DE1292272B - Process for the production of water-soluble fiber-reactive dyes - Google Patents

Description

The invention relates to a process for the production of dichloromethyl, trichloromethyl and / 2-dichloropropyl, of new water-soluble fiber-reactive dyes, acyl-substituted lower alkyl radicals, such as acetylmethyl, dye the textile materials which contain active water and residues of the benzene series, such as methoxyphenyl, Contain material atoms, such as natural and regenerated nitrophenyl and chlorophenyl. Cellulose, wool, silk and synthetic polyamide 5 The group of formula (1) is an in the dye fibers. present carbon atom bound. This atom

The dyes which can be prepared according to the invention can be e.g. B. an aromatic, carbocyclic or hold at least one sulfonic acid or carbon heterocyclic nucleus or belong to one acid group and at least one to a carbon aromatic nucleus of the dye either directly atom of the dye bonded group of the formula io or via an atomic chain that is not exclusive

must consist of carbon atoms and the one

HR ₂ cannot belong to an aromatic ring, bound

j [be. This carbon atom preferably forms

, gQ QQ o COY (D a part of a benzene nucleus, which if necessary

² Ii 15 may belong to a polycyclic system. So

'' can be in the anthraquinone or phthalocyanine series

^{1 3} this carbon atom is one of the a-carbon atoms

of the anthraquinone nucleus or one of the 3- or 4-carbon

where R ₁ , R ₂ and R _{3 are} independently of one another for lenstoffatome of a phthalocyanine nucleus or in the hydrogen or lower alkyl groups and 20 equal two rows of one of the carbon atoms of a - COY be the remainder of a monobasic carboxylic acid benzene ring, which means with one of these nuclei in. According to the invention, this dye compound is, as it is produced in the case of a tetraphenyl substance, by using a dye, phthalocyanine, a phenylsulfamylphthalocyanine or at least one sulfonic acid or carboxylic acid or an anilinoanthraquinone. group and at least one group of the formula which is bonded to a carbon atom according to the invention and which can be prepared according to the invention include dyes of any of the known water

soluble species. This includes in addition to the just

HR ₂ called members of the anthraquinone and phthalo

cyanine series also those of the nitro and triphene / • 2) 30 dioxazine series and preferably members of the azo series

including the mono- and polyazo dyes.

ρ _p The dyes can be metal-free or metal

^{1 3} included; so can z. B. copper, nickel, cobalt

or chromium in a complex bond in links of the

contains, wherein R ₁ , R ₂ and R _{3 have} the meaning given 35 azo or phthalocyanine series, with a monobasic carboxylic acid of the examples of monobasic organic carboxylic acids

Formula Y - COOH or the anhydride or acid of the formula Y - CO ₂ H are acetic acid, propionic acid, halide of such an acid, where COY butyric acid, acrylic acid, methacrylic acid, crotonic acid has the meaning given above. Benzoic acid, chloroacetic acid, methoxybenzoic acid,

In a modification of the procedure described, 4 ° nitrobenzoic acid, chlorobenzoic acid, phenylacetic acid, the new water-soluble dyes also thereby produced toluic acid, cyclohexanecarboxylic acid, dichloroacetic acid be that one dye products, of acid, trichloroacetic acid, /? ~ chloropropionic acid and at least one of at least one group of acetoacetic acid.

Formula The dyes which contain group (2)

45 can be obtained by various methods.

H R2 Suitable dyes can be obtained, for example,

i i by making a dye that is one or more

- SO ₂ - C - C - O - COY contains sulfochloride groups, in the corresponding

j I sulfinic acid or the alkali metal salt of such

R ₁ R ₃ 50 transferred acid and then this product with

jÖ-chloroethyl alcohol or ethylene oxide. In

wherein R ₁ , R ₂ , R ₃ and —COY the above-mentioned way, compounds are obtained which have meaning and at least one carboxylic acid group

or sulfonic acid group, with each other to the c ₍

Converts final dyes. 55

Examples of lower alkyl radicals which contain _{R 1} , R _2. If you can stand in place of / J-chloroethyl and R ₃ in the formula given, alcohol or ethylene oxide compounds are used, are methyl and ethyl. which have the appropriate lower alkyl substituents, for examples of monobasic carboxylic acid residues, e.g. B. / J-chloropropanol, propylene oxide, 1,2-Budie in the above formula by CO - Y 60 tylene oxide, or their lower alkyl derivatives, are those radicals in which Y is given for products which include the group hydrocarbon radicals, z. B. alkyl radicals, such as methyl, tj τ,

Ethyl, n-propyl and isopropyl, alkenyl radicals, such as. , ²

Vinyl and α- and / 3-methylvinyl, cycloalkyl radicals, such as cn η η r »w

Cyclohexyl, aralkyl radicals such as benzyl and naphthyl- 65 ^so a ~~ ^c γ ~~ ^oti

methyl, aryl radicals such as phenyl and tolyl, and substi- '

tuierte hydrocarbon residues is, z. B. halogen Ri R3

substituted lower alkyl radicals such as chloromethyl contain.

3 4

Starting materials of this type can also be 5,8-dichloro-l-naphthol, 5-chloro-l-naphthol, 1,5-di-

by using a dye that belongs to the group hydroxynaphthalene, l-acetylamino-4-, -5- or -6-na-

phthol and 2-acetylamino-7-naphthol, l-naphthol-4-

TT η HR ^unc * -5-sulfonic acid, 2-naphthol-6-, -7- and -8-sulfone- ² ι ² 5 acid, l-naphthol-3,6- and -3,8-disulfonic acid, 2- N / A-

c η η r \ u phthol-3,6- and -6,8-disulfonic acid, 1-naphthol-

~, ι 3,6,8-trisulfonic acid,!, S-dihydroxynaphthalene- ^ o-di-

^! sulfonic acid, 2-acetylamino-5-naphthol-7-sulfonic acid,

Ri R-3 O Ri Rs 2-acetylamino-8-naphthol-6-sulfonic acid and 1-acetyl

lo amino-S-naphthol-3,6- and -4,6-disulfonic acid, amino

contains, oxidized. naphthols and aminonaphthol sulfonic acids, such as

Dyes that are used in the process according to the invention!, S-aminonaphthol-δ-sulfonic acid, 1,8-aminona-

can be used as starting materials, phthol-3,6-and-4,6-disulfonic acid, 2,5-aminonaphthol-

are also obtained by converting them from intermediate 7-sulfonic acid, 2,8-aminonaphthol-6-sulfonic acid,

compounds that may be colored 15 2,5-aminonaphthol-l, 7-disulfonic acid, 2,8-aminona-

and which already contain the group of formula (2), phthol-3,6-disulfonic acid, l-amino-6-naphthol-3-, -4-

generated. In the case of azo dyes, this and -8-sulfonic acid and its lower N-alkyl

