CH629839A5 - 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

AT THE-

F

N ^ C "^ N

(1) ,

I II

n C ^ C ~ 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, n 0 or 1 and p 0 or 1, where A and the benzene radical B can contain further substituents.

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, isobuty

loxy, 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 further substituents besides SChH groups e.g.

65 contain 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

629839

men, such as acetylamino, propionylamino and benzoylamino, amino groups such as - NH2, methylamino and ethylamino, the ureido, hydroxyl and carboxy group, and halogen, such as fluorine, chlorine and bromine.

Fiber-reactive azo dyes of the formula (1) in which A, B, m, n and p have the meanings given and X is methyl, methoxy, carboxy or chlorine are preferred.

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

a) A is a mono- or disulfobenzene radical, m 1 or 2, n = 0,

b) A is a mono- or disulfobenzene radical or a carboxy-benzene radical, m = 2, n = 1, p = 1,

c) A is a di- or trisulfonaphthalene residue, m = 1, n = 0,

d) A is a di- or trisulfonaphthalene residue, m = 2, n = 1, p = 1,

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

mono- or disulfobenzene residue, m = 1, n = 1, p = 0,

f) copper complex compounds, A is an ortho-hydroxy-disul-fobenzene residue, m = 1, n = 0,

g) copper complex compounds, A is an ortho-hydroxy-5 disulfophenylazobenzolrest, m = 1, n = 0,

h) copper complex compounds, A is an ortho-hydroxy-disulfonaphthalene residue, m = 2, n = 0,

i) A sulfophenyl, m = 2, n = 1, p = 1,

j) A di- or trisulfonaphthyH2), m = 1, n = 0, 10 k) A disulfonaphthyl- {2), m = 2, n = l, p = l,

1) A ortho-hydroxy-disulfonaphthyl- (2), m = 2, n = 0,

where in all cases a) to 1) X is methyl, methoxy, carboxy or chlorine.

Valuable fiber-reactive azo dyes of the formula (1) are 15 e.g. the fiber-reactive azo dye of the formula

HO

»Pio-

- 3rd

■ NH — C ^ '

"XJ — NK-

CH.

p

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

HO ^ S '

HO NH -C0- <> -NH-C ^^ C-NH-

N ^ N

0, H I

SO ^ H 0

CH "

40 2,4,6-trifluoro-l, 3,5-triazine of the formula

F

[Sub-group k)].

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

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.

Amino-fluor-s-triazine dyes are known from Swiss patent 510 089. The dyes of the present application differ from similar known dyes and an aminobenzene of the formula ten dyes by the characteristic ortho-substituted phenylamino radical on the s-triazine ring.

The preparation according to the invention of the fiber-reactive azo dyes of the formula (1) is characterized in that a diazotized amino compound of the formula 55

I II

h2n-

(4)

(5)

A-NHz is a coupling component of the formula HO

(S ° 3H) m

"NH—

CO):

"0}

-NH-

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

An ami-60 nobenzene of the formula (5) in which X is methyl, methoxy, carboxy or chlorine is preferably used as the starting material.

In preferred embodiments of the process described above, the starting materials used are diazocomponent (5) components of the formula (2) and coupling components of the formula 65 mei (3), in which A, m, n and p have the same meanings as in those listed above Subgroups a) to 1), and, in

H all cases, aminobenzenes of the formula (5), in which X is methyl,

B is methoxy, carboxy or chlorine.

629839

6

Since the individual method steps specified above can be carried out in different orders, possibly partially also simultaneously, different method variants are possible. The starting materials to be used for each partial reaction result from formula (1). In general, the reaction is carried out step by step, the sequence of the simple reactions between individual reaction components of the formula (2), (3), (4) and (5) being freely selectable.

