DE2541007A1 - HYDRO-SOLUBLE TRISAZO DYES, THEIR PRODUCTION AND USE - Google Patents

Description

CASSKLAFAHHWKiIKBMAINKlIH Ref: 3049 AKTIIiNCKSKLLSCHAl-T

& O00 FRANKFURT (MAIN) -FtCHENHEIM Dl * VE / all

Water-soluble trisazo dyes, their preparation and use

The present invention relates to water-soluble trisazo dyes of the general formula I.

N = N /> NH / \ N = N-fBVOH (I)

SO, Me
(SO ₃ Me) _n

wherein A is a phenyl or naphthyl group which can carry one, two or three additional substituents, Me is hydrogen or a metal cation and η denotes the numbers 1 or 2 and the phenyl nucleus B also has a further substituent may have, as well as the production of these dyes, The dyes according to the invention are suitable for dyeing and printing natural or synthetic fiber materials containing hydroxyl groups or nitrogen and especially for dyeing Leather. Green dyeings with good fastness properties are obtained on the substrates mentioned, in particular on leather.

Water-soluble trisazo dyes whose structure is 1-amino-8-naphtholsulfonic acids and 4,4'-diamino-diphenylamine sulfonic acid are involved, are already from the German patent No. 943 662 and from German Offenlegungsschrift 2 254

inflQ 14 / 1Ai)

Ref. 3049

known. With the dyes described in these publications however, only blue, black and brown shades can be produced

There have now been in the series of water-soluble trisazo dyes also found those which make it possible to produce pure green dyeings and prints. In view of the fact that the hitherto known

and blue trisazo dyes mainly produced black and brown shades, it was very surprising that dyes with pure green shades could also be found in this series.

The new dyes according to the invention have the general formula I.

HO

A-N = N-

'" ^{N = N}

SO ₃ Me (SO ₃ Me) _n

where A is a phenyl or naphthyl group which is unsubstituted, monosubstituted by chlorine, SO ₃ H, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or acylamino having 1 to 4 carbon atoms, disubstituted by two identical or different substituents of the group chlorine, SO ₃ H, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or trisubstituted by 3 chlorine, Me hydrogen or an alkali metal or alkaline earth metal cation and η the number 1 or 2 and the phenyl nucleus B is additionally replaced by an alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,

709811/1042

- 3 - Ref. 3049

Chlorine, COOH or SO ₃ II can be substituted.

A preferred group of trisazo dyes according to the invention contains the i-AmLno-8-naphtholsulphonic acid component is 1-amino-8-naphthol-3,6-disulphonic acid and accordingly corresponds to the general formula II

HO ₂

MeO ₃ S ^^ ^^ SO ₃ Me -SO ₃ Me

Furthermore, those dyes according to the invention are preferred in which A is a phenyl group which is substituted as indicated above can be.

Those dyes according to the invention in which the phenyl or naphthyl radical representing A is either unsubstituted or monosubstituted by chlorine are particularly preferred. SO, H, alkyl with 1 to 2 carbon atoms, alkoxy with 1 to 2 carbon atoms or acylamino with 1 to 2 carbon atoms, or disubstituted by 2 identical or different substituents from the group chlorine, SO-H, alkyl with 1 to 2 carbon atoms Atoms or alkoxy with 1 to 2 "carbon atoms or trisubstituted by 3 is chlorine.

Examples of groups that can stand for A in the general formulas I and II are:

2-, 3- or 4-chlorophenyl, 2-, 3- or 4-sulfophenyl, 2-, 3- or 4-to] yl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4- Propylphenyl _?

709811/1042

- 4 - Ref. 3049

4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2-isobutylphenyl, 4-tert. Butylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-propoxyphenyl, 2- or 3-isopropoxyphenyl, 2-, 3- or 4-butoxyphenyl, 3- or 4-isobutoxyphenyl, 2- or 4-tert. Butoxyphenyl, 2-, 3- or 4-formylaminophenyl, 2-, 3- or 4-acetaminophenyl, 2-, 3- or 4-propionylaminophenyl, 2-, 3- or 4-butyrylaminophenyl, 3-isobutyrylaminophenyl, 4-isobutyrylaminophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,5-dichlorophenyl

