CH634093A5 - 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

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oh i

a-n = n-c

c - n - b

c = h y

(so3h)

n

(l)

■ n-c "c-nh

I! t?

r n n x

r f

1

wherein A is a benzene or naphthalene radical, Y methyl, sulfomethyl, carboxy or carbamoyl, B hydrogen, an alkyl or aryl radical, R hydrogen or alkyl having 1 to 4 carbon atoms, X alkyl or alkoxy having 1 to 4 carbon atoms, carboxy or Halogen, n is a positive integer from 1 to 6, and m = 1 or 2, where A and B may contain further substituents, and the phenylamino radical bonded to the s-triazine ring in addition to X and independently of X as further substituents on Phenyl nucleus can contain an alkyl having 1 to 4 carbon atoms, and in the event that m = 2, the substituents R or X of the two 2-fluoro-4- (2'-X-phenylamino-no) -s-triazine -6-yl-N (R) radicals can be different from one another.

The benzene or naphthalene radical A can be used as further substituents besides S03H groups e.g. 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, such as acetylamino, propionylamino and benzoylamino, amino groups such as -NH2, methylamino and ethylamino, the ureido, hydroxy and carboxy group, and halogen such as fluorine, chlorine and bromine.

If B is an alkyl radical, this is predominantly an unsubstituted alkyl group, e.g. Methyl or ethyl, but the alkyl groups can also be further substituted, e.g. by chlorine, hydroxy, cyan and amino.

B is preferably an aryl radical, in particular a phenyl or naphthyl radical which, in addition to SO3H groups, is e.g. may contain the substituents mentioned above under A. For R com-

Consideration as alkyl with 1 to 4 carbon atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

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 20 atoms: methoxy, ethoxy , Propyloxy, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy, and as halogen: fluorine, chlorine and bromine.

For the other substituents which are optionally present in addition to X and independently of X on the phenyl nucleus of the phenylamino radical bonded to the s-triazine ring, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl .

The sulfo groups can be distributed as desired between the residues A and B.

Fiber-reactive azo dyes of the formula (1) in which m = 1 and the 2-fluoro-4- (2'-X-phenylamino) -s-triazin-6-yl-N (R) - are preferred Rest is bound to the rest A.

Preferably X is methyl, methoxy, carboxy or chlorine.

35

An important subgroup is formed by fiber-reactive azo dyes of the formula (1), in which A is a sulfophenyl radical, Y is methyl or carboxy, B is a phenyl or naphthyl radical which is optionally substituted by sulfo and chlorine, R is hydrogen, and m = 1, and X and n have the meanings given under formula (1).

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

The dyes of the formula (1) are fiber-reactive, since they are to be understood in the sub fiber-reactive compounds

s-triazine residue contain a releasable fluorine atom. hen with the hydroxyl groups of cellulose or with

5

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Amino groups of natural or synthetic polyamides are able to react 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 by the characteristic ortho-substituted phenylamino radical on the s-triazine ring.

The inventive production of the fiber-reactive azo dyes of the formula (1) is characterized in that a diazotized amino compound of the formula

A-NH2

a coupling component of the formula oh

-E-B

(2)

(3)

where A and B together contain 1 to 6 sulfo groups, and A or / and B contain an -N (R) H group, 1 or 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula p-C ^ n? -

! iL

SC '

(4)

and 1 or 2 equivalents of optionally different aminobenzenes of the formula i-yi

(5)

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

implements.

An aminobenzene 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, compounds of the formulas (2) and (3) are used as starting materials, in which only A but not B contains an -N (R) H group.

A further preferred embodiment is characterized in that compounds of the formula (2) in which A is a sulfophenyl radical, of the formula (3) in which Y is methyl or carboxy, and B is a phenyl or naphthyl radical which is optionally substituted by sulfo and chlorine , wherein A and B together contain 1 to 6 sulfo groups, and A or B contains an -NH2 group, one equivalent of 2,4,6-trifluoro-s-triazine of the formula (4) and one equivalent of an aminobenzene of the formula (5) , where X has the meaning given under formula (1), used as starting materials.

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 order of the simple reactions between 5 the individual reaction components of the formula (2), (3), (4) and (5) being freely selectable.

