DE4316539A1 - Water-soluble fibre-reactive dyes, preparation thereof and use thereof - Google Patents

Abstract

Described are dyes which contain one or two fibre-reactive radicals of the general formula <IMAGE> and also the novel amino intermediates of the formula HN(R<0>)-(CH2)3-SO2-Y<1>. In these formulae R<A> is hydrogen or lower alkyl which can be substituted by halogen, hydroxyl, cyano, lower alkoxy, lower alkoxycarbonyl, carboxyl, sulphamoyl, sulpho, sulphato or phosphato; R is alkyl of 1 to 6 carbon atoms which can be substituted by halogen, hydroxyl, cyano, lower alkoxy, lower alkoxycarbonyl, carboxyl, sulphamoyl, sulpho, sulphato, phosphato, phenyl or sulphenyl, or phenyl which can be substituted by halogen, lower alkyl, lower alkoxy, sulpho and/or carboxyl; X is halogen, cyanoamino, methylsulphonylamino, ethylsulphonylamino, carboxypyridinyl, aminocarbonylpyridinyl or a group of the formula -N(R)-W-(SO2-Y)z where R, W, X and z have the above- or below-indicated meaning; W is alkylene of 3 to 8 carbon atoms which can be substituted by alkoxy, halogen, alkoxycarbonyl, carboxyl, sulpho and/or sulphato or by an optionally sulpho-, carboxyl-, methoxy-, ethoxy- and/or methyl-substituted phenyl radical or by such an optionally substituted phenyl radical and a sulpho, sulphato or carboxyl group or by a heterocyclic radical; Y is vinyl, beta -sulphatoethyl, beta -thiosulphatoethyl, beta -phosphatoethyl, beta -alkanoyloxyethyl, beta -sulphobenzoyloxyethyl, ... Original abstract incomplete.

Description

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

The practice of dyeing with fiber-reactive dyes has increased recently increased demands on the quality of the dyeings and the Profitability of the dyeing process. As a result, it continues to exist a need for new fiber-reactive dyes that improved Properties, not only in terms of fastness, but also high Have degree of fixation on the material to be colored. So are from the European Patent Application Publications No. 0 070 806, 0 070 807, 0 374 758 and 0 499 588 and from U.S. Patent Nos. 4 908 436 and 5 138 041 fiber-reactive dyes known, the one Monohalogen-s-triazinylamino radical contained by means of the amino group and an aliphatic bridge member with a fiber-reactive group of Vinyl sulfone series is connected. These well-known dyes are because of mentioned increased requirements especially with regard to their Degrees of fixation and the color strength of the dyeings and prints available with them in need of improvement.

With the present invention, new fiber-reactive dyes have now been developed the general formula (1) given and defined below, which differ advantageously from the known dyes and Deliver dyeings and prints with high color strength.

F - Z _n (1)

in which
F is the remainder of a sulfo group-containing mono-, dis- or polyazo dye, such as trisazo dye, or a heavy metal complex mono-, dis- or trisazo dye or an anthraquinone, azomethine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene -, nitroaryl, naphthoquinone, pyrenquinone, perylene tetracarbimide, formazane, copper formazane, phthalocyanine, copper phthalocyanine, nickel phthalocyanine or cobalt phthalocyanine dye or triphendioxazine dye,
Z is a group of the general formula (2)

means in which
R ^{A is} hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, 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 C atoms, such as carbethoxy and carbomethoxy, carboxy, sulfamoyl, sulfo, sulfato or phosphato, can be substituted, and is preferably methyl or ethyl and particularly preferably hydrogen,
R is alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as in particular methyl or ethyl, which 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, such as carbomethoxy and carbethoxy, carboxy, sulfamoyl, sulfo, sulfato, phosphato, phenyl or sulfophenyl, or phenyl which can be substituted by 1, 2 or 3, preferably 1 or 2, substituents from the group halogen, such as chlorine and bromine, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, sulfo and carboxy, preferably by methyl, methoxy or sulfo , can be substituted,
X halogen, such as fluorine and chlorine, cyanoamino, methylsulfonylamino, ethylsulfonylamino, carboxy-pyridinyl, aminocarbonyl-pyridinyl or a radical of the formula -N (R) -W- (SO₂-Y) _z with R, W, Y and z one of the meanings given below,
W is alkylene of 3 to 8 carbon atoms, preferably of 3 to 6 carbon atoms, is particularly preferably n-propylene which has 1 or 2 substituents, preferably 1 substituent, from the group alkoxy of 1 to 6 carbon atoms , preferably 1 to 4 carbon atoms, halogen, such as chlorine and bromine, alkoxycarbonyl of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carboxy, sulfo and sulfato, can be substituted,
Y is vinyl or β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β- (C₂-C₅-alkanoyloxy) -ethyl, such as β-acetyloxyethyl, β-benzoyloxyethyl, β- (sulfobenzoyloxy) -ethyl, β- (p- Toluenesulfonyloxy) ethyl or β-haloethyl, such as β-bromoethyl or β-chloroethyl, and preferably vinyl and particularly preferably β-chloroethyl or β-sulfatoethyl and
z is the number 1 or 2, preferably 1, and
n is the number 1 or 2, preferably 1.

F is preferably the residue of a mono- or disazo dye or the residue of one Heavy metal complex azo dye, such as a 1: 2 chromium complex, 1: 2- Cobalt complex and especially an o, o'-1: 1 copper complex monoazo or disazo dye, or the rest of an anthraquinone or Copper formazan or a nickel or copper phthalocyanine dye or Triphendioxazine dye.

The dye residue F has one or more, such as 2 to 6, sulfo groups. Of the Residue F can be further substituents customary in organic dyes contain. Examples of such substituents are: alkyl groups from 1 to 4  C atoms such as methyl, ethyl, propyl, isopropyl or butyl are preferred thereof Ethyl and especially methyl; Alkoxy groups of 1 to 4 carbon atoms, such as Methoxy, ethoxy, propoxy, isopropoxy and butoxy, preferably ethoxy thereof and especially methoxy; Alkanoylamino groups of 2 to 5 carbon atoms, such as the acetylamino and propionylamino group; optionally by sulfo, Carboxy, methyl, ethyl, methoxy, ethoxy and / or chlorine substituted Benzoylamino groups; primary and mono- or disubstituted amino groups, where the substituents are, for example, alkyl groups of 1 to 4 carbon atoms and / or are phenyl groups, such as monoalkylamino and dialkylamino groups with 1 to 4 carbon atoms in the alkyl radical, phenylamino or N- (C₁-C₄-alkyl) -N-phenyl amino groups, where the alkyl radicals can still be substituted, for example by phenyl, sulfophenyl, hydroxy, sulfato, sulfo and carboxy, and the phenyl groups can still be substituted, such as by chlorine, sulfo, Carboxy, methyl and / or methoxy, for example methylamino, Ethylamino, propylamino, isopropylamino, butylamino, N, N-di- (β- hydroxyethyl) amino, N, N-di (β-sulfatoethyl) amino, sulfobenzylamino, N, N Di- (sulfobenzyl) amino and diethylamino groups as well as phenylamino and Sulfophenylamino groups; Alkoxycarbonyl groups with an alkyl radical from 1 to 4 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl; Alkylsulfonyl groups from 1 to 4 carbon atoms, such as methylsulfonyl and ethylsulfonyl; Trifluoromethyl, Nitro and cyano groups; Halogen atoms such as fluorine, chlorine and bromine; Carbamoyl groups which are mono- and. By alkyl of 1 to 4 carbon atoms can be disubstituted, the alkyl radicals in turn being substituted can, for example by hydroxy, sulfato, sulfo, carboxy, phenyl and Sulfophenyl such as N-methyl-carbamoyl and N-ethyl-carbamoyl; Sulfamoyl groups, which are mono- or by alkyl groups of 1 to 4 carbon atoms can be disubstituted, and N-phenyl-N-alkyl-sulfamoyl groups with one Alkyl group of 1 to 4 carbon atoms, these alkyl groups in turn by Hydroxy, sulfato, sulfo, carboxy, phenyl and sulfophenyl may be substituted can, such as N-methyl-sulfamoyl, N-ethyl-sulfamoyl, N-propyl sulfamoyl, N-isopropyl-sulfamoyl, N-butyl-sulfamoyl, N- (β-hydroxyethyl) - sulfamoyl and N, N-di- (β-hydroxyethyl) sulfamoyl; N-phenyl  sulfamoyl, ureido, hydroxy, carboxy, sulfomethyl and sulfo groups. Of the Dye residue F can also have one or two fiber-reactive groups of have general formula Y-SO₂-W⁰-, in which W⁰ an alkylene radical of 1 to 4 carbon atoms or an amino group of the formula -N (CH₃) - or -N (C₂H₅) - or a group of the formula - (C₂-C₄-alkylene) -NH- or for one direct covalent bond.

In the general formulas (1) and (2) and in the following general ones Formulas can be the individual formula elements, both different and same name within a general formula, in the context of their Meaning mutually identical or different meanings to have.

The groups "sulfo", "carboxy", "phosphato" and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups are groups corresponding to the general formula -SO₃M, thiosulfato groups are groups corresponding to the general formula -S-SO₃M, carboxy groups are groups corresponding to the general formula -COOM, phosphato groups are groups corresponding to the general formula -OPO₃M₂ and sulfato groups are groups according to the general formula -OSO₃M, in which
M is hydrogen or an alkali metal such as sodium, potassium or lithium, or the molar equivalent of an alkaline earth metal such as calcium, and preferably hydrogen or an alkali metal.

Important azo dyes corresponding to the general formula (1) are those in where F is the rest of a dye of benzene-azo-naphthol-, 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, benzene azo pyridone and naphthalene azo pyridone series means, here also the sulfo-containing dyes are preferred.  

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

Preferred mono- and disazo dyes of the general formula (1) are for example those of the general formulas (3a), (3b) and (3c)

D¹-N = N- (EN = N) _v -K²- Z (3a)

Z-D²-N = N- (EN = N) _v -K¹ (3b)

Z-D²-N = N- (EN = N) _v -K²-Z (3c)

and the heavy metal complex compounds derived therefrom, such as 1: 1 copper complex compounds, in which
D¹ is the residue of a diazo component of the benzene or naphthalene series,
D² is the residue of a diazo component of the diaminobenzene or diaminonaphthalene series,
E represents the remainder of a middle component of the benzene or naphthalene series,
K¹ is the remainder of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series,
K² is the bivalent radical of a coupling component of the aniline, aminonaphthalene, acetoacetic acid (aminoaryl) amide or 1-aminophenylpyrazolone series,
where D¹, D², E, K¹ and K² may contain one or more of the substituents mentioned for F, the radicals D¹, D², E, K¹ and K² together having at least one, preferably at least two, sulfo groups,
v is zero or 1 and
Z is a group of the general formula (2) of the above meaning.

Disazo dyes of the general formulas (3d) and (3e) are also preferred

D¹-N = N-K⁰-N = N-D²-Z (3d)

Z-D²-N = N-K⁰-N = N-D²-Z (3e)

in which Z, D¹ and D² have the meanings given above and K⁰ the Represents the rest of a bivalent coupling component of the naphthalene series, where D¹, D² and K⁰ may contain the substituents mentioned for F, where D¹, D² and K⁰ together contain at least one sulfo group.

Azo dyes of the general formulas (3d) and (3e) are special Dyes of the general formula (3f)

in which
n has the meaning given above,
M represents hydrogen or alkali metal, such as sodium, potassium or lithium, or the molar equivalent of an alkaline earth metal, such as calcium,
Z represents a radical of the general formula (2) which, if n is 1, is attached to one of the radicals D and, if n is 2, is bonded to both D, and
D each has the meaning of D 1 or D 2 depending on whether D is attached to D.

Of the 1: 1 copper complex azo dyes, for example, those are general formulas (3g) and (3h)

to emphasize in which
Z, K² and v have the meanings given above,
D⁴ stands for the rest of a diazo component which contains the copper complex-binding oxy group in the ortho position to the azo group, and
K³ stands for the rest of a coupling component which has the copper complex-binding oxy group in the ortho position or vicinal position to the azo group, and
K means the divalent radical of a coupling component.

