CH622818A5 - Process for the preparation of novel reactive dyestuffs - Google Patents

Description

The present invention relates to a process for the preparation of new, valuable reactive dyes of the formula in which F is the residue of a dye containing at least one —SCHH group, R is hydrogen or lower alkyl, X is a substituent which can be split off as an anion, p 1 or 2 and A is a radical of formula II

55

N

^ (alk - S02 - Z) m

II

(Via)

60 mean, in which alk is a lower alkylene radical having 2-6 C atoms, and V is hydrogen or the radical of an optionally substituted hydrocarbon, Z is a β-halogenoethyl or a vinyl radical, m 1 or 2 and n 2 minus m.

Fiber-reactive dyes are to be understood as those 63 which are able to react with the hydroxyl groups of cellulose or with the reactive centers of natural or synthetic polyamides to form covalent chemical bonds. The radical F in formula I can be from any

622818

Known class of dye originate, it preferably belongs to the anthraquinone, metal-free or metal-containing monoazo or disazo, phthalocyanine, formazan or nitroaryl series. Dyes according to the invention are preferred in which F is a dye residue of the anthraquinone, the 5 metal-free or metal-containing monoazo or disazo or the phthalocyanine series.

F preferably contains two to four sulfonic acid groups.

The substituent R is hydrogen or a straight-chain or branched low molecular weight alkyl group with 1 to 4 10 C atoms, such as methyl, ethyl, propyl, isopropyl or n-butyl, 2-methyl-propyl, sec. Butyl, tert. Butyl, furthermore a substituted alkyl radical such as carboxymethyl, sulfomethyl, sulfoethyl, cyanoethyl, ß-chloropropyl or ß-hydroxyethyl. The methyl radical is preferred. Hydrogen is particularly preferred as R. 15

Substituents which can be removed as anions are in particular chlorine, bromine, fluorine, alkylsulfonyl such as methyl or ethylsulfonyl, phenylsulfonyl or the -S03H radical.

X is preferably a chlorine atom.

The rest of the optionally substituted hydrocarbon V is, in particular, a methyl group optionally substituted by the carboxyl group or the sulfonic acid group or its derivatives or an optionally substituted by alkoxy groups having 1 or 2 carbon atoms, by carboxy or sulfonic acid groups or by halogen atoms or hydroxy 25 group-substituted alkyl radicals with 2-6 carbon atoms or an unsubstituted alkyl radical with 7-20 carbon atoms, a cyclohexyl radical, or one which is optionally substituted by methyl, ethyl, methoxy, ethoxy, carboxylic acid or sulfonic acid groups or phenyl radical substituted by halogen atoms. 30th

The invention relates in particular to the preparation of dyes according to the formula I, in which X is halogen and in the formula II Z is the β-chloroethyl radical.

A particularly preferred group of dyes according to formula I are those in which X represents a chlorine atom and in formula II alk the ethyl radical, Z the β-chloroethyl radical and m 2.

In the event that m is 2, the two residues -alk-SO2-Z can be identical or different within the definitions of alk and Z. Dyes in which both 40 residues -alk-SChZ are identical are preferred.

Lower alkylene radicals which can stand for alk in A are the ethylene, the trimethylene, the tetramethylene, the penta-methylene or the hexamethylene radical and their branched isomers. The ethylene radical is preferred. 45

The following radicals may be mentioned as examples of V: hydrogen, methyl, carboxymethyl, carbomethoxymethyl, carbo-ethoxymethyl, sulfomethyl, sulfamidomethyl, ethyl, carboxy-ethyl, sulfoethyl, propyl, ß-carboxypropyl, ß-sulfatoethyl, ß-ethoxyethyl, ß- Methoxypropyl, y-chloropropyl, y-bromopropyl, 50 butyl, isobutyl, pentyl, hexyl, nonyl, dodecyl, hexadecyl, pentadecyl, cyclohexyl, phenyl, o-, m- or p-chlorophenyl, o-, m- or p -Sulfophenyl, o-methylphenyl, p-methoxyphenyl, m-methylphenyl, p-ethylphenyl. The optionally substituted alkyl radicals having 1 to 4 carbon atoms are preferred, particularly preferably hydrogen and the methyl radical.

The reactive dyes of the general formula I are prepared by using a dye of the formula V

have meanings mentioned, with an amine of the formula IIa

(alk-S0o-Z),

HN

/

r *

2 m

IIa n

in which alk, Z, V, n and m have the meaning given above.

The starting dyes of formula V can be prepared by using a dye of formula III

H - H

1

R

III

J P

in which F, R and p have the meaning given above, with a reactive derivative of 1,3,5-triazine of the formula IV

"6"

IV

in which X and X 'independently of one another have one of the meanings given for X above.

The preparation of the starting dyes V and the reactive dyes I can also be combined with one another in an advantageous manner, so that first a dye of the formula III with a reactive derivative of the 1,3,5-triazine of the formula IV to give the dye V and then without it Isolation of the dye V with an amine of the formula IIa is reacted according to the invention to give a reactive dye of the formula I. The reaction of the dyes of the formula III with the triazine derivatives of the formula IV is advantageously carried out at low temperatures, for example between −2 and +10 ° C., preferably between 0 and 5 ° C., with the addition of acid-binding agents, such as sodium hydroxide solution, sodium carbonate or sodium hydrogen carbonate , in a pH range between 1.5 and 9, preferably between 4 and 6.

Water is preferably used as the solvent, which contains a certain proportion of organic solvents, such as. B. acetone contains. However, the implementation can also be carried out in pure water.

For the further reaction of the dyes of the formula V thus obtained with the amines of the formula IIa, the amines are expediently used in the form of a salt, preferably in the form of the hydrochloride. The reaction is carried out at elevated temperature, for example between 25 and 70 °, preferably between 35 and 55 °, with the addition of acid-binding agents, preferably sodium bicarbonate, in a pH range of 2-6.5, preferably 3.5 to 4.5. carried out.

If the dye residue F is composed of several components such. B. in azo dyes or forma-zan dyes, the dyes of the formula I are also available in such a way that the starting dyes V are first built up in a manner known per se from components of F, one of which, but optionally also two, a group of Formula Va

J P

in which F, R and p have the meanings given above and X and X 'independently of one another are one of the above for X.

65

Va

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wherein R, X and X 'have the meanings given above, and then reacting them as described above with an amine of the formula IIa to give dyes of the formula I. Such components can be obtained by acylation of the corresponding, a group of formula 5 purple

-N-H IIIa t

R

10th

containing components with a reactive triazine derivative of the formula IV under conditions which correspond to those described above in the corresponding reaction of the dye.

The amines of formula IIa with the meaning of a ß-halo is ethyl for Z are z. B. prepared by bringing an amine corresponding to formula IIa, which contains a chlorine atom instead of the -SO2-Z group, in an alkaline medium with ß-hydroxyethyl mercaptan to react and then the thioether contained according to the teachings of DP 20 887 505 Halogen oxidized in hydrogen halide solution. Amines of the formula IIa in which Z denotes the vinyl radical can be obtained from the amines IIa in which Z represents β-halogenoethyl by elimination of hydrogen chloride.

In an analogous manner, dyes of the formula I in which Z is vinyl means by elimination of hydrogen chloride, for. B.

by treatment with sodium hydrogen carbonate in water at 50-60 ° C., from dyes of the formula I in which Z represents β-chloroethyl.

Reactive derivatives of 1,3,5-triazine of the formula IV 30 are known. Examples include: trichlorotriazine, tri-bromotriazine, trifluorotriazine, trisulfotriazine, tris-methylsulfonyltriazine, tris-ethylsulfonyltriazine, tris-phenylsulfonyltriazine, dichlorofluorotriazine, chlorodisulfonyltriazine, chlorotinotriazine, chlorotinotriazine. 35

Examples of amines of the formula IIa are: β- (β-chloroethyl-sulfonyl> ethyl-amine, β- (β-bromoethyl-sulfonyl) -ethyl-amine,

ß-vinylsulfonyl-ethyl-amine,

y- (β-chloroethylsulfonyI) propyl amine, 40

a- (ß-chloroethyl-sulfonyl) -isopropyl-amine,

8- (ß-chloroethyl-sulfonyl) -butyl-amine,

ß- (ß-chloroethyl-sulfonyl) -isobutyl-amine,

s- {ß-chloroethyl-sulfonyl> -pentyl-amine,

ß <ß-chloroethyI-sulfonyl> hexyl-amine, 45

N-methyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-ethyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-propyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-ButyI-N-ß- {ß-chloroethyl-sulfonyl) -ethyI-amine,

N-pentyl-N-ß- (ß-chloroethyl-sulfonyl> ethyl-amine, 50

N-hexyl-N-ß- (ß-chloroethyl-sulfonyl> ethyl-amine,

N-nonyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-dodecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-hexadecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-octadecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine, 55

N-carboxymethyl-N-ß- (ß-bromethyl-sulfonyl) -ethyl-amine,

N-sulfatomethyl-N-ß- <ß-chloroethyl-sulfonyl) ethyl-amine,

N-ß-carboxyethyl-N-y- (ß-chloroethyl-sulfonyl) propyl amine,

N-ß-sulfatoethyl-N-y- (ß-chloroethyl-sulfonyl) propyl-amine,

N-ß-sulfatoethyl-N- 8- {ß-chloroethylsulfonyl> butylamine, 60

N-ß-ethoxyethyl-N-ö- (ß-chloroethylsulfonyl) butylamine,

N-y-chloropropyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-phenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-p-chlorophenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-o-methylphenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine, it

N-p-methoxyphenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyI-amine,

N-m-sulfophenyl-N-ß <ß-chloroethyl-sulfonyl) ethyl amine,

N-p-sulfophenyl-N-ß- (ß-chloroethyl-sulfonyl) ethyl amine,

Bis- {ß <ß-chloroethylsulfonyl> ethyl] amine, bis- [ß- (ß-bromoethylsulfonyl> ethyl] amine, bis- [y- {ß-chloroethylsulfonyl> propyl] amine, Bis- [8- (ß-chloroethyl-sulfonyl) butyl] amine, bis- [ß-vinyl-sulfonyl-ethyl) amine. :

Preferred are the low molecular weight amines such as the ß- (ß-chloroethylsulfonyl) ethyl amine and its N-methyl derivative. The bis- [ß- (ß-chloroethy sulfonyl) ethyl] amine is particularly preferred.

In the dyes of the formula III used for the preparation of the starting dyes of the formula V, F represents, for example, the remainder of a water-soluble dyestuff which carries at least 1 sulfonic acid group, in particular the remainder of a mono- or disazo dye which may be metal-free or metallized, for which Residue of a derivative of 1-amino or

1-anilino-anthraquinone, in particular for the remainder of a 4-phenylamino-l-amino-anthraquinone-2-sulfonic acid derivative or for the remainder of a sulfophthalocyanine dye, in particular a derivative of a phthalocyanine sulfanilide carrying at least two sulfonic acid groups in the phthalocyanine nucleus or sulfalkylamids with 2-6 C atoms in the alkyl chain, or for a residue of a formazan or nitroaryl dye.

An important group of dyes of the formula III are those in which F is the remainder of a mono- or disazo dye of the formula Via or VIb

D-N = N- (M-N = N-) nK- or -D-N = N- (M-N = N-) nK (Via) (VIb)

or a metal complex derived therefrom, in the formulas Via and VIb D for the remainder of an optionally substituted alkanoylamino group with 2-4 C, optionally substituted by substituents customary in azochemistry, in particular hydroxy, methyl, ethyl, methoxy or ethoxy groups -Atoms, optionally substituted benzoylamino groups or halogen atoms, substituted diazo components of the benzene or naphthalene series, K for the rest of an optionally substituted alkanoylamino group, which may be substituted by substituents which are customary in azochemistry, in particular hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups With

2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms substituted coupling component of the J benzene, naphthalene or ketomethylene series, M for the remainder of a substituent which may be customary in azo chemistry, in particular hydroxyl, methyl, ethyl, methoxy or ethoxy groups optionally substituted alkanoylamino groups with 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms substituted middle component of the benzene or naphthalene series and n stand for the numbers 0 or 1, and D, M and K together represent at least two sulfonic acid groups, preferably three to four sulfonic acid groups , contain. K is preferably derived from a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid aryl-mid series.

Another valuable group of dyes of the formula III in which p is 2 contains for F the divalent radical of the formula VIc

-D-N = N- (M-N = N-) nK-VIc where D, K, M and n have the meanings given above, or a metal complex derived therefrom.

The dyes of the formula III, in which F is a radical of one of the formulas Via-VIc, can, if n = 0, be obtained in a manner known per se by diazotization of aromatic amines and coupling to coupling components, either the diazo component or the coupling component or both a radical of the formula -N (R) -acyl

5

622818

or the coupling component contains a radical of the formula -N (R) -H, and the acyl group is cleaved off after the coupling by saponification.

For the preparation of disazo dyes of the formula III, d. H. In those in which F represents a radical of one of the formulas Via-VIc 5 f, where n = 1, the diazonium compound of an aromatic amine is first coupled to a central component.

In principle, all benzene or naphthalene derivatives containing a diazotizable amino group are the central components. 10th

The then present aminoazo compound is then diazotized and coupled to a coupling component, either the diazo component of the first coupling or the coupling component of the second coupling or both containing a radical of the formula -N (R> acyl, and the 15 acyl group after the coupling Saponifying is split off.

