DE1275232B - Process for the preparation of azo dyes containing one or more thiosulphuric acid groups and optionally further water-solubilizing groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C09b

German class: 22 a -1

Number: 1275 232

File number: P 12 75 232.8-43 (F 33971)

Filing date: April 24, 1959

Opening day: August 14, 1968

It has been found that water-soluble azo dyes which contain one or more thiosulfuric acid groups and optionally other water-solubilizing groups can be prepared by azo dyes which contain one or more reactive halogen atoms and optionally water-solubilizing groups, such as sulfonic acid groups, with aliphatic or aromatic amines, contain one or more Thioschwefelsäuregruppen and optionally further water-solubilizing groups, in an aqueous or non-aqueous medium, optionally in the presence of organic solvent, acid binding in the presence of agent at temperatures between about 0 and 6O ⁰ C, preferably between about 10 and 30 ⁰ C, at pH Values between approximately 7 and 10 condensed.

Inorganic compounds, for example sodium hydroxide solution, sodium carbonate, can be used as acid-binding agents or sodium bicarbonate, or organic compounds, for example pyridine or picolines, come into use.

The condensation is carried out in a non-aqueous medium in an organic solvent, for example dimethylformamide, with possibly other organic solvents, for example methanol, can be added. Even when performing the condensation in aqueous medium can also organic solvents, for example acetone or methylene chloride, can be added. The selection of the reaction medium to be expediently to be used in the individual case is directed according to the solubility properties of the thiosulfuric acid groups used Amines and the solubility properties and reactivity of the azo dyes used.

The use of an excess of the amine component can, for example, with regard to the The yield to be achieved, the degree of purity of the product obtained and the condensation time are advantageous be.

The azo dyes used as starting materials can contain the reactive halogen atoms in In the form of sulfochloride groups, such as azobenzene disulfonic acid chloride.

The reactive halogen atoms can also be attached to the in the form of carboxylic acid halide groups Azo dye molecule be bound, as in azobenzene dicarboxylic acid chloride.

Furthermore, those used as starting compounds can be used Azo dyes also contain the reactive halogen atom bonded to a triazine nucleus.

Process for the preparation of one or more thiosulfuric acid groups and optionally
further water-solubilizing groups
containing azo dyes

Applicant:

Farbwerke Hoechst Aktiengesellschaft,
formerly Master Lucius & Brüning,
6230 Frankfurt-Höchst

Named as inventor:

Dr. Werner Schultheis, 6240 Koenigstein;

Dr. Kurt Schimmelschmidt,

6230 Frankfurt-Hoechst;

Dr. Hermann Hoffmann,

Coventry, R. I. (V. St. Α.);

Dr. Edwin Baier, 6000 Frankfurt-Schwanheim

The last-mentioned compounds are obtained by known processes by partial condensation of cyanuric chloride with azo dyes containing amino groups, for example with the coupling products of 2-amino-8-naphthol-6-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid or 1-amino-8-naphthol-3,6-disulfonic acid with diazotized water-insoluble or water-soluble aromatic amines, the solubilizing groups also include thiosulfuric acid groups may contain.

Amines containing one or more thiosulphuric acid groups are both aliphatic Amines (German patent 869 066), for example 2 - aminoethylthiosulfuric acid, 2 - (methylamino) ethylthiosulfuric acid; 2,2'-Imiho-di- (ethylthiosulfuric acid, 3-aminopropylthiosulfuric acid or 2-aminohexylthiosulfuric acid, as well as aromatic Amines under consideration (German Auslegeschrift 1086 239). Suitable aromatic amines are for example:

3-aminophenylthiosulfuric acid, 3-aminobenzylthiosulfuric acid, 3-amino-4-methoxybenzylthiosulfuric acid, S-amino ^ o-dichlorobenzylthiosulfuric acid, 5-aminonaphthyl- (l) -methylthiosulfuric acid, 3-aminoacetophenone - 4 - - - aminoacetophenone - - - aminonaphthylthiosulfuric acid, β-thiosulfuric acid, 3-aminoacetophenone - 4 - - ethylthiosulfuric acid, β - (4 - aminophenyl - (äthylamino)) - ethylthiosulfuric acid, 4 - aminoacetanilide - ω - thiosulfuric acid, 4-aminophenyl acetate-w-thiosulfuric acid, ß- ( 4-ami-

809 590/413

nophthaliminoj-ethylthiosulfuric acid, / i- (4-aminonaphthalimino) -ethylthiosulfuric acid, 7- (4-aminobenzoylamino) propylthiosulfuric acid, N- (4-aminophenyl) -N'-methyl-N '- (/? - ethylthiosulfuric acid) urea, 4-aminodiphenyl-4'-sulfonylamino- / i-ethyl- thiosulfuric acid, 4-aminodiphenyl ether-4'-carbonylamino-ß-ethylthiosulfuric acid or salts of 3-aminobenzenesulfonylimino - /?, /? '- di- (ethylthiosulfuric acid).

For the reaction with azo dyes that contain reactive halogen atoms, also come one or more thiosulfuric acid groups containing colored amines into consideration, which by Coupling of diazotized aromatic compounds containing one or more thiosulphuric acid groups Amines with coupling compounds containing amino groups, for example m-toluidine, 2 - methoxy - 5 - methylaniline, m - phenylenediamine, 1-naphthylamine, 2-amino-8-naphthol-6-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid or 1-amino-8-naphthol-3,6-disulfonic acid or l- (aminophenyl) -3-methylpyrazolones, can be obtained. The coupling components can for their part also contain one or more thiosulfuric acid groups, like 5-aminonaphthyl- (l) -methylthiosulfuric acid or ethylaniline-o-thiosulfuric acid.

