,7-
Mixture of diaminoanthraquinones (1,6-isomer:
1.7-isomer = 6:4) 23.8g (0.1g-mol)
was diazotized by adding it to nitrosyl sulfuric acid prepared by dissolving 7.0 g of sodium nitrite in 93 g of 98% sulfuric acid at 20 to 25°C. This diazo solution was added to a solution consisting of 22.2 g (0.1 g-mol) of 1-(3-methoxy-propyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone, 10 g of sodium hydroxide, and 400 g of water. ~5℃
It took 30 minutes to drip. The coupling reaction was completed by adding sodium acetate to the reaction solution at 0 to 5°C and adjusting the pH to 8. After further stirring at room temperature for 2 hours, the precipitated crystals were filtered, washed with water, and dried.
A tan powder was obtained. The λmax of this product was 428 nm (solvent: acetone, same hereinafter). When polyester fibers were dyed at high temperature (130°C) using this dye in a conventional manner, a yellow dyed product was obtained. This dyed product had excellent light fastness, sublimation and washing fastness after post-processing. Example 2 1,6-diaminoanthraquinone 23.8g (0.1
g-mol) at 50-55°C, sodium nitrite 7
diazotization was carried out using nitrosyl sulfuric acid prepared by dissolving 100g of the product in 90g of concentrated sulfuric acid. This diazo solution was added to 1-(n-butyl)-3-cyano-4-methyl-6-hydroxy-2-pyridone21
g (0.1 g-mol), sodium hydroxide 15 g, water
It was added dropwise to a solution consisting of 500 g over a period of 30 minutes at 0-5°C. The coupling reaction was completed by adding sodium acetate to the reaction solution at the same temperature and adjusting the pH to 5. After further stirring for 2 hours, the precipitated crystals were filtered, washed with water, and dried to obtain a brown powder. The λmax of this product was 430 nm. When polyester fibers were dyed at high temperature (130°C) using this dye in a conventional manner, a yellow dyed product was obtained. The light fastness and sublimation fastness of this dyed product were excellent. Example 3 1,7-diaminoanthraquinone 23.8g (0.1
g-mol) in a mixture of 80 g of concentrated hydrochloric acid and 500 g of water, and a solution of 7.0 g of sodium nitrite dissolved in 60 g of water was added dropwise at 0 to 5°C, followed by stirring for 1 hour at 0 to 5°C. Diazotized. Excess nitrous acid is decomposed by adding 0.5 g of sulfamic acid, and 3-cyano-4
-Methyl-6-hydroxy-2-pyridone 15.0g
(0.1g-mol), sodium hydroxide 10g, water 400g
It was added dropwise to a solution consisting of at 0 to 5°C over 30 minutes. At the same temperature, add sodium acetate to adjust the pH of the reaction solution.
Coupling was completed by adjusting to 5. After further stirring for 2 hours, the precipitated crystals were filtered, washed with water, and dried to obtain a yellowish brown powder. The λmax of this product was 425 nm. When polyester fibers were dyed at high temperature (130°C) using this dye in a conventional manner, a yellow dyed fabric was obtained. This product had good light fastness and sublimation fastness. Examples 4 to 12 1.
A mixture of 6-diaminoanthraquinone and 1,7-diaminoanthraquinone was diazotized and coupled with a pyridone compound in which R ₁ of formula () is shown in the middle column of Table 1 to synthesize the corresponding dye. Polyester fibers were dyed at high temperature (130°C) using these dyes in a conventional manner. The color tones of the dyed fabrics obtained were as shown in the right column of Table 1, and were excellent in various fastnesses. 【table】

Claims (1)

[Scope of Claims] 1 1,6-diaminoanthraquinone and/or 1,7-diaminoanthraquinone is diazotized to produce the formula () {In formula (), R ₁ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a lower alkoxyalkyl group} 3-cyano-4-methyl-6-hydroxy-2-pyridone The expression () is characterized by being coupled with the class {In formula (), R ₁ represents the same meaning as in formula (), and the azo group and amino group are present at the α and β' positions, respectively, with respect to anthraquinone} A method for producing an azo dye represented by the following.