pheny] 3,5-dichlorophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 2-chloro-4-sulfophenyl, 2-chloro-5-sulfophenyl, 3-chloro-4-sulfophenyl, 3-chloro-5-sulfophenyl, 2-chloro-6-sulfophenyl, 2-chloro-4-ethylphenyl, 2-chloro-5-ethylphenyl, 3-chloro-4-propylphenyl, 3-chloro-2-methylphenyl, 3-chloro-5-methylphenyl, 3-chloro-5ethylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3-ethylphenyl, 2-chloro-4-butylphenyl, 2-chloro-5-tert-butylphenyl, 2-chloro-4-methoxyphenyl, 2-chloro-5-propoxyphenyl, 3-chloro-2-methoxyphenyl, 3-chloro-4-butoxyphenyl, 3-chloro-S-ethoxyphenyl, S-chloro-o-methoxyphenyl, 4-chloro-2-πlethoxyphenyl, 4-chloro-3-inethoxyphenyl, 2,4-dimethylphenyl, 2-methyl-4-propylphenyl, 2,5-dimethylphenyl, 2-methyl-5-butylphenyl, 3,4-diethylphenyl, 3,5-dimethylphenyl, 2,4-dimethoxyphenyl, 3,4-dimethoxyphenyl, 2,5-dibutoxyphenyl, 2,5-diethoxyphenyl, 3,5-dimethoxyphenyl, 2-methoxy-4-isobutoxyphenyl, 2-Sul £ o-4-ethy! Phenyl, 2-sulfo-5-butylphenyl, 3-sulfo-4-methylphenyl, 3-sulfo-5-ethylphenyl, 3-sulfo-6-ethylphenyl, 4-sulfo-2-methylphenyl, 4-sulfo-37methylphenyl, 2-sulfo-4-propylphenyl, 2-Sul £ o-4-methylphenyl, 2-Sulpho-4-ethylphenyl, 2-Sul £ o-4-tert.-butylphenyl, 2-Sul £ o-5-isobutylphenyl, 2-Sul £ o-4-ethoxyphenyl,

709811/1042

- 5 - Ref. 3049

2-sulfo-5-butoxyphenyl, 3-sulfo-4-methoxyphenyl, 3-sulfo-5-ethoxyphenyl, 3-sulfo-6-ethoxyphenyl, 4-sulfo-2-ethoxyphenyl, 4-sulfo-3-methoxyphenyl, 2- Sulfo-4-propoxyphenyl, 2-Sul £ o-4-methoxyphenyl, 2-sulfo-4-isopropoxyphenyl, 2-methyl-4-methoxyphenyl, 3-propyl-S-propoxyphenyl, 3-methyl-2-ethoxyphenyl, 3- Methyl-4-butoxyphenyl, 3-ethyl-5-ethoxyphenyl, 3-methyl-6-methoxyphenyl, 4-ethyl-2-ethoxyphenyl, 4-ethyl-3-methoxyphenyl, 2,4,6-trichlorophenyl, 2,4, 5-trichlorophenyl, 2,3,5-trichlorophenyl, 3,4,5-trichlorophenyl, naphthyl-1, naphthyl-2, 2-, 4-, 6-, or 8-chloronaphthyl-1, 4-, 6-, or 8-chloronaphthyl-2, 2-methyl-naphthyl-1, 4-ethyl-naphthyl-1, 5-propyl-naphthyl-1, 4-methyl-naphthyl-1, 5-methyl-naphthyl-1, 8-methyl -naphthyl-1,8-ethyl-naphthyl-1,3-methyl-naphthyl-1,3-propyl-naphthyl-1,6-methyl-naphthyl-1,6-butyl-naphthyl-1,7-methyl-naphthyl -1, i-methyl-naphthyl-2, 1-propyl-naphthyl-2, 1-isopropyl-naphthyl-2, 5-methyl-naphthyl-2, 5-ethyl-naphthyl-2, 3-methyl-naphthyl-2 , 3-ethyl-naphthyl-2, 6 -Methyl-naphthyl-2, 7-ethyl-naphthyl-2, 2-methoxy-naphthyl-1, 4-ethoxy-naphthyl-1, 5-isopropoxy-naphthyl-i, 5-methoxy-napthyl-i, 8-ethoxy -naphthyl-1, 3-methoxy-naphthyl-1, 6-ethoxy-naphthyl-1, 6-butoxy-naphthyl-1, 7-methoxy-naphthyl-1, 7-ethoxy-naphthyl-1, i-methoxy-naphthyl -2, 1-Ethoxy-naphthyl-2, 5-methoxy-naphthyl-2-5-ethoxy-naphthyl-2, 5-propoxy-naphthyl-2, 3-methoxy-naphthyl-2, 3-ethoxy-naphthyl -2, 6-Ethoxy-naphthyl-2, 7-methoxy-naphthyl-1, '2-, 4-, 5-, 6- or 7-sulfonaphthyl-1, 1-, 5-, 6-, 7- or 8-sulfonaphthyl -2, 2-acetylaminohaphthyl-1, 2-formylaminonaphthyl-1, 3-formylaminonaphthyl-1, 3-acetylaminonaphthyl-1, 3-propionyl