Group single or multiple derivatives in the diazo component, such as l-butylamino-8-naphthol-3,6-disulf one-

or in the coupling component or in acid and 2-methylamino-5-naphthol-7-sulfonic acid

both are present, and the product obtained can be 20 and their N-aryl derivatives, such as l-phenyl-amino-8-na-

optionally with a metal-donating agent phthol-3,6-disulfonic acid, ketomethylene compounds,

treated to obtain an azo dye such as l- (2'-methoxyphenyl) -3-methyl-5-pyrazolone, 1-Ph

contains complex bound metal. As examples such as l- (2'-methoxyphenyl) -3-methyl-5-pyrazolone,

for such agents are mentioned: copper, manganese, l-phenyl-3-methyl-5-pyrazolone, l- (2'-, 3'- or

Nickel, zinc and vanadyl sulfate, chromium, cobalt- 25 4'-methylphenyl) -3-methyl-5-pyrazolone, 1- (2'-, 3'- or

and iron chloride, copper ammonium sulfate, chromium-4'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2-, 3'- or

acetate, cobalt tartrate and chromium salicylate. 4'-nitrophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'- or

Examples of diazo components that form a group 3 ', 4'-dichlorophenyl) -3-methyl-5-pyrazolone, l- (2'-, 3'-

of formula (2) contain p - /? - hydroxyethyl or 4'-sulfamylphenyl) -3-methyl-5-pyrazolone, 3-Me-

sulfonylaniline, 2-amino-4 - ^ - hydroxyäthylsulfonylphe- 30 thyl-5-pyrazolone, 1- (2'-, 3'- or 4'-methylsulfonyl-

nol, 5 - /? - hydroxyethylsulfonylaniline-2-sulfonic acid, phenyl) -3-methyl-5-pyrazolone, l-phenyl-5-pyrazolone-

2- Amino -5-ß- hydroxyethylsulfonylphenol, 4 - (/? - Hy- 3 - carboxycresidid, 1 - phenyl - 5 - pyrazolone - 3 - carboxy-

hydroxyethylsulfonyl) anthranilic acid, 2-chloro-5 - (/ 3-hy- 2 '- toludid, 1 - phenyl - 5 - pyrazolone - 3 - carboxyanilide,

droxyäthylsulfonyl) aniline, 4-amino-3-chlorophenyl- l, 3-diphenyl-5-pyrazolone, l- (2'-, 3'- or 4'-N-methyl-

/? - hydroxyethyl sulfone, 4-amino-l-naphthyl-ß-hydroxy-35 sulfamylphenyl) 3-methyl-5-pyrazolone, l- (2'-, 3'- or

ethyl sulfone and 3- β- hydroxyethyl sulfonylmethyl 4'-N, N-diethyl sulfamylphenyl) -3-methyl-5-pyrazolone,

4-methylaniline. Acetoacetanilid, Acetoacet-o-anisidid and Acetoacet-

These diazo components can be used with coupling anilide-4-sulfonamide, l- (4'-sulfophenyl) -3-methyl-

components are coupled which do not have a group 5-pyrazolone, l- (6'-chloro-3'-methyl-4'-sulfophenyl) -

of formula (2), e.g. B. with in p-position 40 S-methyl-S-pyrazolone, l- (2 ', 5'-dichloro-4'-sulfophenyl) -

coupling amines of benzene or naphthalene 3-methyl-5-pyrazolone, l- (2'-methyl-5'-sulfophenyl) -

series, such as 4-sulfo-l, 3-phenylenediamine, Ν, Ν-dimethyl-3-methyl-5-pyrazolone, l- (2'-chloro-5'-sulfophenyl>

aniline, Ν, Ν-diethylaniline, N, N-diethyl-m-tolu-3-methyI-5-pyrazolone, l- (4'-chloro-2'-sulfophenyl) -

idin, N-ethyl-N-jS-hydroxyethylaniline, N ₉ N- S-methyl-S-pyrazolone, l- (2'-chloro-4'-methyl-5'-sulfo-

Di - (/? - hydroxyethyl) -m-toluidine, N-ethyl-N - ^ - cy- 45 phenyl) -3-methyl-5-pyrazolone, 1- (6'-chloro-4'-sulfo-

anoethylaniline, N-ß-hydroxyethyl-N-ß'-cyanoäthyl- 2 '- methylphenyl) - 3 - carboethoxy - 5 - pyrazolone,

aniline, N, N-di - (/? - acetoxyethylaniline), N, N-di - (/ S-car- l- (6'-chloro-4'-sulfo-2'-methylphenyl) -3-methyl- 5-pyr-

boäthoxyäthyl) aniline, N - ^ - cyanoethyl-N-jS-methoxy-azolone, 1- (4'-methyl-2'-suÖophenyl) -3-methyl-5-pyr-

ethylaniline, S-NjN-Di-OS-acetoxyäthy ^ -aminoacetani- azolon, 1- (2 ', 5'-disulfophenyl) -3-methyl-5-pyrazo-

lid, N - /? - hydroxyethylaniline and N - /? - hydroxyethyl- 50 ion, l- (4'-ethoxy-2'-suhOphenyl) -3-methyl-5-pyrazo-

1-naphthylamine, other ions coupling in the o-position, 1- (2 ', 4'-dichloro-5'-sulfophenyl) -3-methyl-5-pyr-

Amines, such as l-naphthylamine-4-sulfonamide, 2-naphthyl-azolone, l- (6'-chloro-3'-sulfo-2'-methylphenyl) -3-me-

amine-6-sulfonamide and 4-chloro-l-naphthylamine, phenyl-5-pyrazolone, l- (4'-sulfophenyl) -3-carboxy-5-pyr-

nols, such as l-phenol-4-sulphonic acid, p-cresol, 3,4- or azolone, l- (3 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone,

2,4-dimethylphenol, 2- or S-acetylamino ^ -methyl- 55 l- (4'-carboxyphenyl) -3-methyl-5-pyrazolone, 1- (3'-Ca-

phenol, t-butylphenol, 4-thiocyanophenol, 4-sulf- 1 - (4 '- carboxyphenyl) - 3 - methyl - 5 - pyrazolone,

amyl-phenol, 4-acetylphenol, 2-hydroxy-5,6,7,8-tetra- 1 - (3 '- carboxyphenyl) - 3 - methyl - 5 - pyrazolone,

hydronaphthalene, 2-hydroxy-3-sulfamyl-5,6,7,8-tetra- l- (2'-caboxyphenyl) -3-methyl-5-pyrazolone, 1-phenyl-

hydronaphthalene, 4-methoxyphenol, 2-carboethoxy- 3-carboxy-5-pyrazolone, l-p-tolyW-carboxy-S-pyr-

amino-4-methylphenol, o- and p-phenylphenol, 60 azolone, S-carboxy-S-pyrazolone.