The coupling component can also contain an -NH (R> group instead of the -N (R) -acyl group.

For the preparation of dyestuffs of the formula II in which F 20 is a radical of the formula Via, for example the aromatic amines listed in the following list No. 1 are suitable as diazo components.

List 1:25

Aniline; o-, m-, p-toluidine; o-, m-, p-anisidine; o-, m-, p-chlorani-lin; Aniline-2-, -3-, 4-carboxylic acid or sulfonic acid; Aniline-2,4-, -2,5-dicarboxylic acid or disulfonic acid; 2-aminophenol4-sulphonic acid; 2-aminophenol4,6-disulfonic acid; 4-chloro-2-aminophenol-5- or -6-sulfonic acid; 6-chloro-2-aminophenol4-sulfonic acid 30; 6-nitro-2-aminophenol4-sulfonic acid; 4-nitro-2-aminophenol-6-sulfonic acid; 3- or 4-acetylamino-aniline-6-sulfonic acid; 3- or 4-benzoylamino-aniline-6-sulfonic acid; 4-amino4'-sulfobenzanilide; 2-aminoanisole-4-sulfonic acid; 4-aminoanisole-2-or -3-sulfonic acid; 3-aminoanisole4-sulfonic acid; 6-chloro-2-35 aminobenzenesulfonic acid; 5-nitro-2-aminobenzenesulfonic acid;

4-chloro-3-aminobenzenesulfonic acid; 6-chloro-3-aminobenzenesulfonic acid; 3-chloro4-aminobenzenesulfonic acid; 2-amino-toluene-4-sulfonic acid; 2-aminotoluene-5-sulfonic acid; 3-aminotoluene-6-sulfonic acid; 4-aminotoluene-2-sulfonic acid; 4-amino-40-toluene-3-sulfonic acid; 5-chloro-2-aminotoluene-3-sulfonic acid; 3-chloro-2-aminotoluene-5-sulfonic acid; 2-chloro-4-aminotoluene-6-sulfonic acid; 3-nitro-2-aminotoluene-5-sulfonic acid; 3-nitro4-aminotoluene-2-sulfonic acid; 3-amino-1,2-dimethylbenzene-4-sulfonic acid; 4-amino-1,3-dimethyl-benzene-5-sulfonic acid; 4-amino- 45

1,3-dimethyl-benzene-6-sulfonic acid; 4-chloro-2-amino-anisole-5-sulfonic acid; 4-aminophenetol-2-sulfonic acid; 4-aminophenetol-3-sulfonic acid; 2-aminophenetol4-sulfonic acid; 2-amino-toluoI-

3,4-disulfonic acid; 2-aminotoluene-3,5-disulfonic acid; 4-amino-2-sulfo-2'- or 4'-methoxydiphenylamine; 2-amino-diphenyl 50 ether; 2-, 3- or 4-aminobenzenesulfamide; 2-naphthylamine-l-,

-5-, -6-, -7- or -8-sulfonic acid; 2-naphthylamine-l, 5-, -1,7-, -3,6-, -3,7-, 4,7-, 4,8-, -5,7- or -6,8-disulfonic acid; 2-naphthylamine-1,5,7-, -3,6,8- or 4,6,8-trisulfonic acid; l-naphthylamine-2-, 4-, -5-, -6- or -7-sulfonic acid; l-naphthylamine-3,6-, -3,7-, -3,8-, 4,6-, 4,7-, 55 4,8-, -5,7- or -6,8-disulfonic acid; l-naphthylamine-2,3,6-, -3,6,8-or 4,6,8-trisulfonic acid, 2-amino-l-naphthol4-sulfonic acid; 2-amino-1-naphthol-7-sulfonic acid; l-amino-2-naphthol4-sul-fonic acid; 4-nitro-2-amino-l-naphthol-7-sulfonic acid and

5-nitro-l-amino-2-naphthol4-sulfonic acid. eo On the construction of dyes of the formula III, in which F is a

The rest of the formula VIb or VIc is, for example, the diamines listed in list No. 2 are used in the form of their monoacyl derivatives.

Particularly suitable acyl groups are lower alkanoyl 65 groups with 1 to 5 carbon atoms, preferably formyl or acetyl. As indicated above, the acyl groups are cleaved off after coupling to form the dyes of the formula

III get.

List 2:

p-phenylenediamine; 1,4-phenylenediamine-2-sulfonic acid; 1,4-phenylenediamine-2-carboxylic acid; 1,4-diamino-naphthalene-2-sulfonic acid; 2,6-diamino-naphthalene-8-sulfonic acid; 2,6-diamino-naphthalene-4,8-disulfonic acid; 1,6-diamino-naphthalene-4,8-disulfonic acid; m-phenylenediamine, 1,3-phenylenediamine4-sulfonic acid; 1,3-phenylenediamine4,6-disulfonic acid; 1,4-phenylenediamine-2,6-disulfonic acid; 1,4-phenylenediamine-2,5-disulfonic acid; 1,4-diaminonaphthalene-6-sulfonic acid; 4,4'-diaminodiphenyl-3-sulfonic acid; 4,4'-diaminostilbene-2,2'-disulfonic acid.

Examples of middle components which can be involved in the construction of the residues Via to VIc are listed in list 3 below.

List No. 3:

Aniline; m-toluidine; 2,5-dimethyl or dimethoxy aniline; m-amino anisole; m-acetylamino, m-propionylamino, m-butyrylamino or m-benzoylamino-aniline; m-aminophenyl urea; 4-acetamino-2-aminotoluene or anisole; 2-amino4-methylanisole; l-aminonaphthalene-6- or 7-sulfonic acid; 2-amino4-acetylaminobenzenesulfonic acid; 2-amino-5-naphthol-7-sulfonic acid; 2-amino-8-naphthol-6-sulfonic acid; 2- (4-amino-benzoyl-amino) -5-naphthol-7-sulfonic acid; 1- (4-amino-2-sulfo-phenyl) -3-methyl or -3-carboxy-pyrazolone-5; Acetoacet-3-sulfo4-amino-anilide.

Examples of coupling components which are suitable for the preparation of dyes of the formula III, in which F is a group of the formula VIb, are listed in list 4 below.

List No. 4:

2-naphthol; l-naphthol-6-, -7- or -8-sulfonic acid; 2-naphthol-3,6-, -3,7-, 4,8- or -6,8-disulfonic acid; 2-naphthol-3,6,8-tri-sulfonic acid; l-naphthol4-, -5-, -6- or -8-sulfonic acid; 1-naphthol-3,6-, -3,7-, -3,8- or 4,8-disulfonic acid; l-naphthol-3,6-, -3,7-, -3,8- or 4,8-disulfonic acid; l-naphthol-3,6,8-trisulfonic acid;

2-naphthylamine-5-, -6- or -7-sulfonic acid; 2-naphthylamine-3,6-, -3,7-, -5,7- or -6,8-disulfonic acid; l-amino-8-naphthol-2,4-disulfonic acid; 2-ureido-5-naphthol-7-sulfonic acid; 1- (4-sulfophenyl) -

3-methyl- or -3-carboxypyrazolone-5; l <4-Methyl-2-sulfophe-nyl> 3-methyl- or 3-carboxy-pyrazolon-5; 1- (2,5-dichloro-4-sulphophenyl) -3-methyl or -3-carboxy-pyrazolone-5; 4-aceto-acetylamino-benzenesulfonic acid; 4-acetoacetyIamino-3,6-di-methoxy-benzenesulfonic acid; Barbituric acid; 6-Hydroxy4-methyl-3-sulfo- or -3-carbonamidopyridone-2.

Examples of coupling components which are suitable for building up dyes of the formula III, in which F is a group of the formula Via or VIc, are listed in list 5 below.

List No. 5:

Aniline; m-toluidine; 2,5-dimethyl or dimethoxy aniline; m-amino anisole; m-acetylamino, m-propionylamino, m-butyrylamino or m-benzoylamino-aniline; m-aminophenyl urea; 4-acetamino-2-aminotoluene or anisole; 2-amino4-methylanisole; l-amino-naphthalene-6-, -7-, or -8-sulfonic acid; 2-amino4-acetylamino-benzenesulfonic acid; 2-amino-5-naphthol-7-sulfonic acid; 2-amino-8-naphthol-6-sulfonic acid; 2- (4-ami-nobenzoyl-amino) -5-naphthol-7-sulfonic acid; l- (4-amino- or

4-acetylamino) -2-sulfophenyl) -3-methyl- or -3-carboxy-pyra-zolon-5; Acetoacet-3-sulfo4-amino-anilide; l-amino-8-naphthol-3,6- or 4,6-disulfonic acid; 1- (3- or 4-aminobenzoyl) amino-8-naphthol-3,6- or 4,6-disulfonic acid; l-acetylamino-8-naphthol-3,6- or 4,6-disulfonic acid; 2-acetylamino-5-naphthol-7-sulfonic acid; 2-acetylamino-8-naphthol-6-sulfonic acid; 1- (3-amino- or 3-acetylamino-6-sulfophenyl) -3-methyl- or

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6

-3-carboxypyrazolon-5; 2-acetyl-methylamino or 2-methylamino-5-naphthol-7-sulfonic acid; N-methylaniline; N-propyl-m-toluidine.

Disazo dyes which carry one or two -N (R) H- or -N (R) -acyl groups and are suitable for the preparation of reactive dyes of the formula I can also be obtained by tetrazotating an aromatic diamine containing two primary amino groups and coupling the tetrazo compound thus obtained with 2 molar proportions of a coupling component containing an -N (R) H- or -N (R> acyl group, for example one of the 10 indicated in list 5, or with 1 molar fraction each of two different such coupling components or with 1 molar fraction of such a coupling component and with 1 mole fraction of a coupling component which does not contain any -N (R) H- or -N (R> AcyI group, for example one of those given in list 4. Listed as examples of such aromatic diamines are:

List No. 6:

3,3'-dimethoxybenzidine, benzidine-2,2'-disulfonic acid, benzi- 20 1 ^. din-3,3'-dicarboxylic acid, benzidine-3,3'-diglycolic acid and 4,4'-diaminostilbene-2,2'-disulfonic acid.

Further disazo dyes suitable for the preparation of reactive dyes of the formula I and containing one or two -N (R) H groups can be obtained by adding either 2 molar proportions of a diazotizing agent bearing an N (R> acyl group) to a coupling component which can be coupled twice. ten amine, for example an acyl derivative of one of the amines ^ of list 2, or 1 molar portion of one of these diazotized amines j and 1 molar portion of a diazotized amine which does not carry an -N (R> acyl group, for example one of the amines of list 1,

couples and the dyes obtained then saponified.

If 2 molar parts of the amines carrying an -N (R) -acyl group are used, 2 molar parts of the same amine or 1 molar part of two different amines can be used.

Suitable coupling components which can be coupled twice are e.g. B. l-amino-8-naphthol-3,6- or 4,6-disulfonic acid, resor-cin or 5,5'-dihydroxy-7,7'-disulfo-2,2'-dinaphthylurea.

The dyes of the formula III can be obtained in a completely analogous manner to the production possibilities described above if, instead of the diazo or coupling components given in lists 2, 3 and 5, compounds are used which instead of the -N (R) H or -N (R) -acyl group contain a nitro group and the nitro group of the azo compounds composed of these 45 components is reduced to the amino group. The conditions for this reduction are known per se. A known reducing agent for this purpose is alkali sulfide, which reduces the nitro group in an aqueous medium at 40 to 70 ° C. without attacking the azo group. 50

Examples of the radicals F which are particularly valuable mono- and disazo dyes which are suitable for the preparation of dyes of the formula I are represented by the following formulas, the benzene and naphthalene nuclei according to those for D,

M and K given explanations may be substituted, 55 and the position of the rest of the formula purple is indicated by the open bond:

rv »-N.

30th

35

N »N

N-C-.CH «-

-2

N "N- | -j (CH3 or COOH)

N

N

60

65

00 "'O

622818

- N

O ^ 0

/

- n

Where

O-.-.

O

0

N - N -r- '

V * 1

Examples of diazo components from which particularly valuable monoazo dyes of the formula III can be prepared are: aniline-2-sulfonic acid; Aniline-2,5-disulfonic acid; 2-naphthylamine-l-sulfonic acid; 2-naphthylamine-1,5-disulfonic acid; 2-naphthylamine 4,8-disulfonic acid; 2-naphthylamine-3,6,8-trisulfonic acid; 2-naphthylamine 4,6,8-trisulfonic acid;

Examples of coupling components from which particularly valuable monoazo dyes can be produced are: l-amino-8-naphthol-3,6-disulfonic acid; l-amino-8-naphthol4,6-disulfonic acid; 2-amino-5-naphthol-7-sulfonic acid; 1- (4-amino-2-sulfophenyl) -3-carboxy-pyrazolone; 1- (5-amino-2-sulfophenyl) -3-carboxy-pyrazolone-5; Aniline; N-methylaniline; 3-aminotoluene; 3-amino-acetanilide; 3-aminophenylurea.