Aromatic residues of diazo components that are not a fiber-reactive group of Formula (2), such as those of the general formulas D¹-NH₂ or D³-NH₂ correspond, for example, those of the general formulas (4a), (4b), (5a) and (5b)

in which
R ^{G is} hydrogen, sulfo or a group of the formula Y-SO₂-W⁰- with W⁰ and Y of the above meaning,
P¹ is hydrogen, methyl, ethyl, methoxy, ethoxy, alkanoyl of 2 to 5 carbon atoms, such as acetyl and propionyl, cyano, sulfo, carboxy, alkoxycarbonyl of 2 to 5 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl, carbamoyl, N- ( C₁-C₄-alkyl) -carbamoyl, fluorine, chlorine, bromine or trifluoromethyl,
P² is hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, nitro, carboxy, sulfo, chlorine, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino, alkoxycarbonyl of 2 to 5 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl, carbamoyl, N. - (C₁-C₄-alkyl) -sulfamoyl, sulfophenylamidocarbonyl, phenylamidocarbonyl, alkylsulfonyl of 1 to 4 carbon atoms, phenylsulfonyl or phenoxy,
where the benzene nucleus in formulas (4a) and (4b) may additionally contain a hydroxyl group in the ortho position to the free bond which leads to the azo group,
m denotes the number zero, 1 or 2 (where this group denotes a hydrogen atom if m is zero) and
M has the meaning given above.

Of these, P 1 is preferably hydrogen, methyl, methoxy, bromine, chlorine, Sulfo and carboxy as well as P² are hydrogen, methyl, methoxy, chlorine, Carboxy, sulfo and acetylamino.

Groups of the general formulas (4a) and (4b) are for example: Phenyl, 2-methylphenyl, 3- and 4-methylphenyl, 2-methoxyphenyl, 3- and  4-methoxy-phenyl, 2-chlorophenyl, 3- and 4-chlorophenyl, 2,5-dichlorophenyl, 2,5-dimethyl-phenyl, 2-methoxy-5-methyl-phenyl, 2-methoxy-4-nitro-phenyl, 4-phenyl-phen-1-yl, 3-phenoxy-phenyl, 2-sulfamoyl-phenyl, 3- and 4-sulfamoyl- phenyl, 2-, 3- and 4- (N-methyl-sulfamoyl) -, - (N-ethyl-sulfamoyl) -, - (N, N-dimethyl-sulfamoyl) - and - (N, N-diethyl-sulfamoyl) -phenyl, 2-sulfo-5- trifluoromethyl-phenyl, 2-nitro-phenyl, 3- and 4-nitro-phenyl, 3-acetylamino phenyl, 4-acetylamino-phenyl, 2-carboxy-phenyl, 4-carboxy-phenyl, 3-carboxy- phenyl, 3-chloro-6-carboxy-phenyl, 2-sulfo-phenyl, 3-sulfo-phenyl, 4-sulfo phenyl, 2,5-disulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, 2-methyl-5- sulfo-phenyl, 2-methoxy-5-sulfo-phenyl, 2-methoxy-4-sulfo-phenyl, 2-sulfo-5- methyl-phenyl, 2-methyl-4-sulfo-phenyl, 3-sulfo-4-methoxy-phenyl, 5-sulfo-2- ethoxy-phenyl, 4-sulfo-2-ethoxy-phenyl, 2-carboxy-5-sulfo-phenyl, 2-carboxy- 4-sulfophenyl, 2,5-dimethoxy-4-sulfophenyl, 2,4-dimethoxy-5-sulfophenyl, 2-methoxy-5-methyl-4-sulfo-phenyl, 2-sulfo-4-methoxy-phenyl, 2-sulfo-4- methyl-phenyl, 2-methyl-4-sulfo-phenyl, 2-chloro-4-sulfo-phenyl, 2-chloro-5-sulfo phenyl, 2-bromo-4-sulfo-phenyl, 2,6-dichloro-4-sulfo-phenyl, 2-sulfo-4- and -5-chlorophenyl, 2-sulfo-4, 5-dichlorophenyl, 2,5-dichloro-6-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2-sulfo-5-chloro-4-methylphenyl, 2-sulfo-4-chloro-5- methyl-phenyl, 2-sulfo-5-methoxy-phenyl, 2-methoxy-5-sulfo-phenyl, 2-methoxy-4-sulfo-phenyl, 2,4-dimethoxy-6-sulfo-phenyl, 2-sulfo-5- acetylamino-4-methylphenyl, 2-methyl-4, 6-disulfophenyl, 2,5-disulfo-4- methoxy-phenyl, 2-sulfo-5-nitro-phenyl, 2-sulfo-4-nitro-phenyl, 2,6-dimethyl-3- sulfo-phenyl, 2,6-dimethyl-4-sulfo-phenyl, 3-acetylamino-6-sulfo-phenyl, 4-acetylamino-2-sulfo-phenyl, 4-sulfo-naphth-1-yl, 3-sulfo-naphth-1-yl, 5-sulfo naphth-1-yl, 6-sulfonaphth-1-yl, 7-sulfonaphth-1-yl, 8-sulfonaphth-1-yl, 3,6-disulfo- and 5,7-disulfonaphth-1-yl, 3,7-disulfonaphth-1-yl, 3,6,8-trisulfo- naphth-1-yl, 4,6,8-trisulfonaphth-1-yl, 5-sulfonaphth-2-yl, 6- or 8-sulfo- naphth-2-yl, 3,6,8-trisulfonaphth-2-yl, 1,5,7-trisulfonaphth-2-yl, 1,7-disulfon naphth-2-yl, 5,7-disulfonaphth-2-yl, 2,5,7-trisulfonaphth-1-yl, 4,6,8-trisulfon naphth-2-yl, 6,8-disulfonaphth-2-yl, 1,6-disulfonaphth-2-yl, 1-sulfonaphth- 2-yl, 1,5-disulfonaphth-2-yl, 3,6-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl, 2-hydroxy-5-sulfo-phenyl, 2-hydroxy-4-sulfo-phenyl, 2-hydroxy-3,5-disulfo  phenyl, 2-hydroxy-5-acetylamino-3-sulfophenyl, 2-hydroxy-3-acetylamino-4- sulfo-phenyl, 2-hydroxy-5-chloro-4-sulfo-phenyl, 2-hydroxy-5-methylsulfonyl- phenyl, 2-hydroxy-6-nitro-4-sulfonaphth-1-yl and 1-hydroxy-4,8-disulfo- naphth-2-yl, 2- (β-sulfatoethylsulfonyl) phenyl, 3- (β-sulfatoethylsulfonyl) phenyl- 4- (β-sulfatoethylsulfonyl) phenyl, 2-carboxy-5- (β-sulfatoethylsulfonyl) phenyl, 2-chloro-3- (sulfatoethylsulfonyl) phenyl, 2-chloro-4- (β-sulfatoethylsulfonyl) - phenyl, 2-bromo-4- (β-sulfatoethylsulfonyl) phenyl, 4-methoxy-3- (β- sulfatoethylsulfonyl) phenyl, 4-chloro-3- (β-sulfatoethylsulfonyl) phenyl, 2-ethoxy- 4- or 5- (β-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) - phenyl, 2-methoxy-5- or -4- (β-sulfatoethylsulfonyl) phenyl, 2,4-diethoxy-5- (β- sulfatoethylsulfonyl) phenyl, 2,4-dimethoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β- sulfatoethylsulfonyl) phenyl, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) - phenyl, 2-methoxy-5- (β-thiosulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β- phosphatoethylsulfonyl) phenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-hydroxy-4- or -5- (β-sulfatoethylsulfonyl) phenyl, 2-chloro-4- or -5- (β-chloroethylsulfonyl) - phenyl, 2-hydroxy-5- (β-sulfatoethylsulfonyl) phenyl, 2-hydroxy-3-sulfo-5- (β- sulfatoethylsulfonyl) phenyl, 3- or 4- (β-acetoxyethylsulfonyl) phenyl, 6-carboxy-1-sulfonaphth-2-yl, 5- (β-sulfatoethylsulfonyl) napth-2-yl, 6- or 7- or 8- (β-sulfatoethylsulfonyl) naphth-2yl, 6- (β-sulfatoethylsulfonyl) -1-sulfo- naphth-2-yl, 5- (β-sulfatoethylsulfonyl) -1-sulfo-naphth-2-yl, 8- (β-sulfatoethylsulfonyl) -6-sulfonaphth-2-yl, 4- [N-methyl-N- (β- sulfatoethylsulfonyl)] - aminophenyl, 3- [N-methyl-N- (β-sulfatoethylsulfonyl)] - aminophenyl, 4- [β- (β'-sulfatoethylsulfonyl) ethyl] phenyl, 3- or 4- [γ- (β'- Chloroethylsulfonyl) ethylamino] phenyl, 3- or 4- [β- (β'-sulfatoethylsulfonyl) - ethylamino] phenyl, 3- or 4- [γ- (β-chloroethylsulfonyl) propylamino] phenyl, 3- or 4- [γ- (β'-sulfatoethylsulfonyl) propylamine] phenyl, 3- or 4- [γ- (vinylsulfonyl) propylamino] phenyl, 4- [β- (β′-sulfatoethylsulfonyl) - ethylamino] -2- or -3-sulfo-phenyl, 4- [β- (β'-chloroethylsulfonyl) ethylamino] -2- or -3-sulfo-phenyl, 4- [γ- (β'-sulfatoethylsulfonyl) propylamine] -2- or -3-sulfo- phenyl, 4- [γ- (β'-chloroethylsulfonyl) propylamino] -2- or -3-sulfo-phenyl, 4- [β- (β'-chloroethylsulfonyl) ethylamino] -2-carboxyphenyl,  4- [β- (β′-sulfatoethylsulfonyl) ethylamino] -2-carboxyphenyl, 4- [y- (β'-chloroethylsulfonyl) propylamino] -2-carboxyphenyl and 4- [γ- (β'-sulfatoethylsulfonyl) propylamino] -2-carboxyphenyl.

Groups corresponding to the general formula residues D-N = N-E or D 1 -N = N-E- are, for example, 4- (4'-sulfophenyl) azo-2-sulfophenyl, 4- (2 ′, 4′- Disulfo-phenyl) -azo-2-methoxy-5-methyl-phenyl, 4- (2 ′, 5′-disulfo-pheny-l) -azo-2- methyl-5-methoxy-phenyl 4- (3 ′, 6 ′, 8′-trisulfonaphth-2′-yl) -azo-3-ureido-phenyl, 4- (4 ′, 8′-disulfonaphth-2′-yl) -azo-3-acetylamino-phenyl, 7- (1 ′, 5′-disulfonaphth- 2'-yl) -azo-6-sulfo-8-hydroxy-naphth-3-yl and 4- (4'-sulfo-phenyl) -azo-6-sulfo naphth-1-yl, 4- [4 ′ - (β-sulfatoethylsulfonyl) phenyl] -azo-2-methyl-5-methoxy- phenyl, 4- [3 ′ - (β′-sulfatoethylsulfonyl) phenyl] -azo-3-methylphenyl, 4- [4 ′ - (β- Sulfatoethylsulfonyl) phenyl] -azo-3-ureido-phenyl, 4- [6 ′ - (β-sulfatoethylsulfonyl) - naphth-2′-yl] -azo-3-ureido-phenyl, 7- [2′-methoxy-5 ′ - (β-sulfatoethylsulfonyl) - phenyl] -azo-8-hydroxy-6-sulfo-naphth-3-yl, 4- (2 ', 5'-disulfo-phenyl) -azo-6- or -7-sulfo-naphth-1-yl, 4- (2 ′, 4′-disulfo-phenyl) -azo-6- or -7-sulfo-naphth-1-yl, 4- (4 ′, 8′-disulfonaphth-2′-yl) -azo-6- or -7-sulfonaphth-1-yl, 4- (3 ′, 6 ′, 8′-trisulfonaphth-2′-yl) -azo-6- or -7-sulfonaphth-1-yl and 4- (4 ′, 6 ′, 8′-trisulfonaphth-2′-yl) -azo-6- or -7-sulfonaphth-1-yl.

Aromatic residues Z-D²- of compounds serving as diazo components of the general formulas Z-D²-NH₂ or their diaminobenzene and Diaminonaphthalene compounds according to the general formulas H₂-N-D²-NH₂ are preferably radicals of the general formulas (6a) and (6b)

in which Z, M, m, P¹ and P² the above, in particular have preferred meanings, the respective benzene nucleus in ortho-  Position to free bond that leads to the azo group, additionally one May contain hydroxy group.

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

in which
P¹, M and m have the meanings given above and
P³ hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, chlorine, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, benzoylamino, ureido , Phenylureido, alkylureido with 1 to 4 carbon atoms in the alkyl radical, phenylsulfonyl or alkylsulfonyl of 1 to 4 carbon atoms.