7flQfl1

- 6 - Ref. 3049

aminonaihthyl-1, 4-Acetylamin.onaphthyl-i, 4-Butyrylaminonaphthyl-i, 5-Formylaminonaphthyl-i, 5-Acetylaminonaphthyl-i, 5-Propionylaminonaphthyl-1, 6-Acetylaminonaphthyl-l, 1-Acthylaminonaphthyl, 1-Acthylaminonaphthyl-1, 1-Acthylaminonaphthyl-1, " -Formylaminonaphthyl-2, 4-acetylaminonaphthyl-2, 4-propionylaminonaphthyl-2, 5-acetylaminonaphthyl-2, 6-formylaminonaphthyl-2 _> 6-acetylaminonaphthyl-2, 6-butyrylaminonaphthyl-2, 7-formylaminonaphthyl -2, 8-Acetylaminonaphthyl-2, 4,7-dichloronaphthyl-1, 4,8-dichloronaphthyl-1, 5,7-dichloronaphthyl-i, 5,8-dichloronaphthyl-1, 4 _u 8-dichloronaphthyl-2, 5 , 8-dichloronaphthyl-2, 2,4-disulfonaphthyl-1, 3,6-disulfonaphthyl-1, 4,6-disulfonaphthyl-1, 4,7-disulfonaphthyl-1, 5,7-disulfonaphthyl-1, 1,5 -Disulfonaphthyl-2, 1, o-Disulfonaphthyl-2, 1,7-Disulfonaphthyl-2, 3,6-Disulfonaphthyl-2, 4,7-Disulfonaphthyl-2, 5,7-Disulfonaphthyl-2, 5,8-Disul £ onaphthyl-2, 6,8-disulfonaphthyl-2, 2,4-dimethylnaphthyl-1, 5,8-diethylnaphthyl-1, 4,8-diethylnaphthyl-1, 2-methyl-4-propylnaphthyl-1, 4-Met hyl-7-ethylnaphthyl-ΐ, 4,7-diethylnaphthyl-1, 2,7-diethylnaphthyl-1, 1,7-dimethylnaphthyl-2, l, 7-diethylnaphthyl-2, 1,8-dimethylnaphthyl-2, 1, e-diethylnaphthyl-2, 1-methyl-8-propylnaphthyl-2, 1-methyl-8-ethylnaphthyl-2, 1,4-diethylnaphthyl-2, 1, S-dimethylnaphthyl-2, 1,6-diraethylnaphthyl-2, 2,4-dimethoxynaphthyl-1, 5,8-diethoxynaphthyl-1, 4,8-diethoxynaphthyl-1, 4,7-dimethoxynaphthyl-1, 2-methoxy-7-isopropoxynaphthyl-1, 2,7-dimethoxynaphthyl-1, 1,7-dimethoxynaphthyl-2, 1,7-diethoxynaphthyl-2, 1-methoxy-7-eth-.oxynaphthyl-2, 1,8-dimethoxynaphthyl-2, 1, S-diethoxynaphthyl-2, 1,4-dimethoxynaphthyl -2, '1, S-diethoxynaphthyl-2, 1,6-diethoxynaphthyl-2, 1,6-dimethoxynaphthyl-2, 2-methyl-4-methoxynaphthyl-1,

709811/1042

- 7 - Ref. 3049

5-ethyl-8-ethoxynaphthyl-1, 8-ethyl-5-ethoxynaphthyl-1, 4-methoxy-8-ethylnaphthyl-1, 4-methoxy-7-ethylnaphthyl-1, 2-methoxy-7-methylnaphthyl-1, 2-methyl-7-methoxynaphthyl-1, 1-methyl-7-methoxynaphthyl-2, 1-ethyl-8-methoxynaphthyl-2, 1-ethyl-4-ethoxynaphthyl-2, 1-ethoxy-5-methylnaphthyl-2, i-methoxy-o-methylnaphthyl-Z, 2-methoxy-6-sulfonaphthyl-1, 2-ethoxy-8-sulfonaphthyl-1, 2-ethoxy-4-sulfonaphthyl-1, 5-isopropoxy-7-sulfonaphthyl-1, 5-methoxy-7-sulfonaphthyl-1, S-methoxy-6-sulfonaphthyl-i, 2-ethyl-6-sulfonaphthyl-1, 8-methyl-6-sulfonaphthyl-1, 2-propyl-8-sulfonaphthyl-1, 2-methyl-S-sulfonaphthyl-i, 2-methyl-4-sulfonaphthyl-1,5-ethyl-7-sulfonaphthyl-1 , 1-ethyl-4-sulfonaphthyl-2, 1-methyl-5-sulfonaphthyl-2, 3-propyl-5-sulfonaphthyl-2, 3-methyl-6-sulfonaphthyl-2, 8-methyl-6-sulfonaphthyl-2, 8-ethyl-6-sulfonaphthyl-2, 5-methyl-7-sulfonaphthyl 2, 5-ethyl-7-sulfonaphthyl-2, 2-methyl-6-chloronaphthyl-1, 2-ethyl-6-chloronaphthyl-1, 2-propyl-4-chloronaphthyl-1 2-methyl-4-chloronaphthyl-1, 1-ethyl-S-chloronaphthyl ^, 1-methyl-8-chloronaphthyl-2, 2-methoxy-6-chloronaphthyl-1, 2-ethoxy-6- · chloronaphthyl-1, 2-propoxy-6-chloronaphthyl-1, 2-ethoxy-4-chloronaphthyl-1, 1-methoxy-8-chloronaphthyl-2, 1-ethoxy-e-chloronaphthyl-Z, 2,3,4-trichloronaphthyl-1j 4,5,8-trichloronaphthyl-1; 1,3,4-trichloronaphthyl-2.