Examples of particularly valuable monoazo dyes of the formula III are:

OH NH,

wherein Di is the 2-sulfophenyl, l-sulfo-2-naphthyl or l, 5-disu! fo-2-naphthyl radical and the coupling component is substituted by a further sulfonic acid group in the 3- or 4-position. QJJ

where Di is the 2-sulfophenyl, the 2,5-disulfophenyl or the 1,5-disulfo-2-naphthyl radical, the coupling component has no 60 further substituents and R2 is hydrogen or

Methyl stands. D - N = N - COOH

O

65

622818

8th

wherein Dì is the 2-sulfophenyl or the l-sulfo-2-naphthyl radical and the amino group in the 2-sulfophenyl nucleus of the coupling component is in the 4- or 5-position.

D4 - N - N

NH

t

R "

where Ö4 is the 2,5-disulfophenyl, the 4,8-disulfo-2-naphthyl, the 3,6,8-trisulfo-2-naphthyl or the 4,6,8-trisulfo-2-naphthyl radical, the coupling component in the o-position to the azo group can be substituted by a methyl group, an acetamino group or the urea radical and R.2 is hydrogen or methyl.

Examples of individual dyes of the formula III in which F is a radical of a mono- or disazo dye are: 1- (3'-aminobenzoylamino) -8-hydroxy-7- (2'-sulfophenylazo) -naphthalene-3,6- disulfonic acid,

H4'-aminobenzoylamino) -8-hydroxy-7,2'-azonaphthalene-1 ', 3,5', 6-tetrasulfonic acid,

l-amino-8-hydroxy-7,2'-azonaphthalene-l ', 4,6-trisulfonic acid,

1- (aminoacetylamino) -8-hydroxy-7,2'-azonaphthalene-l ', 3,5'-6-tetrasulfonic acid,

2-methylamino-5-hydroxy-6,2'-azonaphthalene-l ', 5', 7-tri-sulfonic acid,

2-amino-8-hydroxy-7,2'-azonaphthalene-1 ', 6-disulfonic acid,

2-methylamino-8-hydroxy-7,2'-azonaphthalene-1 ', 6,5'-trisulfone

acid,

2-amino-5-hydroxy-6- <2 /, 5'-disulfophenylazo) -naphthalene-7-sulfonic acid,

2-methylamino-5-hydroxy-6- {4'-methoxy-2'-sulfophenylazo) -naphthalene-7-sulfonic acid,

1-amino-8-hydroxy-7 - (2 '-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

1-amino-8-hydroxy-7- (4'-chloro-2'-sulfophenylazo> naphthalene-4,6-disulfonic acid,

2- (4'-amino-2'-methylphenylazo) naphthalene 4,8-disulfonic acid, 2- (4'-amino-2'-methylphenylazo) naphthalene 4,6,8-trisulfonic acid,

2- {4'-amino-2'-acetylaminophenylazo) -naphthalene-5,7-disulfonic acid,

2- (4'-amino-2'-acetylaminophenylazo) naphthalene-3,6,8-trisulfonic acid,

4-nitro4 '- (4 "-methylaminophenylazo) -stilbene-2,2'-disulfonic acid,

4-nitro4 '- (4 "-amino-2" -methyl-5 "-methoxy-phenylazo) -stilbene-2,2'-disulfonic acid,

H2 ', 5'-dichloro4'-sulfophenyl) -3-methyl4- {3 "-amino-6" -sulfophenylazo) -5-pyrazolone,

l- {4'-Sulfophenyl) -3-carboxy4- {4 "amino-2" sulfophenylazo>

5-pyrazolone,

l- (2'-methylphenyl) -3-methyl4- {4 "-amino-2", 5 "-disulfo-phenylazo) -5-pyrazolone,

1- (2'-sulfophenyl) -3-methyl4- (3 "-amino-6" -sulfophenylazo) -5-pyrazolone,

2- <3 '-sulfophenylamino) -5-hydroxy-6- <4'-amino-2' -sulfo-phenylazo> naphthalene-7-sulfonic acid, l- (3'-aminophenyl) -3-methyl-4- ( 2 ", 5" -disulfophenylazo) -5-pyrazolone,

l- <3'-amino-6'-sulfophenyl) -3-carboxy4- (2'-sulfophenylazo) -5-pyrazolone,

I- (4'-amino-2'-sulfophenyl-3-carboxy4- (2'-sulfophenylazo> 5-pyrazolone,

H4'-amino-2'-sulfophenyl> 3-carboxy4- [4 "- (2" ', 5 "' disulfo-phenylazo> 2" -methoxy-5 "-methylphenylazo] -5-pyrazolone, the copper complex of 1 -Amino-8-hydroxy-7- (2'-hydroxy-5 '-sulfophenylazo> naphthalene-3,6-disulfonic acid,

the copper complex of 2-amino-5-hydroxy-6- (2'-hydroxy-3'-sulfo-5'-nitrophenylazo) -naphthalene-7-sulfonic acid, the copper complex of 2-amino-5-hydroxy-6- ( 2'-hydroxy-5'-sulfophenylazo> -naphthalene-l, 7-disulfonic acid, 5 the copper complex of l-amino-8-hydroxy-7- (2'-hydroxy-3'-chloro-5 '-sulfophenylazo> naphthalene -3,6-disulfonic acid, the copper complex of 2-methylamino-5-hydroxy-6- (2'-car-boxy-5'-sulfophenylazo) -naphthalene-7-sulfonic acid, 4,4'-bisn (l "- amino-8 "-hydroxy-3", 6 "-disulfo-7" -naphthylazo> 10 3,3'-dimethoxydiphenyl,

2-amino-5-hydroxy-6- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene-l, 7-disulfonic acid, l-amino-8-hydroxy-2- (2 ', 5'-disulfophenylazo) -7- (3'-amino - 6'-sulfophenylazo> naphthalene-3,6-disulfonic acid,

i s the copper complex of l-amino-8-hydroxy-7- [4 '- (2 "-sulfo-phenylazo) -2'-hydroxy-5'-methylphenylazo] -naphthalene-3,6-disulfonic acid,

the copper complex of 2-amino-5-hydroxy-6- {4 '- (2 ", 5" -disulfo-

20 phenylazo) -2'-hydroxy-5'-methylphenylazo] naphthalene-7-sulfonic acid,

the copper complex of l- (4'-amino-2'-sulfophenyl) -3-carboxy4- [4 "- (2" ', 5 "' disulfophenylazo) -2" -hydroxy-5 "-methylphenylazo] -5- pyrazolone,

25 the copper complex of 2- (4'-amino-3'-sulfoanilino) -5-hydroxy-

6 ^ 2 "-carboxyphenylazo) -naphthalene-7-sulfonic acid, the 2: 1 chromium complex of 2-amino-6'-nitro-8,2-dihydroxy-7,1 '-azonaphthalene-6,4'-disulfonic acid, 30 of the 2: 1 chromium complex of 2-amino-5-hydroxy-6- (2'-carboxy-phenylazo> naphthalene-7-sulfonic acid,

the 2: l chromium complex of l-amino-8-hydroxy-7- (4'-nitro-2'-hydroxyphenylazo) naphthalene-3,6-disulfonic acid, the 2: l cobalt complex of 2- (4'- Amino-3'-sulfoanilino) -5-, 5 hydroxy-6 <5 "-chloro-2" -hydroxyphenylazo) -naphthalene-7-sulfonic acid,

the copper complex of 2-amino-6'-nitro-2 ', 8-dihydroxy-l', 7-azonaphthalene4 ', 6-disulfonic acid,

the copper complex of 1,6'-diamino-2 ', 8-dihydroxy-l' 7-40 azonaphthalene-2,4,4'-trisulfonic acid,

the copper complex of 6'-amino-l ', 2-dihydroxy-l, 2'-azonaphthalin-3,4', 6,8'-tetrasulfonic acid,

the copper complex of 1-amino-1 ', 8-dihydroxy-2', 7-azonaphthalene-3,4 ', 6,8' -tetrasulfonic acid.

45

Another way of producing mono- or disazo dyes or, where appropriate, their metal complexes of the formula V

50

55

(V)

in which F is a radical of one of the formulas Via to VIc given above and X and X 'have the meanings given above, consists in the fact that diazo and coupling components, 60 of which one, but optionally also both, are a group of the formula Va

(Va)

9

622818

contain, produced directly and then, as described above, reacted with an amine of the formula IIa.

The starting materials required for this can be obtained by reacting diazo or coupling components which contain a radical of the formula -N (R) H with acylating agents of the formula IV.

Diazo components for the direct preparation of azo dyes of the formula V, in which F is a radical of the formula VIb or VIc, are, for example, by acylation of the -N (R) H group of an aromatic amine listed in List 2 with an acylating agent of the formula Get IV.

Coupling components for the direct production of azo dyes of the formula V, in which F is a radical of the formula Via or VIc, are, for example, by acylation of the -N (R) H group of a coupling component mentioned in list 5 with an acylating agent of the formula IV to obtain.

Examples of complex-forming metals which may be present in residues of metal-containing mono- or disazo dyes are chromium, manganese, cobalt, nickel and copper. Copper, chromium and cobalt are preferred.

Another important group of dyes of the formula III are those in which F is the residue of a derivative of 1-amino or 1-anilinoanthraquinone, in particular the residue of a 4-phenylamino-1-amino-anthraquinone-2-sulfonic acid derivative. Suitable aminoanthraquinones contain, for example, 2 to 3, preferably 2, amino groups, which can also be substituted by alkyl or aryl.

Alkyl radicals have in particular 1 to 4, preferably 1-2 carbon atoms, and phenyl is preferred as the aryl radical. The aminoanthraquinone derivatives can contain 1 or 2 sulfonic acid groups directly in the anthraquinone nucleus and one or two sulfonic acid groups in any aromatic substituents of the anthraquinone nucleus which may be present. The group

HgN-Ph-N-H R

5 or its monoacyl derivative

H „N-Ph-N-Acyl ß

io with an anthraquinone derivative that contains a reactive substituent, for example a Br atom, in the 4-position. Acyl has the meanings given above, in particular those characterized as preferred.

Suitable diamines of the formula

15 HgN-Ph-N-H,

R

which can also be used in the form of their acyl derivatives,

20 are, for example: 2,4-diaminobenzenesulfonic acid, 2,4-diamino-notoluene-6-sulfonic acid, 2,6-diaminotoluene-4-sulfonic acid, 3,5-diamino-2,4,6-trimethylbenzoI-sulfonic acid, p- Phenylenediamine, 2,5-diaminobenzene sulfonic acid, 2,4-diaminobenzene carboxylic acid.

25 Examples of dyes of the formula III in which F is the residue of a 1-amino-anthraquinone are 1-amino-4- (3 '-amino-4' -sulfoanilino) -anthraquinone-2-sulfonic acid,

l-amino-4- {3-amino-2 ', 4', 6'-trimethyl-4'-sulfoanilino) anthra-

30 quinone-2-sulfonic acid,

l-amino-4- (4'-amino-3'-sulfoanilino) anthraquinone-2,5-disulfonic acid,

l-Amino-5,8-bis (4'-methyl-2'-sulfoanilino) anthraquinone Another important group of dyes of the formula

35 III are, for example, those in which F represents the remainder of a sulphophthalocyanine dye, in particular a derivative of phthalocyanine sulphanilide or sulphalkyl amide with 2-6 C atoms in the alkyl chain which contains at least 2 sulphonic acid groups in the phthalocyanine nucleus.

40 A preferred group of phthalocyanine dyes of the formula III are those in which F represents a radical of the formula VIII,

can be bound directly to the anthraquinone nucleus, but preferably to a substituent of the anthraquinone nucleus.

In a preferred group of anthraquinone dyes of the formula I which can be prepared according to the invention, F represents a radical of the formula VII

(VII)

Pc

(S ° 3w) k

in which the anthraquinone nucleus can be substituted by a further sulfonic acid group. Ph stands for a phenyl radical which carries a radical of the formula purple. The phenyl radical Z can be substituted by a sulfonic acid or carboxylic acid group, so that the dye contains at least two groups which make it highly water-soluble. The phenyl radical can further be substituted by an alkoxy group having 1-3 C atoms, by a halogen atom or by 1-3 alkyl groups having 1-3 C atoms.

The preferred anthraquinone dyes of the formula III, in which F is a radical of the formula VII, are, for. B. prepared by condensation of a diamine of the formula

(S02-N-B-)

B '

where Pc is the remainder of a metal-containing or metal-free phthalocyanine nucleus, preferably copper or nickel phthalocyanine, W -OH and / or -NR 'R ", where R' and R" independently of one another are hydrogen or alkyl with 1-4 C- Atoms are, k is the number 2 or 3, p is the number 1 or 2 and B is a phenyl radical which is optionally substituted by halogen, 1-3 alkyl groups having 1-2 55 carbon atoms or by one or two sulfonic acid or carboxylic acid groups or an alkyl radical 2-6 C atoms mean.

The phenyl radical substituted by 1 sulfonic acid group or the rest of the ethylene is preferred. 60 The dyes of the formula III, in which F represents a radical of the formula VIII, can be prepared in a manner known per se by condensation of a sulfochloride of the formula

: so0w),

Pc

> o2cl) p

622818

10th

wherein Pc, W and k have the meanings given above, with a diamine of the formula HN (R ') - BN (R) H or its monoacyl derivative HN (R') - BN (R) -AcyI, wherein acyl has the abovementioned meanings , in particular which has been characterized as preferred, can be produced.