Important process variants are characterized in that

1) couples a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to an azo compound, this is condensed with 2,4,6-trifluoro-1,3,5-triazine of the formula (4) and the resultant condensed primary condensation product with an aminobenzene of the formula (5) to a fiber-reactive azo dye of the formula (1); 15 2) 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 is condensed with an aminobenzene of the formula (5) and the secondary formed Couples the 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-trifluoro-1,3,5-triazine of the formula (4), a diazotized amino compound is obtained on the primary condensation product obtained

25 coupling of the formula (2) couples and the azo compound obtained is condensed with an aminobenzene of the formula (5) to give a fiber-reactive azo dye of the formula (1);

4) an amino compound of the formula (2) is condensed with 2,4,6-trifluoro-s-triazine of the formula (4), the primary

30 re condensation product with an aminobenzene of formula (5) condensed, the resulting secondary condensation product diazotized and coupled to a coupling component of formula (3) to a fiber-reactive azo dye of formula (1);

5) an amino compound of the formula (2) is condensed with 2,4,6-tri-fluoro-s-triazine of the formula (4), the primary condensation product obtained is diazotized and coupled to a coupling component of the formula (3) and the azo compound obtained is also used an aminobenzene of the formula (5) to a fibrous

40 reactive azo dye of the formula (1) condensed;

6) couples a diazotized amino compound of the formula (2) with a coupling component of the formula (3) to an azo compound, this is condensed with 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula (4) and the diprimera obtained

45 condensation product with 2 equivalents of an aminobenzene of the formula (5) condensed to a fiber-reactive azo dye of the formula (1);

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

50 binds coupling, and this is condensed with 2 equivalents of the primary condensation product of 2,4,6-trifluoro-s-triazine of the formula (4) and an aminobenzene of the formula (5) 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-aminobenzene-2-, -3- and -4-sulfonic acid, 60 l-aminobenzene-2,4- and -2,5-disulfonic acid, l-amino-4-methylbenzene- 2-sulfonic acid,

1 - amino-3-methylbenzene-6-sulfonic acid, l-amino-6-methylbenzene-3- or -4-sulfonic acid, l-amino-2,4-dimethylbenzene-6-sulfonic acid, 65l-amino-2-carboxybenzene- 4-sulfonic acid, l-amino-4-carboxybenzene-2-sulfonic acid,

l-amino-4- or -5-chlorobenzene-2-sulfonic acid, l-amino-6-chlorobenzene-3- or -4-sulfonic acid,

35

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

l-amino-4- 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, 1,4-diaminobenzene-2-sulfonic acid,

1,3-diaminobenzene-6-sulfonic acid,

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

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

2-aminonaphthalene-l, 5,7-, -3,6,8- or 4,6,8-trisulfonic acid, l-hydroxy-2-aminobenzene-4-sulfonic acid, l-hydroxy-2-aminobenzene-5-sulfonic acid , l-Hydroxy-2-aminobenzene-4,6-disulfonic acid, l-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, l-hydroxy -2-amino-4-chlorobenzene-5-sulfonic acid, l-hydroxy-2-amino-4-methylsulfonyl-benzene,

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

2-amino-l-hydroxynaphthalene-4,8-disulfonic acid.

Coupling components of the formula (3)

