DE1270709B - Process for the preparation of chromium complexes of azo dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

• C09b

German class: 22a-l

Number: 1 270 709

File number: P 12 70 709.4-43

Filing date: February 23, 1960

Opening day: June 20, 1968

The subject of the invention is a process for the production of chromium complexes of azo dyes.

The German patent specification 436 179 describes the production of azo dyes including metallizable ones Azo dyes are described which contain triazinyl groups including halotriazinyl groups contain.

From British patent specification 888 960 are complex chromium or cobalt compounds of Monoazo dyes known, which are derived from diazo ίο components of the benzene series, and the in addition to the groups involved in the complex formation, a single sulfonic or carboxylic acid group and a monohalogen -1,3,5-triazine radical which, if it has salt-forming substituents carries, contains only strongly ionized substituents of this type, and in which a chromium or cobalt atom is bound in a complex bond to two dye molecules.

It has now been found that chromium complexes of azo dyes can be obtained if a monoazo dye of the formula COOH

OH

Process for the preparation of chromium complexes of azo dyes

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr.-Ing. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

8000 Munich 5, Müllerstr. 31

Named as inventor:

Alistair Howard Berrie,

Cyril Eric Vellins,

Manchester, Lancashire (UK)

Claimed priority:

Great Britain from February 23, 1959,:

dated December 18, 1959 (6120)

CO

N-

M-I

where R is a hydrogen atom or a no longer 35 formula COOH OH

as an alkyl radical containing 4 carbon atoms and η 1 or 2 and the benzene ring A 'further. Jj can carry substituents other than sulfonic acid groups,

with a chromium donating agent and then with cyanuric acid chloride or bromide to form of a chromium complex of an azo dye der

N-

wherein R, /; and A 'has the meaning given above have and X stands for a chlorine or bromine atom, converts.

The dyes produced according to the invention produce, when dyed with them at 40 C in the presence of an acid-binding agent, colorations on cellulose textile materials,
and British Patent 888,961
baren, from the German Patentsch
and British Patent 888
metallized azo dyes obtainable
are clearly superior.

the JK Aufanned 436 179 known colorations

809 560 437

Examples of further substituents which may be present in the benzene ring A 'are: chlorine, bromine, nitro, acetylamino, methoxy, benzoyl, trifluoromethyl, sulfamoyl, substituted sulfamoyl, such as N ₇ N -dimethylsulfamoyl and N-ethylsulfamoyl, methanesulfonyl and carboxy groups.

The chromium complexes of the azo compounds represented by the above formula can either 1: 2 or 1: 1 chromium complexes, i.e. that is, either 1 atom of chromium with 2 molecules of the above Azo dyes or 1 atom of chromium forms a complex with 1 molecule of the azo dyes.

Treatment of the monoazo compound with the chromium donating agent can be any one of the known processes for the preparation of chromium complexes made of azo compounds for example by heating an aqueous solution of the monoazo compound with an aqueous solution of the chromium-supplying agent, adding salt and filtering off the precipitated Chromium complex.

The reaction of the chromium complex ■ with the cyanuric chloride or cyanuric bromide can expediently be carried out by an aqueous solution of the chromium complex with a aqueous suspension of cyanuric chloride or cyanuric bromide, preferably at one temperature between 0 and 5 ° C, with the addition of sodium carbonate, in order to bring the mixture to pH 7 hold, stir. Add salt and the precipitated metallized azo dye filtered off.

As examples of chromium supplying agents that can be used to make the new metallized To obtain azo dyes are mentioned: chromium acetate, chromium formate, chromium chloride, chromium sulfate, Chromium fluoride, chromium sesquioxide (which can be used in its hydrated form can) and mixtures of chromium salts with alkali or ammonium salts of hydroxycarboxylic acids, for example tartaric acid and salicylic acid.

The monoazo compounds used in the process according to the invention can be diazotized a substituted or unsubstituted anthranilic acid that has no sulfonic acid groups, and coupling the diazo compound thus obtained with a coupling component of the formula

OH

HO ₃ S

NO

OC

N-

where R and η have the abovementioned meaning. can be obtained.