Of the foregoing, alkyl or alkoxy groups bearing residues, preferred are those in which the alkyl or contain only alkoxy groups 1 or 2 carbon atoms. Those dyes are particularly preferred according to the invention

7038 11/1042

p ref. 3049

in which A

Phenyl, 2-tolyl, 3-ToIyI, 4-ToLyI, 4-Athyι phenyl, 2-methoxyphenyl, 4-methoxyphenyl, S-xthoxyphenyl, 4-ethoxyphenyl, 4-Acetylaminopheny 1, 2-ClilorphenyI, 3-Chlorophenyl, 4-Chlorophenyl, 2, 5-dichlorophenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulf ophenyi, 4-chloro-b-suli ophenyl, i ^ aphthyl-1, 4-sulfonaphthyl-1,5-sulfonaphthyl-1, 6- or 7-sulfonaphthyl-1,5 means.

709811/1042

Ref. 3049

The dyes according to the invention can either be used as free Acids or in the form of their water-soluble salts. If the dyes are in the form of the free acids, Me means a Hydrogen atom. If they are in the form of their salts, Me means a metal cation. With regard to the solubility of the dyes Me preferably denotes an alkali metal or alkaline earth metal cation, in particular a sodium or potassium cation.

The phenyl nucleus B of the dyes according to the invention can, as already indicated above, in addition to those in the 4-position relative to the azo group Hydroxyl group, have another substituent,

Examples of 4-hydroxyphenyl radicals of the formula

are:

2- or 3-methyl-4-hydroxyphenyl, 2- or 3-ethyl-4-hydroxyphenyl, 2- or 3-propyl-4-hydroxyphenyl, 2- or 3-isopropyl-4 · hydroxyphenyl, 2- or 3-butyl -4-hydroxyphenyl, 3-tert. Butyl-4- hydroxyphenyl, 2- or 3-methoxy-4-hydroxyphenyl, 2- or 3-ethoxy -4-hydroxyphenyl, 2- or 3-propoxy-4-hydroxyphenyl, 2- or

709811/1042

- \ - AO

Ref. 3049

3-butoxy-4-hydroxyphenyl, 3-sec. Butoxy ^ hydroxyphenyl, 3-tert. Butoxy-4-hydroxyphenyl, 2- or 3-chloro-4-hydroxyphenyl, 2- or 3-carboxy-4-hydroxyphenyl, or 2- or 3-sulfo-4-hydroxyphenyl.

Dyes according to the invention with the Residues 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 3-carboxy-4-hydroxyphenyl, 2-methyl-4-hydroxyphenyl, 2-sulfo-4-hydroxyphenyl, 3-sulfo-4-hydroxyphenyl.

The dyes of the formula I according to the invention are prepared by using a diazonium compound of the general formula III

A-N = N

SO ₃ Me

III

(SO ₃ Me) _n

strengthen

in which / '"' stands for an anion of an / acid, preferably a mineral acid, such as, for example, sulfuric acid or hydrochloric acid, and A, Me and η have the abovementioned meanings jinit a phenol derivative of the general formula IV · ^;

H-f B VOH

709811/1042

Ak Ref. 3049

in which the phenyl nucleus B can additionally be substituted, as indicated above, couples. The coupling of the diazo compound III with the coupling component IV takes place in a manner known per se in an aqueous medium which can also contain organic solvents such as alcohols, especially lower aliphatic alcohols, for example methanol, ethanol or isopropanol , at temperatures of -5 ° C to + 80 ° C, preferably at 30 to 60 ° C, in a pH range from 6 to 12, preferably from 9 to 11. In this coupling reaction, the diazo compound III is combined with the coupling component IV in a molar ratio of 1: 1. The coupling can also be carried out in the presence of known coupling accelerators such as, for example, pyridine, urea or thiourea .

