DE2102217C3 - Reactive dyes, process for their preparation and their use - Google Patents

Description

N N

y \ y \

F ₁ -NC C-N-C CNF ₂

R ₁ N

NR ₂ N

NR ₃

IX ₂

(D

wherein F ₁ and F ₂ each represent a radical of an organic dye, R ₁ and R ₃ independently of one another are hydrogen, methyl or ethyl, X ₁ and X _{2 are} each a halogen atom and R _{2 is} hydrogen, an alkyl radical having 1 to 5 carbon atoms or an optionally through Denotes cyano, chlorine, bromine, hydroxy or alkoxy substituted with 1 to 3 carbon atoms, a phenyl radical or a benzyl radical.

The third substituent R ₂ on the nitrogen atom of Amino group, which the two reactive radicals with-

Eitiander connects, can preferably be a methyl,

Ethyl, 9-methoxyethyl or propyl radical or a Be phenyl or benzyl.

The preferred reactive group is monochloro-1,3,5-triazine resin

The dyes can be of any known class of dyes, and preferably belong ίο the mono- or polyazo series or the nitro, Anthraquinone or phthalocyanine series. They preferably contain at least one water-solubilizing group, in particular a carboxylic acid or sulfonic acid group. If desired, the ■ 5 dyes also coordinated metal, such as contain coordinated copper, chromium or cobalt. Basic dyes can also be used.

Dyes according to Claim 1 of the formula are preferred

F ₁ -NH-C

C-N-C

NR ₂ N

C C

Cl

Cl

C-NH-F ₂

where F ₁ and F _{2 are the} same dye _{radicals and R 2 is} a phenyl radical.

Of particular importance are dyes according to claim 1 of the formula (3) in which F ₁ and F ₂ denote the same dye _{radicals and R 2 is} hydrogen or an alkyl radical having 1 to 5 carbon atoms.

The invention further relates to a process for the preparation of dyes of the formula (1) [and also of the formula (3)], in which compounds of the formula

X ₄ C

y \

CNC CX ₃ (4)

NR ₂ N

X,

wherein X ₁ , X ₂ , X ₃ and X _{4 are} halogen atoms and R _{2 has} the meaning given under formula (1), with dyes of the formula F ₁ - N (R ₁ ) H and F ₂ --N (R ₃ ) H , where F ₁ , F ₂ , R ₁ and R _{3 have} the meanings given under formula (1), condensed to form dyes of formula (1), it being possible for the order of the partial reactions to be different.

The preparation of the starting compounds of formula (4) is in the Journal of the heterocyclic. Chem., Vol. 7, No. 3, pages 519-525 (1970).

According to a preferred embodiment of the process according to the invention, the procedure is that compounds of the formula (4) in which X ₁ , X ₂ , X and X _{4 are} chlorine atoms and R _{2 is} a phenyl radical , with amino group-containing dyes of the formulas F ₁ - NH ₂ and F ₂ --NH ₂ , in which F ₁ and F _{2 represent the} same dye radicals, is converted.

According to a further advantageous embodiment of the process according to the invention, the procedure is to use compounds of the formula (4) in which X ₁ , X ₂ , X ₃ and X ₄ are chlorine atoms and R _{2 is} hydrogen or an alkyl radical having 1 to 5 carbon atoms amino group-containing dyes of the formulas F ₁ -NH ₂ and F ₂ -NH ₂ , in which F ₁ and F _{2 represent the} same dye radicals. The implementation of the preparation of the tetrahalogen compound of formula (4) with the halo tifazines, such as. B. 2,4,6-trichloro (-tribromo or -trifluoro) -1,3,5-triazines are expediently carried out in the presence of acid-binding agents, such as. B. sodium carbonate, and in an organic solvent or at a relatively low temperature in an aqueous medium .

One proceeds advantageously so that first 1 mole of ammonia or primary amine, such as. B. aniline, is reacted with 1 mol of trihalotriazine and the product obtained is then condensed with 1 mol of the same or a different trihalotriazine. The reactions can be carried out in a manner known per se in the presence of an acid-releasing agent, such as. B. sodium hydroxide, are made. In this way, the compounds of the general formula (4) are obtained.

Primary amines are preferably used as amines, so z. B. alkylamines, such as methylamine, Ethylamine, propylamine, isopropylamine, butylamine, amylamine, // - chloro- or / i-bromoethylamine,

f> 5, i-cyanoethylamine, / i-hydroxylethylamine,; -hydroxypropylamine, methoxymethylamine, / i-methoxyethylamine. y-Methoxypmnyhimin, Äthoxymethylamin, // - Äthoxyäthylamin, y-Äthoxypropylamin, y-lso-

propoxypropylamine, benzylamine or arylamines such as aniline or the ammonia itself.

The bisreactive grouping of the formula (4) obtained in this way is then reacted with a dye which contains at least one acylatable -NHR ₁ or _{-NHR 3} group, in which R ₁ and R _3, independently of one another, represent a hydrogen atom, a methyl or ethyl radical .

One arrives so z. B. to compounds of formulas (1) and (3).

The reaction takes place in a manner known per se, preferably also in the presence of one acid binding agent.

The dye compounds of the azo series which are used as starting materials and which _{contain at least one —NHR 1} or —NHR ₃ group can be obtained by various processes. One method consists in diazotizing an aromatic primary amine and coupling the diazonium compound thus obtained with a coupling component containing _{an - NHR 1} or - NHR _{3 group.} As examples of aromatic primary amines which can be used in this way to obtain aminoazo compounds, there may be mentioned:

Aniline,

o-, m- and p-toluidines,

o-, m- and p-anisidines,

o-, m- and p-chlorailines,

2,5-dichloroaniline,

(χ- and / J-naphthylamine,

2,5-dimethylianiline,

5-nitro-2-aminoanisole,

4-aminodiphenyl,

Aniline-2,3- and -4-carboxylic acids,

2-aminodiphenyl ether,

2-, 3- or 4-aminobenzenesulfonamide or

-sulfomonomethyl- or

-äthylamide or

-sulfondimethyl- or

-sulfondiäthylamide,

Dehydrothio-p-toluidine monosulfonic acid or

Dehydrothio-p-toluidinedisulfonic acid,

Aniline-2, -3- and -4-sulfonic acid,

Ani! In-2,5-disulfonic acid,

2,4-dimethylaniline-6-sulfonic acid,

3-aminobenzotrifluoride-4-sulfc> n acid,

5-chloro-4-methylaniline-2-sulfonic acid,

S-acetylaminoaniline-o-sulfonic acid,

4-acetylaminoaniline-2-sulfonic acid,

4-chloroaniline-2-sulfonic acid,

S ^ dichloroaniline-6-sulfonic acid,

4-methylaniline-2-sulfonic acid,

3-methylaniline-6-sulfonic acid,

2,4-dimethoxyaniline-6-sulfonic acid,

4-methoxyaniline-2-sulfonic acid and

5-methoxyaniline-2-sulfonic acid,

2,5-dich'oraniline-4-sulfonic acid,

2-naphthylamine-4,8- and -6,8-disulfonic acid,

l-naphthylamine-2-, -4-, -5-, -6- or

-7-monosulfonic acid,

l-naphthylamine-3,6-disulfonic acid,

2-naphthylamine-3,6- and -5,7-disulfonic acid,

2-naphthylamine-3,6,8-trisulfonic acid,

m- and p-nitroaniline,

4-nitroaniline-2-sulfonic acid,

3-nitroaniline-6-sulfonic acid.

m- or p-aminoaceanilide and
4-Amino-2-acetylaminotoluene-5-sulfonic acid.