Examples of diamines of the formula HN (R ') - BN (R) H which are suitable for the preparation of the preferred phthalocyanine dyes of the formula III are: m-phenylenediamine, p-phenylenediamine, 2,4-diaminobenzenesulfonic acid, 2,5- Diaminobenzenesulphonic acid, 2,5-diaminobenzene carboxylic acid, 2,5-diaminobenzene-1,4-disulfonic acid, 2,4-diaminotoluene-6-sulfonic acid, ethylenediamine, hexamethylenediamine.

Examples of dyes of the formula III in which F is the radical of an N-substituted phthalocyanine sulfonamide are 3- [N- (3-amino-4-sulfophenyl) sulfamyl] copper phthalocyanine-3 ', 3 ", 3'" - trisulfonic acid,

Bis-4,4 '- [N-3-amino-4-sulfophenyl) sulfamyl] copper phthalocya-nin-4 ", 4" disulfonic acid,

3- [N- (4-amino-3-sulfophenyl) sulfamyl] nickel phthalocyanine-3 ', 3 ", 3"' trisulfonic acid,

3- [N- <3-aminophenyl) -sulfamyl] -3'-sulfamyl-copper phthalocyanon-3 ", 3" '- disulfonic acid,

3- {N-ß-Aminoethyl-sulf amyl> copper phthalocyanine-3 ', 3 ", 3"' -trisulfonic acid.

The reactive dyes of formula I are ideally suited for dyeing and printing cellulose and cellulose-containing materials. They stand out particularly at Druck10

15

25th

proceed through a uniformly high fixation yield regardless of the type of fixation, e.g. B. with fixation by steaming or dry heat or one or two-phase process. Very good results are also obtained with the various dyeing processes, e.g. B. in pull-out or block-docking process or block-heat-setting process. The dyeings and prints obtained are of high brilliance and color strength with very good light fastness properties, even when wet, very good wet fastness properties, such as washing at 60 ° C and 95 ° C, as well as good usage fastness properties, such as seawater fastness, sweat fastness acidic and alkaline, chlorine bathing water fastness, peroxide fastness and exhaust gas fastness. Furthermore, the dyes are not sensitive to atmospheric influences.

Very good results are also obtained when using reactive dyeing processes on polyamides, especially wool. In addition to very good light fastness, the excellent wash and sweat fastness are particularly noteworthy as well as the excellent build-up ability.

The temperatures given in the following examples relate to ° C., parts are parts by weight and percentages by weight.

Example 1:

18.5 parts of cyanuric chloride are dissolved in 110 parts of acetone and added to 250 parts of ice with vigorous stirring. A solution of 55.3 parts of the dye of the following constitution is left to do so

30th

so3H

40

Add at 0 °. 50 parts of 2-normal sodium carbonate solution are then added dropwise, giving a pH of 6-6.5. 36.3 parts of bis [ß- (ß-chloroethylsulfonyl) ethyljamine hydrochloride are then added as a powder. The mixture is heated to 40 ° in the hour and held at this temperature for 3 hours. At the same time, 100 parts of 2-normal soda solution in one

45

pH of 4.0-4.5 added dropwise For separation, 25% potassium chloride is added, the mixture is allowed to cool to 20-25 ° with stirring and filtered. About 235 parts of dye paste are obtained, which are dried at 60-65 ° in vacuo. The reactive dye produced has the following constitution:

2nd

The dye 1 amino-8-hydroxy-2 '> 7-60 azonaphthalene-1', 3,5 ', 6-tetrasulfonic acid used above can be obtained as follows: 60.6 parts of 2-naphthylamine-1,5-disulfonic acid with 300 parts of water and about 20 ml of 10 normal sodium hydroxide solution with heating to 60 ° at pH 7-8. In addition there is a solution of 14 parts of sodium nitrite in 60 parts of 65 water. This 60 ° warm mixture is allowed to run to a mixture of 50 parts of 10 normal hydrochloric acid and 500 parts of ice, a temperature of 0-5 ° being to be maintained during the diazotization. The mixture is stirred for an hour and the excess nitrous acid present is destroyed by adding aminosulfonic acid. The diazo compound is a slightly yellowish precipitate. This suspension is allowed to run in at 0-5 ° to 72.2 parts of l-acetamino-8-naphthol-3,6-disulfonic acid, which were neutral in 500 parts of water, 200 parts of ice and 17 parts of sodium hydrogen carbonate. The coupling is completed at a pH of 7. After adding 60 parts 10 normal

11

622818

25th

Sodium hydroxide solution is heated to 70 ° for 3 hours, which saponifies the acetyl group. To separate the saponified dye, the dye solution is mixed with 10% potassium chloride and 15% sodium chloride, neutralized with 22 parts of 10 normal hydrochloric acid, cooled to 20-25 °, filtered and washed with 5600 parts of salt water (density 1.142). If the 2-naphthylamine-1,5-disulfonic acid is replaced by molar amounts of one of the diazo components mentioned below and the procedure is otherwise as described, valuable dyes according to the invention are also obtained: 10

3-amino-benzenesulfonic acid

4-amino-benzenesulfonic acid

5-chloro-2-amino-benzenesulfonic acid

6-chloro-2-amino-benzenesulfonic acid

5-nitro-2-amino-benzenesulfonic acid 15 4-chloro-3-amino-benzenesulfonic acid

6-chloro-3-aminobenzenesulfonic acid 3-chloro-4-aminobenzenesulfonic acid 2-aminotoluene-4-sulfonic acid

2-aminotoluene-5-sulfonic acid 20

3-aminotoluene-6-sulfonic acid

4-aminotoluene-2-sulfonic acid

4-aminotoluene-3-sulfonic acid

5-chloro-2-aminotoluene-3-sulfonic acid

3-chloro-2-aminotoluene-5-sulfonic acid

6-chloro-3-aminotoluene-4-sulfonic acid 2-chloro-4-aminotoluene-5-sulfonic acid

2-chloro-4-aminotoluene-6-sulfonic acid

4-nitro-2-aminotoluene-6-sulfonic acid 6-nitro-4-aminotoluene-2-sulfonic acid

3-amino-1,2-dimethyl-benzene-4-sulfonic acid

4-amino-1,3-dimethyl-benzene-5-sulfonic acid 4-amino-1,3-dimethyl-benzene-6-sulfonic acid 2-amino-anisole-4-sulfonic acid 4-amino-anisole-2-sulfonic acid 4-amino- anisole-3-sulfonic acid 4-chloro-2-amino-anisole-5-sulfonic acid 4-amino-phenetol-2-sulfonic acid 4-amino-phenetol-3-sulfonic acid 2-amino-phenetol4-sulfonic acid 4-amino-benzene-l , 3-disulfonic acid 2-amino-benzene-l, 4-disulfonic acid 2-amino-toluene-3,4-disulfonic acid 2-amino-toluene-3,5-disulfonic acid aniline

4-aminotoluene 4-amino-anisole 4-amino-chlorobenzo 2-aminobenzene-sulfonic acid 2-naphthylamine-l-sulfonic acid 2-naphthylamine-5-sulfonic acid 2-naphthylamine-6-sulfonic acid 2-naphthylamine-7-sulfonic acid 2- Naphthylamine-8-sulfonic acid 2-naphthylamine-1, 7-disulfonic acid 2-naphthylamine-3,6-disulfonic acid 2-naphthylamine-3,7-disulfonic acid 2-naphthylamine4,7-disulfonic acid 2-naphthylamine4,8-disulfonic acid 2-naphthylamine -5,7-disulfonic acid 2-naphthylamine-6,8-disulfonic acid 2-naphthylamine-l, 5,7-trisulfonic acid 2-naphthylamine-3,6,8-trisulfonic acid 2-naphthylamine4,6,8-trisulfonic acid l-naphthylamine4- sulfonic acid 1 -N aphthylamine-5-sulfonic acid l-naphthylamine-6-sulfonic acid 1 -naphthylamine-7-sulfonic acid l-naphthylamine-3,6-disulfonic acid l-naphthylamine-3,7-disulfonic acid l-naphthylamine-3,8-disulfonic acid l-Naphthylamine4,6-disulfonic acid 1 -N aphthylamine4.7-disulfonic acid l-naphthylamine4,8-disulfonic acid l-naphthylamine-5,7-disulfonic acid l-naphthylamine-6,8-disulfonic acid 1 -N aphthylamine-2,4,6 -trisulfonic acid 1 -N aphthylamine-3,6, 8-trisulfonic acid l-naphthylamine 4,6,8-trisulfonic acid

If the l-acetamino-8-naphthol-3,6-disulfonic acid used as coupling component for the preparation of the starting dye is replaced by molar amounts of the acetyl compound of one of the coupling components mentioned below and the procedure is as described above, valuable dyes of the formula are also obtained I:

1-amino-8-naphthol4,6-disulfonic acid

2-amino-8-naphthol-6-sulfonic acid 2-methylamino-8-naphthol-6-sulfonic acid 2-carboxymethylamino-8-naphthol-6-sulfonic acid 2-ß-sulfoethylamino-8-naphtol-6-sulfonic acid 2-iso- Propylamino-8-naphthol-6-sulfonic acid 2-amino-5-naphthol-7-sulfonic acid 2-methylamino-5-naphtol-7-sulfonic acid 2-ethylamino-5-naphthol-7-sulfonic acid 2-n-butylamino-5- naphthol-7-sulfonic acid

1-amino-8-naphthol-4-sulfonic acid

2-amino-8-naphthol4-sulfonic acid 2-amino-8-naphthol-3,6-sulfonic acid

Preparation of bis [ß- (ß-chloroethylsulfonyl) ethyl] amine: 156 parts of ß-hydroxyethyl mercaptan and then 178.5 parts of hydrochloric bis (ß-chloroethyl) amine are added to a solution of 69 parts of sodium in 1200 parts by volume of ethyl alcohol (J. former Soc. 1934,464), the temperature rising to 40-50 ° C. The mixture is then heated to 78 ° for 1 hour, cooled, the precipitated sodium chloride is filtered off and the ethyl alcohol is distilled off. The residue is taken up in 1000 parts by volume of water and adjusted to pH 3 with about 90 parts by volume of 37% hydrochloric acid. Then 295 parts of chlorine are introduced within 90 minutes. The precipitated hydrochloride is filtered off and washed with ice water. It can be recrystallized from water. Mp 205 °.

45

Analysis:

calc .: C26.5%; H 5.0%; Cl 29.3%; N3.9%; S 17.7% found: C 26.6%; H 5.2%; Cl 29.4%; N4, 1%; S 18.3;

If the hydrochloride is stirred with sulfuric acid at room temperature and is poured onto ice, the neutral sulfate is obtained. Mp 150-152 °.

55

60

Analysis: calculated: Cl 18.9%; found: Cl 18.9%;

N 3.7%; N 3.8%;

SO «12.8% SO« 13.0%

Example 2:

42.3 parts of the dye 2-amino-5-hydroxy-6- (2-sulfophe-nylazo) -naphthalene-7-sulfonic acid are, as described in Example 1, with 18.5 parts of cyanuric chloride and 36.3 parts of bis- (ß-Chloroethyl-sulfonyl-ethyl) amine hydrochloride implemented. To separate the dye, the neutral solution is mixed with 20% sodium chloride and 10% potassium chloride and filtered. The paste obtained is dried in vacuo at 50-70 °. The reactive dye thus produced has the following constitution:

622818

12

SOoH 0H Cl

• I I

V = / Hn3S QQ-NH _ ^ X-N (CH2CH2S02CH2CH2C1) 2

The starting dye 2-amino-5-hydroxy-6- <2-sulfophenylazo) -naphthalene-7-iosulfonic acid required for the preparation of the dye can be obtained as follows: 34.4 parts of 2-amino-benzenesulfonic acid are in 120 parts Dissolved water neutral and diazotized as usual. The diazo compound is then run in at 0-5 ° to a mixture of 56.2 parts of 2-acetamino-5-naphthol-7-sulfonic acid, which have been dissolved in 300 parts of water, 25 parts of sodium hydrogen carbonate and 150 parts of ice . The pH is initially 6.5 and increases to 7.5-7.8 after long stirring. After the coupling has ended, 60 parts of 10 normal sodium hydroxide solution are added and the mixture is heated at 90 ° for 2 hours to saponify the acetamino group. The alkaline solution of the orange intermediate dye is neutralized with about 22 parts of 10 normal hydrochloric acid, mixed with 20% sodium chloride and 15% potassium chloride, stirred for some time and filtered.

