JPH0420947B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heterocyclic compound useful for dyeing or coloring hydrophobic fiber materials, synthetic resins, etc. More specifically, the present invention relates to the general formula () [In the formula, R ₁ and R ₂ are hydrogen atoms, optionally substituted alkyl groups, cycloalkyl groups, alkenyl groups, or alkynyl groups, or optionally substituted phenyl groups, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
NHSO ₂ R ₆ , Y is a cyano group, a nitro group, -SO ₂ R ₆
or - represents CONHR. However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group. A and A' represent oxygen atoms or sulfur atoms. ] The present invention relates to a heterocyclic compound represented by the following, and a method for dyeing hydrophobic fiber materials or a method for coloring synthetic resins using the same. In the present invention, substituents for the optionally substituted alkyl group in R ₁ and R ₂ include, for example, chlorine, bromine, hydroxyl group, cyano group, -OR ₇ , -
CO ₂ R ₇ , −OCOR ₇ , −OCO ₂ R ₇ , −OSO ₂ R ₇ , −
NHSO ₂ R ₇ , −NHR ₇ , −OCONHR ₇ , −NHCOR ₇ ,
−NHCO ₂ R, −SR ₈ , alkenyl group,

【formula】

【formula】

[expression] or

[Formula] can be given. Examples of substituents for the phenyl group include a lower alkyl group, a lower alkoxy group, and a halogen atom. However, R ₃ represents the above meaning, and R ₇ is an alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or phenyl group (lower alkyl group, lower alkoxy group, halogen atom, lower alkanoylamino group, cyano group, lower (optionally substituted with an alkoxycarbonyl group). R ₈ represents a lower alkyl group, an optionally substituted phenyl group, a benzothiazolyl group or a benzoxazolyl group. R ₉ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower alkanoylamino group, a cyano group, or a lower alkoxycarbonyl group. n represents an integer of 1 or more. Specifically, R ₆ is, for example, methyl, ethyl, propyl, butyl, phenyl, chlorophenyl, bromphenyl, methylphenyl, ethyl phenyl, propylphenyl, butylphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl or butoxyphenyl. Examples include bases. Examples of R ₇ include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, i-butyl, t-butyl, cyclohexyl, cyclopentyl, vinyl, -CH= _CHCH3 , -CH=C( _CH8 ) ₂ ,
-CH=CHCl, -CH=CHBr, phenyl, methylphenyl, ethyl phenyl, propylphenyl,
Methoxyphenyl, ethoxyphenyl, chlorphenyl, bromphenyl, benzyl, methylbenzyl, ethylbenzyl, propylbenzyl, methoxybenzyl, ethoxybenzyl, chlorbenzyl, brombenzyl, phenethyl, methylphenethyl, ethylphenethyl, methoxyphenethyl,
Ethoxyphenethyl, chlorphenethyl, bromphenethyl, acetylaminophenyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, cyanophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylphenyl or butoxycarbonyl Examples include phenyl group. Examples of R ₈ include methyl, ethyl, propyl, butyl, phenyl, methylphenyl, ethyl phenyl, propylphenyl, butylphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, cyanophenyl, chlorphenyl, bromphenyl, acetylaminophenyl, Examples include enyl, propionylaminophenyl, propylcarbonylaminophenyl, butylcarbonylaminophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, propoxycarbonylaminophenyl, and butoxycarbonylphenyl groups. A compound represented by the general formula () is a compound represented by the general formula () (In the formula, A, A', Y represent the above meanings) and a compound represented by the general formula () (In the formula, X, R ₂ , R ₃ .R ₄ , R ₅ represent the above-mentioned meanings.)
The reaction is carried out in an inert solvent, and if necessary, a group is added.
It can be synthesized by introducing R ₁ .
Examples of inert solvents include dimethylformamide, dimethylsulfoxide, acetonitrile,
Ethyl acetate, sulfolane, tetrahydrofuran,
Examples include toluene. In addition, to introduce a group R ₁ if necessary, the reaction product of the compound () and () and the general formula () R ₁ −W () (where W is chlorine, bromine, iodine, −OSO ₂ CH ₃ ,