Important process variants are characterized in that

5 1) a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to an azo compound of the formula

AT THE-

(6)

-H

couples, this condenses with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and the primary condensation product obtained is 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-tri- "fluoro-1,3,5-triazine of the formula (4), the primary condensation product obtained is condensed with an aminobenzene of the formula (5) and the couples the resulting secondary condensation product with a diazotized amino compound of the formula (2) to a fiber-reactive azo dye of the formula (1);

3) a coupling component of the formula (3) is condensed with 2,4,6-tri-fluoro-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 obtained azo compound with an aminobenzene of the formula (5) condensed to a fiber-reactive azo dye of the formula (1).

The following may be mentioned as starting materials which can be used to prepare the fiber-reactive azo dyes of the formula (1):

Amino compounds of the formula (2) (diazo components) l-aminobenzo I-2-, -3- and -4-sulfonic acid,

l-aminobenzene-2,4- and -2,5-disulfonic acid, l-amino-4-methylbenzene-2-sulfonic acid, l-amino-3-methylbenzene-6-sulfonic acid, l-amino-6-methylbenzene-3- or -4-sulfonic acid, l-amino-2,4-dimethylbenzene-6-sulfonic acid, 1-amino-2-carboxybenzene-4-sulfonic acid, l-amino4-carboxybenzene-2-sulfonic acid,

l-amino-4- or -5-chlorobenzene-2-sulfonic acid, l-amino-6-chlorobenzene-3- or 4-sulfonic acid, l-amino-3,4-dichlorobenzene-6-sulfonic acid, l-amino-2 , 5-dichlorobenzene-4-sulfonic acid, l-amino4-methyl-5-chlorobenzene-2-sulfonic acid, l-amino-5-methyl4-chlorobenzene-2-sulfonic acid,

l-amino4- or -5-methoxybenzene-2-sulfonic acid, l-amino-6-methoxybenzene-3- or 4-sulfonic acid, l-amino-6-ethoxybenzene-3- or 4-sulfonic acid, l-amino-2, 4-dimethoxybenzene-6-sulfonic acid, l-amino-2,5-dimethoxybenzene-4-sulfonic acid, l-amino-3-acetylaminobenzene-6-sulfonic acid, l-amino-4-acetylaminobenzene-2-sulfonic acid, l-amino-3- acetylamino-4-methylbenzene-6-sulfonic acid,

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

2-aminonaphthalene-1-, -5- or -6-sulfonic acid,

1-aminonaphthalene-3,6- or -5,7-disulfonic acid,

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

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

2-aminonaphthalene-l, 5,7-, -3,6,8- or 4,6,8-trisulfonic acid, 20 Ì -hydroxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-aminobenzene-5-sulfonic acid, l-Hydroxy-2-aminobenzene4,6-disulfonic acid, l-hydroxy-2-amino4-acetylaminobenzene-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene4-sulfonic acid, 25 1 -hydroxy-2-amino4-chlorobenzene -5-sulfonic acid, l-hydroxy-2-amino4-methylsulfonyl-benzene,

1-amino-2-hydroxy-6-nitronaphthalene4-sulfonic acid,

2-amino-l-hydroxynaphthalene4,8-disulfonic acid.

3o coupling components of formula (3)

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

2-methyl- or -ethylamino-5-hydroxynaphthalene-7-sulfonic acid,

2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfone-35 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-8-hydroxynaphthalene-6-sulfone-40 acid,

2- (N-acetyl-N-methylamino> 8-hydroxynaphthalene-6-sulfonic acid,

2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 45 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, l-amino-5-hydroxynaphthalene-7 sulfonic acid, l-amino-8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid, l-acetylamino-8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid,

so l- (4'-aminobenzoylamino> 8-hydroxynaphthalene-3,6- or 4,6-disulfonic acid,

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

l- (3'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- or 55 4,6-disulfonic acid,

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

2- (4'-amino-3'-sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid.

60

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

l-amino-2-methyl-, -ethyl- or -propylbenzene, l-amino-2-methoxy- or -ethoxybenzene, l-amino-2-carboxybenzene, 65 l-amino-2-chlorobenzene, l-amino-2 -bromobenzene, l-amino-2-fluorobenzene.