3-methyl-5-pyrazolone,

5-pyrazolone-3-carboxylic acid,

1-phenyl-3 -sulfomethyl-5-pyrazolone,

l- (4'-sulfophenyl) -3-methyl-5-pyrazolone,

1- (4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid,

l- (3'-sulfophenyl) -3-methyl-5-pyrazolone,

1- (3'-sulfophenyl) -5-pyrazolone-3-carboxylic acid,

l- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone,

l- (2'- or 3'- or 4'-chlorophenyl) -3-methyl-5-pyrazolone,

l- (2'-chloro-4'-sulfophenyl) -3-methyl-5-pyrazolone,

l- (2'-chloro-5'-sulfophenyl) -3-methyl-5-pyrazolone,

1 - (2 '-sulfo-4'-chlorophenyl) -3-methyl-5-pyrazolone,

l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone,

1- (2'-methyl-4'-sulfophenyl) -3-methyl-5-pyrazolone,

1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid,

1- (6'-chloro-2'-methyl-4'-sulfophenyl) -3-methyl-5-pyrazolone,

1- (4 ', 8'-disulfonaphthyl [2']) -3-methyl-5-pyrazoIon,

1- (4 ', 8'-disulfonaphthyl [2']) - 5-pyrazolone-3-carboxylic acid,

l- (5 ', 7'-disulfonaphthyl [2']) - 3-methyl-5-pyrazolone,

1- (5 ', 7' -disulfonaphthyl [2 ']) - 5 -pyrazolon-3-carboxylic acid,

l- (4 ', 6', 8'-trisulfonaphthyl- [2 ']) - 3-methyl-5-pyrazolone,

1- (4 ', 6', 8'-trisulfonaphthyl- [2 ']) - 5-pyrazolone-3-carboxylic acid,

l- (6'-amino-4 ', 8'-disulfonaphthyl [2']) - 3-methyl-5-pyrazolone,

l- (3'- or 4'-aminophenyl) -3-methyl-5-pyrazalone,

1- (3'-aminophenyl) -5-pyrazolone-3-carboxylic acid,

l- (4 '- amino-2' -sulfophenyl) -3-methyl-5-pyrazolone,

1 - (4 '- amino-2' -sulfophenyl) -5-pyrazolone-3-carboxylic acid,

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

Aminobenzenes of the formula (5)

l-amino-2-methylbenzene,

l-amino-2-ethylbenzene,

l-amino-2-propylbenzene,

l-amino-2-methoxybenzene,

l-amino-2-ethoxybenzene,

l-amino-2-carboxybenzene,

l-amino-2-chlorobenzene,

l-amino-2-bromobenzene,

s l-amino-2-fluorobenzene,

1 - amino-2,4-dimethylbenzene,

l-amino-2,5-dimethylbenzene.

The diazotization of the amino compounds of the formula (2) is generally carried out by the action of nitrous acid in aqueous / mineral-acidic solution at low temperature, the coupling to the coupling components of the formula (3) at weakly acidic, neutral to weakly alkaline pH values .

The condensations of 2,4,6-trifluoro-1,3,5-triazine with 15 the amino compounds of the formula (2) or the coupling components of the formula (3) 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 hydro-25 xy or carboxy group, metal complexes of the fiber-reactive azo dyestuffs of the formula (1) can also be prepared by treating azo compounds obtained by the process described above before or after the condensation with fluorine-s-triazine with metal-donating agents. The copper complexes are of particular interest; they are prepared by using corresponding azo compounds, 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 fluoro-1,3,5-35 triazine copper-donating agents.

As a method of coppering, not only the method described above can be considered, 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 Copper reaction is introduced 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-45-naphthalene-4,8-disulfonic acid as the diazo component.

However, for the preparation of the compounds of the formula (1) it is also possible to use diazo components which contain an alkoxy group, in particular the methoxy group, in the 1-position of a naphthalene nucleus instead of a hydroxyl group, which, under suitable reaction conditions during the coppering reaction, by splitting off the alkyl radical in 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 55 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 complex 60 bound, e.g. complex copper compounds of the alkali salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, such as glycollate, lactic acid and especially tartaric acid, such as sodium copper tartrate.

Treatment with the copper donor can be carried out according to methods known per se, e.g. at room temperature, if there are readily metallizable starting compounds or, if a dealkylation has to take place at the same time as the metallization, by heating to temperatures

7

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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 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.

s It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if necessary with the addition of a dispersing agent which promotes the diffusion of the non-fixed portions.

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

example 1

To an aqueous solution containing 65 parts of the trina-15 trium salt of l- (2'-naphthyl) -3-methyl-4- (5 "-aminophenyl-azo) -pyrazoIon- (5) -2", 4 ', 8'-trisulfonic acid, 14 parts of 2,4,6-trifluoro-l, 3,5-triazine are added dropwise at 0 to 5 ° within 30 minutes. At the end of the addition, the free amino group of the starting product is no longer detectable. Throughout the addition, the pH of the solution is kept at 6.5 to 7.5 by simultaneously metering in 2N sodium hydroxide solution. 11 parts of 2-aminotoluene are now added, the temperature is slowly increased to 20 ° and the pH is kept at 7 during the condensation. The clear dye solution obtained is used to precipitate the 25 dye of the formula by sprinkling potassium chloride. After filtering, drying and milling, a yellow dye powder is obtained. The dye dyes cotton in real yellow tones.

The procedure is as described in Example 1, using that in column I of the following

Table 1 contains pyrazolone dyes containing amino groups and carries out the second condensation with the amine specified in column II 40, so that further valuable dyes with similar dyeing properties are obtained.

Table 1

I from pyrazolone dye containing amino groups

45

Diazo component

1 l-amino-3-acetyIaminobenzene-6-sulfonic acid (saponified)

do. do.

do. do. do.

do.

