DE4005929A1 - Reactive dyestuff cpds. with chloro fluoro pyrimidinyl amino gp. - Google Patents

Abstract

Dyestuffs (I) contg. a 5-chloro-6-fluoro pyrimidin-4-yl amino gp. and one or two reactive heterocyclyl-amino gps. are of formula (I). In (I) FB is the radical of a dyestuff of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethin, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series, B and B' are a direct bond or a bridge to a ring C atom of an aromatic-carbocyclic or a ring C or N atom of an aromatic-heterocyclic ring in FB, esp. B is B' is a direct bond, X is the 5-chloro-6-fluoropyrimidin-4-yl gp., Z is a heterocyclic fibre-reactive gp., R and R' are H or (substd.) 1-6C alkyl. Dyestuff 4-(4-p-sulphoanilin-achloro-s-triazin-2-ylamino) benzenesulphonic acid (2-azo-2) 8-(5-chloro-6-fluoropyrimidin 4-ylamino)-1-naphthol -3,6-disulphonic acid is excluded. (I) can be prepd. by reacting the corresp. di- or tri-amino dyestuff cpd. (of formula (I) with X = Z is H) or their precursors with 1-2 mole 4-halo-5-chloro-6-fluoropyrimidine and opt. 1-2 mole Z-Hal (Hal is Cl, Br or F) and, if necessary, converting the precursors to (I).

Description

The invention relates to reactive dyes formula

in particular dyes of the formula

wherein
FB = the rest of a dye or the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl , Naphthoquinone, pyrenequinone or perylene tetracarbimide series,
B or B ′ = direct bond or bridge member to a ring C atom of an aromatic-carbocyclic ring or to a ring C or N atom of an aromatic-heterocyclic ring in FB,

Z = heterocyclic fiber-active radical,
R, R ′ = H, optionally substituted C₁-C₆-alkyl (preferred substituents: halogen, OH, COOH, SO₃H, OSO₃H),
with the exception of the dye of the formula

Suitable bridge members B and B ', the same or different can be, for example

where the asterisk marks the link with FB,
R has the meaning given above,
Alk optionally heteroatoms or heteroatoms such as groups containing N, O or S, interrupted, straight-chain or branched C₁-C₆alkylene,
Ar optionally substituted phenylene or naphthylene or radical of a diphenyl or stilbene,

where Alk or Ar may contain further substituents, for example F, Cl, Br, C₁-C₄-alkyl, C₁-C₄-alkoxy, carboxy or sulfo,
LF, Cl, Br, optionally substituted amino, OH, C₁-C₄-alkoxy, optionally substituted phenoxy, C₁-C₄-alkylthio.

Suitable fiber reactive Z, d. H. those with the OH or NH groups of the fiber under dyeing conditions react to form covalent bonds especially those that have at least one reactive Substituents on a 5- or 6-membered aromatic-heterocyclic Ring bound included, for example Monoazine, diazine or triazine ring, especially one Pyridine, pyrimidine, pyridazine, pyrazine, thiazine, Oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system, which one or more fused aromatic-carbocyclic Has rings, for example a quinoline, phthalazine, Quinoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system.

Among the reactive substituents on the heterocycle are to mention for example halogen (Cl, Br or F), Ammonium including hydrazinium, pyridinium, picolinium, Carboxypyridinium, sulfonium, sulfonyl, azido (N₃), Rhodanido, thiol ether, oxiether, sulfinic acid and Sulfonic acid.  

The following can be mentioned in detail, for example:

2,4-difluorotriazinyl-6-, 2,4-dichlorotriazinyl-6-, monohalogen-sym.-triazinyl residues, especially monochloro and Monofluorotriazinyl radicals which are substituted by alkyl, aryl, amino, Monoalkylamino, dialkylamino, aralkylamino, arylamino, Morpholino, piperidino, pyrrolidino, piperazino, alkoxy, Aryloxy, alkylthio, arylthio are substituted, wherein Alkyl, preferably optionally substituted C₁-C₄ alkyl, Aralkyl preferably optionally substituted Phenyl-C₁-C₄-alkyl and aryl preferably optionally is substituted phenyl or naphthyl and preferred substituents for alkyl halogen, hydroxy, Cyan, vinylsulfonyl, substituted alkylsulfonyl, Dialkylamino, morpholino, C₁-C₄ alkoxy, vinylsulfonyl-C₂-C₄ alkoxy, substituted alkylsulfonyl-C₂-C₄-alkoxy, Carboxy, sulfo or sulfato are for Phenyl and naphthyl, sulfo, C₁-C₄-alkyl, C₁-C₄-alkoxy, Carboxy, halogen, acylamino, vinylsulfonyl, substituted Alkylsulfonyl, hydroxy, amino.