Examples of diazo compounds of the general formula III in the form of the chlorides are given in the following list . Here

(A)
the substituent is defined in column 1, in column 2 the number η of the sulfo groups present in the aminonaphthol component and in column 3 their position.

709811/1042

Ref. 3049

HO

SO ₃ Me

Position of the sulfo group

2-methylphenyl

2.5 dimethylphenyl

2-methoxyphenyl

2-ethoxyphenyl

2-methyl-5-methoxyphenyl

4-chloro-2-methylphenyl

5-chloro-2-methylphenyl

2,3-dichlorophenyl

2-chlorophenyl

2,5-dichlorophenyl

2,4,3-trichlorophenyl

2,4-disulfophenyl

2,5-disulfophenyl

Naphthyl (t)

4-sulfonaphthyl- (1)

3,6-disulfonaphthyl- (1)

5-sulfonaphthyl- (2)

3,6-disulfonaphthyl-C2)

2-sulfophenyl

3-methylphenyl

4-methylphenyl

2,4-dimethylphenyl

6-sulfonaphthyl- (l)

7-sulfonaphthyl- (l)

2 2 2 2 2 2 2 2 2 2 2

3.6 3.6

3.6

3.6

3.6

3.6

3.6 3.6 3.6 3.6 3.6

3.6 "3.6 3.6

3.6 3.6 3.6 3.6 3.6 3.6 3.6

3.6 3.6 3.6

709811/1042

Ref. 3049

Position of the sulfo group

4-methoxyphenyl 2

4-ethoxyphenyl 2

2,4-dichlorophenyl 2

2,5-dichlorophenyl 2

3-chlorophenyl '2

4-chlorophenyl 2

3-sulfophenyl 2

4-sulfophenyl 2
S-methoxy-S 1-4 -disulfonaphthyl-CI) 2 8-ethoxy-4,6-disulfonaphthyl- (1) 2 8-methoxy-4,6-disulfonaphthyl- (1) 2

8-methoxy-4-sulfonaphthyl- (1) 2

4-chloro-2-sulfophenyl 2

4-chloro-3-sulfophenyl 2

2-chloro-4-sulfophenyl 2

2-chloro-5-sulfophenyl 2

4-methoxy-5-sulfophenyl 2

2-methyl-5-sulfophenyl 2

Phenyl 2

4-methylphenyl 2

Naphthyl- (l) 2

Phenyl I.

2-methylphenyl 1

Naphthyl- (l) 1

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3.6

3, * 6

3.6

3.6

4.6

4.6

4.6

709811/1042

■ ν

Ref. 3049

The required diazo compound of the general formula III can be obtained by adding 4,4'-diamino-diphenylamine -2-sulfonic acid the formula IV

N-C> ΝΗ,

SO ₃ H

CiV)

tetrazotized in a manner known per se and one side with a 1-amino-8-hydroxynaphthalene sulfonic acid of the general formula V

OH NH.

(V)

CSO ₃ H) _n

is coupled. A diazotized monoazo dye is formed which, in the form of the free acid, has the general formula VI:

OH NH

SO ₃ H

Then an amine of formula VII is

(VI)

A - NH,

(VII)

70981 1/1042

^Ref 3049

diazotized and coupled with the monoazo dye VI, the required diazo compound of the general formula III is obtained.

The tetrazotization of 4,4'-diaminodiphenylamine-2-sulfonic acid of the formula IV is in a manner known per se in acidic, aqueous © medium by the action of nitrous acid or nitrous acid Acid-releasing agents at temperatures between -5 and +20 C. executed.

The half-sided coupling of the tetrazo compound with the 1-amino-8-hydroxynaphthalene-sulfonic acid of the general formula V is carried out in an acidic aqueous medium, preferably at a pH of 2 to 4 and in the temperature range from -10 to +30 ° C., preferably from 0 to +20 ⁰ C carried out.

The reactants, the tetrazo compound and the 1-amino-8-hydroxynaphthalene sulfonic acid are in the oil ratio Implemented 1: 1 with each other. The coupling can also be carried out in the presence of coupling accelerators known per se, such as pyridine, Urea or thiourea. The amine of the general formula VII is also diazotized in in a manner known per se. You can, for example, in an aqueous acidic medium by the action of nitrous acid or its Salts, such as sodium nitrite or agents that split off nitrous acid, are carried out. However, it can also be used in

709811/1042

X-

Ref. 3049

see solvents, for example in mixtures of lower, organic acids, such as jissetic acid and propionic acid, carried out in the presence of mineral acids or in concentrated sulfuric acid will. In general, temperatures between -5 and +20 C are used here. The coupling of the diazotized aromatic amine of the general formula VII with the diazotized monoazo dye of the general formula Vi takes place in the aqueous alkaline medium, preferably at pH values between 7 and 12 and at temperatures from -10 to +30 C, preferably from 0 up to 20 C. In this reaction, too, the reactants are reacted with one another in a molar ratio of 1: 1 and the coupling can take place take place in the presence of known coupling accelerators.