2-hydroxydiphenylene oxide and 2,4-dihydroxyquinoline, examples of coupling components, which one

Naphthols and naphtholsulfonic acids, such as 2-naphthol, group of formula (2) contain 6 - /? - hydroxy

1-acetylamino, 1-propionylamino, 1-benzenesulfonylethylsulfonyl-2-naphthol-3-sulfonic acid, 2-naphthol

amino-, 1-carbomethoxyamino-, 1-carboethoxy- 6-j8-hydroxyethyl sulfone, l-naphthol-4 - ^ - hydroxyethyl

amino-, 1-carboisopropoxyamino- and 1-phenyl- 65 sulfone, l- (3'- or 4'- | ß-hydroxyethylsulfonylphenyl) -

amino-7-naphthole, 6-acetyl-2-naphthol, 4-acetyl-3-methyl-5-pyrazolone, m- (N, N-diethylamino) -phenyl-

1-naphthol, l-naphthol-3-, -4- or -5-sulfonamide, / 3-hydroxyethyl sulfone and 6 - ^ - hydroxyethyl sulfonyl

2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonamide, 2-naphthylamine.

5 6

On the other hand, these coupling components can contain 4-, 5- and 6-aminoindazole, 6-amino-5-methoxymite Diazo components are coupled which 2- (4'-sulfophenyl) -benz-l, 2,3-triazole, 6-methyl Group of formula (2) contain e.g. B. with 2- (4'-aminophenyl) benzothiazole and their mono- and diazotizable amines of the benzene series, e.g. B. aniline, disulfonation products, 2 - (4 '- aminophenyl) -o-, m- and p-toluidine, o-, m- and p-anidisine, m- and 5-naphtha-lAS-triazole-S '^ - disulfonic acid, 2- (3'- and p-NitroaniHn, m- and p-Aminoacetanilid, o- and 4'-aminophenyl) -naphtha-l, 2,3-triazole-4,7,9-trisulfonm-anihenesulfonic acid, Sulfanilic acid, aniline-2,4-, -2,5- acids, 2 - (4'-aminophenyl) -naphtha -1,2,3 -triazole- and -3,5-disulfonic acid, 4-methylaniline-2-sulfonic acid, 3 ', 4,7,9-tetrasulfonic acid, 5-nitro-2-aminothiazole and 5-methylaniline-2-suhoic acid, 2-methylaniline-5-suho-3-aminopyridine.

acid, 2,4-dimethylaniline-6-sulfonic acid, 4-methyl- io anthraquinone dyes, which are used as starting materials for aniline-2,5-, -3,5- and -2,6-disulfonic acid, 2-methyl processes according to the invention can be used aniline - 4,6 - disulfonic acid, 5 - chloro - 2 - aminoanisole, can be obtained by z. B. an anthra-4-methoxyaniline-2-sulfonic acid, 5-Methoxyanüin-2-sulquinone, which has a halogen atom in the α-position, phonic acid, 2-methoxyaniline-5-sulfonic acid, 2,4-dime with an amine and preferably with an arothoxyaniline-6-sulfonic acid, 4-chloroaniline-2-sulfon- 15 matic amine, which is a group of the formula (2) acid, 4,5-dichloroarulin-2-sulfonic acid, 2,5-dichloro-contains, condensed; so can z. B. l-Amino-4-bromaniline-4-sulf onic acid, 4-acetylaminoaniline-2-suhOn- anthraquinone-2-sulfonic acid with 3- or 4 - /? - hydroxy acid, 5-Acetylaminoanüin-2-sulfonic acid, 2-Trifluor- ethylsulfonylanilin be condensed, methylaniline, 4- trifluoromethylaniline-2-sulfonic acid, dyes of the o-nitrodiphenylamine series, which are used in

4-CMor-5-methylariiline-2-sulfonic acid, 3-chloro-2-me- 20 process according to the invention as starting materials angethylanüin-4,6-disulfonic acid, 5-chloro-4-methylanüin- can be used, for example, by 2- sulfonic acid, 4-nitroaniline-2-sulfonic acid, 5-nitro- condensation of an o-halonitrobenzois with an aniline-2-sulfonic acid, 4-nitro-2-methoxyanine-5-sulfone- primary aromatic amine of the benzene series obtained acid, S-Ammo-i-methylacetanilide ^ -sulfonic acid, where one of the starting materials is a group aniline-2-, -3- and -4-carboxylic acid and its ester, 25 of the formula (2) and the other a carboxylic acid or such Contains methyl and butyl anthranilate, 2-aminophenol, sulfonic acid group. So you can 4-chloro-2-aminophenol-4-sulfonic acid, 2-aminophenol-4,6-di-3-nitrophenyl- / S-hydroxyethylsulfone with, for example, sulfonic acid ^ -ethanesulfonyl-i-aminophenoljS-amino- m-anilinesulfonic acid , m-aminobenzoic acid or its 4-hydroxyacetophenone, 4-nitro-2-aminophenol-6-sulfonic nuclear substituted derivatives condense or one sulfonic acid, 6 - nitro - 2 - sulfonic acid aminophenol -A-, condensed 30 m-jff-Hydroxyäthylsulfonylanilin example -4-chloro-2-aminophenol-6-sulfonic acid, 6-chloro-wise with 4-chloro-3-nitrobenzoic acid or 4-chloro-2-aminophenol - 4-sulfonic acid, 4- and 5-nitro-3- nitrobenzenesulfonic acid.

2-aminophenols, 4,6-dinitro-2-aminophenol, 4-, 5- dyes of the phthalocyanine series, which at

or o-CHor ^ -suifamyl ^ -ammophenol, 4-methyl- process according to the invention as starting materials Versulfamyl-2-aminophenol, 4- and 5-sulfo-2-amino- 35 can be used, for example, benzoic acid, aminoterephthalic acid, 4-amino-iso- by condensing an amine and preferably phthalic acid, 5 - nitro - 2 - aminophenoxyacetic acid, an aromatic amine, which is a group of 5-chloro-2-aminobenzoic acid, 5-nitro-2-aminobenzoe- formula (2) contains, with a phthalocyanine sulfonic acid, 2-sulfamylaniline, 2-ethyl sulfamylaniline, chloride obtained.