The following residues are mentioned in detail:

2-amino-4-fluorotriazinyl-6, 2-methylamino-4-fluorotriazinyl-6, 2-ethylamino-4-fluorotriazinyl-6, 2-isopropylamino-4-fluorotriazinyl-6, 2-dimethylamino-4-fluorotriazinyl-6, 2-diethylamino-4-fluorotriazinyl-6, 2-β-methoxy-ethylamino-4-fluoro-triazinyl-6, 2-β-hydroxyethylamino-4-fluoro-triazinyl-6, 2-di- (β-hydroxyethylamino) -4-fluoro-triazinyl-6, 2-β-sulfoethylamino-4-fluoro-triazinyl-6,  2-β-sulfoethyl-methylamino-4-fluoro-triazinyl-6, 2-carboxymethylamino-4-fluoro-triazinyl-6, 2-di- (carboxymethylamino) -4-fluoro-triazinyl-6, 2-sulfomethyl-methylamino-4-fluoro-triazinyl-6, 2-β-cyanoethylamino-4-fluoro-triazinyl-6, 2-benzylamino-4-fluoro-triazinyl-6, 2-β-phenylethylamino-4-fluoro-triazinyl-6, 2-benzyl-methylamino-4-fluoro-triazinyl-6, 2- (4′-sulfobenzyl) amino-4-fluoro-triazinyl-6, 2-cyclohexylamino-4-fluoro-triazinyl-6, 2- (o-, m-, p-methylphenyl) amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2 ′, 5′-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-chlorophenyl) amino-4-fluorotriazinyl-6, 2- (o-, m-, p-methoxyphenyl) amino-4-fluorotriazinyl-6, 2- (2′-methyl-4′-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-methyl-5'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-chloro-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2′-chloro-5′-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-methoxy-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (o-, m-, p-carboxyphenyl) amino-4-fluorotriazinyl-6, 2- (2 ′, 4′-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (3 ′, 5′-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-carboxy-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-carboxy-5'-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (6′-sulfonaphthyl- (2 ′)) - amino-4-fluorotriazinyl-6, 2- (4 ′, 8′-disulfonaphthyl- (2 ′)) - amino-4-fluorotriazinyl-6, 2- (6 ′, 8′-disulfonaphthyl- (2 ′)) - amino-4-fluorotriazinyl-6, 2- (N-methyl-N-phenyl) amino-4-fluoro-triazinyl-6, 2- (N-ethyl-N-phenyl) amino-4-fluoro-triazinyl-6, 2- (N-β-hydroxyethyl-N-phenyl) amino-4-fluoro-triazinyl-6, 2- (N-iso-propyl-N-phenyl) amino-4-fluorotriazinyl-6,  2-morpholino-4-fluorotriazinyl-6, 2-piperidino-4-fluorotriazinyl-6, 2- (4 ′, 6 ′, 8′-trisulfonaphthyl- (2 ′)) - amino-4-fluorotriazinyl-6, 2- (3 ′, 6 ′, 8′-trisulfonaphthyl- (2 ′)) - amino-4-fluorotriazinyl-6, 2- (3′-6′-disulfonaphthyl- (1 ′)) - amino-4-fluorotriazinyl-6, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-dimethylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl- or N-ethyl-N- (2,4-dichlorotriazinyl-6) -aminoacetyl-, 2-methoxy-4-fluoro-triazinyl-6, 2-ethoxy-4-fluoro-triazinyl-6, 2-phenoxy-4-fluoro-triazinyl-6, 2- (o-, m- or p-sulfophenoxy) -4-fluoro-triazinyl-6, 2- (o-, m- or p-methyl or -Methoxy-phenoxy) -4-fluoro-triazinyl-6, 2-β-hydroxyethylmercapto-4-fluoro-triazinyl-6, 2-phenylmercapto-4-fluorotriazinyl-6, 2- (4'-methylphenyl) mercapto-4-fluorotriazinyl, 2- (2 ′, 4′-dinitrophenyl) mercapto-4-fluoro-triazinyl-6, 2-methyl-4-fluoro-triazinyl-6, 2-phenyl-4-fluorotriazinyl-6 and the corresponding 4-chloro or 4-bromo-triazinyl residues and the corresponding by halogen exchange with tertiary Bases such as trimethylamine, triethylamine, dimethyl-β-hydroxyethylamine, Triethanolamine, N, N-dimethylhydrazine, Pyridine, α-, β- or γ-picoline, nicotinic acid or Isonicotinic acid, sulfinates, especially benzenesulfinic acid or residues available from hydrogen sulfite.  

