JPS6150982B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula In the formula, the benzene ring or naphthalene ring A, in addition to the sulfo group, further carries other substituents such as fluorine, chlorine, bromine, _C1 - _C4 alkyl, _C1 - _C4 alkoxy, nitro, carboxy, amino, ureido or acylamino. groups, R is hydrogen or _C1 - _C4 alkyl, _R1 and _R2 are hydrogen, _R3 is hydrogen, _C1 - _C4 alkyl, acylamino, especially optionally substituted R ₄ is hydrogen, C _{1 -C 4} alkyl, C ₁ -C _{4 alkoxy} , carbonyl or and n is 1, 2 or 3. Examples of substituents on the benzene or naphthalene ring A are fluorine, chlorine or bromine, _C1 - _C4 alkyl such as methyl, ethyl or n-propyl, methoxy, ethoxy, iso-propoxy or n-butoxy. _C1 - _C4 alkoxy, acylamino such as acetylamino, formylamino, oxarylamino, ureido, nitro, carboxyl and amino. Examples of acylamino groups R ₃ are acetylamino, ureido, hydroxyacetylamino, benzoylamino and the like. The formula below In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and n have the above meanings, where R, R ₁ , R ₂ , R ₃ and R ₄ have the above meanings and m is 1 or 2, where R ₁ , R ₂ and n have the meanings given above and R ₅ is acetylamino or ureido, and In the formula, R ₁ , R ₂ , R ₅ and m have the above meanings, and dyes of the following are preferred. The invention further relates to a method for producing the dye. In particular, the following method may be mentioned. formula In the formula, R, R ₃ , R ₄ , A and n have the above meanings, and the dye is 2,4,6, trifluoro-1,3,5
A condensation reaction with triazine liberates hydrofluoric acid, and the resulting difluoro compound has the formula reaction with an amine to liberate hydrofluoric acid to give (). The condensation of the dye () with s-trifluorotriazine is preferably carried out in aqueous solution or suspension at low temperatures and at slightly acidic, neutral to slightly alkaline pH values. The condensation reaction is advantageously carried out in the PH range of 3 to 5. The liberated hydrogen fluoride is buffered by adding an aqueous solution of alkali metal hydroxide, carbonate or bicarbonate. The reaction of difluoro compounds with amines () is likewise preferably carried out in aqueous solution or suspension at low temperatures and at neutral to slightly alkaline pH values. Hydrogen fluoride liberated during the condensation reaction is neutralized by adding aqueous solutions of alkali metal hydroxides, carbonates and bicarbonates. Neutralization is also the second equivalent substance of amine (),
It is particularly advantageous to use ammonia. Generally, separation of difluoro compounds is omitted. dye () also formula dye () In the formula, R ₁ and R ₂ have the above-mentioned meanings. It can also be produced by a method of reacting with aminodifluorotriazine to liberate hydrofluoric acid. The condensation reaction is preferably carried out in aqueous solution or suspension at low temperatures and at slightly acidic, neutral to slightly alkaline pH values. Hydrogen fluoride liberated during the condensation reaction is an alkali metal hydroxide,
Continuous neutralization by adding an aqueous solution of carbonate or bicarbonate is advantageous. Azo compounds of formula () used as starting materials for the production of fiber-reactive azo dyes of formula () are obtained by diazotizing aminobenzenesulfonic acid or aminonaphthalenesulfonic acid and producing the diazotization product with -NHR groups. It can be obtained by coupling with a suitable benzene-based coupling component. Diazotization is generally carried out by the action of nitrous acid in an aqueous mineral acid solution at low temperatures, and coupling is carried out at weakly acidic, neutral to slightly alkaline pH values. The following can be mentioned as the azo component and coupling component that can be used in the production of the azo compound of formula (). Diazo component: 1-aminobenzene-2-, -3- and -4
-sulfonic acid, 1-aminobenzene-2,4- and -2,5-disulfonic acid, 1-amino-4-