2-Aminophenyläthylsulfon, 4- and 5-aminosalicyl 40 Of course, in all processes for acid; diazotizable amines from the naphtha series Production of dyes, which are used as starting materials linderivate and other condensed ring systems, are suitable for the process according to the invention, the such as 1- and 2-naphthylamines, l-naphthylamine-4-, -5-, intermediates chosen so that ultimately a color -6- and -7-monosulfonic acid, 2-naphthylamine-l, -6-, substance is obtained which contains one or more sulfonic acid -7- and -8-monosulfonic acid, l-naphthylamine-2,4-, 45 or carboxylic acid groups. -2,5-, -3,6- and 3,8-disulfonic acid, 2-naphthylamm-l, 5-, the above-explained inventive method

-3,6-, -4,8-, -5,7- and -6,8-disulfonic acid, 1-naphthyl- driving can be carried out suitably by amine-2,4,6- and -2,5 , 7-trisulfonic acid, 2-naphthyl- the anhydride or acid halide of the acid of amine-1,5,7- and -3,6,8-trisulfonic acid, 2-methoxy- formula Y - COOH and the at least one group l-naphthylamine -6- and -7-sulfonic acid, 1-amino- 50 of the formula (2) containing dye in a liquid 2-eththol-4-sulfonic acid, l-amino-6-nitro-2-naphthol tertiary amine or in an organic liquid 4 -sulphonic acid, 1- and 2-aminoanthraquinone, 1-amino- in the presence of a tertiary amine, preferably with "pyrene-monosulphonic acid, 3-aminochrysene-sulphonic acid; a temperature between 0 and 50 ° C that can be diazotized amines with more than one non-condensate stirred together and, when the reaction has ended, phenyking, such as 4-aminodiphenyl-3-and-4'-sul- 55 a liquid such as water or diethyl ether, or acidic acid, 4'-nitro-4-aminostilbene-2,2'- disulfonic acid, an aqueous sodium ch loride solution, which is able to dissolve the ter-4'-acetylamino-4-aminostilbene-2,2'-disulfonic acid, tiary amine and / or the organic liquid to 4'-benzoylamino-4-aminostilbene-2,2'-disulfonic acid, in which the dye is insoluble, however, 4'-CMor-4-armnostilbene-2,2'-disulfonic acid, 4'-bromine is added and the precipitated dye is filtered off. 4-aminostilbene-2,2'-disulfonic acid, 4'-dimethylamino- 60 Examples of anhydrides or acid halides which stilbene 4-aminostilbene-2,2'-disulfonic acid, 4'-anilino-4-amino- in the above process according to the invention - 2,2 '- disulfonic acid, 2 - amino - 2'-methyldi- can be used are acetic anhydride, phenyl ether, 2-amino-2'-methyldiphenyl ether-4'-sul- acetyl chloride, acetyl bromide, propionyl chloride, butyfonic acid, 2 -AminodiphenylsuÜ ^? on, 4-aminodiphenyl ryl chloride, a-chloroacetyl chloride, benzoyl chloride, benamin, i-amino ^ '- nitrodiphenylamine ^' - suKonsäure, 65 zoyl bromide, methoxybenzoyl chloride, chlorobenzoyl-3- and 4-aminobenzanilide, 3'- and 4'-aminobenz - chloride, ^ -chloropropionyl chloride, α-bromoacetylanilide, 3'- and 4'-aminobenzanilide-3- and -4-sulfone bromide, acrylchloride, α-phenylacetyl chloride and acid; and heterocyclic amino compounds such as nitrobenzoyl chloride.

7 8

The new dyes which can be prepared according to the invention form a group of the formula (1) directly or via methylene

can also be obtained by adding dye to an aryl nucleus contained in the amines

Intermediate products react with each other, which contain bonds, are 2-chloro-5 - /? - acetoxyethyl

already contain the group of formula (1) and the sulfonyl-aniline, 4-jft-acetoxyethylsulfonylaniline, 3-ß are chosen so that products are obtained that contain 5 acetoxyethylsulfonylaniline, 4 - /? - acetoxyethylsulfonyl

Contain sulfonic acid or carboxylic acid groups. aniline, 3 - (/ 3-AcetoxyäthylsuhOnylmethyl) -4-methyl-

The sulfonic acid or carboxylic acid groups can be in aniline, 2-methoxy-5 - /? - acetoxyäthylsulf onylanilin, 5-ß-

the intermediate product or z. B. by Acetoxyäthylsulfonylanilin-2-sulfonic acid and 2-

Hydrolysis of sulfochloride or carbonyl chloride, aniino-4-ß-acetoxyethylsulfonylphenol.
groups simultaneously with the formation of the dye io Examples of dyes or dye intermediates

be generated. products containing reactive halogen atoms,

So you can according to a preferred embodiment - which with these primary aromatic amines to-

form of the process according to the invention azo dyes that can be set are phthalocyanine, in particular

which contain at least one group of the formula (1), in particular copper phthalocyaninesulfonic acid sulfonyl chloro thereby obtained that a primary aromatic 15 ride, ^ chloro-S-nitrobenzenesulfonic acid, a-halogeno-

Amine, which can be an aminoazo compound, anthraquinone sulfonic acid, such as l-amino-4-bromo

diazotized and the resulting diazo compound with anthraquinone-sulfonic acid.wiel-Amino ^ -bromanthra-

a coupling component, where either quinone ^ -j ^ jo-j ^ T- and ^ S-disulfonsäurejl-amino-

the primary aromatic amine or the coupling 2,4-dibromoanthraquinone-5-, -6-, -7- and -8-sulfonic acid, component or both at least one group ao l, 4-bis- (p-phenylanilino) -anthraquinone-tetrasuhOnyl-

of formula (1) and contain either the primary chloride and 4-chloro-3-nitrobenzoic acid.

aromatic amine or the coupling component A preferred class of the new according to the invention

or both at least one sulfonic or carboxylic acid preparable dyes are those dyes which

group carry. at least one sulfonic or carboxylic acid group and

The primary aromatic amine is preferably one or two groups of the formula
a primary aromatic amine of the benzene or

Naphthalene optionally substituted with a -SO ₂ -CH ₂ - CH ₂ - O - COY
Arylazo is substituted and which optionally

contain a group of the formula (1) corresponding to the above, where Y has the meaning given.

given definition. Such pri- 30 Preferably, however, Y is a lower alkyl radical or

Aromatic amines, which are a group of a monocyclic aryl radical.

