DE3710077A1 - Copper complex dyes - Google Patents

Abstract

Dyes of the formula <IMAGE> are suitable for dyeing cellulose-containing materials and leather, and give blue dyes with good fastness properties.

Description

The present invention relates to dyes the general formula

wherein

R₁, R₂ = H, NH₂, NH-alkyl, OH, O-alkyl, NH-acyl, n, m = 0 - 3,

with the naphthalene residues not simultaneously for residues of the formulas

stand, and a process for their production, characterized in that that dyes of the general formula II

wherein R₁, R₂, n and m and the naphthalene radicals have the meaning given above,
treated with oxidizing agents in aqueous solution in the presence of at least equimolar amounts of copper salts,
and their use for dyeing and printing cellulosic materials, especially cotton, viscose and paper, and leather.

Dyes of the following formulas are preferred

wherein

R₃NH₂, NH-alkyl, NH-acyl, R₄OH, O-alkyl and R₂, n and m have the meaning given above,

the naphthalene residues are not simultaneously the residues of the Formulas

could be.  

Alkyl generally represents optionally substituted C₁-C₄ alkyl, especially for methyl, ethyl, propyl and Butyl.

Acyl is preferably C₁-C₄ alkylcarbonyl, if appropriate substituted phenylcarbonyl or for the rest a dibasic carboxylic acid, especially maleinyl.

The compounds of general formula II, the z. B. in a known manner from 4,4'-diaminostilbene-2,2'-disulfonic acid or from 4-nitro-4'-aminostilbene-2,2'-disulfonic acid and naphthols, aminonaphthols, naphtholsulfonic acids or aminonaphtholsulfonic acids will, in a manner known per se, in the presence of copper salts with oxidizing agents, preferably with Hydrogen peroxide, in the copper complex dyes of Formula I or III, IV and V transferred.

Any amino groups present are preferred by conversion into the corresponding carboxamides protected from attack by the oxidizing agent; the The protective group can be removed after the oxidative coppering be split off again.

You can also use the intermediate products of the formula II acylaminonaphthols or acylaminonaphtholsulfonic acids deploy.

Suitable for the preparation of the intermediates of formula II Naphthols are for example 1-naphthol,  2-naphthol, 4-methyl-1-naphthol and aminonaphthols such as 5-amino-1-naphthol, 6-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-2-naphthol, preferred but naphtholsulfonic acid such as 3-hydroxynaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-1-sulfonic acid, 5-hydroxynaphthalene-1-sulfonic acid, 6-hydroxynaphthalene-1-sulfonic acid, 7-hydroxynaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-2-sulfonic acid, 5-hydroxynaphthalene-2-sulfonic acid, 6-hydroxynaphthalene-2-sulfonic acid, 7-hydroxynaphthalene-2-sulfonic acid, 3-hydroxynaphthalene-2,6-disulfonic acid, 3-hydroxynaphthalene-2,7-disulfonic acid, 4-hydroxynaphthalene-2,7-disulfonic acid, 4-hydroxynaphthalene-1,5-disulfonic acid, 7-hydroxynaphthalene-1,3-disulfonic acid, 4-hydroxynaphthalene-2,5-disulfonic acid, 4,5-dihydroxynaphthalene-2,7-disulfonic acid, 5-methoxy-4-hydroxynaphthalene-1-sulfonic acid, 5-ethoxy-4-hydroxynaphthalene-2,7-disulfonic acid, 8-hydroxynaphthalene-1,3,6-trisulfonic acid and aminonaphtholsulfonic acid such as 4-hydroxy-6-aminonaphthalene-2-sulfonic acid, 4-hydroxy-7-aminonaphthalene-2-sulfonic acid, 5-hydroxy-4-aminonaphthalene-1-sulfonic acid, 4-hydroxy-5-aminonaphthalene-2-sulfonic acid, 4-hydroxy-8-aminonaphthalene-2-sulfonic acid, 3-hydroxy-7-aminonaphthalene-1-sulfonic acid, 4-hydroxy-6-aminonaphthalene-1-sulfonic acid, 4-hydroxy-7-aminonaphthalene-1,5-disulfonic acid, 5-hydroxy-2-aminonaphthalene-1,7-disulfonic acid, 5-hydroxy-3-aminonaphthalene-2,7-disulfonic acid, 4-hydroxy-5-aminonaphthalene-2,7-disulfonic acid, 5-hydroxy-4-aminonaphthalene-1,7-disulfonic acid, 5-hydroxy-4-aminonaphthalene-1,3-disulfonic acid used.  