If the 2-amino-benzenesulfonic acid is replaced by molar 25 amounts of one of the diazo components mentioned below and the procedure is otherwise as described, valuable dyes of the formula I are also obtained:

3-amino-benzenesulfonic acid

4-amino-benzenesulfonic acid 30

2-naphthylamine-1,5-disulfonic acid

5-chloro-2-amino-benzenesulfonic acid

6-chloro-2-amino-benzenesulfonic acid

5-nitro-2-amino-benzenesulfonic acid

4-chloro-3-aminobenzenesulfonic acid 35

6-chloro-3-amino-benzenesulfonic acid

3-chloro-4-amino-benzenesulfonic acid 2-aminotoluene-4-sulfonic acid

2-aminotoluene-5-sulfonic acid

3-aminotoluene-6-sulfonic acid 40

4-aminotoluene-2-sulfonic acid

4-aminotoluene-3-sulfonic acid

5-chloro-2-aminotoluene-3-sulfonic acid

3-chloro-2-aminotoluene-5-sulfonic acid

6-chloro-3-aminotoluene-4-sulfonic acid 45 2-chloro-4-aminotoluene-5-sulfonic acid

2-chloro-4-aminotoluene-6-sulfonic acid

4-nitro-2-aminotoluene-6-sulfonic acid 6-nitro-4-aminotoluene-2-sulfonic acid

3-amino-1,2-dimethyl-benzene-4-sulfonic acid 50

4-amino-1,3-dimethyl-benzene-5-sulfonic acid 4-amino-1,3-dimethyl-benzene-6-sulfonic acid 2-amino-anisole-4-sulfonic acid 4-amino-anisoI-2-sulfonic acid

4-amino-anisole-3-sulfonic acid 55

4-chloro-2-amino-anisole-5-sulfonic acid

4-aminophenetol-2-sulfonic acid

4-aminophenetol-3-sulfonic acid

2-aminophenetol4-sulfonic acid

4-amino-benzene-1,3-disulfonic acid 60

2-amino-benzene-1,4-disulfonic acid

2-aminotoluene-3,4-disulfonic acid

2-aminotoluene-3,5-disulfonic acid

aniline

4-aminotoluene 65

8-amino anisole

4-amino-chlorobenzene

2-amino-chlorobenzene

2-naphthylamine-l-sulfonic acid 2-naphthylamine-5-sulfonic acid 2-naphthylamine-6-sulfonic acid 2-naphthylamine-7-sulfonic acid 2-naphthylamine-8-sulfonic acid 2-naphthylamine-l, 7-disulfonic acid 2-naphthylamine- 3,6-disulfonic acid 2-naphthylamine-3,7-disulfonic acid 2-naphthylamine 4,7-disulfonic acid 2-naphthylamine-5,7-disulfonic acid 2-naphthylamine-6,8-disulfonic acid 2-naphthylamine-l, 5,7-trisulfonic acid 2-Naphtylamine-3,6,8-trisulfonic acid 2-Naphtylamine4,6,8-trisulfonic acid

If the 2-acetamino-5-naphthol-7-sulfonic acid used as the coupling component for the preparation of the starting dye is replaced by molar amounts of the acetyl compound of one of the coupling components mentioned below and the procedure is otherwise as described above, valuable dyes of the formula I are also obtained:

1-amino-8-naphthol4,6-disulfonic acid

2-amino-8-naphthol-6-sulfonic acid 2-methylamino-8-naphthol-6-sulfonic acid 2-carboxymethylamino-8-naphthol-6-sulfonic acid 2-ß-sulfoethylamino-8-naphthol-6-sulfonic acid 2-iso- Propylamino-8-naphthol-6-sulfonic acid

1-amino-8-naphthol-3,5-sulfonic acid

2-methylamino-5-naphthol-7-sulfonic acid 2-ethylamino-5-naphthol-7-sulfonic acid 2-n-butylamino-5-naphthol-7-sulfonic acid

1-amino-8-naphthol-4-sulfonic acid

2-amino-8-naphthol-4-sulfonic acid 2-amino-5-naphthol4,7-disulfonic acid

Example 3:

In Example 1, the 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl> ethyl} amine hydrochloride are replaced by 37.6 g of the corresponding sulfate or by a molar amount of the hydrochloride of one of the following Amines, this is how you get valuable dyes of formula I:

ß <ß-chloroethyl-sulfonyl) ethyl amine,

ß- (ß-bromoethyl-sulfonyl> ethyl-amine,

ß-vinylsulfonyl-ethyl-amine,

y- (ß-chloroethylsulfonyl) propyl amine,

a- (ß-chloroethyl-sulfonyl-isopropyl-amine,

8- (ß-chloroethyl-sulfonyl} -butyl-amine,

ß- (ß-chloroethyl-sulfonyl) -isobutyl-amine,

e- (ß-chloroethyl-sulfonyl) -pentyl-amine,

ß- (ß-chloroethyl-sulfonyl) -hexyl-amine,

N-methyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-ethyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-propyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-butyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-pentyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-hexyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-nonyl-N-ß- (ß-chloroethylsulfonyl) -ethyI-amine,

N-dodecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-hexadecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-octadecyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

13

622818

N-carboxymethyl-N-ß- (ß-bromethyl-sulfonyl> ethyl-amine,

N-sulfatomethyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-ß-carboxyethyl-N-y- (ß-chloroethyl-sulfonyl) propyl amine,

N-ß-SuifatoäthyI-N-y- (ß-CIiloräthyl-suIfonyl) -propyl-amine,

N-ß-sulfatoethyl-N- 5- (ß-chloroethyl-sulfonyl) butylamine, 5

N-ß-ethoxyethyl-N-5- (ß-chloroethyl-sulfonyl) -butyl amine,

N-y-chloropropyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-phenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-p-chlorophenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyI-aniine,

N-o-Methylphenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine, ok

N-p-methoxyphenyl-N-ß- (ß-chloroethyl-sulfonyl) -ethyl-amine,

N-m-sulfophenyl-N-ß- {ß-chloroethyl-sulfonyl) -ethyl-amine,

N-p-sulfophenyl-N-ß- (ß-chloroethyl-sulfonyl) ethyl amine,

Bis- [ß- (ß-chloro-sulfonyl) -ethyl] amine,

Bis- {ß- (ß-bromethylsulfonyl) ethyl] amine, »s

Bis- [y- (ß-chloroethylsulfonyl) propyl] amine, bis {8- (ß-chloroethylsulfonyl) butyl] amine, bis- {ß-vinylsulfonyl-ethyl) amine.

Example 4: 20

Replacing the 18.5 parts of cyanuric chloride in Example 2 with the molar amount of one of the derivatives of 1,3,5-triazine mentioned below also gives valuable dyes of the formula I:

Tribromotriazine, 25

Trifluorotriazine,

Trisulfotriazine,

Tris-methylsulfonyltriazine,

Tris-ethylsulfonyltriazine,

Tris-phenylsulfonyltriazine, 30

Dichlorofluorotriazine,

Chloro-disulfotriazine,

Chloro-bis-methylsulfonyltriazine.

Example 5:

76.6 parts of 2-naphthylamine-4,6,8-trisulfonic acid are dissolved neutral with 250 parts of water. In addition there are 50 parts of 4-normal sodium nitrite solution. This mixture runs to a mixture of 50 parts of 10 normal hydrochloric acid and 400 parts of ice. A solution of 21.4 parts of 3-toluidine in 100 parts of water and 20 parts of 10 normal hydrochloric acid is added to the suspension of the diazo compound at 0-5 °. 150 parts of 4-normal sodium acetate solution are first blunted to a pH of 3.5 and then brought to a pH of 5.5 with sodium hydroxide solution. When the coupling is complete, filter.

50.1 parts of the dye thus prepared 2- (4-amino-2-methylphenylazo> naphthalene 4,6,8-trisulfonic acid are dissolved neutral with 250 parts of water. This neutral solution is added to a suspension prepared as in Example 1 of cyanuric chloride in acetone and water. The temperature is kept at -1 to 3 ° by cooling with ice. In the course of the acylation reaction, 9 g of bicarbonate are introduced in such a way that the pH remains between 5.5 and 7. If none Starting dye is more detectable in the chromatogram, 36.3 g of bis [ß <ß-chloroethylsulfonyl> ethyl] amine hydrochloride are added in the form of an approximately 50% paste and heated to 50 ° by adding a further 18 g bicarbonate, the pH is kept in the range of 4.5-6.0. The reaction is complete when no more alkali is used. The resulting dye of the formula:

N - \ ZyNH T ^ y N (CH2CH2SQ2CH2CH2C1) 2

CEU

V

Cl is separated by adding sodium chloride and dried in vacuo at 50-75 °.

Similar valuable reactive dyes are also obtained if instead of the starting dye used above 2- (4-amino-2-methyl-phenyl-azo) -naphthalene-4,6,8-trisulfonic acid, the 50 from the diazo- listed in the table below and coupling components available azo dyes and otherwise operates as described above.

Diazo components: 55

2-N-aphthylamine-1,5-disulfonic acid 2-naphthylamine-4,8-disulfonic acid 2-naphthylamine-5,7-disulfonic acid 2-naphthylamine-6,8-disulfonic acid

2-naphthylamine-l, 5,7-trisulfonic acid eo

2-naphthylamine-3,6,8-trisulfonic acid aniline-2,5-disulfonic acid

Coupling components:

Aniline 65

N-methylaniline

3-amino-toluene 3-amino-anisole

2-amino4-acetaminotoluene

2-amino4-acetamino-anisole

3-amino-acetanilide 3-amino4-methoxy-toluene 3-amino-phenylurea l-naphthylamine-6-sulfonic acid l-naphthylamine-7-sulfonic acid l-naphthylamine-8-sulfonic acid

Example 6:

63.1 parts of l- [2'-sulfo-4- (3,5-dichlorotriazinylamino) phenyl] -3-carboxy4- (2-sulfophenylazo) pyrazolone-5 are dissolved in water at pH 6.8-7 , 2 dissolved 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) ethyl] amine are added to this solution at about 25 ° and heated to 35-40 °. The pH begins to drop. When it has reached a value of about 3.5, it is kept in a range of 3.5-4.5 by adding about 11 g of soda in portions. The reaction is complete after about 3 hours, which can be seen from the fact that no further alkali is consumed. The dye solution is now adjusted to pH 7.0 by adding dinatrium hydrogen phosphate. The dye of constitution obtained

622818

14

NCCHnCHpSOgCHoCHrtCl)

h -2-2-2.2.2-2

il can be isolated by salting out or spray drying.

Preparation of the starting dye: 20

49.7 parts of diazotized l-amino-benzene-2-sulfonic acid and l- {4-amino-2-sulfo-phenyl) -5-pyrazolone-3-carbon acid according to DE-AS 1 922 940, Example 2, the yellow azo dye obtained are dissolved neutral and reacted at 0-5 ° with a slurry of 25 18.5 parts of cyanuric chloride prepared according to Example 1 in water / acetone at pH 6.5. To maintain the pH range, approx. 6 parts of soda are added. The reaction is complete when the dye is no longer diazo-animal

Similar valuable reactive dyestuffs of the formula I are obtained if, instead of the intermediate dyestuff used above, the condensation products of the azo dyestuffs obtainable from the diazo and coupling components given in the table below are used with cyanuric chloride and the procedure is otherwise as described above

Diazo components:

3-amino-benzenesulfonic acid

4-amino-benzenesulfonic acid

5-chloro-2-amino-benzenesulfonic acid 2,5-dichloro-4-amino-benzenesulfonic acid 2-aminotoluene-4-sulfonic acid 4-aminotoluene-3-sulfonic acid 2-amino-anisole-4- sulfonic acid 4-amino-benzene-1,3-disulfonic acid 2-amino-benzene-1,4-disulfonic acid 2-amino-toluene-3,5-disulfonic acid

35

40

45

2-amino-naphthalene-1,5-disulfonic acid

2-amino-naphthalene-4,8-disulfonic acid

2-amino-naphthalene-6,8-disulfonic acid

2-amino-naphthalene-1-sulfonic acid

2-amino-naphthalene-6-sulfonic acid

Coupling components:

1- (3-amino-6-sulfophenyl) -3-methyl-5-pyrazolone 1- (4-amino-3-sulfophenyl) -3-methyl-5-pyrazolone 1- (4-amino-2 -sulfo-phenyl) -3-methyl-5-pyrazolone

H3-amino-6-sulfo-phenyl> 5-pyrazolone-3-carboxylic acid 1- (4-amino-3-sulfo-phenyl) -5-pyrazolone-3-carboxylic acid 1- (3-amino-5-sulfo-6 -methyl-phenyl) -5-pyrazolone-3-carboxylic acid 1- (2-methyl-3-amino-5-sulfo-phenyl> 5-pyrazolone-3-carboxylic acid

H2-methyl-3-amino-5-sulfophenyl) -3-methyl-5-pyrazolone l- (3-amino-5-sulfo-6-methylphenyl) -3-methyl-5-pyrazolone l- { 4-amino-2,5-disulfophenyl) -5-pyrazolone-3-carboxylic acid

Example 7:

50.3 parts of the monoazo dye 1 <5'-amino-2'-sulfo-phenyl-azo) -2-naphthol-6,8-disulfonic acid are first at 0-5 ° and at a pH of 6-6, 5 with a slurry of 18.5 parts of cyanuric chloride, which were prepared by dissolving the cyanuric chloride in 100 parts of acetone and precipitating with 250 g of ice, and then at 30-40 ° and at a pH of 4.0-4.5 implemented with 36.3 parts of bis ^ ßKß-chloroethyl-sulfonyl) ethyl] amine hydrochloride. The orange reactive dye of the formula obtained

(ci-ch2-ch2-so2-ch2-ch2) 2 n

OH

is concentrated from the neutral solution in vacuo at 55-60 ° to the dry or separated with sodium chloride, filtered and dried in vacuo.

The starting dye l- <5-Amino-2-sulfo-phenyl-azo> 2-naphthol-6,8-disulfonic acid is obtained by coupling dia-65-quoted 2-amino-4-acetamino-benzenesulfonic acid with 2-naphth -thol-6,8-disulfonic acid and subsequent saponification of the acetyl group with sodium hydroxide solution or hydrochloric acid.

