DE3930704A1 - New reactive dyestuff cpds. with cyanamido triazinyl-amino substit - Google Patents

Abstract

New water-soluble reactive dyestuffs are mono- or bis-(2-substd.-4-cyanamido-s- triazine-6-ylamino) dyestuff derivs. of formula F-(N(Rx)-Z)n (I), where F = the radical of a mono-, poly- or metal complex azo, anthraquinone, phthacyanine, azomethin, dioxazine, phenazine, stilbene, pyerenequinone or perylenetetracarbimide dyestuff; Rx = H; or 1-4C alkyl (opt. substd. by halogen, OH, CN, 1-4C alkoxy, 2-5C alkoxycarbonyl, COOH, , Z = a 2-substd.-4-cyanomido-s-triazin-6-yl gp. of the formula (II) where n = 2 or pref. 1; Q = a substd. amino gp. of formula (IIa) or (IIb): Rz = H; -4C alkyl (opt. substd. by halogen, OH, CN, 1-4C alkoxy COOH, sulphamoyl, SO3H or OSO3H or by a phenyl gp.. ); cyclohexyl; or phenyl (opt. substd. by halogen, 1-4C alkoxy, 1-4C alkyl, SO3H or COOH); W = (substd.) arylene or alkylene-arylene, arylene-alkylene, or arylene-alkylene-arylene in which the alkylene gps. have 1-8C, are opt. substd. and may contain 1 or more hetero gps., the arylene gps. are (substd.) phenylene or naphthylene gps. and the alkylene and arylene pts. in the combined arylene/alkylene gps. may each be sepd. by one hetro gp.; Y = vinyl, beta-(thio)sulphatoethyl, beta-phosphatoethyl, beta-(2-5C alkanoyloxy)-ethyl, beta-benzoyloxy-ethyl, beta -(sulphobenzoyloxy) -ethyl, beta- (p-toluenesulphonyloxy) -ethyl or beta-haloethyl; z = 1 or 2; A = 0 or 1; B = 1 or 2; A + B = 2: if B = 2, the -W-(SO2-Y)k gps. may be the same or different; X with the N atom = the bivalent radical of a heterocycle formed from 1 or 2 1-5C alkylene gps. and opt. 1 or 2 hetero gps.; alk = 1-4C alkylene.

Description

The invention is in the technical field of fiber-reactive dyes.

The practice of dyeing with reactive dyes has in recent times to increased demands on the quality of the Colorings and the economics of the dyeing process guided. As a result, there continues to be a need new reactive dyes, the improved properties, not only in terms of authenticity, but also one have a high degree of fixation on the material to be colored.

So from US Patent No. 47 40 592 and from Japanese patent designs Sho-40-17 113 and Sho-50-31 566 fiber-reactive dyes known to have an s-triazine residue contain to which a fiber-reactive group from the Vinyl sulfone series is bound and its third Substituent an optionally substituted amino group or is a methoxy group. Furthermore are from the US-PS 37 58 470 dyes known that a 2-chloro-4-cyanamido-s-triazin-6-ylamino radical contain. The well-known Dyes, however, have certain application defects; so they have a degree of fixation, from today's perspective is no longer fully satisfactory and they provide colorings with insufficient coloristic color strength.

With the present invention, new, Water-soluble, improved azo dyes in this regard and copper complex azo dyes found which the correspond to the general formula (1) below.

In formula (1):

F is the residue of a monoazo or disazo dye or a copper complex monoazo or disazo dye;
R ^x is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, which is replaced by halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, Alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo or sulfato may be substituted, preferably the methyl or ethyl group and in particular a hydrogen atom;
n is the number 1 or 2, preferably 1;
Q is a group of the general formula (2a) or (2b)

in which
R ^{z is} a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as in particular the methyl or ethyl group, which is replaced by halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as methoxy and Ethoxy, carboxy, sulfamoyl, sulfo or sulfato or by an optionally by substituent from the group halogen, such as chlorine and bromine, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, alkyl of 1 to 4 carbon atoms, such as methyl , Sulfo and carboxy substituted phenyl radical, or a cyclohexyl radical or an optionally substituted by substituents from the group halogen, such as chlorine and bromine, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, alkyl of 1 to 4 carbon atoms such as methyl, sulfo and carboxy substituted phenyl,
W is an optionally substituted arylene radical or an alkylene-arylene or arylene-alkylene or alkylene-arylene-alkylene or arylene-alkylene-arylene radical, the alkylene radicals being from 1 to 8, preferably from 2 to 6, in particular from 2 to 4 carbon atoms and can be substituted and the arylene radicals are optionally substituted phenylene or naphthylene radicals, and wherein the alkylene radicals are replaced by 1 or more, such as 1 or 2, hetero groups, such as amino groups or oxygen or sulfur atoms or groups of the formulas -SO₂-, -CO-, -SO₂-NH- or -CO-NH-, may be interrupted and the alkylene and arylene portions in the combined alkylene / arylene radicals may each be separated from one another by such a group,
Y is the vinyl group or a β-sulfatoethyl, β-thiosulfatoethyl or β-phosphatoethyl group or a β-alkanoyloxy-ethyl group with 2 to 5 carbon atoms in the alkanoyl radical, such as the β-acetyloxyethyl group, or the β -Benzoyloxy-ethyl-, β- (sulfobenzoyloxy) -ethyl or the β- (p-toluenesulfonyloxy) -ethyl group or a β-haloethyl group such as the β-bromoethyl or β-chloroethyl group, preferably the Vinyl group and in particular the β-sulfatoethyl group,
z is the number 1 or 2,
A represents the number zero or 1 and
B represents the number 1 or 2,
where the sum of (A + B) is equal to the number 2 and where in the case of B is 2 the groups of the formula -W- (SO₂-Y) _{z may have} the same meaning to one another or a different meaning from one another
X together with the N atom forms the divalent radical of a heterocyclic ring consisting of 1 or 2 alkylene groups of 1 to 5 C atoms and optionally 1 or 2 hetero groups, such as nitrogen and oxygen atoms or a group -NH-, such as, for example Piperazin-1,4-ylene or a piperidinylene radical, and
alk is an alkylene radical of 1 to 4 carbon atoms, preferably of 2 or 3 carbon atoms, such as the n-ethylene or n-propylene radical.

The contained in the dyes of the invention fiber-reactive grouping according to the invention accordingly has the general formula (3)

Formula residues R ^x are, for example: hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, carboxymethyl, β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl, β- Ethoxyethyl, β-methoxypropyl, β-chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl, amidosulfonylmethyl and β-sulfatoethyl.

Formula residues R ^z are, for example: hydrogen, methyl, ethyl, carboxymethyl, carbomethoxymethyl, carbethoxymethyl, sulfomethyl, sulfamidomethyl, β-carboxyethyl, β-sulfoethyl, n-propyl, β-carboxypropyl, β-sulfatoethyl, β-ethoxyethyl, β-methoxypropyl, γ-chloropropyl, γ-bromopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-nonyl, n-dodecyl, n-hexadecyl, n-pentadecyl, cyclohexyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2- or 3- or 4-sulfophenyl, 2-methylphenyl, 4-methoxyphenyl, 3-methylphenyl and 4-ethylphenyl. Of these, preference is given to the optionally substituted alkyl groups and particularly preferably the methyl and ethyl groups and the hydrogen atom.