The diazotization of the amino compounds of the formula (2) is generally carried out by the action of nitrous acid in water

629839

Serous mineral acid solution at low temperature, the coupling to the coupling components of formula (3) at weakly acidic, neutral to weakly alkaline pH values.

The condensations of 2,4,6-trifluoro-1,3,5-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 with a weakly acidic, neutral to weakly alkaline pH. The hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

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 of the formula (1) can also be prepared. The copper complexes are of particular interest; they are prepared by azo compounds of the formula (6), in which A is a benzene or naphthalene radical which contains a complex-forming group in the ortho position to the azo group, before or optionally after the acylation with the 2,4,6 -Trifluoro-l, 3,5-triazine of the formula (4) treated with copper donating agents.

The method of coppering is not only the method described above, in which an o, o'-dihydroxy-azo compound is used as the starting substance for the complex formation, but also the oxidative coppering, in which the hydroxyl group required for complex formation is only used during the coppering reaction by the simultaneous action of an oxidizing agent in the naphthalene core. You then use e.g. instead of an l-hydroxy-2-amino-naphthalene-4,8-disulfonic acid, the corresponding 2-amino-naphthalene-4,8-disulfonic acid as the diazo component.

However, for the preparation of the compounds of formula (1) it is also possible to use diazo components which, in the 1-position of a naphthalene nucleus, contain an alkoxy group, in particular the methoxy group, instead of a hydroxyl group, which, under suitable reaction conditions during the coppering reaction, by splitting off the alkyl radical into the Hydroxy group is converted.

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.

s 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, if a de-alkylation must take place simultaneously with the metallization, 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. an acidic copper with copper sulfate, an alkaline copper 15 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 reaction 20 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 superpolyurethanes, but in particular cellulosic 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 cotton, 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 40 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.

45

example 1

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

50

° 5

4 na.

+

14 parts of 2,4,6-tri-65-methylbenzene are added dropwise at 0 to 5 ° in the course of 15 minutes, the mixture is allowed to warm to room temperature and fluoro-1,3,5-triazine is kept, the pH being increased by simultaneous addition of at 6 to 7. The red dye solution is kept at a pH between 5 and 6 with sodium hyproxide solution. Sodium chloride is added and the separated dye of the after the condensation is 10.7 parts of 1-amino-2-formula

629 839

8th

F

filtered off and dried after adding 2.5 parts of sodium bicarbonate. It dyes cotton from an aqueous bath in bright scarlet tones with excellent wet fastness properties.

Instead of being salted out, the dye can also be isolated by evaporating the reaction mixture or by spray drying.

If, instead of l-amino-2-methylbenzene, an equivalent amount of l-amino-2-ethylbenzene, l-amino-2-methoxy-xybenzene, l-amino-2-ethoxybenzene, l-amino-2-carboxybenzene is used,

1-amino-2-chlorobenzene, l-amino-2-bromobenzene or 1-amino-

2-fluorobenzene, this gives dyes with similar coloring properties.

If, instead of the amino azo dye listed in the example, the amino azo dyes given in Table 1 below and l-amino-2-methylbenzene as the aminobenzene of the formula (5), or an equivalent amount of 15 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, more are obtained valuable dyes that dye cellulose fibers in the specified shade.

20th

Table 1

Aminoazo dye

Hue on

No.