Coupling component

1- (4 ', 6', 8 '-Trisulfonaphthyl [2'] - 3-methyl-5-pyrazolone do.

1- (4 ', 6', 8 '-Trisulfonaphthyl [2'] -5 -pyrazolon-3-carboxylic acid do.

do.

1 - (2 ', 5' -Disulfophenyl) -3-methyl-5-pyrazolone l-phenyl-3-sulfomethyl-5-pyrazolone

II amine for 2nd condensation l-amino-2-methylbenzene l-amino-2-chlorobenzene 1-amino-2-methylbenzene

1 - Amino-2-methoxybenzoI

l-amino-2-carboxybenzene l-amino-2-methylbenzene l-amino-2-methylbenzene

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Table 1 (continued)

I from pyrazolone dye containing amino groups

Diazo component 8 l-aminobenzene-2-sulfonic acid

9 l-amino-3-acetylaminobenzene-6-sulfonic acid (saponified)

10 do.

11 l-amino-4-acetylamino-2-sulfonic acid (saponified)

12 l-amino-3-acetylamino-benzene-6-sulfonic acid (saponified)

13 do.

14 l-aminobenzene-2,5-disulfonic acid

15 l-aminobenzene-2,4-disulfonic acid

16 2-aminonaphthalene-1,5-disulfonic acid

17 do.

18 l-aminobenzene-2,5-disulfonic acid

19 l-aminobenzene-2,4-disulfonic acid

20 l-aminobenzene-2,5-disulfonic acid

21 2-aminonaphthalene-1,5-disulfonic acid

Coupling component l- (4'-amino-2'-sulfophenyl) -5 -pyrazolon-3-carboxylic acid l- (4 ', 6', 8 '-Trisulfonaphthyl [2'] -5 -pyrazolon-3-carboxylic acid do.

l- (2 ', 5'-dichloro-4'-

sulfophenyl) -3-methyl-

5-pyrazolone l- (4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid l- (3'-su! Fophenyl) -5-pyrazolone-3-carboxylic acid l- (6'-amino-4 ', 8' -disulfonaphthyl- [2 ']) - 3-methyl-5-pyrazolone do.

do.

do.

1- (3'-aminophenyl) -5-pyrazolone-3-carboxylic acid 1- (4'-aminophenyl) -3-methyl-5-pyrazolone

1 - (4 '- Amino-2' -sulfophenyl) -3-methyl-5-pyrazolone do.

II amine for 2nd condensation l-amino-2-ethylbenzene l-amino-2-ethoxybenzene l-amino-2,4-dimethylbenzene 1 - amino-2,5-dimethylbenzene l-amino-2-carboxybenzene l-amino-2 -methylbenzene l-amino-2-methylbenzene l-amino-2-chlorobenzene

1 - Amino-2-ethybenzene l-amino-2-carboxybenzene l-amino-2-methylbenzene l-amino-2-carboxybenzene l-amino-2-methoxybenzoI

1 - amino-2-carboxybenzene

Example 2

66 parts of the intermediate of the formula

0

r-so h nh,

obtained by coupling diazotized l-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid to l- (4 ', 8'-disulfonaphthyl [2']) - 3-methyl-5-pyrazolone, followed by saponification of the

50

Acetylamino group and complex formation with a copper donor are dissolved in 700 parts of water at pH 7 and 0 °. This pH value is maintained by further addition of sodium hydroxide solution after 14 parts of 2,4,6-trifluoro-1,3,5-55 triazine have been added dropwise. When the condensation has ended (demonstrable by the absence of free amino groups), 13.3 parts of 1-amino-2-chlorobenzene are added. The temperature is raised to 35 ° and the pH is kept at 8.5 with further sodium hydroxide solution. The dye obtained in this way is precipitated by adding 60 table salt, filtered off with suction and ground after drying. It dyes cotton in red-brown shades very real.

Further brown dyes with similar properties are obtained if the Cu complex dyes listed in column I of the following 65 table 2 with equivalent parts of 2,4,6-trifluoro-l, 3,5-triazine and then with those listed in column II Amines condensed according to the information in Example 2.

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Table 2

I Pyrazolone dye containing amino groups from diazo component Coupling component l-hydroxy-2-amino-6-acetylamino-benzene-4-sulfonic acid (saponified)

l-hydroxy-2-amino-4-acetyl-

amino-benzene-6-sulfonic acid

(saponified)

l-hydroxy-2-amino-6-acetylamino-benzene-4-sulfonic acid (saponified)

do.

do.

do.