Examples of groups of the general formulas (2a) and (2b) are, for example: 2- (β-sulfatoethylsulfonyl) phenylamino,  3- (β-sulfatoethylsulfonyl) phenylamino, 4- (β-sulfatoethylsulfonyl) - phenylamino, 2-carboxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2-chloro-3- (β-sulfatoethylsulfonyl) phenylamino, 2-chloro-4- (β-sulfatoethylsulfonyl) phenylamino, 2-ethoxy-4- or -5- (β-sulfatoethylsulfonyl) phenylamino, 2-ethoxy-4- (β-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2,4-diethoxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2,4-dimethoxy-5- (β-sulfatoethylsulfonyl) phenylamino, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenylamino, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (β-thiosulfatoethylsulfonyl) phenylamino, 2-sulfo-4- (β-phosphatoethylsulfonyl) phenylamino, 2-sulfo-4-vinylsulfonylphenylamino, 2-hydroxy-4- or -5- (β-sulfatoethylsulfonyl) phenylamino, 2-chloro-4- or -5- (β-chloroethylsulfonyl) phenylamino, 2-hydroxy-3-sulfo-5- (β-sulfatoethylsulfonyl) phenylamino, 3- or 4- (β-acetoxyethylsulfonyl) phenylamino, 2-methoxy 4- [β- (N-methyl-tauryl) ethylsulfonyl] phenylamino, 5- (β-sulfatoethylsulfonyl) naphth-2-yl-amino, 6- or 7- or 8- (β-sulfatoethylsulfonyl) -naphth-2-yl-amino, 6- (β-sulfatoethylsulfonyl) -1-sulfonaphth-2-yl-amino, 5- (β-sulfatoethylsulfonyl) -1-sulfonaphth-2-yl-amino, 8- (β-sulfatoethylsulfonyl) -6-sulfonaphth-2-yl-amino,  β- [4- (β′-sulfatoethylsulfonyl) phen] ethylamino, β- [2-sulfo- 4- (β′-sulfatoethylsulfonyl) phen] ethylamino, β- (β'-chloroethylsulfonyl) ethylamino, β- (β'-sulfato- ethylsulfonyl) ethylamino, β- (vinylsulfonyl) etylamino, γ- (β'-chloroethylsulfonyl) propylamino, γ- (β'-sulfato- ethylsulfonyl) propylamino, γ- (β'-bromoethylsulfonyl) propylamino, γ- (vinylsulfonyl) propylamino, 1-methyl-1- (β-sulfatoethylsulfonyl) -1-ethylamino, δ- (β′-sulfatoethylsulfonyl) butylamino, 2-methyl-2- (β-chloro ethylsulfonyl) -1-propylamino, ω- (β'-chloroethylsulfonyl) pentylamino, β- (β'-chloroethylsulfonyl) -n-hexylamino, N-methyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-ethyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-propyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-butyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-pentyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-hexyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-nonyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-dodecyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-hexadecyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-n-octadecyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N-carboxymethyl-N- [β- (β'-bromethylsulfonyl) ethyl] amino, N-sulfatomethyl-N- [β- (β'-chloroethylsulfonyl) ethyl] amino, N- (β-carboxyethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, N- (β-sulfatoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, N- (β-sulfatoethyl) -N- [δ ′ - (β ′ ′ - chloroethylsulfonyl) butyl] amino,  N- (β-ethoxyethyl) -N- [δ ′ - (β ′ ′ - chloroethylsulfonyl) butyl] amino, N- (γ-chloropropyl) -N- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethyl] amino, N-phenyl-N- [β-β′-chloroethylsulfonyl) ethyl] amino, N- (4-chlorophenyl) -N- [β-β′-chloroethylsulfonyl) ethyl] amino, N- (2-methylphenyl) -N- [β-β′-chloroethylsulfonyl) ethyl] amino, N- (4-methoxyphenyl) -N- [β-β′-chloroethylsulfonyl) ethyl] amino, N- (3-sulfophenyl) -N- [β-β′-chloroethylsulfonyl) ethyl] amino, N- (4-sulfophenyl) -N- [β-β′-chloroethylsulfonyl) ethyl] amino, Bis- [β- (β'-chloroethylsulfonyl) ethyl] amino, Bis- [β- (β'-bromethylsulfonyl) ethyl] amino, Bis- [γ- (β′-chloroethylsulfonyl) propyl] amino, Bis- [δ- (β′-chloroethylsulfonyl) butyl] amino, Bis- (β-vinylsulfonyl-ethyl) amino, N- (β-cyanoethyl) - N- (γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, β- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethylamino] ethylamino, β- [β ′ - (β ′ ′ - sulfatoethylsulfonyl) ethylamino] ethylamino, β- [β ′ - (β ′ ′ - chloroethylsulfonyl) ethoxy] ethylamino, β- [β ′ - (β ′ ′ - sulfatoethylsulfonyl) ethoxy] ethylamino, 4- [β- (β'-chloroethylsulfonyl) ethyl] piperazin-1-yl, 4- [γ- (β′-chloroethylsulfonyl) propyl] piperazin-1-yl, 4- [β- (β′-sulfatoethylsulfonyl) ethyl] piperazin-1-yl, 4- [γ- (β′-sulfatoethylsulfonyl) propyl] piperazin-1-yl, 4- {N- [β- (4'-β'-sulfatoethylsulfonylphenyl) ethyl] - amidocarbonyl-methoxy} -phenylamino,  4- {N- [3′- or -4 ′ - (β-sulfatoethylsulfonyl) - phenyl] amidocarbonyl methoxy} phenylamino, 3,4-di- (β-sulfatoethylsulfonyl) phenylamino, 2,5-di- (β-sulfatoethylsulfonyl) phenylamino, 4- [γ- (β′-sulfatoethylsulfonyl) propoxyl] phenylamino, 2,5-bis - [(β-sulfatoethylsulfonyl) methyl] phenylamino, 3- or 4- {N- [γ- (β'-sulfatoethylsulfonyl) propyl- amidocarbonyl]} - phenylamino, 3,5-bis- {N- [γ- (β′-sulfatoethyl- sulfonyl) propyl amidocarbonyl]} - phenylamino, 3-sulfo-4 - {[N-γ- (β'-sulfatoethylsulfonyl) propyl- amidocarbonyl] -methoxy} phenylamino, 4 - {[N-γ- (β′-sulfato- ethylsulfonyl) propyl amidocarbonyl] methoxy) phenylamino.

Arylene radicals in the bridge member W are preferably phenylene and naphthylene residues containing one or more such as 1, 2 or 3, preferably 1 or 2, may contain substituents which for example the group of the substituents alkyl from 1 to 4 carbon atoms, such as methyl and ethyl, halogen, such as fluorine, chlorine and bromine hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as Methoxy and ethoxy, carboxy, sulfamoyl, sulfo, trifluoromethyl and alkoxycarbonyl of 2 to 5 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. W is preferred here Phenylene radical represented by the above-mentioned substituents may be substituted, the substituents from the Group alkyl of 1 to 4 carbon atoms, chlorine, alkoxy of 1 to 4 carbon atoms, carboxy and sulfo are preferred.  

Alkylene residues in the binding member W are preferably straight-chain and branched alkylene groups of 2 to 6 carbon atoms, the by the given hetero groups, such as 1 or 2 of these Heterogroups can be interrupted. Preferred of these are straight-chain alkylene groups of 2 to 4 carbon atoms or one by an oxygen atom or an amino or Methylamino group interrupted alkylene group of 4 C atoms. Of the alkylene groups is particularly preferred the 1,3-propylene residue. Substituents in the alkylene groups of W can, for example, sulfo, carboxy, hydroxy and Be cyano groups.

If the formula radical W is an alkylene-arylene or an alkylene-arylene-alkylene radical, this is the case in these groups Alkylene radical preferably a straight-chain alkylene radical of 1 to 3 carbon atoms and the arylene radical is preferably a 1,3- or especially 1,4-phenylene. Alkylene arylene radicals are in particular the radicals of the formulas -CH₂-CH₂-phenylene and -CH₂-phenylene.  

The fiber-reactive grouping of formula (3) is preferred a radical of the general formula (3a) or in particular preferably a radical of the general formula (3b)

wherein in formula (3a) R 'is the methyl or ethyl group or in particular represents a hydrogen atom, R '' a Means hydrogen atom or the methyl or ethyl group and W, Y and z are the above, particularly preferred Have meanings, and in formula (3b) R '' the methyl group or in particular is a hydrogen atom, Y is the has above-mentioned, particularly preferred meaning and W 1 is an alkylene group of 2 to 4 carbon atoms, preferably of 2 or in particular of 3 carbon atoms, means or a Phenylenrest is, which by 1 or 2 substituents from the Group methyl, methoxy, ethoxy and chlorine may be substituted can, preferably of which the 1,3- or 1,4-phenylene radical, or a group of the general formula (a)

- (CH₂) _w - phenylene - (a)

means in which w the number 1, 2, 3 or 4, preferably 2, is and phenylene is the 1,3- or 1,4-phenylene radical.

Important azo dyes according to the general Formula (1) are those in which A is a residue of a Dye of benzene-azo-naphthol, the  Benzene-azo-1-phenyl-5-pyrazolone-, the benzene-azo-benzene-, the naphthalene-azo-benzene, the benzene-azo-aminonaphthalene, the naphthalene azo-naphthalene, the naphthalene azo-1-phenyl-5-pyrazolone, the benzene-azo-pyridone and the Naphthalene-azo-pyridone series means, the here too dyes containing sulfo groups are preferred.

Of the 1: 1 copper complex azo dyes according to the invention those of the benzene and naphthalene series are preferred.

Preferred mono- and disazo dyes of the general Formula (1) are, for example, those of the general Formulas (4a), (4b) and (4c)

D₁ - N = N - (E - N = N) _v - K - Z (4a)

Z - D₁ - N = N - (E - N = N) _v - K (4b)

Z - D₁ - N = N - (E - N = N) _v - K - Z (4c)

and the metal complex compounds derived therefrom, such as 1: 1 copper complex compounds, in which
D₁ is the remainder of a diazo component of the benzene or naphthalene series,
E represents the remainder of a middle component of the benzene or naphthalene series,
K is the rest of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series,
where D₁, E and K for azo dyes common substituents, such as hydroxy, amino, methyl, methoxy, ethoxy, sulfo, carboxy, optionally substituted alkanoylamino groups of 2 to 4 carbon atoms in the alkanoyl radical, optionally substituted benzoylamino groups and halogen atoms, such as bromine and chlorine atoms, and D₁, E and K together have at least two sulfo groups, preferably three or four sulfo groups,
v represents the number zero or 1 and
Z is a group of the formula (3) or preferably of the formula (3a) or (3b).

Disazo dyes of the general are also preferred Formula (4d) or (4e)

D₁ - N = N - K⁰ - N = N - D₂ - Z (4d)

Z - D₁ - N = N - K ° - N = N - D₂ - Z (4e)

in which D₁ and D₂ independently of one another the rest of one Diazo component of the benzene or naphthalene series and K ° den Remaining of a bivalent coupling component of the naphthalene series represents, D₁, D₂ and K ° the usual for azo dyes Can carry substituents such as those mentioned above, where D₁, D₂ and K ° together have at least two sulfo groups, preferably three or four sulfo groups.