Examples of coupling components that can be used are:

2-amino and

2-methylamino-5-naphthol-7-sulfonic acid,
2-amino and

2-methylamino-8-naphthol-7-sulΓonic acid,
1-amino and

l-ethylamino-8-naphthol-6-sulfonic acid and
corresponding 3,6- and 4,6-disuironic acids,
H3'- or 4'-aminobenzoylamino) -8-naphthol-3,6- and -4,6-disulfonic acid,
Aniline,

o- and m-anisidine,
o- and m-toluidine,
2,5-dimethylaniline,
3-amino-methoxytoluoI,
2,5-dimethoxyaniline,
N-methylaniline,
N-EthyI-o-toluid: n,
N-methyl-m-anisidine,
S-methylamino ^ methoxytoluene,
l- (3'-aminophenyl) -3-methyl-, -carboxy- and
-carboethoxy-5-pyrazolone,
1- (4'-aminophenyl) -3-methyl-, -carboxy- and
carboethoxy-5-pyrazolone and
ib

5-pyrazolone.

The aminoazo compounds to be used in the process according to the invention are not restricted to compounds containing only one azo group. Disazo compounds can, for example, by tetrazotizing an aromatic diamine containing two primary amino groups and coupling the tetrazo compound obtained in this way with 2 molar proportions of one of the coupling components defined above or with 1 molar proportion of one of two of the coupling components defined above or with 1 mol of one of the coupling components defined above and with 1 molar proportion of a coupling component containing no amino group can be obtained. Examples of such aromatic diamines are: benzidine-3,3'-dimethoxybenzidine, benzidine-2,2'-disulfonic acid, benzidine-3,3'-dicarboxylic acid, benzidine-3,3'-diglycolic acid and 4,4'-diaminostilbene -2,2'-disulfonic acid. Furthermore, disazo or polyazo compounds can be obtained by using azo group-containing primary aromatic amines or diamines. Examples of such primary aromatic amines or diamines containing azo groups are: 4-aminoazobenzene - 4 '- sulfonic acid, 4' - amino -T- methylphenylazo - 2 - naphthalene - 4,8 - disulfonic acid, 4 - amino-5-methoxy- 2-methyl-4'-nitro-2'-sulfazobenzene.

Instead of -NHR ₁ - ₃ groups assumed free amines or -NHR can also, if desired, a-NHR ₁ -bzw.-NHR ₃ group-containing coupling component with a -NHR _1, - or - NHR ₃ group Coupling containing diazonium compound. Such diazonium compounds can be obtained according to known processes by diazotizing primary or aromatic amines which contain a second amino group or a monosubstituted amino group, wprHpn

Examples of such primary aromatic amines are: p-phenylenediamine, 1,4-phenylenediamine - 2 - sulfonic acid, 1,4 - phenylenediamine - 2 - carboxylic acid, 1,4 - diaminonaphthalene - 2 - sulfonic acid. Examples of coupling components which can be used in this way are the mentioned above coupling components and also / ^ - naphthol, 2-naphthol-6- or -7-sulfonic acid, 2 - naphthol - 3,6 - or - 6,8 - disulfonic acid, 1 - naphthol - 4 - sulfonic acid, 1 - phenyl - 3 - methyl-5-pyrazolone, 1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1 - (2 ', 5' - dichloro - 4 '- sulfophenyl) - 3 - methyl-5-pyrazolone, 2-benzoylamino-5-naphthol-7-sulfonic acid, 1 - benzoylamino - 8 - naphthol - 3,6 - or -4,6-disulfonic acid, phenol, p-cresol, acetoacetanilide and acetoacet ^ -methoxyaniliri-S-sulphuric acid.

Further processes for preparing the _{dye compounds of the azo series containing an —NHR 1} or —NHR ₃ group, which can be used in the process according to the invention, consist in reducing a nitro group-containing dye or an azo or polyazo compound which contains at least one acylamino group contains to treat with aqueous acid or aqueous alkali in order to hydrolyze the acylamino group or groups. Such azo or polyazo compounds can be obtained from primary aromatic amines and / or coupling components which contain acylamino groups. Examples of such primary aromatic amines are: monoacetylbenzidine, 4-amino-1-acetylaminonaphthalene-6-sulfonic acid, 4 - amino - 4 '- acetylaminodiphenyl - 3 - sulfonic acid, 4-amino-3-sulfoacetanilide, 3-amino-4- sulfoacetanilide and 4 - amino - 4 '- acetylaminostilbene-2,2'-disulfonic acid; and examples of such coupling components include: 2-acetylamino-5-naphthol-7-sulfonic acid, 2-N-acetyl-N-methylamino-5-naphthol-7-sulfonic acid, 2-acetylamino and 2-N-acetyl-N - methylamino - 8 - naphthol-6-sulfonic acids and 1-acetylamino-8-naphthol-3,6- and -4,6-disulfonic acids.

As examples of the anthraquinone FarbstotTverbindungen, which can be used in the present process as starting materials, may be mentioned anthraquinone compounds having a group defined above of the formula -NHR ₁ or -NHR ₃ at an alkylamino or arylamino group, which itself to the " -Position of the anthraquinone nucleus is bound, included. Examples of such anthraquinone compounds are:

l-amino-4- (4'-aminoaniline) anthraquinone

2,3'-disulfonic acid and the corresponding

2,3 ', 5-, 2,3', 6- and 2,3 ', 7-trisulfonic acids,

l-Amino-4- (4 "-amino-4'-benzoylaminoaniline) -

anthraquinone-2,3-disulfonic acid

and the corresponding

-2,3 ', 5-trisulfonic acid,

l-amino-4- [4 '- (4 "-aininophenylazo) -anilino] -

anthraquinone-2,2 ", 5-trisulfonic acid,

l-amino-4- (4'-amino-3'-carboxyanilino) -

anthraquinone-2,5-disulfonic acid,

1 -Amino-4- (3 '-aminoanilino) -anthraquinone-

2,4 ', 5-trisulfonic acid and

the corresponding 2,4-disulfonic acid,

l-Amino-4- [4 '- (4 "- aimnophenyl) -anUmo] -

anthraquinone-2,3 ", 5-trisulfonic acid,

l-Amino-4- (4'-methylamino) -anilinoanthraquinone-2,3'-disulfonic acid and the corresponding
2,3 ', 5-trisulfonic acid: re,
l-amino-4- (4'-n-butylamino) -anilinoa.nthraquinone-2,3'-disulfonic acid,

1-amino-4- (4'-methy lamino-3 '-carboxyanilino) -anthraquinone-2-sulfonic acid,
l-Amino-4- (3 '- /? - hydroxyäthylamino) -anilinoanthraquinone-2,5-disulfonic acid,
ι ο 1 - (4'-aminoanilino) anthraquinone-2,3-disulfonic acid and
l-Amino-4- (4'-ami: no-2'-methoxyanilino) -anthraquinone-2,3'-disulfonic acid.

Such dye compounds of the anthraquinone series can even be made from anthraquinone compounds, which a halogen atom or a nitro group at the corresponding «position of the anthraquinone nucleus contain bound, or from the leuco derivative of a 1,4-dihydroxy-, -diamino- or -aminohydroxyanthrequinone by reacting the corresponding anthraquinone compound in at least one molar proportion an aliphatic or aromatic diamine can be obtained.