The trisazo dyes of the invention are very good in water soluble. They are suitable for dyeing and printing natural or synthetic fiber materials containing hydroxyl groups or nitrogen Example of cotton, regenerated cellulose, wool, semi-wool, silk, polyamide, and also of wood and in particular for Dyeing and printing of leather.

The fiber materials can be present in all processing states, such as continuous yarn, flake, staple fiber, cable, sliver, yarn, strands, bobbins, muffs, woven, knitted or bound or unbound non wovens. The dyeing and printing of the fiber materials mentioned with the trisazo dyes according to the invention takes place in the white known per se for acid dyes

70981 1/1042

3049

se, for example according to the discontinuous or continuous processes described in Ullmanns Enzyklopadie der Technischen Chemie, Volume 7, pages 15 to 18, 30 to 33, 37 * 40 and &.

In the discontinuous exhaust process, the fiber material is treated with the dye according to the invention and other customary additives, such as neutral salts, possibly wetting agents and depending on the type of substrate to be dyed, at temperatures between 30 and 100 ° C., optionally with a slow temperature increase during the dyeing process Acid or alkali-containing dye liquor is treated until the dye is largely absorbed onto the fiber material. In general, a liquor ratio of 1:10 to 1:30, preferably about 1:20, is used. The amount of dye used depends on the desired depth of color and is a rule for moderate color depths 1 to 2 I, for low frequencies up to 12% of the dyeings obtained Warengewichts.-green shade and very good coloristic own sheep purely have ten, such as light fastness and wet fastness _t Schweiüechtheit.

In an analogous manner, the ILT process can also be used in pressure-resistant dyeing machines at temperatures from 110 to 130 ° C., provided the fiber materials can withstand such temperatures. Continuously example, can be worked by known dew pad-steam process or pad Roil method.

709811 / .1642

Ref. 3049

Here, the fiber materials are impregnated with the dye liquor, then heated to temperatures of approx. 90 to 110 ° C. and kept at this temperature until the dye is absorbed onto the fibers. Depending on the chemical nature of the fiber material, weakly alkaline or weakly acidic dye liquors are used, an alkaline pH value being achieved by adding alkali carbonate, preferably soda, in an amount of about 0.5 % of the weight of the fabric and a weakly acidic pH value Addition of about 3 to 4 % of the weight of the goods of an acid, preferably sulfuric acid or an equivalent amount of sodium hydrogen sulfate, formic acid or ammonium salts, in particular ammonium acetate, ammonium formate or ammonium sulfate, is set.

In particular, the trisazo dyes according to the invention are outstandingly suitable for dyeing different types of leather, for example pure chrome leather (cattle box, box calf, split velor) but also chrome leather retanned by synthetic synthetic means. The leather dyeing with the dyes according to the invention can be carried out by all known processes, ζ.B. in the trough, in the reel, in the fulling barrel, by brush dyeing or spray dyeing (cf. Üllmanns Enzyclopadie der Technischen Chemie, Volume 11, page 576).

When dyeing in the trough, in the fulling barrel or in the reel, the leather is generally used with the dye liquors in a liquor ratio of about 1: 1 to 1: 6 at temperatures between

temperature and about 70 C. The dye liquors contain Usually, depending on the desired depth of color, 1 to 10 g of dye per liter and, if necessary, other known additives, such as neutral salts, wetting agents, fat liquors or tanning agents. Towards the end of the staining can be used to complete the undressing some acid can be added to the liquor. If dyeing is carried out using the brush or spray process, liquors that are used are used somewhat higher dye concentrations, preferably 5 to 25 g / l exhibit.

According to the methods mentioned, with the inventive Dyes obtained very level full dyeings with excellent lightfastness, solventfastness, lickfastness and with very good resistance to water hardness, formaldehyde, formic acid and alkali. The coloration is excellent and the dyes are completely absorbed by the substrate during dyeing, so that a clear residual liquor is obtained.

In the following exemplary embodiments, the percentages mean percentages by weight; the temperatures are given in degrees Celsius.

709811/1042

'' - \> - 9Φ Ref. 3049

example 1

27.9 g of 4,4'-diaminodiphenylamine-2-sulfonic acid are in one Mixture of 200 g of water and 50 g of 30% hydrochloric acid with addition of ice at 0 - 5 C with a solution of 13.8 g of sodium nitrite tetrazotized in 50 g of water.

After the sodium nitrite solution has been added, the mixture is stirred for about 1 1/2 hours at 0-5 ° C. and then excess nitrous oxide is removed Acid with sulfamic acid.