Formula (1) can be obtained by The new dyes which can be prepared according to the invention one the corresponding nitro compounds, which are used for dyeing natural and synthetic contain a group of formula (2), with an on textiles suitable, z. B. Textiles, which include cotton, hydride or an acid halide of an acid of the 35 viscose silk, regenerated cellulose, wool, silk, Formula Y - COOH treated and then the cellulose acetate, polyamides, polyacrylic acid nitriles, mo-nitro group reduced to the amino group. Special differentiated polyacrylonitriles and aromatic poly examples for primary aromatic amines which contain an ester fiber. For this purpose you can use the Group of formula (2) contain, dyes have already been applied to the textile materials by dyeing, listed above. 40 Padding or Printing Using Print Die Coupling components mentioned can apply pastes that contain the usual thickeners any of the known series of coupling compounds or oil-in-water emulsions or water-in-oils belong, but are preferably contained Kupp emulsions, whereby the textile materials components of the acylacetarylide, 5-pyrazolone, are colored to luminescent tints, which against -phenol-, Naphthol or arylamine series, excellent against 45 wet treatments such as washing if necessary contain a group of formula (1) are genuine. The new dyes pull well on them can. Such coupling components, which a textile on and give very deep shades. Containing group of the formula (1) can be obtained by loading The new dyes which can be prepared according to the invention act of the corresponding coupling components, are particularly useful for dyeing cellulosic containing a group of formula (2), suitable with a 50 textiles. For this purpose are the color anhydride or acid halide of an acid of the substances on the cellulose-containing textile material preferred formula Y - COOH can be obtained. Special evidence in connection with treatment with a games for coupling components that have a group of acid-binding agents, e.g. B. sodium carbonate, Nader Formula (2) contain trium metasilicate, trisodium phosphate, or sodium have already been mentioned above. Examples of coupling components, the 55 hydroxyd, applied, this treatment before, contain a group of formula (1) are 4 - /? - acetoxy during or after the application of the dye äthylsulfonyl-l-naphtholundö - ^ - Acetoxyäthylsulfonyl- can be carried out. On the other hand, if that 2-naphthol-3-sulfonic acid. dyed textile is then heated or with water-too can be primary aromatic amines that a vapor should be treated, one can also subgroup of formula (1) directly or via a methylene 60 punch such as sodium bicarbonate or sodium tri group to an aryl nucleus contained in the amine use chloroacetate, which when heated or bound contain, with dyes or dye- act with water vapor an acid-binding agent Intermediate products are condensed, which release react.

Carrying capable halogen atoms, as in the α-position The new dyes which can be prepared according to the invention

halogenated anthraquinones, chlorosulfonated anthra-65 are also used for dyeing nitrogen-containing textiles

quinones, o-chloronitrobenzenes and phthalocyanines, ζ. B. Textiles made from wool and polyamides,

sulfo- and carbonyl chlorides. suitable. For dyeing such textiles, the

Examples of primary aromatic amines, which dyes preferably consist of a weakly alkaline,

909515/1690

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neutral or acid dye bath applied. The coloring can be constant or nearly constant pH can be carried out, d. H. that the pH of the dyebath is constant or during dyeing remains almost constant, or the pH of the dyebath can be adjusted in any stage of the dyeing process can be changed by adding acids or acidic salts or alkalis or alkaline salts. For example, the pH of the dye can be adjusted until it is no longer acidic to Congo red reacted. The diazo solution obtained is poured into a solution of 21.12 parts of 2-naphthol-6-sulfonic acid, with stirring, 4.4 parts of sodium hydroxide and 20 parts of sodium carbonate in 200 parts of water, which has been cooled to 2 ° C. The mixture is stirred for 4 hours and added with 100 parts of sodium chloride offset. The precipitated dye is filtered off, treated with a 10% aqueous salt solution

bath from 3.5 to 5.5 begin and wash the pH io and finally dried. It stains cellulose orange hues to 6.5 to 7.5 or above during dyeing. raise. The dye bath can also contain substances which are commonly used for dyeing nitrogen-containing textiles. Examples for such substances, ammonium acetate, 15 benzene and acetic anhydride are converted into pyridine, Sodium sulfate, ethyl tartrate, nonionic dispersing water is added, the precipitated 1-chloro-2-nitro agent, such as condensation products of ethylene oxide with amines, fatty alcohols or phenols, surface-active cationic agents, such as quaternary ammonium

The 2-chloro-5 - ^ - acetoxyäthylsulfonylanüin used in the above example can be obtained by adding l-chloro ^ -nitro ^ / S-hydroxyäthylsulfonyl-

4-jff-acetoxyethylsulfonylbenzene isolated and the nitro group converted into an amino group by adding an ethanolic solution of the nitro compound in

salts, e.g. B. cetyltrimethylammonium bromide and cetyl-20 presence of Raney nickel as a catalyst pyridinium bromide, and organic liquids, treated as hydrogen. n-butanol and benzyl alcohol.

It is believed that the new dyes which can be prepared according to the invention, if you have them on Applies to textiles, with hydroxyl and / or 25 amino groups that are contained in the textiles, convert, whereby the dyes are chemically bound to the textiles. This assumption is based ensure that the dyeings obtained are stirred against vigorous washing treatments and also against 30 and then filtered. The product on Extraction of solvent extremely resistant - the filter is stirred in diethyl ether, again

Example 2

12 parts of 1-ammo-4- (3'-jff-hydroxyethylsulfonylanilino) -anthraquinone-2-suhOnäure are dissolved in 60 parts of dry pyridine. The solution is ^{cooled to 0 °} C. and 7.6 parts of acetic anhydride are added. The mixture is left at 0-4 ° C for 4 hours

35

are capable.

In comparison to the azo dyes which can be prepared according to German patent specification 1002 099, which one

- SO ₂ - (CHg) ₂ , - O - SO ₂ - Z group

where y is 2 or 3 and Z denotes an aliphatic or aromatic radical, the azo dyes produced according to the invention produce more saturated colors when printing cellulose textiles. They also have a better absorption capacity.

In the following examples, parts mean parts by weight and the percentages are percentages by weight.

filtered, washed with diethyl ether and dried.

The product obtained is the pyridine salt of l-amino-4- (3'-j5-acetoxyethylsulfonylanuino) -anthraquinone-2-sulfonic acid. It can be obtained in the form of the sodium salt by putting it in hot water dissolves, add sodium bicarbonate until the solution is alkaline, whereupon sodium chloride is added, and the dye is precipitated as the sodium salt.

It dyes cellulose in bright reddish blue tints.

The following table gives further examples of new dyes which can be prepared according to the invention, which are obtained if, in place of the 27.75 parts of 2-CUor-5-j9-acetoxyäthylsulfonylanilm, the in Example 1, equivalent amounts were used

example 1

27.75 parts of 2-chloro-5-jff-acetoxyethylsulfonylaniline of the amines listed in the second column of the table

are in a mixture of 25 parts of a concentrated and / or instead of 21.12 parts of 2-naphthol-6-sulfon

trated aqueous hydrochloric acid and 500 parts of acidic amounts equivalent to those in the third table-water solved. The solution is cooled to 2 ° C and 50 columns of the coupling components listed are used, a solution of 6.9 parts of sodium nitrite in 60 parts of water is added while stirring. The mixture is stirred for 15 minutes and with sodium bicarbonate

The fourth column of the table lists the shades that are obtained when the dyes can be applied to textiles.

at
game Amine Coupling component Color tint 3
4th
5
. 6th 2-methoxy-5 - /? - acetoxyethylsulfonyl-
aniline
2-methoxy-5- / S-benzoyloxyäthylsuhOnyl-
aniline
2-methoxy-5-) 2-acetoxyethylsulfonyl-
aniline
the same l- (2'-methyl-4'-sulfo-6'-chlorophenyl) -
3-methyl-5-pyrazolone
l-amino-jS-naphthol-3,6-disulfonic acid
2-N-acetylamino-5-naphthol-7-sulfonic acid
l-naphthol-5-sulfonic acid Greenish yellow
Reddish
violet
orange
Red