Methylbenzene-2-sulfonic acid, 1-amino-
3-Methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-amino-2,4-dimethylbenzene-6-sulfonic acid, 1-amino-4- or -5
-Chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or -4-sulfonic acid, 1-amino-3,4-dichlorobenzene-
6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1
-amino-5-methyl-4-chlorobenzene-2
-Sulfonic acid, 1-amino-4- or -5-methoxybenzene-2-sulfonic acid, 1-amino-
6-methoxy-benzene-3- or -4-sulfonic acid, 1-amino-6-ethoxybenzene-3
-or-4-sulfonic acid, 1-amino-2,4
-Dimethoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfonic acid, 1-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-acetylaminobenzene- 2-sulfonic acid, 1-amino-3
-Acetylamino-4-methylbenzene-6-sulfonic acid, 1-amino-4-methoxybenzene-
2,5-disulfonic acid, 1-amino-4-methyl-2,5-disulfonic acid, 1-amino-2-carboxybenzene-4- or -5-sulfonic acid,
1-aminonaphthalene-2-, -4-, -5-,
-6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7
-, -4,8- or -6,8-disulfonic acid,
1-aminonaphthalene-2,5,7-trisulfonic acid and 2-aminonaphthalene-1,5,7
-, -3,6,8- or -4,6,8-trisulfonic acid. Coupling component: aminobenzene, N-methyl-, -ethyl- or -butyl-aminobenzene, 1-amino-2
-or-3-methylbenzene, 1-methylamino-3-methylbenzene, 1-ethylamino-3
-Methylbenzene, 1-amino-2,5-dimethylbenzene, 1-amino-2,5-diethylbenzene, 1-amino-2-ethoxybenzene, 1-
Amino-3-acetylaminobenzene, 1-amino-3-ureidobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1-amino-
3-sulfoacetylaminobenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-3-acetylamino-6-methylbenzene,
1-amino-3-acetyl-amino-6-methoxybenzene, 1-amino-3-ureido-6-methylbenzene, 1-amino-2-methoxy-5-
Methylbenzene and 1-amino-3-sulfatoacetylamino-benzene. The novel dyes of the invention are suitable for dyeing and printing materials containing hydroxyl or amide groups, such as wool, silk and synthetic polyamide textile fibers, filaments and textile fabrics and polyurethane fibers, and for dyeing and printing natural or regenerated cellulose. dyeings and prints which are resistant to washing and are fast to wash are obtained; Processing takes place. The formulas given for dyes are those of the corresponding free acids. Generally, dyes were isolated in the form of alkali metal salts, specifically Na salts, and used for dyeing. Example 1 3,6,8-trisulfonaphthalene<2azo4
>54.5 g of a dye of the formula 1-amino-3-ureido-benzene are stirred in a mixture of 400 ml of water and 300 g of ice. 13.5 g of trifluorotriazine are added dropwise and the liberated hydrofluoric acid is buffered by adding 20% strength sodium carbonate solution at a rate such that the pH value is between 3 and 5. The resulting solution, in which the starting material is no longer detectable, is adjusted to a pH of 9 using a 12% strength ammonia solution, and the ammonia is then added to 0 until the pH value remains constant.
Add dropwise to ~10°C. Salting out the dye,
Strain, dry and grind. An orange dye powder is obtained which dissolves easily in water to give a reddish-yellow solution. The dye has the formula corresponds to The dye can also be separated by evaporation or spray drying of the entire reaction mixture. Examples of dyeing, printing, etc. Printing method Each kilogram contains 20 g of the dye prepared according to Example 1, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g of sodium alginate/1 Kg of thickener) and 10 g of sodium carbonate and water. Cotton nettle was printed using a printing paste with a total amount of 1 kg, and the cotton nettle was dried.
If exposed to steam for 1 minute at 103° C., rinsed with hot water and soaped at boiling temperature, a reddish-yellow print with good fastness to wet processing and to light is obtained. Padding method: Add 30 parts of the dye prepared according to Example 1 to 1000 parts of water.
Dissolve in parts. A cotton fiber cloth is padded with this solution and pressed to a weight loss of 90%. The damp cotton should be heated with calcined sodium sulfate.