1-Hydroxy-2-aminobenzene-4-sulfonic acid

1-Hydroxy-2-aminobenzene-4,6-disulfonic acid do.

1- (4 '-sulfophenyl) -3-methyl-5-pyrazolone (Cu complex)

l- (3'-sulfophenyl) -3-

methyl-5-pyrazolone

(Cu complex)

1 - (2'-chloro-4 'sulfophenyl) -3-methyl-5-pyrazolone (Cu complex)

l- (4'-sulfophenyl) -5-

pyrazolone-3-carboxylic acid

(Cu complex)

l- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone (Cu complex)

1- (2 ', 5'-disulfonaphthyl [2']) - 5-pyrazolone-3-carboxylic acid (Cu complex)

l- (6'-Amino-4 ', 8'-disulfonaphthyl- [2']) - 3-methyl-5-pyrazolone (Cu complex)

l- (4'-aminophenyl) -3-

methyl-5-pyrazolone

(Cu complex)

1 - (4 '- Amino-2' -sulfophenyl) -3-methyl-5-pyrazolone (Cu complex)

II amine for 2nd condensation l-amino-2-fluorobenzene l-amino-2-carboxybenzene

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

Example 3

26.8 parts of 1,4-diaminobenzene-2,5-disulfonic acid are dissolved in 300 parts of water at pH 7 and 0 °. 14 parts of 2,4,6-trifluoro-l, 3,5-triazine are added dropwise with vigorous stirring, at the same time the pH is kept at 6.5-7.5 by metering in 2N sodium hydroxide solution and the temperature is kept at 0 ° by adding ice. After 1 equivalent of sodium hydroxide solution has been consumed, 12.1 parts of 1-amino-2-ethylbenzene are poured in, the mixture is heated to 40 ° and the pH is kept at 8 with a further equivalent of sodium hydroxide solution. When the condensation has ended, the mixture is cooled to 0-5 ° by adding ice, acidified with 30 parts of 45 concentrated hydrochloric acid and diazotized by dropwise addition of an aqueous solution of 7 parts of sodium nitrite. This suspension of the diazo compound is added to a neutral solution of 29 parts of l- (2'-chloro-5'-sulfophenyl) -3-methyl-5-pyrazolone, to which 30 parts of soda have been added. After the coupling has ended, the pH is corrected to 7, and the dye of the formula is precipitated by adding a 1: 1 mixture of potassium and sodium chloride. After vacuuming, drying and grinding, a yellow dye powder is obtained, which dyes cotton in real reddish-yellow tones.

Dyes with similar properties are obtained if 2,4,6-trifluoro-1,3,5-triazine with the diaminobenzenesulfonic acids ch2ch3 listed in column I of Table 3 below

and then condensed with the amines mentioned in column II, the secondary condensation products diazotized 65 and the resulting diazonium compounds coupled according to the instructions in Example 3 with the coupling components mentioned in column III.

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Table 3

I diamine

1 1,4-diaminobenzene

2.5 disulfonic acid

2 do.

3 1,3-diaminobenzene

4.6-disulfonic acid

4 do.

5 do.

6 l, 4-diaminobenzene-2-sulfonic acid

7 th.

8 l, 3-diaminobenzene-6-sulfonic acid

9 th.

10th

II amine l-amino-2-methylbenzene l-amino-2-carboxybenzoI

l-amino-2-ethoxybenzene l-amino-2-chlorobenzene l-amino-2-carboxybenzene do.

l-amino-2-methylbenzene l-amino-2-carboxybenzene l-amino-2-methylbenzene

III coupling component 1- (2'-chloro-4'-sulfophenyl) -3-methyl-5-pyrazolone

1 - (6'-Chloro-2 'methyl-4' sulfo-phenyl) -3-methyl-5-pyrazolone 1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid 1- (2'-sulfo-4'-chlorophenyl) -3-methyl-5-pyrazolone 5-pyrazolone-3-carboxylic acid l- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone l- ( 4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid 1- (5 ', 7'-disulfonaphthyl [2']) - 5-pyrazolone-3-carboxylic acid do.