11 12th Coupling component Color tint At.
game Amine lN-phenylamino-S-naphthol-Sjo-disulfon-
acid Gray-brown 7th 2-methoxy-5- / 3-acetoxyethylsulfonyl-
aniline 2-N-phenylamino-5-naphthol-7-sulfonic acid Red 8th the same l- (3'-amino-4'-sulfophenyl) -5-pyrazolone-
3-carboxylic acid yellow 9 the same l- (2'-methyl-5'-sulfophenyl) -3-methyl-
5-pyrazolone yellow 10 the same l- (3'-methyl-4'-sulfo-6'-chlorophenyl) -
3-methyl-5-pyrazolone yellow 11 the same l-phenyl-S-pyrazolone-S-carboxylic acid yellow 12th the same l- (3'-nitrophenyl) -5-pyrazolone-3-carbon-
acid yellow 13th the same l- (2'-methyl-3'-sulfo-6'-chlorophenyl) -
3-methyl-5-pyrazolone yellow 14th the same l- (2'-chloro-5'-sutfophenyl) -3-methyl-
5-pyrazolone yellow 15th the same l- (2'-methyl-4'-sulfo-6'-chlorophenyl) -
3-carbethoxy-5-pyrazolone yellow 16 the same 2-naphthol-3,6-disulfonic acid Red 17th 2-methoxy-5 - /? - benzoyloxyethyl
sulfonvlaniline l- (2'-methyl-4'-sulfo-6'-chloroplienyl) -
3-methyl-5-pyrazolone yellow 18th * J ^ n * ■ ^^ ü J A14A444 & UI
the same l-naphthol-5-sulfonic acid Bluish red 19th 2-chloro-5 - /? - acetoxyethylsulfonylaniline 2-N-acetylamino-5-naphthol-7-sulfonic acid orange 20th the same 1- (3'-sulfophenyl) -3-methyl-5-pyrazolone yellow 21 the same

Example 22

46.5 parts of the monosodium salt of l- (2'-methoxy-5 '- / S-hydroxyethylsulfonylphenylazo) -2-naphthylamine-6-sulfonic acid (which is obtained by coupling diazotized 2-methoxy-5-hydroxyethylsulfonylaniline with , 2-naphthylamine-6-sulfonic acid obtained under acidic conditions) are stirred in 460 parts of pyridine at 2O ⁰ C and gradually added 30Teilen acetic anhydride, wherein the temperature of the mixture is kept by cooling to 20 ⁰ C. The resulting mixture is stirred for 16 hours at 2O ⁰ C, mixed with 1,000 parts of water, and the precipitated dyestuff is filtered off, washed with benzene and dried. If you apply it to wool from a weakly acidic dye bath, the dye produces bright-orange tints that are extremely wet-fast.

The following table are more examples of

new dyes which can be prepared according to the invention are listed, which are obtained if one in place of the 46.5 parts of the monosodium salt of the azo compound used in Example 22, equivalent men " gene of the sodium salts of the azo compounds used, which are obtained by the in the second Table column listed amine is diazotized and the diazo compounds obtained with those in the third The coupling components listed in the table column under acidic or alkaline conditions, as in the in the fourth column of the table, coupling and / or by replacing the one used in Example 22 30 parts of acetic anhydride are equivalent amounts of the acylating agents listed in the fifth column of the table begins. The sixth column of the table shows the shades that are obtained when the dyes are applied to textile materials.

at
game Amine Coupling component Clutch
conditions Acylation
middle Color tint 23 2-methoxy-5-) S-hy- l- (2'-methyl-4'-sulfo-6'-chlorophenyl) - alkaline Acetic anhydride yellow hydroxyethylsulfonyl- 3-methyl-5-pyrazolone aniline 24 the same l-naphthol-4-sulfonic acid alkaline Acetic anhydride Red 25th the same l- (2 ', 5'-dichloro-4'-sulfophenyl) - alkaline Acetic anhydride yellow 3-methyl-5-pyrazolone 26th the same 2-naphthol-6-sulfonic acid alkaline Acetic anhydride orange 27 the same 2-naphthol-7-sulfonic acid alkaline Acetic anhydride Reddish orange

at
game Amine Coupling component Clutch
conditions Acylation
' ^! middle Color: 28 " ^ Mefhoxy-5 - ^ - hy- 2-naphthol-7-suTfbic acid alkaline' Axetyl chloride Reddish hydroxyethylsulfonyl-
ariiün * orange 29 the same l ^ Naphthol-5-sulphonic acid - alkah'sch Acetic anhydride Red 30th the same 2-Amino-5-napolithol-7-sulphonic acid alkaline Acetic anhydride orange 31 the same l- (3 * -Sülf öptienyl) ^: 3-methyl- ' alkah'sch Acetic anhydride yellow 5-pyrazolone 32 the same 2-Amiho-8'-riaphthbl-6isulfonic acid angry Acetic anhydride Red 33 the same m-phenylenediaminesulfonic acid angry Acetic anhydride yellow 34 the same 2-N-methylamino-8-naphthol-
6-sulfonic acid " alkaline Acetic anhydride Braunf 35 the same ^ -N-acetylamino-S-naphthol-
7-sulfohic acid alkaline Acetic anhydride orange 36 the same m-phenylenediaminesulfonic acid angry Propionyl yellow chloride' 37 the same ^ -N-methylamino-S-napnthol-
o ^ sulfonic sauce alkah'sch Benzoyl
chloride' Red 38 the same o - ^ - Hydroxyethylsulfonyl ^ -riaplithol- alkaline Acetic anhydride Reddish x-sulfönsäüfe ^ orange 39 o-anisidine the same alkaline Acetic anhydride Feces 40 4-j8-hydroxyethyl
sulfonylaniline 1-naphthol'4-sulfoic acid alkaline Acetic anhydride orange 41 the same l- (3'-Sidfophenyl) -3-methyl- alkah'sch Acetic anhydride yellow 42 4-j8'-hydroxyethyl
sulfonylaniline 2-AnünÖ-8-nMphthbi-6 ^: sulfonic acid angry Acetic anhydride Red 43 4-j9-hydroxyethyl - rPhenyl-3-methyl-5-pyrazolone- alkaline Acetic anhydride yellow sulfonylaniHn ' 2,6-disulfonic acid 44 -Niüöamlin eTÖ-HyaroxyäthyiäuKonyl ^ -näphfh ^ · alkaline Acfetaniiydridi Orange; x-sulfonic acid 45 -Naphthylamm- - (J'-zS'-Hydroxyethylsulfonylphenyl) - alkah'sch Acetic anhydride Oräuge 6-sulfonic acid 3-methyl-5-pyrazoion 46 -Aniline sulfoa acid oil -Naphthylamine-o - ^ - hydroxy- · angry Acetic anhydride orange ethyl sulphon

Example 47

53.1 parts of the Küpfer complex of "2- (2" ^{-hydroxy i} - S'-ß- hydröxyäthylstilfonylphenylazg) -1-naphthol-4-sulfonMure \ verderi in 500 TeHen Pyndin ¹ to 2 (f C stirred and similar 30 parts of acetic anhydride are added, the temperature of the mixture being kept by cooling at 20 ° C. The mixture is then ^{stirred for 16 hours at 2G 0} G, whereupon 1000 parts of diethyl ether are added and the dyestuff which has precipitated out is filtered off, with 6in 10% aqueous sodium chloride solution is washed and dried.

