CH633822A5 - Process for preparing fibre-reactive azo dyes - Google Patents

Description

The present invention relates to a method for producing fiber-reactive azo dyes of the formula

60

0

Cu —0 NH— (R-NH -)

X1 - NH - D - N =

ho3S

n

• X,

(1)

S03H

5

633 822

where the grouping

0

1

X1-NH-D-N = N-

(2)

a rest of the formula

H03S 0 -

Xx-NH

N = N -

(3)

or the formula

(4)

0-

one of the two residues Xi and X2 is a fluorine-s-triazine residue and the other 30 is a fluorine (chlorine or bromine) -s-triazine residue, R is a bridging member and n = 0 or 1.

Suitable radicals Xi and X2 are in particular a 2,4-difluoro-s-triazin-6-yl radical or a 2-fluoro-4-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine -6-yl residue or 35 a 2,4-difluoro (chlorine or bromine) -s-triazin-6-yl residue or a 2-fluorine (chlorine or bromine> 4-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazin-6-yl radical.

The bridge member R can be any; e.g. a chain aliphatic radical, an aromatic radical or also a heterocyclic radical, and it can also consist of several different radicals, e.g. aromatic and heterocyclic radicals. R is preferably an aromatic radical which is bonded via an intermediate member to the amino group of the 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid component in formula (1), e.g.

-CQ-NH- <> - CO-NH-

SO ^ H

S0 "H

-C * N ^ C-NH- <~ V-I II

SO ^ H

C ^ X! -NH- <> —SO ^ H I «

I.

F

i II

S0, H

I 3

Br

-C ^ C-NH-I II

N ^ c-N

I.

Cl .N.

NH-

I II

I.

Cl

S0, H 5

Tn1 <^ s ° 3h

K * c-N 1 I

0CH (CH)

-co-o-

—CO — UH- <> -S0 “H

—C ^^ C-NH-I II

so3H

-co <ij>

The bridge member R is thus preferably derived from an acyl compound, e.g. a haloacyl compound, which still contains a free amino group, to which the external halogen-s-triazine radical X2 can be condensed. In particular, R is an m- or p-benzoyl radical.

If only one of the two residues Xi and X2 is a fluoro-s-triazine residue and the other is a chloro or bromo-s-triazine residue,

633822

6

may be either Xi or X2 the fluorine-s-triazine residue, preferred important subgroups of the fiber-reactive azo dyes in this case, however, Xi is the fluorine-s-triazine residue. of formula (1)

Fiber-reactive azo dyes of the formula (1), a) fiber-reactive azo dyes of the formula in which n = 0 and Xi and X2 are identical radicals are preferred.

(5)

wherein Y1 and Yi are each independently a fluorine atom, an optionally substituted amino group, a hydroxyl group, an optionally substituted alkoxy, aryloxy, alkylthio or arylthio group; and b) fiber-reactive azo dyes of the formula

0 Cu

0 NH

-

C-Y,

Y - C ^ NJ-NH 1 I II

I.

F

(6)

wherein Y1 and Y2 are each independently a fluorine atom, an optionally substituted amino group, a hydroxyl group, an optionally substituted alkoxy, aryloxy, alkylthio or arylthio group.

The dyes of the formula (1) are fiber-reactive, since they contain fluorine, chlorine or bromine atoms which can be split off from the fluorine-s-triazine and fluorine (chlorine or bromine) -s-triazine radicals Xi and X2.

Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

Fluro-s-triazine dyes, which contain an amino, alkoxy, etc. group as colorless substituents on the triazine ring, are known from Swiss patent specification 510 089. The dyes of the present application differ from known copper complex dyes by the special azochromophore in connection with two terminal halogen-s-triazine residues, one of which must be a fluoro-s-triazine residue.

The preparation according to the invention of the fiber-reactive azo dyes of the formula (1) is characterized in that an azo compound of the formula in which D, R and n have the meanings given under formula (1), a copper-donating agent, an equivalent of a 20 fluoros-triazine , and converting another equivalent of a fluorine (chlorine or bromine) -s-triazine by coppering and acylation to give a fiber-reactive azo dye of the formula (1).

