DE2731258A1 - FIBER-REACTIVE AZO DYES, THEIR PRODUCTION AND USE - Google Patents

Description

DRW. MOUNTAIN DlPL-ING. 0. STAPF ^ ₀

oik, ;;: g.schabe DR.CR sandmaib Attorney's file: 28 292

PATf.; TANWr.T £ 2731258

8 MÖNCHEN 80, MAUtKMÄUC-RSTR. 45

Case 1-10593 / + * Germany

Fiber-reactive azo dyes, their production and

use

The present invention relates to fiber-reactive azo dyes of the formula

HO

I *

F H) I

^ HJt ^ Ot ^ fBJJ. _ _NH J _c ^ j_ _NH - ^>

X wherein A is a benzene or naphthalene radical, X is alkyl or alkoxy having 1 to 4 carbon atoms, carboxy or Halogen, m 1 or 2, η 0 or 1 and ρ 0 or 1, where A and the benzene radical B are further substituents may contain.

For X come into consideration as alkyl with 1 to 4 carbon atoms: methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, sec-butyl and tert-butyl, as alkoxy with 1 to 4 carbon atoms: methoxy, ethoxy, propyloxy, Isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy, and as halogen: fluorine, chlorine and bromine.

The benzene or naphthalene radical A and the benzene radical B can be used as additional substituents

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SO- ^ H groups contain e.g. the following: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl and propyl, alkoxy groups with 1 to 4 carbon atoms, such as Methoxy, ethoxy, propyloxy and isopropyloxy, acylamino groups with 1 to 6 carbon atoms, such as acetylamino, Propionylamino and benzoylamino, amino groups such as -NHo, methylamino and ethylamino, the ureido, hydroxy and Carboxy group, and halogen such as fluorine, chlorine and bromine.

Fiber-reactive azo dyes of the formula (1) in which A, B, m, η and ρ are those indicated are preferred Have meanings and X is methyl, methoxy, carboxy or chlorine.

Important subgroups of the fiber-reactive azo dyes of the formula (1) are characterized as follows:

a) A is a mono- or disulfobenzene radical, m 1 or 2, η = O ₁

b) A is a mono- or disulfobenzene radical or a carboxybenzene radical, m = 2, η = 1, ρ - I ₁

c) A is a di- or trisulfonaphthalene radical, m = 1, η = O ₁

d) A is a di- or trisulfonaphthalene radical, m = 2, η - 1,

PI,

e) copper complex compounds, A is an ortho-hydroxy mono-

or -disulfobenzene radical, m = l, n = l, p = 0,

f) Copper complex compounds, A is an ortho-hydroxydisulfobenzene radical, m = 1, η = O ₁

g) Copper complex compounds, A is an ortho-hydroxydisulfophenylazobenzene radical, m = I ₁ η - O ₁

h) copper complex compounds, A is an ortho-hydroxy-di-

sulfonaphthalene radical, m = 2, η - O ₁ i) A sulfophenyl, m = 2, η = 1, ρ = I ₁ j) A di- or trisulfonaphthyl- (2), m = I ₁ η - O ₁ k) A Disulfonaphthyl- (2), m = 2, η = 1, ρ = I ₁ 1) A ortho-hydroxy-disulfonaphthyl- (2), m = 2, η = 0,

709683/0920

v / obei in all cases mentioned a) to 1) X methyl, Is methoxy, carboxy or chlorine.

Valuable fiber-reactive azo dyes of the formula (1) are, for example, the fiber-reactive azo dyes of the formula

SO H HO

SO ₅ H ^ C ⁵ * CH

[Subgroup c)] and the fiber-reactive azo dye of the formula

SO H HO NH -CO- <r ~> -NH .-- C ^ ^N ^ C-NH- <r ~~> N = N AA M ^ jxN _CH

_{H0 S} AAA _{SO H} |

SO ₅ H

[Subgroup k)].

The dyes of the formula (1) are fiber-reactive since they contain a removable fluorine atom in the s-triazine radical contain.

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

The preparation of the fiber-reactive azo dyes of the formula (1) is characterized in that one diazotized amino compound of the formula

A-NH ₂ (2),

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a coupling component of the formula

HO

2,4,6-trifluoro-1,3,5-triazine of the formula

I Il

and an aminobenzene of the formula

(5)

by coupling and condensation in any order to a fiber-reactive azo dye of the formula (1) implements.

The starting material used is preferably an aminobenzene of the formula (5) in which X is methyl, methoxy, carboxy or chlorine.