As examples of substituted anthranilic acids. oaks for the production of the monoazo compounds used in the process according to the invention may be mentioned: 4 -baths of 5-chloranthobxanilic acid. 3-, 4- or 5-nitroanthranilic acid, 4- or 5-bromoanthranilic acid, 4- or / 5-acetylatninoanthranilic acid. 4-methoxyanthranilic acid, 4-benzoyanthranilic acid. 4-trifluoromethylanthranilic acid. 4-sulfamoylanthranilic acid, 4-N, N-dimethylsulfamoylanthranilic acid, 4-methanesulfonylanthranilic acid and 2-aminoterephthalic acid.

As examples of coupling components that are used to produce the in the invention Process used monoazo compounds may be mentioned: 2-amino-5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 2-methylamino-5-naphthol-7-sulfonic acid, 2 - (4 '- aminobenzoylamino) - 5 - naphthol-7-sulfonic acid and 2- (4'-aminobenzoylamino) -8-naphthol-6-sulfonic acid.

The new metallized ones that can be produced according to the invention Azo dyes from the medium in which they were formed, preferably at pH from 6 to 8 are isolated. It has been found that the elimination of chlorine or bromine atoms from the triazine ring present in the dyes by the addition of buffering agents, which one pH between 6 and 8, especially those which have a pH of about 6.5 result can be significantly reduced. Examples of such buffering agents are mentioned: mixtures of disodium hydrogen phosphate and sodium dihydrogen phosphate or potassium dihydrogen phosphate and mixtures of sodium diethyl metanilate and sodium hydrogen sulfate.

The buffering agents can be metallized at any point during the manufacture of the new Azo dyes are added, but it is advantageous to add them to the reaction mixture before Add isolation of the dye and, after filtering off the dye, the dye paste obtained in this way before drying, which is preferably is carried out at a temperature below 65 C, to mix with further buffering agent. The dried dye preparations obtained in this way are generally more stable than the unbuffered ones dried dyes.

The metallized azo dyes that can be produced according to the invention are valuable for dyeing cellulose textiles, for example textiles containing natural or regenerated cellulose. To the Dyeing of such textiles are the new metallized azo dyes on the cellulose textiles either by one of the known dyeing or printing processes, preferably in conjunction with a treatment with an acid-binding agent, for example sodium hydroxide, sodium carbonate or sodium bicarbonate. upset. The acid binding agent can therefore be applied to the cellulosic textile material before, during or after the treatment with the dyes. if Cellulose textiles are treated in this way with the new metallized azo dyes, the result is yellow to brown shades with excellent fastness to light, bleach, washing, acids and Alkalis.

In the following examples, parts are parts by weight and percentages are percentages by weight.

B e i s ρ i e 1 1

A mixture of 10.8 parts of the disodium salt of 2-amino-6- (2'-carboxy-phenylazo) -5-naphthol-7-sulfonic acid. 4.9 parts of chromium triacetate and 200 parts of water are kept at the boil for 3 hours with stirring and reflux cooling. The solution thus obtained is cooled to 10 C ^r, made acid to Congo red by the addition of concentrated aqueous hydrochloric acid and the separating out -Chromkomplex 1 ^ of the 2-amino-6- (2'-carboxy-phenylazo) -

5-naphthol-7-sulfonic acid filtered off and dried, dissolved in 100 parts of water and treated with sodium carbonate until the pH of the solution 7.4. The solution thus obtained becomes a solution of 4.6 parts of cyanuric chloride in 100 parts Given acetone. The mixture is then left for 3 hours at a temperature between 0 and 5 ° C stirred, with a 10% aqueous at intervals Solution of sodium carbonate is added to keep the pH of the mixture at 7. then 6.4 parts of sodium dihydrogen phosphate, 3.6 parts of disodium hydrogen phosphate and 10 parts of sodium chloride are used admitted. The dye which separates out is filtered off with 0.7 parts of disodium hydrogen phosphate and 1.3 parts of sodium dihydrogen phosphate mixed and dried.

The dye preparation thus obtained showed in the analysis a content of 1 atom of chromium and 4.0 atoms of organically bound chlorine for each dye molecule.

When used on cellulose textiles in conjunction with a treatment with an acid-binding agent Medium gives the dye brown shades with excellent fastness to light, Bleach, washing. Acids and bases.