Residues K¹ of coupling components of the general formula H-K¹, which none carry fiber-reactive group of formula (2), for example those of general formulas (8a) to (8h)

in which
R ^G , P¹, P², m and M have the meanings given above,
P⁴ alkanoylamino of 2 to 5 carbon atoms, such as propionylamino and especially acetylamino, or phenylureido, which is in the phenyl radical by substituents from the group chlorine, methyl, methoxy, sulfo and carboxy and / or by a group -SO₂-Y with Y one of the above meanings may be substituted, or is benzoylamino which may be substituted in the phenyl radical by substituents from the group chlorine, methyl, methoxy, nitro, sulfo and carboxy and / or by a group -SO₂-Y with Y of one of the above meanings,
P⁵ 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 sulfo,
P⁶ 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, alkanoylamino of 2 to 7 carbon atoms, such as acetylamino and propionylamino, ureido or phenylureido is
P⁷ is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, cyano, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy,
P⁸ is alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxy, cyano, carboxy, sulfo, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, or benzyl or phenyl or by alkyl of 1 to 4 carbon atoms, alkoxy of 1 is up to 4 carbon atoms, chlorine and / or sulfo substituted phenyl,
P⁹ 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 carboxy
T represents a benzene or naphthalene ring, preferably a benzene ring,
P¹⁰ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl, or alkyl of 1 to 4 carbon atoms, such as methoxy, or cyano-substituted alkyl of 1 to 4 carbon atoms or phenyl, preferably alkyl of 1 to 4 Is carbon atoms or phenyl,
P¹¹ is hydrogen, chlorine, bromine, sulfo, carbamoyl, methylsulfonyl, phenylsulfonyl, cyano or sulfoalkyl of 1 to 4 carbon atoms, preferably hydrogen, sulfo, sulfoalkyl with an alkyl radical of 1 to 4 carbon atoms, such as sulfomethyl, cyano or carbamoyl is
B alkylene of 1 to 4 carbon atoms, methylenephenylene, ethylenephenylene, phenylenemethylene, phenyleneethylene or phenylene or in the benzene residue by fluorine, chlorine, bromine, methyl, methoxy, cyano, sulfo, carboxy, acetyl, nitro, carbamoyl and / or sulfamoyl substituted methylenephenylene , Ethylene phenylene or phenylene and
D¹ is a radical of the general formula (4a) or (4b).

Residues -K²-Z of coupling components of the general formula H-K²-Z or H-K²-N (R ^A ) H, into which the fiber-reactive radical corresponding to the group Z¹ specified later must be introduced, are, for example, radicals of the general formulas (9a) to (9h)

in which
P¹, P², P⁹, P¹⁰, P¹¹, B, T, M, m and Z have the abovementioned, particularly preferred, meanings and
D⁵ as the residue of a diazo component is a residue of the above-mentioned and defined general formula (6a) or (6b).

In the formulas (8a), (8b) and (9a) above, the free bond that is used for Azo group leads to the aromatic nucleus in the ortho position to the hydroxyl group bound.

Residues K³ in formulas (3g) and (3h) with a metal complex binding Oxygen atoms are in particular those of the formulas (10a) to (10e)

in which the individual formula members have one of the meanings mentioned above and
P * is hydrogen or a radical Z or a grouping of the formula -N = N-K²-Z or -N = NKH with K², Z and K of the abovementioned meaning.

Of the azo dyes, preference is furthermore given to those which correspond to the general Formulas (12A) to (12S)

correspond in which mean:
Z 1 is a radical of the general formula (2A)

in which X, R, W, Y and z have the above-mentioned, particularly preferred meanings;
M has one of the meanings mentioned above;
D is a benzene ring or is a naphthalene ring, the azo group being preferably attached to the naphthalene ring in the β-position and where, when D is the naphthalene ring, R² and R³ preferably each, independently of one another, represent a hydrogen atom or a sulfo group;
R¹ is hydrogen or sulfo or a group Y-SO₂-W⁰- above meaning;
R² is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, halogen, such as chlorine and bromine, carboxy or sulfo and is preferably hydrogen, methyl , Methoxy, bromine, chlorine, sulfo or carboxy and particularly preferably hydrogen, methoxy or sulfo;
R³ is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, halogen, such as chlorine and bromine, nitro, carboxy or sulfo, preferably hydrogen, Methyl, methoxy, chlorine, carboxy, sulfo or acetylamino and particularly preferably hydrogen, methoxy or sulfo;
R⁴ is hydroxy or amino, preferably hydroxy;
R⁵ is methyl, carboxy, carbomethoxy or carbethoxy, preferably methyl or carboxy;
R⁶ is acetylamino, propionylamino, ureido or methyl;
R⁷ 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, halogen, such as bromine and especially chlorine, preferably hydrogen, methyl, ethyl, methoxy or ethoxy ;
R⁸ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, or ureido, preferably hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino or ureido;
R⁹ is hydrogen, cyano, carbamoyl, sulfamoyl or sulfomethyl, preferably hydrogen or carbamoyl;
R²¹ has one of the meanings of R¹;
R²² has one of the meanings of R²;
R²³ has one of the meanings of R³;
ALK is alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, or alkyl of 2 to 4 carbon atoms, such as ethyl and propyl, which can be substituted by hydroxy, carboxy, sulfo or sulfato;
G is alkylene of 1 to 4 carbon atoms, such as ethylene and propylene, or is phenylene or phenylene substituted by sulfo, carboxy and / or alkyl of 1 to 4 carbon atoms, such as methyl;
G¹ is a group of the formula -NH-alk-, -NH-phen- or -alk-, in which alk represents alkylene of 2 to 4 carbon atoms and represents phen sulfo-phenylene or phenylene;
m is the number zero, 1 or 2 (where if m is zero this group is hydrogen);
in the compounds of the formulas (12A), (12D), (12E), (12K) and (12S) the amino or amido group is bonded in the 2- or 3-position to the 8-naphthol radical and in the compounds of the formulas (12B), (12C), (12J), and (12R) the group -SO₃M is bound in the meta or para position to the amino or acylamino group.

Radicals corresponding to the general formula (2a)

which are contained in the radicals Z and Z¹ are, for example:
N-methyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N-ethyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, Nn-propyl-N- [γ - (β'-chloroethylsulfonyl) propyl] - amino, Nn-butyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino-N-carboxymethyl-N- [γ- (β'-bromomethylsulfonyl) - propyl] amino, N-sulfatomethyl-N- [γ- (ß'-chloroethylsulfonyl) propyl] 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- (β-ethoxyethyl) -N- [γ ′ - (β '' -Chloroethylsulfonyl) propyl] amino, N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (4-chlorophenyl) -N- [γ- (β'- chloroethylsulfonyl ) -propyl] -amino, N- (2-methylphenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] -amino, N- (4-methoxyphenyl) -N- [γ- (β'-chloroethylsulfonyl ) propyl] amino, N- (3-sulfop henyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (4-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amino, N- (β- Cyanoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amino, N-phenyl-N- (γ- vinylsulfonyl-propyl) -amino, N- (4-chlorophenyl) -N- (γ -vinylsulfonyl-propyl) -amino, N- (2-methylphenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N- (4-methoxyphenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N- (3-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N- (4-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amino, N-phenyl-N- [γ- (β ′ - sulfatoethylsulfonyl) propyl] amino, N- (4-chlorophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (2-methylphenyl) -N- [γ- (β ′ - sulfatoethylsulfonyl) propyl] amino, N- (4-methoxyphenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N- (3-sulfophenyl) -N- [γ- (β ′ - sulfatoethylsulfonyl) propyl] amino, N- (4-sulfophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amino, N-phenyl-N- [a-carboxy-γ- (β ′ - chloroethylsulfonyl) propyl] amino, N-phenyl-N- [α-e thoxycarbonyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phenyl-N- [α-methoxycarbonyl-γ- (β'- chloroethylsulfonyl) propyl] amino, N-phenyl-N- [β- methyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phenyl-N- [β-ethyl-γ- (β'-chloroethylsulfonyl) propyl] amino, N-phenyl-N- [δ- (β'-chloroethylsulfonyl) butyl] amino, N-phenyl-N- [ε- (β'-chloroethylsulfonyl) pentyl] amino and N-phenyl-N- [β- (β'-chloroethylsulfonyl) - hexyl ] -amino.

Of these groups (2a), the groups N-phenyl- [γ- (β'-chloroethylsulfonyl) propyl] amino and N-phenyl- [γ- (β'-sulfatoethylsulfonyl) - to call propyl] -amino.

Heavy metal complex azo dyes are of particular importance for example the 1,2-chromium complex and 1,2-cobalt complex and especially the 1: 1 copper complex monoazo compounds of Azo compounds of the following general formulas (12T) and (12U):

in which
M, m, Z 1, RA and R 1 have the above-mentioned, particularly preferred meanings,
p stands for the number zero or 1 (where if p is zero this group means hydrogen) and
m₁ is the number zero or 1 (where in the case of m is zero, this group means hydrogen).

Of the phthalocyanine dyes of the invention are those preferred that of the general formula (13)

correspond in which mean:
Pc is the balance of a nickel or preferably copper phthalocyanine;
R⁰ is an amino group of the formula -NR¹³R¹⁴, in which R¹³ and R¹⁴ independently of one another are hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by hydroxyl or sulfo, or is a heterocyclic, N-containing radical, such as Morpholino or piperidino residue;
R¹² is a hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl;
G² is phenylene, which can be substituted by 1 or 2 substituents from the group alkyl of 1 to 4 carbon atoms, such as ethyl and methyl, halogen, such as chlorine and bromine, carboxy and sulfo, for example sulfophenylene, or is alkylene from 2 to 6 carbon atoms, such as ethylene;
Z is the fiber reactive group of formula (2);
a is a number from zero to 3,
b is a number from zero to 3 and
c is a number from 1 to 2,
where the sum of (a + b + c) is a number from 2 to 4.

Of these, those that are of general interest should be mentioned Formulas (13a) and (13b)

correspond, in which a stands for a number from 1 to 3, b stands for a number from 0 to Is 2 and c is a number from 1 to 2, the sum of (a + b + c) is a number from 2 to 4, Pc is the balance of a nickel or preferred Represents copper phthalocyanine and alk alkylene of 2 to 4 carbon atoms, preferred Ethylene, is.

Copper formazan dyes according to the invention are in particular those which of the general formula (14)

correspond in which mean:
X¹ is an oxygen atom or preferably the carbonyloxy group of the formula -COO-;
P₁ and P₂, independently of one another, each represent a benzene or naphthalene ring, with P₁ the nitrogen atom and the group X¹ being ortho to one another at all times and the oxygen atom and the nitrogen atom to P₂ being ortho to one another and the benzene nuclei or naphthalene nuclei still being bound by one or two substituents from the group halogen, such as chlorine, nitro, alkyl of 1 to 4 carbon atoms, such as methoxy and ethoxy, sulfamoyl, sulfamoyl mono- or disubstituted by alkyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms -Atoms, such as methylsulfonyl and ethylsulfonyl, and phenylsulfonyl may be substituted, both P₁ and P₂ both preferably denoting a benzene ring;
P₃ is a straight-chain or branched alkylene group of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, which may be substituted by a sulfophenyl group, or is a phenylene group or a naphthylene group which has 1 or 2 substituents from the group methyl , Ethyl, methoxy, ethoxy and chlorine may be substituted, P₃ preferably being a benzene ring;
T¹, T² and T³ each independently represent a sulfo or carboxy group, preferably sulfo group;
e, f and g each independently represent the number zero, 1 or 2, the sum of (e + f + g) being an integer from 1 to 4 and preferably being 2 or 3, in particular 2, where in the case of e or f or g equals zero the group T 1 or T 2 or T 3 represents a hydrogen atom;
p stands for the number 1 or 2, preferably 1, where the group -NH-Z¹ can be bound to an aromatic radical of P₁, P₂ or P₃ and is preferably bound to P₂.

Preferred of the copper formazan dyes of the general formula (14) are those in which P₁ and P₂ both represent a benzene ring, the group -NH-Z¹ is bonded to P₂ and T¹ and T² each represents a sulfo group, where e and g both represent Number 1 stand. If the group -NH-Z¹ is bound to P₁, e is zero, g is 2 and T² is a sulfo group. Also preferred is the grouping -P₃- (T³) _f the phenyl or a 2- or 4-sulfo-phenyl radical.

Of these, in particular those copper formazan dyes are to be emphasized, that of the general formula (14a)

correspond in which M and Z¹ the above, particularly preferred Have meanings.

Of the triphendioxazine dyes according to the invention are those to emphasize that of the general formula (15)

correspond in which M and Z have one of the meanings given above,
B⁰ is the oxy group -O- or the amino group -NH- and A⁰ is alkylene of 2 to 6 carbon atoms, which is replaced by 1 or 2 hetero groups, such as groups of the formulas -O-, -NH-, -NH-CO- and / or -CO-NH-, interrupted and / or which can be substituted, for example by hydroxy, sulfo, sulfato or carboxy, or cyclohexylene, or in which the grouping Z-A⁰-B bzw.- or -B⁰-A⁰- Z together represents the radical Z¹-NH- or -NH-Z¹ of the above meaning, wherein the two sulfo groups -SO₃M are preferably bonded to the benzene nucleus in the ortho position to the oxygen atom of the heterocyclic ring.