It can be carried out by reacting a compound represented by [Formula] or -R ₁ OSO ₃ in the presence of a base. Examples of the base include L(OH), L ₂ CO ₃ , LHCO ₃ , M
(OH) ₂ (L represents an alkali metal and M represents an alkaline earth metal). The compound of general formula () can be obtained by treating a reaction product of malonamide and diethyl oxalate with phosphorus oxychloride. The compound of the general formula () thus obtained has excellent dyeing properties on hydrophobic fibers, and also has good dye bath stability and build-up properties. Further, it provides a dyed product having a clear color tone ranging from reddish yellow to greenish blue, and has excellent fastness such as water fastness, sublimation fastness, light fastness, and washing fastness. When the obtained compound is used as a dye, it is first dispersed according to a conventional method. For example, in a sand mill, naphthalene sulfonic acid formalin condensate,
Anionic dispersants such as lignin sulfonic acid, gresol/scheffic acid formalin condensate, etc., or various dispersants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, and other nonionic dispersants as desired. It may be treated with a dispersant selected by the manufacturer and an appropriate amount of water, and it may be processed in a liquid state or dried to form a powder or granules. Synthetic resins to which the dyeing method of the present invention can be applied include synthetic polyamide fibers, polyester fibers, and other so-called hydrophobic synthetic fibers, and semi-synthetic fibers such as g- or triacetate, and these may be used alone or in combination. Furthermore, it refers to various forms of fiber materials mixed with other natural fibers. Among these, polyester fibers and mixed products of polyester fibers and natural or regenerated cellulose fibers are also particularly suitable. Dyeing methods in the present invention include dip dyeing, continuous dyeing, textile printing, and transfer printing. In particular, the compound of the present invention is an extremely suitable dye for dyeing and continuous dyeing of mixed products of polyester fibers and cellulose fibers, since stains on cellulose fibers can be easily removed. In textile printing, it is particularly suitable as a base dye for alkaline resist discharge printing in addition to ordinary direct textile printing. The compound of the present invention is also useful as a coloring agent for synthetic resins, and it is possible to obtain various colored synthetic resins having vivid color tones ranging from reddish yellow to greenish blue, which are robust with respect to light, heat and migration. can. Suitable synthetic resins for coloring with the compound of the present invention include polystyrene-based, polyolefin-based, polyacrylate-based, polyvinyl acetate-based, polyvinyl chloride-based, polyamide-based, polycarbonate-based, polyacetal-based, polyester-based resins, Furthermore, acrylonitrile-styrene copolymer (AS resin), acrylonitrile. Examples include butadiene-styrene copolymer (ABS resin). In order to color a synthetic resin using the compound of the present invention, for example, the required amount of the compound of the present invention represented by the general formula () is blended with the synthetic resin, kneaded, and then subjected to compression molding, injection molding, or calendar molding. Film,
It is possible to obtain solid molded products such as plates and pipes colored in colors ranging from reddish-yellow to greenish-blue. If desired, in addition to the compound of the present invention represented by the general formula (), one or more of known colorants and additives such as organic pigments, inorganic pigments, lubricants, ultraviolet absorbers, and antioxidants may be added. Favorable results can also be obtained by adding and using . The compound of the present invention can also be used as a dye for various recording materials. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the Examples, unless otherwise specified, parts represent parts by weight, and color tones represent those on polyester fibers. Example 1 Formula (a) below Dissolve 15.6 parts of the compound shown in 50 parts of N,N-dimethylformamide, and add N-ethyl-
40 parts of 2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline are added at room temperature. After 30 minutes, 50 parts of water is added, and the precipitate is filtered, washed with water, and dried.
25 parts of compound (1) having the following structural formula are obtained. λmax: 532 nm (dimethylformamide) Color tone: bluish red Example 2 15 parts of the compound (1) obtained in Example 1 was dissolved in 50 parts of N,N-dimethylformamide, and 9.7 parts of anhydrous potassium carbonate and iodide were dissolved therein. Add 14.5 parts of ethyl and heat to 60°C. After 30 minutes, add 100 parts of water while cooling with ice-water. The precipitated solid is filtered, washed with water, and dried. 15.5 parts of a compound (2) having the following structural formula is obtained. λmax: 531 nm (dimethylformamide) Color tone: bluish red Example 3 7.8 parts of the compound (a) shown in Example 1 was mixed with N,
Dissolve in 30 parts of N-dimethylformamide and add N-β-phenoxyethyl 2,2,4-trimethyl-1,2,3,4,-tetrahydroquinoline.
Add 29.5 parts at room temperature. After 30 minutes, add 30 parts of water, filter the precipitate, wash with water, and dry. This product is N,
Dissolve in 30 parts of N-dimethylformamide, add 10 parts of anhydrous potassium carbonate and β-bromopropionitrile, and heat to 60°C. After 30 minutes, add 100 parts of water while cooling with ice-water. Filter the precipitated solid, wash with water,
After drying, 17 parts of compound (3) of the lower structural formula are obtained. λmax: 534 (dimethylformamide) Color tone: Bluish red Example 16 parts of the compound (1) obtained in Example 1 was dissolved in 50 parts of dimethyl sulfoxide, and 14 parts of potassium hydroxide was added to this.
1 part, add 11.1 parts of phenethyl bromide and stir at room temperature.
Stir for an hour. Add 100 parts of water while cooling, filter the precipitated solid,
After washing with water and drying, 18 parts of compound (4) of the following formula are obtained. λmax: 530 nm (dimethylformamide) Color tone: bluish red Example 5 Using the compound (2) obtained in Example 2, staining was carried out by the following procedure. a Preparation of dispersion Compound (2) 20 parts Anionic dispersant (Note 1) 20 parts Water 60 parts (Note 1) Naphthalene sulfonic acid formalin condensate The above mixture was treated in a sand mill for 4 hours to obtain a dispersion. . b. Staining Add 3 parts of the dispersion obtained in a) to a dyeing pot with 3000 parts of water and adjust the pH to 5 using acetic acid. Next, 100 parts of polyester fabric was added to this, and 130 parts of
Perform staining for 60 min at °C. After finishing dyeing, wash and rinse using the usual method. To obtain a vivid bluish-red dyed product with excellent color fastness. Example 6 Using the compound (2) obtained in Example 2, a dispersion is prepared according to a) of Example 5. Using this dispersion, a printing paste having the following composition is prepared. (Printing paste composition) Above dispersion 3 parts Half emulsion base paste (Note 2) 60 parts Tartaric acid 0.3 parts Sodium chlorate 0.2 parts Water Remaining total 100 parts (Note 2) Half emulsion base paste composition Kerosene 70 parts Water 25 Part Viscon KM-3 (Note 3) 5 parts Total 100 parts (Note 3) Shin-Nakamura Chemical Co., Ltd.: Emulsifier Emulsion made by mixing the above in a high-speed mixer
Mix 30 parts with 70 parts of Maypro Gum NP 12% paste (Greenough product) to make a half emulsion base paste. Using the dyeing paste thus obtained, hand printing is performed on polyester cloth. The cloth is then dried and subjected to superheated steam treatment at 175°C for 7 minutes. Thereafter, washing and drying are performed using a conventional method. A robust and vivid bluish-red printed fabric is obtained. Example 7 Using a dispersion of the compound of Example 3 prepared according to the method of Example 5, the polyester fabric of Example 5 was prepared.
Dyeing is performed using 100 parts of polyester and 100 parts of cotton cloth instead of 100 parts. After dyeing, the temperature of the dye bath is set to 60℃.
6 parts of sodium carbonate was added to the dye bath and kept at 60°C for 1 hour. Next, the cloth to be dyed is taken out and washed with hot water and water. Polyester fabrics are dyed in a vivid and strong bluish-red color, whereas cotton fabrics are dyed with virtually no staining. Example 8 0.2 part of the finely powdered compound (14) and powdered ABS resin
After heating and mixing 100 parts at 120°C, pellets are made through an extruder. This is then molded using an injection molding machine at 230°C. A clear bluish-red molded product is obtained that is robust to heat, light and migration. Example 9 30 parts of Sumikaron Turquoise Blue S-GL (Sumitomo Chemical Disperse Dye) was dispersed in 170 parts of warm water, then 50 parts of potassium carbonate, 10 parts of glucose, 150 parts of polyethylene glycol (MW300) and Kiprogum P-
Add 570 parts of 12% paste of 20N (Nippon Chemical Co., Ltd.) to prepare a total of 1000 parts of uniform printing paste, and print on this polyester fiber cloth. Separately, 100 parts of the dispersion obtained in Example 5 was dispersed in 300 parts of hot water, and then 665 parts of Kiprogum P-20N 12% concentration paste and 5 parts of metanitrobenzenesulfonic acid soda were added to make a total of 1000 parts of uniform printing paste. Adjust. This printing paste is overprinted on the previously printed fabric, dried, and then subjected to HT steam treatment at 175℃ for 8 minutes. Next, wash with water, add 2 ml/l of caustic soda (40°B′e), and 2 ml of hydrosulfite.
g/l, treated with a cleaning solution containing 1 g/l of a nonionic detergent at 75°C for 5 minutes, and finished by washing with water. In this way, a greenish-blue pattern on a red background was obtained. Example 10 The compounds shown in the table below are obtained by the same method as in Examples 1 to 4.