Such azo dyes of the general formula (1) are especially dyes of the general formulas (4f), (4g) and (4h)

in which
D in each case represents the remainder of a diazo component which may have meanings which are the same or different from one another, such as, for example, a remainder D 1 of the above meaning,
E is the bivalent radical of a coupling and diazotizable compound, for example of the above meaning,
K represents the rest of a coupling component, for example of the above meaning,
v represents the number zero or 1,
Z represents a radical of the general formula (3) or (3a) or (3b),
n is the number 1 or 2, preferably 1, and the radical Z is bonded to the radical D or the radical K or in the case of n = 2 to D and K or to both D and
M is a hydrogen atom or an alkali metal such as sodium, potassium or lithium.

Starting compounds, for example for the synthesis of azo compounds according to the invention can be used, Examples are the following amino compounds that can serve as diazo components: Aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 4-aminobiphenyl, 1-aminobenzene-2-, -3- or -4-carboxylic acid, 2-aminodiphenyl ether, 1-aminobenzene-2-, -3- or -4-sulfonic acid amide, -N-methylamide, -N-ethylamide, -N, N-dimethylamide or -N, N-diethylamide, dehydrothio-p-toluidine sulfonic acid, 1-amino-4-trifluoromethyl-6-sulfonic acid, 1-amino-3- or -4-nitrobenzene, 1-amino-3- or -4-acetylaminobenzene, 1-aminobenzene-2-, -3- or -4-sulfonic acid, 1-aminobenzene-2,4- and -2,5-disulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-amino-2-carboxybenzene-4-sulfonic acid, 1-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or -5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or -4-sulfonic acid,  1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-amino-2,5- dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4- sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-5-methyl-4-chlorobenzene-2-sulfonic acid, 1-amino-4- or -5-methoxybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or -4-sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-sulfonic acid, 1-amino-2,4-dimethoxybenzene-6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfonic acid, 1-amino-3- acetylaminobenzene-6-sulfonic acid, 1-amino-4-acetylaminobenzene 2-sulfonic acid, 1-amino-3-acetylamino-4-methylbenzene-6-sulfonic acid, 2-amino-1-methylbenzene-3,5-disulfonic acid, 1-amino-4-methoxybenzene-2,5-disulfonic acid, 1-amino-3- or -4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8-, or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene 4,6-disulfonic acid, 1-hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, 1-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-hydroxy-2-amino-4-methylsulfonylbenzene, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-3,4′-disulfonic acid, 3-methoxy-4-amino-6- methylazobenzene-2'-4'-disulfonic acid, 3-methoxy-4-amino-6- methylazobenzene-2'-5'-disulfonic acid, 1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene,  1,4-diamino-2,5-diethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl (benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine, 3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine, 4,2'-diaminodiphenyl (diphenylin), 2,6-diaminonaphthalene-4,8-disulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid, 1,4-diamino-2- methylbenzene-5-sulfonic acid, 1,5-diamino-6-methylbenzene-3-sulfonic acid, 1,3-diamino-6-methylbenzene-4-sulfonic acid, 3- (3′-aminobenzoylamino) -1-aminobenzene-6-sulfonic acid, 3- (4′-aminobenzoylamino) -1-aminobenzene-6-sulfonic acid, 1- (4′-aminobenzoylamino) -4-aminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene, 4,4'-diaminodiphenyl oxide, 4,4'-diamino-diphenylurea-2,2'-disulfonic acid, 4,4'-diaminodiphenyloxyethane-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylethane-2,2'-disulfonic acid, 2-amino-5- aminomethylnaphthalene-1-sulfonic acid, 2-amino-5- aminomethylnaphthalene-1,7-disulfonic acid, 1-amino-4-methoxy- 5-aminomethylbenzene-6-sulfonic acid, 2- (β-sulfatoethylsulfonyl) phenyl aniline, 3- (β-sulfatoethylsulfonyl) aniline, 4-β-sulfatoethylsulfonyl) aniline, 2-carboxy-5- (β-sulfatoethylsulfonyl) aniline, 2-chloro-3- (β-sulfatoethylsulfonyl) aniline, 2-chloro-4- (β-sulfatoethylsulfonyl) aniline, 2-ethoxy-4- or -5- (β-sulfatoethylsulfonyl) aniline, 2-ethyl-4- (β- sulfatoethylsulfonyl) aniline, 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline, 2,4-diethoxy-5- (β-sulfatoethylsulfonyl) aniline, 2,4-dimethoxy-5- (β-  sulfatoethylsulfonyl) aniline, 2,5-dimethoxy-4- (β- sulfatoethylsulfonyl) aniline, 2-methoxy-5-methyl-4- (β- sulfatoethylsulfonyl) aniline, 2- or 3- or 4- (β- Thiosulfatoethylsulfonyl) aniline, 2-methoxy-5- (β- thiosulfatoethylsulfonyl) aniline, 2-sulfo-4- (β- phosphatoethylsulfonyl) aniline, 2-sulfo-4-vinylsulfonyl-aniline, 2-hydroxy-4- or -5- (β-sulfatoethylsulfonyl) aniline, 2-chloro-4- or -5- (β-chloroethylsulfonyl) aniline, 2-hydroxy-3-sulfo-5- (β-sulfatoethylsulfonyl) aniline, 3- or 4- (β-acetoxyethylsulfonyl) aniline, 2-methoxy-4- [β- (N-methyl- tauryl) ethylsulfonyl] aniline, 5- (β- Sulfatoethylsulfonyl) -2-amino-naphthalene, 6- or 7- or 8- (β-sulfatoethylsulfonyl) -2-amino-naphthalene, 6- (β- Sulfatoethylsulfonyl) -1-sulfo-2-amino-naphthalene, 5- (β- Sulfatoethylsulfonyl) -1-sulfo-2-amino-naphthalene, 8- (β- Sulfatoethylsulfonyl) -6-sulfo-2-amino-naphthalene.

If in the synthesis according to the invention as a diazo component an amino-acetylamino compound instead of a diamine is used, from which the acetyl group subsequently When saponification is split off again, they come Monoacetyl compounds of the above diazo components in Question, such as 1-acetylamino-3-aminobenzene-4-sulfonic acid and 1-acetylamino-4-aminobenzene-3-sulfonic acid.

Coupling components required for the synthesis of the invention Azo dyes can be used, for example: Phenol, 1-hydroxy-3- or 4-methylbenzene, 1-hydroxybenzene-4-sulfonic acid, 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxynaphthalene-6- or -7-sulfonic acid, 2-hydroxynaphthalene-3,6- or -6,8-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6- or -4,7-disulfonic acid, 1-amino-3-methylbenzene, 1-amino-2- methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene,  1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-sulfonic acid, 1-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8- hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3- aminonaphthalene-5,7-disulfonic acid, 1-amino-8- hydroxynaphthalene-2,4,6-trisulfonic acid, 1-hydroxy-8- acetylaminonaphthalene-3-sulfonic acid, 1-benzoylamino-8- hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino 5-hydroxynaphthalene-7-sulfonic acid, 2-methyl or 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5- hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8- hydroxynaphthalene-6-sulfonic acid, 2-methylamino or 2-ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8- hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8- hydroxynaphthalene-3,6-disulfonic acid, 1-amino-5- hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-acetylamino-8- hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-Aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4′-nitrobenzoylamino) -8- hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-Aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-nitrobenzoylamino) -8- hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2- (4′-amino- 3′-sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, 1- (4′-sulfophenyl) -5-pyrazolone-3-carboxylic acid, 1- (3'-aminophenyl) -3-methyl-5-pyrazolone, 1- (2 ′, 5′-disulfonphenyl) -3-methyl-5-pyrazolone, 1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid,  1- (4 ′, 8′-disulfonaphthyl- [2 ′]) - 3-methyl-5-pyrazolone, 1- (5 ′, 7′-disulfonaphthyl- [2 ′]) - 3-methyl-5-pyrazolone, 1- (2 ′, 5′-dichloro-4′-sulfophenyl) -3-methyl-5-pyrazolone, 3-aminocarbonyl-4-methyl-6-hydroxy-2-pyridone, 1-ethyl-3-cyano- or -3-chloro-4-methyl-6-hydroxy-2-pyridone, 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxy-2-pyridone, 2,4,6-triamino-3-cyanopyridine, 2- (3′-sulfophenylamino) -4,6- diamino-3-cyanopyridine, 2- (2'-hydroxyethylamino) -3-cyan-4- methyl-6-aminopyridine, 2,6-bis- (2'-hydroxyethylamino) -3-cyan- 4-methylpyridine, 1-ethyl-3-carbonyl-4-methyl-6- hydroxy-2-pyridone, 1-ethyl-3-sulfomethyl-4-methyl-5- carbonyl-6-hydroxy-2-pyridone, N-acetoacetylaminobenzene, 1- (N-acetoacetylamino) -2-methoxybenzene-5-sulfonic acid, 4-hydroxyquinol-2-one, 1-amino-8-hydroxy-2- (phenylazo) - naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy- 2- (4′-sulfophenylazo) naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-2- (2 ′, 5′-disulfonphenylazo) naphthalene 3,6-disulfonic acid, 1- (β-aminoethyl) -3-cyano-4-methyl- 6-hydroxy-2-pyridone, 1- (γ-aminopropyl) -3-sulfomethyl- 4-methyl-6-hydroxy-2-pyridone, 1,3-diaminobenzene, 1-amino 3-N, N-di- (β-hydroxyethyl) aminobenzene, 1-amino 3-N, N-di- (β-sulfatoethyl) aminobenzene, 1-amino 3-N, N-di- (β-hydroxyethyl) amino-4-methoxybenzene, 1-amino 3-N, N-di- (β-sulfatoethyl) amino-4-methoxybenzene, 1-amino- 3-sulfo-benzylamino-benzene, 1-amino-3-sulfo-benzylamino-4-chlorobenzene, 1-amino-3-N, N-di- (sulfobenzyl) aminobenzene, 2- (4-β-sulfatoethylsulfonylphenyl) -3-methyl-5-pyrazolone and 1- (4-β-sulfatoethylsulfonylphenyl) -3-carboxy-5-pyrazolone.