For conversion into dyes of the formula I, the Intermediates of formula II dissolved in water or suspended; they are in the form of their lithium, Sodium or potassium salts or their ammonium salts, in particular their alkanolammonium salts, e.g. B. their salts of N, N, N-tris- (2-hydroxyethyl) amine, N, N-bis (2-hydroxyethyl) methylamine, N, N-bis (2-hydroxypropyl) -2-hydroxyethylamine, 2-hydroxyethyldimethylamine used. The oxidizing agent is added at pH values between 2 and 10, preferably between 4 and 7 at Temperatures between 0 and 80 ° C, preferably between 30 and 60 ° C. As the oxidizing agent is preferred Hydrogen peroxide use. As copper salts preferably water-soluble copper (II) salts are used, e.g. B. copper (II) sulfate or copper (II) chloride.

Since the space-time yield of the oxidative copper formation from the intermediate of formula II is proportional to the solubility of these compounds, substances which increase the solubility can optionally be added. Such substances are e.g. B. ethylene glycol, diethylene glycol, triethylene glycol, polyglycol, formamide, dimethylformamide, M-methylpyrrolidone, ε- caprolactam, pyridine, urea, thiourea.

To neutralize the oxidative copper liberated acid is preferably used alkali salts weak acids, e.g. B. sodium carbonate, sodium hydrogen carbonate, Sodium acetate, potassium carbonate, sodium acetate, Potassium carbonate, potassium acetate, lithium carbonate,  Lithium acetate; You can also use tertiary amines use, e.g. B. the alkanolamines given above.

The dyes are isolated in a known manner, e.g. B. by salting out and filtering, and dried.

The formulas given are those of the free acids. in the generally the dyes are in the form of their salts, in particular the alkali salts (Li, Na, K) or the amine salts, in particular the C₁-C₄ alkylamine salts or C₂-C₄ alkanolamine salts, preferably mono-, di- and Triethanolamine salts isolated and used.

The dyes dye cellulosic materials especially paper, cotton and viscose as well as leather in blue tones with good wet and light fastness.

Example 1

65.5 g of the intermediate of the formula

are dissolved in 2000 ml of water at 60 ° C. The pH this solution is set to 6 with a little glacial acetic acid, then a solution of 25 g of copper (II) sulfate 5H₂O in 75 ml of water added. Now 200 ml of 3% hydrogen peroxide solution is left dropwise, taking the pH keeps at 5-6 by adding soda solution. After completion the oxidative copper is the approach to 80 ° C. heated and mixed with 450 g of salt. The fancy The dye is isolated and dried. It dyes paper and cotton in blue tones.

Example 2

Work as above using the corresponding intermediates with

you also get dyes, cotton and Dye paper in blue tones.

If you work as described, but continue after finishing the coppering to 200 ml of 30% sodium hydroxide solution and saponified at 90 ° C and then salted out, is obtained also valuable blue dyes.

Example 3

Work as described in Example 1 using of the intermediate products with

and saponifies the maleinyl residue after the end of the Coppering by heating to 90 ° C for 1 hour and addition 200 ml of 30% sodium hydroxide solution gives dyes, that dye paper and cotton in blue tones.

Example 4

44.8 g of the intermediate of the formula

are dissolved at 40 ° C in 700 ml of water + 100 g ε- caprolactan. The pH is adjusted to 5 with acetic acid. Then a solution of 12.5 g of copper (II) sulfate 5 H₂O in 75 ml of water is added and 20 ml of 3% hydrogen peroxide solution (pH = 5-6 content with Li₂CO₃) is added dropwise.

As soon as the oxidative coppering has ended, Salt out 320 g of table salt and separate the dye and dried. It dyes paper, cotton and leather in blue tones.

Example 5

According to the procedure given above, the dyes listed in the following table formula

produce.

table

Example 6

53.7 g of the intermediate of the formula

are dissolved at 60 ° C in 1000 ml of water + 200 ml of polyethylene glycol (Mg ^∼ 400) and adjusted to pH 6 with acetic acid. After adding 25 g of copper (II) sulfate, 75 ml of water, 200 ml of hydrogen peroxide solution are added dropwise, the pH being kept at 5-6 with Li₂CO₃. After coppering is complete, the mixture is briefly heated to 80 ° C., 300 g of sodium chloride are added and, as usual, isolated and dried. The dye obtained dyes paper and cotton in blue tones.

According to the procedure of Examples 6 and 4, using the following coupling components K 1, K 4, K 7 and K 12-K 15 are the dyes of the formula

the following table.

table

They represent blue dyes that are used for coloring of paper and cotton.

Claims (3)

1. Dyes of the formula whereinR₁, R₂ = H, NH₂, NH-alkyl, OH, O-alkyl, NH-acyl, n, m = 0-3, the naphthalene radicals not being simultaneously for radicals of the formulas stand. 2. Dyes of claim 1 of the formulas whereinR₃NH₂, NH-alkyl, NH-acyl and R₄OH, O-alkyl and R₂, m and n have the meaning given in claim 1. 3. Use of the dyes of claims 1-2 for Dyeing cellulosic materials and leather.