DE1958711A1 - New azo compounds, processes for their preparation and their uses - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6606 / E
Germany

New azo compounds, processes for their preparation and their

Use.

The present invention relates to new valuable azo compounds of the general formula

-N = N-A-N

2
Ag ^

009825/1809

wherein D is a residue of a diazo component, A is a phenylene residue, R and R alkylene radicals having 1 to 3 carbon atoms, which each have at least one negative substituent, and Ac is a residue of a fiber-reactive residue bonded via an amino group Is heterocycle.

For the purposes of the invention, negative radicals are those substituents which have a sigma value, which is larger than that of a hydroxyl group. A list of The British patent specification contains sigma values, for example No. 1.098.65 ^, where other references are also given, or the textbook by H.A. Staab, Introduction to Theoretical Organic Chemistry, 2nd edition, Weinheim / Bergstrasse 1960, p. 584 (List of the para substituents). Those radicals which contain more than one atom are particularly preferred, above all Residues with more than one heteroatom and aromatic residues, and in particular residues containing carbonyl groups or cyano groups.

As examples of fiber-reactive heterocyclic groups are for example mentioned: 2-chlorobenzothiazolecarbonyl or -sulfonyl-, dichloroquinoxalinearbony1-, dichlorchinaζοlinearbony1- and especially halopyrimidyl groups.

Of particular interest are the azo compounds of the formula given, which are a fiber-reactive substituent Triazine grouping, especially the grouping of the formula

- C ^ N} -z,

Ji ¹ ■

N N

Ci 009825/18 09

contain, in which Z is a halogen atom, an NH _p group or an organic radical, such as an alkyl, aralkyl or phenyl group, or the radical of an alcohol, phenol, mercaptan or amine, for example an aliphatic or aromatic amine, furthermore those fiber-reactive groups whose detachable substituent represents a quaternary ammonium or hydrazine group bonded in particular to a carbon atom of a heterocyclic radical, ie a group of the formula

Jl

/ \ -NH-C N

■ I + l ~ l

-CC-N- (CH ₃ J ₂ NH ₂ Cl

Cl "" or

N (CH,) - NH,

J C-

Cl

where Z _? denotes a hydrogen atom, an optionally substituted amino group or an etherified oxy or mercapto group.

Preference is given to those free from water-solubilizing groups Compounds of the formula

V N = N

wherein c is a hydrogen or halogen atom, an alkyl, alkoxy, aryl, aryloxy, alkylmercapto, ary, lmercapto, benzyl, eenzyloxy or cyclohexyl group, D, Ac, R and R_ the same as above mean.

Particularly interesting are the compounds in which the acylamino group is in the ortho position to the azo group, and the amino radical therein is either methylated or

009825/1809

BATH

preferably contains a free hydrogen atom.

The new connections can be made by one diazonium compound of a diazo component with an amine of the formula

Ac

009825/1809

couples and optionally the fiber-reactive dye obtained then modified on the fiber-reactive group. The coupling components are obtained by one e.g. the amines of the formula

condensed with acylating agents containing primary amino groups react to form a fiber-reactive moiety.

Such compounds are e.g. the anhydrides or chlorides of acrylic acid, but especially the following heterocyclic ones Mention connections:

2-halopenzothiazole or oxazole carbon or sulfonic acid chloride, 4,5-dichloropyridazon (6) -yl propionic acid chloride, 4,5-dichloro-1-phenylpyridazone carbon or sulfonic acid chloride, 1,4-dichlorophthalazine carbon or sulfonic acid chloride, 2,3-dichloroquinoxaline carbonic or sulfonic acid chloride, 2,4-dichloroquinazoline carbonic or sulfonic acid chloride, tetrachloropyridazine,
Dichloropyridazine carboxylic acid chloride,
2,4,6-tri- or 2,4,5,6-tetrachloropyrimidine, 2,4,6-tri- or 2,4,5,6-tetrabromopyrimidine, 5-nitro- or 5-cyano-2,4 , 6-trichloropyrimidine, 5-nitro-6-methyl-2,4-dichloropyrimidine, 2,6-dichloropyrimidine-4-carboxylic acid chloride, 2,4-dichloropyrimidine-5-sulfonic acid chloride, but especially 2-methanesulfonyl-4,5- dichloro-6-methylpyrimidine, 2,4-dimethanesulfonyl-5-chloro-6-methylpyrimidine,

. 009825 / 18Ό9

2, h, 6-trichloro-1,3,5-triazine,
2,4,6-tribromo-1,3 * 5-triazine and

h, 6-dichloro-1,35-triazines which are substituted in the 2-position, for example by an aryl, aralkyl or alkyl radical, for example a phenyl, benzyl, methyl, ethyl or butyl radical, or by the remainder of an aliphatic, araliphatic or aromatic mercapto compound bonded via the sulfur atom or hydroxyl compound bonded via the oxygen atom, or in particular through an NH group or through the remainder of an aliphatic, heterocyclic or aromatic amino compound bonded via the nitrogen atom. Such compounds, the radicals of which can be bonded to the triazine nucleus in the 2-position by reaction with trihalotriazines, include, for example, the following: aliphatic or aromatic mercapto or hydroxy compounds such as thioalcohols, thiourea, thiophenols, methyl, ethyl, Isopropyl alcohol, phenol, chloro- or nitrophenols, naphthols, but in particular compounds containing ammonia and acylatable amino groups, such as hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulfonic acids, carbamic acid and its derivatives, semi- and thiosemicarbazides and -carbazones, methyl-, ethyl-, isopropyl- , Methoxyethyl, methoxypropylamine, dimethyl, diethyl, methylphenyl, ethylphenylamine, chloroethylamine, ethanolamine, propanolamine, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic acid ester, aminoacetic acid ethyl ester, but above all aromatic amines such as aniline , Xylidines, chloranilines, p- or m-Aminoaeetanilid, Nitrani-

009825/1809

line, aminophenols, nitrotoulidines, phenylenediamines, toluylenediamines, Anisidine, phenetidine, diphenylamine, naphthylamine, aminonaphthols, diaminonaphthalenes, and also colored compounds, or compounds with a dye character. e.g., 4-nitro-4'-aminostilbene and aminoazo dyes or aminoanthraquinones or phthalocyanines which still have at least one reactive amino group contain.

The introduction of the in 2 position by the rest of one Hydroxyl, mercapto or amino compound or ammonia-substituted triazine radicals can also conveniently be done in the manner that in an azo dye prepared by coupling which has a 4,6-dihalo-1,3,5-triazinyl group, replaced a halogen atom by reaction with one or different of the above-mentioned compounds.