Aromatic residues D of the diazo components D-NH₂, the no fiber-reactive group of the general formula (3) wear, for example those of the amines general formulas (5a) and (5b)

in which
P¹ is a hydrogen atom, a sulfo group or a group of the general formula -SO₂-Y with Y of the abovementioned meaning,
P² is hydrogen, methyl, ethyl, methoxy, ethoxy, alkanol of 2 to 5 carbon atoms, such as acetyl and propionyl, cyano, carboxy, sulfo, alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N- (C₁-C₄-alkyl ) -carbamoyl, fluorine, chlorine, bromine or trifluoromethyl,
P³ hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, carboxy, sulfo, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino, alkoxycarbonyl of 2 to 5 carbon atoms, carbamoyl, N- (C₁-C₄-alkyl) - carbamoyl, fluorine, chlorine, nitro, sulfamoyl, N- (C₁-C₄-alkyl) -sulfamoyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl or phenoxy,
where the benzene or naphthalene nucleus is also ortho to the NH₂ group may contain a hydroxy group,
m denotes the number zero, 1 or 2 (where this group denotes a hydrogen atom if p is zero) and
M has the meaning given above.

Of these, P 2 is preferably hydrogen, methyl, methoxy, Bromine, chlorine, carboxy and sulfo and P³ is hydrogen, Methyl, methoxy, chlorine, carboxy, sulfo and acetylamino.

The groups "Sulfo", "Carboxy", "Phosphato", "Thiosulfato" and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups mean groups according to the general formula -SO₃M, carboxy groups Groups corresponding to the general formula -COOM, Phosphato groups according to the general formula -OPO₃M₂, thiosulfato groups according to the general formula -S-SO₃M and sulfato groups according to the general formula -OSO₃M, each with M of the above meaning.  

Aromatic amines of the general formula D-NH₂ corresponding to formulas (5a) and (5b) are, for example: 2-amino or 4-aminobenzoic acid, 3-amino-benzoic acid, 3-chloroaniline-6-carboxylic acid, aniline-2- or -3- or -4-sulfonic acid, 2,5-disulfo-aniline, 2,4-disulfo-aniline, 3,5-disulfoaniline, 2-aminotoluene-4-sulfonic acid, 2-amino-anisole-4-sulfonic acid, 2-amino-anisole-5-sulfonic acid, 4-amino-anisole-2-sulfonic acid, 2-ethoxy-aniline-5-sulfonic acid, 2-ethoxy-aniline-4-sulfonic acid, 4-sulfo-2-aminobenzoic acid, 2,5-dimethoxy-aniline-4-sulfonic acid, 2,4-dimethoxyaniline-5-sulfonic acid, 2-methoxy-5-methyl-aniline-4-sulfonic acid, 4-amino-anisole-3-sulfonic acid, 4-amino-toluene-3-sulfonic acid, 2-aminotoluene-5-sulfonic acid, 2-chloro-aniline-4-sulfonic acid, 2-chloro-aniline-5-sulfonic acid, 2-bromo-aniline-4-sulfonic acid, 2,6-dichloroaniline-4-sulfonic acid, 2,6-dimethylaniline-3-sulfonic acid or -4-sulfonic acid, 3-acetylamino-6-sulfoaniline, 4-acetylamino-2-sulfo-aniline, 1-aminonaphthalene-4-sulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-3,7-disulfonic acid, 1-aminonaphthalene-3,6,8-trisulfonic acid, 1-aminonaphthalene-4,6,8-trisulfonic acid, 2-naphthylamine-5-sulfonic acid or -6- or -8-sulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-1,6-disulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 4- (β-sulfatoethylsulfonyl) aniline, 3- (β-sulfatoethylsulfonyl) aniline, 2-sulfo-5- (β-sulfatoethylsulfonyl) aniline, 2-sulfo-4- (β-sulfatoethylsulfonyl) aniline, 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) aniline, 2-amino-5- (β-sulfatoethylsulfonyl) phenol, 2-amino-4- (β-sulfatoethylsulfonyl) phenol, 2-amino-6- (β-sulfatoethylsulfonyl) naphthalene-8-sulfonic acid, 2-amino-8- (β-sulfatoethylsulfonyl) naphthalene  6-sulfonic acid, 2-amino-5- (β-sulfatoethylsulfonyl) - naphthalene-7-sulfonic acid and 2-amino-7- (β-sulfatoethylsulfonyl) - naphthalene-5-sulfonic acid.

Aromatic amines of the diazo component Z-D-NH₂ with the fiber-reactive radical Z are preferably aromatic Amines of the general formulas (6a) and (6b)

from in which R ^x , M, m, P² and R³ have the above-mentioned, particularly preferred meanings, where the benzene nucleus in formulas (6a) and (6b) may additionally contain a hydroxyl group ortho to the amino group -NH₂.

Amines of the general formulas (6) are, for example: 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,3-diaminobenzene, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1,4-diamino-2-methyl-benzene, 1,4-diamino-2-methoxybenzene, 1,3-diamino-4-methyl-benzene, 1,5-diamino-4-methoxybenzene-2-sulfonic acid, 1,5-diamino-4-methoxy-benzene-2-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5-methyl-benzene, 2,6-diamino-naphthalene, 2,6-diamino-naphthalene-4,8-disulfonic acid, 2-amino-5- methylamino-naphthalene-1-sulfonic acid, 2-amino-5-methylamino- naphthalene-1,7-disulfonic acid and 1,4-diamino-naphthalene-6-sulfonic acid.

Preferred radicals D₁ or Z-D₁- and -D₂-Z in formulas (4a) to (4e) and preferred radicals D in formulas (4f) and (4g) are those of the general formulas (5c), (5d) and (5g) and in formula (4h) those of the general formulas (5e), (5f) and (5h):  

in which P¹, P², P³, m and M have the meanings given above to have.

Aromatic residues E of a couplable and diazotizable compound of the general formula H-E-NH₂ are, for example, those of the general formula (7a), (7b) and (7c)

in which
P² and M have the meanings given above,
P⁴ is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, an alkoxy group of 1 to 4 carbon atoms, such as the methoxy and ethoxy group, a chlorine atom, an alkanoylamino group of 2 to 5 carbon atoms such as the acetylamino and propionylamino group, the benzoylamino group, the ureido group, a phenylureido group, an alkylureido group having 1 to 4 carbon atoms in the alkyl radical, a phenylsulfonyl group or an alkylsulfonyl group of 1 to 4 carbon atoms and
m stands for the number zero, 1 or 2 (where this group means a hydrogen atom if p is zero).

Compounds of the formula H-E-NH₂ are for example: Aniline, 3-methylaniline, 3-chloroaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline, 3-methoxyaniline, 3-methyl-6-methoxyaniline, 3-aminophenylurea, 3-acetylamino-6-methylaniline, 2-amino-4-acetyl-aminobenzene-1-sulfonic acid, 1-aminonaphthalene, 1-aminonaphthalene-6- or -7- or -8-sulfonic acid, 3-acetylaminoaniline, 2-methylaniline, 2-methoxyaniline, 3-benzoylamino-aniline, 2,3-dimethylaniline, 3,5-dimethylaniline, 1-amino-2-methoxy-5-acetylamino-benzene, 3-propionylamino-aniline, 3-buturylamino-aniline, 2-sulfo-5-acetylamino-aniline, 2-amino-5-naphthol-7-sulfonic acid and 2-amino-8-naphthol-6-sulfonic acid.

The residues K of the coupling component preferably originate the aniline, naphthalene, pyrazole and acylacetarylide series; they can have fiber-reactive groups.

Coupling components of the formula H-K of the aniline and Examples of naphthalene series are the anilines, N-mono- and N, N-disubstituted anilines, m-phenylenediamines and their derivatives, naphtholsulfonic acids, aminonaphthalenes, Naphthols, hydroxynaphthoic acid derivatives, Aminonaphthalenesulfonic acids or aminonaphtholsulfonic acids.