Of the anthraquinone dyes according to the invention are in particular to mention those of the general formula (16)

correspond in which
M, Z and q have one of the meanings mentioned above and
Ph is phenylene which is substituted by 1 or 2 substituents from the group alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, halogen, such as chlorine and bromine, carboxy and Can be sulfo substituted, or is phenylene which is substituted by 3 or 4 methyl groups.

The present invention further relates to methods for producing the Dyes of the general formula (1) according to the invention. You get in on and known for themselves in a conventional manner, for each Produce dye class specific synthetic routes by for each dye typical precursors, of which at least one is a  Group of the general formula (2) contains, reacted with one another, or by a halogenotriazine compound of the general formula (21)

in which X has one of the above-mentioned, particularly preferred meanings and Hal represents halogen, such as chlorine or fluorine, such as 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) or 2,4,6-trichloro-1,3,5-triazine (Cyanuric chloride), in any order with an amino group Compound of the general formula (20)

with F, R ^A and n of the abovementioned meanings in an equimolar amount and an amino compound of the general formula (22)

with R, W, Y and z of the above meanings in equimolar or twice the molar amount.

Process variants of this invention according to the invention Procedures are characterized, for example, that one Compound of the general formula (23)

in which F, R ^A , X, Hal and n have the meanings given above, with an amino compound of the general formula (22) in equimolar or, if X is a halogen, optionally in a double molar amount, or in that a compound of general formula (24)

in which Hal, X, R, W, Y and z have the meanings given above, with a compound of the general formula (20) of the abovementioned meaning implements. From this is the procedure of implementing a compound of general formula (23) with a compound of general formula (22) prefers.

In the condensation reactions, care must be taken that the fiber-reactive Groups in the alkaline range must not be damaged.

The starting compounds are reacted in aqueous or aqueous organic medium in suspension or solution. Do the implementations in through an aqueous-organic medium, so is the organic medium for example acetone, dimethylformamide, dimethyl sulfoxide or N-methyl pyrrolidone. The one released during the condensation is advantageous Hydrogen halide continuously by adding aqueous alkali or Alkaline earth metal hydroxide carbonates or bicarbonates neutralized. The first Condensation reaction of the halogen-s-triazine of the general formula (21) usually takes place at a temperature between -5 ° C and + 20 ° C, in the case Hal is fluorine, preferably at a temperature between -5 ° C and + 5 ° C, and at a pH between 2 and 10, preferably between 4 and 6. Die subsequent condensation reaction with the second amino compound takes place in usually at a temperature between 0 and 50 ° C, equal in the case of Hal  Fluorine preferably at a temperature between 0 and 20 ° C, and at a pH Value between 3 and 9, preferably between 6 and 8.

In particular, the conversion takes place between a compound of the general Formula (23) and a compound of general formula (22) in one Temperature between 0 and 50 ° C, preferably between 10 and 30 ° C, and at a pH value between 3 and 9, preferably between 6 and 8, If Hal is a fluorine atom in the compound for formula (23), preferably the Reaction carried out at a temperature between 0 and 20 ° C.

The reaction of a compound of the general formula (24) also takes place with a compound of general formula (20) at a temperature between 0 and 40 ° C, preferably between 10 and 30 ° C, and at one pH between 3 and 9, preferably between 4 and 6, wherein in the case of Use of a compound of general formula (24) with Hal equal to fluorine preferably the reaction at a temperature between 0 and 20 ° C. is carried out.

The starting compounds of the general formula (23) can be started of the compounds (20), in a manner known per se Implementation of halogen-substituted triazines with amino groups Make connections like this for example above Procedures according to the invention is described, so also in aqueous or aqueous-organic medium usually at a temperature between -5 ° C and + 40 ° C, preferably between 0 and 30 ° C, and at a pH between 2 and 10, preferably between 5 and 7, where in the case of a Starting compound of formula (21) with Hal equal to fluorine preferably one Select reaction temperature between -5 ° C and + 5 ° C. In the same way and under the same process conditions Starting compounds of the general formula (24) by reacting a Compound of general formula (21) with a compound of general Prepare formula (22).  

If you go to the preparation of the dyes of the general Formula (1) from starting compounds of the general formula (23), in which X is a radical of the general formula -N (R) -W-SO₂-Y of the above What is important is the reaction with the amino compound general formula (22) at a temperature between 60 and 95 ° C, preferably between 80 and 90 ° C, and at a pH between 6 and 10, preferably between 8 and 9.5, provided that Hal is chlorine and Y both in Amino radical X and also in the starting compound of the formula (22) hydroxy means; the dye compound thus obtained with β-hydroxyethylsulfonyl Groups can then be esterified into an inventive Dye are converted, for example into the β-sulfatoethylsulfonyl Colorants containing sulfuric acid or sulfur trioxide Sulfuric acid, preferably at a temperature between 20 and 40 ° C. Is in the starting compounds of formula (23) with X equal to one Rest of the formula -N (R) -W-SO₂-CH₂-CH₂-OH with R and W of the above If Hal is fluorine, the reaction takes place with the Amino compound of the general formula (22) at a temperature between 25 and 70 ° C, preferably between 40 and 60 ° C, and at a pH between 3 and 8, preferably between 4 and 7.

The starting compounds of the general formula (21) and the general Formula (20) and its precursors are generally known and in the literature described in numerous. Are compounds of general formula (21) for example cyanuric chloride and cyanuric fluoride.

Aromatic amines, which are used as diazo components for the synthesis of Azo dyes of the general formula (1) according to the invention serve and correspond to general formulas D¹-NH₂, for example: 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-aminodiphenyl, 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-3-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, 1,4- Diaminobenzene-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-3,6- or -5,7-disulfonic acid, 1- Aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-amino-naphthalene-1- sulfonic 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-aminoazabenzene-3,4′-disulfonic acid, 3-methoxy-4-amino-6- methylazobenzene-2 ', 4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene 2 ′, 5′-disulfonic acid, 2- (β-sulfatoethylsulfonyl) aniline, 3- (β-sulfatoethylsulfonyl) - aniline, 4- (β-sulfatoethylsulfonyl) aniline, 2-carboxy-5- (β-sulfatoethylsulfonyl) - aniline, 2-chloro-3- (sulfatoethylsulfonyl) aniline, 2-chloro-4- (β-sulfatoethylsulfonyl) - aniline, 2-bromo-4- (β-sulfatoethylsulfonyl) aniline, 4-methoxy-3-β-  sulfatoethylsulfonyl) aniline, 4-chloro-3- (β-sultatoethylsulfonyl) aniline, 2-ethoxy-4- or -5- (β-sulfatoethylsulfonyl) aniline, 2-methyl-4- (β-sulfatoethylsulfonyl) aniline, 2-methoxy-5- or -4- (β-sulfatoethylsulfonyl) aniline, 2,4-diethoxy-5- (β-sulfato ethylsulfonyl) 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-5- (β-sulfatoethylsulfonyl) aniline, 2-hydroxy-3-sulfo-5- (β-sulfato ethylsulfonyl) aniline, 3- or 4- (β-acetoxyethylsulfonyl) aniline, 6-carboxy-1-sulfo-2-aminonaphthalene, 5- (β-sulfatoethylsulfonyl) -2- aminonaphthalene, 6- or 7- or 8- (β-sulfatoethylsulfonyl) -2-aminonaphthalene, 6- (β-sulfatoethylsulfonyl) -1-sulfo-2-aminonaphthalene, 5- (β-sulfatoethylsulfonyl) - 1-sulfo-2-aminonaphthalene, 8- (β-sulfatoethylsulfonyl) -6-sulfo-2-aminonaphthalene, 4- [N-methyl-N- (β-sulfatoethylsulfonyl)] - amino-aniline, 3- [N-methyl-N- (β- sulfatoethylsulfonyl)] - amino-aniline, 4- [β- (β'-sulfatoethylsulfonyl) -ethyl] -aniline, 3- or 4- [β- (β'-chloroethylsulfonyl) ethylamino] aniline, 3- or 4- [β- (β'- Sulfatoethylsulfonyl) ethylamino] aniline, 3- or 4- [γ- (β'-chloroethylsulfonyl) - propylamino] aniline, 3- or 4- [γ- (β'-sulfatoethylsulfonyl) propylamino] aniline and 3- or 4- [γ- (vinylsulfonyl) propylamino] aniline.

Starting compounds corresponding to the general formula H₂N-D²-NH₂ are for example 1,4-phenylenediamine, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2-carboxylic acid-1,4-diamino-naphthalene-2-sulfonic acid-e, 2,6-diamino-naphthalene-8-sulfonic acid, 2,6-diamino-naphthalene-4,8- disulfonic acid, 1,3-phenylenediamine, 1,3-phenylenediamine-4-sulfonic acid, 1,3-phenylene-diamine-4,6-disulfonic acid, 1,4-phenylene diamine-2,6-disulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid, 1,4-diamino-naphthalene-6-sulfonic acid, 4,4'-diamino-diphenyl-3-sulfonic acid and 4,4'-diamino-stilbene-2,2'- disulfonic acid.

Starting compounds for the preparation of the invention Disazo dyes of the general formula (1) initially as  Coupling component and then, in the form of the amino Azo compound, the diazo component and the general formula H-E-NH₂ correspond, for example, aniline, 3-methyl-aniline, 2-methoxy-5- methyl aniline, 2,5-dimethyl aniline, 3-ureido aniline, 3-acetylamino aniline, 3-propionylamino-aniline, 3-butyrylamino-aniline, 3-methoxy-aniline, 2-methyl-5- acetylamino-aniline, 2-methoxy-5-acetylamino-aniline, 2-methoxy-5-methyl-aniline, 3- (hydroxyacetylamino) aniline, 1,3-diaminobenzene-4-sulfonic acid, 1-amino naphthalene-6-, -7- or -8-sulfonic acid, 1-amino-2-methoxy-naphthalene-6- sulfonic acid, 2-amino-5-hydroxy.naphthalene-7-sulfonic acid, 2-amino-5-hydroxy- naphthalene-1,7-disulfonic acid, 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2- (4′-amino.benzoylamino) -5-naphthol-7-sulfonic acid, 1- (4′-amino-2′-sulfo- phenyl) -3-methyl-5-pyrazolone, 1- (4'-amino-2'-sulfo-phenyl) -3-carboxy-5- pyrazolone and N- (acetoacetyl) -3-sulfo-4-amino-anilide.

Starting compounds for the preparation of the azo compounds of the general formula (1) according to the invention which can serve as coupling components and correspond to the general formulas H-K¹ or H-K²-N (R ^A ) H or HKH are, 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-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- and 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-methyl- or 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- and -4,6-disulfonic acid (1- (4'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- and -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- Methylpyrazolone- (5), 1-phenyl-3-methyl-5-pyrazolone, 1- (4'-sulfophenyl) -3- methyl-5-pyrazolone, 1- (4'-sulfophenyl) pyrazolone- (5) - 3-carboxylic acid, 1- (3'-aminophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-disulfophenyl) -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-hydroxypyridone-2- , 1-ethyl-3-cyano- or -3-chloro-4-methyl-6-hydroxypyridone-2, 1-ethyl-3-sulfomethyl-4-methyl-6-hydroxypyridone 2,2,4,6-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-cyano-4-methylpyridine, 1-ethyl 3-carbamoyl-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypyridone- (2), N-acetoacetylaminobenzene, 1- (N-acetoacetylamono ) -2-methoxybenzene-5-sulfonic acid, 4 hydroxyquinolone- (2), 1-amino-8-hydroxy-7- (phenylazo) -naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7- ( 4′- sulfophenylazo) -naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-7- (2 ′, 5′- disulfophenylazo) -naphthalene-3,6-disulfonic acid, 1- [4 ′ - (β -Sulfatoethyl-sulfonyl) - phenyl] -3-methyl-5-pyrazolone, 1- [4 '- (vinyl-sulfonyl) -phenyl] -3-methyl-5-pyrazolone, 1- [4' - (β-sulfatoethylsulfonyl ) -phenyl] -3-carboxy-5-pyrazolone, 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-su lfo-8-naphthol, 3- [3 ′ - (β-chloroethylsulfonyl) benzoylamino] -6-sulfo-8-naphthol, 3- [3 ′ - (vinylsulfonyl) benzoyl-amino] -6-sulfo- 8- naphthol, 6-sulfo-1- [3 ′ - (β-chloroethylsulfonyl) benzoylamino] naphthol, 7-sulfo- [3 ′ - (vinylsulfonyl) benzoylamino] 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′-vinylsulfonyl-phenyl) -ureido] - 3,6-disulfo-8-naphthol, 1- [N ′ - (3′-vinylsulfonyl-propyl) -ureido] -3,6-disulfo- 8- naphthol, 1- [N ′ - (3′-β-chloroethylsulfonylphenyl) phenido] -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-sulfatoethylsulfonyl-phenyl) -ureido] -6-sulfo-8-naphthol, 2- [N '- (3'- chloret hylsulfonyl-propyl) -ureido] -6-sulfo-8-naphthol, 3- [N ′ - (3'-β-chloroethylsulfonyl-phenyl) -ureido] -6-sulfo-8-naphthol, 3- [N′- (3'-vinylsulfonyl-propyl) -ureido] -6-sulfo-8-naphthol, 2-sulfo-5- [N '- (3''- β-chloroethylsulfonyl) - phenyl] -ureido-aniline, 3- [ N ′ - (3 ′ ′ - β-sulfatoethylsulfonyl) phenyl] -ureido-aniline and 6-sulfo-1- [N ′ - (3 ′ ′ - β-sulfatoethylsulfonyl) phenyl] -ureido-8-naphthol.