The following are especially mentioned as halotriazines:

2,4,6-trichlorotriazine, 2-methyl-4,6-dichlorotriazine, 2-ethyl-4,6- ^M

2-butyl-4,6- ^N

2-phenyl-4,6- ⁿ , 2-methoxy-4,6- ⁿ , 2-ethoxy-i |, 6- "

2-phenoxy-4,6- "

2- Benzyl oxy -4,6- ", 2-Dimethylamino-", 2-9-Cyanäthylamino- ^w ,

009825/1

2-phenylamino-4,6-diehlortriazine,
2-di (ß-hydroxyethyl) amino-4,6-dichlorotriazine and 2-di (ß-hydroxyethyl) amino-4,6-dibromo-triazine.

The groups R ₁ and R _? are lower / ie 1 to 3 carbon atoms containing alkyl groups which have at least one negative substituent, ie substituted methyl, ethyl, n-propyl or isopropyl groups, such as benzyl or ß-phenylethyl groups, * halogenated alkyl groups such as ß-chloroethyl -, β, β, β-trifluoroethyl and ß, 7-diehlorpropyl groups and ß-cyanoethyl, ß-cyanoethoxyethyl, alkoxyalkyl, such as ß-ethoxyethyl, or ί -methoxybutyl, β- or 7-carbo- ( methoxy or ethoxy) propyl / acylaminoalkyl, such as ß- (acetyl or pormyl) -aminoethyl, fatty acid aoyl-oxyalkyl, such as ß-formyloxyethyl, ß-acetyloxyethyl, ß, * y-diacetoxypropyl, * y-butyryloxypropyl, ß-arylsulfonylalkyl, such as ß-phenylsulfonylethyl, ß- (p-toluenesulfonyl) ethyl or ß- (p-chlorobenzenesulfonyl) ethyl, ß- (p-toluenesulfonyl) ethyl, alkyl or Arylcarbamoyloxyalkyl, such as ß-Methylcarbamyloxyäthyl- and ß-Phenylcarbamyloxyäthyl-, Alkyloxycarbonylälkyl-, such as ß- (methoxy, ethoxy or isopropyloxy) -carbonyloxyäthyl-, 7-acetamidopropyl, ß- (p-N itrophenoxy) -ethyl-, ß- (p-hydroxyphenoxy) -ethyl-, ß- (ß'-AcetyläthoxyearbonylJ-ethyl-, ß - [(ß'-cyano, hydroxy, methoxy or acetoxy -) - ethoxycarbonyl] ethyl, ß-carboxyethyl, ß-acetylethyl, ß-diethyl-aminoethyl, ß-cyanoacetoxyethyl, ß-benzoyl and β- (ρ-alkoxy or phenoxybenzoyl) -oxyethyl groups. The groups R, and R ₃ generally contain '

no more than 18 carbon atoms, and preferably no amino or ammonium groups. < -. - "- · -., · ;; '.-.'

Of any diazotizable, of water- soluble- 009825/1809 '- .. -

making groups free amines, which can be used as the diazo component

into the-/
come, be / especially the amines which have a heterocyclic five-membered ring with 2 or J5 heteroatoms, especially one nitrogen atom and one or two sulfur, oxygen or nitrogen atoms as heteroatoms, and aminobenzenes, such as those of the formula

• b

called, wherein a is a hydrogen or halogen atom, an alkyl or alkoxy, nitro, cyano, carbalkoxy or alkylsulfone group, b is a hydrogen or halogen atom, an alkyl, cyano or trifluoromethyl group and c is a nitro, cyano -, carbalkoxy or alkylsulfonyl group. Examples include: 2-aminothiazole,
2-amino-5-nitrothiazole,

009825/1809

2-Amino-5-thy! Sulfonyl-thiazole

2-Amino-5-cyanthiazole _i 2-Air.ino-4-ir.ethyl-5-nitrothiazoI _A 2-Amino-4-methylthiazole, 2-amino-4-phenylthiazole, 2-amino-4- (4 ⁱ - chlorine) -phenylthiazole, 2-amino-4- (4'-nitro) -phenylthiazole, 3-aminopyridine, ^ -aminoquinoline, 3-aminopyrazole, 35-amino-1-phenylpyrazole, 3-aminoindazole, 3-amino-1, 2,4-triazole, 5- (methyl-, ethyl-, phenyl- or benzyl) -l, 2,4-triazole, 3-amino- ^{1- (4!} -Methoxyphenyl) pyrazole, 2-aminobenzthiazole, 2 -Amino-6-raethylbenzthiazole, 2-amino-6-raethoxybenzthiazole, 2-amino-6-chlorobenzothiazole,

2-Amino-6-eyanbenzthiazole, - ^ - '

2-amino-6-rhodanbenzthiazolj 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, 2-amino- (4- or 6) -methylsulfonylbenzthiazole, 2-amino-l, 3,4-thiadiazole, 2- Amino-l _i 3i5-thiadiazole,

009825/1809

2-Amino- ^ - phenyl- or ~ 4-methyl-1, jJ> 5-thiadiazole, 2-Amino-5-phenyl-1 _i 3 "j-thiadiazole, 2-Arr, ino-3-nitro -5-methyl sulfony 1-thiophene, 2-arr.ino-3 # 5-bis (methylsulfonyl) thiophene, 5-amino-2-rcethyl-isothiazole, 2-arr.ino-4-cyano-pyrazole , 2- (4 ^t -nitrophenyl) -3-amino-4-cyanopyrazole, 3- or 4-aminophthalimide, aminobenzenes

l-Araino-4-chlorobenzene, l-amino-4-brorabenzene, l-amino-4-methylbenzene, l-amino-4-nitrobenzene, l-amino-4-cyanobenzene, l-amino-2,5- dicyanobenzene, l-amino-4-raethylsulfonylbenzene, l-amino-4-carbalkoxybenzene, l-amino-2,4-dichlorobenzene, l-affiino-2,4-dibromobenzene, i-araiho-2-methyl-4-chlorobenzene, l-Amino - ^ - trifluoromethyl - ^ - chlorobenzene, l-Aπιino-2-cyano-4-chlorobenzene _J l-Aöιino-2-carbomethoxy-4-chlorobenzene, l-Alino-2-carbomethoxy-4-nitrobenzene _J l- Aa »ino-2-chloro-4-cyanobenzene, 1-alino-2-chloro-4-nitrobenzene _J