Diazo component

Coupling component

cotton

1

1-aminobenzene-2-sulfonic acid

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

orange

2nd

1-aminobenzene-2,5-disulfonic acid

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

orange

3rd

1-aminobenzene-2,4-disulfonic acid

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

orange

4th

l-amino-4-methoxybenzene-2-sulfonic acid

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

Scarlet fever

5

2-aminonaphthalene-1,5-disulfonic acid

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

orange

6

1-aminobenzene-2-sulfonic acid

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

red

7

2-aminonaphthalene-1,5-disulfonic acid l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

red

8th

1-aminobenzo I-2,4-disulfonic acid l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

red

9

l-aminobenzene-2,5-disulfonic acid l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

red

10th

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

red

11

2-aminonaphthalene-l, 5,7-trisulfonic acid l- (4'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid (reduced)

red

12th

1-aminobenzene-2-sulfonic acid

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

red

13

2-aminonaphthalene-1,5-disulfonic acid

2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid (saponified)

red

14

1-aminobenzene-2-sulfonic acid l-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid (saponified)

red

15

1-aminobenzene-2-sulfonic acid

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

red

16

1-aminobenzene-2,5-disulfonic acid l- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-4,6-disulfonic acid (reduced)

red

17th

2-aminonaphthalene-3,6,8-trisulfonic acid l- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-4,6-disulfonic acid (reduced)

red

18th

l-Hydroxy-2-aminobenzene-4,6-disulfonic acid

2- (4'-amino-3'-sulfophenylamino) -5-hydroxynaphtha-lin-7-sulfonic acid (Cu complex)

violet

19th

l-hydroxy-2-aminobenzene-4-sulfonic acid

2- (4 '-amino-3' -sulfophenylamino) -5-hydroxynaphtha-lin-7-sulfonic acid (Cu complex)

violet

20th

l-Hydroxy-2-aminobenzene-4,6-disulfonic acid

2-amino-5-hydroxynaphthalene-7-sulfonic acid (Cu complex)

ruby

21st

2-amino-l-hydroxynaphthalene-4,8-disulfonic acid l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

blue

9

629839

Aminoazo dye from No. diazo component

Coupling component '

Color on cotton

22 3-methoxy-4-amino-6-methylazobenzene-2 '5' disulfonic acid (demethylated copper)

23 3-methoxy-4-amino-6-methylazobenzene-2 '5' disulfonic acid (demethylated copper)

24 3-methoxy-4-amino-6-methylazobenzene-2 '4' disulfonic acid (demethylated copper)

25 3-methoxy-4-amino-6-methylazobenzene-2 '4' disulfonic acid (demethylated copper)

26 3-methoxy-4-amino-6-methylazobenzene-2 '4' disulfonic acid (demethylated copper)

27 1-Hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid

28 l-hydroxy-2-amino-4-chlorobenzene-5-sulphonic acid

29 1 -hydroxy-2-amino-4-methylsulfonybenzene

30 1-hydroxy-2-aminobenzene-5-sulfonic acid

31 l-Hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid

32 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid

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

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

2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid

2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid

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

2-methylamino-8-hydroxynaphthalene-6-sulfonic acid (Cu complex)

l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

l-amino-8-hydroxynaphthalene-4,6-disulfonic acid (Cu complex)

l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (Cu complex)

2-amino-5-hydroxynaphthalene-7-sulfonic acid (Cu complex)

navy blue navy blue navy blue navy blue navy blue violet bluish violet violet violet bluish violet ruby

Example 2

13.5 parts of 2,4,6-trifluoro are added dropwise at 0 to 5 ° to an aqueous solution of 48.2 parts of the 1- (3'amino-benzeneamino> 8-hydroxynaphthalene-3,6-disulfonic acid, disodium salt) -l, 3,5-triazine and maintains the pH between 5 and 6 by simultaneous addition of sodium hydroxide solution. To dissolve the condensation product, add one of 25.3 parts of 1-amino-benzene-2,5-disulfonic acid diazo solution prepared in the customary manner and coupling at a pH of 7 to 7.5 After the coupling has ended, 10.7 parts of l-amino-2-methylbenzene are added, the mixture is allowed to warm to room temperature and neutralized those which are released during the condensation Hydrogen fluoride continuously by adding dilute sodium hydroxide solution. After the reaction has ended, the dye is separated by sprinkling in sodium chloride, filtered off and dried. It dyes cellulosic material in true brilliant red tones.