Dye compounds of the phthalocyanine series which can be used in the process according to the invention are preferably metal-containing phthalocyanines, such as copper phthalocyanines, which contain at least one water-solubilizing group, such as a sulfonic acid group, and at least one group of the formula —NHR ₁ or —NHR ₃ , as defined above, contain. The _{—NHR 1} or —NHR ₃ group or groups can be bonded to the benzene rings of the phthalocyanine nucleus directly or via a divalent bridge, for example via a —phenylene— _{, —CO-phenylene—, - SO 2 -phenylene—} -, —NH-phenylene—, —S-phenylene—, - O-phenylene—, - CH ₂ S-phenylene—, -CH ₂ O-phenylene—, —CH ₂ -phenylene -, - SCHj-phenylene—, SO ₂ CH ₂ -phenylene-, - SC ^ NR ^ phenylene-, -CH ₂ -, - SO ₂ NR ₁ - arylene -, - NR ₁ CO - phenylene -, NR ₁ SO ₂ - phenylene -, - SO ₂ O - Phenylene -, -CH ₂ -, -CH ₂ NR ₁ -phenylene-, -CH ₂ NH-CO-phenylene-, - SO ₂ NR _r alkylene -, -CH ₂ -NRr alkylene-, -CONR ₁ phenylene-, - CH ₂ , -CONR ₁ -arylene, —SO ₂ —- or a —CO— bridge. In the abovementioned divalent bridge members, R ₁ denotes hydrogen, alkyl or cycloalkyl, and arylene denotes a bivalent aromatic, optionally e.g. B. halogen, alkyl or alkoxy substituted radical, in which the terminal bonds can be bonded to the same or different nuclei, and alkylene is a divalent aliphatic radical which can include heteroatoms, such as nitrogen, in the atomic chain, for example the radical -CH ₂ CH ₂ -NH-CH ₂ CH ₂ -.

As examples of such divalent aromatic radicals denoted by aiylene are mentioned: aromatic nuclei, for example a ben-

zol, naphthalene, acridine and carbazole nuclei, which may carry further substituents, and radicals of the formula

in which the benzene rings can carry further substituents and —D— a bridging group

means, for example

-CH = CH- —NH- —S— - O-
-SO ₂ - -NO = N- -N = N-— NH-CO — NH-CO — NH-

- O — CH ₂ CH ₂ O-
or

N-

-N

—C

r-

As specific examples of the phthalocyanine series dye compounds used in the invention Methods that can be used are: copper phthalocyanine-4-N- (4-amino-3-sulfophenyl) -sulfonamide-4 ', 4 ", 4"' - trisulfonic acid, Cobalt phthalocyanine 4,4-di-N- (4'-amino-4'-sulfophenyl) carbonamide - 4 ", 4 '" - dicarboxylic acid and copper 4- (4'-amino-3'-sulfobenzoyl) -phthalocyanine.

Mixtures of aminophthalocyanines can also be used. For example, a Mixture of approximately equal parts of copper phthalocyanine - N - (4 - amino - 3 - sulfophenyl) - sulfonamide trisulfonic acid and copper phthalocyanide di-N- (4-amino-3-sulfophenyl) sulfonamide disulfonic acid be used.

The aminophthalocyanines containing a sulfonic acid can be obtained either by sulfonation of known phthalocyanines containing primary or secondary amino groups or by synthesis from mixtures of phthalic acid derivatives and sulfonated phthalic acid derivatives. The sulfonating agent used is, for example, oleum, ζ. B. a 20% solution of sulfur trioxide in sulfuric acid. Furthermore, they can be obtained by jointly heating suitable derivatives of sulfonated phthalic acid and substituted phthalic acids by the generally known methods, for example by jointly heating a mixture of 4-sulfophthalic anhydride and 4-p-nitrobenzoylphthalic anhydride, urea, copper (H) chloride and ammonium molybdate in o-dichlorobenzene at about 15O ⁰ C. also, by sulfonation of the corresponding primary and secondary amines or by reacting a primary (or secondary alkyl or N-cycloalkyl) -Nitroanilins with a phthalocyanine containing chloromethyl and sulfonic acid or carboxylic acid groups, Phthalocyanines are produced, which are used as starting materials. Furthermore, such aminophthalocyanines can also by reacting a phthalocyanine containing chlorosulfonyl groups with a monoacetylalkylenediamine or an amino-N-benzylacetamide in the presence of water and handling of the product thus obtained (which contains both Snlfonamid- and sulfonic acid groups) with aqueous alkali to hydrolyze the Acetylamino group are produced or by reacting a phthalocyanine which contains chloromethyl and sulfonic acid or carboxylic acid groups with a monoacetylalkylenediamine and treating the product thus obtained with aqueous alkali to hydrolyze the acetylamino groups. In addition, by direct sulfonation or by joint heating of a mixture of suitable carboxy or sulfophthalic acid derivatives with substituted phthalic acid derivatives, for example by heating the anhydrides with urea and a catalyst, in an organic solvent and reducing the nitrophthalocyanine sulfonic or carboxylic acid or hydrolysis of the resulting Acylaminophthalocyaninesulfonic or carboxylic acid or by reacting a phthalocyanine compound which contains carboxylic acid chloride groups with a diaminobenzenesulfonic or carboxylic acid, an aminobenzenesulfonic acid or an aminobenzoic acid, which also contains a nitro group, and reduction of the nitro compound obtained in this way, or finally by reacting a phthalocyanine compound which has carboxylic acid chloride groups contains, with an N-aminobenzylacetamide and subsequent hydrolysis of the product thus obtained with aqueous alkali.

Nitro-series dye compounds which are used in the process of the invention are preferably those of the formula

NO ₂ -DNQ

where D denotes a naphthalene or benzene nucleus, which can be further substituted, the nitrogen atom N is in the ortho position to the nitro group, Z denotes hydrogen or an optionally substituted hydrocarbon radical and Q denotes hydrogen or an organic radical bonded to the nitrogen through a carbon atom, and in which Q and Z are not both hydrogen and Q can be bonded to Z when Z is a hydrocarbon radical or to D in the ortho position to the nitrogen atom N to form a heterocyclic ring, and which at least one group of the formula —NHR ₁ or —NHR ₃ as defined above.
As particular examples of at least one - NHR ₁ - or - NHR ₃ group-containing dye compounds, which can be used as starting materials in the process according to the invention, the compounds of the following classes may be mentioned:

1. Monoazo compounds of the formula

OH

D ₁ -N = N
HQ ₃ S

NHR

(IV)

wherein D _{1 is} a maximum bicyclic, of azo and -NHR _x - ^DZW · -NHR ₃ groups and the free aryl radical -NHR ₁ - or -NHR ₃ group is preferably at the 6-, 7- or 8-position of the naphthalene nucleus is bonded, and which may contain a sulfonic acid group in the 5- or 6-position of the naphthalene nucleus.

D ₁ can mean a radical of the naphthalene or benzene series which does not contain any azo substituents, for example a stilbene, diphenyl, benzene

NHR

wherein D ₁ denotes an at most bicyclic aryl radical, as described in class 1, and preferably a disulfonaphthyl or stilbene radical and the benzene nucleus can contain further substituents such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups.
4. Mono- or disazo compounds of the formula

HND ₁ -N = NK (VI)

where D _{1 is} an arylene radical, such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series, or preferably an at most bicyclic arylene radical of the benzene or naphthalene series and K is the radical of a naphtholsulfonic acid or the radical of an enolized or enolizable ketomethylene compound (such as an acetoacetarylide or a 5 -Pyrazolone) with the OH group in the ortho position to the azo group. D ₁ preferably denotes a radical from the benzene series which contains a sulfonic acid group.
5. Mono- or disazo compounds of the formula

D ₁ -N = NK ₂ -NHR

(VII)

thiazoylphenyl or diphenylamine radical. In this class, attention should also be paid to the related dyes in which the —NHR, - or —NHR ₃ group, instead of being bound to the naphthalene nucleus, is bound to a 6-, 7- or 8-position of the naphthalene nucleus Benzoylamino or anilino group is bound.

Particularly valuable starting dyes are those in which D ₁ denotes a sulfonated phenyl or naphthyl radical, in particular those which _{contain an - SO 3} H group in the ortho position to the azo bond; the phenyl radical can be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino, and alkoxy radicals such as methoxy.