· - ■■■ ι ^ ΐ ' 009825/1809

l-Aπlino-2-bromo-4-nitrobenzene,

i *

l-amino - ^ - chlorine - ^ - carbethoxybenzene, l-amino-2-chloro-4-methylsulfonylbenzene, 1-Amino-2-methylsulfony1-4-chlorobenzene, l-amino-2,4-dinitro-6-methylsulfonylbenzene, l-amino-2,4-dinitro-6- (2'-hydroxyethylsulfonyl) benzene, l-amino-2,4-dinitro-6- (2'-chloroethylsulfonyl) benzene, l-Amino-2-methylsulfony1-4-nitrobenzene,

\ l-Amino ^ -methylsulfinyl - ^ - nitrobenzene, _% "

l-amino-2,4-dinitrobenzene, l-amino-2,4-dicyanobenzene, l-amino-2-cyano-4-methylsulfonylbenzene, l-amino-2,6-dichloro-4-cyanobenzene, l-amino 2,6-dichloro-4-nitrobenzene, l-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, l-amino-2,4-dinitro-6-chlorobenzene and in particular l-amino-2 -cyano-4-nitrobenzene, l-aminobenzene-2-, -J> - or -4-sulfonic acid amides, such as N-Kethyl- or Ν, Ν-dimethyl or -Diäthylamid, N, 7-amino-2-IsopropylQxypropyl -naphthalene-6-sulfonic acid amide, * N, ⁱ y-isopropyloxypropyl-1-aminobenzene-2-, -3- or -4-sulfonic acid amide, '

N-isopropyl-l-aminobenzene-2-, - ^ - or -4-sulfonic acid amide, N, 7-methoxypropyl-l-aminobenzene-2-, -J> - or -4-sulfonic acid amide, N, N-bis (ß -hydroxyethyl) -l-aminobenzene-2-, -3- or -4-sulfonic acid amide, 009825/1809

l-Amino ^ -ehlorbenzol ^ -sulfonsäureamid, and the N-substituted derivatives, 2-, 3- or 4-amihophenylsulfamate, 2-amino-4-, -5- or -6-methylphenylsulfamate,

2-amino-5-methoxy-phenylsulfamate, jS-amino-ö-chlorophenylsulfamate, 3-amino-2,6-dichlorophenylsulfamate, 4-amino-2- or -3-methoxyphenylsulfamate, N, N-dimethyl-2-aminophenylsulfamate, N, N-Di-n-butyl-2-aminophenylsulphamate, NjN-dimethyl ^ -amino ^ -chlorophenylsulphamate, N, n-Propy1-2-aminophenylsulphamate, N, N ~ di-n-butyl -; 5-aminophenylsulphamate , 0 (3-aminophenyl) -N-morpholine-N-sulfonate, 0 (5-aminophenyl) -N-piperidine-sulfonate, N-cyclohexy1-0- (3-aminophenyl) -sulfamate, N (N-methylaniline) - O- (3-aminophenyl) -sulfonate, N, N-diethyl-3-amino-6-methylphenyl-sulfamate, N-ethyleneimine-O- (4-aminophenyl) -sulfonate, '.. · N, N-dimethyl -4-aminophenyl sulfamate, 0 (n-propyl) -0 (3-aminophenyl) sulfonate, 0, ß-chloroethy1-0 (2-aminophenyl) ^! sulfonate, 0-3enzy 1-0 (3-aminophenyl) sulfonate and O-ethy1-0 (4-amino-2,6-dimethyl-phenyl) sulfonate.

4-Aminoazobenzenes, which can be used as diazo components are, for example, 4-aminoazobenzene, 4-amino-2-nitroazobenzene,

009 8 25/1809

3,2'-dimethyl-4-aminoazobenzene,,

2-Methyi-5-n ~ '3thoxy-' ^! T-aniinoazobenzene,

2,5-dimethoxy-4-aminoazobenzene,

4'-Xethoxy-4-aminoazobenzene,

2-Kethy1-4 '-niethoxy-4-aminoazobenzene, 3, o, 4'-trimethoxy-4-aminoazobenzene,

4'-chloro-4-aminoazobenzene,

2'- or 3'-chloro-4-aminoazobenzene,

3-nitro-4-amino-2 ', 4'-dlchlorazobenzene and 4-aminoazobenzene-4'-sulfonic acid amide.

Instead of the above-mentioned diazo components free of ionogenic, water-solubilizing groups, those which contain fiber-reactive groups can also be used, such as s-triazinyl radicals which have 1 or 2 chlorine or bromine atoms on the triazine ring, pyrimidyl radicals which have one or two chlorine atoms or one or carry two arylsulfonyl or alkanesulfonyl groups on the pyrimidine ring, mono- or bis (7-halo-ß-hydroxypropyl) -amino groups, ß-haloethylsulfamyl, ß-haloethoxy groups, β-haloethy! mercapto groups, 2-chloro-benzthiazolyl-6-azo groups , 2-chlorobenzothiazolyl-6-amino groups, 7-halo-ß-hydroxypropylsulfamyl radicals, ^f

Chloroacetylamino groups,
α, ß-dibromopropionyl groups,
Vinylsulfonyl groups or 2,3-epoxy propylene groups.

009825/1809

Suitable fiber-reactive diazo components are, for example, N, S-chloroethyl-3-chloro-4-aminobenzenesulfamide (hydrochloride), N, βM} chloroethyl * -4 ~ aminobenzene-sulfamide (hydrochloride), J-bromo ^ -amino-iw-chloroacetophenone ,
N, 7-chloro '* g-hydroxypropyl-4-aminobenzene-sulfamide, N / f ^ ChlöfUthyl-1-amino ^ -naphthylsulfonamid, N ^ -Chlorätihyi-l-amino-JiS-dichlorobenzene-sulfamide and ¹ 4- (γ-Ohlo ^ ß-hydroxy-propoxy) -aniline. "

Those made with such diazo components Compound »contain instead of just that present according to the invention fiber-reactive acylamino group Ac is another fiber-reactive group Group whose reactivity can be greater or lesser than that of group Ac.

The diazotization of the diazo components mentioned

can according to methods known per se, e.g. with the help of mineral acid and sodium nitrite or, for example, with a solution of nitrosylsulfuric acid in concentrated sulfuric acid.

The coupling can also in a known manner, for example in neutral to acidic medium, optionally in the presence of sodium acetate or the like, the clutch speed influencing buffer substances or catalysts such as _v dimethylformamide, pyridine, resp. its salts, are made.