The halotriazinyl residues can also be combined with a second one Halotriazinylrest or a halodiazinylrest or one or more vinylsulfonyl or sulfatoethylsulfonyl radicals be linked, for example, via a bridge link

or in the case of the sulfatoethylsulfonyl or vinylsulfonyl group over a pontic

Mono-, di- or trihalopyrimidinyl residues, such as 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6, 2,4-dichloro-5-nitro or -5-methyl- or -5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, -di or -trichloromethyl- or -5-carbalkoxy-pyrimidinyl-6-, 2,6-dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methyl-pyrimidine-5-carbonyl-, 2-methyl-4-chloropyrimidine-5-carbonyl-, 2-methylthio-4-fluoropyrimidine-5-carbonyl-, 6-methyl-2,4-dichloropyrimidine-5-carbonyl-, 2,4,6-trichloropyrimidine-5-carbonyl-, 2,4-dichloropyrimidine-5-sulfonyl-, 2-chloro-quinoxaline-3-carbonyl-, 2- or 3-mono-chloroquinoxaline-6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulfonyl-, 2,3-dichloroquinoxaline-5 or -6-carbonyl-, 2,3-dichloroquinoxaline-5- or -6-sulfonyl-, 1,4-dichlorophthalazine-6-sulfonyl- or -6-carbonyl-, 2,4-dichloroquinazoline-7- or -6-sulfonyl- or -carbonyl-, 2- or 3- or 4- (4 ′, 5′-dichloropyridazon-6′-yl-1 ′) phenylsulfonyl or -carbonyl-, β- (4 ′, 5′-dichloropyridazon-6′-yl-1 ′) - ethylcarbonyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) aminoacetyl, N-methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) aminoacetyl-, such as the corresponding bromine and fluorine derivatives of the above  mentioned chlorine-substituted heterocyclic radicals, among these, for example, 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5,6-dichloro-4-pyrimidinyl-, 2,6-difluoro-5-methyl-4-pyrimidinyl-, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl-, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl-, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyan-4-pyrimidinyl-, 2-fluoro-5-methyl-4-pyrimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-6-dichloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-6-trichloromethyl-2-fluoro-4-pyrimidinyl-, 5-chloro-2-chloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-dichloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-trichloromethyl-6-fluoro-4-pyrimidinyl-, 5-chloro-2-fluoro-dichloromethyl-6-fluoro-4-pyrimidinyl-, 2,6-difluoro-5-bromo-4-pyrimidinyl-, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl-, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl-, 2,6-difluoro-5-nitro-4-pyrimidinyl-, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl-, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl-, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl-, 2-fluoro-5-nitro-4-pyrimidinyl-, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl-, 2-fluoro-5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl-, 2-fluoro-5-carbonamido-4-pyrimidinyl-, 2-fluoro-5-carbmethoxy-4-pyrimidinyl-, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl-, 2-fluoro-6-carbonamido-4-pyrimidinyl-, 2-fluoro-6-carbmethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl, 2-fluoro-6-cyan-4-pyrimidinyl-, 5-chloro-6-fluoro-2-methyl-4-pyrimidinyl-,  5,6-difluoro-2-trifluoromethyl-4-pyrimidinyl-, 5-chloro-6-fluoro-2-dichlorofluoromethyl-4-pyrimidinyl-, 2-fluoro-5-chloropyrimidinyl-4-yl, 2-methyl-4-fluoro-5-methylsulfonylpyrimidinyl-6, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl-, 2,6-dichloro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl-, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl-, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl; containing sulfonyl groups Triazine residues, such as 2,4-bis (phenylsulfonyl) triazinyl-6-, 2- (3'-carboxyphenyl) sulfonyl-4-chlorotriazinyl-6-, 2- (3'-sulfophenyl) sulfonyl-4-chlorotriazinyl-6-, 2,4-bis (3'-carboxyphenylsulfonyl) triazinyl-6; pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2,6-bis-methylsulfonyl-pyrimidinyl-4-, 2,6-bis-methylsulfonyl-5-chloro-pyrimidinyl-4-, 2,4-bis-methylsulfonyl-pyrimidinyl-5-sulfonyl-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonyl-pyrimidinyl-4-, 2-trichloromethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-chloromethyl-pyrimidinyl-4-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl-, 2-methylsulfonyl-5-nitro-6-methylpyrimidinyl-4-, 2,5,6-tris-methylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloro-pyrimidinyl-4-, 2,6-bis-methylsulfonyl-5-chloropyrimidinyl-4-,  2-methylsulfonyl-6-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-sulfopyrimidinyl-4-, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-carboxy-pyrimidinyl-4-, 2-methylsulfonyl-5-cyan-6-methoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-pyrimidinyl-4-, 2-β-sulfoethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloropyrimidinyl-4-, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl-, 2,6-bis (methylsulfonyl) pyrimidine-4- or -5-carbonyl-, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl-, 2,4-bis (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl- or -carbonyl-; 2-chlorobenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-, 2-arylsulfonyl- or alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-, such as 2-methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5- or -6-sulfonyl- or -carbonyl-, 2-phenylsulfonylbenzthiazole-5- or -6-sulfonyl- or-carbonyl- and the corresponding ones in the condensed 2-Sulfonylbenzthiazole-5- containing benzene ring sulfo groups or -6-carbonyl or -sulfonyl derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulfonyl-, 2-chlorobenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl- or -4- or -5-sulfonyl-, N-oxide of 4-chloro or 4-nitroquinoline-5-carbonyl.  

