CH638555A5 - Reactive dyes and their preparation. - Google Patents

Description

638 555

2nd

PATENT CLAIMS 1. Reactive dyes of formula (1)

i f

wherein 15 ring carbon atom from D2 is bonded, R2 is hydrogen or

Dj is a benzene or naphthalene radical which is substituted by C 1-4 alkyl, which may be substituted, and R3 may be hydrogen, optionally substituted alkyl, cycloalkyl, aralkyl or

D2 is a benzene radical which can be substituted, except by aryl, where for the amino radical -NR2R3 an o-sulfophenyl-

a sulfo group in the o-position to the bridge member -N (Rj) -, Rj NH residue is excluded.

Hydrogen or C ^ alkyl, the bridge member -N ^ J- to a 20 2. reactive dyes according to claim 1, the formula d1-n = n

n = n-d0-n-c c-

(so3h) 1-2 R,

n n "^ C

i f

No,

i j

Ro

(2),

wherein one Y is hydrogen and the other Y is sulfo and D1; R2 is hydrogen, ethyl, ß-hydroxyethyl, butyl, phenyl, and R3 have the meanings given in claim 1. Methyl, methoxy, ethoxy, chlorine, acetylamino, ureido,

3. Reactive dyes according to claim 2, wherein Dj is a Ben-carboxy and sulfo can be substituted, or wherein the zolrest, which is substituted by sulfo, methoxy and chlorine 35 amino group -NR2R3 represents the morpholino group.

can, or a naphthalene residue, which can be substituted by sulfo and nitro. 4. Reactive dyes according to claim 3, of the formula, R2 is hydrogen, methyl or ethyl and R3

nh-c c - n - ro

I tl I

n n ro

2nd

I.

f

50

wherein R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl which is substituted by methyl, methoxy, chlorine and sulfo sub (3),

can be, is.

5. The reactive dye according to claim 4, the formula

3rd

6. Process for the preparation of reactive dyes of the formula (1)

638 555

D1-N = N

* N \

= n-d2-n-c c (s03h) 1.2 rx n ^ n

I.

f n - r, »

Marg

(1),

wherein

D1 is a benzene or naphthalene residue which can be substituted,

D2 is a benzene radical which can be substituted, except by a sulfo group in the o-position to the bridge member -NÇR ^ -, Rt hydrogen or C ^ alkyl, the bridge member -N (Rj) - bonded to a ring carbon atom of D2, R2 is hydrogen or C, _j-alkyl, which may be substituted, and R3 is hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl, an o-sulfophenyl-NH radical being excluded for the amino radical —NR2R3, characterized in that one has a coupling component of the formula and an amino compound of the formula

ISHN-R3 I

R2

(9)

diazotized, coupled and condensed in any order. 20 7. The method according to claim 6, characterized in that a compound of the formula h2n as the coupling component of the formula (5)

(s03h)

1-2

(10),

a diazo component of the formula in which one Y is hydrogen and the other Y is sulfo, and as a diazo component of the formula (7) is a compound of the formula

D, -NH2

another diazo component of the formula

H2N-D2-NH

I.

R!

2,4,6-trifluoro-s-triazine of the formula

(6) 35

(7),

(S03H) 1_2

(11)

40

f -

c c -

I tv n n c

I.

f used.

8. The method according to claim 7, characterized in that compounds of the formulas (6) and (9) are used as starting materials, in which Dx is a benzene radical which can be substituted by sulfo, meth-45 oxy and chlorine, or a naphthalene radical which can be substituted by sulfo and nitro, R2 hydrogen (8), methyl or ethyl and R3 hydrogen, ethyl, ß-hydr-oxyethyl, butyl, phenyl by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxy and sulfo may be substituted 50, or naphthyl, which may be substituted by sulfo, or wherein the amino group -NR2R3 represents the morpholino radical.

9. The method according to claim 8 for the production of reactive dyes of the formula

55

s03h h03s c c - n - r,

V V »v 3

n n r "

2nd

1

f

(3),

638 555

4th

wherein R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo, characterized in that one has a diazo component of the formula

çy ™ 2

s03h

(12),

l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound of the formula (9), in which R2 and R3 have the meanings given above, diazotized in any sequence , couples and 5 condenses.