If you use the dye in conjunction with a treatment with an acid-binding agent cellulose-containing textiles are applied red tints which are very real to washing and light.

The copper complex used in the previous example can be obtained by using diazotized 2-aminophenol-4-) S-hydroxyethyl sulfone

l-naphthol-4-sulphuric acid in an alkaline medium coupling and · the preserved Azoverbiüdurig. afterwards

5b heated with an aqueous pot acetate solution.

The following table are more "examples of new dyes that can be prepared according to the invention leads, which get pastures, whom® one instead of the 53.1 parts of the copper complex used in Example 47 are equivalent amounts of the metal complexes uses 'which are obtained by' adding that in the Amine listed in the second column of the table is diazotized with the amine listed in the third column of the table Coupling component couples and then the

The azo compound held with a metallizing agent of the metal listed in the fourth column of the table is treated and / or by using equivalent amounts of the acylating agents listed in the fifth column of the table instead of the 30 parts of acetic anhydride used in Example 50. The sixth column of the table shows the color shades that are obtained _- when the dyes are applied to textiles.

15th Amine Coupling component metal 16 Color
tint At-
' game 2-aminophenol
4 - /? - hydroxyethyl
sulfone 2-amino-5-naphthol-7-sulfonic acid copper Acylating agents ruby 48 the same the same. .-.-... copper Acetic anhydride ruby 49 the same l- (2 \ 5'-dichloro-4'-sulfophenyl) -
3-methyl-5-pyrazolone copper Benzoyl chloride yellow 50 the same l-naphthol-4-sulfonic acid, copper Acetic anhydride Red 51 the same 2-naphthol-6-sulfonic acid copper Acryloyl chloride Red 52 the same l- (2 ', 5'-dichloro-4'-sulfophenyl) -
3-methyl-5-pyrazolone chrome Acetic anhydride orange 53 the same the same cobalt Acetic anhydride yellow 54 Acetic anhydride

Example 55

A solution of 28.9 parts of 2-methoxy-5 - /? - acetoxyethylsulfonylaniline in a mixture of 25 parts of a concentrated aqueous hydrochloric acid as and 500 parts of water is cooled to 2 ° C and stirred with a solution of 6.9 parts of sodium nitrite added in 60 parts of water. The mixture is stirred for 15 minutes, excess nitrous acid then removed by adding sulfamic acid and the mixture is now in a suspension of 24.5 parts Entered 2-naphthylamine-6-sulfonic acid in 500 parts of water. Sodium acetate is now added, until the mixture no longer reacts acidic to Congo red, whereupon the mixture lasts for 16 hours 5 ° C is stirred. The deposited precipitate is filtered off and stirred in 750 parts of water, with Sodium carbonate is added until the mixture becomes alkaline. 75 parts of sodium chloride are added, whereupon the precipitated dye is filtered off and dried.

If you apply it to cellulosic textiles in conjunction with a treatment with an acid-binding agent, the dye turns orange, very much wet-fast tints.

Are used in place of those used in the previous example 28.9 parts of 2-methoxy-5 - /? - acetoxyäthyk sulfonylaniline 27.75 parts of 2-chloro-5-acetoxyethylsulfonylaniline and / or instead of the 24.5 parts of 2-naphthylamine-6-sulfonic acid used in the previous example 26.1 parts of ^ -ammo-S-naphthol-δ-sulfonic acid applied ,, so one obtains similar dyes.

Example 56

55

A solution of 1.4 parts of sodium nitrite in 10 parts of water is added to a solution of 6.6 parts of 2-methoxy-5- | # -acetoxyäthylsulfonylanilin in a mixture of 100 parts of water and 3 parts of concentrated aqueous hydrochloric acid at 0 ^c C eingegebea and the mixture obtained was stirred for 15 minutes. Sulphamic acid is then added to remove any excess nitrous acid. The resulting solution is then added to a solution of 8.5 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 100 parts of water and the mixture is ^{kept at 5 °} C. for 3 hours. The precipitated monoazo compound is filtered off, the solid obtained is stirred in 200 parts of water and an aqueous 2N sodium hydroxide solution is added until the mixture has an alkaline reaction to brilliant yellow. The solution obtained is now mixed with a solution of diazotized! 2-Methoxy-5- / S-acetoxyäthylsuUonylanilin, which is obtained as described in the first sentence of this example, and the mixture is stirred for 16 hours at 5 ° C, whereupon sodium carbonate is added until the mixture is alkaline to brilliant yellow. 35 parts of sodium chloride are then added and the dyestuff which has precipitated out is filtered off, washed with a 5% strength aqueous sodium chloride solution and dried.

If you put it on cellulosic textiles in conjunction with a treatment with an acid-binding agent Applies agent, the dye gives navy blue tints that are excellent against wet treatments are real.

Example 57

A mixture of 27 parts of 3-nitro-4-chlorobenzolyS-hydroxyethylsulfone, 21.5 parts of m-anilinesulfonic acid, 30 parts of calcium carbonate, 100 parts of ethyl alcohol and 200 parts of water is refluxed for 17 hours and the mixture is then filtered; The filtrate obtained is ^{cooled to 15 °} C. and the precipitated solid is filtered off, washed with ethyl alcohol and dried. The solid obtained is dissolved in 300 parts of pyridine at 2O ⁰ C, then 20 parts of acetic anhydride are added and the mixture for 17 hours at 2O ⁰ C stirred. The mixture is then distilled under reduced pressure in order to separate off the pyridine, and the residue is stirred with diethyl ether. The precipitated dye is then filtered off, washed with ether and dried.

If it is used in conjunction with a treatment with an acid-binding agent on cellulosic Applies to textiles, the dye gives yellow tints that are very wet fast.