Reactive dyes of the formula (1) in which FB the rest of a mono- or disazo dye or a metal complex azo dye.

In this case the residues are -B-N (R) -X and -B′-N (R ′) - Z to different or identical residues of starting components, d. H. Diazo and clutch components, bound. The radicals are preferably -B-N (R) -X and -B'-N (R ') - Z to one component, diazo component or Coupling component, bound. The reactive dyes then have z. B. the formula

wherein -K- in formulas (1d) and (1e) for the rest of one double clutch component is available.

If both residues -B-N (R) -X and -B′-N (R ′) - Z to the same remainder of a starting component D or K bound are, this is in particular the rest of the coupling component K. The reactive dyes then correspond to formula  

wherein
D, D₁, D₂ = residue of a diazo component of the benzene or naphthalene series,
K = residue of a coupling component of the benzene, naphthalene, acetoacetic acid arylide or heterocyclic series; preferably a pyrazolone or pyridone radical in the heterocyclic series.

The radicals D, D₁, D₂ and K can be further azo groups or with residues containing azo groups and likewise, as listed above for the rest of FB of formula (1) is substituted, where X, Z, B, B ', R and R 'have the meanings given above.

Examples of D, D₁ and D₂ are preferably optionally by SO₃H, chlorine, C₁-C₄-alkoxy, C₁-C₄-alkyl, Carbalkoxy or sulfonamido substituted phenyl or Phenylene, optionally by SO₃H, chlorine, C₁-C₄ alkoxy or C₁-C₄-alkyl substituted naphthyl or naphthylene, 4- (Phenylazo) phenyl optionally substituted by SO₃H and optionally substituted by SO₃H Biphenyls.  

K stands for the rest of a coupling component, for example from the hydroxybenzene, hydroxynaphthalene, Aminobenzene, aminonaphthalene, aminohydroxynaphtaline series, for a 5-hydroxy-3-methyl (or carboxy) pyrazolone, a 6-hydroxy-2-pyridone or optionally C₁-C₄-alkyl or C₁-C₄-alkoxy ring-substituted Acetoacetic arylide residue.