2. Disazo compounds of the formula IV, in which D _{1 is} a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the naphthalene nucleus is substituted by the —NHR ₁ or —NHR ₃ group and, if desired, by sulfonic acid, as in class 1 .

3. Monoazo compounds of the formula

7. Anthraquinone compounds of the formula

O NHR

SO ₃ H
O NH-Z-NHR

wherein the anthraquinone nucleus has an additional sulfonic acid group in the 5-, 6-, 7- or 8-position and Z 'denotes a bridge member, which is preferably is a divalent radical of the benzene series, for example a phenylene, diphenylene or 4,4'-stilbene or azobenzene radical. Preferably, Z 'should have a sulfonic acid group for each Benzene ring included.

8. Phthalocyanine compounds of the formula

Pc

(P

(V) (SO ₂ NH- Z'-NHR) "

where Pc is a phthalocyanine nucleus, preferably copper phthalocyanine, ω-ΟΗ and / or - NH ₂ , Z 'is a bridge member, preferably an aliphatic, cycloaliphatic or aromatic bridge, and η and m are each 1, 2 or 3 and can be identical or different, provided that η + m is not greater than 4.
9. Nitro dyes of the formula

V-NH-B-NHR

NO ₂

where D _{1 is} a radical of the _{types defined above for D 1} in classes 1 and 2 and K _{2 is} the radical of an enolizable ketomethylene compound (such as an acetoacetarylide or a 5-pyrazoion) with the OH group in the ortho position to the azo group

6. The metal complex compounds, for example the copper, chromium and cobalt complexes, of the dyes of the formulas IV, VI and VII, in which D ₁ , K and K _{2 have} the meanings given in each case and also a metallizable group (for example a hydroxyl, lower Alkoxy or carboxylic acid group) in ortho position to the azo group m D _{1 is} present in which V and B are monoeyclic aryl nuclei and the nitro group is in V ortho position to the NH group.

As starting dyes, for example, the following are possible in the dye classes mentioned:

In class 1

6-amino-1-hydroxy-2- (2'-sulfophenylazo) -

naphthalene-3-sulfonic acid,

6-methylamino-1-hydroxy-2- (4'-2cetylamino-

2'-sulfophenylazo) -naphthalene-3-sulfonic acid,

8-amino-1-hydroxy-2- (2'-sulfophenylazo) -

naphthalene-3,6-disulfonic acid,

8-amino-1-hydroxy-2- (4'-chloro-2'-sulfophenyl-

azo) -naphthalene-3,5-disulfonic acid,

7-amino-2- (2 ', 5' -disulfophenylazo) -1 -hydroxy-

naphthalene-3-sulfonic acid,

7-methylamino-2- (2'-sulfophenylazo) -l-hydroxynaphthalene-3-sulfonic acid,

7-methylamino-2- (4'-metiioxy-2'-sulfopheEyl-

azo) -l-hydroxynaphthalene-3-sulfonic acid,

8- (3'-aminobenzoylamino) -i-hydroxy-2- (2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

S-amino-l-hydroxy ^ Z'-azonaphthalene-

1 ', 3', 5 ', 6-tetrasulfonic acid,

8-amino-1-hydroxy-2,2 ^f -azonaphthalene-

r, 3,5'-trisulfonic acid,

o-amino-l-hydroxy - ^ '- azonaphthalene-

1 ', 3,5'-UiSuIfOnSaUTe,

6-methylamino-1-hydroxy-2,2'-azonaphthalene-

1 '^, S'-trisulfonic acid,

7-Amino-1-hydroxy ^ '- azonaphthalene-1', 3-disulfonic acid,

8-amino-1-hydroxy-2- (4'-hydroxy-3'-carboxyphenylazo) -naphthalene-3,6-disulfonic acid, 6-Amino-1-hydroxy-2- (4'-hydroxy-3'-carboxyphenylazo) -naphthalene-3,5-disulfonic acid.

In class 2

8-Amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene- 3,6-disulfonic acid,

8-Amino-1-hydroxy-2- [4 '- (4 "-methoxyphenylazo) -2'-carboxyphenylazo] -naphthalene- 3,6-disulfonic acid, 8-amino-1-hydroxy-2- [4 '- (2 "-hydroxy-3", 6 "-disulfo-1" -naphthylazo) -2'-carboxy- phenylazo] -naphthalene-3,6-disulfonic acid, 4,4'-bis (8 "-amino-1" -hydroxy-3 ", 6" -disulfo-2 "-naphthylazo) -3,3'-dimethoxydiphenyl, 6-Amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methylphenylazo] -naphthalene- 3,5-disulfonic acid.

In class 3

2- (4'-Amino-2'-methylphenylazo) -naphthalene-4,8-disulfonic acid,

2- (4'-Amino-2'-acetylaminophenylazo) -naphthalene-5,7-disulfonic acid,

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

4-nitro-4 '- (4 "-amino-2" -methyl-5 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid, 4-Amino-4 '- (4 "-methoxyphenylazo) -stilbene-2,2'-disulfonic acid, 4-Amino-2-methylazobenzene-2 ', 5'-disulfonic acid.

In grade 4

1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (3' '-amino-4 "-sulfophenylazo) -5-pyrazolone, 1- (4'-sulfophenyl) -3-carboxy-4- (4'-amino-3" -sulfophenylazo) -5-pyrazolone, 1- (2'-methyl-5'-sulfophenyl) -3-methyl-4- (4 "-amino-3" -sulfophenylazo) -5-pyrazolone, 1 - (2'-sulfophenyl) -3-methyl-4- (3 "-amino-4" -sulfophenylazo) -5-pyrazolone, 4-Amino-4 '- (3 "-methyl-1" -phenyl-4 "-pyrazole-5' '-onylazo) -stilbene-2,2'-disulfonic acid, 4-amino-4' - (2 "-hydroxy-3", 6 "-disulfo-1 "-naphthylazo) -stilbene-2,2'-disulfonic acid, 8-acetylamino-1-hydroxy-2- (3'-amino-4'-sulfophenylazo) -naphthalene-3,6-disulfonic acid,

7- (3 '-Sulfophenylamino) ^ - 1 -hydroxy-2- (4'-amino-2'-carboxyphenylazo) - naphthalene-3-sulfonic acid, 8-phenylamino-1-hydroxy-2- (4 "-ainino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid, 6-acetylamino-1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -naphthalene-3-sulfonic acid.

In class 5 ^

l- (3'-aminophenyl) -3-methyl-4- <2 ', 5'-disulfophenylazoy-S-pyrazolone,

1 - <3'-aminopnenyl) -3-carboxy-4- {2'-carboxy-4'-sulfophenylazo) -5-pyrazolone, 4-Amino-4 '- [3 "-methyl-4" - {2' ", 5" '- disulfophenylazo) -l "-pyTazol-5" -onyl] -stilbene- Z2'-disulfonic acid.

y ^

sulfophenylazo) -. 2 "-methoxy-5" -methylphenylazo] -5-pyrazolori.