Coupling components of the formula H-K, none carry fiber-reactive group of the general formula (3), are, for example, compounds of the general formulas (8a) to (8g)  

in which
P¹, P², P³, m and M have the meanings given above,
r represents the number zero, 1, 2 or 3 (where this group means a hydrogen atom if m is zero),
P⁵ alkylureido with alkyl groups of 1 to 6 carbon atoms, phenylureido, in the phenyl radical by chlorine, methyl, methoxy, nitro, sulfo and / or carboxy and / or a group -SO₂-Y with Y of the above meaning substituted phenylureido, alkanoylamino of 2 to 7 carbon atoms, such as, for example, acetylamino and propionylamino, cyclohexanoylamino, benzoylamino or in the benzene radical by chlorine, methyl, methoxy, nitro, sulfo and / or carboxy and / or a group -SO₂-Y with Y of the above meaning benzoylamino,
P⁶ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, bromine chlorine or alkanoylamino of 2 to 7 carbon atoms, such as acetylamino and propionylamino,
P⁷ is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine or alkanoylamino of 2 to 7 carbon atoms, such as acetylamino and propionylamino, an ureido or phenylureido group,
P⁸ is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, cyan, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy,
P⁹ represents alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, cyan, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, or benzyl or phenyl or by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and / or sulfo substituted phenyl,
P¹⁰ hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano, carboxy, carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carbamoyl or phenyl, preferably methyl, carboxy, methoxycarbonyl, ethoxycarbonyl or phenyl and especially methyl or is carboxy,
T represents a benzene or naphthalene ring, preferably a benzene ring,
P¹¹ is hydrogen, alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, which can be substituted by phenyl or sulfophenyl or by hydroxy, amino, methoxy, ethoxy, carboxy, sulfo, acetylamino, benzoylamino or cyano, cyclohexyl , Phenyl or phenyl substituted by carboxy, sulfo, benzoylamino, acetylamino, methyl, methoxy, cyano or chlorine and preferably hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfo or sulfophenyl,
P¹² is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, such as the methyl group, or an alkyl group of 1 to 4 carbon atoms substituted by alkoxy of 1 to 4 carbon atoms, such as methoxy or cyano, preferably an alkyl of 1 to 4 carbon atoms or phenyl, and
P¹³ is hydrogen, chlorine, bromine, sulfo, carbamoyl, methylsulfonyl, phenylsulfonyl, cyano or sulfoalkyl of 1 to 4 carbon atoms, preferably hydrogen, sulfo or sulfoalkyl with an alkyl radical of 1 to 4 carbon atoms, such as sulfomethyl, or cyano or Is carbamoyl.

Compounds of the general formulas (8) are, for example:
1-naphthol-3-sulfonic acid, 1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid, 1-naphthol-8-sulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8- disulfonic acid, 2-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid, 2-naphthol-8-sulfonic acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-6, 8-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-acetylamino-8- hydroxynaphthalene-4,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid, 2-acetylamino-5-hydroxy-naphthalene-7-sulfonic acid, 3-acetylamino-5-hydroxy-naphthalene-7-sulfonic acid, 2-methyl-amino-8-hydroxy-naphthalene-6-sulfonic acid or 2- (3'- and 4'-sulfophenyl) - amino-8-hydroxynaphthalene-6-sulfonic acid, 3- (3'-and 4'-sulfophenyl ) -amino-8-hydroxy-naphthalene-6-sulfonic acid, N, N-di- (β-sulfoethyl) aniline and its mono- in the benzene nucleus by methyl, methoxy and / or ethoxy or disubstituted derivatives, N-ethyl-N- (β-sulfoethyl) aniline, N- (β-sulfoethyl) aniline, N- (β-carboxyethyl) aniline and those mono in the benzene nucleus by methyl, methoxy and / or ethoxy - or disubstituted derivatives, further 1- [3 ′ - (β-chloroethylsulfonyl) benzoylamino] -3,6-disulfo-8-naphthol, 1- [3 ′ - (vinylsulfonyl) benzoylamino] -3,6-disulfo -8-naphthol, 1- [3 ′ - (vinylsulfonyl) benzoylamino] -4,6-disulfo-8-naphthol, 1- [3 ′ - (β-sulfatoethylsulfonyl) benzoylamino] -4,6-disulfo- 8 -naphthol, 2- [3 ′ - (β-chloroethylsulfonyl) benzoylamino] - 6-sulfo-8-naphthol, 2- [3 ′ - (vinylsulfonyl) benzoylamino] - 6-sulfo-8-naphthol, 3- [ 3 ′ - (β-chloroethylsulfonyl) benzoylamino] - 6-sulfo-8-naphthol, 3- [3 ′ - (vinylsulfonyl) benzoylamino] - 6-sulfo-8-naphthol, 2- [N-methyl-N- (β-sulfatoethylsulfonyl) amino] -6-sulfo-8-naphthol, 3- [N-methyl- N- (β-sulfatoethylsulfonyl) amino] -6-sulfo-8-naphthol, 2- [N-ethyl- N- (β-sulfatoethylsulfonyl) amino] -6-sulfo-8-naphthol, 1- [N ′ - (3'-β-chloroethylsulfonylphenyl) -ureido] - 3,6-disulfo-8-naphthol, 1- [N ′ - (3′-vinylsulfonylphenyl) - ureido] -3,6-disulfo-8-naphthol, 1- [N ′ - (3rd '-Vinylsulfonylpropyl) - ureido] -3,6-disulfo-8-naphthol, 1- [N' - (3'-β-chloroethylsulfonylphenyl) -ureido] -4,6-disulfo-8-naphthol, 1- [N ′ - (3′-vinylsulfonylphenyl) -ureido] -4,6-disulfo-8-naphthol, 1- [N ′ - (3′-β-chloroethylsulfonyl-propyl) -ureido] - 4,6- disulfo-8-naphthol, 2- [N ′ - (3′-β-sulfatoethylsulfonylphenyl) ureido] -6-sulfo-8-naphthol, 2- [N ′ - (3′-β-chloroethylsulfonylpropyl) -ureido ] -6-sulfo-8-naphthol, 3- [N ′ - (3′-β-chloroethylsulfonylphenyl) -ureido] -6-sulfo-8-naphthol and 3- [N ′ - (3′-vinylsulfonyl- propyl) -ureido] -6-sulfo-8-naphthol.

Of these, sulfo-containing, optionally azo groups, such as 1 or 2 azo groups, load-bearing coupling components in the o- or p-position couple a hydroxy and / or amino group, such as for example 2-acetylamino-5-hydroxy-naphthalene 7-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6- sulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene 3,6-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene 4,6-disulfonic acid or 1-benzoylamino-8-hydroxynaphthalene 4,6-disulfonic acid.

Pyrazolone coupling components are, for example, 3-methyl-, 3-carboxy- and 3- (C₂-C₅-alkoxycarbonyl) -5-pyrazolones which are hydrogen in the 1-position, optionally by methyl, ethyl, fluorine, chlorine, bromine, trifluoromethyl, Methoxy, ethoxy, cyano, phenoxy, phenylsulfonyl, methylsulfonyl, sulfo, benzoyl, acetyl, acetylamino, nitro, hydroxy, carboxy, carbamoyl and / or sulfamoyl carry substituted phenyl or sulfo-substituted 1- or 2-naphthyl, for example:
1- (2′-methoxy-5′-methylphenyl) -, 1- (2′-chloro-5′-sulfophenyl) -, 1- (2′-methoxy-5′-sulfophenyl) -, 1- (2 ′ -Methyl-4′-sulfophenyl) -, 1- (2 ′, 5′-dichloro-4′-sulfophenyl) -, 1- (2 ′, 5′-disulfophenyl) -, 1- (2′-carboxyphenyl) - , 1- (3′-sulfophenyl) -, 1- (4′-sulfophenyl) - 1- (3′-sulfamoylphenyl) -3-carboxy-5-pyrazolone, 1- (3′- or 4′-sulfophenyl) - , 1- (2′-chloro-4′- or -5′-sulfophenyl) -, 1- (2′-methyl-4′-sulfophenyl) -, 1- (4 ′, 8′-disulfo-2′- naphthyl) - and 1-) 6'-sulfo-1'-naphthyl) - 3-methyl-5-pyrazolone, 1-phenyl-5-pyrazolone-3-carboxylic acid ethyl ester, 5-pyrazolone-3-carboxylic acid ethyl ester, 5-pyrazolone 3-carboxylic acid, 1- [4 ′ - (β-sulfatoethylsulfonyl) -2′-sulfo] -phenyl-3-methyl-pyrazol-5-one, 1- [4′-β-sulfatoethylsulfonyl)] - phenyl- 3-carboxy-pyrazol-5-one, 1- [4'-β-sulfatoethylsulfonyl)] - phenyl-3-methyl-pyrazol-5-one, 1- [3'-β-sulfatoethylsulfonyl)] - phenyl-3- carboxy-pyrazol-5-one, 1- [3′-β-sulfatoethylsulfonyl)] - phenyl-3-methyl-pyrazol-5-one, and 1- (4 ′ -Sulfophenyl) -3-carboxy-pyrazol-5-one.