The following table gives further examples of new dyes which can be prepared according to the invention, which are obtained if, instead of the 12 parts of l-amino-4- (3 '- /? - hydroxyäthylsulfonylanilino) used in Example 2 - anthraquinone - 2 - sulfonic acid equivalent amounts of the anthraquinone compounds listed in the second column of the table and /

909515/1690

or instead of the 7.6 parts of acetic anhydride used in Example 2, equivalent amounts of that in the third column of the table uses acylating agents. In the fourth column of the table are the color shades indicated, which are obtained when the dyes are applied to textiles.

at
game Anthraquinone compound Acylating agents Color tint 58 l-Amino- ^ iS'-jS-hydroxyäthylsulfonylanilinoJ-anthraquinone-
2-sulfonic acid Propionic anhydride Reddish blue 59 the same Benzoyl chloride Reddish blue 60 l-Amino-4- (4'-methyl-3'-0S-hydroxyethylsuHonyhTiethyl) -
anilino) anthraquinone-2-sulfonic acid Benzoyl chloride blue 61 the same Acetyl chloride blue 62 l-amino-4- (4'-j8-hydroxyäthylsulfonylanih'no) -anthraquinone-
2-sulfonic acid Acetic anhydride Reddish blue

Example 63

14.4 parts of copper phthalocyanine are inputted into 163 parts of chlorosulfonic acid and the resulting mixture stirred for 4 hours at 135 to 14O ⁰ C. Subsequently, the mixture to 10 ⁰ C is cooled, ice-water mixture and poured into a filtered das.ausgefallene chlorosulfonated copper phthalocyanine and washed with iced water. The solid obtained is stirred with 120 parts of water and 120 parts of ice, whereupon an aqueous 10N sodium hydroxide solution is added until the mixture reacts neutrally towards methyl orange. A solution of 9.1 parts of m-aminobenzene-acetoxyethylsulfonate in 100 parts of acetone and 16.8 parts of sodium bicarbonate are then added, whereupon the mixture obtained is stirred between 20 and 25 ° C. for 24 hours. 50 parts of sodium chloride are added and the dyestuff which has precipitated out is filtered off and dried.

If it is used in conjunction with a treatment with an acid-binding agent on cellulosic Applies textiles, the dye gives excellent wetfast greenish-blue tints.

If 9.1 parts of m-aminobenzene - /? - acetoxyethylsulfone are used in place of the used in the previous example 11.4 parts of m-aminobenzene - ^ - benzoyloxyethyl sulfone or 12.5 parts of 3-09-Benzoyloxyäthylsulfonylmethyl) - 4 - methylaniline or 10.2 parts of 3 - (/ 5-acetoxyethylsulfonyhnethyl) -4-methylaniline, similar dyes are obtained in this way.

Example 64

14.4 parts of copper phthalocyanine are entered in 68 parts of chlorosulfonic acid and the resulting mixture stirred for 3 hours between 135 and 14O ⁰ C. Then, the mixture is cooled to 95 ⁰ C and treated over 2 hours with 6.9 parts of phosphorus trichloride, and the mixture is stirred for 2 hours at 100 ° C. The mixture is cooled to 1O ⁰ C, poured into an ice water mixture and filtered, the precipitated chlorosulfonated copper phthalocyanine and washed with 125 parts of an aqueous L ° / o hydrochloric acid. The solid obtained is stirred with 125 parts of water and 75 parts of ice, whereupon 6.1 parts of m-aminobenzene - /? - acetoxyethylsulfone are added. An aqueous 2N ammonia solution is added until the pH value of the mixture is 8, whereupon the mixture is ^{heated to 40 °} C. and kept at this ao temperature until no further aqueous 2N ammonia solution has to be added, around the pH value to keep the mixture at 8. An aqueous hydrochloric acid solution is then added until the pH of the mixture is 7, whereupon 50 parts of sodium chloride are added and the dyestuff which has precipitated out is filtered off and dried.

If it is used in conjunction with a treatment with an acid-binding agent on cellulosic

3Q textiles apply the dye excellent wet-fast greenish-blue tints.

If 6.1 parts of m-aminobenzene-zS-acetoxyethylsulfone are used in place of the one used in the preceding example 11.4 parts of m-aminobenzene-ZJ-benzoyloxyethyl sulfone or 10.15 parts of 3-05-acetoxyethylsulfonylmethyl) -4-methylanihn or 12.5 parts of 3-GS-benzoyloxyethylsulfonylmethyl) -4-methylaniline one, similar dyes are obtained.

Example 65

Instead of the chlorosulfonated used in Example63 Copper phthalocyanine is an equivalent amount of the copper phthalocyanine tetrasulfonyl chloride used, which according to the method described in Example 1 of British Patent 515,637 can be obtained, whereupon similar dyes are obtained.

Example 66

Instead of the used in Example 64 chlorosulfonated copper phthalocyanine a chlorosulfonated copper phthalocyanine is used, which is obtained by reacting 24.7 parts of tetrasodium salt of Kupferphthalocyanintetra-4-sulfonic acid in 120 parts of chlorosulfonic acid enters, the mixture is stirred for 3 hours at 12O ⁰ C, the resulting mixture is cooled to 80 ⁰ C, added with 12 parts of thionyl chloride for 2 hours at 12O ⁰ C the mixture is stirred and cooled to 20 ⁰ C, pouring into an ice-water mixture and the precipitated chlorosulfonated copper filtered off, are obtained whereupon similar dyes.

Claims (3)

Patent claims: 1. A process for the preparation of water-soluble fiber-reactive dyes, the at least one Sulfonic acid or carboxylic acid group and minor at least one group of the formula attached to a carbon atom of the dye HR ₂ I I -SO ₂ -CCO-COY R _x R ₃ contain, wherein R ₁ , R ₂ and R _{3 are} independently hydrogen or lower alkyl groups and - COY is the radical of a monobasic carboxylic acid, characterized in that a dye which has at least one sulfonic acid or carboxylic acid group and at least one on a carbon atom of the Dye-bound group of the formula HR ₂ II ^ao -SO ₂ -CC-OH I I R ₁ R ₃ contains, wherein R ₁ , R ₂ and R _{3 have} the meaning given, with a monobasic carboxylic acid of the formula Y - COOH or the anhydride or acid halide of such an acid, where COY has the meaning given above. 2. A method for producing the according to claim 1 available water-soluble fiber-reactive dyes as a modification of the method according to claim 1, characterized in that dye precursors, of which at least one at least one group of the formula HR ₈
-SO ₂ -CCO-COY I I R ₁ R ₃ in which R ₁ , R ₂ , R ₃ and - COY have the meaning given in claim 1 and contain at least one carboxylic acid or sulfonic acid group, are reacted with one another to give the final dyes. 3. The method according to claim 2, characterized in that that a primary aromatic amine is diazotized and the diazo compound obtained with a coupling component couples, either the primary aromatic amine or the Coupling component or both at least one group of the formula 1 i ^! -SO ₂ -C- CO- COY R ₁ R ₃ wherein R ₁ , R ₂ , R ₃ and - COY have the meaning given in claim 1 and contain either the primary aromatic amine or the coupling component or both at least one sulfonic acid or carboxylic acid group.