In grade 6

The copper complex of 8-amino-1-hydroxy-2- (2'-hydroxy-5 "-sulfophenylazo) -naphthalene- 3,6-disulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene- 3-sulfonic acid,

the copper complex of 6-amino-l-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene- 3,5-disulfonic acid,

the copper complex of 8-amino-l-hydroxy-2- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) - naphthaIin-3,6-disulfonic acid, the copper complex of 6-methylamino-1-hydroxy-2- (2'-carboxy-5'-sulfophenylazo) - naphthalene-3-sulfonic acid,

the copper complex of 8-amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2'-methoxy-5'-methyl- phenylazo] naphthalene-3,6-disulfonic acid, the copper complex of 6-amino-1-hydroxy-2- [4 '- (2 ", 5' '-disulfophenylazo ^' - methoxy-5'-methylphenylazo] -naphthalene-3,5-disulfone- acid,

the copper complex of l- (3'-amino-4'-sulfophenyl) -3-methyl-4- [4 "- (2 '", 5' "- disulfophenyl- azo) -2 "-methoxy-5" -methylphenylazo] 5-pyrazolone,

the copper complex of 7- (4'-amino-3'-sulfoanilinoH-hydroxy-2- [4 "- (2 '", 5' "- disulfophenyl- azo) -2 "-methoxy-5" -methylphenylazo] -naphthalene-3-sulfonic acid,

the copper complex of 6- (4'-amino-3'-sulfoanilino) -l-hydroxy-2- (2 "-carboxyphenylazo) - naphthalene-3-sulfonic acid,

the 1,2-chromium complex of 7-amino-6'-nitro, 2'-dihydroxy-2, l'-azonaphthalene-3,4'-disulfone acid,

the 1,2-chromium complex of 6-amino-1-hydroxy-2- (2'-carboxyphenylazo) -naphthalene-3-sulfone- acid,

the 1,2-chromium complex of 8-amino-l-hydroxy-2- (4'-nitro-2'-hydroxyphenylazo) -naphthalene- 3,6-disulfonic acid,

the 1,2-cobalt complex of 6- (4'-amino-3'-su! foanilino) -1 -hydroxy-2- (5 "-chlor-2" -hydroxyphenylazo) -naphthalene-3-sulfonic acid, the 1,2-chromium complex of l- (3'-amino-4'-sulfophenyl) -3-methyl-4- (2 "-hydroxy-4" -sulfo- 1 "-naphthylazo) -5-pyrazolone, the 1,2-chromium complex of 7- {4'-sulfoanilino) -l-hydroxy-2- (4" -aniino-2 "-carboxyphenylazo) - naphthalene-3-sulfonic acid,

the 1,2-chromium complex of l- (3'-aminophenyl) -3-methyl-4- {4 "-nitro-2" -carboxyphenylazo) - 5-pyrazolone.

In grade 7

1-Amino-4- (3 '-amino ^' - sulfoanilino) -anthraquinone-2-sulfonic acid,

l-amino-4- (4'-amino-3 '-sulfoanilino) -anthraquinone-2,5-disulfonic acid, l-Amino-4- [4 '- (4 "-amino-3'-sulfophenyl) -anilino] -anthraquinone-2,5-disulfonic acid, l-Amino-4-r4'-i4 "-amino-2" -sulfoDhenvlazoV ·

anilino] anthraquinone-2,5-disulfonic acid,
l-Amino-4- (4'-methylamino-3-sulfoanilino) -anthraquinone-2-sulfonic acid.

In K'asseS

3- (3'-Amino-4'-sulfophenyl) -sulfamyl copper, r-

phthalocyanine tri-3-sulfonic acid,

Di-4- (3 '-amino ^' - sulfopheny 1) -sulfamy Ik upfer-

phthalocyanine-di-4-sulfonic acid,

3- (3'-AminophenyIsulfamyl) -3-sulfamyl copper

phthalocyanine-di-3-sulfonic acid.

In grade 9

4-Amino-2'-nitro-diphenylamine-3,4 ^r -disulfonic acid.

It should be noted that one is Fsserrtactive dyes that two over the remainder of an aromatic egg or aliphatic diamine linked together Contains halotriazine residues through condensation of 2 moles of dihalotriazinyl dye with 1 mo Can produce diamine. This procedure is also used for the dyes of the above-mentioned Austria! See patents 2,98,630, 298,631 and 2,98,61 applicable since the hydrazine is in the manner of a diamine

ίο responds. In the production of the inventive i However, dyes must have two halotriazines on one and the same nitrogen atom as the condensate primary amine used react. However, this is no longer possible if a dye residue is bound to the triazine ring. The reaction

namely does not lead to the desired product of the formula

Cl

As with aniline above, this reaction is unlikely to work with other primary amines, e.g. B. methylamine, Ethylamine or ammonia feasible. The dyes according to the invention were thus able to conventional route can not be obtained, but only from the bis (dihalotriazinyl) amines. Your manufacture became possible only after one had learned bis (dihalogentriazinyl) amines of the formula (4) (cf. Journal of the Heterocyclic Chem., Vol.7, No. 3, pp. 519-525 [1970]). Since you The dyes according to the application were only obtained via these intermediate compounds and were produced not readily available to the person skilled in the art.

The new dyes according to the invention are suitable for dyeing and printing a wide variety of materials, such as B. silk, leather, wool, blended fabrics containing wool, synthetic fibers made from super polyamides, Super-polyurethanes, polyhydroxylated materials, such as. B. cellulosic materials fibrous Structure such as linen, pulp, regenerated cellulose, cotton and the like. The dyes are preferably used for dyeing and printing cellulose materials, especially cotton, z. B. after Ausziehverfallren from long liquor, from alkaline, possibly very salty aqueous bath and especially after the padding dye process, after which the goods with aqueous and optionally also salt-containing dye solution is impregnated, and the dyes after eini Alkali treatment or in the presence of alkali, optionally fixed under the action of heat used.

However, the new dyes of the invention are particularly excellent for use in dyeing and printing cotton and regenerated cellulose suitable.

The dyes are characterized by a high reactivity, so that dyeings at lower temperatures or with a shorter fixing time than are usually used for comparable dyes can be. The new dyes achieve a high degree of fixation and good binding stability between dye and fiber. The dyeings obtained show good wet fastness properties, such as. B. washing, Full or water fastness and also, depending on the structure of the chromogen, easy washability Recommended to improve the wet fastness

the dyeings and prints obtained are thoroughly rinsed with cold and hot water, optionally with the addition of a dispersing component and the diffusion of the non-fixed components subject to promotional agent.

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages are percentages by weight, and the temperature Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same like between grams and cubic centimeters.