Then 30 g of i-amino-S-hydroxy-naphthalene-Sjo-disulfonic acid dissolved in 100 g of water and 30 l sodium hydroxide solution so that the solution has a pH of 6.5 to 6.7.

The neutral solution of 1-amino-S-hydroxy-naphthalene-Sjo-disulphonic acid is subsequently slowly added dropwise to the liger with 10 sodium carbonate solution to pH 2 truncated solution of the tetrazo component and the half-side coupling by stirring at 10 to 15 ⁰ C and addition of 10 sodium carbonate solution to a pH of 2.5.

A diazobenzene solution prepared in a known manner from 8.54 g of aniline, 25 g of 30% hydrochloric acid and a solution of 6.3 g of sodium nitrite in 30 g of water at ^{0 ° C. is then added to the suspension of the diazotized monoazo dye, which is cooled with ice to 0-5 ° C} and with 10 liter sodium carbonate solution

709611/1042

Ql Ref. 3049

pH adjusted to 8.5 - 9.

After 1/2 hour, a solution of 9.9 g of phenol in
50 g of water and 7.9 g of 30 L sodium hydroxide solution were added. The coupling is complete after stirring for four hours at 20 ° -40 ° C.

The dye is deposited by adjusting the pH to 2 and adding 100 g of sodium chloride.

The dye to which the forael in the form of the free acid

N = N-

~~ (VII)

is filtered off and dried * It is obtained as a dark powder that dissolves in water with a green color.
The yield based on pure dye is: 82 %

Dyeing example I

In a dye liquor composed of 250 g of water and 0.5 g of the dye of the formula VII prepared according to Example 1, 100 g are obtained

70881.1 / 10 * 2

Ref. 3049

freshly tanned and neutralized chrome grain leather during » Drummed in the dyeing drum at 60 ° C. for 50 minutes. The leather is then in the same dyebath for 30 minutes with 2 g of one treated with anionic grease. After drying and trimming of the leather in the usual way, a very level, yellowish green coloration with good lightness properties, in particular, is obtained good lightfastness as well as excellent lickfastness, Solvent fastness, resistance to water hardness and compatibility with formaldehyde, formic acid and alkali.

Dyeing example II

In a dyeing drum 100 g chromvegetabil tanned lambskin be in a dye bath consisting of 8 g of the dye obtained according to Example VII 1 1000 g of water at 60 ⁰ C and drumming was 1.5 g of an anionic fatliquor for 45 minutes. The dye is then fixed by adding 5 g of 85% formic acid.

The green color obtained after drying and trimming has very good levelness and fastness properties, such as good lightfastness, very good lickfastness and solventfastness on.

The following table shows the structure of other dyes can be found, which can be prepared according to the information in Example 1.

09811/1042

^{Ref 3049}

The table shows:

In column 1: The used diazo component A-NH ₇ In column 2: The used 1-Am.ino-8-

hydroxy-naphthalene-3,6-disulfonic acid of the formula

Oil NH ₂

The table only shows the number and position of the sulfonsauric groups.

In column 3: The coupling component of the formula IV used.

In column 4: the shade of the dye on leather.

709811/1042

Diazo component
A-NH ₂ l-amino-8-hydroxy
naphthalene sulfonic acid, Coupling component
of formula IV Hue on
leather aniline 3 ,, 6-IMiSuJ. £ onsäiur e 2-methylphenol green
tinged aniline Il 2-hydroxy-benzoic acid green
b moody aniline 4 :, 6-disulfonic acid phenol green Aniline 4-sulfonic acid phenol green 4-aminotoluene 3,6-disulfonic acid Phenol j green 4-Ac e ty1amiη c an i1in Il Phenol i green 4 - Ami η oä thy! Benzene. It I.
phenol green 2-aminoariisole 2-methylph.enol green

Diazo component
A-XL ₀ l-amino-8-hydroxy
.naph thai in-sulionic acid Coupling component
of formula IV Shade aui
Lee he aniline 3,6-disulfonic acid 3-methylphenol green aniline ti 2-kydroxy-3-methyl-
benzoic acid green 4-acetylaminoaniline π 2-hydroxybenzenesulfone
acid green 2-chloroaniline ti phenol green 4-chloroaniline ti phenol B rün 2,5-dichloroaniline ! I phenol green 3-amino-6-chloro
benzenesulfonic acid Π phenol gj ^ ün 4-aminobenzene sulfone
acid Il phenol green 1-Ami nonaphtha1i η Il phenol green l-aminonaphthalene-4-
sulfonic acid ti phenol rrün l-aminonaphthalene-7-
sulfonic acid Il phenol green

Claims (1)