K can have the usual substituents, especially sulfonic acid groups exhibit.

Also to be considered are reactive dyes Formula (1b) to (1f), wherein the radicals D, D₁, D₂ and K can still contain a further reactive radical. Consequently tri- and tetrareactive dyes are also included, where however, at least one reactive radical of the 6-fluoro-5-chloro-4-pyrimidinyl radical is. The additional ones enclosed in D or K. Reactive residues can, like Z and X, over Amino groups, or in some other way, e.g. B. by a be bound directly to D or K. The above Explanations also apply analogously to the metal complexes of the mono- and disazo dyes (1b-1f).

Reactive dyes according to the invention are particularly preferred of the formula (1) or (1a) - (1f), in which Z is a Rest of the formula

is
wherein R₄ and R₅ independently of one another hydrogen, C₁-C₄-alkyl, which is optionally substituted by halogen, cyano, C _1-4 alkoxy, hydroxy, carboxy, sulfo or sulfato, benzyl, phenethyl, cyclohexyl, phenyl or -NHCH₂CH₂OCH₂CH₂-SO₂M (M = -CH = CH₂ or -CH₂CH₂-V with V = alkaline eliminable residue); Phenyl, which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C _1-4 alkyl, C _1-4 alkoxy, C _1-4 alkanoylamino, benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or Sulfo, or naphthyl, which is optionally substituted by halogen, nitro, C _1-4 alkoxy, C _1-4 alkanoylamino, hydroxy, carboxy or sulfo,
or in which R₄ and R₅ together with the amino nitrogen atom form a morpholino, piperidino or piperazino radical, and in which Y = Cl, F or optionally substituted pyridinium radical.

Dyes with Y = F are preferred. As part of the Dyes with Y = Cl are preferred in which -NR₄R₅ has the meaning given above

is.

Those according to the invention are further particularly preferred Dyes where X and Z are both for the 5-chloro-6-fluoro-4-pyrimidinyl residue stand.  

Dyes of the formula (1) are also preferred to them

stands in what
Y = Cl, F or optionally substituted pyridinium radical,
M = CH = CH₂ or CH₂CH₂-V, wherein
V = alkaline eliminable residue, e.g. B. OSO₃H, SSO₃H, OCOCH₃, OPO₃H₂, OSO₂CH₃, SCN, NHSO₂CH₃, Cl, Br, F, OCOC₆H₅, OSO₂-C₆H₄, N (CH₃) ₃] ⁺anion⁻ or optionally substituted pyridinium radical (substituents, in particular optionally substituted C₁- C₄-alkyl, COOH, SO₃H, CN, carbonamide) and
R₂ = H, Cl, Br, C₁-C₄-alkyl, C₁-C₄-alkoxy, CO₂H or SO₃H.

Reactive dyes of the formula are preferred  

wherein both residues A = X or one A = X and the other A = Z, and X and Z are those given in formula (1) Have meanings, R₃ is hydrogen, methyl or ethyl is, and the benzene ring E optionally further substituted is.

Reactive dyes of the formula are also preferred

where A and E have the meaning given above.

Reactive dyes of the formula are particularly preferred (2), in which the benzene ring E is not further substituted and reactive dyes of the formula (3), in which the Benzene ring E is no longer substituted.  

Reactive dyes of the formula are also preferred

where A has the meaning given above.

Except for the reactive dyes described above of formulas (2), (3) and (4) are more valuable Represent the reactive dyes of the following formulas to call:

where Pc represents a Cu or Ni phthalocyanine residue and the maximum number of substituents on the Pc skeleton 4 is; R and R ′ have the meaning given above,

where T = Cl, Br, OCH₃ and A, E, R and Alk have the meanings given above,
R₆ = H, C₁-C₄-alkyl, C₁-C₄-alkoxy, acylamino, especially C₁-C₄-alkylcarbonylamino, C₁-C₄-alkylsulfonylamino, aminocarbonylamino, optionally substituted phenylcarbonylamino Cl, Br,
R₇ = H, C₁-C₄-alkyl, C₁-C₄-alkox, OH, SO₃H,
W = aliphatic bridge member, especially C₂-C₄ alkylene.