Pyridone coupling components are for example 1-ethyl-2-hydroxy-4-methyl-5-carbonamido-pyridone-6, 1- (2'- Hydroxyethyl) -2-hydroxy-4-methyl-5-carbonamido-pyridon-6, 1- (4'-sulfo-phenyl) -2-hydroxy-4-methyl-5-carbonamido pyridone-6, 1- (2'-sulfoethyl) -2-hydroxy-4-methyl-5-cyanopyridone- 6, 1-ethyl-2-hydroxy-4-sulfomethyl-5-carbonamido pyridone-6, 1-ethyl-2-hydroxy-4-methyl-5-sulfomethyl- pyridone-6, 1-methyl-2-hydroxy-4-methyl-5-cyano-pyridone-6, 1-methyl-2-hydroxy-5-acetyl-pyridone-6, 1,4-dimethyl-2- hydroxy-5-cyanopyridone-6, 1,4-dimethyl-2-hydroxy- 5-carbonamido-pyridon-6, 2,6-dihydroxy-4-ethyl-5-cyanopyridine, 2,6-dihydroxy-4-ethyl-5-carbonamido-pyridine, 1-ethyl-2-hydroxy-4-methyl-5-sulfomethyl-pyridon-6, 1-methyl-2-hydroxy-4-methyl-5-methylsulfonyl-pyridon-6, 1-carboxymethyl-2-hydroxy-4-ethyl-5-phenylsulfonyl- pyridone-6 and 1- (2'-sulfo-ethyl) -2-hydroxy-4-carboxy- pyridon-6, and acetoacetyl-arylamide coupling components are, for example, acetoacetyl- (2-methoxy-4-sulfo-5- methyl) aniline, acetoacetyl (2,4-dimethoxy-5-methyl) aniline and acetoacetyl- (4-β-sulfatoethylsulfonyl) aniline.  

As coupling components H-K continue to be special name: 1-amino-8-hydroxynaphthalene-3,6- and 4,6-disulfonic acid as well as those obtained by acid coupling Arylazo coupling products of formula (9a)

in which
D¹ is the residue of a diazo component, for example a residue of the formula (10a) or (10b)

where P¹, P², P³, M and m are those given above Have meanings.

Individual residues D 1 are, for example: phenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 1,5-disulfonaphth- 2-yl, 4,8-disulfonaphth-2-yl, 3,6,8-trisulfonaphth-2-yl, 4,6,8-trisulfonaphth-2-yl, 3,6,8-trisulfonaphth-1-yl, 4,6,8-trisulfonaphth-1-yl, 4-sulfonaphth-1-yl, 1-sulfo- naphth-2-yl, 3-acetylamino-phenyl, 4-acetylamino-phenyl, 4-acetylamino-2-sulfophenyl, 5-acetylamino-2-sulfophenyl, 4-nitro-phenyl, 4-nitro-2-sulfo-phenyl, 6-acetylamino-4,8- disulfonaphth-2-yl, 4- (β-sulfatoethylsulfonyl) phenyl and 3- (β-sulfatoethylsulfonyl) phenyl.

Coupling components according to the invention the fiber-reactive Contain group of formula (3) or in which fiber-reactive group, possibly only after the Coupling reaction that can be introduced for example compounds of the general formulas (11a) to (11h) or their Z ° -free preliminary products:  

in which
R ^x , P², P³, P¹⁰, P¹², P¹³, D², M, m and T have the above-mentioned, particularly preferred meanings given, B alkyl of 1 to 4 carbon atoms, benzyl or phenethyl or phenyl or in the benzene radical by fluorine, Chlorine, bromine, methyl, methoxy, cyano, sulfo, carboxy, acetyl, nitro, carbamoyl and / or sulfamoyl is substituted benzyl, phenethyl or phenyl, where in the case of "benzyl" and "phenethyl" the group -N (R ^x ) -Z ° is bound to the benzene nucleus,
Z ° is a radical of the formula (3), (3a) or (3b) free from the group -N (R ^x ) - or -N (R ′) -,
D² is the residue of a diazo component having a fiber-reactive group, in particular of the formula (3), preferably a residue of the above-mentioned formula (10a) or (10b) with P¹ being a group of the formula -SO₂Y or a residue of the formula (10c)

is in which R ^x , P², P³ and Z ° have the above-mentioned, particularly preferred meanings.

Aromatic diamines from the rest of the formula (10c) are, for example:
1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diaminobenzene, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene 2,5-disulfonic acid, 1,4-diamino-2-methyl-benzene, 1,4-diamino-2-methoxybenzene, 1,3-diamino-4-methyl-benzene, 1,4-diaminobenzene-2,6- disulfonic acid, 1,5-diamino-4-methylbenzene-2-sulfonic acid, 1,5-diamino-4-methoxybenzene-2-sulfonic acid, in all of these diamino compounds the one primary or secondary amino group is substituted by the fiber-reactive radical Z °.

Radical K in the formulas (4b) and 4f), which the group Z not included are, in particular, residues of the general Formulas (12a) to (12h)

in which the individual formula members the above Have meanings.

Radical K in the formulas (4a), (4c) and (4f), which the group Z contain, are therefore in particular residues of the general Formulas (12j) to (12p)

in which the individual formula members the above Have meanings.

Residues K in the formula (4h) with a metal complex-binding Oxygen atom, which may contain group Z, are in particular those of the formulas (13a) to (13f)

in which Z * has one of the meanings of P¹ or Z and the formula members have one of the meanings mentioned above to have.

The abovementioned coupling components of the general formulas (11a) and (11d) to (11h) can be derived from their Z ° -free starting compounds, ie those amino starting compounds which, instead of the group -N (R ^x ) -Z °, the group -N ( R ^x ) -H have, can be prepared by reaction with a compound of the general formula (60) given later. In contrast, the compounds of the general formulas (11b) and (11c) are themselves not useful as coupling components. They must be used as coupling components in the form of their Z-free amino compounds; after the coupling reaction, the fiber-reactive radical Z ° can be introduced into the azo compound thus formed by reaction with a compound of the general formula (60). This method can also be chosen for the Z ° -free amino starting compounds of the compounds (11a) and (11d) to (11h).

In all of the formulas above, the individual formula elements, both different and the same name within a general formula, within the meaning mutually identical and different meanings to have.

The present invention further relates to methods for Production of the dyes of the general Formula 1). They are more common in and of themselves Way known analog, for the respective dye class produce specific synthetic routes by for respective dye typical intermediate products, of which at least one a group of the general formula (3)  contains, with each other or by one of amino group-containing starting compound of the general Formula (55)

in which F, R ^x and n have the meanings given above, and these with a trihalo-s-triazine of the general formula (56)

in which Hal for a halogen atom, such as especially chlorine or fluorine atom, stands with cyanamide or a Alkali metal salt thereof and with an amine of the general Formula H-Q with Q of the meaning given above in stoichiometric amounts in any order with each other implemented and, if appropriate, then further, to the expert carries out common, required conversion reactions.

In particular, the dyes of the invention produce according to the invention by connecting according to the general formula (57)

in which F, R ^x and n have the meanings given above and Hal represents a halogen atom, in particular a chlorine or fluorine atom, is reacted with cyanamide or an alkali metal salt thereof and the compound of the general formula (58) thus obtained

in which F, R ^x and Hal have the abovementioned meanings, reacted with an amine of the general formula HQ with Q of the abovementioned meaning or in that a compound of the general formula (59)

in which F, R ^x , Hal, Q and n have the meanings given above, with cyanamide or an alkali metal salt thereof, or by reacting a compound of the general formula (55) with a compound of the general formula (60)

with Hal and Q of the meaning given above.

Leave the starting compounds of general formula (58) in addition to the procedure of Reaction of a compound of formula (57) with cyanamide also so that, analogously to known procedures, a corresponding 2,4-dihalo-6-cyanamido-s-triazine with reacting a starting compound of the general formula (55) or, also analogously to known procedures, by Reaction of a dye precursor which is a group of general formula (61)

contains, in which R ^x and Hal have the abovementioned meanings, reacted with a further preliminary product which may contain a group of the formula (61).

Leave the starting compounds of general formula (59) produce yourself by, analogous known Procedures, such as connecting the general formula (57) with an amine of the general Formula H-Q with Q of the meaning given above or a Compound of the general formula (62)

in which Hal and Q have the meanings given above, with a starting compound of the general formula (55) implements. The output connection (62) itself can in turn analogous to known procedures by implementing one Trihalogen-s-triazine with an amine of the general formula H-Q with Q of the meaning given above.

The dyes according to the invention can, starting from one or more starting products with one β-hydroxyethylsulfonyl group, such as from an amine general formula H-Q with Q of the meaning given above, but with the difference that the group (s) of the formula -SO₂-Y are β-hydroxyethylsulfonyl groups, according to the invention also be prepared so that one analogously to the above specified inventive procedures first a Establishes the initial connection that of the general Formula (1) with the meaning given corresponds, however with the difference that the group (s) -SO₂-Y are β-hydroxyethylsulfonyl groups, and in this Starting compound the β-hydroxyethylsulfonyl groups analogous to known procedures in other groups -SO₂-Y transferred according to the compound (1) according to the invention, for example in their ester derivatives, such as for example of polyvalent inorganic acids or of aliphatic and aromatic carbon or  Sulfonic acids, for example in compounds in which Y for the β-chloroethyl, β-sulfatoethyl, β-phosphatoethyl, β-thiosulfatoethyl, β-acetyloxyethyl or β-tolylsulfonyloxyethyl group. Suitable for this Esterification and acylating agents are, for example corresponding inorganic or organic acids or their anhydrides or halides or amides, such as for example containing sulfuric acid, sulfur trioxide Sulfuric acid, chlorosulfonic acid, amidosulfonic acid, Phosphoric acid, polyphosphoric acid, phosphorus oxychloride, Mixtures of phosphoric acid and phosphorus pentoxide, Acetic anhydride, toluenesulfochloride and thionyl chloride.