In preferred embodiments of the process described above, the starting materials used are diazo components of the formula (2) and coupling components of the formula (3) in which A, m, η and ρ have the same meanings as in the subgroups a) to 1) listed above, as well as , in all cases, aminobenzenes of formula (5) in which X is methyl, methoxy, carboxy or chlorine.

Since the individual process steps specified above are in different order, possibly in part can also be carried out at the same time, different process variants are possible. The for each part -

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■ 4-

Reaction to be used starting materials result from formula (1). In general, the implementation is carried out gradually one after the other, with the order of the simple reactions between the individual reaction components the formulas (2), (3), (4) and (5) can be freely selected.

Important process variants are characterized in that one

1) a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to form one Azo compound of the formula

coupled, this condensed with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and the primary condensation product obtained condensed with an aminobenzene of the formula (5) to give a fiber-reactive azo dye of the formula (1);

2) a coupling component of the formula (3) is condensed with 2,4,6-trifluoro-1,3,5-triazine of the formula (4), the primary condensation product obtained is condensed with an aminobenzene of the formula (5) and the resultant secondary condensation product with a diazotized amino compound of formula (2) to form a fiber-reactive one Azo dye of formula (1) couples;

3) a coupling component of the formula (3) is condensed with 2,4,6-trifluoro-1,3,5-triazine of the formula (4), a diazotized amino compound of the formula (2) is coupled to the primary condensation product obtained and the azo compound obtained with an aminobenzene of the formula (5) to form a fiber-reactive azo dye

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Formula (1) condensed.

As starting materials that can be used for the preparation of the fiber-reactive azo dyes of the formula (1), are mentioned:

Amino compounds of the formula (2) (diazo components )

l-aminobenzene-2-, -3- and -4-sulfonic acid, l-aminobenzene-2,4- and 2,5-disulfonic acid, l-Amino-A ^ methylbenzene ^ -sulfonic acid, l-amino-ß-methylbenzene-o-sulfonic acid, l-amino-o-methylbenzene-S- or -4-sulfonic acid, l-amino ^^ - dimethylbenzene-o-sulfonic acid, 1-amino-2-carboxybenzo1-4-sulfonic acid, 1-amino-4-carboxybenzene-2-sulfonic acid, l-amino-4- or -S-chlorobenzene ^ -sulfonic acid, l-amino-o-chlorobenzene-S- or -4-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-Amino-2, S-dichlorobenzene ^ -sulfonic acid, 1-Amino-4-DnCtIIyI-S-ChIo ^ eHZoI-2-sulfonic acid, l-Amino-S-methyl ^ -chlorobenzene ^ -sulfonic acid, l-amino-4- or -S-methoxybenzene ^ -sulfonic acid, l-amino-o-methoxybenzene-S- or -4-sulfonic acid, l-amino-o-ethoxybenzene-S- or -4-sulfonic acid, l-amino-2,4-dimethoxybenzene-6-sulfonic acid, l-amino-2,5-dimethoxybenzene-4-sulfonic acid, 1-amino-3-acetylaminobenzene-6-sulfonic acid, l-amino-4-acetylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid,

l-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid,

2-aminonaphthalene-1-, -5- or -6-sulfonic acid, l-aminonaphthalene-3,6- or -5,7-disulfonic acid,

2-aminonaphthalene-1,5, -1,7-, -3,6-, -5,7-, -4,8-, or

-6,8-disulfonic acid,

l-aminonaphthalene-2,5,7-trisulfonic acid,

2raminonaphthalene-l, 5,7-, -3.6,8- or -4,6,8-trisulfonic acid,

7d9SÖ3 / 0 92 0

1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-4,6-disulfonic acid, 1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, 1-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-Hydroxy-2-amino-4-methylsulfonyl-benzene, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid.

K upplung skomp onenten of formula (3)

2-amino-5-hydroxynaphthalene-7-sulfonic acid,

2-methyl- or -ethylamino-S-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid,

2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid,

2-methyl- or -ethylamino-e-hydroxynaphthalene-o-sulfonic acid, 2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid,

2-acetylainino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, l-amino-S-hydroxynaphthalene ^ -sulfonic acid,

l-amino-S-hydroxynaphthalene-Sjö- or -4,6-disulfonic acid, l-acetylamino-e-hydroxynaphthalene-Sjo- or -4,6-disulfonic acid,

1- (4'-Aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,

1- (4'-Nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,

1- (3'-Aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,

1- (3'-Nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid,

2- (4'-Amino-3'-sulfophenylamino) -5-hydroxynaphthalene-7-sulfone-

acid. 709883/0920

-X-

2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) of the formula (4) Aminobenzenes of formula (5)

l-amino-2-methyl-, -ethyl- or -propylbenzene, l-amino-2-methoxy- or ethoxybenzene, l-amino-2-carboxybenzene, 1-atnino-2-chlorobenzene, l-amino-2-bromobenzene, l-amino-2-fluorobenzene.