Example 4

26.8 parts of 1,3-diaminobenzene-4,6-disulfonic acid are added at pH 7 in 400 parts of water and, after cooling to 0 °, 14 parts of 2,4,6-trifluoro-l, 3,5- triazine too. The pH is kept at 7 by adding sodium hydroxide solution. After the condensation has ended, the mixture is acidified with 30 parts of concentrated hydrochloric acid and diazotized by adding 7 parts of sodium nitrite. At the same time, 32 parts of l- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone are dissolved in 300 parts of water at pH 8. The diazo suspension is allowed to run into this solution

30 and keeps the pH at 8-9 by adding sodium hydroxide solution. When the reaction components are no longer detectable, 12.3 parts of 1-amino-2-methoxybenzene are added dropwise and the temperature is increased to 20-30 ° at the same time. In the meantime, the pH is kept at 8 by further addition of sodium hydroxide solution 35. When the condensation has ended, the product is salted out and filtered off with suction, and the residue is dried and ground. A yellow dye powder is thus obtained. The dye has the formula nh-c c-nh-

! II

n no

i f

The dye dyes cellulose in greenish-yellow tones very real.

Further dyes are obtained if, analogously to the procedure described above, 2,4,6-trifluoro-1,3,5-triazine with a diaminobenzenesulfonic acid from column I of the following

Table 4

thus condensed Table 4, diazotized the condensation product thus obtained and combined with the coupling component listed in column II and finally condensed with the amine mentioned in column III.

55

I diamine

1,3-diaminobenzene-4,6-disulfonic acid

II coupling component 3-methyl-5-pyrazolone

III amine l-amino-2-carboxybenzene do.

l- (3 '-sulfophenyl) -3-methyl-5-pyrazolone l-amino-2-chlorobenzene

3 1,4-diaminobenzene-2,5-disulfonic acid 1- (2'-methyl-4'-sulfophenyl) -3-methyl-5-pyrazolone

1-amino-2-carboxybenzene

11

634 093

Table 4

1 diamine

4 do.

1,3-diaminobenzene-4,6-disulfonic acid do.

1,3-diamino-benzene-6-sulfonic acid do.

do.

II Coupling component 1- (4 ', 8'-disulfonaphthyl [2']) -3-methyl-5-pyrazolone 1- (2'-chloro-4'-sulfophenyl) -3-methyl-5-pyrazolone

1 - (5 ', 7' -Disulfonaphthyl [2 ']) - 3-methyl-5-pyrazolone

1 - (2 'Chloro-5' sulfophenyl) -3-methyl-5-pyrazolone 1- (4 ', 8'-disulfonaphthyl [2']) - 5-pyrazolone-3-carboxylic acid

1 - (4 '-Sulfophenyl) -3-methyl-5-pyrazolone

III amine

1-amino-2-propylbenzene

1-Amino-2-methylbenzene l-amino-2-ethylbenzene l-amino-2-carboxybenzene l-amino-2-methylbenzene

1-amino-2-carboxybenzene

Example 5

249.2 parts of l- (4'-amino-2'-sulfophenyl) -4- (5 "-amino-2" - 25 le 2,4,6-trifluoro-l, 3,5-triazine were added dropwise. The pH - Value will be sulfophenylazo) -5-pyrazolone-3-carboxylic acid, produced by constant diazotization of l-amino-3-acetylamino-benzene-6-sulfonic acid by further metering in sodium hydroxide solution. If no free amino group can be detected, domes are added dropwise to l- (4'-amino-2'-sulfophenyl) -5-pyrazolon-3- 107.2 parts of l-amino-2-methylbenzene. The tempera carboxylic acid and subsequent saponification of the acetyl amino acid is rapidly increased to 40 ° and by adding another group, the pH value is kept at 8 in 1000 parts of water at pH 7.5 by adding 30 sodium hydroxide solution. The dye dissolved in caustic soda. After cooling to 0 °, 135 parts of formula

50

is salted out, filtered off, dried and ground. It is a yellow powder that dyes cotton in true yellow colors.

Further bireactive dyes with similar properties can be obtained if one looks at those in Table 5 below

Table 5

I diamino azo dye

1,3-diaminobenzene-4,6-disulfonic acid-> 1- (4'-amino-2'-sulfophenyl) -3-methyl-5-pyrazolone

1,4-diaminobenzene-2,5-disulfonic acid->

1 - (3 '- aminophenyl) -5 -pyrazolone-3-carboxylic acid l-amino-3-acetylaminobenzene-6-sulfonic acid -> 1 - (6' -amino-4 ', 8' -disulfonaphthyl [2 ']) -3-methyl-5-pyrazolone (saponified)

Diamino-azo dyes listed in column I with 2,4,6-45 trifluoro-1,3,5-triazine and then condensed with the amines mentioned in column II analogously to the information given in Example 5 above.