In particular, the fiber-reactive azo dyes of the formula (1) are prepared in such a way that an azo compound of the formula (7) in which D, R and n have the meanings given under the formula (1), a copper donor, one equivalent 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine and another equivalent of 2,4,6-trifluoro (chlorine or 30 bromo) triazine or a 2,4-difluoro (chloro or bromo) -6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine by coppering and acylation to give a fiber-reactive azo dye Formula (1) is implemented, or that 2,4,6-trifluoro-s-triazine and 2,4,6-trifluoro (chlorine or 35 bromo) -s-triazine are used as the acylating agent, and by condensation with ammonia or an amine, a halogen atom in the s-triazine ring is replaced by an amino group. Coppering and acylation can be done in any order.

The preferred embodiment of the process for preparing the fiber-reactive azo dyes of the formula (1) is characterized in that an azo compound of the formula (7), in which D has the meaning given and n = 0, a copper donor and 2 Equivalents of 2,4,6-tri-fluoro-s-triazine or a 2,4-difluoro-6-amino (hydroxy, alkoxy, 45 aryloxy, alkylthio or arylthio) -s-triazine by coppering and acylation to give a fiber-reactive azo dye Formula (1), or that 2,4,6-trifluoro-s-triazine and 2,4,6-trifluoro (chlorine or bromine) -s-triazine are used as the acylating agent and a 50 by condensation with ammonia or an amine Halogen atom in the s-triazine ring replaced by an amino group.

The important fiber reactive azo dyes of formulas (5) and (6) are prepared by a) an azo compound of the formula

55

H03S

H2N-D-N = N

R-NH H

(7)

65 in any order with a copper donor and with 2 equivalents of 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine acylated, or that an azo compound

7

633822

tion of the formula (8) in any order with a copper donor and acylated with 2 equivalents of 2,4,6-tri-fluoro-s-triazine, and that after acylation by condensation with ammonia or an amine a fluorine atom in the s -Triazine ring replaced by an amino group; respectively.

b) an azo compound of the formula oh nh

■ n

HO

nh in any order with a copper donor and with 2 equivalents of 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine acylated, or that an azo compound of the formula (9) is reacted in any order with a copper donor and is acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine, and that after the acylation by condensation with ammonia or an amine a fluorine atom in the s-triazine ring is replaced by an amino group.

The fiber-reactive azo dyes of the formula (5) can also be prepared by using azo compounds of the formula

HO, S

HO NH,

with an equivalent of 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine and a further equivalent of 2,4,6- Tri-fluor (chlorine or bromine) -s-triazine or a 2,4-difluoro (chlorine or bromine) -6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazine acylated, and then oxidatively coppered, or that aco compounds of the formula (10) are acylated with one equivalent of 2,4,6-trifluoro-s-triazine and another equivalent of 2,4,6-trifluoro (chlorine or bromine) -s-triazine, and by condensation with ammonia or a Amine a halogen atom on the s-triazine ring replaced by an amino group, and then oxidatively coppered.

The o, o'-dihydroxyazo compounds of the formula (7) or (8) and (9) used as starting materials for the production of the fiber-reactive azo dyes of the formula (1), and of the o-mono-hydroxyazo compounds of the formula (10) manufactured in the following way:

1. by diazotization of 2-amino-6-nitro-naphthalene-4,8-disulfonic acid, coupling to the N-acetyl compound of l-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid (H- or K-acid), oxidative coppering of the o-mono-hydroxyazo compound obtained and subsequent reduction of the nitro group to the amino group and simultaneous copper removal and saponification of the acetylamino group;

2. by diazotization of the nitrodiazoxy acid, coupling to the H or K acid and subsequent reduction of the nitro group to the amino group;

3. by diazotization of the 2-amino-6-nitro (or acetylamino) naphthalene-4,8-disulfonic acid, coupling to the H- or

K-acid or its N-acetyl derivatives and subsequent conversion of the nitro group or acetylamino group into the amino group by reduction or saponification.

The diazotization is usually carried out by the action of nitrous acid in an aqueous mineral acid solution at low temperature, the coupling at weakly acidic, neutral to weakly alkaline pH values.

If there are azo compounds of the formula (7) in which n = 1, the radical -R-NH2 must be introduced into the H or K acid. This is preferably done by acylation of the 1-position amino group of the H or K acid with corresponding acyl compounds which still contain a free amino group or a group which can be converted into an amino group. Examples of such acyl compounds are: p-nitrobenzoyl chloride (subsequently reduced), 2,4-dichloro-6- (3 '-amino-4' -sulfophenylamino) -s-triazine and 2,4-difluoro-6- (4 '-amino-2', 5 '-disulfophenylamino) -s-triazine. The rest of -R-NH2 can be introduced before or, if necessary, after the coupling.