SO3H

Similar valuable reactive dyestuffs of the formula I are obtained if one starts from those amino group-containing monoazo dyestuffs which can be prepared from the diazo and coupling components below with subsequent saponification of the acetyl group or reduction of the nitro group, and otherwise proceed according to the information given above.

15

622818

Diazo components:

2-amino-5-acetamino-benzenesulfonic acid

2-amino-4-acetamino-toluene-5-sulfonic acid

2-amino-4-acetamino-toluene-6-sulfonic acid

2-amino-6-acetamino-toluoI-4-sulfonic acid

5-nitro-2-aminobenzenesulfonic acid

6-Acetamino-2-aminonaphthalene4,8-disulfonic acid 4-nitro-2-amino-toluoI-6-sulfonic acid 6-nitro-4-amino-toluene-2-sulfonic acid 6-nitro-2-amino-naphthalene-8-sulfonic acid 6-nitro-2-amino-naphthalene-4,8-disulfonic acid

Coupling components:

l-NaphthoI-3,6-disulfonic acid l-naphthol-3,8-disulfonic acid

1-naphthol-3,7-disulfonic acid

2-Naphthol-3,7-disulfonic acid 2-Naphthol4,8-disulfonic acid 1-Naphthol-3,6,8-trisulfonic acid

2-N aphthol-3,6,8-trisulfonic acid

2-amino-naphthalene-3,6-disulfonic acid

2-amino-naphthalene-5,7-disulfonic acid

H2- or 3- or 4-sulfophenyl) -3-methyl-5-pyrazolone l- (2-methyl4-sulfophenyl) -3-methyl-5-pyrazolone l- (2,5-dichlor4-suIfophenyl) -3-methyl -5-pyrazolone l- (2,5-disulfophenyl) -3-methyl-5-pyrazolone l- {2- or 3- or 4-sulfophenyl) -5-pyrazoion-3-carboxylic acid l- (2-chloro-5 -sulfophenyl) -5-pyrazolone-3-carboxylic acid

Example 8:

65.1 parts of l-dichlorotriazinylamino-8-naphthol-7- (2-sulfophe-nylazo> naphthalene-3,6-disulfonic acid are stirred in 500 parts by volume of water at 40 °. 36.3 parts of bis- [ ß- (ß-chloroethylsulfonyl> ethyl] amine hydrochloride and continue stirring at 40 °. The pH is kept between 3.8 and 4.2 by adding about 17 parts of sodium bicarbonate. If the pH after about 3 The reaction is complete for hours, the resulting dye of the formula

H03s so3h is completely solved. The solution is adjusted to pH 7 and the dye is isolated by salting out or by spray drying.

Preparation of the starting dye:

31.9 parts of l-amino-8-naphthol-3,6-disulfonic acid are dissolved with 35 150 parts by volume of water at 50 ° at pH 6. This solution is added over a period of about 90 minutes to a suspension of 20 parts of cyanuric chloride in 80 parts by volume of water and 60 parts by volume of acetone at a temperature of 0-10 ° and stirred until no free l-amino-8-naphthol-3,6 - 40 disulfonic acid is more detectable. The pH drops to about 1.5 in the course of the reaction. The diazo component obtained in a conventional manner by diazotizing 17.3 parts of aniline-o-sulfonic acid is added to the suspension of the coupling component thus obtained and the coupling is completed at a pH of about 6.5. The dye is separated by adding 10% by volume of sodium chloride, filtered off with suction and washed with 300 parts by volume of 10% sodium chloride solution. Example 9:

50.3 parts of the dye l-amino4- (3-amino4-methyl-5'-sulfophenylamino) anthraquinone-2-sulfonic acid are dissolved neutral with water and the necessary amount of soda. This solution is added at 0-5 ° to a slurry of 18.5 parts of cyanuric chloride, which was prepared by dropping the cyanuric chloride dissolved in 110 parts of acetone onto 250 parts of ice. The hydrogen chloride formed during the reaction is neutralized by dropwise addition of 50 parts of 2 normal sodium carbonate solution, a pH of 6-6.5 being established. Then 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) ethyl] amine hydrochloride are added, the mixture is warmed to 30-40 ° and kept at this temperature for 3 hours. At the same time, the pH is kept at 4.0-4.5 by dropwise addition of 100 parts of 2-normal soda solution. The reactive dye of the formula n (ch2-ch2-so2-ch2-ch2-ci) 2 obtained

So3h is salted out with sodium chloride, filtered and dried at 55-60 °.

Similar valuable dyes of the formula I are obtained if, instead of the starting dye, 1-amino4- (3-65 amino4-methyl-5-sulfo-phenyl-amino) -anthraquinone-2-sulfonic acid, dyes from the following table are used and the rest proceed as described above.

Intermediate dyes l-amino4- (3-amino-4-sulfo-phenyl-amino) -anthraquinone-2-sulphonic acid l-amino4- {4-amino-3-sulfo-phenyl-amino) -anthraquinone-2-sul- fonic acid l-amino4- (3-amino-2-methyl-5-sulfo-phenyl-amino) -anthrachi-non-2-sulfonic acid

622818

16

l-Amino4- (4-amino-2,2'-disulfodiphenyl- (4 ') - amino) -anthrachi-non-2-sulfonic acid

1-Amino-4- (3-aniino4-methy 1-5-suIfo-phenyl-sulfonylphenyl- (3 ') -amino) -anthraquinone-2-sulfonic acid l-Amino4- (4-amino-phenyl-amino) -anthraquinone -2,5-disulfonic acid l-amino4- (4'-amino-2,2'-disulfo-stilbyl- (4 ') - amino) -anthrachi-non-2-sulfonic acid

Example 10: 1

106.6 parts of the dye 3- (3-amino4-sulfophenylaminosulfonyl) copper phthalocyanine-3 ', 3 ", 3"' - trisulfonic acid are dissolved neutral with water and the necessary amount of soda. This solution is allowed to run at 0-5 ° to a slurry of 18.5 parts of cyanuric chloride, which was prepared by dropping the cyanuric chloride dissolved in 110 parts of acetone onto 250 parts of ice. During the reaction, the pH is kept at 6-6.5 by dropwise addition of 50 ml of 2 normal sodium carbonate solution. 36.3 parts of bis- [ß- <ß-chloroethylsulfonyl) ethyl] amine hydrochloride are added to the intermediate obtained and the mixture is heated at 35-45 ° for 4 hours. By adding 100 parts of 2-normal sodium hydroxide solution dropwise, the pH is kept at 4.0-4.5 at the same time. The reactive dye produced has the following constitution:

CuPc

<S03H) 3

SOgNH

I_n (ch2ch2so2ch2ch2ci) 2

It is separated with sodium chloride, filtered and dried. Furthermore, one obtains a similarly valuable reactive color vacuum at 55-60 °. Substances of formula I, if instead of copper phthalocya

The starting dye 3- (3'-amino dyes from corresponding nickel phthalocyanine-4'-sulfo-phenyl-aminosulfonyl) copper phthalocyanine-3 ', 3 ", 3"' substances.

trisulfonic acid can be obtained by reacting copper phthalocyanine tetrasulfochloride with 2,4-diamino-benzenesulfonic acid in Example 11:

Presence of pyridine at pH 5-9. A neutral solution of 48.9 parts of 4-amino4 '- (2,6-dini). To obtain similarly valuable dyes of the formula I, tro4-carboxy-phenylamino> diphenylamine-2-sulfonic acid is obtained if such starting dyes are used, which instead of at 0-5 ° with a slurry of 18.5 parts of cyanuric chloride, implemented by dropping the in 110 parts of acetone

2,4-diamino-benzenesulfonic acid with 35 dissolved cyanuric chloride on 250 parts of ice was obtained.

2.4-Diamino-toluoI-6-sulfonic acid By adding 50 parts of 2-normal sodium

2.5-Diamino-benzene-sulfonic acid lye, the pH is kept at 6.0-6.5. After finished

2.6-Diamino-toluene-4-sulfonic acid reaction is added 36.3 parts of bis- {ß- (ß-chloroethyl-sulfonyl) -4,4'-diamino-diphenyl-2,2'-disulfonic acid ethylj-amine hydrochloride as a powder , heated to 30-40 ° 3,3'-diamino4-methyl-diphenyl-sulfone-5-sulfonic acid 40 and holds this temperature for 3 hours, the pH being produced and the rest of the reaction with Cya- with 100 parts 2-normal sodium hydroxide solution is kept at 4.0-4.5% by weight and bis {ß- (ß-chloroethylsulfonyl) ethylamine. The yellow-brown reactive dye produced carried out fol hydrochloride as described above. constitution:

no "so3h

HOOC (CHJCHJSOJCHjCHJCI) 2

dl

It is separated with sodium chloride, filtered and at 55 acid with subsequent copper in acetic acid solution

55-60 ° dried. Copper complex dye are produced in water

The starting dye used 4-Amino4 '- (2,6-dinitro-neutral dissolved. This dye solution is allowed at 0-5 °

4-carboxy-phenylamino) diphenylamine-2-sulfonic acid can be added to a slurry of 18.5 parts of cyanuric chloride.

are produced in the following way: 27.9 parts of 4,4'-diaminodiene, which are dissolved in water by dissolving the cyanuric chloride in 110 parts of phenylamine-2-sulfonic acid. 60 acetone and drops to 250 parts of ice was prepared.

24.7 parts of l-chloro-2,6-dinitro-benzene-4-carbon are added. During the reaction, the pH is kept

acid and 8.5 parts of anhydrous sodium acetate, boil 5-6 hours from 50 parts of 2-normal soda solution to 4.5-5.5. It becomes long at 95-98 ° and separates the condensation product as 1-2 hours at 0-5 °, stirred until the reaction

Sodium salt. is finished. Then 36.5 parts of bis- ß- (ß-chloroethylsulfo-

65 nyl) ethyl] amine hydrochloride added, heated to approx. 45 ° and

Example 12: maintains the pH by adding 100 parts in portions

58.1 parts of the by diazotization of 2-aminophenol4.6-2 normal soda solution to 4.5-5.0. The ruby-red disulfonic acid obtained and coupling to 2-amino-5-naphthol-7-sulfone reactive dye corresponds to the following formula:

17th

622818

It is separated with sodium chloride, filtered and dried at 10 55-60 °.

Similar valuable reactive dyes of the formula I are obtained if, instead of the copper complex dye from 2-amino-phenol4,6-disulfonic acid and 2-amino-5-naphthol-7-sulfonic acid, the copper complex dyes from the following diazo and Coupling components produced dye is used and the rest of the reactions with cyanuric chloride and bis- [ß- (ß-chloroethyl-sulfonyl-nyl) ethyl] amine hydrochloride is carried out as described above.

20th

Diazo components:

2-amino-phenol-4-sulfonic acid

2-aminophenol-5-sulfonic acid

6-nitro-2-aminophenol-4-sulfonic acid

4-nitro-2-aminophenol-6-sulfonic acid

4-chloro-2-aminophenol-6-sulfonic acid

2-amino-4-methylphenol-6-sulfonic acid

2-amino-4-acetaminophenol-6-sulfonic acid

1-amino-2-naphthol-4-sulfonic acid

6-nitro-l-amino-2-naphthol-4-sulfonic acid

Coupling components: l-amino-5-naphthol-7-sulfonic acid 1-amino-8-naphthol-4-sulfonic acid

1-amino-8-naphthol-6-sulfonic acid e

2- (N-methylamino) -5-naphthol-7-sulfonic acid

2- (N-ethylamino) -5-naphthol-7-sulfonic acid

2- (N-ß-Hydroxyethylamino> 5-naphthol-7-sulfonic acid

2-amino-8-naphthol-6-sulfonic acid

2- (N-methylamino) -8-naphthol-6-sulfonic acid

2- {N-ethylamino) -8-naphthol-6-sulfonic acid l-amino-8-naphthol-3,6-disulfonic acid

1-amino-8-naphthol-4,6-disulfonic acid

2-amino-5-naphthol-l, 7-disulfonic acid 2-amino-8-naphthol-3,6-disulfonic acid

Example 13:

To a slurry of 79.4 parts of the copper complex of 7- [6- (3,5-dichloro-2,4,6-triazinylamino) -2-hydroxy4-sulfo-l-naphthylazo] -l-amino-8 -hydroxy-naphthalene-2,4-disulfonic acid in approx. 800 parts of water at 0-5 ° and a pH of 6.5, 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) - ethyl] amine hydrochloride as powder. The mixture is warmed to 30-40 ° and kept at this temperature for 4 hours. At the same time, the pH is kept at 4.0-4.5 by dropwise addition of 100 parts of 2-normal sodium carbonate solution. The end of the reaction can be recognized by the fact that the pH remains constant at 4.5. The blue reactive dye shown has the following constitution:

It is either evaporated in vacuo at 55-60 ° or deposited with sodium chloride.