The diazotization of the amino compounds of

Formula (2) is usually made by the action of nitrous acid in aqueous-mineral acid solution at deeper Temperature, the coupling on the coupling components of the formula (3) at weakly acidic, neutral to weakly alkaline p "values.

The condensations of 2,4,6-trifluoro-l, 3,5-triazine with the coupling components of the formula (3) or with the Azo compounds of the formula (6) and the aminobenzenes of the formula (5) are preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline p "value. Advantageous the hydrogen fluoride released during condensation is continuously added by adding aqueous alkali metal hydroxides, carbonates or bicarbonates neutralized.

If the benzene or naphthalene radical A ortho to the azo group is a complex-forming group, e.g. contains a hydroxyl or carboxy group, metal complexes of the fiber-reactive azo dyes can also be used Formula (1) can be prepared. The copper complexes are of particular interest; they are made by azo compounds of the formula (6) in which A is a benzene or naphthalene radical which is in the ortho position to the azo group contains a complex-forming group, before or optionally also after the acylation with the 2,4,6-trifluoro-1,3,5-triazine of the formula (4) treated with copper releasing agents.

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As a method of coppering, not only the method described above comes into consideration, in which one 0,0'-dihydroxyazo compound as starting substance for complex formation is used, but also oxidative coppering, in which the complex formation is used Required hydroxyl group only during the coppering reaction due to the simultaneous action of an oxidizing agent is introduced into the naphthalene core. One then uses, for example, instead of a 1-hydroxy-2-aminonaphthalene-4,8-disulfonic acid the corresponding 2-amino-naphthalene-4,8-disulfonic acid as a diazo component.

You can also use diazo components for the preparation of the compounds of formula (1), which are described in 1-position of a naphthalene nucleus instead of a hydroxyl group contain an alkoxy group, in particular the methoxy group, under suitable reaction conditions during the copper plating reaction by splitting off the alkyl radical is converted to the hydroxy group.

As a copper-releasing agent, e.g. salts can be used which 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-ammine complexes, such as copper tetrammine sulfate from copper sulfate and ammonia, pyridine or mono-sthanolamine, or in the form of compounds which contain the copper bound in a complex, e.g. complex copper compounds the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids such as glycocolla, lactic acid and especially tartaric acid such as sodium copper tartrate.

The treatment with the copper-releasing agent can be carried out according to methods known per se, e.g. Room temperature, if starting compounds that can be easily metallized present or, if at the same time as the

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T5.11.329 »

Metallization a de-alkylation must take place by Warming to temperatures between 50 and 120 C in an open vessel, e.g. under reflux cooling or if necessary in a closed vessel under pressure, with the p "ratios are given by the type of metallization process chosen; e.g. an acidic copper plating with copper sulphate, an alkaline copper plating with copper tetrammon sulfate. Wlinschtenfall can also be used in the metallization Solvents such as alcohol, dimethylformamide, etc. can be added. In the case of oxidative copper plating, an oxidizing agent, in particular hydrogen peroxide, is added to the reaction mixture, and the reaction takes place in the rest carried out in the manner described.

The fiber-reactive azo dyes of the formula (1) are characterized by high reactivity and high Degree of fixation off.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, Super polyamide fibers and super polyurethanes, but especially cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable for both the exhaust process as well as for dyeing by the padder dyeing process, after which the goods with aqueous and optionally also salt-containing dye solutions is impregnated, and the dyes after an alkali treatment or fixed in the presence of alkali, optionally with the action of heat.

They are also suitable for printing, in particular on cotton, but also for printing on nitrogen-containing materials Fibers, e.g. from wool, silk or blended fabrics containing wool.

It is advisable to rinse the dyeings and prints thoroughly with cold and hot water.

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75.1f.329a

2731259

if necessary with the addition of a dispersing agent and promoting the diffusion of the non-fixed components Means of submitting.

In the following examples, parts are parts by weight and temperatures are in Degrees Celsius.