II amine l-amino-2-carboxybenzene do.

l-amino-2-methylbenzene

65

Example 6

26.8 parts of 1,4-diaminobenzene-2,5-disulfonic acid are diazotized and to 26.9 parts of 1- (4'-amino-2'-sulfophenyl) -3-

methyl-5-pyrazolone coupled. To neutralize this intermediate product in 500 parts of water, 47.2 parts of

634 093

12

Condensation product of one equivalent of 2,4,6-tri-fluoro-1,3,5-triazine and l-amino-2,5-dimethylbenzene as a suspension in 250 parts of water. The pH is kept between 7.5 and 8.5 by adding sodium hydroxide solution.

At room temperature is continued as long as free amino groups can still be detected. Then the solution is evaporated and the residue is ground. The dye of the formula ci-i cil thus prepared

"\

nh-c c-nh-

/ '"\ n n

CK. ^ C

$ I

f dyes cotton in reddish-yellow shades of high fastness.

ch,

6 listed diamino azo dyes according to Example 6 with the primary condensation product of 2,4,6-trifluoro

Bireactive dyes with similar properties are 2ol, 3,5-triazine and the amines of column II condensed, obtained if one in column I of the table below

Table 6

I diamino azo dye

1 l, 4-diaminobenzene-2,5-disulfonic acid -> l- (4'-amino-2'-sulfophenyl) -5-pyrazolone-3-carboxylic acid

2 l, 3-DiaminobenzoI-4,6-disulfonic acid - * • l- (4'-aminophenyl) -3-methyl-5-pyrazolone

3 1,3-diaminobenzene-4,6-disulfonic acid- »l- (6'-amino-4 ', 8'-disulfonaphthyl [2']) - 3-methyl-5-pyrazolone

4 l-amino-4-acetylaminobenzene-2-sulfonic acid— »l- (4'-amino-2'-sulfophenyl) -5-pyrazolone-3-carboxylic acid (saponified)

II amine l-amino-2-methylbenzene l-amino-2-carboxybenzene l-amino-2-ethylbenzene l-amino-2-carboxybenzene

Dyeing Instructions 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-nitrobenzenesulfonate. 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.

40 Staining Instructions 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, rinsing and then soaping the dyeing for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsing and drying.

C.

Claims (14)