10. The method according to claim 9, for the preparation of the reactive dye of the formula, characterized in that sulfanilic acid and 1,3-Phe-nyIendiamin-4-sulfonic acid and diazotized on l-amino-8-hydr-

\

C.

I.

n

I.

f s - »- q

(4),

Cl oxynaphthalene-3,6-disulfonic acid couples, the intermediate compound obtained of the formula h0n oh

2I I

n = n

(13)

mi,

condensed with cyanuric fluoride and the primary condensation product condensed with m-chloroaniline.

35 The invention relates to reactive dyes of the formula h2n oh dx - n n — r ^ v ^ w - n = n - d,

y ^^ (s03h) 1_2

, N,

n - c t

n

I.

r i

f

C.

ti n

- No,

i

Ro

(i).

where Dj is a benzene or naphthalene residue which can be substituted, D2 a benzene residue which can be substituted, except by a sulfo group in the o-position to the bridge member -N ^) -, Rj is hydrogen or C ^ alkyl, the bridge member -N (Rt) - bonded to a ring carbon atom of D2, R2 is hydrogen or C 1-4 alkyl, which may be substituted, by R3 is hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl, where an o-sulfophane for the amino radical -NR2R3- nyl-NH radical is excluded.

The residues Dj and D2 can contain the substituents customary for azo dyes. Further substituents are e.g. the following are considered: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propyloxy, isopropyloxy and butyloxy, acylamino groups with 1 to 6 carbon atoms, such as acetyl -amino, propionylamino and benzoylamino, carbamoyl, sulf-amoyl, amino groups, such as -NH2, methylamino and ethylamino-no, the ureido, hydroxyl and carboxy group, halogen, such as fluorine, chlorine and bromine, and the sulfonic acid group.

The radicals Dx and D2 contain, as further substituents 50, in particular one or more sulfonic acid groups. For Rt, the following can be considered as C 1-4 -alkyl: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. If R2 is an alkyl radical this can be substituted, e.g. by chlorine, hydroxy, cyan, methoxy, carboxy and sulfo. Examples of R2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, ß-hydroxyethyl, ß-chloroethyl, ß-cyanoethyl, cyanomethyl, γ-cyanopropyl, ß-methoxyethyl , ß-carboxyethyl, sulfomethyl and ß-sulfoethyl, For R3 come for example into consideration: hydrogen, the same substituted and unsubstituted alkyl radicals mentioned above for R2, methoxypropyl, ethoxy ethyl, ethoxypropyl and methoxybutyl, cyclohexyl, benzyl, 4-suifobenzyl, 4-methylbenzyl, phenethyl and especially phenyl, which is substituted by Ci_j-alkyl , C 1-4 alkoxy, acetylamino, ureido, carboxy, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl and carbamoyl, or naphthyl, which may be substituted by sulfo; furthermore, R2 and R3 can be closed to form a six-membered N-heterocyclic ring which can contain a further heteroatom, such as nitrogen, oxygen and sulfur. As

55

60

65

Examples of the amino radical -NR2R3 in formula (1) may be mentioned: -NH2, methylamino, ethylamino, propylamino, isopropylamino, butylamino, ß-methoxyethylamino, y-methoxypropylamino, N, N-dimethylamino, N, N-diethylamino , N-methyl-N-phenylamino, N-ethyl-N-phenylamino, ß-chloroethylamino, ß-hydroxyethylamino, y-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, piperidino, pipe-razino, and especially aromatic amino groups such as phenylamino, toluidino, chloranilino, anisidino, phenetidino, 3-and 4-sulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 3-and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino,

5 638 555

3,6-disulfonaphthyl- (l) -amino, 3,6,8-trisulfonaphthyl- (l) -amino and 4,6,8-trisulfonaphthyl- (l) -amino.

The disazo dyes of the formula (1) are fiber-reactive since they contain a releasable fluorine atom in the s-triazine radical. 5 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.

io The rest of Dj contains no reactive residue.