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Example 1

To an aqueous solution containing 72.1 parts of the dye of the formula

4 Na ⁺

14 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0 ° to 5 ° within 15 minutes, the p _u value being kept between 5 and 6 by simultaneous addition of sodium hydroxide solution. After the condensation has ended, 10.7 parts of 1-amino-2-methylbenzene are added, the mixture is allowed to warm to room temperature and the pH is maintained at 6 to 7. Sodium chloride is added to the red dye solution and the dye of the formula which has separated out is added

F SO ₃ Na HO I

filtered off and after addition of 2.5 parts of sodium bicarbonate dried. He dyes cotton from watery baths in brilliant scarlet shades of excellent Wet fastness properties.

Instead of salting out, the dye can also be obtained by evaporating the reaction mixture or by Spray drying to be isolated.

709883/0920

-üti -

Used instead of l-amino-2-methylbenzene an equivalent amount of l-amino-2-ethylbenzene, l-amino-2-methoxybenzene, l-amino-2-ethoxybenzene, l-amino-2-carboxybenzene, l-amino-2-chlorobenzene, l-amino-2-bromobenzene or l-Amino-2-fluorobenzene, dyes with similar ones are obtained coloring properties.

If the aminoazo dye listed in the example is used instead of the one given in Table 1 below Aminoazo dyes and, as aminobenzene of the formula (5), l-amino-2-methylbenzene, or an equivalent amount of 1-amino-2-ethylbenzene, l-amino-2-methoxybenzene, l-amino-2-ethoxybenzene, l-amino-2-carboxybenzene, l-amino-2-chlorobenzene, l-amino-2-bromobenzene or l-amino-2-fluorobenzene, you get more valuable ones Dyes that dye cellulose fibers in the specified shade.

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Table 1

No.

Aminoazo dye

Diazo component

Coupling component

Shade on cotton

O <D Ο »OB CU

2 3 4th 5 6th

! 10
11

12th

l-aminobenzene-2-sulfonic acid

1-aminobenzene-2,5-disulfonic acid

l-aminobenzene-2,4-disulfonic acid

l-amino ^ -methoxybenzene ^ - sulfonic acid

2-aminonaphthalene-1,5-disulfonic acid

l-aminobenzene-2-sulfonic acid

2-aminonaphthalene-1,5-disulfonic acid

1-aminobenzene-2,4-disulfonic acid

l-aminobenzene-2,5-disulfonic acid

l-aminobenzene-4-carboxylic acid

2-aminonaphthalene-1,5,7-trisulfonic acid

1-aminobenzene-2-sulfonic acid 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

2-amino-5-hydroxynaphthalene-7-sulfonic acid

2-Acetylaτnino-5-hydroxynaphthalene-7-sulfonic acid (saponified)

1- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

If
Il

1- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

orange

Scarlet fever

orange

Red

No Aminoazo dye the end Hue on It 13th Diazo component Coupling component cotton it 14th 2-aminonaphthalene-1,5-di-
sulfonic acid 2-acetylamino-8-hydroxynaphthalene-6-
sulfonic acid (saponified) Red Il l-aminobenzene-2-sulfonic acid l-acetylamino-e-hydroxynaphthalene-Sjö-
disulfonic acid (saponified) ti 16 M. 1- (3'-nitrobenzoylamino) -8-hydroxy-
naphthalene-4,6-disulfonic acid (reduced) violet 17th l-aminobenzene-2,5-disulfone
acid M. ti 098 18th 2-aminonaphthalene-3,6,8-tri-
sulfonic acid M. rub in 83/1 19th l-hydroxy-2-aminobenzene-4,6-
disulfonic acid 2- (4'-amino-3'-sulfophenylamino) -5-hydr-
oxynaphthalene-7-sulfonic acid (Cu complex) blue CD
Κ> 20th l-hydroxy-2-aminobenzene-4-
sulfonic acid M. navy blue O 21 ] .- Hydroxy-2-aminobenzene-4,6-
disulfonic acid 2-amino-5-hydroxynaphthalene-7-sulfonic acid
re (Cu complex) ti 22nd 2-amino-1-hydroxynaphthalene
4,8-disulfonic acid 1-amino-8-hydroxynaphthalene-3,6-disul-
fonsäure (Cu complex) 23 3-methoxy-4-amino-6-methy1-
azobenzene-2 ', 5'-disulfonic acid
(demethylating coppered) 2-amino-5-hydroxynaphthalene-7-sulfone
acid It 2-methylamino-5-hydroxynaphthalene-7-sul
fonic acid