Ref. 3049 PATl-NTANS J ¹ RU LTIL 1. Water-soluble trisazo dyes of the general formula I HO NH, A-N = N-, -N = N (SO, Me) ^S ° 3 ^Me wherein A is a phenyl or naphthyl group which is unsubstituted, monosubstituted by chlorine, -SO, H, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or acylamino with 1 to 4 carbon atoms, disubstituted by two identical or different substituents of the group chlorine, -SO, H, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or trisubstituted by 3 chlorine, Me hydrogen or an alkali or earth alkaline cation and η means the number 1 or 2 and the phenyl nucleus B can additionally be substituted by an alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine, -COOH or -SO-H. 2. Water- soluble trisazo dyes of the general formula II HO NH A-N = N- MeO ₃ S N = N SO ₃ Me 70981 1/1042 ' Λ. 254100? Ref. 3049 wherein A, Me and η have the meanings given in claim 1 and the core B as indicated in claim 1 can additionally be substituted. 3. Water-soluble trisazo dyes according to Claims 1 and 2, characterized in that Λ is a phenyl group which can be substituted as indicated in claim 1. 4. Water-soluble trisazo dyes according to claims 1. · to 3, characterized in that A is a phenyl or naphthyl group which is unsubstituted, iiionosubstituiert by chlorine, -SO ₃ H, alkyl with 1 to 2 carbon atoms, alkoxy with 1 up to 2 carbon atoms or acylamino with 1 to 2 carbon atoms, disubstituted by two identical or different substituents of the group chlorine, -SO ^ H, alkyl with 1 to 2 carbon atoms or • alkoxy with 1 to 2 carbon atoms or trisubstituted by 3 can be chlorine. 5. Water-soluble trisazo dyes according to claims 1 to 4, characterized in that ^: that the Pheriylkern B additionally ait by an alkyl having 1 to 2 carbon atoms, alkoxy 'May be substituted 1 to ₃ H 2 C-atoms, chlorine, -COOH or -SO. 703811/1042 - 2 Ref. 3049 ό. Process for the preparation of water-soluble trisazo dyes of the general formula 1 A-N = N -NWN (SO Me). SO ₃ Me where ^v ~ 3
A is a phenyl or naphthyl group which is unsubstituted, monosubstituted by chlorine, -SO ₃ H, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms or acylamino with 1 to 4 carbon atoms, disubstituted by two identical or different substituents of the group chlorine, -SO ₃ H, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or trisubstituted by 3 chlorine, Me is hydrogen or an alkali metal or alkaline earth metal cation and η is the number 1 or 2 and the phenyl nucleus B can additionally be substituted by an alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine, -COOH or -SO ₃ H, characterized in that a diazonium compound of the general formula III NlL A-N = N , -n = n / Vnh / VnH SO ₃ Me (III) (SO ₃ Me) _n wherein y is an anion of a strong acid and A, Me and η have the meanings given above, with a 70981 1/1042 Phenol derivative of the general formula IV H-f ß VüII (IV) in which the phenyl ring B may be additionally substituted as indicated above, is coupled in an aqueous medium at temperatures between -5 C and +80 ⁰ C. 7. The method according to claim 6, characterized in that a diazonium compound of the general formula IIIa HÜ NH. A-N = N- MeO ₃ S -N = N- / SO ₃ Me γ (Ilia) where y, A, Me and η have the meanings given above, is used. 8. Process according to Claims 6 and 7, characterized in that a diazonium compound of the general formula III is used in which A is a phenyl group which may be substituted as indicated in claim 6. 9. Process according to claims 6 to 8, characterized in that a diazonium compound of the general formula III is used in which A is a phenyl or naphthyl group, 70SB1 1/1042 • jU Νκ - Ref. 3049 those unsubstituted, monosubstituted by chlorine, -SO ₃ H, alkyl having 1 to 2 carbon atoms, alkoxy with 1 to 2 carbon atoms or acylamino with 1 to 2 carbon atoms, disubstituted by two identical or different substituents of the chlorine group, -SO ₃ H, alkyl with 1 to 2 carbon atoms or alkoxy with 1 to 2 carbon atoms or trisubstituted by 3 chlorine, 10. The method according to claims 6 to 9, characterized in that that is coupled with a phenol derivative of the general formula IV in which the phenyl nucleus B is additionally can be substituted by an alkyl having 1 to 2 carbon atoms, chlorine, -COOH or -SO7H. 11. Use of the water-soluble trisazo dyes of the formula I according to Claims 1 to 5 for dyeing leather. water soluble 12. Use of the trisazo dyes of the formula I according to Claims 1 to 5 for dyeing and printing hydroxyl- or nitrogen-containing fiber materials. 13. The leather dyed according to claim 151. 14. The fiber materials dyed according to claim 12, 7D9811 / KU2