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

40

Table 2

acylated no coupling component

Diazo component

Aminobenzene

Color on cotton

1 2-amino-5-hydroxynaphthalene-7-sulfonic acid

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

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

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

5 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid

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

7 l- (3'-aminobenzoylamino> 8-hydroxynaphthalene-3,6-disulfonic acid

1-amino-4-methylbenzene-2-sulphonic acid

1-aminobenzene-2,5-disulfonic acid

1-aminobenzene-2,4-disulfonic acid

2-aminonaphthalene-l, 5-disulfonic acid l-amino-4-ethoxybenzene-2-sulphonic acid

1-amino-4-chlorobenzene-2-sulfonic acid

1-amino-4-carboxybenzene-2-sulphonic acid l-amino-2-carboxybenzene orange l-amino-2-methylbenzene orange l-amino-2-ethoxybenzene orange l-amino-2-chlorobenzene orange l-amino-2 -carboxybenzol red l-amino-2-ethylbenzene red l-amino-2-methylbenzene red

629839

10th

Example 3

43.8 parts of l- (4'-aminobenzoylamino> 8-hydroxynaphthalene-4,6-disulfonic acid, disodium salt are dissolved neutral in 700 parts of water. Dropwise to this solution at 0 to 5 ° and a pH of 4.5 to 5 13.5 parts of 2,4,6-trifluoro-l, 3,5-triazine within 15 minutes The hydrogen fluoride released during the condensation is continuously neutralized by adding dilute sodium hydroxide solution, and 10.7 parts are added after the reaction has ended 1-Amino-2-methylbenzene and, while gradually warming to room temperature, maintains the pH between 4.5 and 5.5 After the reaction has ended, a suspension of 30.3 parts adjusted to pH 4 with sodium carbonate is left diazotized 2-ami-

Flow in nonaphthalene-1,5-disulfonic acid while increasing the pH to 8. The dye formed is separated by sprinkling sodium chloride, filtered off and dried. It is a dark red powder and dyes 5 fabrics made of cellulose material in real brilliant reds.

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

Table 3

Acylatable No. coupling component

Aminobenzene

Diazo component

Color on cotton

1 2-amino-5-hydroxynaphthalene-7-sulfonic acid

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

3 2-amino-8-hydroxynaphthalene-6-sulfonic acid

4 2-amino-8-hydroxynaphthalene-6-sulfonic acid

5 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid

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

7 l- (4'-aminobenzoylamino) -8-hydroxynaphthalene-3,6-disulfonic acid

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

1-amino-2-bromobenzene 1-amino-2-methylbenzene 1-amino-2-carboxybenzene 1-amino-2-methoxybenzene l-amino-2-methylbenzene 1-amino-2-ethylbenzene 1-amino-2-ethoxybenzene l -Amino-2-methylbenzene

2-aminonaphthalene-l, 5,7-tri-orange sulfonic acid

1-Amino4-carboxybenzene-2-orange sulfonic acid

2-aminonaphthalene-1,5-disul-red fonic acid l-aminobenzene-2,5-disulfonic scarlet acid

1-aminobenzene-2,4-disulfonic scarlet acid

2-aminonaphthalene-l, 5-disul-red fonic acid l-amino-2-carboxybenzene4-red sulfonic acid l-amino-2-carboxybenzene-l-red

Amino-2-carboxybenzene4-

sulfonic acid

Staining instruction I:

2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitobenzenesulfonic acid. A cotton fabric is impregnated with the solution obtained so that it increases by 75% 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 75% weight gain, the dye is dampened for 30 seconds at 100 to 101 °, rinsed, soaped in for a quarter of an hour a 0.3% boiling solution of an ion-free detergent, rinses and dries.