Treat for 30 minutes at 70° C. in a bath containing 300 parts and 10 parts of calcined sodium carbonate dissolved in 1000 parts of water. Then finish the dyeing using the usual method. A reddish-yellow dyeing is obtained which has excellent fastness to wet processing and to light. Dyeing method 168 ml of water at 20-25°C is first placed in a 300 ml dyeing beaker and placed in a heated water bath. 0.3 g of the dye obtained according to Example 1 is thoroughly mixed with 2 ml of cold water to make a paste and heated (70° C.) for 30 minutes.
ml, thereby dissolving the dye. Add this dye solution to the initially introduced water and add 10 g of cotton thread.
is continuously moved in this dye solution. The temperature of the dye liquor is raised to 40-50 DEG C. within 10 minutes, 10 g of anhydrous sodium sulfate are added and dyeing is continued for 30 minutes. Next, 4 g of anhydrous sodium carbonate is added to the dye solution and dyeing is carried out at 40-50 DEG C. for 60 minutes. The dyed material is then removed from the dye liquor, the adhering liquor is removed by squeezing or squeezing, and the material is rinsed first with cold water and then with warm water until the rinse liquor is no longer contaminated. The dyed material is then soaped for 20 minutes at the boiling point in 200 ml of a solution containing 0.2 g of sodium alkyl sulfate, rinsed again and dried at 60-70 DEG C. in a drying box. A reddish-yellow dyeing is obtained which has good fastness to washing and to light. λ _nax was 418 nm. The procedure is carried out as described in Example 1, except that instead of the aminoazo dye used in that example, the equivalents of the aminoazo dyes listed in the table below are used, and the ammonia is replaced by the second fluorine atom. When used as a replacement amine, an equally valuable dye is obtained which dyes cotton in yellow to reddish yellow shades.

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Claims (1)

[Claims] 1 formula In the formula, the benzene ring or naphthalene ring A, in addition to the sulfo group, further carries other substituents such as fluorine, chlorine, bromine, _C1 - _C4 alkyl, _C1 - _C4 alkoxy, nitro, carboxy, amino, ureido or acylamino. R is hydrogen or _C1 - _C4 alkyl, _R1 and _R2 are hydrogen, _R3 is hydrogen, _C1 - _C4 alkyl, acylamino, especially optionally substituted R ₄ is hydrogen, C _{1 -C 4} alkyl, C ₁ -C ₄ alkoxy, _carboxyl or The dye is sulfo and n is 1, 2 or 3. 2 formulas The dye according to claim 1, wherein R, R ₁ , R ₂ , R ₃ , R ₄ and n have the meanings given in claim 1. 3 formulas In the formula, R, R ₁ , R ₂ , R ₃ and R ₄ have the meanings given in claim 1, and m is 1 or 2. dye. 4 formula In the formula, R ₁ , R ₂ and n are defined in claim 1.
A dye according to claim 1, having the meaning given in claim 1, and in which R ₅ is acetylamino or ureido. 5 formula where R ₁ and R ₂ have the meaning as defined in claim 1, m has the meaning as defined in claim 3, and R ₅ is acetylamino or ureido. The dye according to claim 1. 6 formula In the formula, the benzene ring or naphthalene ring A, in addition to the sulfo group, further carries other substituents such as fluorine, chlorine, bromine, _C1 - _C4 alkyl, _C1 - _C4 alkoxy, nitro, carboxyl, amino, ureido or acylamino. R is hydrogen or _C1 - _C4 alkyl, _R1 and _R2 are hydrogen, _R3 is hydrogen, _C1 - _C4 alkyl, acylamino, especially optionally substituted R ₄ is hydrogen, C _{1 -C 4} alkyl, C ₁ -C ₄ alkoxy, _carboxyl or sulfo, and n is 1, 2 or 3, for the preparation of dyes of the formula In the formula, R, R ₃ , R ₄ , A and n have the meanings described in claim 1.
-Condensation reaction with triazine to separate and release hydrofluoric acid, and the resulting difluoro compound has the formula A production method characterized by reacting with the amine of the following formula, wherein R ₁ and R ₂ have the meanings as defined in claim 1, to separate and release hydrofluoric acid.