Coupling components according to the general formula HKN (R ^A ) H, which can be used to build up the azo dyes according to the invention, in which the fiber-reactive radical Z is contained in the coupling component, with the amino group-containing azo dye according to the general formula (20) in the amino group obtained initially -N (R ^A ) H the fiber-reactive radical Z 1 can or will subsequently be introduced, for example aniline, 3 methyl aniline, 2,5-dimethyl aniline, 2,5-dimethoxy aniline, 3-methoxy aniline, 3-acetylamino aniline, 3-propionylamino aniline, 3-butyrylamino aniline, 3-benzoylamino aniline, 3- (hydroxyacetylamino) aniline, 3-ureido aniline, 2-methyl-5-acetylamino aniline, 2- Methoxy-5-acetylamino-aniline, 2-methoxy-5-methyl-aniline, 1-amino-naphthalene-6-sulfonic acid, 1-amino-naphthalene-7-sulfonic acid, 4-sulfo-1,3-diamino-benzene, 6-sulfo-2-methoxy-1-amino-naphthalene, 5,7-disulfo-2-aminonaphthalene, 1-amino-8-hydroxy-naphthalene-4-sulfonic acid, 1-amino-8-hydro xynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-hydroxy-4,6-disulfonic acid, 1- Amino-8-hydroxy-naphthalene-2,4,6-trisulfonic acid, 2- (methylamino) - and 2- (ethylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid , 2- (methylamino) - and 2- (ethylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2- (4'-amino-3'-sulfophenylamino) - 5-hydroxynaphthalene-7-sulfonic acid, 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′-disulfophenylazo) naphthalene-3,6-disulfonic acid, 1- (β-aminoethyl) -3-cyano-4- methyl-6-hydroxy-pyrid-2-one, 1- (γ-aminopropyl) -3-sulfomethyl-4-methyl-6-hydroxy-pyrid-2-one, 1,3-diaminobenzene, 3- [N, N -Di- (β-hydroxyethyl)] - amino-aniline, 3- [N, N-Di- (β-sulfatoethyl)] - amino-4-methoxy-aniline, 3- (sulfo-benzylam ino) -aniline, 3- (sulfobenzoylamino) -4-chloro-aniline and 3- [N, N-di- (sulfobenzyl)] - amino-aniline, 2-sulfo-5-acetylamino-aniline, 2-amino-5 -naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 1- (4'-aminobenzoyl) -amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1- (4'-aminobenzoyl) amino -8- hydroxynaphthalene-4,6-disulfonic acid, 1- (3'-aminobenzyl) amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1- (3'-aminobenzoyl) amino-8-hydroxynaphthalene-4,6 -disulfonic acid, 1- (2'-aminobenzoyl) amino-8-hydroxy naphthalene-3, 6-disulfonic acid, 1- (2'-aminobenzoyl) amino-8-hydroxyphaphthalene-4,6-disulfonic acid, 2- (3rd '-Aminobenzoyl) amino-5-hydroxy-naphthalene-7-sulfonic acid, 2- (2'-aminobenzoyl) amino-5-hydroxy.naphthalene-7-sulfonic acid, 2- (4'-aminobenzoyl) amino-8 -hydroxynaphthalene-6-sulfonic acid, 2- (3'-aminobenzoyl) -amino-8-hydroxynaphthalene-6-sulfonic acid, 2- (2'-aminobenzoyl) - amino-8-hydroxynaphthalene-6-sulfonic acid, 2- (4 ' -Aminobenzoyl) -amino-5-naphthol-7-sulfonic acid, 1- (4'-A mino- or 1- (4'-acetylamino-2-sulfophenyl) -3-methyl- or -3-carboxy-5-pyrazolone, N- (3-sulfo-4-amino) -acetoacetyl-anilide, 1-amino- 8-naphthol-3,6- or -4,6-disulfonic acid, (1- (3'-aminobenzoyl) - or 1- (4'-aminobenzoyl) -amino-8-naphthol-3,6- or -4, 6-disulfonic acid, 1-acetylamino-8-naphthol-3,6- or -4,6-disulfonic acid, 2-acetylamino-5-naphthol-7-sulfonic acid, 2-acetylamino-8-naphthol-6-sulfonic acid, 3- Acetylamino-8-naphthol-6-sulfonic acid, 3- (N-methyl-amino) -8-naphthol-6-sulfonic acid, 1- (3'-amino- or 1- (3'-acetylamino-6'-sulfophenyl) -3-methyl or -3-carboxy-5-pyrazolone, 2- (N-methyl-N-acetylamino) - or 2-methylamino-5-naphthol-7-sulfonic acid, N-methyl-aniline and N-propyl-m -toluidine.

If one starts from diazo components of the formula H₂N-D²-NH₂, then these are also used in the form of the monoacylamino-amino compounds are, wherein the acyl radical is in particular the acetyl radical. This Monoacylamino-amino compounds are first diazotized and with a coupled connection coupled; then the acyl residue split off hydrolytically, and the one that has now become free again Amino group can be connected to the fiber-reactive radical Z¹. Such monoacylated diamines are, for example, 2-sulfo-5-acetylamino-aniline and 2- Sulfo-4-acetylamino-aniline. In the same way, those containing amino groups Coupling components in the form of the acylamino derivative in the Coupling reaction are used, the subsequent Acyl residue can be split off hydrolytically to release the Connect amino group with the fiber-reactive group Z¹.

Bivalent coupling components that are used to construct the invention Disazo dyes can serve, in which the bivalent coupling residue with two diazo components, one or both of which is connected contain fiber-reactive radical Z, for example of dyes of the general Formula (3d) are, for example, resorcinol, 1,3-diaminobenzene, 5,5′-dihydroxy 7,7'-disulfo-2, 2'-dinaphthylurea, 1,8-dihydroxy-3,6-disulfonaphthalene and especially 1-amino-8-naphthol-3, 6-disulfonic acid and 1-amino-8-naphthol 4,6-disulfonic acid.  

If one goes in the synthesis of the azo dyes according to the invention from diazo or coupling components, which are already the group of the general formula (2) contain, the implementations take place in the usual procedure of Diazotization and coupling reactions, so the diazotization usually a temperature between -5 ° C and + 15 ° C and a pH below 2 using a strong acid and alkali nitrite in a preferably aqueous medium and the coupling reaction usually at a pH between 1.5 and 4.5 im In the case of a coupling component containing amino groups and at a pH between 3 and 7.5 in the case of a hydroxy group Coupling component and at a temperature between 0 and 25 ° C, as well preferably in an aqueous medium.

In the inventive synthesis of heavy metal complex azo dyes, for example those corresponding to the general formulas (3g) and (3h) one usually starts from such heavy metal free azo compounds which are found in the coupling component is a phenolic or naphtholic hydroxy group contain bound in the ortho position or vicinal position to the azo group and whose diazo component residue is ortho to the azo group Hydrogen atom or a hydroxy group or a lower alkoxy group, such as Contains methoxy group, bound, the heavy metal-free starting Azo compounds can also contain an acylamino radical, such as an acetylamino residue. For example, in the synthesis of the Copper complex azo dyes of the formula (3h) from a starting compound according to the general formula (25)

go out, in which D³, K, K³ and v have one of the abovementioned meanings and R ^{k is} a hydrogen atom or a hydroxyl or methoxy group bonded to D³ in the ortho position to the azo group, and this starting azo compound containing acylamino groups is analogous to known and customary procedures a copper releasing agent such as a copper salt. If R ^{k is} a hydrogen atom or a methoxy group, the compound (25) can be subjected to an oxidative or dealkylative copperation reaction which is to be carried out in a customary manner. The copper complex azo compound now obtained with the acylamino group can then be reacted analogously to known procedures after or with hydrolysis of the acylamino group to the amino group with a compound of the formula (21) or (24) to give the dye of the general formula (1) according to the invention.

Some of the starting compounds of the general formula (22) are known, for example from some of the prior art documents mentioned at the beginning and British Patent No. 1,576,237.

Starting compounds of the general formula (22) are, for example N-methyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N-ethyl-N- [γ- (β'- chloroethylsulfonyl) propyl] amine, N-n-propyl-N- [γ- (β'-chloroethylsulfonyl) propyl] - amine, N-n-butyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N-carboxymethyl-N- [γ- (β'-bromethylsulfonyl) propyl] amine, N-sulfatomethyl-N- [γ- (β'-chloroethylsulfonyl) - propyl] amine, N-β-carboxyethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amine, N- (β- Sulfatoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amine, N- (β-sulfatoethyl) -N- [δ′- (β ′ ′ - chloroethylsulfonyl) butyl] amine, N- (β-ethoxyethyl) -N- [δ ′ - (β ′ ′ - chloroethylsulfonyl) butyl] amine, N- (β-ethoxyethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) - propyl] amine, N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4- Chlorophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (2-methylphenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4-methoxyphenyl) -N- [γ- (β'- chloroethylsulfonyl) propyl] amine, N- (3-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) - propyl] amine, N- (4-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (β-cyanoethyl) -N- [γ ′ - (β ′ ′ - chloroethylsulfonyl) propyl] amine, N-phenyl-N- (γ- vinylsulfonyl-propyl) -amine, N- (4-chlorophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- (2-methylphenyl) -N- (γ-vinylsulfonylpropyl) amine, N- (4-methoxyphenyl) -N- (γ-  vinylsulfonyl-propyl) -amine, N- (3-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- (4-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N-phenyl-N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine, N- (4-chlorophenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (2-methylphenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (4-methoxyphenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (3-sulfophenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N- (4-sulfophenyl) -N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine, N-phenyl-N- [α-carboxy-γ- (β′- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [α-carboxyethyl-γ- (β'- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [α-carboxymethyl-γ- (β'- chloroethylsulfonyl) propyl] amine, N-phenyl-N- [β-methyl-γ- (β'-chloroethylsulfonyl) - propyl] amine, N-phenyl-N- [β-ethyl-γ- (β'-chloroethylsulfonyl) propyl] amine, N-phenyl-N- [δ- (β'-chloroethylsulfonyl) butyl] amine, N-phenyl-N- [ε- (β'- chloroethylsulfonyl) pentyl] amine and N-phenyl-N- [β- (β'-chloroethylsulfonyl) hexyl] - amine, preferably of which in particular N-phenyl- [γ- (β′-chloroethylsulfonyl) propyl] - amine and N-phenyl- [γ- (β'-sulfatoethylsulfonyl) propyl] amine.

The compounds of the general formula (22) in which W is the n-propylene Group is and z stands for the number 1, have not yet been described and thus new. The present invention therefore also relates to compounds according to the general formula (22A)

in which Y¹ is one of the particularly preferred ones specified for Y, Has meanings or the β-hydroxyethyl group and R⁰ for phenyl stands by 1, 2 or 3, preferably 1 or 2, substituents from the group Halogen, such as chlorine and bromine, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy from 1 to 4 carbon atoms, such as methoxy and ethoxy, sulfo and carboxy, are preferred  Methyl, methoxy and sulfo, may be substituted. The invention also relates the salts of these amino compounds of the general formula (22), in particular of which the salts of strong inorganic acids, such as hydrochloric acid and Sulfuric acid.

The invention further relates to the use of the compounds of general formula (22A) and their salts as starting compounds for Synthesis of fiber-reactive compounds, especially dyes, such as for example of dyes of the general formula (1).