4o dyeing instruction II:

2 parts of the dye obtainable according to 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 of a cotton-45 wool 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 soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

G

Claims (18)

629839 2nd PATENT CLAIMS 1. Process for the production of fiber-reactive azo dyes of the formula A-N = N (S03H) m i CO 4- B -NH- F A N N I !! -C C - NH n "N (1) , wherein A is a benzene or naphthalene radical, X alkyl or alkoxy having 1 to 4 carbon atoms, carboxy or halogen, m 1 or 2, n 0 or 1 and p 0 or 1, where A the benzene radical B may contain 20 further substituents, thereby characterized in that a diazotized amino compound of the formula X A-NHz is a coupling component of the formula (2), F A N N I IT F - C. C - F V (4) 25th and an aminobenzoì of the formula (S03H) m fco h B -NH- -H n (3) 2,4,6-trifluoro-l, 3,5-triazine of the formula HO A-N = N (5) by coupling and condensation in any order to give a fiber-reactive azo dye of the formula (1). 2. The method according to claim 1, characterized in that an aminobenzene of the formula (5), in which X is methyl, methoxy, carboxy or chlorine, is used as the starting material. 3. The method according to claim 1, characterized in that a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to an azo compound of the formula (6) couples, this condenses with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and the primary condensation product obtained is condensed with an aminobenzene of the formula (5) to give a fiber-reactive azo dye of the formula (1). 4. The method according to claim 1, characterized in that a coupling component of the formula (3) with 2,4,6-trifluoro-l, 3,5-triazine of the formula (4) is condensed, the primary condensation product obtained with an aminobenzene Formula (5) is condensed and the secondary condensation product formed is coupled with a diazotized amino compound of the formula (2) to a fiber-reactive azo dye of the formula (1). 5. The method according to claim 1, characterized in that a coupling component of the formula (3) with 2,4,6- 55 trifluor-l, 3,5-triazine of the formula (4) condensed, a diazotized amino compound of the formula (2) coupled to the primary condensation product obtained and the azo compound obtained with an aminobenzene of the formula (5) to give a fiber-reactive azo dye Formula (1) condensed. 6. The method according to any one of claims 1 to 5, 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 a mono- or disulfide fobenzene residue, m 1 or 2, n = 0 and X is methyl, methoxy, Car-65 boxy or chlorine, used as starting materials. 7. The method according to any one of claims 1 to 5, characterized in that a diazotized amino compound of the formula (2), a coupling component of the formula (3) and 3 629839 an aminobenzene of the formula (5), in which A is a mono- or disul 11. Process according to one of claims 1 to 5, characterized by fobenzene radical or a carboxybenzene radical, m = 2, n = 1, p = 1, characterized in that one is diazotized Amino compound and X is methyl, methoxy, carboxy or chlorine, as the starting of formula (2), a coupling component of formula (3) and substances used. an aminobenzene of the formula (5), in which A is di- or trisulfo 8. The method according to any one of claims 1 to 5, characterized 5 naphthyI- (2), m = 1, n = 0 and X methyl, methoxy, carboxy, characterized in that diazotized amino compound or chlorine is used as starting materials. Formula (2), a coupling component of formula (3) and a 12th method according to any one of claims 1 to 5, characterized Aminobenzene of the formula (5), in which A is a di- or trisulfo, that a diazotized amino compound is naphthalene, m = 1, n = 0 and X is methyl, methoxy, carboxy of the formula (2), a coupling component of the formula (3 ) and or chlorine is used as starting materials. io an aminobenzene of the formula (5), in which A is disulfonaphthyl- (2), 9. The method according to any one of claims 1 to 5, characterized in that m = 2, n = 1, p = 1 and X methyl, methoxy, carboxy or characterized in that a diazotized amino compound is chlorine, is used as starting materials. of the formula (2), a coupling component of the formula (3) and 13. A process for the preparation of metal complexes of an aminobenzene of the formula (5), in which A is a di- or trisulfofiber-reactive azo dye of the formula (1), in which the naphthalene residue, m = 2, n = 1, p = 1 and X is methyl, methoxy, Car-15 zol or naphthalene residue A ortho to the azo group boxy or chlorine, used as starting materials. contains a complex-forming group, and otherwise A, X, m, 10. The method according to any one of claims 1 to 5, characterized in that n, p and B have the meanings given under formula (1), that one has a diazotized amino compound, characterized in that one has a diazotized amine of the formula (2), one Coupling component of the formula (3) and novo compound of the formula an aminobenzene of the formula (5), in which A is sulfophenyl, m = 2, 20 A-NH2 (2), n = 1, p = 1 and X is methyl, methoxy, carboxy or chlorine, as Starting materials used. a coupling component of the formula 2,4,6-trifluoro-l, 3,5-triazine of the formula F i ? N N IV F - G C - F N / and an aminobenzene of the formula H2N ^ 0 x (4) (5) by coupling and condensation in any sequence to a fiber-reactive azo dye of the formula (1), and treating the azo compound obtained in an intermediate stage or the finished fiber-reactive azo dye of the formula (1) with metal-donating agents. 14. The method according to claim 13, characterized in that a diazonated 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 mono- or di sulfobenzene residue, m = 1, n = 1, p = 0 and X is methyl, methoxy, carboxy or chlorine, and a copper donor is used as starting materials. 15. The method according to claim 13, 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 an ortho-hydroxydisulfobenzene radical, m = 1, n = 0 and X is methyl, methoxy, carboxy or chlorine, and a copper releasing agent is used as raw materials 45. 16. The method according to claim 13, 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 an ortho-hydroxy-disulfophe- 50 nylazobenzenerest, m = 1, n = 0 and X is methoxy, carboxy or chlorine, and a copper donating agent is used as starting materials. 17. The method according to claim 13, characterized in that a diazotized amino compound of the formula 55 (2), a coupling component of the formula (3) and an aminobenzene of the formula (5), in which A is an ortho-hydroxy-disulfonaphthalene radical, m = 2, n = 0 and X is methyl, methoxy, carboxy or chlorine, and a copper donor is used as a raw material. 60 18. The method according to claim 13, 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, n = 0 and X is methyl, methoxy, carboxy or chlorine 65, and a copper donor is used as starting materials. 19. The method according to claim 18 for the preparation of the fiber-reactive copper complex azo dye of the formula 629839 4th Iio ^ s 0 C ^ N-Ç-NH CH. characterized in that coupling diazotized 2-amino-l-hydroxynaphthalene-4,8-disulfonic acid with l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and treating the azo compound obtained with a copper-donating agent, the copper complex obtained with 2,4,6-trifluoro-l, 3,5-triazine con- io densified and the primary condensation product obtained condensed with 1-amino-2-methylbenzene. 20. Process for the preparation of the fiber-reactive azo dye of the formula 15 -c ^ Nc-I II -NH- CH, 3rd 25th characterized in that diazotized 2-amino-naphthalin-l, 5-disulfonic acid is coupled with 2-acetylamino-5-hydroxynaphtha-lin-7-sulfonic acid, the acetyl group is split off by saponification, and the azo compound obtained is 2,4,6 -Trifluor-l, 3.5- S0vH 110 NU —C € triazine condensed and the primary condensation product obtained condensed with l-amino-2-methylbenzene. 21. Process for the preparation of the fiber-reactive azo dye of the formula 30th NH — C — K1I-1 I! F CH .. 'J> characterized in that diazotized 2-amino-naphthalene-l, 5-disulfonic acid is coupled with l- (4'-nitrobenzoylamino) - 8-hydro-xynaphthalene-3,6-disulfonic acid, the nitro group is reduced to the amino group, which is obtained Azo compound condensed with 2,4,6-trifluoro-l, 3,5-triazine and the primary condensation product obtained condensed with l-amino-2-methylbenzene.