No. Aminoazo dye the end Hue on 24 Diazo component Coupling component cotton 25th S-methoxy ^ -amino-o-methyl-
azobenzene-2 ', 4'-disulfonic acid
(demethylating coppered) 2-ethylamino-5-hydroxynaphthalene-7-
sulfonic acid navy blue 26th Il 2-amino-5-hydroxynaphthalene-l, 7-di-
sulfonic acid M. 27 Il 2-amino-8-hydroxynaphthalene-3,6-di-
sulfonic acid M. -J
O 28 l-hydroxy - ^ - amino - ^ - chlorobene-
zol-5-sulfonic acid 2-methylamino-8-hydroxynaphthalene-6-
sulfonic acid (Cu complex) violet j 988 29 π 1-amino-8-hydroxynaphthalene-3,6-di-
sulfonic acid (Cu complex) bluish, purple
I. 3/0 30th l-hydroxy ^ -amino ^ -methyl-
sulfonylbenzene 1-amino-8-hydroxynaphthalene-4,6-di-
sulfonic acid (Cu complex) violet j
I. 920 31 l-hydroxy-2-aminobenzene-5-
sulfonic acid 1-amino-8-hydroxynaphthalene-3,6-di-
sulfonic acid (Cu complex) ti;
j 32 l-hydroxy-2-amino-4-acetyl-
aminobenzene-6-sulfonic acid Il I.
blue, violet » 1-amino-2-hydroxy-6-nitro-
naphthalene-4-sulfonic acid 2-amino-5-hydroxynaphthalene-7-sulfone
acid (Cu complex) ruby I
!

Example 2

To an aqueous solution of 48.2 parts of 1- (3'-aminobenzoylamino ) -8-hydroxynaphthalene-3,6-disulfonic acid, disodium salt 13.5 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0 ° to 5 ° and maintained by the simultaneous addition of sodium hydroxide solution the pH is between 5 and 6. To the solution of the condensation product, one of 25.3 parts of 1-aminobenzene-2,5-disulfonic acid is then added diazo solution prepared in the usual way and couples at a pH of 7 to 7.5. After the coupling is completed 10.7 parts of 1-amino-2-methylbenzene are added and the mixture is allowed to come to room temperature heat and neutralize the hydrogen fluoride released during condensation by adding dilute 'Sodium hydroxide solution. When the reaction is complete, the dye becomes deposited by sprinkling with sodium chloride, filtered off and dried. He dyes cellulosic fabric in real brilliant reds.

Used instead of 1- (3'-aminobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid equivalent parts of the coupling components listed in the second column of Table 2 below, instead of l-aminobenzene-2,5-disulfonic acid, equivalent parts of the diazo components mentioned in the third column and instead of 1-amino-2-methylbenzene, equivalent parts of the Aminobenzenes mentioned in the fourth column, dyes are obtained which dye cotton in the shades mentioned in the fifth column.

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Table 2

No.

acylated
Coupling component

Diazo component

Aminobenzene

Shade on cotton

! 2
3

oj 5

2-amino-5-hydroxynaphthalene-7-sulfonic acid

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid

l-amino-5-hydroxynaphthalene-7-sulfonic acid

2-amino-8-hydroxynaphthalene-3, 6-disulfonic acid

1- (4'-aminobenzoylamino) ■ 8-hydroxynaphthalene-3,6-disulfonic acid

1- (3'-aminobenzoylamino) ■ 8-hydroxynaphthalene-3,6-disulfonic acid

1-amino-4-methylbenzene-il-amino-2-carboxybenzene 2-sulfonsMure

1-aminobenzene-2,5-disulfonic acid

1-aminobenzene-2,4-disulfonic acid

1-amino-2-methylbenzene l-amino-2-ethoxybenzene

2-aminonaphthalene-1,5-, 1-amino-2-chlorobenzene disulfonic acid ^;

l-amino-4-ethoxybenzene-2-sulfonic acid

l-amino-2-carboxybenzene

1-amino-4-chlorobenzene-J1-amino-2-ethylbenzene 2-sulfonic acid i

1-amino-4-carboxybenzene-2-sulfonic acid

1-amino-2-methylbenzene

orange

Red

2731253

Example 3

A3.8 parts of 1- (4'-Aininobenzoylaraino) -8-hydroxynaphthalene-4,6-disulfonic acid, Disodium salt are dissolved in 700 parts of water until neutral. To this solution is added dropwise at 0 to 5 ° and a pH fourth of 4.5 to 5 within 15 minutes 13.5 parts 2,4,6-trifluoro-1,3,5-triazine. The hydrogen fluoride released during condensation is continuously diluted by adding Sodium hydroxide solution neutralized. When the reaction has ended, 10.7 parts of 1-amino-2-methylbenzene are added and the mixture is kept under gradual Warm to room temperature the pH between 4.5 and 5.5. After the reaction has ended, one leaves one with sodium carbonate set to a pH of 4 suspension of 30.3 parts of diazotized 2-aminonaphthalene-l, 5-disulfonic acid with simultaneous Increase the pH value to 8 flow in. The dye formed is deposited by sprinkling with sodium chloride, filtered off and dried. It is a dark red powder and colors tissue made of cellulose material in real brilliant red tones .