Reactive dyes of the formula n = n n - r are preferred,

i -j

Ro

(2),

wherein one Y is hydrogen and the other Y is sulfo and Dl5 R2 and R3 have the meanings given under formula (1).

Reactive dyes of the formula (2) are particularly preferred, in which Dx is a benzene radical which can be substituted by sulfo, methoxy and chlorine or a naphthalene radical which can be substituted by sulfo and nitro, R2 is hydrogen, methyl

30th

or ethyl and R3 is hydrogen, ethyl, β-hydroxyethyl, butyl, phenyl, which can be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino-no, ureido, carboxy and sulfo, or in which the amino group -NR2R3 represents the morpholino radical . Reactive dyes of the formula are particularly preferred

^ VN =

h2n oh

so3h ho3

sooh

\ L

n = n- ^ 3 03h- nh

- c

I.

n

(3)

C - N - Ro

Ii i 3

n ro

I.

f

A valuable reactive dye which is defined by formula (3)

so3h

wherein R2 is hydrogen, methyl or ethyl and R3 is hydrogen or phenyl, which is the class subdivided by methyl, methoxy, chlorine and sulfo, the reactive dye of the formula can be.

h0n oh i l h03s— <v3 ~ n = n — c

* N \ // - \

- c c - nh - {/ y

NN \

Cl

I.

f

The preparation of the reactive dyes of the formula (1) is 60 a diazo component of the formula characterized in that a coupling component of the formula Dx — NH2

(4)

(5).

(S03h) i_2

65

another diazo component of the formula

H2N-D2-NH I

Ri

(6),

(7),

638 555

6

2,4,6-TrifIuor-s-triazine of the formula

Ä

f - c c - f f n

N N

I.

f and an amino compound of the formula

HN-R3 I

Margin

0- «2

(8th)

so, h

5 Ì

(12)

(9)

diazotized, coupled and condensed in any order.

A preferred embodiment is characterized in that a compound of the formula is used as the coupling component of the formula (5)

(10)

wherein one Y is hydrogen and the other Y is sulfo, and as a diazo component of the formula (7) a compound of the formula

(S03H) l-2

H2N-f ^

35

(il)

used.

In particular, compounds of the formulas (6) and (9) are used as starting materials, in which Dt is a benzene radical which may be substituted by sulfo, methoxy and chlorine or a naphthalene radical which may be substituted by sulfo and nitro, R2 is hydrogen, methyl or Ethyl and R3 is hydrogen, ethyl, ß-hydroxyethyl, butyl, phenyl, which may be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxy and sulfo, or naphthyl, which may be substituted by sulfo, or wherein the amino group -NR2R3 represents the morpholino radical.

The preferred reactive dyes of formula (3) are obtained by condensing a diazo component of the formula with cyanuric fluoride and condensing the primary condensation product with m-chloroaniline.

l-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1,3-di-aminobenzene-4-sulfonic acid, cyanuric fluoride and an amino compound

Binding of formula (9), in which R2 and R3 have the meanings given under formula (3), diazotized, coupled and condensed in any order.

Since the individual process steps mentioned above, namely diazotization, coupling and condensation can be carried out in different orders, if necessary partly also simultaneously, different process 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 the individual reaction components of the formulas (5) to (9) being freely selectable.

Important process variants are characterized in that

25th

1. a coupling component of the formula (5) with diazotized diazo components of the formulas (6) and (7) is converted into a disazo compound, this is condensed with 2,4,6-trifluoro-s-triazine of the formula (8) and the primary condensation product

3o condensed with an amino compound of formula (9).

The last two reaction steps can also be carried out in a different order by first condensing the 2,4,6-tri-fluoro-s-triazine with an amino compound of the formula (9) and condensing the primary condensation product obtained with the disazo compound mentioned above.

In the preparation of the above-mentioned disazo compound, it is expedient to proceed by first coupling a diazotized diazo component of the formula (6) with a coupling component of the formula (5) and then the mono-azo compound obtained with a diazotized diazo component of the formula (7 ) couples.