The following may also be mentioned as starting materials for the production of the fiber-reactive azo dyes of the formula (1): 2,4,6-trifluoro-s-triazine,

2,4,6-T richlor-s-triazine,

2.4.6-tribromo-s-triazine,

2,4-difluoro (chlorine or bromo) -6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazines, where the amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio substituent e.g. the remainder can be one of the amines, alcohols, aromatic hydroxy compounds, aliphatic or aromatic thiol compounds mentioned below or the hydroxyl radical of the water. However, as described above, the amines can also be subsequently condensed with a dihalo-s-triazine residue already bonded to the azo dye, in order to replace a halogen atom in the dihalo-s-triazine residue with an amino substituent.

Examples of the above-mentioned amino, hydroxy and thiol compounds are:

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec-butylamine, tert-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxy Dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, ß-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- and p-toluidine, 2,3-, 2,4-,

2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylamirfoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitro-aniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitro-aniline, 2-nitro-4-methyl-aniline, 3-nitro-4-methyl-aniline, o-, m- and p-phenylenediamine, 3-amino-4-methyl-aniline, 4-amino-3-methyl- aniline, 2-amino-4-methyl-aniline, o-, m- and p-anisidine, o-, m- and p-phenetidine, naphthylamine- (l), naphthyl-amine (2), 1,4- Diaminonaphthalene, 1,5-diaminonaphthalene, 2-amino-l-hydroxy-naphthalene, l-amino-4-hydroxy-naphthalene, 1-amino-8-hydroxy-naphthalene, 1-amino-2-hydroxy-naphthalene, l- Amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene -5-sulfonic acid, p-aminosalicylic acid, l-amino-4-carboxy-benzene-3-sulfonic acid, l-amino-2-carboxy-benzene-5-su lfonic acid, l-amino-5-carboxybenzene-2-sulfonic acid, l-naphthylamine-2-, -3-, -4-, -5-, -6- -7- and -8-sulfonic acid, 2-naphthylamine -1-, -4-, -5-, -6-, -7- and -8-sulfonic acid, l-naphthylamine-2,4-, -2,5-, -2,7-, -2,8 -, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, 4,8- and -5,8-disulfonic acid, 2-naphthylamine-l, 5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8 -, - 5,7- and -6,8-disulfonic acid, l-naphthylamine-2,4,6 -, - 2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-

1.3.7-, -1.5.7-, -3.5.7-, -3.6.7-, -3.6.8- and -4.6.8-trisulfonic acid, 2-, 3 -

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

633 822

8th

and 4-aminopyridine, 2-aminobenzothiazole, 5-, 6- and 8-amino-quinoline, 2-aminopyrimidine, morpholine, piperidine, piperazine, water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec. Butanol, tert-butanol, hexanol, cyclohexanol, ß-methoxy-ethanol, ß-ethoxy-ethanol, y-methoxy-propanol, y-ethoxy-propanol, ß-ethoxy-ß-ethoxy-ethanol, glycolic acid, phenol, o -, m- and p-Chlorophenol, o-, m- and p-nitrophenol, o-, m- and p-hydroxybenzoic acid, o-, m- and p-phenolsulfonic acid, phenol-2,4-disulfonic acid, a-naphthol , β-naphthol, 1-hydroxy-naphthalene-8-sulfonic acid, 2-hydroxynaphthalene-l-sulfonic acid, l-hydroxynaphthalene-5-sulfonic acid, l-hydroxynaphthalene-4-sulfonic acid, l-hydroxynaphthalene-6- or -7 -sulfonic acid, 2-hydro-xynaphthalene-6-, -7- or -8-sulfonic acid, 2-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-4,8- or -6,8-disulfonic acid, l-hydroxynaphthalene-3 , 6- or -3,8-disulfonic acid, 1-hydroxy-naphthalene-4,8-disulfonic acid, 2-hydroxynaphthalene-3,6-disulfonic acid, methanethiol, Ä thanthiol, propanethiol, isopropanethiol, n-butanethiol, thioglycolic acid, thiourea, thiophenol, a-thionaphthol, ß-thionaphthol.