Other dyes with similar properties are obtained, if you equivalent parts of the acylatable coupling components listed in Table 3 of the second Column according to the information in the preceding example with 2,4,6-trifluoro-1,3,5-triazine condensed, then reacted with equivalent parts of the aminobenzenes listed in the third column and then combined with the diazo components mentioned in the fourth column.

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Table 3

No. acylatable Aminobenzene Diazo component Hue on Red ro!
-j ' 1 Coupling component 1-amino-2-bromobenzene 2-aminonaphthalene-1,5,7-
trisulfonic acid cotton
i Scarlet fever 2 2-amino-5-hydroxynaphtha-
lin-7-sulfonsMure 1-amino-2-methylbenzene l-amino-4-carboxybenzene
2-sulfonsMure orange It 3 Il l-amino-2-carboxybenzene 2-aminonaphthalene-1,5-di-
sulfonic acid ti Red ! 4th 2-amino-8-hydroxy
naphthalene-6-sulfonic acid 1-amino-2-methoxybenzene l-aminobenzene-2,5-disul-
fonic acid dd 098 5 ti 1-amino-2-methylbenzene 1-aminobenzene-2,4-disul-
fonic acid 83/1 6th 2-methylamino-8-hydroxy
naphthalene-6-sulfonic acid 1-amino-2-ethylbenzene 2-aminonaphthalene-1,5-di-
sulfonic acid 0920 7th 2-amino-8-hydroxy
naphthalene-3,6-disulfone-
acid l-amino-2-ethoxybenzene 1-amino-2-carboxybenzene
4-sulfonic acid 8th 1- (4'-aminobenzoylamino) -
8-hydroxynaphthalene-3,6-
disulfonic acid 1-amino-2-methylbenzene l-Air.ino-2-carboxybenzene-
4-sulfonic acid 1- (3'-aminobenzoylamino) -
8-hydroxynaphthalene-3,6-
disulfonic acid

2731253

Dyeing instruction I:

2 parts of the dye obtained in Example 1 are, with the addition of 0.5 part, of in-nitrobenzenesulfonic acid Sodium dissolved in 100 parts of water. A cotton fabric is made with the solution obtained impregnated so that it gains 757 "of its weight, and then dried.

Then the fabric is impregnated with a 20 warm solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to a 757o weight gain, the dyeing is dampened for 30 seconds at 100 to 101 °, rinsed, soaped for a quarter of an hour in a 0 , 37 _o boiling solution of a non-ionic detergent, rinsed and dried.

Dyeing instruction II:

2 parts of the dye obtainable in Example 1 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 are added a cotton fabric in this dye bath.

The temperature is increased to 40 °, after 30 minutes 40 parts of calcined soda and again 60 parts of sodium chloride are added. The temperature is kept at 40 ° for 30 minutes, rinsed and then soaped the dye is rinsed for 15 minutes in a 0.37 boiling solution of an ion-free detergent and dries.

709883/0920

Claims (46)