The copper complex of 7- [6- {3,5-dichloro-2,4,6-triazinyl-amino) -2-hydroxy4-suIfo-l-naph-thylazo] -l-amino-8-hydroxy- used as the starting dye Naphthalene-2,4-disulfonic acid is produced in the following way:

60.8 parts of 6-nitro-l-diazonio4-sulfo-2-naphtholate are coupled at 0-5 ° in the presence of soda with 63.8 parts of l-amino-8-hydroxynaphthalene-2,4-disulfonic acid. In order to reduce the nitro group, a solution of 27.3 parts of sodium sulfide in water is added dropwise to the dye solution at about 40-50 ° and the mixture is stirred for 1-2 hours. The amino group-containing dye is separated with sodium chloride, filtered, dissolved in about 800 parts of water and adjusted to pH 5-5.3 with acetic acid. Add 40 parts of copper ace

tat or 50 parts copper sulfate and stir for 5 hours at 55 20-30 °. The copper complex dye obtained is deposited with sodium chloride, filtered and dissolved neutral with 800 parts of water. The dye solution then runs at 0-5 ° to a slurry of 37.0 parts of cyanuric chloride, which was prepared by adding the cyanur-60 chloride dissolved in 200 parts of acetone to 500 parts of ice. The mixture is subsequently stirred at 0-5 ° for 1-2 hours until no diazotizable amino groups can be detected.

Similarly valuable reactive dyes of the formula I are obtained if the diazo compounds of the following amines are used instead of the 6-nitro-l-diazonio4-sulfo-naphtho-65 late: 4-nitro-2-amino-l-hydroxy-naphthalene-6- sulfonic acid 6-nitro-2-amino-phenol4-sulfonic acid 4-nitro-2-amino-phenol-6-sulfonic acid.

622818

18th

Example 14:

36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) ethyl] amine hydrochloride in powder form are added to a neutral dye slurry of 82.4 parts of the copper complex of N- (2-hydroxy-4- sulfo-phenyl) -N '- (2-carboxy-4-sulfo-phenyl) -ms- [4- 5 (3,5-dichloro-2,4,6-triazinyl-amino) -2-sulfo-phenyl] -formazan in about 800 parts of water, the temperature being 0-5 °.

The mixture is then heated to 30-40 ° for 4 hours and during this time the pH is kept at 4.0-4.5 by adding dilute sodium hydroxide solution in portions. When no more caustic soda is needed, d. H. if the pH remains constant, the blue reactive dye shown is isolated by spray drying at 55-60 ° or by salting out. It has the following constitution:

3uC cu n (ch2ch2so2ch2ch2ci) 2

&

4h r ©

The copper complex of N- (2-hydroxy-4-sulfo-phenyl) -N '- (2-carboxy-4-sulfo-phenyl) -ms- [4- {3,5-dichloro-2,4 , 6-triazinyl-amino) -2-sulfo-phenyl] -formazane is obtained in the following way: 46.4 parts of 2-carboxy-phenylhydrazine-4-sulfonic acid and 48.6 parts of 4-acetamino-benzal-35 dehyd -2-sulfonic acid is condensed in aqueous solution, and the hydrazone obtained is coupled in the presence of soda with the diazo compound of 37.8 parts of l-amino-2-hydroxybenzene-4-sulfonic acid at 0-5 °. The formazan formed is adjusted to pH 5-5.3 with acetic acid and with copper-40 releasing agents, such as. B. 40 parts of copper acetate or 50 parts of copper sulfate, transferred to the copper complex with heating at 40-50 ° for 5 hours. This is separated with sodium chloride and dissolved neutral in about 800 ml of water. The dye solution runs at 0-5 ° to a slurry of 45 37.0 parts of cyanuric chloride, which is prepared by dissolving the cyanuric chloride in 200 parts of acetone and precipitating with 500 parts of ice. The mixture is stirred at 0-5 ° for 1-2 hours until the reaction is complete.

Similarly valuable reactive dyestuffs of the formula I are obtained if formazans are prepared from the hydrazine, aldehyde and diazo components below, where at least one acetamino group must optionally be present in the aldehyde or diazo component, converting the formazans into the copper complex and saponifying the acetamino group who reacted 55 dyes with cyanuric chloride and otherwise proceeded as indicated above. The components should be selected so that there are at least three sulfonic acid groups per dye molecule.

If a saponifiable acetamino group is present in each of the aldehyde 60 and diazo components, reactive residues can be introduced twice into the dye.

Hydrazine components:

2-hydroxy-phenylhydrazine

6-nitro-2-hydroxy-phenylhydrazine

4-chloro-2-carboxy-phenylhydrazine

5-nitro-2-carboxy-phenylhydrazine

65

4-methoxy-2-carboxy-phenylhydrazine

4-nitro-2-hydroxy-6-sulfo-phenylhydrazine

6-nitro-2-hydroxy-4-sulfo-phenylhydrazine

2-carboxy-5-sulfo-phenylhydrazine

2-hydroxy-6-carboxy-4-sulfo-phenylhydrazine

2-hydroxy-4,6-disulfophenylhydrazine

2-hydroxy-4-sulfonaphthylhydrazine

2-hydroxy-4,6'-disulfonaphthyl-l-hydrazine

Aldehyde components:

Benzaldehyde

4-methyl-benzaldehyde benzaldehyde-2- or 3- or 4-sulfonic acid benzaldehyde-2,4-disulfonic acid

2- or 3- or 4-nitro-benzaldehyde 2-chloro-benzaldehyde-5-sulfonic acid

2- or 3- or 4-acetaminobenzaldehyde

3-acetamino-benzaldehyde-4-sulfonic acid

5-acetaminobenzaldehyde-2-sulfonic acid

Diazo components:

l-amino-3-acetamino-2-hydroxy-benzene-5-sulfonic acid l-amino-5-acetamino-2-hydroxy-benzene-3-sulfonic acid

3-chloro-l-amino-2-hydroxy-benzene-5-sulfonic acid

5-nitro-l-amino-2-hydroxy-benzene-3-sulfonic acid

5-nitro-l-amino-2-hydroxy-benzene-4-sulfonic acid l-amino-2-hydroxy-benzene-4,6-disulfonic acid

Example 15:

91.9 parts of the dichlorotriazinylaminophenazine obtainable according to DE-OS 2 305 990, Example 31, is in the form of a slurry in 800 parts of water at 0-5 ° with a slurry of 36.5 parts of bis- [ß- (ß-ChIoräthyl-suIfonyI) -ethyl] amine hydrochloride added and heated to 30-40 ° for 3-4 hours. The hydrogen chloride split off is neutralized by dropwise addition of 100 parts of 2 normal sodium hydroxide solution and the pH is kept at 4.0-4.5. If the pH value

19th

622818

remains constant, the implementation is finished. The blue obtained was deposited with sodium chloride. It corresponds to the following For reactive dye is evaporated in vacuo at 55-60 ° or mei:

HO "S NH

NH _j ^^ - N (CH2CH2S02CH2CH2Cl) 2

SO_ © Cl

20th

Example 16:

To an aqueous slurry of 81.4 parts of the N, N'-bis (3,5-dichloro-2,4,6-triazinyl> compound of the 7- (5-amino-2-sulfo-phenyl-azo) - 1-Amino-8-naphthol-3,6-disulfonic acid is allowed to run in at 0-5 ° an aqueous suspension of 72.6 parts of bis- [ß- (ß-chloroethylsulfonyl) ethyl] amine hydrochloride Then heat to 30-40 °, this temperature is kept 3-4

For hours and at the same time dropwise dropwise a solution of 100 parts of 2 normal sodium carbonate solution to keep the pH at 4.0-4.5. If the pH remains constant, the conversion is complete. The bluish red reactive dye obtained is either evaporated at 55-60 ° in vacuo or deposited with sodium chloride. It has the following constitution:

à (ch2ch2s02ch2ch2c1) 2

cl "- ^^ x-ncchgchgsogchgchgcdg

To the N, N 'bis (3,5-di-45 chloro-2,4,6-triazinyl> compound serving as the starting dye) of the 7 <5-Amino-2-sulfo-phenyl-azo> l-amino- 8-naphthol-3,6-disulfonic acid can be obtained in the following way: At a temperature of 0-5 ° and a pH of 6-7, a neutral solution of 37.6 parts of 2,4-diaminobenzoI-sulfonic acid with a Slurry of 50 37.0 parts of cyanuric chloride and a neutral solution of 63.8 parts of l-amino-8-naphthol-3,6-disulfonic acid are reacted with a slurry of 37.0 parts of cyanuric chloride, and the pH is 6-7 in both cases by adding 100 parts of 2-normal soda solution in each case, the diazocomponent 55-2-amino-5- (3,5-dichloro-2,4,6-triazinyl-amino) -benzenesulfonic acid is reduced to usual Diazotized in hydrochloric acid solution with sodium nitrite at 0-5 ° and then combined with the coupling component 1 - (3,5-dichloro-2,4,6-triazinyl-amino> 8-naphthol-3,6-disulfonic acid to form the monoazo dye. 60

Similar valuable reactive dyes of the formula I are obtained if, instead of the condensation product of l-amino-8-naphthol-3,6-disulfonic acid with cyanuric chloride, the condensation products of the coupling components mentioned in Example 1 are used with 65 cyanuric chloride and the rest of the procedure is used to prepare the starting dye procedure described above.

If the condensation product of 2,4-diaminobenzenesulfonic acid with cyanuric chloride used as the diazo component for the preparation of the starting dye is replaced by the corresponding condensation products of cyanuric chloride with 2.5 diaminobenzenesulfonic acid or 2,5-diaminobenzene-1,4-disulfonic acid, the procedure is otherwise as described above , you also get valuable dyes of formula I.

Example 17:

A neutral solution of 72.8 parts of the copper complex of the dye 6-amino-1,2 'is added to a slurry of 18.5 parts of cyanuric chloride, which was dissolved warm in 70 parts of acetone and added to 300 parts of ice with stirring. Add 8'-trihydroxy-2,1 '-azonaphthalene-3', 4,6 ', 8-tetrasulfonic acid in 400 parts of water at 0-5 °. The hydrochloric acid formed in the reaction is neutralized by dropwise addition of 50 parts of 2 normal sodium hydroxide solution (pH 5.5-6.5). Then 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) ethyl] amine hydrochloride are added as a powder. The mixture is heated to 40 ° within about 1/2 hour and held at this temperature for 3 hours. At the same time, the pH is kept at 4.0-4.5 by adding 17 g of sodium bicarbonate. The blue reactive dye of the formula obtained

622818

20th

Cl nh

_ n (ch2ch2s02ch2ch2c.1) 2

h ° 3s is salted out with sodium chloride, filtered and dried in vacuo at 60 °. 15

The copper complex dye used as the starting material is prepared in the following manner according to the specifications of DE-PS 1 117 235: 81.8 parts of the O-benzenesulfonyl ester of l-amino-8-naphthol-3,6-disulfonic acid are diazotized and 72.2 Divide 2-acetamino-5-naphthol4,8-disulfonic acid 2o soda-alkali coupled. The monoazo dye obtained is converted in a known manner into the copper complex by oxidative coppering with copper sulfate and hydrogen peroxide in acetic acid solution and then the benzene sulfonyl and acetyl groups are split off by hydrolysis. 25th

If the diazo component is replaced by molar amounts of the following diazo components during the preparation of the starting dye and the procedure is otherwise as described above, valuable dyes of the formula 1: 30 l-amino-8-naphthol4,6-disulfonic acid-o- are also obtained. benzenesulfonyl ester

1-Amino-8-naphthol-4,7-disulfonic acid-o-benzenesulfonyl ester

2-amino-naphthalene4,8-disulfonic acid 2-amino-6-nitro-naphthalene4,8-disulfonic acid 2-amino-naphthalene4,6,8-trisulfonic acid 35 2-amino-naphthalene-6-sulfonic acid 2-amino-naphthalene-8 -sulphonic acid, the pH being maintained by adding 50 parts of 2-normal soda solution dropwise. Subsequently, the coupling component 2-acetamino-5-naphthol4,8-disulphonic acid by molar amounts of the N-acetyl compound of the following coupling components, furthermore valuable dyes of the formula I: 2-amino-8-naphthol-6-sulfonic acid 2 are obtained -Amino-5-naphthol-7-sulfonic acid 2-amino-5-naphthol-l, 7-disulfonic acid 2-amino-8-naphthol-3,6-disulfonic acid

Example 18:

70.2 parts of the disazo dye l-amino-2- (4-sulfopheny-lazo) -7- (2-sulfo-5-aminophenylazo) -8-naphthol-3,6-disulfonic acid are in the form of a neutral solution at 0- 5 ° reacted with a slurry of 18.5 parts of cyanuric chloride, which were dissolved in 110 parts of acetone and precipitated again with 250 parts of ice. The reaction is carried out at pH 6.0-6.5, 36.3 parts of bis- [ß- (ß-chloro-ethyl-sulfonyl) -ethyl] amine hydrochloride added as a powder, heated to 30-40 ° and the pH was kept at 4.0-4.5 by dropwise addition of 100 parts of 2 normal sodium carbonate solution. The dye of constitution obtained so3h

H03S

- ^ y.n -n ho3s n (ciiq ch0 s 0 0 ch0 cii0 c1),

n "\

N / An ^ s01

is isolated by salting out or by spray drying.

The disazo dye used as the starting material can be prepared in the following manner:

The diazo compound of 34.6 parts of sulfanilic acid is in the first stage in acidic medium at pH 2-4 with 63.8 parts of l-amino-8-naphthol-3,6-disulfonic acid and then in the second stage soda-alkaline with the Diazo compound of 46.0 parts of 2-amino-4-acetamino-benzene-sulfonic acid coupled. The acetyl group of the disazo dye is saponified in the presence of excess sodium hydroxide solution with heating to 90-100 °.