The condensations of the 2,4-difluoro-6-amino (hydroxy, alkoxy, aryloxy, alkylthio or arylthio) -s-triazines or the 2,4-difluoro (chlorine or bromo) -6-amino (hydroxy, alkoxy, aryloxy , alkylthio or arylthio) -s-triazines with the azo compounds of the formulas (7), (8), (9) or (10) and of 2,4,6-trifluoro-s-triazine or 2,4,6 -Trifluoro (chlorine or bromine) -s-triazines with the azo compounds of the formulas (7), (8), (9) or (10) and optionally amines, are preferably carried out in aqueous solution or suspension, at low temperature and in the case of weakly acidic , neutral to weakly alkaline pH. Advantageously, the hydrogen, chlorine or bromine released during the condensation is continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

As a copper releasing agent, one can e.g. Use salts that contain the copper as a cation, e.g. Copper sulfate, copper acetate. In some cases the use of complex copper compounds is advantageous, e.g. in the form of copper-amine complexes, such as copper tetrammine sulfates from copper sulfate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain the copper in a complex bond, e.g. complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxy-carboxylic acids, such as glycollate, lactic acid and especially tartaric acid, such as sodium copper tartrate.

The treatment with the copper donor can be carried out according to methods known per se, e.g. at room temperature, if readily metallizable starting compounds are present or by heating to temperatures between 50 and 120 ° C in an open vessel, e.g. with reflux cooling or, if appropriate, in a closed vessel under pressure, the pH ratios being given by the type of metallization process chosen; e.g. acidic coppering with copper sulfate, alkaline coppering with copper tetrammine sulfate. If desired, solvents such as e.g. Alcohol, dimethylformamide, etc. can be added. In the case of oxidative coppering, an oxidizing agent, in particular hydrogen peroxide, is added to the reaction mixture and the reaction is otherwise carried out in the manner described.

The fiber-reactive azo dyes of the formula (1) are notable for high reactivity and high degree of fixation.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyurethane fibers, but especially cellulose-containing materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

They are also suitable for printing, especially on Baum-i5 wool, but also for printing nitrogen-containing fibers, e.g. of blended fabrics containing wool, silk or wool.

It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent which promotes the diffusion of the unfixed portions.

In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

25th

example 1

A solution of 2.97 parts of cyanuric fluoride in 5 parts of toluene is added dropwise to an ice-cold, neutral solution of 7.25 parts of the copper complex of the formula in 150 parts of water with thorough stirring in the course of 40 minutes, and this is kept pH of the reaction mixture with in sodium hydroxide solution between 6 and 7.

After acylation, a neutral solution of 3.46 parts of metanilic acid in 20 parts of water is added to the suspension of the di-primary condensation product, the mixture is warmed to 30 to 35 ° and the pH is kept between 7 and 8 during the second condensation with sodium hydroxide solution. The dye is salted out of the resulting clear solution by adding 10% by volume of potassium chloride and filtered off. The dye isolated in this way is treated with a conc. aqueous solution of 1 part of disodium hydrogen phosphate mixed and dried in vacuo at 50 °. The dye thus obtained dyes cotton in pure blue tones.

Similar dyes are obtained if the copper complexes listed in column 551 of the table below are reacted first with cyanuric fluoride and then with the amines mentioned in column II, as described in example 1.

9

633822

10th

ho3s o Cu O NIL

N = N-

h03s so3h

H2N

il

If

It

H2

Metanilic acid

Aniline o-toluidine

N-methylaniline

2-aminonaphthalene-6-suifonic acid

4-aminosalicylic acid

2-aminonaphthalene-4,8-disulfonic acid

Methylamine p-aminobenzoic acid

Metanilic acid

11

633822

I.

II

HO-S 0 Cu 0

NH0 i 1

1 i 1

nrVN = N-r

O

Ammonia h n1 ^! hoos

2 S03H

V

so3h

fi

-

2-aminonaphthalene-6-sulfonic acid

0 Cu 0

1 i

NH0 I 1

H03S ~ Ì ^ N = N "tì for \ H03S

Jk so3h o-toluidine

1

NH2

II

Sulfanilic acid

II

ammonia

0 Cu 0

1 1

NH0 1 L

H03S <^ J) N = N—

A

Metanilic acid

Ö H03s nh2

V

so3h

TI

Ethylamine

M

2-aminonaphthalene-5-sulfonic acid ir

4-aminosalicylic acid

633822

12th

Cl y ff

H03S 0 Cu 0 NH—

h2-n yyCrN "