2. diazotizing a diazo component of the formula (6) and coupling it to a coupling component of the formula (5), that further condensing 2,4,6-trifluoro-s-triazine of the formula (8) with an amino compound of the formula (9), the primary condensation product is condensed with a diazo component of the formula (7), the secondary condensation product is diazotized and coupled to the initially produced monoazo compound.

In this production variant, too, the condensation with the amino compound of the formula (9) can be carried out as under 1 as the last reaction step.

The preferred method of preparing the reactive dye of the formula (4) is characterized in that sulfanilic acid and 1,3-phenylenediamine-4-sulfonic acid are diazotized and coupled to l-amino-8-hydroxynaphthalene-3,6-disulfonic acid, the intermediate compound of the formula obtained

(13)

The diazo components are usually diazotized by the action of nitrous acid in aqueous mineral acid solution at low temperature.

40

50

55

7

638 555

The coupling of the diazo components of the formula (6) to the coupling component of the form (5) ortho to the H2N group takes place in a strongly acidic solution, at pH values from 1 to 2; the coupling of the diazo components of the formula (7) to the coupling component of the formula (5) ortho to the HO group in a weakly acidic, neutral to weakly alkaline range, at pH values between 6.5 and 8.

In general, it is necessary to carry out the coupling in acidic solution first. In some cases, the couplings in which a di-aminobenzenesulfonic acid is used as the diazo component of the formula (7) are advantageously not used themselves, but instead an amino-acyalmino-benzenesulfonic acid, e.g. the 5-acetylamino-aniline-2-sulfonic acid, which, after the coupling has been completed, the acetyl group is split off by saponification before condensation is continued. Furthermore, a nitro-amino compound, e.g. Use 5-nitroani-lin-2-sulfonic acid and reduce the nitro group to the amino group after coupling with sulfur sodium or sodium sulfate.

The condensation of the 2,4,6-trifluoro-s-triazine of the formula (8) with the diazo components of the formula (7) and the amino compounds of the formula (9) are preferably carried out in aqueous solution or suspension, at low temperature and in the case of slightly acidic , neutral to weakly alkaline pH, so that at least one fluorine atom remains as a removable residue in the finished reactive dye of the formula (1). The hydrogen fluoride liberated in the condensation is advantageously continuously neutralized by adding aqueous alkylihydr oxides, carbonates or bicarbonates.

The preparation of the diazo intermediate compounds is not described in all cases in the following exemplary embodiments, but it results readily from what has been said above.

Examples of starting compounds for the preparation of the reactive dyes of the formula (1) are:

a) coupling components of the formula (5) l-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K-acid),

1-amino-8-hydroxynaphthalene-4-sulfonic acid.

b) diazo components of the formula (6)

Aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and p-chloroanilines, 2,5-dichloroaniline, a- and ß-naphthylamine, 2.5 -Dimethylaniline, 5-nitro-2-aminoanisole, 4-aminodiphenyl, aniline-2-, -3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 4-aminobenzenesulfonamide or -sulfomono- methyl- or -ethylamides or -sulfonedimethyl- or -sulfone-diethylamides, aniline-2-, -3- and -4-sulfonic acid, aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 4 -Chlor-5-methyl-aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 2-amino-4- or -5-sulfobenzoic acid, 2-methyl-aniline-3,5 disulfonic acid, 2-methylaniline-5-sulfonic acid,

2-methoxyaniline-3,5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 2,3-dimethylaniline-4,6-disulfonic acid, 2,5-dimethylaniline-4,6-disulfonic acid, 5-chloro-4- methylaniline-2-sulfonic acid,

3-acetylaminoaniline-6-sulfonic acid, 4-acetyIaminoaniIin-2-suI-fonic acid, 4-chloroaniline-2-sulfonic acid, 3,4-dichloroaniline-6-sulfonic acid, 4-methylaniline-2-sulfonic acid, 3-methylaniline 6-sulphonic acid, 2,4-dimethoxyaniline-6-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid, 2,4- Dimethylaniline-5-sulfonic acid, 2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid,