The coupling is also advantageously carried out by combining the components in a mixing nozzle. Below is one To understand device in which the liquids to be mixed are combined with one another in a relatively small space

009825/1809

be, at least one liquid, preferably under increased pressure, is passed through a nozzle. The mixing nozzle can, for example, according to the principle of V / water. jet pump be designed and working, with the supply of one liquid in the mixing nozzle of the water supply in the water jet pump and the supply of the other liquid into the mixing nozzle of the connection in the vessel to be evacuated corresponds to the water jet pump, this latter liquid supply can also take place under increased pressure.

en /

The new water-insoluble compound // ~ their

Mixtures with each other and their mixtures with other azo dyes are excellent for dyeing and printing cotton and other cellulose-containing materials Leather, wool, silk and, above all, synthetic fibers, such as acrylic or acrylonitrile fibers, polyacrylonitrile fibers and copolymers of acrylonitrile and other vinyl compounds, such as acrylic esters, acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, copolymers of dicyanethylene and vinyl acetate, and of acrylonitrile block copolymers, Fibers made from polyurethanes, base-modified polyolefins, such as polypropylene, cellulose tri- and 2 l / 2-acetate and in particular Fibers made of polyamides, such as nylon-6, nylon-6,6 or nylon 12, and from aromatic polyesters such as those made from terephthalic acid and ethylene glycol or 1, ^ - dimethylcyclohexane, and mixed poly-

009825/1809

mers from terephthalic and isophthalic acid and ethylene glycol. For dyeing in aqueous liquors, the compounds are advantageously used in finely divided form and under-dyeing Addition of dispersants, such as sulphite cellulose waste liquor or synthetic detergents, or a combination of different Wetting and dispersing agents. As a rule, it is useful to put the dyes to be used in a dye preparation before dyeing transferred, which contains a dispersant and finely divided dye in such a form that when diluting the dye preparations a fine dispersion is formed with water. Such dye preparations can in a known manner, e.g. by grinding the dye in dry or wet form with or without the addition of dispersants during the grinding process.

The new compounds are also particularly suitable for dyeing fully synthetic fibers, such as polyester or nylon fibers, from organic solvents, for example from a mixture of perchlorethylene and 10 % dimethylformamide or acetamide.

The new compounds dye cellulose fibers and fibers containing amino and / or amide groups, in particular wool and nylon fibers from weakly alkaline neutral or especially weakly acidic baths, e.g. acetic acid baths.

To fix it after dyeing, you can treat with alkaline agents such as soda, sodium silicate or soap solutions.

The dyeings and prints obtained on polyamide fibers and wool with these compounds have excellent wet fastness properties, especially good light, washing, sweat, fulling and water

009825/1809

genuinely up.

To achieve strong dyeings on polyethylene terephthalate fibers it proves to be expedient to add a swelling agent to the dyebath, or the dyeing process under pressure to be carried out at temperatures above 100 C. Suitable swelling agents are aromatic carboxylic acids, phenols and aromatic halogen compounds or diphenyl.

For heat setting of the dye The padded polyester fabric, practical by prior drying, for example in a stream of warm air at temperatures of about 100 ⁰ C, for example between l80, heated to 210 ⁰ C.

The dyeings obtained according to the present process can be subjected to post-treatment, for example by heating with an aqueous solution of an ion-free detergent.

Instead of by impregnation, the specified compounds can also be applied by printing according to the present process will. For this purpose, e.g. a printing ink is used which, in addition to the aids customary in the printing shop, such as network and thickeners and optionally alkali containing the finely dispersed dye. >

The present process gives strong dyeings and prints with good fastness properties.

You can also use the new water-insoluble compounds use for spin dyeing of polyamides, polyesters and polyolefins. The polymer to be colored is conveniently in the form of

009825/1809

Powder, grains or chips, as a finished spinning solution or in the molten state mixed with the dye, which in the dry State or in the form of a dispersion or solution in an optionally volatile solvent. is introduced. After more homogeneous Distribution of the compound in the solution or melt of the polymer is the mixture in a known manner by glessening, pressing or Used to extrude into fibers, yarns, monofilaments, films etc.

In the following examples, unless otherwise stated, parts are parts by weight and percentages Percentages by weight and temperatures are given in degrees Celsius.

009825/1809

" Regulation I.

8.4 parts of N-bis-ß-acetoxy-ethyl-3-amino-aniline are dissolved in acetone and reacted with a small excess of dichloromethoxytriazine at a temperature of 0-10 and stirred for a while. After determining the coupling titer, the product of the formula

can be used without further purification.

The 3, N-acylaminoanilines using the following formulas:

G ₀ E. -CN / 24

NH - C%

N) CH,

C_H.-C-C H -CN

^{2 4 2} NJ _o H, -CC _o H. ~ Cli

NH- (T.

M- C-Cl N

N) CH

009825/1809

1/5 38600

VoO _n

C. H

HO-OO-O-HO _x

SL-

ς / HO-O _n HD / 0

/ D-HM

HD-OO-O- ¹ ^ H

/ O = M _n

το-HD—

ΉΟ-00-0- Η

TD _n

/ O = M _n

^ HD-OD-O-Vo _n

M-

HO-OD-O-H

LU8S61

Regulation II.

5.3 parts of N-bis-ß-eyanäthyl-3-amino-aniline are in Dissolved glacial acetic acid, with a small excess of diehloromethyltriazine implemented and stirred for some time. The product of the formula is obtained

Cl

NC // ^

NH-C N \ κ

N = C \ CH.

Regulation III.

14 parts of N-bis-acetoxyethyl-3-amino-aniline are in Dissolved glacial acetic acid. A small excess of dichloromethyl triazine is added and stir the solution for some time. After the determination

ψ of the coupling titer "can be the product of the formula

Cl

NH-C
\

N-C

N = C

CH.

009825/18

can be used without further purification.

The following coupling components are produced in a similar way:

O-*

Cl

NC // ^

NH-C N

N = C

V ₅

O-"

Cl

NH-C

N-C

N = C

009825/1809

Example 1.

1.4 parts of sodium nitrite are added to 30 parts by volume of sulfuric acid and the mixture is stirred for 30 minutes. At a At a temperature of 20-25 one carries 4.1 parts of 4-amino-3-chlorophenyl-methylsulfone and stir for a while. The excess nitrite is then destroyed with urea.

This solution is added dropwise at a temperature of a maximum of 10 ° to a solution of 8.5 parts of N-bis-β-acetoxyethyl-3-chloromethoxy-triazinylamino-aniline in 150 parts by volume of acetone, stir for some time and the dye is precipitated by adding water. After filtering, washing and drying a compound is obtained the formula

CH ₃ O ₂ S-

C ₀ H ₇₁ -O-CO-CH, / 24 3 f
Nj ₂ HO-CC-CH

Cl

N = C

NH-C

which nylon fibers in orange shades of excellent washfastness colors.