> r i

H03S

\

S03H

■ NH— () —NH

so3h

ammonia

Example 2

A solution of 2.97 parts of cyanuric fluoride in 5 parts of toluene is added dropwise to an ice-cold, neutral solution of 3.46 parts of ortha-nilicic acid in 75 parts of water with good stirring over the course of 5 to 10 minutes, and the pH of the reaction mixture is kept constant In sodium hydroxide solution between 6 and 7. After acylation, the suspension of the primary condensation product is poured into a neutral solution of 7.25 parts of the Cu complex of the formula and the reaction mixture is heated to 30 to 35 °, 25 drops of ln -Sodium hydroxide solution the pH is kept between 7 and 8. The resulting reactive dye is then salted out with potassium chloride, filtered off and concentrated with a. mixed aqueous solution of 1 part disodium hydrogen phosphate and dried in vacuo at 50 °. 3o The dye thus obtained dyes cotton in pure blue tones.

By acylating the Cu complexes listed in column I of the table below with the difluorotriazine derivatives of the amines listed in column II, further dyes are obtained which dye cotton in the tones indicated in column III.

I.

0 Cu 0 NH,

EO-S-

j

= * - M

E0 ~ S / ^ s / S30, H 3 5

uh,

HOvS '

J

0- Cu 0 NHCO - <3

—V) 6l ho "s / n / n / xso" h 0 3

nh,

h2n

HO-S 0 Cu 0 NH0

/ ÓÒ_n = kt6ÒL

/ "■ | H03SA> - ^^ S0,

S03H

fi

II

,

III

Orthanilic acid

2-aminonaphthalene-4,8-disulfonic acid

2-aminotoluene-4-sulfonic acid

2-aminonaphthalene-1-sulfonic acid blue blue

Aniline-2,4-disulfonic acid

15

633822

Dyeing Instructions I

2 parts of the dye obtained according to the example are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the solution obtained so that it increases by 75% in weight, and then dried.

Then the fabric is impregnated with a 20 ° warm solution, which contains 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75% weight gain, the dyeing is dampened for 30 seconds at 100 to 101 °, rinses and soaps during a quarter of an hour in a 0.3% boiling solution of an ion-free detergent, rinses and dries.

15 Staining Instructions II

2 parts of the dye obtainable according to the example are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a 20 cotton fabric are added to this dye bath.

The temperature is increased to 40 °, 40 parts of calcined soda and another 60 parts of sodium chloride being added after 30 minutes. The temperature is kept at 40 ° for 30 minutes, rinsed and then the color is soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

Claims (5)