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Claims (1)

[Claims] 1 General formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, or an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -NHSO ₂ R ₆ , Y is a cyano group, a nitro group, -SO ₂ R ₆ or -CONHR ₆
represents. However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group. A and A' represent oxygen atoms or sulfur atoms. ] A heterocyclic compound represented by 2 General formula () [In the formula, R ₁ and R ₂ are a hydrogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, or an alkynyl group, or an optionally substituted phenyl group, R ₃ , R ₄ , and R ₅ each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHCOR ₆ or -
NHSO ₂ R ₆ , Y is a cyano group, a nitro group, -SO ₂ R ₆
or - represents CONHR ₆ . However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group. A and A' represent oxygen atoms or sulfur atoms. ] A method for dyeing a phobic fiber material, characterized by using a heterocyclic compound shown in the following. 3 General formula [In the formula, R ₁ and R ₂ are hydrogen atoms, optionally substituted alkyl groups, cycloalkyl groups, alkenyl groups, or alkynyl groups, or optionally substituted phenyl groups, R ₃ , R ₄ , and R ₅ are Each represents a hydrogen atom or a lower alkyl group. X is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, -NHSO ₂ R ₆ or -
NHSO ₂ R ₆ , Y is a cyano group, a nitro group, -SO ₂ R ₆
or - represents CONHR ₆ . However, R ₆ represents a hydrogen atom, a lower alkyl group, a phenyl group optionally substituted with a halogen atom or a lower alkoxy group. A and A' represent oxygen atoms or sulfur atoms. ] A method for coloring a synthetic resin, characterized by using a heterocyclic compound represented by the following.