If the diazonium compounds of the diazo components given in column I of the table below are coupled with those in column II specified coupling components, compounds are obtained

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which dye the substrates indicated in column III in the shades indicated in column IV.

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I. II < 2-4 Xn TT r \ r% r \ ηττ I. III IV 1 2-chloro-4-methyl-
sulfonyl-ai'.ilin Wool ) range N .JN C - Cl
H-CT ^N N / NC ^ -Cl
IH- (/ ^ N \) CH_ 2 4-nitroaniline CH-O-CO-CH-
<> -N / ^{2 4 3} polyester Red N) ₂ HO-CO-CH 3 2-cyano-4-nitroani-
lin N C-Cl
NH - <y % nylon UV LT
\) CH nylon violet thiazole η blue 5 2-T'r i fluorine thy 1-
4-chloroaniline Il nylon Sharlacl

009825/1809

2-Amino-6-Äv.hoxy-benzothiazole

nyll.hiadiazole

2-Air.ino-6-nitro benzthiazole

2,5-dimethoxy- ² * cyananiline

NH

C ₂ HO-CC-CH

\ j _o H.-0-CC-CH_ 2 4, 3

, N C-Cl

2 ^H 5

/ 24 3

-N

N ^ H.-O-CO-CH, 2 4 3

NH

Ν C - Cl

ch

Ν? Η

-N

\; ₂ h ₄ -cn

NH - </

CH ₄ -O-CO-CH, / 24 3

-N

N] _n H _-1 -O-CO-CH, 2 4 5

.N Ch-Cl

NH-

N) CH_

COPY BADORiQINAL

nylon

nylon

nylon

nylon

00982

reddish purple '

Red

blaustichii "red

Red

5/1809

ιο ·

2-chloro - ^ - methylsulfonyl aniline

2-cyano-4-nitroaniline

2-amino- ■ cere ph tha acid-dime-hy1-ester

-'— meohylsulfony! Aniline

II

NH- </

C ₀ H ₁ -OC ₀ H ₁ -CN ^{2 4 2 4}

24

N C! - Cl

C_H.-O-CO-CH- / 24 5

-N

H -C-CO-CH

NH- (/ ^N N

N) C ₂ H ₄ OC ₂ H ₅

C ₂ HO-CO-CH ₃

Nl ₂ HO-CO-CH

_N c Cl

NH

N) CH

N) H

NJ ₂ H ₄ -O-CO-CH ₃

N Cr Cl

HH-

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III

IV

Orange-red nylon

polyester

nylon

nylon

violet

Orange red

orange

II

III

14th

2-chloro-4-methyl s-Ifony! Aniline

2-cyano-4-chloroaniline

-N

ν - σ - σι

Nt

N) -CH

-YY

Njbl

C _o H, -O-C0-CH_ ■ / 2 4 3

C _o H, -0 _{-CO-CH "2} H -C-CO-CH

NH-C

= σ - σι Νϊ

-N

_O H -OC-CH., 2 4 " y

Cl O

NH-C ^

N = C '

Nji

009825/1809

nylon

orange

nylon

orange

nylon

orange

nylon

yellowish red

18th

! 19 IO ₂ N-

20 ι

21 CH-N

O ₀ NC C-NH ₀ 2 V _n / 2

II

C ₀ H.-CN / 24

-N

-CN

NH-C

₀ H, 2 4

Cl

CA
Nile

C ₀ H ₇₁ -O-CO-CE ₂ / 24h 3

-N

NH-C

Nj ₂ HO-CC-CH Cl N

C ₂ H ₄ -CN Cl

'NH-C N

^{Ν =} Νϊΐ

-N

-0-CO-CH

Cl

NH-C

N-C

J /
N / A

III

IV

polyester

nylon

^; orange

Red

Red

blue

009825/1809

I. ... N
jfY \ -NH_ II < NC ₂ H ₄ -C CC-CH ₃ N-C •
C ₀ H. -CN
> -N III IV ! _22nd Cl SS "" «V
NH-C N Cl nylon rotst.
violet 1 NC
// ^
iH-C N N) CH NC
ϊΗ-σ ν C ₂ H ₄ -O-CO-CH ₃
<% -N 2-cyano-4-nitro-
aniline < polyester violet __ ^ / ^C 2 ^H 5
₂ H ₄ -OC-OH3 ₂ H ₅ Nj ₂ H ₄ -O-CH ₃ • Cl 0 Cl 4-nitroaniline NC
sy w 24 NH-C N polyester Red I-
< 1 2-cyano-4-chlorane
lin 25th Wool orange

009825/1809

I. ■ Il II i < • / ^C 2V ^C1 I. ff TT Γ \ ΤΤ
^ Xl ν / ΧΙ I. Cl III IV 26th
- j 2-trifluoromethyl
4-chloroaniline i Cl Cl IH-C N nylon yellowish
Red i j CiH-C N NC
Λ 'W N) CH N) CH NH-C N
^^^^ f \ TT
^ w \ j .. Xi . <- C ₀ H -C-CO-CH,
/ 24 5 ft TT / ^ Λ1 / "" \ / * tT_T
\ y Xi ^^ '^ \ J \ j Xi, 27 2-chloro-4-methyl-
sulfonylaniline nylon Orange red Ν - (/ NH-C N 2-cyano-4-chloro
aniline polyamide yellowish
Red 29 η • ι

009825/1809

II

III

IV

2-cyano-4-chloroaniline

C ₀ H ₇₁ -C-CO-CH- / 24

Cl

NH-C

N-C

-N

N) «Η- -CN
2 4 Cl
/ > N-C NH-C N

-N

N) ₂ H ₅

Cl

NC
NH-C N

/ V C.
μ / ₂ Η -0-CO-CH Sj Λ Νϊ H-O-CO-CH Cl
S. N-C NH-C N

NC / 3

Nh-CH

N) H

009825/1809 polyamide

Wool

yellowish! red I.

orange

yellowish red

I. II ' < III IV 34 2-cyano-4-chloro
aniline polyamide orange -> N ^{/ 2 4}
NJ ₂ H ₄ -CN Cl
κ
NC NH-C N _r "
NmK / ^υη 3
Nd-ch NjH ₃

009825/1809

Example 2.