634 093 2nd PATENT CLAIMS 1. Process for the production of fiber-reactive azo dyes of the formula a-n = n-c oh c - n b c = n i y (s03h) n (1) ^ N \ / - \ n - c c - nh - <) N N / X T f R - ra in which A is a benzene or naphthalene radical, Y is methyl, sulfomethyl, carboxy or carbamoyl, B is hydrogen, an optionally substituted alkyl or aryl radical, R is hydrogen or alkyl having 1 to 4 carbon atoms, X is alkyl or alkoxy having 1 up to 4 carbon atoms, carboxy or halogen, n is a positive integer from 1 to 6, and m = 1 or 2, where A and B may contain further substituents, and the phenylamino radical bonded to the s-triazine ring other than X and independently of X as further substituents on the phenyl nucleus may contain an alkyl having 1 to 4 carbon atoms, and in the event that m = 2, the substituents R or X of the two 2-fluoro-4- (2'-X-phenylamino ) -s-triazin-6-yl-N (R) radicals can be different from one another, characterized in that a diazotized amino compound of the formula A — NH2 a coupling component of the formula oh '-n -b (2) (3) fl \ =. K n where A and B together contain 1 to 6 sulfo groups, and A or / and B contain an -N (R) H group, 1 or 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula f - c * sc - f IN THE n n I. f and 1 or 2 equivalents of optionally different aminobenzenes of the formula (4) h2n (5) by coupling and condensation in any order to a fiber-reactive azo dye of the formula (1). 2. The method according to claim 1, characterized in that that aminobenzenes of the formula (5), vorin X is methyl, methoxy, carboxy or chlorine, are used as starting materials. 20th 3. The method according to claim 1, characterized in that compounds of the formulas (2) and (3), in which only A but not B contains an -N (R) H group, are used as starting materials. 25th 4. The method according to claim 1, characterized in that compounds of the formula (2) in which A is a sulfophenyl radical, of the formula (3) in which Y is methyl or carboxyl, and B is a phenyl or naphthyl radical, which is optionally by sulfo 30 and chlorine is substituted, where A and B together contain 1 to 6 sulfo groups, and A or B contains an -NH2 group, one equivalent of 2,4,6-trifluoro-s-triazine of the formula (4) and one equivalent of an aminobenzene of the formula (5), in which X has the meaning given in claim 1, as starting materials 35 used. 5. The method according to any one of claims 1 to 4, characterized in that coupling a diazotized amino compound of formula (2) with a coupling component of formula (3) to an azo compound, this with 2,4,6-trifluoro-s-tria - 40 zin condensed in the formula (4) and the primary condensation product obtained is condensed with an aminobenzene of the formula (5) to a fiber-reactive azo dye of the formula (1). 6. The method according to any one of claims 1 to 4, characterized in that an amino compound of the formula 45 (2) condensed with 2,4,6-trifluoro-s-triazine of the formula (4), the primary condensation product obtained is condensed with an aminobenzene of the formula (5), the resulting secondary condensation product is diazotized and onto a coupling component of the formula (3 ) to a fiber-reactive azo color 50 substance of formula (1) couples. 7. The method according to any one of claims 1 to 4, characterized in that an amino compound of the formula (2) is condensed with 2,4,6-trifluoro-s-triazine of the formula (4), the primary condensation product obtained is diazotized and on egg - 55 ne coupling component of the formula (3) couples and the azo compound obtained is condensed with an aminobenzene of the formula (5) to give a fiber-reactive azo dye of the formula (1). 8. The method according to any one of claims 1 to 4, characterized 60 characterized in that a diazotized amino compound of the formula (2) is coupled with a coupling component of the formula (3) to form an azo compound, this is condensed with 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula (4) and the resulting diprimal condensation product with 2 equivalents 6S of an aminobenzene of the formula (5) condensed to give a fiber-reactive azo dye of the formula (1). 9. The method according to any one of claims 1 to 4, characterized in that a diazotized amino compound 3rd 634 093 of formula (2) couples with a coupling component of formula (3) to an azo compound, and this with 2 equivalents of the primary condensation product of 2,4,6-trifluoro-s-triazine of formula (4) and an aminobenzene of formula (5 ) condensed to a fiber-reactive azo dye of the formula (1). 10. A process for the preparation of a fiber-reactive azo dye of the formula characterized in that diazotized l-amino-3-aceto-aminobenzene-6-sulfonic acid with l- (4 ', 8'-disulfonaphthyl [2']) - 3-methyl-5-pyrazolone couples, the azo compound obtained after saponification of the acetyl group with 2,4,6-trifluoro-s- triazine condensed and the primary condensation product condensed with 2-aminotoluene. 11. Process for the preparation of a fiber-reactive azo-20 dye of the formula sooh oh n - n - c, characterized in that diazotized l-amino-3-ace-tylaminobenzene-6-sulfonic acid with l- (4 ', 6', 8 '-Trisulfonaphthyl- [2']) - 5-pyrazolone-3-carboxylic acid couples, the azo compound obtained is condensed after saponification of the acetyl group with 2,4,6-trifluoro-s-triazine and the primary condensation product is condensed with 2-aminotoluene. 12. A process for the preparation of metal complexes of fiber-reactive azo dyes of the formula (1), characterized in that a diazotized amino compound of the formula and 1 or 2 equivalents of optionally different aminobenzenes of the formula 35 h2n- (5) (2) (3) A-NH2 a coupling component of the formula -n - b V ^ N wherein A and B together contain 1 to 6 sulfo groups, and A or / and B contain an -N (R) H group, 1 or 2 equivalents of 2,4,6-trifluoro-s-triazine of the formula 40 converted into a fiber-reactive azo dye of the formula (1) by coupling and condensation in any sequence, and the azo compound obtained in an intermediate stage or the finished fiber-reactive azo dye of the formula (1) treated with metal-donating agents. 13. The method according to claim 12, characterized in that coupling a diazotized amino compound of the formula (2) 50 with a coupling component of the formula (3), treating the azo compound obtained with a copper-donating agent, the resulting copper complex with 2,4,6- Tri-fluoro-l, 3,5-triazine of the formula (4) is condensed and the primary condensation product obtained is condensed with an aminobenzene of the formula (5) to give the copper complex of a fiber-reactive azo dye of the formula (1). 60 * Nv. f - c c - f i »i n n! f (4) 65