Similarly valuable dyes of the formula I are obtained if, instead of the diazo dye used as the starting dye, the following dye is used and the rest of the procedure is as described above.

l-Amino-2- (2-sulfophenylazo) -7- <2-sulfo-5-aminophenylazo) -8-naphthol-3,6-disulfonic acid l-amino-2- (2,4-disulfophenylazo) -7 - (2-sulfo-5-aminophenylazo> 8-naphthol-3,6-disulfonic acid l-amino-2- (2,5-disulfophenylazo) -7- (2-sulfo-5-aminophenylazo> 8- naphthol-3,6-disulfonic acid l-amino-2- <4-sulfophenylazo> 7- (2-sulfo4'-aminophenylazo) -8-naphthol-3,6-disulfonic acid l-amino-2- (2,5-disulfophenylazo > 7- (2-sulfo4-aminophenylazo) -50 8-naphthol-3,6-disulfonic acid l-amino-2- (2-sulfo-4-aminophenylazo) -7- (4-sulfophenylazo) -8-naphthol-3 , 6-disulfonic acid l-amino-2- (2-sulfo-4-aminophenylazo> 7- (2,5-disulfophenylazo) ~ 8-naphthol-3,6-disulfonic acid 55 l-amino-2- {2,5- disulfo4-aminophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid l-amino-2- (2-sulfo-5-aminophenylazo> 7- (4-sulfophenylazo) -8-naphthol-3,6 -disulfonic acid l-amino-2- (2-sulfo-5-aminophenylazo) - (2-sulfophenylazo) -8-60 naphthoI-3,6-disulfonic acid l-amino-2- {2-sulfo-5-aminophenylazo) - 7- (2,5-disulfophenyIazo) -8-naphthol-3,6-disulfonic acid

If the l-amino-8-naphthol-3,6-disulfonic acid is replaced by the l-amino-8-naphthol4,6-disulfonic acid in the preparation of the above-mentioned disazo-65 dyes, and the procedure is otherwise as described above, so obtained valuable dyes of the formula I are also

21st

622818

Example 19:

36.3 parts of bis- [ß- (ß-chloroethylsulfonyl) - are added at 0-5 ° to a neutral solution of 80.8 parts of the dichlorotriazinyl compound of an aminoxanthene described in DE-OS 2 442 839, Example 7. ethyl] amine hydrochloride, warmed to 35-45 ° and holds this temperature for 3-4 hours.

At the same time, the hydrogen chloride formed is neutralized by dropwise addition of 100 parts of 2-normal sodium hydroxide solution, while maintaining the pH at 4.5-5.5. The reaction is complete when the pH remains constant, s The blue-violet reactive dye shown has the following constitution:

CH2CH2N

so3h

NH N (CH2CH2S02CH2CH2C1),

It is evaporated in vacuo at 55-60 ° or deposited with sodium chloride.

Similar valuable reactive dyes of the formula I can be obtained if the starting dyes used are the dichloro- or dibromotriazinyl compounds of aminoxanthenes, which in turn are derived from the monoamines 25 taurine according to DE-OS 2 442 839

N-ethyl taurine

Amino acetic acid

Diethanolamine

2- or 3- or 4-amino-benzenesulfonic acid

1-amino-benzene-2,4- or 2,5-disulfonic acid

2-amino-toluene-4-sulfonic acid

3-aminotoluene-6-sulfonic acid

4-aminotoluene-2-sulfonic acid and from the diamines

1,3-diamino-benzenesulfonic acid

2,5-diamino-benzene-1,4-disulfonic acid

2,4-diamino-toluene-6-sulfonic acid

2,6-diamino-toluene-4-sulfonic acid

30th

4,4'-diamino-diphenyl-2,2'-disulfonic acid

4,4'-DiaminostiIben-2,2'-disulfonic acid

4,4'-diamino-diphenylurea-2,2'-disulfonic acid

2,6-diaminonaphthalene4,8-disulfonic acid can be prepared. The dyes should contain at least two solubilizing groups.

Example 20:

73.0 parts of the copper complex of the dye 4- (2-hydroxy-5-nitro-3-sulfo-phenyl-azo) -6- (5-dichlorotriazinyl-amino-2-sulfophenyl-azo) -l, 3-dihydroxybenzene at pH 6.5 and about 10 ° mixed in 700 parts of water. 36.3 parts of bis- [ß- (ß-chloroethylsulfonyl> ethyl] amine hydrochloride are added. The temperature is then raised to 45-50 ° C. When the pH has dropped to 3.8 17 parts of sodium bicarbonate are added over the course of 4-5 hours in such a way that the pH remains between 3.8 and 4.8 If the pH is constant, it is adjusted to 7.0 with 2 normal sodium hydroxide solution and the resulting dye of the formula

° 2

N (CH2CH2S02CH2CH2C1) 2

1

Cl isolated by salting out or spray drying. 55

The copper complex used as the starting material can be obtained as follows: A diazo compound prepared from 23.4 parts of 4-nitro-2-aminophenol-6-sulfonic acid is added at 0-5 ° and pH 5.5-6.5 11.0 parts of 1,3-dihydroxy-benzene coupled. This monoazo dye is converted into the copper complex in acetic acid bo solution by adding 25.0 parts of crystallized copper sulfate. The dye is separated by salting out with sodium chloride, filtered and redissolved in water. Then it is coupled at 5-15 ° with the addition of sodium bicarbonate with the diazo compound prepared from 23.0 parts of 2-amino-5-acetone-65 amino-benzenesulfonic acid to form the disazo dye. This is heated to 80 ° with sodium hydroxide solution, the acetyl group being split off. The dye thus obtained is then reacted at 0-5 ° and pH 6-6.5 with 18.5 parts of cyanuric chloride.

Similar valuable dyes of the formula I are obtained if, instead of the copper complex dye used as the starting material, the following dyes are used: 4- (2-hydroxy-5-sulfo-phenyl-azo> 6-dichlorotriazinylamino-2-sulfo-phenyl-azoM, 3 -dihydroxy-benzene, copper complex 4- {2-hydroxy-5-sulfo-phenyl-azo) -6- (4-dichlorotriazinylamino-

2-sulfo-phenyl-azo) -l, 3-dihydroxy-benzene, 2: 1 chromium complex

4- (2-hydroxy-3-chloro-5-sulfo-phenyl-azo) -6- (4-dichlorotriazinyl-

amino-2-sulfo-phenyl-azo) -l, 3-dihydroxy-benzene, copper complex

4- (2-hydroxy-6-nitro-4-sulfo-naphthyl-l-azo) -6- (4-dichlorotriazonylamino-2,5-disulfo-phenyl-azo) -l, 3-dihydroxy-benzene, 2: l

622 818 22

Cobalt complex

4- (2-Hydroxy-3,5-disulfophenyl-azo) -6- (6-dichlorotriazinylamino-

4,8-disulfonaphthyl-2-azo) -l) 3-dihydroxy-benzene, copper complex

Preparation of the starting dye:

38.9 parts of the dye obtained by soda-alkaline coupling from 6-nitro-2-diazo-l-hydroxy-benzene-4-sulfonic acid and 2-hydroxy-naphtha-lin are in 200 parts of water at pH 8 and at a temperature mixed from 70-80 °. In io this suspension is carried 67.9 parts of the chromium complex compound of the azo dye comprising 4-chloro-2-diazo-l-hydroxy-benzene-6-sul-fonic acid and l-amino-8-hydroxy- naphthalene-3,6-disulfonic acid, the pH being maintained between 7 and 9 by dropwise addition of soda solution. After 20 minutes at 70-80 ° a dark blue solution has formed. The paper chromatogram shows that a uniform mixed complex has emerged. The mixed complex is aeylated within one hour at 0 ° and pH 6.5-7.5 with 18.5 parts of cyanuric chloride.

Preparation of the dye of formula I.

36.3 parts of bis {β- (β-chloroethylsulfonyl> ethyl} amine hydrochloride are added to the resulting solution of the starting dye and the mixture is heated to 50 ° in the course of 30 minutes. This temperature is maintained for 4 hours During this time, the pH is kept between 5.0 and 5.5 by adding 11.5 parts of soda, and if the pH remains constant, it is adjusted to 7.0 with dilute sodium hydroxide solution and the dye of the formula o2N

"1

lòò-

so.

5 Na-1

isolated by spray drying.

Example 21:

To a slurry of 115.6 parts of the bis (di-chlorotriazinyl) compound of bis- [6- (5-amino-2-sulfo-phenylazo) -5-hydroxy-7-sulfo-naphthyl- (2)] -amines are separated 72.6 45 rid. It has the following constitution: parts of bis- [ß- {ß-chloroethylsulfonyl> ethyl> amine hydrochloride. The approach is heated to 35-40 °. By adding 200 parts of 2-normal sodium hydroxide solution in portions, the pH is kept at 4.5-5. If this remains constant, the implementation is complete. Then the orange-red reactive dye is evaporated in vacuo at 55-60 ° or with sodium chloride.

nyl> compound of bis- [6- (5-amino-2-sulfo-phenyl-azo> 5-mino-benzenesulfonic acid is used.hydroxy-7-sulfo-naphthyl- (2)] - amine turns 60 in the following way

obtained: 37.6 parts of 2,4-diamino-benzenesulfonic acid. In addition, the bis- [5-hydroxy-7-sulfo-naphthyl-0-5 ° and a pH of 6-7 with a slurry of (2)} - amine against the following coupling components - 37.0 parts of cyanuric chloride aeylated. See the 2-amino-4 obtained:

(3,5-dichloro-2,4,6-triazinyl-amino) -benzenesulfonic acid is diazotized in a bis- [5-hydroxy-7-sulfonaphthyl- (2)] - urea manner and with addition of 25 Parts of sodium 65 bis- [5-hydroxy-7-sulfo-naphthyl- (2)] thiourea umbicarbonat coupled at 0-5 °. Bis- [8-hydroxy-6-sulfonaphthyl- (2)] amine

Similar valuable reactive dyes of the formula I are bis- [8-hydroxy-6-sulfo-naphthyl- (2)] - urea obtained if instead of the 2,4-diamino-benzenesulfone bis- [8-hydroxy-6 -sulfo-naphthyl- (2)] - thiourea.

G

Claims (7)

622818 2. The method according to claim 1, characterized in that the reaction at a temperature of 25-70 ° C, preferably 35-55 ° C, and at a pH of 2-6.5, preferably 3.5-4 , 5, in an aqueous medium. 2nd PATENT CLAIMS 1. Process for the preparation of reactive dyes of the formula -D-N = N- (M-N = N-) nK -D-N = N- (M-N = N-) nK- (X) 10th in which F is the residue of a dye containing at least one —SCHH group, R is hydrogen or lower alkyl, X is a substituent which can be split off as an anion, p 1 or 2, and A is a residue of the formula -N . (älk - SO „- Z) / 2 m X 15 (II) n 20th mean in which alk is a lower alkylene radical having 2-6 C atoms, V is hydrogen or the radical of an optionally substituted hydrocarbon, Z is a β-halogenoethyl or vinyl radical, m is 1 or 2, and n is 2 minus m, characterized in that a dye of the formula N I R (V) wherein X and X 'independently of one another have one of the meanings given above for X, with an amine of the formula H-N ^ (alk - S02 Z) m n (IIa) D-N = N- (M-N = N -) "K- 25th 30th or a salt thereof. 3. The method according to claim 1 for the preparation of reactive dyes of the formula I, in which F is a radical of a metal-free or metal-containing mono- or disazo dye containing at least one —SCHh group, a radical of a derivative of 1-amino or 1-anilinoanthraquinone, in particular a residue of a 4-phenylamino-l-amino-anthraquinone-2-sulfonic acid derivative or a residue of a sulfophthalocyanine dye, in particular a derivative of a phthalocyanine-sulfanide or -sulfalkylamide containing 2- sulfonic acid groups in the phthalocyanine nucleus 6 carbon atoms in the alkyl chain, and a residue of a formazan or nitroaryl dye. 4. The method according to claim 1 for the preparation of reactive dyes of the formula I, in which F is a radical of a metal-free or metal-containing mono- or disazo dye containing at least one —SCHh group 5. The method according to claim 1 for the preparation of reactive dyes of the formula I, wherein F is a mono- or disazo dye residue of the formula Via, VIb or VIc (VIb) (VIc) or a metal complex derived therefrom, in the formulas Via, VIb and Vie D for the remainder of an alkanoylamino group with 2-4 C atoms optionally substituted by hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted benzoylamino groups or halogen atoms substituted diazo components of the benzene or naphthalene series, K for the rest of an optionally substituted by hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups with 2-4 C atoms, optionally substituted benzoylamino groups or halogen atoms substituted coupling component of the benzene, naphthalene or keto-methylene series, M for the rest of an alkanoylamino group with 2-4 C atoms optionally substituted by hydroxyl, methyl, ethyl, methoxy or ethoxy group, optionally substituted benzene amino groups or halogen atoms substituted middle component of benzene or naphthali n series, and n stand for the numbers 0 or 1, and D, M and K together contain at least two sulfonic acid groups, preferably three to four sulfonic acid groups. 6. The method according to claim 1 for the preparation of reactive dyes of the formula I, wherein X is chlorine, alk for the ethylene radical, Z for the β-chloroethyl radical or vinyl radical, and m is the number 2. 7. Reactive dyes produced by the process according to claim 1.