3.1 parts of 2-cyano-4-chloroaniline are used in 20 parts by volume of 2N hydrochloric acid registered. At a temperature of 0 to 5 C, diazotization is carried out with 6 ml of 4N sodium nitrite solution and some are stirred Time. In addition, the excess nitrite is destroyed with urea. '

This solution is added dropwise at a temperature of a maximum of 10 ° to a solution of 8.75 parts of N-bis-ß-aeetoxyethyl-3- (chloromethyl-triazinyl) -amino-aniline in 125 parts of 80% acetic acid, stirred overnight at 0 ° to 10 ° and the dye is precipitated by addition from ice water. After filtering, the dye is washed neutral and dried in vacuo. You get a connection the formula

PW

cJH

\ i_H.-0-CO-CH_

2 4 3

NH- €

it — cK

Cl

Ν} Η

which dyes nylon fibers in scarlet shades of excellent washfastness.

If the diazo compounds of the amines mentioned in column I are coupled with the coupling component indicated in column II the conditions given in Example 1 are obtained in water

00S825 / 1809

insoluble, fiber-reactive compounds, the Uylcmfibers in.der color indicated in column III 'nuance, if no other fiber type is indicated.

009825/1809

Mr.

II

III

! 1 i 2-amino-6-ethoxy: ι benzthiazole

lH.-C-C-CH, 4 ι, Cl

2 2-amino-5-nitrothiazole

4-nitroaniline

4 j 2-cyano-4-nitroaniline

i methyl /

- 5 2-Trifluo2 / -4-chloroaniline

6 3-Amino-5-phenyli thiadiazole

NH-C

N-C

Njh

Cl N-C

NH-C N

3

Cl O

NH-C

N
NlH

reddish purple

blue

red purple

yellowish red

Red

009825 / 18Q9

I.
' No
j !
I. 10 I. II 0 i
>
! < / C ₂ H ₄ -OC-CH ₃
Nj ^ h.-oc-ch, Il . ·
III 'f I. yellow-orange ; j 11th t
!
i
^: 1 2 4 "3
Cl 0
NC
mc ν Il blue red
(on polyester) j 7
I. -6-nitro /
2-Asiinclbenzthia-
zol \ NJB ₃ violet yellowish
Red I j
j \
• ; i2
ί ⁿ 1 j j
I.
! < a
i 2,5-dimetftoxy-4-
cyananiline Red 9 2-chloro-4-methyl-
sulfonyl aniline I> N
N3H, orange Cl
NC
// ^
ΓΗ-CN "> -N (C ₂ H ₄ CN) ₂ \ JH Cl
/
N = C
// \
IH-C N 2-cyano-4-nitro * ~
aniline. ^ N = Cr
N) H ₃ 4-nitranoaniline 2-cyan-4-ehloranili

009825/1809

f

1158711

No I. II 1 1
ι J IBH? ' ^ III ■ "" " ο Ü t
* 13th 2 ^ yhl03? '5s4 ~ P ^ ®thyl ~
eiiii ¹ FfInWi -ani Tin Red

IiIi

4-methylsulfonylaniline

Ql

H-O

NH-C

ΝϊΗ,

CJT.-CN

/ 2 4

Cl

N-C

NH-C N

NH-C

C.H.-to-CO-CH,

N; _H.-o-co-CH,

CH, \

N γ

Nji 0.09825 / 1809

; ' Red

reddish purple

orange yellow

orange

No.

18 '2-trifluoromethyl-4-chloroaniline

II

On

N = C

NH-C

N-C

19 '2-trifluoromethyl-4-chloroaniline

Njl

C ₀ H.-CN / 24

NH-C

Cl N

20 2-aminoterephthalic acid dimethyl ester

N-C

Cl

· - NH-C

I. ^ c ₂ H.-CN
4th j Cl j / / N-C ! // '. NH-C
Ni = C N
/
Nj ₂ H,

III

red orange orange

Orange red

golden yellow

0 0 9 8 2 5/1809

No,

II

III

2,5-dimethoxy-4-cyananiline

C ₀ H.-CN / 24

Nj ₂ H-CN

Cl

N = C

NH-C

N-C

2-o ^r -Chlorphenoxy-ι 4-nitroaniline

24 2-Amino-6-acetylamino-benzothiazole

p-aminobenzenesulfonamide

C ₂ HO-CC-CH ₂ H -O-CC-CH

N = C

NH-C

C ₂ HO-CO-CH

N = C / / \

NH-C N

N = C

NH-C N

N-C

Scarlet fever

bluish ι red i

(on polyester)

violet

yellow-orange

009825/1809

No.

II

III

26 j p-aminobenzenesulfonamide

27 - 2-cyano-4-chloroaniline

28 [ 2-cyano-4-chloro- • aniline

C ₀ H ^ -O-CO-CE ₂ / 24h 3

C ₂ HO-CO-CH

Cl

NH-C

N-C

C ^ H.-O-CO-CH-

^{2 4 3}

Cl
/

N-C

NH-C N

N) -C ₆ H ₅

^ C ₂ H ₄ -O-CO-CH ₃ ϊ
Nj ₂ HC-CO-CH

Cl

N-C

NH-C

Ni

Njh,

yellow-orange

yellowish red

009825/1809

No, I. * _N II . < I. 2 4 3 N-C N-C III It !
I. 30th 2-cyano-4-chloro
aniline Cl
NC
iH-C N NH-C ^N c H -OH NH-C N
"N-Ü / ^ 4
Ni yellowish!
Red I.
t C ^ HO-CO-CH
ν / ¹ ^ 4 j
~> -N
V / -Π. j ^ TJ V ^ V / viii » Nj ₂ H ₄ -OH I.
I.
t I. 31 • Cl
NC
ΪΗ-CN <; C _o H.-0-CC-CH_
/ —S_w / 2 4 5 ^ o ^H 4-CN H
( ^ C ₂ H ₄ -O-CO-CH ₃ i ^ yY ^{2 4 3} 1 32 Cl NJ ₂ H ₄ -O-CO-CH )
Il Cl i I.
I. i 33

2-chloro-4-methylsulfonylaniline

35!