The sulfation is carried out, for example, by Reaction with concentrated sulfuric acid in a Temperature between 0 and 20 ° C or by reaction with Chlorosulfonic acid in a polar organic solvent, such as N-methyl-pyrrolidone at one temperature between 10 and 80 ° C. The sulfation is preferably carried out by entering the β-hydroxy group-containing Starting dye in sulfuric acid monohydrate at a Temperature between 5 and 15 ° C.

Those compounds in which Y is for the vinyl group stands, can from their analog ester derivatives Alkali, so in an aqueous medium at a pH of 10 to 12 and a temperature between 30 and 50 ° C for 10 to 20 minutes. The synthesis of for example β- (dialkylamino) ethylsulfonyl and β-thiosulfatoethylsulfonyl derivatives is done by implementing whose vinyl sulfonyl compounds with the corresponding Dialkylamine or with an alkali salt of thiosulfuric acid, like sodium thiosulfate. All of these practices of Transfer from one group -SO₂-Y to another familiar to the expert in this fiber-reactive field and numerous described in the literature.  

The reaction of the starting compound of the general formula (57) with the amine of the general formula H-Q takes place in aqueous or aqueous-organic medium in suspension or Solution at a temperature between 15 and 70 ° C, preferably between 25 and 45 ° C, and at a pH between 3 and 11.5, preferably between 3.5 and 7. If the reaction is carried out in an aqueous-organic medium through, the organic medium is, for example, acetone, Dimethylformamide and N-methyl-pyrrolidone. Will be beneficial the hydrogen halide released during the condensation continuously by adding aqueous alkali hydroxides, carbonates or bicarbonates neutralized.

The reaction of a starting compound of the general Formula (58) with an amine of the general formula H-Q also takes place in an aqueous or aqueous-organic medium in suspension or solution at a temperature between 30 and 100 ° C, preferably between 65 and 85 ° C, and at one pH between 3 and 11.5, preferably between 3.5 and 7.

The condensation of the halotriazine with a compound of the formula H-Q, also preferably in aqueous solution or suspension, at 0 to 30 ° C at a pH between 1.8 and 9.5. Here, too, at the Condensation-releasing hydrogen halide advantageously by continuous addition of aqueous Alkali hydroxides, carbonates or bicarbonates neutralized.

The reaction of the compound of formula (55) with the Compound of the general formula (60) is preferably carried out at a temperature between 25 and 90 ° C, in particular between 45 and 75 ° C, and at a pH between 3 and 11.5, especially between 3.5 and 6.5.  

In the reactions mentioned above, the amine is used Formula H-Q usually in the form of a salt, such as one Sulfate or preferably in the form of the hydrochloride.

If you go in the synthesis of the invention Azo dyes from diazo and coupling components, one or both of which are a group of general Contain formula (3), the implementation takes place in the usual procedure of diazotization and Coupling reactions, so the diazotization usually at a temperature between -5 ° C and + 15 ° C and one pH below 2 using a strong acid and alkali nitrite in preferably aqueous medium and the Coupling reaction usually at a pH between 1.5 and 4.5 in the case of an amino group Coupling component and at a pH between 3 and 7.5 in the case of a coupling component containing hydroxy groups and at a temperature between 0 and 25 ° C as well preferably in an aqueous medium.

In the synthesis of the invention according to the invention Heavy metal complex azo dyes can be used, for example also assume such metal-free azo dyes that correspond to the general formula (1), but in which the diazo and coupling components in the ortho position Azo group each capable of complex formation Contain hydroxy group. This o, o'-dihydroxy Azo starting compound corresponds to the general formula (1) is then carried out in a customary and known manner with an agent which emits a copper ion, such as for example copper chloride and copper sulfate, for copper complex azo dye according to the invention implemented.

The starting amines of the general formula H-Q are numerous described in the literature, for example in the German Patent Nos. 8 87 505 and 9 65 902, in the German Offenlegungsschriften No. 20 40 620 and 26 14 550 and in European patent application publications No. 01 07 614, 01 44 766, 01 59 292 and 02 78 904.  

The dyes of the formula (1) according to the invention are suitable for dyeing and printing various materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and especially cellulosic fiber materials of all Art. Such fiber materials are, for example natural cellulose fibers such as cotton, linen and Hemp, as well as cellulose and regenerated cellulose. The Dyes of formula (1) are also for dyeing or Suitable for printing fibers containing hydroxy groups are contained in blended fabrics, e.g. B. from mixtures Cotton with polyester fibers or polyamide fibers.

The dyes of the invention can be different Apply way to the fiber material and on the fiber fix, especially in the form of aqueous dye solutions and printing pastes. They are suitable for both Extraction process as well as for dyeing after Foulard dyeing process, according to which the goods are mixed with aqueous optionally impregnated with salt-containing dye solutions and the dye after an alkali treatment or in Presence of alkali, possibly under the action of heat, is fixed. Those according to the invention are particularly suitable Dyes for the so-called cold residence process, after which the dye along with the alkali on the foulard applied and then by storage for several hours Room temperature is fixed. After fixing the Dyeing or printing with cold and hot water, optionally with the addition of a dispersing and promote the diffusion of the unfixed portions Medium, rinsed thoroughly.

The present invention therefore also relates to Use of the compounds of the invention general formula (1) for dyeing (including the Printing) of these materials or processes for dyeing (and printing) of such materials in and of itself usual procedure in which a connection of the general formula (1) is used as colorant,  by the compound of general formula (1) in applied aqueous medium to the material and using it Heat or by means of an alkaline compound or fixed on the material by means of both.

The dyes of the formula (1) are notable for high Reactivity, good fixability and a very good one Build up assets. You can therefore after Pull-out dyeing process at low dyeing temperatures are used and only require in the pad-steam process short steaming times. The degrees of fixation are high, and they are not fixed portions can be easily washed out, whereby the difference between the degree of extension and the degree of fixation remarkably small, d. H. the soap loss is very low. The dyes of the formula (1) are also particularly suitable for printing, especially on cotton, but also for printing Printing nitrogen-containing fibers, e.g. B. of wool or silk or of blended fabrics, the wool or silk contain.

The produced with the dyes of the invention Have dyeings and prints on cellulose fiber materials a high color strength and a high fiber dye Binding stability, both in acidic and alkaline Area, continue to have good lightfastness and very good Wet fastness properties, such as washing, water, sea water, Overdye and perspiration fastness, as well as good Fastness to pleating, fastness to ironing and fastness to rubbing.

The following examples serve to explain the Invention. The parts are parts by weight, the percentages represent percentages by weight, unless otherwise noted. Parts by weight refer to parts by volume such as kilograms to liters.  

The formulas described in these examples Compounds are given in the form of the free acids; in the generally they are in the form of their alkali metal salts, such as lithium, sodium or potassium salts, manufactured and isolated and used in the form of their salts for coloring.

Likewise, in the examples below in the form the starting compounds called free acid and Components as such or in the form of their salts, preferably alkali metal salts, in the synthesis be used.

The absorption maxima (λ _max ) given for the compounds according to the invention in the visible range were determined on the basis of their alkali metal salts in aqueous solution. In the table examples, the λ _max values are given in brackets for the color shade; the wavelength specification refers to nm.

Example 1

45.3 parts of 3- (2'-sulfo-4'-methoxy-phenylazo) -4-hydroxy-7- amino-naphthalene-2-sulfonic acid are in aqueous solution at a temperature of 0 to 5 ° C and a pH of 4 reacted with 19 parts of cyanuric chloride. Then there 4.4 parts of cyanamide are added, using sodium hydroxide solution a pH of 10 and carries out the reaction during about 1.5 hours at a temperature of 60 ° C and at pH between 9.5 and 10. The so made Monochlorotriazine azo compound is in the synthesis solution with 29.5 parts of 3- (β-sulfatoethylsulfonyl) aniline in one pH of 4 and a temperature of 85 ° C implemented. To The end of this condensation reaction is the one formed dye according to the invention, the, in the form of the free acid written the formula

by evaporation under reduced pressure or by spray drying as alkali metal salt (sodium salt) isolated. It has very good fiber-reactive Dye properties and delivers after for fiber reactive Dyes usual application procedures, strong, brilliant scarlet colorings and prints with good Authenticity properties, of which in particular the Water fastness and perspiration fastness are emphasized can. It is particularly characterized by a high Degree of fixation both in the exhaust process at temperatures between 40 and 80 ° C as well as in the block cold Dyeing process.  

Example 2

54.5 parts of 3-ureido-4- (3 ′, 6 ′, 8′-trisulfo-2′-naphthylazo) - aniline are in aqueous solution at 0 to 5 ° C and one pH of 4 with 19 parts of finely dispersed cyanuric chloride implemented. Then 4.4 parts of cyanamide are added and carries out the second condensation reaction for about two Hours at a pH between 9.5 and 10 and one Temperature between 60 and 70 ° C. The third Condensation reaction takes place after the addition of 23 parts 4- (β-hydroxyethylsulfonyl) phenethylamine at pH from 9 and a temperature from 80 to 90 ° C. After finished Implementation is the azo compound of the formula (in Form of free acid written)

from which the pH is adjusted to 7 Salt out synthesis solution using potassium chloride, isolated and dried. The organ red powder obtained contains the Azo compound to about 70%.