The amino compounds of the general formula (22A) can be, for example in such a way that N-allyl-N-acetyl-aniline (see J. Org. Chem. 14, 1099 (1949)) analogous to that in German Offenlegungsschrift No. 41 06 106 described procedure with 2-mercapto-ethanol in the presence of a Radical initiator, the resulting N- [γ- (β'-hydroxyethylthio) propyl] -N- Acetyl-aniline compound oxidized to the sulfonyl compound, for example by means of Hydrogen peroxide in the presence of a catalytic amount of one Transition metal compound, such as tungsten oxide. From that The sulfonyl compound obtained is the acetyl group in alkaline or acidic Range, preferably in hydrochloric acid aqueous solution, such as in 5 to 30% aqueous hydrochloric acid, at a temperature between 80 and 100 ° C split off hydrolytically.

The N-phenyl-N- [γ- (β'-hydroxyethylsulfonyl) propyl] amine thus obtained can be from the neutral aqueous synthesis solution from the aqueous phase be separated. Its β-hydroxyethylsulfonyl group can be removed esterify usual methods, for example by means of concentrated Sulfuric acid at a temperature between 10 and 30 ° C in the β-sulfatoethylsulfonyl compound or with thionyl chloride or gaseous Transfer hydrogen chloride to the β-chloroethylsulfonyl compound.

Compounds of the general formula (22A) according to the invention are, for example, N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4-chlorophenyl) -N- [γ- (β'-chloroethylsulfonyl) -propyl] amine, N- (2-methylphenyl) - N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4-methoxyphenyl) -N- [γ- (β'-chloroethylsulfonyl) -propyl] amine, N- (3-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) propyl] amine, N- (4-sulfophenyl) -N- [γ- (β'-chloroethylsulfonyl) -propyl] amine,
N-phenyl-N- (γ-vinylsulfonylpropyl) amine, N- (4-chlorophenyl) -N- (γ-vinylsulfonylpropyl) amine, N- (2-methylphenyl) -N- (γ-vinylsulfonyl -propyl) amine, N- (4-methoxyphenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- (3-sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N- (4th -Sulfophenyl) -N- (γ-vinylsulfonyl-propyl) -amine, N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) -propyl] -amine, N- (4-chlorophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine, N- (2-methylphenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine, N- (4-methoxyphenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine, N- (3-sulfophenyl) -N- [γ- (β'- sulfatoethylsulfonyl) propyl] amine and N- (4-sulfophenyl) -N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and their β-hydroxyethylsulfonyl derivatives.

The dyes of the general formula (1) - hereinafter dyes (1) called - are suitable for dyeing and printing the most diverse Materials such as silk, leather, wool, polyamide fibers and polyurethanes, and in particular cellulose-containing fiber materials of all kinds. Such fiber materials are, for example, the natural cellulose fibers such as cotton, linen and Hemp, as well as cellulose and regenerated cellulose. The dyes (1) are too suitable for dyeing or printing fibers containing hydroxy groups, which in Blended fabrics are included, e.g. B. of mixtures of cotton with Polyester fibers or polyamide fibers.

The dyes (1) can be applied to the fiber material in different ways apply and fix on the fiber, especially in the form of aqueous Dye solutions and printing pastes. They are suitable for both Exhaust process as well as for dyeing according to the foulard dyeing process, after which the goods with aqueous, optionally saline dye solutions impregnated and the dye after an alkali treatment or in the presence of alkali, optionally under the action of heat. Especially  the dyes according to the invention are suitable for the so-called Cold residence process, after which the dye together with the alkali on the Foulard applied and then by storage for several hours Room temperature is fixed. After fixing, the stains or Print with cold and hot water, possibly with the addition of one dispersing and promoting the diffusion of the unfixed portions Medium, rinsed thoroughly. These dyeing and printing processes are numerous in the general specialist literature as well as in the patent literature, such as in the publications mentioned at the beginning.

The present invention therefore also relates to the use of Dyes (1) for dyeing (including printing) these materials or Process for dyeing (and printing) such materials in and of itself usual procedure in which a dye (1) is used as the colorant is by placing the dye (1) in an aqueous medium on the material applied and using heat or an alkaline Connection or by means of both fixed on the material.

The dyes (1) are notable for high reactivity and good fixing properties and a very good build-up ability. You can therefore after Pull-out dyeing processes are used at low dyeing temperatures and require only short steaming times with pad-steam processes. The degrees of fixation are high, and the unfixed portions can be washed out easily the difference between the degree of exhaustion and the degree of fixation is remarkably small, d. H. the soap loss is very low. The dyes (1) are also particularly suitable for printing, especially on cotton, but also for printing on nitrogen-containing fibers, e.g. B. of wool or silk or of mixed fabrics, that contain wool or silk.

The dyeings and prints produced with the dyes (1) have especially on cellulose fiber materials, a high color strength and a high Fiber-dye binding stability in both acidic and alkaline  Area, continue to have good lightfastness and very good Wet fastness properties, such as washing, water, seawater, over-dyeing and Sweat fastness, as well as good pleating fastness, ironing fastness and Fastness to rubbing.

The following examples serve to explain the invention. The parts are Parts by weight, the percentages are percentages by weight, if not noted otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

The compounds described by formula in the examples are in the form of specified free acid; generally they are in the form of their Alkali metal salts, such as lithium, sodium or potassium salts, prepared and isolated and used in the form of their salts for coloring. Likewise, in the following examples, especially table examples, in the form of the free Starting compounds and components mentioned as such or in acid Form of their salts, preferably alkali metal salts, used in the synthesis become.

The absorption maxima (λ _max ) in the visible range specified for the dyes according to the invention 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 when specifying the color; the wavelength specification refers to nm.

example 1

A solution with a pH of 5.5 from 16 parts of 1-amino-8-hydroxy- naphthalene-3,6-disulfonic acid in 200 parts of water is at a temperature from 0 to 3 ° C with 7.2 parts of 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) Adherence to a pH value of 4 to 4.5 with good stirring. Man stirs the mixture for a while at a pH of 4.5 and gives then 16.8 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and carries out the reaction at a pH of about 5 and a slow of 5 ° C after 20 ° C rising temperature. Then you give one on usual Ways out of 8.7 parts of 2-sulfo-aniline in 100 parts of water using 10 parts by volume of concentrated aqueous hydrochloric acid and 25 parts by volume of an aqueous 2N sodium nitrite solution Add diazonium salt solution and conduct the coupling reaction at pH from 6 and a temperature slowly increasing from 5 ° C to 20 ° C. Man stirs for a while and isolates the dye according to the invention, which, in Written form of free acid, the formula

has, in the usual way, for example by salting out with sodium chloride.

The dye according to the invention shows very good application and fiber-reactive properties and colors those mentioned in the description Materials, such as cellulose fiber materials, according to the in  Technology for fiber-reactive dyes usual dyeing and printing processes in strong red tones with good fastness properties, of which in particular the good chlorine bathing water rights are emphasized can.

Example 2

It is added while maintaining a pH of 5 to 6 and one Temperature of 0 ° C a neutral solution of 18.1 parts of the azo compound 7- (2'-Sulfo-4'-methoxy-phenyl) -azo-6-sulfo-8-hydroxy-3-amino-naphtha-lin in 500 parts of water with 7.1 parts of cyanuric fluoride, then stir for a while and then gives in compliance with the specified temperature and pH Areas of 16.8 parts of N-phenyl-N- [γ- (β′-sulfatoethylsulfonyl) propyl] amine were added. After completion of the reaction, the obtained invention Dye, written in the form of free acid, the formula

has, in the usual way, for example by salting out with sodium chloride, isolated as an alkali metal salt.

The dye according to the invention shows very good application properties Properties and colors the fiber materials mentioned in the description, such as Wool and in particular cellulose fiber materials, such as cotton, in strong, brilliant, yellowish red tones with good Authenticity properties.  

Example 3

Maintaining a pH between 5 and 6 and a temperature of around 0 ° C, 14.2 parts of cyanuric fluoride are slowly added to a neutral solution of 54.5 parts of the azo compound 4- (3 ′, 6 ′, 8′-trisulfonaphth-2′-yl) -azo-3- ureido-aniline in 800 parts of water. The mixture is stirred in for some time Compliance with these reaction conditions until the completion of the implementation and then gives at about 5 ° C and while maintaining the pH between 5 and 6 33.8 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] - amine added. The approach is stirred for some time and the Rise reaction temperature to 20 ° C.

After the reaction has ended, the dye according to the invention is isolated of the formula (written in the form of the free acid)

in the usual way as an alkali metal salt (sodium salt). He shows very good ones fiber-reactive dye properties and colors those in the description mentioned materials, such as in particular cellulose fiber materials, according to the in the technology for fiber-reactive dyes usual application and Fixing process in bright reddish yellow tones with good Authenticity properties.  

Example 4

At a temperature of 0 ° C and maintaining a pH between 5 and 6 using an aqueous sodium hydroxide solution are slowly added 19.5 parts of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) to a neutral solution of 54.5 parts of 4- (3 ′, 6 ′, 8′-trisulfonaphth-2′-yl) -azo-3-ureido-aniline in 800 parts of water. The approach is stirred for some time with these Reaction conditions until the reaction is complete, the Temperature rise to 25 ° C and then drops to around 5 ° C and below Compliance with the pH between 5 and 6 31, 2 parts of N-phenyl-N- [γ- (β′- chloroethylsulfonyl) propyl] amine hydrochloride. The approach is still stirred for some time and the reaction temperature rises to 30 to 40 ° C.

After the reaction has ended, the dye according to the invention is isolated of the formula (written in the form of the free acid)

in the usual way as an alkali metal salt (sodium salt). He shows very good ones fiber-reactive dye properties and colors those in the description mentioned materials, such as in particular cellulose fiber materials, according to the in the technology for fiber-reactive dyes usual application and Fixing process in strong, brilliant, reddish yellow tones with good Authenticity properties.  

Example 5

A solution with a pH of 5.5 from 16 parts of 1-amino-8-hydroxy- naphthalene-3,6-disulfonic acid in 200 parts of water is at a temperature from 0 to 3 ° C with 9.8 parts of cyanuric chloride while maintaining a pH of 4 to 4.5 mixed with good stirring. The approach is stirred for some time at a pH of 4.5 after, warmed to 25 ° C and then gives 15.5 parts N-Phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine.hydrochloride and leads the reaction at a pH of about 5 and a slow of 5 ° C after 35 ° C rising temperature. Then you give one in the usual way from 8.7 parts of 2-sulfo-aniline in 100 parts of water using 10 parts by volume of concentrated aqueous hydrochloric acid and 25 parts by volume of one diazonium salt solution prepared in aqueous 2N sodium nitrite solution and carries out the coupling reaction at a pH of 6 and a slow of 5 ° C to 20 ° C rising temperature. Stir for a while longer and isolates the dye according to the invention, the, in the form of the free acid written the formula

has, in the usual way, for example by salting out with sodium chloride.

The dye according to the invention shows very good application and fiber-reactive properties and colors those mentioned in the description Materials, such as cellulose fiber materials, according to the in Technology for fiber-reactive dyes usual dyeing and printing processes in  strong red tones with good fastness properties, of which in particular the good chlorine bathing water rights are emphasized can.

Example 6

It is added while maintaining a pH of 5 to 6 and one Temperature of 0 ° C a neutral solution of 18.1 parts of the azo compound 7- (2'-Sulfo-4'-methoxy-phenyl) -azo-6-sulfo-8-hydroxy-3-amino-naphtha-lin in 500 parts of water with 9.5 parts of cyanuric chloride, stir for a while, warmed to 25 ° C, given the specified pH range 16.8 Add N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and increase the Reaction temperature slowly to 40 ° C. After the implementation is finished the dye according to the invention obtained, in the form of the free acid written the formula

has, in the usual way, for example by salting out with sodium chloride, isolated as an alkali metal salt.

The dye according to the invention shows very good application properties Properties and colors the fiber materials mentioned in the description, such as Wool and in particular cellulose fiber materials, such as cotton, in strong yellowish red tones with good fastness properties.  

Example 7

A neutral solution of 40.9 parts of the diazo compound 4- [4 ′ - (4 ′ ′, 6 ′ ′, 8 ′ ′ - Trisulfo-naphth-2 ′ ′ - yl) -azo-6′-sulfo-naphth-1′-yl] -3-methyl-aniline (in the usual Paths can be produced by coupling 6-sulfo-1-amino-naphthalene with the Diazonium salt of 2-aminonaphthalene-4,6,8-trisulfonic acid and diazotization of obtained monoazo compound and coupling with 3-methyl-aniline) in 300 parts Water is maintained at a temperature between -3 ° C and + 5 ° C a pH value between 6 and 7 with 9.2 parts of cyanuric fluoride. Man Stir for some time under the specified reaction conditions then adds 21.5 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and carries out this second condensation reaction at a pH between 6 and 7 and a temperature of initially about 5 ° C, which one in the course of Reaction can rise to 20 ° C by. The mixture is stirred at 20 ° C. for some time and then adds to the aqueous synthesis solution obtained Disazo dye according to the invention 8.9 parts of disodium hydrogen phosphate.