Nj ₂ HO-CO-CH Cl

NC // ^

NH-C N

- / ^CH 3

C ^ H.-O-CO-CH

Cl

NH-C N

N-C H ₄ -O-CC-CH ₃ Cl NH-C N

00 9 825/1809 _/ C ₂ H ₄ -O-CO-CH ₃ j

II III

2-chloro-4-methyl- '■.
sulfonylaniline

4-nitroaniline

On -0-CO-CH

NH-C

N-C

C.H.-OH

Nj η-oh

N) ₂ HO-CO-CH

Cl

NC // ^

NH-C / π Η -CN

■ NH-C

N-C

Cl

Ni ₂ HO-CO-CH

N-C /

Cl

j NH-C

Oh

009825/1809 Ni ₂ H ₄ -CN I

C _o H, ~ 0-C0-CH_ κ 2 4 3

Nlh.-o-co-ch_

2 4 orange

Red

(on polyester)

! 42! 4-nitroaniline

"

II

Nlh.-o-co-cr,

2 4

N
NH-C

N-C

C ₂ H ₄ -O-CO-CH ₃

"H.-O-CO-CH, έ 4 y

N-C

/ if N>,

NH-C N

NJ ₂ H ₄ -O-CO-CH

NC
NH-C N ,

-OH

NH-C

N-C

C ₀ H ₁ Cl

Y ²⁴
Nj ₂ H ₄ -CN

III

red (on polyester)

009825/1809

No.

• 46 2-cyano-4-chloroaniline

47 I "

II

C ₉ H-CN

Ο »

Cl

NH-C

N-C

C.
N) -C ₆ H ₅

CLH.-OT

₂ H ₄ -CN

Cl NC
NH-C N,

Njh

C _O H.-CN

₂ H ₄ -CN

Cl NC
NH- ^ CN

C _O H.-CN

NH-C

N-C

C /

N ₃ -C

₆ H ₅

009825/1809

III

orange

No.

50 2-cyano-4-chloroaniline

51: "

II

O*

Cl

N-C

NH-C N

Ni = C / C _D H.-0H

Nj ₂ H ₄ -OH

C ₀ H.-CN ^{2 4} Cl

Ni

Nj ₂ H ₄ -CN

Il

Cl N-C NH-C N

N) -C ₆ H ₅

009825/1809

III

orange

Red

(on wool)

No. ¹ 53

= 54

: 55

2-cyano-4-chloroaniline

56 "

II

C ₀ H-O-CO-CH ^{2 4}

Cl

N-C NH-C N,

Cl /

N-C / ^ ^

NH-C N

N) ₂ H ₅

Cl

^ N-C NH-C N

Cl

NC
NH-C N

2

III

ι red

(on wool)

^ C ₂ HO-GO-GH j

009825/1809

II III

57 j 2-cyano-4-chloro-1 aniline

59 ■ 2-chloro-4-methyl-isulfonylaniline

60 -4-nitroaniline

61 '2-chloro-4-nitro-

aniline

62 2-cyano-4-chlorianiline

C ₂ HO-CO-CH,

Cl

N-C

NH-C N

Nl = CJ / C

2 ⁿ 4

Nj ₂ H ₄ -CN

^ C ₂ H ₄ -O-CO-CH ₃

Nj ₀ H ^ -O-CO-CH, 2 4

Cl \

NH-C

C-C

Cl

2-chloro-4-yne thylsulfonylaniline

c _o Cl // H, -CN \ NH-C 4th C-C H ₄ -CN Cl N \ N

009825/1809 red (on wool)

yellowish red

orange

j red

(on polyester)

bluish red (on wool)

orange

yellow-orange

ι
No, I. II < QE -CN It C _o H.-C-C0-CH_
- w / 2 4 3
^C < Cl H III Red
(on wool)
Red 64 4-nitroaniline 1 Cl Cl
\ /
CC
ra-c ν ] IH-C N M. yellowish red
(on polyester) N / A Nji • yellowish red
(on polyester) 65
66
1 2-chloro-4-nitro-
aniline
2-cyano-4-chloro
aniline Red
(on polyester) blue red
(on wool) • 67 2-chloro-4-methyl-
su3fi> nyl-aniline 68 4-nitro-aniline 69 2-chloro-4-nitro-
aniline

009825/1809

ill * *

, 5i - 1 9 S β 711

BeisfrieX! »

10 parts of Nyloh-6,6-Trlcot fabric ("Helanea ¹ '") are placed in a dyebath at 30 which, in 400 parts by volume of water, 8 parts of sodium lumbica carbonate and 2 parts of a 5% aqueous dispersion of the according to Example 2 contains and has a P.sub.1 value of 7.9. It is heated to boiling temperature in the course of 45 minutes and then dyed at the boil for 75 minutes. The textile material is then rinsed well with water and dried receives a brilliant scarlet color with a high proportion of non-extractable dye.

Example #*

Proceed as in example _3, but use instead of sodium bicarbonate 0.8 part of an adduct of 9 mol of ethyl oxide and 1 mole of nonylphenol, the p ^ value of the dyebath being 7 * 0 amounts to. A similarly brilliant coloration as in the example is obtained

W 3. The dye can then be soaped with an alkaline soap in order to achieve better fixation of the dye on the fiber.

Example 5 «

The procedure is as in Example J>, but 0.4 part of ammonium acetate is used instead of the sodium bicarbonate and, after 75 minutes, 0.1 part of 80% acetic acid is added. The p n value of the dyebath after the addition of acetic acid is 5.6. The textile material used is 10 parts of nylon 6 tricot fabric ("Perlon"). A similarly brilliant coloration as in Example J> is obtained.

0098 2 5/1809

Example 6.

The procedure is as in example k ₃ , but 10 parts of bleached wool tricot fabric are used as the textile material. A similarly brilliant coloration as in Example 13 is obtained.

Example 7

The procedure is as in Example 5 * but used as a textile material 10 parts of bleached wool tricot fabric. A similarly brilliant dyeing as in Example 5 is obtained.

Example 8.

The procedure is as in Example 3 * but instead of sodium bicarbonate, 0.8 part of an adduct of 9 mol of ethylene oxide and 1 mol of nonylphenol and 1.2 parts of a mixture of 75 $ o-dichlorobenzene, 23 $ of a cationic alkylarylsulfonate and 2% are used conc. Ammonia solution, and as textile material 10 parts of polyester tricot fabric (textured polyester fabric "Crimplene"). The result is a brilliant, washable, scarlet color. The dye can be removed from the fiber by extracting it with hot monochlorobenzene.

Example 9-

In a dyebath which, in 400 parts of water, contains 0.8 parts of an adduct of 9 moles of ethylene oxide and 1 mole of nonylphenol and - _: · - 2 parts of a 5% dispersion of the one described in Example 1 ^. ■;, compound contains, one starts at 30 in a high temperature

009825/1809

dyeing machine a. dyeing on 10 parts of polyester tricot Gfwebe (textured polyester fabric "Crimplene"). The p "value of the fleet is 7.0. The temperature is increased to 120 ° in 15 minutes, a pressure of about 2 atmospheres being created. It is dyed at 120 for 45 minutes and then cooled to 65 within 10 minutes. The textile material is then rinsed with cold water and dried. A brilliant, boil-fast and washable, but extractable, scarlet coloration is obtained.