10 parts of this powder are at 5 to 10 ° C with stirring entered in 100% sulfuric acid. After more complete Solution of the product gives this approach to 80 parts  Ice and make using dilute aqueous potassium hydroxide solution carefully enter a pH of 6. The educated dye according to the invention is by means of salting out Potassium chloride as an alkali metal salt (mainly potassium salt) isolated. It has, written in the form of free acid, the formula

and colors the materials mentioned in the description, such as in particular cellulose fiber materials, for example Cotton, in strong, reddish yellow, real tones.

Example 3

48.3 parts of 1- (4′-sulfophenyl) -3-carboxy-4- (5 ″ -amino-2 ″ - sulfo-phenylazo) -5-pyrazolone are in aqueous solution at 0 to 3 ° C and a pH of 3.5 to 4 with 19 parts Implemented cyanuric chloride. Then you give 4.4 parts Adding cyanamide, using aqueous sodium hydroxide solution pH to 10 and warms the batch to 50 to 60 ° C. Man stir in at 50 to 60 ° C for 90 to 120 minutes Compliance with the pH between 9.5 and 10 and gives after the condensation reaction has ended, aqueous hydrochloric acid to to a pH of 5 and then 29.5 parts Add 3- (β-sulfatoethylsulfonyl), warm the batch 85 ° C and stirred with a pH of 3.5 to 4 until the complete condensation reaction continues.

The azo dye according to the invention formed is in the form its alkali metal salt (sodium salt) by evaporation the synthesis solution under reduced pressure or by Spray drying isolated. He owns, in the form of free Written acid, the formula  

and has very good fiber-reactive dye properties on. He colors the according to the known application techniques materials mentioned in the description, such as in particular Cellulose fiber materials in bright yellow tones with good fastness properties, of which in particular the can be highlighted. He also excels due to a very high fixation yield both during dyeing in the extraction process between 40 and 80 ° C as well as in the block-cold-retention dyeing process.

Example 4

A suspension of 19 parts of cyanuric chloride in 200 parts Ice water is mixed with 18.8 parts of 1.3 diaminobenzene-4- sulfonic acid added. The approach is initially stirred two hours at 0 to 5 ° C and at a pH of 2.5 and then about 30 minutes at 0 to 5 ° C and one pH value of 4. Then 4.4 parts of cyanamide are added, sets a pH of 10 using sodium hydroxide solution, slowly increase the temperature to 50 to 60 ° C and stir about 1.5 hours while maintaining a pH value of 10 and a temperature of 50 to 60 ° C further. Then the pH is adjusted to 7 using aqueous hydrochloric acid , gives 20 volumes of an aqueous 5n sodium nitrite Solution added and diazotized by slowly adding this Approach concentrated in a mixture of 50 parts by volume Hydrochloric acid and 600 parts of ice. Stir for about 2 hours more and in the usual way destroys any Excess nitrous acid using amidosulfonic acid.  

The diazonium salt suspension obtained is then in a aqueous solution of the sodium salt of 60 parts of 4-hydroxy 5-amino-6- [4 ′ - (β-sulfatoethylsulfonyl) phenylazo] - given naphthalene-2,7-disulfonic acid. You run it Coupling reaction at 15 to 25 ° C and a pH of 4.5 to 5.5 through, then gives 29.5 parts 4- (β-sulfatoethylsulfonyl) aniline is added and leads the Condensation reaction at 85 ° C and pH 3.5 to 4 for about 2 hours. The approach is clarified then with a little kieselguhr at about 40 ° C and filtration and evaporate the filtrate.

A black, electrolyte-containing powder of Alkali metal salt (sodium salt) of the disazo compound of the formula

It shows very good fiber-reactive dye properties and dyes cotton in strong, navy blue tones.

Example 5

For the production of an azo dye according to the invention the procedure of Example 4 is followed, sets instead of the 29.5 parts 4- (β-sulfatoethylsulfonyl) aniline in the reaction with the same amount of the chlorotriazine compound 3- (β-sulfatoethylsulfonyl) aniline. The alkali metal salt of the disazo compound is obtained formula  

for example cotton in strong, navy blue Tones colors.

Examples 6 to 13

In the table examples below there are more Azo dyes according to the invention with the aid of the components according to the general formula (B)

described. They can be used in the manner according to the invention, for example analogously to one of the above exemplary embodiments, using the components which can be seen from the respective table example in conjunction with the general formula (B) (such as a diaminophenylene or naphthylene of the formula HR ^x ND-NH₂, the coupling component HK , a halotriazine, cyanamide and an amine of the formula HQ). They have very good fiber-reactive dye properties and dye the materials mentioned in the description, in particular cellulose fiber materials, such as cotton, in the shades specified in the respective table example (cotton for this) in high color strength and with good fastness properties.

Claims (7)

1. Water-soluble dye according to the general formula (1) in which mean:
F is the residue of a monoazo or disazo dye or a copper complex monoazo or disazo dye;
R ^x is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, which is substituted by halogen, hydroxy, cyano, alkoxy or 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo or sulfato can be;
n is the number 1 or 2, preferably 1;
Q is a group of the general formula (2a) or (2b) in which
R ^{z is} a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, which is replaced by halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, carboxy, sulfamoyl, sulfo or sulfato or by an optionally by substituent from the group halogen , Alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms, sulfo and carboxy substituted phenyl radical, or a cyclohexyl radical or an optionally substituted by substituents from the group halogen, alkoxy of 1 to 4 carbon atoms, Is alkyl of 1 to 4 carbon atoms, sulfo and carboxy substituted phenyl radical,
W is an optionally substituted arylene radical or an alkylene-arylene or arylene-alkylene or alkylene-arylene-alkylene or arylene-alkylene-arylene radical, where the alkylene radicals are those of 1 to 8 carbon atoms and can be substituted and the arylene radicals are optionally substituted phenylene or naphthylene radicals, and the alkylene radicals can be interrupted by one or more hetero groups and the alkylene and arylene portions in the combined arylene / alkylene radicals can each be interrupted by a hetero group,
Y is the vinyl group, a β-sulfatoethyl, β-thiosulfatoethyl or β-phosphatoethyl group, a β-alkanoyloxy-ethyl group with 2 to 5 carbon atoms in the alkanoyl radical, the β-benzoyloxy-ethyl, β- ( Is sulfobenzoyloxy) ethyl, β- (p-toluenesulfonyloxy) ethyl group or a β-haloethyl group,
z is the number 1 or 2,
A represents the number zero or 1 and
B represents the number 1 or 2,
where the sum of (A + B) is equal to the number 2 and where, in the case of B is 2, the groups of the formula -W- (SO₂-Y) _{k can have} the same meaning to one another or a different meaning from one another,
X together with the N atom represents the divalent radical of one of 1 or 2 alkylene groups of 1 to 5 C atoms and optionally 1 or 2 hetero groups and
alk is an alkylene radical of 1 to 4 carbon atoms. 2. Dye according to claim 1, characterized in that R ^{x represents} the methyl or ethyl group or a hydrogen atom. 3. Dye according to claim 1 or 2, characterized in that Q is a group of the general formula (3b) means in which R 'represents the methyl or ethyl group or preferably a hydrogen atom, R ″ represents a hydrogen atom or the methyl or ethyl group, W¹ is an alkylene group of 2 to 4 carbon atoms, preferably 3 carbon atoms, or a Phenylene radical, which may be substituted by 1 or 2 substituents from the group methyl, ethyl, methoxy, ethoxy and chlorine, and Y has the meaning given in claim 1. 4. dye according to at least one of claims 1 to 3, characterized in that Y is the β-sulfatoethyl group is. 5. A process for the preparation of a dye of claim 1, characterized in that typical precursors for the respective dye, at least one of which contains a group of the general formula (3), are reacted with one another analogously to known procedures, or that an amino compound-containing starting compound of the general Formula (55) in which F, R ^x and n have the meanings given in Claim 1, with a trihalogen-s-triazine of the general formula (56) in which Hal represents a halogen atom, with cyanamide or an alkali metal salt thereof and with an amine of the general formula HQ with Q as defined in claim 1 in stoichiometric amounts in any order with one another and optionally subsequently carrying out further necessary conversion reactions, or in that a starting compound which corresponds to the general formula (1), but in which the group (s) of the formula -SO₂-Y are β-hydroxyethylsulfonyl groups, these into another group -SO₂-Y with Y having the meaning given in claim 1 , preferably in the β-sulfatoethylsulfonyl group. 6. Use of a compound of the general formula (1) of claim 1 for dyeing (including printing) of hydroxy- and / or carbonamide group-containing Material, especially fiber material. 7. Process for dyeing (including printing) material containing hydroxyl and / or carbonamide groups, especially fiber material, in which one Applying dye to or into the material Introduces material and it by means of heat and / or with Fixed with the help of an alkaline agent characterized in that a dye is a compound the general specified and defined in claim 1 Formula (1) is used.