The disazo dye is isolated in a conventional manner, for example by Evaporation of the synthesis solution. It has, in the form of free acid written the formula

According to those in the technology for fiber-reactive dye properties one obtains with the disazo dye according to the invention strong, true colorations in reddish brown tones.  

Example 8

A neutral solution of 31.9 parts of 1-amino-3,6-disulfo-8-naphthol in 800 Divide water slowly at 0 ° C and pH 4.5 within 14.2 parts of cyanuric fluoride were added for 5 minutes. Then you give 33.1 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine in compliance a pH of 7 and a temperature of 5 to 15 ° C and stirred some time after. Then give at 50 to 55 ° C and a pH of 6.5, 29.9 parts of this propylamine are added and stirred Temperature and the pH of 6.5 for another 4 hours after. The batch is then mixed with the aqueous at 15 to 30 ° C. hydrochloric acid solution of the diazonium salt of 51.1 parts of 1-sulfo-2-amino-6- (β- sulfatoethylsulfonyl) naphthalene and carries out the coupling reaction at a pH Value of 6 by.

The monoazo dye according to the invention formed is spray dried isolated from the synthesis solution at a pH of 7. He shows very good ones Dye properties and delivers on those mentioned in the description Fiber materials, such as cotton in particular, according to the usual application and fixation process for fiber-reactive dyes strong red dyeings. Of the Dye, written in the form of the free acid, has the formula

Example 9

To produce the invention described in Example 8 The azo dye can also be used according to the invention as follows: with stirring while maintaining a pH of 1.7 to 2.2 155.2 parts Cyanuric chloride in a suspension of 225.2 parts of 1-amino-3,6-disulfo-8- naphthol in 1440 parts water and 720 parts ice. The approach is still stirred about four hours at 0 to 3 ° C and the specified pH range and adds then 280 parts of N-phenyl-N- [γ- (β′-hydroxyethylsulfonyl) propyl] amine Hydrochloride and performs the second condensation reaction at pH Value of 7 and a temperature of 60 ° C. The third Condensation reaction is this after adding another 280 parts Propylamine hydrochloride at pH 9 and temperature 80 up to 90 ° C. The mixture is then at 15 to 30 ° C with the aqueous, hydrochloric acid suspension of the diazonium salt of 411 parts of 1-sulfo 2-amino-6- (β-sulfatoethylsulfonyl) naphthalene added; the coupling reaction takes place within this temperature range and at a pH of 7. Die The synthesis solution is then clarified and spray dried. The electrolyte Product is mixed in a mixture of 800 within one hour at a maximum of 10 ° C Parts by volume of sulfuric acid monohydrate and 424 parts by volume of 20% Oleum registered. After about two hours the esterification is at 10 ° C been 23917 00070 552 001000280000000200012000285912380600040 0002004316539 00004 23798det. The mixture is poured onto ice and excess sulfuric acid neutralized with calcium carbonate. The calcium sulfate is suctioned off and with Washed water. The dye according to the invention is combined from the Filtrates by evaporation under reduced pressure at 60 ° C or through Spray drying isolated as an alkali metal salt.

The azo dye according to the invention produced in this way, which the has chemical constitution of the azo dye described in Example 8, has the same good properties and delivers accordingly same good colors and prints with good fastness properties.  

Example 10

45.3 parts of 7- (2'-sulfo-4'-methoxyphenyl) azo-8-hydroxy-3-amino-naphthalene-6- sulfonic acid are in aqueous solution at a temperature of 0 to 3 ° C and a pH of 3.5 to 4 with 19 parts of cyanuric chloride. To When the condensation reaction is complete, 28.0 parts of N-phenyl-N- [γ- (β′- hydroxyethylsulfonyl) propyl] amine hydrochloride added, and the second Condensation reaction is carried out at 60 ° C and a pH of 7 during two Hours finished (as in the previous examples, the implementation can be followed by thin layer chromatography). Then you give 4.4 parts Add cyanamide and conduct the third condensation reaction at pH of 10 and a temperature of 85 ° C. The azo compound formed with the β-hydroxyethylsulfonyl group is on after adjusting the synthesis solution salted out a pH of 7 by adding potassium chloride, isolated and dried. 10 parts of this product, which is approx. 70% of the azo compound, are at 5 to 10 ° C in 15 parts of 100% sulfuric acid with stirring registered. After the azo compound is released, the approach is abandoned 80 parts of ice, neutralizes the mixture with calcium carbonate, sucks precipitated calcium sulfate, washed the residue with water and evaporated the filtrate under reduced pressure.

The azo dye of the present invention obtained as an alkali metal salt (sodium salt) has the formula written in the form of the free acid

It shows very good fiber-reactive dye properties and colors them in the Description materials mentioned, such as in particular Cellulose fiber materials, such as cotton, in bright, bright colors scarlet tones with a high degree of fixation.

Examples 11 to 161

The table examples below show further examples according to the invention Dyes according to the general formula (A)

based on their components (the rest D of the diazo component D-NH₂, the rest -KN (R ^A ) - the amino group-containing coupling component of the formula HKN (R ^A ) H and the substituents A and B). They can be produced in one of the procedures according to the invention, for example analogously to one of the above exemplary embodiments. They have very good fiber-reactive dye properties and dye, for example, cotton in the shade specified in the respective table example in high color strength and good fastness properties.

Example 162

680 parts of a neutral 0 ° C aqueous solution of 81 parts of the Disazo compound 2- [4 ′ - (β′-sulfatoethylsulfonyl) phenyl] -azo-7- (2 ′ ′ - sulfo-5 ′ ′ - amino-phenyl) -azo-3,6-disulfo-1-amino-8-hydroxy-naphthalene (in the usual way can be produced by coupling reaction of 3,6-disulfo-1-amino-8-naphthol with the diazonium salt of 4- (β-sulfatoethylsulfonyl) aniline in the strongly acidic range and subsequent coupling reaction of the monoazo compound obtained with the monodiazonium salt of 1,3-diaminobenzene-6-sulfonic acid in the weak acidic to neutral range) in 600 parts of water are adhered to a pH between 5 and 5.5 and a temperature of 0 to 5 ° C slowly added 15 parts of cyanuric fluoride. Then you run the second condensation reaction after addition of 38.7 parts of N-phenyl-N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine at a temperature of 0 to 5 ° C and one pH from 7 to 7.5.

The disazo dye according to the invention is isolated after the addition of 1 part Disodium hydrogen phosphate and 3 parts of sodium dihydrogen phosphate Evaporation of the synthesis solution, such as by spray drying. Man receives the alkali metal salt (sodium salt) of the compound of formula

The disazo dye according to the invention has very good fiber-reactive Dye properties and colors according to those in the art for fiber reactive  Dyes usual dyeing and printing processes for example Cellulose fiber materials, such as cotton, depending on the amount of dye used light blue to navy blue tones with good fastness properties, of which in particular the good chlorine bathing water rights are emphasized can.

Example 163

A solution of 19.8 parts of 1,3-diaminobenzene-4-sulfonic acid in 100 parts Water and 12.9 parts of a 33% aqueous sodium hydroxide solution are slowly added at 5 to 10 ° C within 30 minutes in a suspension of 19.7 parts Cyanuric chloride in 50 parts water and 85 parts ice. Using sodium carbonate the pH is adjusted to 4.0 to 4.5 and the batch is stirred a little at 8 to 10 ° C after.

The resulting suspension of the 2-sulfo-5- (dichlorotriazinyl) amino aniline compound are mixed with 6.9 parts of sodium nitrite and 100 parts of ice and diazotized at 0 to 5 ° C using 68.4 parts of a 20% aqueous sulfuric acid. The Diazonium salt suspension obtained is added at 10 to 15 ° C and a pH Value from 6.0 to 6.5 in about 600 parts of an aqueous solution of 53 parts of the compound 1-amino-8-hydroxy-3,6-disulfo-2- [4 ′ - (β-sulfatoethylsulfonyl) - phenyl] -azo-naphthalene. The coupling reaction is carried out while observing this pH value, then gives 32.8 parts of N-phenyl-N- [γ- (β′- chloroethylsulfonyl) propyl] amine hydrochloride and leads the Condensation reaction at a pH of 6.0 to 6.5 and a temperature from 40 to 45 ° C for one hour.

The disazo dye of the formula (in the form of the free acid)

as an alkali metal salt (sodium salt) in the form of an electrolyte-containing black Powder. It shows very good dye properties and delivers on the in the Description materials mentioned, such as in particular Cellulose fiber materials, navy blue dyeings and prints with good Authenticity properties, of which in particular the chlorine bathing fastness can be highlighted.

Example 164

Analogously to Example 154, the starting compound 1-amino-8- hydroxy-3, 6-disulfo-2- [3 ′ - (β-sulfatoethylsulfonyl) phenyl] -azo-7- (2 ′ ′ - sulfo-5 ′ ′ - aminophenyl) -azo-naphthalene and sets them according to the instructions of the Example 155 with the equivalent amount of cyanuric chloride and N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl amine hydrochloride. You get that disazo dye of the formula

as an alkali metal salt (sodium salt). It has very good dye properties and dyes cotton, for example, in real navy blue tones.

Example 165

To produce the azo dye of the formula (in the form of the free acid)

diazotizing 23.0 parts of 2-sulfo-4-acetylamino-aniline in 100 parts of ice water, which contains 6.9 parts of sodium nitrite dissolved, by adding 5 parts of conc. aqueous hydrochloric acid; the diazonium salt suspension obtained is then at  0 to 5 ° C in a solution of 30.3 parts of 2-aminonaphthalene-5,7-disulfonic acid stirred in 570 parts of water. The coupling reaction takes place at one Temperature of 20 ° C and a pH of 4.

After the coupling reaction has ended, 150 parts of a 33% strength aqueous solution are obtained Sodium hydroxide solution added and the acetylamino group at 60 ° C alkaline hydrolyzed for about four hours. To the solution thus obtained the azo compound containing amino groups is added at a temperature of 0 up to 2 ° C and maintaining a pH of 4 to 5 15 parts Cyanuric fluoride. After this condensation reaction has ended, the Approach with 35.4 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and conducts the final condensation reaction at a pH of 6.5 to 7.5 and at a temperature of 5 to 10 ° C.

The dye according to the invention obtained is isolated in a conventional manner, for example by salting out with sodium chloride. He shows very good ones fiber-reactive dye properties and delivers, for example Cellulose fiber materials have strong orange dyeings with good fastness properties.

Examples 166-201

The following table examples show further examples according to the invention Azo dyes according to the general formula (B)

described with the help of the visible components. They can be prepared in one of the procedures according to the invention, for example analogously to the information in Examples 162 to 165, by reacting the starting compounds evident from the formula residues. They have very good fiber-reactive dye properties and, on the fiber materials mentioned in the description, such as, in particular, cotton, provide strong dyeings and prints with the hue specified in the respective table example for cotton according to the application and fixing processes customary for fiber-reactive dyes.

Example 202

A neutral solution of 26.5 parts of 1-amino-4- (2 ', 4', 6'-trimethyl-3'-amino phenylamino) -anthraquinone-2,5'-disulfonic acid is stirred well at 0 ° C and while maintaining a pH of 5 with 7.1 within 30 minutes Parts of cyanuric fluoride added. Stir some time until the end of After reaction, then gives 15.5 parts of N-phenyl-N- [γ- (β'-chloroethylsulfonyl) - propyl] amine hydrochloride, the reaction leads to a pH of 8.5 and at a temperature of 5 ° C and then stirring some time at a pH of 7 and at 20 ° C.

The anthraquinone dye of the formula (in the form of the free Acid written)

is isolated by salting out of the synthesis solution using potassium chloride. He shows very good fiber-reactive dye properties and colors them in the Description materials mentioned, such as Cellulose fiber materials, in brilliant blue tones with good ones Authenticity properties.

Example 203

The procedure for producing an anthraquinone dye according to the invention is carried out according to the procedure of example 202, but instead of  N-phenyl-N- [γ- (β'-chloroethylsulfonyl) propyl] amine hydrochloride the equivalent Amount of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine. The dye of the formula (in the form of the free Acid written)

which has the same good properties as the anthraquinone dye of Example 202 owns and provides real, brilliant blue colorings.

Example 204

The procedure for the preparation of the anthraquinone dye according to the invention of the formula (written in the form of the free acid)

the procedure of Example 202 is followed, with the exception that that instead of the amino-anthraquinone Starting compound of 19.8 parts of 1-amino-4- (3'-aminophenylamino) - anthraquinone-2-sulfonic acid in 500 parts of a neutral aqueous solution of about 0 ° C.