Example 10.

The dyeing is carried out as in Example 9 * but a polyacrylonitrile high-loft tricot fabric is used (high bulk "Orlon" tricot). A brilliant, boil-proof and washable, but extractable product is obtained scarlet color.

Example 11.

You go with 10 parts nylon 6,6 tricot fabric ("Helanca") at 30 ° in a dyebath in 400 parts by volume of water 0.2 Parts of 80 # strength acetic acid and 2 parts of a 5 # strength aqueous dispersion contains the compound obtained according to Example 1 and has a p n value of 4-5. Over the course of 45 minutes heated to boiling temperature and then simmered for 30 minutes colors. Subsequently, by adding soda to a p "value Asked by 12 and cooked for another 30 minutes. Then that will Textile material rinsed well with water and dried. A brilliant scarlet color with a high proportion of is obtained non-extractable dye.

009825/1809

• *

¹ * fr tkf f

The dispersions used above are obtained * to foil dye with IkO parts of Wus ^ tr and 40 layers of sodium methandisulfonate are ground *

009825/1809

Claims (1)

Claims. 1. New azo compounds of the formula which are free from water-solubilizing groups DN = NA -NR ₁ - Rp i » Ac wherein D is a residue of a diazo component, A is a phenylene residue,
R and R _{2 are} alkylene radicals having 1 to 3 carbon atoms, which
^. each have at least one negative substituent, and Ac is a residue of a fiber-reactive compound bonded via an amino group Heterocycleist. 2. Azo compounds according to claim 1, characterized in that the radicals R and / or R _{2 have} substituents with more than one atom. 3. Azo compounds according to claim 2, characterized in that the radicals R and / or R _{2 have} substituents with either at least one heteroatom or with an aromatic h ring. 4. Azo compounds according to claim J5, characterized in that the radicals R and / or Rp cyangruppen- or
Have carbonyl-containing radicals. 5 · Azo compounds according to claim 1, characterized in that the radical Ac is bound via an amino group Is the residue of a fiber-reactive nitrogen-containing heterocycle. 6. Azo compounds according to claim 5, characterized in that that the Ac radical is a triazine radical bonded via an amino group. 009825/1809 7. Azo compounds according to claim 6, characterized in that the Ac radical is a triazine radical bonded via an amino group which has halogen atoms bonded to the ring. 8. Azo compounds according to claim 7, characterized in that that the fiber-reactive triazine radical of the formula -G C-X. I «ι ^λ N N corresponds to, wherein X, a halogen atom and X an amino group or is an organic residue. 9. Azo compounds according to claim 8, characterized in that the radical X is a radical of a via an ether oxygen atom "
Bound hydrocarbon, which is optionally through
further oxygen atoms is interrupted. 10. Azo compounds according to claim 8, characterized in that the radical X _{p is} a radical of a hydrocarbon. 11. Azo compounds according to claim 8, characterized in that the radical X is an optionally substituted NH group. 12. Azo compounds according to Claims 1 to 11, characterized in that that they are of the formula correspond, wherein c is a hydrogen or halogen atom or a
Alkyl, aryl, alkoxy, aryl, aryloxy, alkyl mercapto, aryl is mercapto, benzyl, benzyloxy or cyclohexyl group, and 009825/1809 - 5ο - D, Ac, R, and R mean the same as above. Ij5 ·. Azo compounds according to claim 12, characterized in that that in them the radical c in the ortho position to the amino group and the acylamino radical Ac is ortho to the azo group. 009825/1809 14. Process for the preparation of new azo compounds free of water-solubilizing acidic groups, thereby characterized in that a diazonium compound of a diazo component D-NHp with a coupling component of formula HA-NR ₁ R ₂ Ac wherein A is a phenylene radical, R. and R ^ alkylene radicals with 1 to Carbon atoms each having at least one negative substituent, and Ac one via an amino group bonded residue of a fiber-reactive heterocycle • is, couples and, if necessary, modified on the fiber-reactive radical. 15. The method according to claim 14, characterized in that one starts from coupling components in which the radicals R, and / or R "substituents with more than one Have atom. 16. The method according to claim 15> characterized in that that -man starts from coupling components in which the radicals R. and / or R_ substituents with either at least have a hetero atom or with an aromatic ring. 17. The method according to claim l6, characterized in that one starts from coupling components in which the radicals R and / or B. cyano- or carbonyl-containing • radicals. eat. Method according to claim 14, characterized in that that the remainder Ac is bound via an amino group 009825/1809 Is the residue of a fiber-reactive nitrogen-containing heterocycle. 19. The method according to claim 18, characterized in that that the Ac radical is a triazine radical bonded via an amino group. 20. The method according to claim 19 *, characterized in that that the radical Ac is a triazine radical bonded via an amino group which has halogen atoms bonded to the ring. 21. The method according to claim 20, characterized in that coupling components are used in which the fiber-based: active triazine residue of the formula -C C-X., I Ii ^X N N corresponds to wherein X _{1 is} a halogen atom and X ^ is an amino group or an organic radical. ^ 22. The method according to claim 21, characterized in that that one starts from coupling components in which the rest X_ a Is the remainder of a hydrocarbon bonded via an ether oxygen atom, which is optionally interrupted by further oxygen atoms is. 23 · The method according to claim 18, characterized in that one starts from coupling components in which the radical X _{p is} a radical of a hydrocarbon. 24. The method according to claim 23, characterized in that that one starts from coupling components in which the remainder X 009825/1809 ² is an optionally substituted NH ₂ group. 25. The method according to claims 14 to 24, characterized characterized in that one of coupling components of the formula starts out, wherein c is a hydrogen or halogen atom or a Alkyl, aryl, alkoxy, aryl, aryloxy, alkyl mercapto, aryl mercapto, Benzyl, benzyloxy, or cyclohexyl group, and I D, Ac, R ₁ and R _D mean the same as above » 26. The method according to claim 25, characterized in that that in the coupling components the radical c in the ortho position to the amino group and the acylamino radical Ac in the ortho position to the azo group stands ^ 27. A method for dyeing textile material, thereby characterized in that the compounds according to claims i-13 used. 28. A method for dyeing textile material, which consists at least partially of natural or synthetic polyamides or cellulose, characterized in that the Veri., Bonds according to claims 1 to 1J> in the presence of alkali ^ ä 009825/1809