If you proceed as indicated in Example 1, but the disodium salt used there 2 - Amino - 6 - (2 '- carboxy - phenylazo) - 5 - naphthol-7-sulfonic acid by an equivalent amount of the sodium salt in the second column of the table Replaced azo compound listed, one obtains other dyes, the cellulose textile materials in color the shades given in the last column of the table.

Azo compound On one Cellulose textile Example material 2- (4'-aminobenzoylamino) - preserved 6- (2'-carboxy-phenylazo) - hue Ί 5-naphthol-7-sulfonic acid Brown 6- (2'-carboxy-phenylazo) - 2-methylamino-5-naphthol- 3 7-sulfonic acid Brown 2-amino-7- (2'-carboxy- phenylazo) -8-naphthol- 4th 6-sulfonic acid Matte purple 1-amino-6- (2'-carboxy- phenylazo) -5-naphthol- 5 7-sulfonic acid Matte purple 2-amino-6- (2'-carboxy- 5'-chlorophen ylazo) - 6th 5-naphthol-7-sulfonic acid Brownish 2-amino-6- (2'-carboxy- violet 5'-trifluoromethyl-phenyl- 7th azo) -5-naphthol-7-sulfone- Brownish acid violet 2-amino-6- (2'-carboxy- 5'-sulfamoyl-phenylazo) - 8th 5-naphthol-7-sulfonic acid Brown

thol - 7 - sulfonic acid, 9.8 parts of chromium triacetate, 200 parts of ethylene glycol and 100 parts of water is kept at the boil for 3 hours with stirring and reflux. Then 40 parts of 2 are n-aqueous Hydrochloric acid was added and the mixture was boiled for a further 18 hours with stirring and reflux held. The solution thus obtained is poured into 300 parts of a 10% aqueous sodium chloride solution, and the precipitating 1: 1 chromium complex

of 2-amino-6- (2'-carboxy-phenylazo) -5-naphthol-7-sulfonic acid is filtered off and dried.

A solution of the chromium complex thus obtained in 500 parts of water is made by adding sodium carbonate just made alkaline against lakmus

and added with stirring to a suspension of 4.6 parts of cyanuric chloride in 100 parts of a mixture of ice and water, the temperature being kept below 5 ° C. by external cooling. The mixture is then 3 hours at a temperature

temperature between 0 and 5 C, the pH of the mixture by adding sodium carbonate maintained at 7, and 9.6 parts disodium hydrogen phosphate, 13.2 parts sodium dihydrogen phosphate and 60 parts of common salt are then added and the precipitated dye is filtered off. The thus obtained Dye paste is made with 0.7 parts of disodium hydrogen phosphate and 1.3 parts of sodium dihydrogen phosphate mixed and then dried at 30 ° C. The dye mixture thus obtained contained after the analysis 1 atom of chromium and 1.69 atoms of organically bound chlorine per dye molecule.

When used on cellulose textiles in conjunction with a treatment with an acid-binding agent Medium the dye gives brown shades with excellent wash fastness.

Example 10

Instead of the 10.8 parts of the disodium salt of 2-amino-6- (2'-carboxyphenylazo) used in Example 9 - 5 - naphthol - 7 - sulfonic acid were 10.8 parts of the disodium salt of 2-amino-7- (2'-carboxy-phenylazo) -8-naphthol-6-sulfonic acid used.

The dye obtained in this way contained, according to analysis, 1 atom of chromium and 1.9 atoms of organic bound chlorine per dye molecule.

When used on cellulose textiles in conjunction with a treatment with an acid-binding agent Medium the dye gives bluish brown shades with excellent wash fastness.

Claims (1)

Claim: Process for the production of chromium complexes of azo dyes, characterized in that that you have a monoazo dye of the formula COOH Example 9 A mixture of 10.8 parts of the disodium salt of 2-amino-6- (2'-carboxy-phenylazo) -5-naph- where R is a hydrogen atom or an alkyl radical containing not more than 4 carbon atoms and η is 1 or 2 and the benzene ring A 'can carry further substituents besides sulfonic acid groups, with a chromium donating agent and then with cyanuric acid chloride or bromide to form a chromium complex of an azo dye formula COOH OH in which R, η and A 'are as defined above and X is a chlorine or bromine atom. Considered publications:
German Patent No. ' 436 179;
British Patent No. 888,960. When the application was announced, a coloring table with explanations was laid out.