4-nitroaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 4-ethoxy aniline-3-sulfonic acid, 3,4-dichloroaniline, o-, m- and p-nitroaniline,

m- and p-aminoacetanilide, 4-amino-2-acetylaminotoluene-5-suifonic acid, 4-methoxyaniline-3-sulfonic acid, 1-aminonaphtha-lin-2-, -4-, -5-, -6-, -7 -or -8-sulfonic acid, 2-aminonaphthalene-1-, -5- or -6-sulfonic acid, l-aminonaphthalene-3,6- or 5 -5,7-disulfonic acid, 2-aminonaphthalene-l, 5- , -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulfonic acid, l-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene l, 5,7-, -3,6,8- or -4,6,8-trisulphonic acid, 1 - amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-l- hydroxynaphthalene-4,8-disulfonic acid, 1-amino-3-acetylaminobenzene (saponified), l-amino-3-acetyl-aminobenzene-5- or -6-sulfonic acid (saponified), l-amino-4-ace -tylaminobenzene-2-sulfonic acid (saponified), l-amino-3- (N-acetyl-N-methylamino) -benzene (saponified) 3- or 4-nitroaniline (reduced), 2-methoxy-4- or -5- nitroaniline (reduced), 2-meth-i5 oxy-3-nitro-5-methylaniline (reduced) and 2-methoxy-3-nitro-5-chloroaniline.

c) diazo components of the formula (7)

1,3- and 1,4-diaminobenzene, 1,3- and 1,4-diaminoanisole, 1,3-20 and 1,4-diaminotoluene, 1,3-diamino-4-chlorobenzene, 1,3-di-

amino-4-ethylbenzene, 1,3-diamino-4-ethoxybenzene, 1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid,

1,4-diaminobenzene-2,6-disulfonic acid

25 d) 2,4,6-trifluoro-s-triazine of the formula (8) (cyanuric fluoride) e) amino compounds of the formula (9)

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, tert.-butylamine, hexylamine, 30 methoxyethylamine, ethoxyethylamine, methoxypropylamine, chloroethylamine, hydroxyethylamine amine, dihydroxyethylamine amine, dihydroxyethylamineamine, dihydroxyethylamineamine, dihydroxyethylamineamine, dihydroxyethylamineamine , ß-sulfatoethyl-amine, benzylamine, cyclohexylamine, aniline, o-, m- and p-tolui-din, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, o-, m-35 and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p- Aminophenol, 2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4-methylaniline, o-, m- and p-anisidine, o-, 40 m- and p-phenetidine, 2-methoxy-5-methylaniline, 2-ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamine, 4-aminophenylsulfamide , 3-trifluoromethylaniline, 3- and 4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 2-amino-1-hydro xy-naphthalene, l-amino-4-hydroxy-naphthalene, 1-amino-45 no-8-hydroxy-naphthalene, l-amino-2-hydroxy-naphthalene, l-amino-7-hydroxy-naphthalene, metanilic acid, sulfanilic acid , Aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 4-aminophenylmethanesulfonic acid, aniline-N-methanesulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminotoluene-50 5-sulfonic acid, p Amino salicylic acid, l-amino-4-carboxy-benzene-3-sulfonic acid, l-amino-2-carboxy-benzene-5-sulfonic acid,

1-naphthylamine-2-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid,

2-naphthylamine-l-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid, l-naphthylamine-2,4-, -2,5-, -2, 7-, -2.8-, -3.5-, -3.6-, -3.7-,

55 -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 2-naphthylamine-l, 5-, -1,6-, -1, 7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and -6,8-disulfonic acid, l-naphthylamine-2,4,6- , -2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-l, 3, 7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, 3-60 and 4-aminopyridine, 2-aminobenzothiazole, 5-, 6- and 8-amin-stillolinoline, 2-aminopyrimidine, morpholine, piperidine and pipazin.

The reactive dyes of the formula (1) can be isolated and processed into usable, dry dyeing preparations. 65 Isolation is preferably carried out at the lowest possible temperatures by salting out and filtering. The filtered dyes can optionally be added after adding coupling agents and / or buffering agents, e.g. after adding a mixture

638 555

8th

equal parts of mono- and disodium phosphate are dried; drying is preferably carried out at temperatures which are not too high and under reduced pressure. In certain cases, the drying preparations according to the invention can be directly dried, i.e. Manufacture without intermediate insulation of the dyes. .