633822 2nd reacted in any order with a copper donor and acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine, and that after the acylation by condensation with ammonia or an amine, a fluorine atom in the s-triazine ring is replaced by an amino group. 8. The method according to claim 4, characterized in that 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 2. The method according to claim 1, characterized in that an azo compound of the formula (7), in which D, R and n have the meanings given in claim 1, a copper-donating agent, an equivalent of 2,4,6-trifluoro-s- triazine or a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine and another equivalent of 2,4,6-trifluoro, chlorine or bromo-s-triazine or a difluoro, chlorine or bromo-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine by coppering and acylation to give a fiber-reactive azo dye of the formula (1). 2nd PATENT CLAIMS 1. Process for the production of fiber-reactive azo dyes of the formula 0 Cu-0 NH - £ -R-NH —N = N— / yS HOjS ^ Ng ,, ^ (1) where the grouping 0- X1-NH-D-N = N- (2) a radical of the formula or the formula o H0 "S- one of the two residues Xi and Xz is a 2,4-di-fluoro-s-triazine residue or a 2-fluoro-4-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine residue and the other a 2,4- Di-fluorine, chlorine or bromo-s-triazine residue or a 2-fluorine, chlorine or bromo-4-amino, hydroxy, alkoxy, aryloxy, alkylthio or aryl-thio-s-triazine residue, R is a bridge member and n = 0 or 1 is characterized in that an azo compound of the formula HO NH OH N - D - N = N HO wherein D, R and n have the meanings given under formula (1), a copper donor, an equivalent of a 2,4,6-tri-fluoro-s-triazine or a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine and another equivalent of a 2,4,6-tri-fluorine, chlorine or bromo-s-triazine or a 2,4-difluoro, chlorine or bromo-6-amino , hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine by coppering and acylation in any order to a fiber-reactive azo dye of the formula (1). 3rd 633822 that you have an azo compound of the formula OH reacted in any order with a copper donor and acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine. 9. The method according to Änspruch 5, characterized in that an azo compound of the formula HO NH, reacted in any order with a copper donor and acylated with 2 equivalents of 2,4,6-trifluoro-s-triazine, and that after the acylation by condensation with 15 ammonia or an amine, a fluorine atom in the s-triazine ring is replaced by an amino group . 10. The method according to claim 7, for the preparation of the fiber-reactive azo dye of the formula, characterized in that the copper complex of the formula obtained by coppering the corresponding azo compound HO, S 0 0 NH. Ho s - ^^ SO ^ H J? condensed with 2 equivalents of cyanuric fluoride and the resulting di-primary condensation product was condensed with 2 equivalents of metanilic acid to give the fiber-reactive azo dye of the formula given above. 11. The method according to claim 9, for producing the fiber-reactive azo dye of the formula, characterized in that the copper complex of the formula obtained by coppering the corresponding azo compound 0 Cu 0 NH, HO ^ S— ^> —N = N- l HO ^ S ' I J NH ^ 30 "H condensed with 2 equivalents of cyanuric fluoride and the resulting di-primary condensation product was condensed with 2 equivalents of 60 metanilic acid to give the fiber-reactive azo dye of the formula given above. 12. Process for the preparation of fiber-reactive azo dyes of the formula 633822 3. The method according to claim 1, characterized in that an azo compound of the formula (7), in which D, R and n have the meanings given in claim 1, a copper-donating agent, an equivalent of 2,4,6-trifluoro-s- triazine and another equivalent of 2,4,6-trifluoro, chlorine or bromo-s-triazine by coppering and acylation to give a fiber-reactive azo dye of the formula (1), and by condensation with ammonia or an amine, a halogen atom in the s-triazine ring replaced an amino group. 4th ho7S 0 sN-, Y-Cr G-NH-1 I H N ^ .N -ÒÒ ~ N = K-uy. Cu: N " 0 NH ' HO S ' SO, H 3 SO H? -c ^ C-Y, I II <N ^ N I. F (5) wherein Yi and Y2 are each independently a fluorine atom, an optionally substituted amino group, a hydroxy group, an optionally substituted alkoxy, aryloxy, alkylthio or arylthio group, characterized in that azo compounds of the formula with an equivalent 2,4,6 -Trifluoro-s-triazine or a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or 15 arylthio-s-triazine and a further equivalent of 2,4,6-trifluoro, chlorine or bromo-s- triazine or a 2,4-difluoro, chlorine or bromo-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine acylated, and then oxidatively copper. 13. The method according to claim 12 for the production of 20 fiber-reactive azo dyes of the formula (10) V? \ I. F wherein Y1 and Y2 are each independently a fluorine atom, an optionally substituted amino group, a hydroxy group, an optionally substituted alkoxy, aryloxy, alkylthio or arylthio group, characterized in that azo compounds of the formula C C-Y0 t IV ^ N N 4. The method according to claim 1, characterized in that an azo compound of the formula (7), in which D has the meaning given in claim 1 and n = 0, a copper-donating agent, and 2 equivalents of 2,4,6-trifluoro s-triazine or a 2,4-difluoro-6-amino, hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine by coppering and acylation to give a fiber-reactive azo dye of the formula (1). 5. The method according to claim 1, characterized in that an azo compound of the formula (7), in which D has the meaning given in claim 1 and n = 0, a copper-donating agent, and 2 equivalents of 2,4,6-trifluoro s-triazine or an equivalent of 2,4,6-trifluoro-s-triazine and a further equivalent of 2,4,6-trichlor or bromo-s-triazine by coppering and acylation to form a fiber-reactive azo dye of the formula (1) and by Condensation with ammonia or an amine, a halogen atom in the s-triazine ring replaced by an amino group. 6. The method according to claim 4, characterized in that reacting an azo compound of the formula in any order with a copper donor and with 2 equivalents of 2,4,6-trifluoro-s-triazine or a 2,4-difluoro-6-amino , hydroxy, alkoxy, aryloxy, alkylthio or arylthio-s-triazine acylated. 7. The method according to claim 5, characterized in that one has an azo compound of the formula HO N H (5) with one equivalent of 2,4,6-trifluoro-s-triazine and another equivalent of 2,4,6-trifluoro, chlorine or bromo-s-triazine, and a halogen atom in the s-triazine ring by condensation with ammonia or an amine an amino group 45 replaced, and then oxidatively copper.