2731259 Claims 1. A fiber-reactive azo dyes of the formula HO A-N = N- I χ wherein A is a benzene or naphthalene radical, X is alkyl or alkoxy having 1 to 4 carbon atoms, carboxy or Halogen, m 1 or 2, η 0 or 1 and ρ 0 or 1, where A and the benzene radical B are further substituents may contain. 2. Fiber-reactive azo dyes according to claim 1, wherein A, B, m, η and ρ have the meanings given in claim 1, and X is methyl, methoxy, carboxy or Is chlorine. 3. fiber-reactive azo dyes according to claim 1, where A is a mono- or disulfobenzene radical, m is 1 or 2, η = 0 and X is methyl, methoxy, carboxy or chlorine. 4. A fiber-reactive azo dye according to claim 1, wherein A is a mono- or disulfobenzene radical or a Carboxybenzene radical, m = 2, η = 1, p = 1 and X is methyl, methoxy, carboxy or chlorine. 5. A fiber-reactive azo dye according to claim 1, wherein A is a di- or trisulfonaphthalene radical, m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine. 709883/0920 6. Fiber-reactive azo dyes according to claim 1, wherein A is a di- or trisulfonaphthalene radical, m = 2, η - 1, p = 1 and X is methyl, methoxy, carboxy or chlorine. 7. copper complex compounds of fiber-reactive azo dyes according to claim 1, wherein A is an ortho-hydroxy mono- or -disulfobenzene radical, m = 1, η = 1, p = 0 and X is methyl, "methoxy, carboxy or chlorine. 8. copper complex compounds of fiber-reactive azo dyes according to claim 1, wherein A is an ortho-hydroxy-disulfobenzene radical, m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine. 9. Copper complex compounds of fiber-reactive azo dyes according to claim 1, wherein A is an ortho-hydroxy-disulfophenylazobenzene radical, m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine. 10. Copper complex compounds of fiber-reactive azo dyes according to claim 1, wherein A is an ortho-hydroxy-disulfonaphthalene radical, m = 2, η = 0 and X is methyl, methoxy, carboxy or chlorine. 11. Fiber-reactive azo dyes according to claim 4, wherein A is sulfophenyl, m = 2, n = 1, p = 1 and X is methyl, Is methoxy, carboxy or chlorine. 12. Fiber-reactive azo dyes according to claim 5, wherein A is di- or trisulfonaphthyl- (2), m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine. 13. Fiber-reactive azo dyes according to claim 6, wherein A is disulfonaphthyl- (2), m = 2, n = 1, p = 1 and X 709883/0920 Is methyl, methoxy, carboxy or chlorine. 14. Copper complex compounds of fiber-reactive Azo dyes according to claim 10, wherein A is ortho-hydroxy-disulfonaphthyl- (2), m = 2, η = 0 and X is methyl, methoxy, carboxy or chlorine. 15. The fiber-reactive azo dye according to claim 12, of the formula SO-H HO ί — ΛΛ JiH-C ^ NJ SO, H 1 ·> I ^ ^Η0 ^ 5 "" ^ s ^ K "CH, 709883/0920 - 16 - 16. The fiber-reactive azo dye according to claim 13, the formula '* 3-C ^ ^N "O — NH- SO ₃ H HO NH-CC CH 17. The copper complex compound of the fiber-reactive azo dye according to claim 14, of the formula US 0 Cu λλ ν, ν HO ₃ S 0 Cu 0 NH C ^ ^N X) —NH— <f ~~> ν ii I H0 S0, H 18. Process for the preparation of fiber-reactive azo dyes of the formula A-N = N ~ ^NH t N ^ wherein A is a benzene or naphthalene radical, X is alkyl or alkoxy having 1 to 4 carbon atoms, carboxy or Halogen, m is 1 or 2, η is 0 or 1 and ρ is 0 or 1, where A and the benzene radical B ent ent can hold, characterized in that a diazotized amino compound of the formula 709883/0920 A-NH ₂ (2), a coupling component of the formula 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and an aminobenzene of the formula H ₂ N- <p> (5) X by coupling and condensation in any order to a fiber-reactive azo dye of the formula (1) implements. 19. The method according to claim 18, characterized in that that one an aminobenzene of the formula (5), wherein X is methyl, methoxy, carboxy or chlorine, as Starting material used. 20. The method according to claim 18, characterized in that that a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to an azo compound of the formula 709883/0920 _ _Ν1Ι 1 _Η Jn couples this with 2,4,6-trifluoro-l, 3,5-triazine Formula (4) condensed and the primary condensation product obtained with "an aminobenzene of the formula (5) condensed a fiber-reactive azo dye of the formula (1). 21. The method according to claim 18, characterized in that that a coupling component of the formula (3) with 2,4, o-trifluoro-l ^ S-triazine of Formula (4) condensed, the primary condensation product obtained with an aminobenzene of the formula (5) condensed and the resulting secondary condensation product with a diazotized amino compound of Formula (2) couples to a fiber-reactive azo dye of the formula (1). 22. The method according to claim 18, characterized in that that a coupling component of the formula (3) with 2,4,6-trifluoro-l, 3,5-triazine of Formula (4) condensed, a diazotized amino compound on the primary condensation product obtained of the formula (2) couples and the azo compound obtained with an aminobenzene of the formula (5) to form a fiber-reactive one Azo dye of the formula (1) condensed. 709683/0920 23. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is a mono- or disulfobenzene radical, ni 1 or 2, η = 0 and X methyl, Methoxy, carboxy or chlorine is used as starting materials. 24. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is a mono- or disulfobenzene radical or a carboxybenzene radical, m = 2, η = 1, p = 1 and X is methyl, methoxy, carboxy or chlorine, used as raw materials. 25. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is a di- or trisulfonaphthalene radical, m = 1, η - 0 and X is methyl, methoxy, carboxy or chlorine, used as starting materials. 26. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is a di- or Trisulfonaphthalene radical, m = 2, η = 1, ρ = 1 and X methyl, Methoxy, carboxy or chlorine, used as starting materials, 27. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is an ortho-hydroxy-mono- or disulfobenzene radical, m = 1, η = 1, p = 0 and X is methyl, methoxy, carboxy or chlorine, and In addition, a copper-releasing agent is used as the starting material. 709883/0920 28. The method geraäss one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5) _s wherein A is an ortho-hydroxy-disulfobenzene radical, m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine, and a copper-releasing agent is also used as a starting material. 29. The method according to any one of claims 18 to 22, characterized in that one is a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), in which A is an ortho-hydroxy-disulfophenylazobenzene radical, m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine, and also one which donates copper Means used as raw materials. 30. The method according to any one of claims 18 to 22 _r, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is an ortho-hydroxy-disulfonaphthalene radical, m = 2, η = 0 and X is methyl, methoxy, carboxy or chlorine, and in addition a copper-releasing agent is used as a starting material. 31. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), in which A is sulfophenyl, m = 2, η = 1, p = 1 and X is methyl, methoxy, carboxy or Chlorine is used as a starting material. 32. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound is used of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is di- or trisulfonaphthyl- (2), m = 1, η = 0 and X is methyl, methoxy, carboxy or chlorine, used as starting materials. 709883/0920 33. The method according to any one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is disulfonaphthyl- (2), tn = 2, η = 1, ρ = 1 and X methyl, methoxy, carboxy or chlorine is used as starting materials. 34. The method according to one of claims 18 to 22, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), wherein A is ortho-hydroxydisulfonaphthyl- (2), m = 2, η = 0 and X is methyl, methoxy, carboxy or chlorine, and also a copper donor Means used as raw materials. 35. The method according to claim 32, characterized in that diazotized 2-aminonaphthalene-1,5-disulfonic acid with 2-acetylamino-5-hydroxynaphthalene-7-sulfcmsä'ure coupled, and the acetyl group is split off by saponification, the azo compound obtained is condensed with 2,4,6-trifluoro-1,3,5-triazine and the obtained primary condensation product with 1-amino-2-methyIbenzo1 to the fiber-reactive azo dye of the formula SOJl HO SO _V HI s F condensed. 36. The method according to claim 33, characterized in that diazotized 2-aminonaphthalene-l, 5-disulfonic acid with 1- (4'-nitrobenzoylamino) -8-hydroxynaphthalene ~ 3,6-disulfonic acid couples and reduces the nitro group to the amino group, the azo compound obtained with 2,4,6-trifluoro-1,3,5-triazine condensed and the primary condensation obtained 709883/0920 product with l-amino-2-methylbenzene to the fiber-reactive Azo dye of the formula MH- CH ₃ condensed. 37. The method according to claim 34, characterized in that that one diazotized 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid with l-amino-e-hydroxynaphthalene-S ^ -disulfonic acid couples and treats the azo compound obtained with a copper releasing agent, the copper complex obtained condensed with 2,4,6-trifluoro-1,3,5-triazine and the primary condensation product obtained with 1-amino-2-methylbenzene to the copper complex compound of the fiber-reactive Azo dye of the formula HO ^ S 0 Cu 0 NH C ^ ^N X! -NH I Il ^N ^ C ^ CH .. ι j condensed. 38. The fiber-reactive obtained according to the examples Azo dyes. 709883/0920 273125a 39. Procedure according to the examples given. 40. According to claims 18 to 37 available fiber-reactive azo dyes. 41. Process according to the dyeing and printing examples. 42. Use of the fiber-reactive azo dyes according to claims 1 to 17 or according to the claims 18 to 37 available fiber-reactive azo dyes for dyeing and printing. 43. Method of dyeing and printing using the fiber-reactive azo dyes according to claim 1. 44. The method according to claim 43 for dyeing Cellulose fibers. 45. Dyeing and printing preparations which contain fiber-reactive azo dyes according to Claims 1 to 17. 46. The dyed or printed textile material obtained according to claims 43 and 44. FO 7.1 Il / dk 709883/0920