example 1

21.8 parts of the dye of the formula
SO ₃ H

HO ₃ S

SO ₃ H NHCONH ₂

709 685/178

21 02 17th 5 21 7th 18th 1 11; are in 250 parts of water at room temperature dissolved neutrally with sodium hydroxide solution and with 13.1 parts anhydrous sodium acetaf added. Under vigorous IO 2- (4'-amino-2'-acetylamino- golden yellow Stirring is then added to the dye solution phenylazo) -naphthalene- Solution of 7.78 parts of N, N-bis-i4,6-dichloro-s-tri- 5,7-disulfonic acid azinyl- (2)) - aniline in 40 parts of acetone. 3 2- {4'-aminophenylazo) -
naphtha! in ~ 4,6,8-sulfonic acid yellow \ After acylation of the amino group has taken place , 5 2- (4'-amino-2'-methylphenyl- golden yellow! the dye is salted out with potassium chloride, removed
trated and dried in vacuo at 50 to 60 °.
The dye thus obtained dyes cotton in gold azo) -naphthalene-3,6,8-trisulfone- yellow tones. 4th acid Similar dyes are obtained when for the 5 4-amino-4 '- (2 "-hydroxy-
3 ", 6" -disulfonaphthy 1- orange \ Acylation of the above aminoazo dye in place of 20th azo- [l "]) - stilbene-2,2'-di- of 7.78 parts of N, N-bis- (4,6-dichloro-s-triazinyl- (2)) -
corresponding amounts of aniline sulfonic acid b) N, N-bis- (4,6-dichloro-s-triazinyl- (2)) -2'-chloro- ό 4-amino-4 '- (4 "-methoxy- reddish yellow \ aniline. phenylazo) stilbene-2,2'-di-
sulfonic acid c) N, N-bis (4,6-dichloro-s-triazinyl- (2)) - 2 ^r -methyl- 25th 4-amino-4 '- (1 ", 2" -naph- yellow aniline,
d) N, N-bis (4,6-dichloro-s-triazinyl- (2)> -
2 ', 4'-dimethylaniline,
e) N, N-bis (4,6-dichloro-s-triazinyl- (2)) - 7th ethylene) -triazole-stilbene- 2 ', 6'-dimethylaniIine, 2,2'-5 ", 7" -tetrasulfonic acid 0 N, N-bis (4,6-dichloro-s-triazinyl- (2)) ethylamine, 3 ° 8th l- [naphthyl- (2 ') - azo] - brown orange g) N, N-bis (4,6-dichloro-s-triazinyl- (2)) methylamine 4- (4 '' -aminophenylazo) -
naphthalene-4 ', 6', 7,8 '-tetra- or
h) N, N-bis [4,6-dichloro-s-triazinyl- (2)] amine sulfonic acid be used. 9 4-nitro-4 '- (4 "-methylamino- yellow (Examples b) to h) were submitted later) .15 phenylazo) -stilbene- Example 2 2,2'-disulfonic acid 17.52 parts of the dye of the formula 10 4-amino-2'-nitrodiphenyi- yellow amine-3,4'-disulfonic acid NH ₂ 1- (2 ', 5'-DiChIoM ^ SuIfO- golden yellow I ^ 40 11th pheny l) -3 -methyl-4- (4 "-amino- <ζ ^> N = N ^ y NH 2 "-sulfophenylazo) -5-pyr- \ = / \ = / 12th azolone / \ QII / \ ν SO ₃ H l- (2 ', 5'-dichloro-4'-sulfo- greenish I. 45 phenyl) -3-methyl-4- (5 "-amino- yellow SO ₃ H 2 "-sulfophenylazo) -5-pyr- 13th azolone are in 600 parts of water at room temperature 50 l- [4 ', 8'-disulfonaphthyl- (2')] -
3-methyl-4- (5 "-amino- yellow dissolved neutrally and according to the information in Example 1
with 7.78 parts of N, N-bis- (4,6-dichloro-s-triazinyl- (2)) - 2 "-sulfophenylazo) -5-pyr- aniline implemented.
After the acylation has taken place, the precipitated one becomes Dye is filtered off and in a vacuum at 50 to 60 " 55 14th 1 - (4'-sulfophenyl) -3-carboxy-
4- (5 "-amino-2" -sulfophenyI-
azo) -5-pyrazolone yellow dried. The dye thus obtained stains the tree
wool in blue-tinged red tones. 1 - (3'-aminophenyl) -3-methyl- yellow Example 3 (submitted later) 4- (2 ", 5" -disulfopheny lazo) - By implementing 2 equivalents of the in Ko 60 15th 5-pyrazolone lonne I of the following table listed amino- 16 l-amino-4- (4'-aminoanilino) - greenish group-containing dyes with 1 equivalent of N, N-bis- anthraquinone-2,3-disulfonic acid blue [4,6-dichloro-s-triazinyl- (2)] - aniline is obtained in color l-amino-4- (3'-aminoanilino) -
anthraquinone-2,4'-disulfone- reddish blue substances that cotton in the specified in column II
color the same nuances. 17th acid fts l-amino-4- (3'-amino- reddish blue I Il 18th 2 ', 4', 6'-trimethylanilino) - anthraquinone-2,5 -disulfone- 1 4-Amino-2-methyl-5-methoxy · · yellow 19th acid azobenzene-2 ', 5'-disulfonic acid 1-amino-4- (4'-amino- blue 2 2- (4'-amino-2'-methylphenyl yellow 2 ', 3', 5 ', 6'-tetramethylanilino) - azo) -naphthalene-4,8-disulfone- anthraquinone-26-disulfonic acid acid 20th

Continuation

6-amino-1-hydroxy-. 2- (2'-sulfophenyla2O) 'naphthalene-3-sulfonic acid

6-methylamino-1-hydroxy-2- (4'-methoxy-2'-sulfophenylazo) -naphthalene-3-sulfonic acid Acid 7-amino-2- (2 ', 5'-disulfophenylazo) -1 -hydroxynaphtha! in-3-sulfonic acid 8-amino-1-hydroxy-2- (2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid 8-Amino-1-hydroxy-2- (4'-ynethyl-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid

8-amino-1-hydroxy-2,2'-azonaphthalene- 1 ', 3,5', 6-tetrasulfonic acid 1-hydroxy-2- (2 \ 5'-disulfophenylazo) -8- (3 "-aminobenzoylamino) -naphthalene-3,5-disulfonic acid

8-acetylamino-1-hydroxy-2- (5'-amino-2'-sulfopheny! - azo) naphthalene-3,6-disulfonic acid

2-Amino-8-hydroxyl- (4'-amino-2-sulfophenylazo) -naphthalene-3,6-disulfonic acid

2-Hydroxy-1- (4'-amino-2'-sulfophenylazo) -naphthalene-6,8-disulfonic acid 1-Hydroxy-2- (4'-amino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid c 1-Hydroxy-2- (5'-amino-4'-methyl-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid 1,8-Dihydroxy-2- (5'-amino-2'-sulfophenylazo) -naphthalene-3,6-disulfonic acid 8-chloro-1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -naphthalene -3,6-disulfonic acid

8-phenylamino-1-hydroxy-2- (4'-amino-2'-sulfophenyl-azo) -naphthalene-3,6-disulfonic acid

7- (3'-sulfophenylamino) -1-hydroxy-2- (4 "-amino-2", 5 "-disulfophenylazo) - naphthalene-3-sulfonic acid Copper complex compound from 8-amino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenylazo) -naphthalene-3,6-disulfonic acid

Il

orange

Scarlet fever

Red

ίο 39

blue braided- ' ⁵ 40 red

42

bluish red

bluish red scarlet fever

red bluish red

Red

4 ° red

Red

bluish red

Scarlet fever

violet

Brown

violet

Copper complex compound blue from 8-amino-l-hydroxy-2- (l '-hydroxy-4', 8'-disulfonaphthyl- [2 ']) -naphthalene-3,6-disulfonic acid

Blue copper complex compound from 8-amino-1-hydroxy-2- (2'-hydroxy-5'-amino-3'-sulfophenylazo) -naphthalene-5,7-disulfonic acid

Copper complex compound blue from 8-amino-1-hydroxy-2- [2'-hydroxy-6'-aiKinonaphthyl- (l ') -azo] -naphthalene-5,7,4'-trisulfonic acid

Ruby copper complex compound from 6-methylamino-1-hydroxy-2- (2'-hydroxy-5'-sulfophenyl azo) -naphthalene-3-sulfonic acid

Violet copper complex compound from 8-amino-1-hydroxy-2- (2'-hydroxy-3'-chloro-5'-sulfophenylazo) -naphthalene-3,6-disulfonic acid

Violet copper complex compound from 6- (4'-Amino-3'-sulfophenylamino) -1 -hydroxy-2- (2 "-hydroxy-3", 5 "-disulfophenylazo) -naphthalene-3-sulfonic acid

Copper complex compound blue from 8-amino-1-hydroxy-2 (2'-hydroxy-3'-amino-5'-sulfophenylazo) -naphthalene-5,7-disulfonic acid

Copper complex of blue

2- (2 ', 8-dihydroxy-3 \ 6'-disulfonaphthyl-l-azo) -l-hydroxy- 6-aminonaphthalene-4,8-disulfonic acid

2- (2 ', 5'-Disulfo-phenylazo) - bluish-7- (2 "-sulfo-5' '-aminopheny 1- green azo) -1 -amino-8-hydroxynaphthalene-3,6-disulfonic acid