The reactive dyes of formula (1) are new. They are characterized by high reactivity and they give dyeings with good wet and light fastness. It is particularly noteworthy that the dyes have good solubility and electrolyte solubility with good extraction properties and high dye fixation, and that the non-fixed portions can be removed easily. The colors are etchable.

The reactive dyes of the formula (1) are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyamide urethanes, but in particular cellulose-containing materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

They are also suitable for printing, especially on 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 with the addition of a dispersing agent which promotes diffusion of the unfixed portions.

Reactive dyes similar to those claimed in accordance with the present invention are known from German Offenlegungsschrift 25 56 640. These differ from the reactive dyes according to the invention in that they have a special constitution.

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

20 Example 1

A neutral solution of 70.2 parts of the disazo dye of the formula ho ^ s - ^ - n = n in 500 parts of water is cooled to 0 to 5 ° C. by adding 300 parts of ice. In the course of 5 to 10 minutes, 10 parts of cyanuric fluoride are run in with vigorous stirring and at the same time the pH of the reaction mixture is kept between 6 and 7 by dropwise addition of 2N sodium hydroxide solution. After complete acylation, the solution of the difluorotriazine dye 10 is added. 7 parts of o-toluidine, heated to 30 to 35 ° C. and keeping the pH of the reaction mixture between 7 and 8 by dropwise addition of 2N sodium hydroxide solution. After the reaction is complete, 5 parts of disodium hydrogenphosphate are added to the solution of the monofluorotriazine dye and the solution is evaporated dry in a rotary evaporator at 40 to 45 ° C.

The dye obtained in this way dyes trees in navy blue tones.

Similar dyes, which also dye cotton in navy shades, are obtained if, according to the example given above, instead of o-toluidine, equivalent amounts of the amines listed below are used. Ex. Amines

Ex. Amines

35

45

50

2m toluidine

3 p-toluidine

4 2,4-dimethylaniline

5 2,5-dimethylaniline

6 2,6-dimethylaniline

55

Ethanolamine

8 aniline

9 N-methylaniline

10 N-ethyl aniline

11m chloroaniline

12 p-chloroaniline

13 acetyl-m-phenylenediamine

14 acetyl-p-phenylenediamine

15 o-anisidine

16 p-anisidine

17 4-aminophenylurea

18 3-aminophenyl urea

19 p-aminobenzoic acid

20 metanilic acid

21 2-aminonaphthalene-6-sulfonic acid

22 ammonia

23 m anisidine

24 4-ethoxyaniline

25 morpholine

26 taurine

Further dyes that dye cotton in the shades listed in column III are obtained, the amino-containing disazo dyes in column I are reacted with cyanuric fluoride and the amines in column II.

II

III

nh;

Aniline greenish blue

65

638 555

II

III

s03h h2n oh

3-aminotoluene greenish blue

/

ch.

jo- ^ y-N =

3h h2n oh n = n

\

"^ n-n = n-

ho ,!

^ So3h so.h ho3s - ^ _ n =:

h2n ho3s

/

p-

so3h h2n oh

TÌ

1

UJ,

ho3s

h2 (n oh

^ o3H N = N - <^ s03h nh2

n-butylamine

AniIin-3-sulfonic acid

3-chloroaniline

Ethylamine do.

do.

4-aminoanisole blue strong greenish blue teal

638 555

10th

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% in weight, and then dried.

Then the fabric is impregnated with a 20 ° warm solution, which contains 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75% weight gain, steamed the dyeing 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.

Staining instructions II

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.

15 The solution is added to 190 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dye bath.

The temperature is raised to 40 °, 4 parts by volume of 30% sodium hydroxide solution, 10 parts of calcined sodium carbonate 20 and another 60 parts of sodium chloride being added after 30 minutes. The temperature is kept at 40 ° for 30 minutes, rinsed and the soap is then soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

C.