The anthraquinone dye according to the invention also shows very good fiber-reactive dye properties and, for example, dyes cotton the usual in the art for fiber-reactive dyes and Printing process in real, strong blue tones.

Example 205

The procedure for the preparation of the anthraquinone dye according to the invention following the procedure of Example 202, except that instead of the amino-anthraquinone starting compound of 19.8 parts of 1-amino-4- (4'-aminophenylamino) anthraquinone-2-sulfonic acid in 500 parts of a neutral aqueous solution starts from about 0 ° C. The anthraquinone dye according to the invention also shows very good fiber-reactive dye properties and, for example, dyes cotton the usual in the art for fiber-reactive dyes and Printing process in real, strong blue tones.

Example 206

A neutral solution of 55 parts of the triphendioxazine compound of the formula

in 500 parts of water at 0 ° C and maintaining a pH between 5 and 6 slowly with good stirring with 29 parts of cyanuric fluoride  transferred. The mixture is stirred for a short time and then 68 parts of N-phenyl-N- Add [γ- (β'-sulfatoethylsulfonyl) propyl] amine and carry out the reaction at 0 to 10 ° C while maintaining a pH value of 8 to 9.

The triphendioxazine dye according to the invention, in the form of the free acid written the formula

is isolated by salting out with sodium chloride. He shows good ones fiber-reactive dye properties and dyes according to the technology for fiber-reactive dyes usual application and fixing methods on the in the Description materials mentioned, such as in particular Cellulose fiber materials, in strong blue tones with good Authenticity properties.

Example 207

While stirring well, add to a neutral solution of 65 parts of the Starting compound 1,6-disulfo-2,7-di- (γ-aminopropyl) amino-5,10-dichlor triphendioxazin in 500 parts of water at 0 ° C and 25 parts of cyanuric fluoride here the pH at about 6 using an aqueous 2N sodium hydroxide solution upright. Stir for a while, add the approach 68 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and leads the Reaction at a temperature of 0 to 10 ° C while maintaining a pH Value from 8 to 9 end.  

The triphendioxazine dye according to the invention is carried out in a conventional manner Salting out with sodium chloride isolated from the synthesis solution. He has, in shape written the free acid, the formula

and dyes the fiber materials mentioned in the description, in particular Cellulose fiber materials, according to those used in fiber reactive dye technology usual application and fixing methods in strong, blue tones with good fastness properties.

Examples 208 to 229

The following table examples show further examples according to the invention Triphendioxazine dyes according to the general formula (C)

described with the help of the visible components. You let yourself in inventive manner, for example analogous to the information in Examples 206 and 207, by reacting those from the formula residues of formula (C) Establish apparent output connections. You have very good ones fiber-reactive dye properties and deliver on the in the description mentioned fiber materials, such as especially cotton, according to the fiber-reactive dyes usual application and fixing processes strong color Colorings and prints with the in the respective table example for Cotton specified shade.

Example 230

A solution of 48.4 parts of the sodium salt of N-phenyl-N- [γ- (β′- sulfatoethylsulfonyl) propyl] amine in 1300 parts of a water / ice mixture within a short time with intensive stirring with 12 parts by volume Cyanuric fluoride added. Stir for a short time and then admit of this solution 124.6 parts of the starting compound N- (2-carboxy-5-sulfo phenyl) -N '- (2'-hydroxy-3'-amino-5'-sulfo-phenyl) -ms-phenyl-Kupferfor-mazan added and leads the reaction at a pH of 9.5 and a temperature from 0 to 3 ° C. Stir for a while, adjust the pH to 7 and warmed the batch to 20 ° C.

The copper formazan dye of the formula (in the form of the free Acid written)

is salted out of the synthesis solution by sodium chloride. It colors for example cotton according to the technology for fiber-reactive dyes usual color proofs in strong blue tones with good fastness properties.

Example 231

A neutral solution of 50.3 parts of the compound 3- (m-amino-p-sulfo-  phenylaminosulfonyl) copper phthalocyanine-3 ', 3' ', 3' '' - trisulfonic acid - in 500 parts Water is at 0 to 3 ° C while maintaining a pH of 6 to 7 7.1 parts of cyanuric chloride were added within about 30 minutes. You stir in compliance with these process conditions for some time 16.8 parts of N-phenyl-N- [γ- (β'-sulfatoethylsulfonyl) propyl] amine and leads the reaction at a pH of about 5 and a temperature of about 35 ° C through.

The copper phthalocyanine dye of the formula (in Form of free acid)

is salted out of the synthesis solution by sodium chloride. It colors for example cotton, cellulose and regenerated cellulose in strong colors, turquoise blue, real tones.

Example 232

For the production of a copper phthalocyanine dye according to the invention the procedure of Example 231 is followed, but the procedure is set instead of the copper phthalocyanine starting compound used there 3- (p-amino-m-sulfo-phenyl-aminosulfonyl) copper phthalocyanine-3 ′, 3 ′ ′, - 3 ′ ′ ′ - trisulfonic acid.

The copper phthalocyanine dye according to the invention shows in aqueous solution in visible range an absorption maximum at 670 nm and provides as a dye with good fiber-reactive properties, for example on cotton  strong turquoise blue, real colors and prints.

Example A

A solution of 350 parts of N-allyl is added with stirring at about 20 ° C. N-acetyl-aniline in 1500 parts by volume of acetone with 145 parts of 2-mercapto-ethanol, heats the batch under reflux to boiling temperature and gives in portions, distributed over several hours, 25 parts of azoisobutyronitrile. You stir it Start at boiling temperature for a few more hours, then distill the Acetone and 2 parts of sodium tungstate are added to the residue. Under 340 parts by volume of 35% strength are slowly added at about 70 ° C. aqueous hydrogen peroxide solution and maintains the reaction temperature 70 to 80 ° C. After the oxidation reaction has ended, 200 parts by volume are added a 31% aqueous hydrochloric acid and cleaves the acetyl group hydrolytically at 100 ° C. The mixture is then cooled to room temperature and neutralized it with solid sodium hydroxide, whereupon the N-phenyl-N- [γ- (β'-hydroxyethylsulfonyl) propyl] amine deposits as a brown oil. It is from separated from the aqueous phase and dried under reduced pressure.

The compound N-phenyl-N- [γ- (β-hydroxyethylsulfonyl) propyl] amine according to the invention shows the following 1 H-NMR data in deuterochloroform with tetramethylsilane as internal standard in the 300 MHz field:
2.02-2.21 ppm (m, 2H), 3.16-3.23 ppm (m, 2H), 3.30 ppm (t, 2H), 3.81 ppm (t, 2H), 4, 04-410 ppm (m, 2H), [6.59-6.74 + 7.14-7.20 + 7.35-7.48] ppm (m, 5H).

Example B

312 parts of the compound N-phenyl-N- [γ- (β'-hydroxyethylsulfonyl) propyl] amine are as a viscous oil at a temperature of 10 to 15 ° C within a Hour slowly stirred into 700 parts of sulfuric acid monohydrate. The approach Stir for about an hour at 15 ° C and then pour it slowly to 3000 parts of a mixture of water and ice and stir for some time to.  

The solution obtained is filtered and with 1200 parts of calcium carbonate and Sodium bicarbonate added until it has a pH of 5. The precipitated calcium sulfate is filtered off, washed with 1500 parts of water and evaporated the combined filtrate under reduced pressure at 60 ° C. Of the the residue obtained is stirred in 2000 parts by volume of acetone, the solution suction filtered and the filtrate evaporated.

About 250 parts of N-phenyl-N- [γ- (β′-sulfatoethylsulfonyl) propyl] amine are obtained. Sodium salt as a solid compound.

1H NMR analysis (100 MHz) with Si (CH₃) ₄ in d₆-dimethyl sulfoxide:
1.71-2.03 ppm (m, 2H), 2.94-3.24 ppm (dt, 2H), 3.25-3.50 ppm (t, 2H; t, 2H), 4.07 ppm (t, 2H) 5.61 ppm (broad, 1H), 6.40-6.63 ppm (m, 3H), 6.87-7.14 ppm (m, 2H).

Claims (17)

1. Dye of the general formula (1) F-Zn (1) in which:
F is the remainder of a sulfo group-containing mono-, dis- or polyazo dye or a heavy metal complex mono-, dis- or trisazo dye or an anthraquinone, azomethine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl -, Naphthoquinone, pyrenequinone, perylene tetracarbimide, formazane, copper formazane, phthalocyanine, copper phthalocyanine, nickel phthalocyanine or cobalt phthalocyanine dye or a triphendioxazine dye;
Z is a group of the general formula (2) in which
R ^{A is} hydrogen or alkyl of 1 to 4 carbon atoms, which is substituted by halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo, sulfato or phosphato can be,
R is alkyl of 1 to 6 carbon atoms, that is halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo, sulfato, phosphato, phenyl or sulfophenyl may be substituted, or is phenyl, which may be substituted by 1, 2 or 3 substituents from the group halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo and carboxy,
X is halogen, cyanoamino, methylsulfonylamino, ethylsulfonylamino, carboxypyridinyl, aminocarbonylpyridinyl or a radical of the formula -N (R) -W- (SO₂-Y) _z with R, W, Y and z being one of the meanings given below,
W is straight-chain or branched alkylene of 3 to 8 carbon atoms, which is substituted by 1 or 2 substituents from the group alkoxy of 1 to 6 carbon atoms, halogen, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfo and sulfato a phenyl radical or a phenyl radical substituted by 1 or 2 substituents from the group sulfo, carboxy, methoxy, ethoxy and methyl or by such an optionally substituted phenyl radical and a sulfo, sulfato or carboxy group or by a heterocyclic radical,
Y vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β- (C₂-C₅-alkanoyloxy) -ethyl, β-benzoyloxyethyl, β- (sulfobenzoyloxy) -ethyl, β- (p-toluenesulfonyloxy) -ethyl or β -Halogenoethyl, and
z is the number 1 or 2, and
n is the number 1 or 2. 2. Dye according to claim 1, characterized in that F is the rest of a sulfo-containing mono- or disazo dye. 3. Dye according to claim 1, characterized in that F is the rest of a 1: 1 copper complex mono- or disazo dye.   4. Dye according to claim 1, characterized in that F is the rest of a Anthraquinone dye is. 5. Dye according to claim 1, characterized in that F is the rest of a Copper formazan dye. 6. Dye according to claim 1, characterized in that F is the rest of a Copper phthalocyanine or nickel phthalocyanine dye. 7. Dye according to claim 1, characterized in that F is the rest of a Triphendioxazine dye. 8. Dye according to at least one of claims 1 to 7, characterized records that X is chlorine or fluorine. 9. Dye according to at least one of claims 1 to 7, characterized records that X is cyanoamino. 10. Dyestuff according to at least one of claims 1 to 9 characterized records that W is n-propylene. 11. Dye according to at least one of claims 1 to 10, characterized characterized in that R is phenyl consisting of 1 or 2 substituents the group methyl, methoxy and sulfo can be substituted. 12. Dye according to at least one of claims 1 to 11, characterized in that R ^{A is} hydrogen. 13. A process for the preparation of a dye corresponding to the general formula (1) of claim 1, characterized in that precursors typical of the respective dye, of which at least one contains a group of the general formula (2), are reacted with one another or that one Halogenotriazine compound of the general formula (21) in which X has one of the meanings given in Claim 1 and Hal represents halogen, with a compound of the general formula (20) containing amino groups with F, R ^A and n of the meanings given in Claim 1 and an amino compound of the general formula (22) with R, W, Y and z of the meanings mentioned in claim 1 in any order. 14. Use of a dye of claim 1 or one of claim 13 dye for dyeing (including printing) of material containing hydroxyl and / or carbonamide groups, in particular Fiber material.   15. Process for dyeing (including printing) of hydroxy and / or material containing carbonamide groups, in particular fiber material which one applies a dye to the material and the Dye on the material using heat or with the help of an alkaline fixed agent or by means of both measures, thereby characterized in that the dye is a dye of claim 1 or uses a dye prepared according to claim 13. 16. Compound according to the general formula (22A) in which Y¹ is vinyl or β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β- (C₁-C₅) alkanoyloxy-ethyl, β-benzoyloxyethyl, β- (sulfobenzoyloxy) -ethyl, β- (p-toluenesulfonyloxy) - is ethyl, β-haloethyl or β-hydroxyethyl and R⁰ phenyl, which may be substituted by 1, 2 or 3 substituents from the group halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo and carboxy can. 17. Use of a compound of claim 16 as the starting compound for the synthesis of fiber-reactive compounds, especially dyes.