Copper-N- (2-hydroxypheny 1- blue 3,5-disulfonic acid-) N '- (2'-carboxy-4'-aminophenyl) -ms-2 "-sulfophenyl-formazan

1: 2 chromium complex compound from 6-amino-1-hydroxy-2- (2'-carboxyphenylazo) -naphthalene-3-sulfonic acid

1: 2 chromium complex compound dark blue from 8-amino-1-hydroxy-2 (2'-hydroxy-5'-nitrophenyl- azo) naphthalene-3,6-disulfonic acid

continuation

50 1: 2 cobalt complex connec- korintl ·
formation from 8-amino-1-hydroxy-2- {2'-hydroxy-5'-nitrophenylazo) -naphthalene-3,6-disulfone-

acid

51 Mono-p-aminophenylamide turquoise
the copper phthalocyanine

3,3 ', 3 ", 3"' -Tetrasulfonic acid

52 Kupfeφh ^ halocyanintri- turquoise
sulfonic acid-sulfonic acid- (3'-amino) -phenylamide

53 Kupfeφhthalocyanintri- turquoise
sulfonic acid-sulfonic acid- (4'-amino-3'-sulfo) -phenyIamide

54 copper phthalocyanine disulfone turquoise
acid disulfonic acid (4'-amino-3'-sulfo) -phenylamide

55 Kupfeφhthalocyanintrisulfonsä ure-sulfonic acid- (2'-amino) -ethylamide

turquoise

ίο Example 4 (submitted later)

7.52 parts of m-phenylenediamine sulfonic acid are used in 250 parts of water at room temperature dissolved neutrally with sodium hydroxide solution and 13.1 parts of anhydrous Sodium acetate added. A solution of 7.78 parts is added to the resulting solution with vigorous stirring N, N-bis (4,6-dichloro-s-triazinyl) - (2)) - aniline in 40 parts of acetone and allowed to react for about 24 hours. After a clear filtration, the reaction product is separated off by adding 20% by volume of potassium chloride and dried in vacuo at 50 °.

13.8 parts of the thus obtained diamine of the presumed formula

are dissolved in 400 parts of water with 20 parts of 2N sodium nitrite solution and 10 parts of 10N hydrochloric acid added, whereupon the tetrazo compound partially precipitates crystalline.

The resulting suspension of the tetrazo compound is then poured into a neutral solution of 16.92 parts of 1-hydroxy-8-benzoylaminonaphthalene-3,6-disulfonic acid in 300 parts of water, which also contains 20 parts of sodium bicarbonate. After finished Coupling, the dye is salted out with 15 vol .-% sodium chloride, filtered off and in a vacuum 60 ° dried.

The dye thus obtained dyes cotton in blue-tinged red shades.

If the tetrazo compound described above is combined with the coupling components of column I. of the following table, dyes are obtained, the cotton in the nuances indicated in column II to dye.

Ii

1 - (2 ', 5'-dichloro-4'-sulfo- green-tinged-

phenyl) -3-methyl-5-pyrazolone yellow

l-EthyM-methyl-o-hydroxy- strong green-

3-sulfomethyl-pyridone- (2) pungent yellow

6-ureido-1-hydroxy-naphtha- orange
lin-3-sulfonic acid

1 - (4'-sulfophenyl) -3-carboxy- greenish-

5-pyrazolone yellow

Barbituric acid greenish yellow

6 8-acetylamino-1-hydroxy red
naphthalene-3,5-disulfonic acid

7 2-hydroxynaphthalene orange
3,6-disulfonic acid

8 2-hydroxynaphthalene orange
6,8-disulfonic acid

9 1-Ethyl ^ -methyl-o-hydroxy-green-tinged pyridone- (2) -3-carboxamide yellow

10 1-hydroxynaphthalene orange
3,6-disulfonic acid

11 1-hydroxynaphthalene red
4,8-disulfonic acid

12 1- (4 ', 6', 8'-trisulfo-yellow
naphthyl- [2 ']) -3-methyl-5-pyrazolone

13 Acetoacetanilide-4-sulfonic acid with a green tinge-

yellow

14 1 -Ethyl ^ methyl-ö-hydroxy- green-tinged pyridone- (2) yellow

Example 5 (submitted later)

12.76 parts of 1-hydroxy-S-amino-naphthalene-S.ö-disulfonic acid are dissolved in 250 parts of water at room temperature with sodium hydroxide solution, and ¹ 3.1 parts of anhydrous sodium acetate are added. A solution of 7.78 parts of N, N-bis (4,6-dichloi-s-triazinyl) - (2)) - aniline in 40 parts of acetone is added with vigorous stirring and the mixture is left to react for about 24 hours.

For a clear solution of the reactive The coupling component is then added in the customary manner from 6.92 parts of orthanilic acid Diazo component.

After the coupling is complete, the resulting dye is treated with a mixture of Kochsair, and Potassium chloride isolated, filtered off and dried in vacuo at 50 to 60 °.

The dye obtained in this way dyes cotton in shades of blue-tinged red.

Example 6 (Nachgercicht)

A neutral solution of 10.62 parts of 1-amino-4 - (3 '- amino - 2', 4 ', 6' - trimethyianilino) - anthraquinone-2,5'-disulfonic acid 13 parts of anhydrous sodium acetate are added and an acetone is added Solution of 7.78 parts of N.N-Bis-L ^ o-dichloro-s-triazinyl- (2)] - aniline. After the condensation has taken place, a neutral solution of 10.9 parts of 2- (4'-amino-2'-ureidophenylazo) naphthalene-3,6,8-trisulfonic acid is added to the reaction mixture and lets react for another 24 hours.

In this way, a dye is obtained which dyes cotton in green shades.

Dyeing instruction I

2 parts of the dye obtained in Example 1 are added with 0.5 parts of m-nitrobenzenesulfonic acid Sodium dissolved in 100 parts of water. A cotton fabric is made with the solution obtained impregnated so that it increases by 75% of its weight, and then dried.

The fabric is then impregnated with a 20 ^{° C} solution containing 5 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezed to a 75% weight gain, the dyeing is dampened for 20 to 30 seconds at 100 to 10Γ, rinsed and soaped for a quarter of an hour in a 0.3% boiling solution of an ion-free wash nut ice, rinses and dries.

Printing specification

2 parts of the dye prepared according to Example 2 are added, with rapid stirring, to 100 parts of a stock thickener containing 45 parts of 5% sodium alginate thickener, 32 parts of water and 20 parts

ίο urea, 1 part sodium m-nitrobenzenesulfonate and 2 parts of sodium bicarbonate, sprinkled.

The printing paste thus obtained is used to print a cotton fabric on a roller printing machine and attenuates the obtained printed

is fabric for 1 to 2 minutes at 100 ° in saturated steam. The printed fabric is then rinsed thoroughly in cold and hot water, whereby the Non-chemically fixed parts can be easily removed from the fiber and then dried.

Color regulation II

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.

The solution is added to 3900 parts of cold water, 80 parts of sodium chloride are added and 100 parts are added a cotton fabric in this dye bath.

The temperature is increased to 90 ° in 45 minutes, 40 parts of trisodium phosphate after 30 minutes and another 80 parts of sodium chloride are added. The temperature is held for 30 minutes to 90 °, then rinsed and soaped the dye for 15 minutes in a 0.3% boiling solution an ion-free detergent, rinses and dries.