The new water-soluble dyes obtainable by the process of the present invention are usually in the form of well-crystallizing alkali salts of the sulfur alkyl or sulfur arylthiosulfuric acid ester obtained by concentration and / or salting out. They dye wool, silk, polyamides or polyurethanes from acid baths in a wide variety of shades. The colors stand out, especially when using sulfonic acid group-free azo dyes, due to excellent wet fastness properties the end.

Compared to the water-soluble azo dyes containing thiosulfuric acid groups and containing l-amino-4-nitrobenzene - »(N-ethyl-N- / Mhiosulfatoethyl) -aminobenzene, l-amino-2-chloro-4-nitrobenzene - * ■ (N -Ethyl-N- / i-thiosulfatoethyl) aminobenzene and l-amino-2,4-dinitrobenzene - »· (N-ethyl-N - /? - thiosulfatoethyl) -aminobenzene, the dyes of similar structure obtainable according to the process are characterized by better potting fastness the wool dyeings and better wash and perspiration fastnesses of the polyamide dyeings.

For example

To a mixture of 25 parts by weight of 3-amino-4-methoxybenzylthiosulfuric acid, 13 parts by weight of sodium bicarbonate and 100 parts by volume of water are added to a solution of 7.7 parts by weight of azobenzene-4,4'-dicarboxylic acid dichloride in 250 parts by volume of methylene chloride and stir for 14 hours at room temperature. The reaction mixture becomes after removal of the methylene chloride taken up with saturated sodium chloride solution and the dye formed filtered off. The dye dyes wool in yellow shades with good fastness properties.

Example 2

19.5 parts by weight of the disulfochloride obtained from the coupling product of diazotized metanilic acid with l- (2'-chloro-4'-sulfo-6'-methylphenyl) -3-methyl-5-pyrazolone is obtainable by known methods. is concentrated in a with at 20 to 25 "C Sodium hydroxide solution of 19 parts by weight of methylaminoethylthiosulfuric acid brought to a pH of 9 entered in 25 parts by volume of water. After adding 80 parts by volume of acetone holds the pH to 9 to 9.2. The reaction mixture is after the end of condensation on a Set pH 6, evaporated in vacuo and the dye formed precipitated with sodium chloride. He dyes polyamides in real yellow tones.

Example 3

78 parts by weight of the triacid chloride obtained from the dye of the formula

NaOOC - C C-N =]

Il II

N C-OH

-SO ₁ Na

SO ₁ Na

is obtainable by known processes, is introduced into a mixture of 94 parts by weight of β- aminoethylthiosulfuric acid, 100 parts by volume of water and 60 parts by volume of 30% by weight potassium hydroxide solution at 20 to 25 ° C. The pH is kept at 9 to 9.5 by adding dropwise potassium hydroxide solution until the condensation has ended. The pH is then adjusted to 6 by adding hydrochloric acid and the dye formed is precipitated by adding potassium chloride. It dyes polyamide fibers in real golden yellow tones.

Example 4

A solution of 20 parts by weight of 2-aminoethylthiosulfuric acid is added in a mixture from 50 parts by volume of water and 6 parts by volume of 33 weight percent sodium hydroxide solution with 50 parts by volume Acetone. 20 parts by weight of the disulfochloride obtained from the coupling product of diazotized sulfanilic acid with 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone are carried into this mixture is obtainable by a known method and maintains the pH value Add dropwise 33 weight percent sodium hydroxide solution to 9.5 to 9.8. After the condensation has ended the pH is reduced to 8, the acetone is evaporated off and the dye formed is stirred with sodium chloride the end.

34 parts by weight of a dye which is readily soluble in water with a yellow color and which is obtained are obtained acid bath with good fastness properties on wool.

Example 5

30 parts by weight of the disulfochloride obtained from the coupling product of diazotized 1-methyl-4-aminobenzene-2-sulfonic acid with 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone is prepared by a known method, are in a with 60 parts by volume of methanol and 60 parts by volume of acetone added a solution of 25 parts by weight of 2-aminoethylthiosulfuric acid in a mixture of 30 parts by volume of water and 9 parts by volume of 33 weight percent sodium hydroxide solution

registered. The pH is kept at 9 to 9.2 by adding 33 weight percent sodium hydroxide solution dropwise.

When the reaction has ended, the mixture is evaporated and the residue is reduced to 400 parts by volume with water brought and the dye formed precipitated at a pH of 6.5 to 7 with sodium chloride.

60 parts by weight of a dye which is readily soluble in water with a yellow color and which is obtained are obtained acid bath in real yellow tones on wool.

Claims (1)

Claim: IO Process for the preparation of azo dyes containing one or more thiosulfuric acid groups and optionally further water-solubilizing groups, characterized in that azo dyes which contain one or more reactive halogen atoms and optionally water-solubilizing groups are mixed with aliphatic or aromatic amines which contain one or more thiosulfuric acid groups and optionally further water-solubilizing groups groups, in an aqueous or non-aqueous medium, optionally in the presence of organic solvents, in the presence of acid-binding agent at temperatures between 0 and 6O ⁰ C at pH values 7-10 condensed. Considered publications:
British Patent No. 510 453. When the application was announced, four coloring tables with explanations were laid out. 809 590/413 8.61 O Bundesdruckerei Berlin