The result is a color that is washable and lightfast.
There were also a number of dyes of the Austrian patent 298 631 of the general formula type (A)

N N

F-NH-C C -C -N N-C C -C -NH-F

! ! III! Il

NN CH ₃ CH ₃ NN

Λ / N /

c c

Cl

CI

and the corresponding dyes according to the invention of the general formula type (B)

F-NH-C

I Il

N N

Cl

C-NH-F

CH ₃ NN

Cl

produced which each had the same chromophoric residues F. The chromophoric residues F had the following Formulas:

25th

Nuance rest l ^: Nuance rest V

SO ₃ H

_n . - (\ N = N-- ζ Λ- CH ₂ -SO ₃ H .....,. ""

Citron (I Jl I Turquoise CuPc-

. νΛ,

SO ₃ H HO I CH ₂ CH ₃

HO ₃ S

Orange

SO ₃ H

OH

N = N

SO ₃ H

HO ₃ S

SO ₃ H

violet

SO ₃ H

Navy blue

SO ₃ H

HO ₃ SO Cu

- SO ₂ NH ₂
SO ₂ NH

Royal blue

HO ₃ S

SO ₃ H

NH ₂ CO I

Y V-SO ₃ H

SO ₃ H

CO

/ Vc

CH ₃ SO ₃ H NH - <^ ~ y ^ CH ₃ CH ₃

Pc means the halocyanine residue.

Pieces of cotton sateen fabric were printed in a known manner with printing pastes which contained the abovementioned dyes of the Austrian patent specification 2 98 631 of the formula (A) or the dyes of the formula (B) according to the invention. The prints were dried and 0.5, 1, 2, 4 and 8 minutes (Dämpfstufen a to e) attenuated at about 10O ⁰ C. This was followed by rinsing, soaping and drying.

The concentration of the dyes in the printing pastes was 50 g of dye per kg of printing paste. the The printing pastes used consisted of dye and stem thickener, the latter being composed as follows was:

Sodium alginate thickener 5% .... 400 g

Urea 100 g

Reserve salt G 10 g

Sodium bicarbonate 20 g

Water 470 g

The printing pastes consisted of 50 g of dye and 950 g of the stock thickening described above.

The shelf life of the printing pastes used in the comparison tests is sufficient when used a bicarbonate as alkali meets the requirements of practice.

A comparison of the print samples showed that those obtained with the dyes of the present application Prints in citron, yellow, orange, purple, navy blue, royal blue and turquoise at each steam level have a greater color strength than the corresponding with the dyes according to the known Prior art prints obtained. The same applies to the red on attenuation levels a and b the color strengths of the comparison prints are roughly the same for the other attenuation levels (c to e).

The pressure tests also showed in particular that

SS the from one damping level to the next observable increase in color strength in those obtained with the dyes of the present application Printing is greater in all nuances than with the dyes according to the known state prints obtained by the technique. In contrast to the comparison samples of the dyes according to the known Prior art is obtained with those with the dyes of the present application Printing in all the nuances already on the third

6s damping level almost reached the maximum color strength. The dyes of the present application are thus drawn onto the fiber more quickly and in greater quantities than the corresponding comparative dyes and show

compared to the closest comparable dyes of the Austrian patent 2 98 631 in print obvious advantage.

There were also dyeings on mercerized cotton sateen using the cold pad process 4, 8 and 24 hours (samples a to c) residence time at 25 ° C. A comparison of the dye samples showed that the dyes of the present application in citron, yellow, orange, purple, royal blue and Turquoise with all three dwell times dyeings with a significantly greater color strength than the dyes provide the known state of the art. In the red, the color strength was the same for both comparison dyes, however, there was a clear difference in nuances, which makes it difficult to compare the color strengths. The only exception was the navy blue, the dye of the present application somewhat weaker at 4 and 8 hour dwell times

Colorings gave as the known dye. After a residence time of 24 hours, there were stains both dyes have about the same color strengths.

The dyes of the present application already gave in citron, yellow, orange, red and violet with the shortest dwell time of 4 hours, colorations with almost the maximum color strength. The is not the case with any of the prior art dyes. In orange and royal blue became unusable with the dyes according to the known prior art at all three residence times Colorations obtained, these dyes are therefore not suitable for the application process mentioned suitable.

In general, the dyes of the present application exhibit an overt cold pad process Advantage over the closest comparable known dyes.

Claims (1)

21 02
1 217
2; 1. Dyes of the formula N N \ ι Ii ι i
NNR ₃ I. I.
R ₂ I Il
N N I. Patent claims: y \ \ / I Λ / F ₁ -NC C-
Il 11 -NC C — N — F, (1)
II Il I i ι i
X ₂ I. C.
I. Reactive dyes that contain two via a diamine I I Il
R ₁ NN I.
R ₂ if necessary by cyan, chlorine, bromine, hydroxyl \ I:
egg Containing triazine residues connected to one another are known. \ / or alkoxy with 1 to 3 carbon atoms sub- { 6. The method according to claim 4, characterized ge In these, there is always a between the reactive residues C. substituted alkyl radical with 1 to 3 carbon atoms, an I. indicates that there are compounds of the formula more or less large pontic present, wherein F ₁ and F ₂ each represent a residue of an organic Denotes phenyl radical or a benzyl radical. ' .15 (4) wherein X ₁ , X ₂ , X ₃ and X ₄ are chlorine atoms and and there are both reactive residues on different stick Dyestuff, R ₁ and R ₃ independently of one another 2. Dyestuffs according to Claim 1 of the formula R _{2 is} hydrogen or an alkyl radical with 1 to: atoms bound. Hydrogen, methyl or ethyl, X ₁ and X ₂ each one N 5 carbon atoms means with amino groups From Austrian patents 2 98 630, Halogen atom and R ₂ hydrogen, an alkyl radical F ₁ -NH-C C-N-C C-NH-F ₂ (3)
I Μ I I Il containing dyes of the formulas F ₁ —NH ₂ and 2 98 631 and 2 98 632, especially the Austrian with 1 to 5 carbon atoms or an opposing 20th I Il
N N F ₂ —NH ₂ , in which F ₁ and F _{2 are} identical dye radicals patent 2,98631, are also dyes N \ / 40 mean., implements. known that contain a bis-triazinyl hydrazine radical. C.
I. 7. Use of dyes according to the It has now surprisingly been found that I.
Cl Claims 1 to 3 or according to the claims one can produce reactive dyes, the two over wherein F ₁ and F _{2 represent the} same dye radicals Chen 4 to 6 available dyes for dyeing a single amino group linked together and R _{2 is} phenyl. and printing on cotton and regenerated Contain reactive radicals, so that both reactive radicals with 3. Dyestuffs according to Claim 1, of the formula (3), 45 Cellulose. linked to the same nitrogen atom. wherein F ₁ and F _{2 represent the} same dye radicals The present invention now relates to dyes, and R _{2 is} hydrogen or an alkyl radical with 1 to the two via the nitrogen atom of an amino group 5 carbon atoms. 5 ° interconnected fiber-reactive triazine residues 4. Process for the preparation of dyes contain, namely dyes of the form! of formula (1) according to claim 1, characterized ge indicates that compounds of the formula N N 55 X ₄ -CC-N-C CX ₃
I Il I I Il I Il I I Il
NNR ₂ NN (4) \ / \ / C C
I I 6o I I
X ₁ χ, wherein X ₁ , X ₂ , X ₃ and X _{4 represent} halogen atoms and R _{2 has} the meaning given under formula (1) <> 5 has, with dyes of the formula F ₁ - N (R ₁ ) H and F ₂ -N (R ₃ ) H, where F ₁ , F ₂ , R ₁ and R _{3 are} the under Formula (1) have given meanings, too Dyes of the formula (1) condensed, the The order of the partial reactions is different can be. 5. The method according to claim 4, characterized ge indicates that there are compounds of the formula (4) wherein X ₁ , X ₂ , X ₃ and X ₄ are chlorine atoms and R ₂ denotes a phenyl radical, with amino groups containing dyes of the formulas F ₁ - NH ₂ and F ₂ -NH ₂ , in which F ₁ and F _{2 are} identical dye radicals , 'VvIe ¹ UtCn, ufTiSvt / t.