In the preferred reactive dyes of the formulas (2) and (3) the benzene rings E are preferably also not further substituted; as diazo components in this case especially 1,3-phenylene-4-sulfonic acid, 1,4-phenylenediamine-2-sulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid or 1,3-phenylenediamine-4,6-disulfonic acid used. The rest R₃ in formula (2) especially hydrogen, methyl or ethyl.

Preferred are especially reactive dyes of the formulas (2) to (40), in which A is an unsubstituted or substituted aminofluoro-s-triazine radical, where -NR₄R₅ preferably stands for: -NH₂, morpholino, N-β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino, phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl, ethyl, methoxy, ethoxy, acetylamino, hydroxy, carboxy, sulfomethyl or sulfo, NC _1-4 -alkyl-N- phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl or ethyl, N-sulfo-C _1-4 -alkyl-N-phenylamino, which is optionally substituted in the phenyl nucleus by chlorine, methyl or ethyl, N-hydroxy-C _{1- 4} -alkyl-N-phenylamino or sulfonaphthylamino, and the second reactive radical A represents the 6-fluoro-5-chloropyrimidyl (4) radical.

Dyes (2) to (40), in which both are preferred Residues A stand for X, as well as those in which a residue A for X and the other for

stands.

There is a process for producing the dyes (1) in that you have dyes

or the corresponding dye precursors with 1 to 2 moles of a reactive component  

and optionally 1 to 2 moles of a reactive component

Z-Hal (VI)

where Hal = Cl, Br or F, and in the case of Use of preliminary products then in the desired final dyes transferred and optionally further conversion reactions follows.

In the manufacture of the preferred azo dyes the diazo components and the coupling components together two amino groups -N (R) H and -N (R ′) H, and optionally contain further acylatable amino groups. If necessary, appropriate ones are used Acetylamino or nitro compounds in which the acetylamino or nitro group before condensation with a Halotriazine, halopyrimidine or the like Saponification or reduction converted into the NH₂ group becomes. The reactive residues X and Z are introduced by condensation of dyes or dye precursors, which contain acylatable amino groups, with fiber-reactive halogenated acylating agents. At the production of the final dyes from intermediate products it is mostly couplings that lead to azo dyes to lead.  

Since the individual process steps specified above in different order can be executed different process variants are possible. In general one carries out the implementation step by step from, the order of simple reactions between the individual reaction components advantageously depends on the special conditions. There under certain conditions hydrolysis of a halotriazine or halopyrimidine residue etc. occurs, an intermediate product containing acetylamino groups are saponified to remove the acetyl groups, before with an aminodifluorotriazine or trifluorotriazine etc. is condensed. As another transformation reaction comes z. B. the subsequent implementation of a Dihalotriazinylrestes with an amine into consideration. What reaction when making a secondary Condensation product from amine HNR₄R₅, 2,4,6-trihalogen-s-triazine and diaminobenzenesulfonic acid suitably that of trihalotriazine is carried out first with the amine or with the diaminobenzenesulfonic acid differs from case to case and mainly depends according to the solubility of the amino compounds involved and the basicity of the amino groups to be acylated. The the most important process variants are in the exemplary embodiments shown.  

Suitable starting compounds for the production of Examples of mono- or polyazo dyes (1) are:

Diazo components (D, D₁ and D₂)

1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene, 1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene, 1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxybenzene, 2,6-diamino-naphthalene, 1,3-diamino-2,4,6-trimethylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene, 4,4′-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl (Benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine, 3,3'-dicarboxymethoxy-benzidine, 2,2'-dimethylbenzidine, 4,2'-diaminodiphenyl (diphenylin), 2,6-diaminonaphthalene-4,8-disulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,6-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid, 1,4-diamino-2-methylbenzene-5-sulfonic acid, 1,5-diamino-6-methylbenzene-3-sulfonic acid, 1,3-diamino-6-methylbenzene-4-sulfonic acid, 3- (3'- or 4'-aminobenzoylamino) -1-aminobenzene-6-sulfonic acid, 1- (4′-aminobenzoylamino) -4-aminobenzene-2,5-disulfonic acid,  1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylic acid, 1,2-diaminobenzene-4-carboxylic acid, 1,3-diaminobenzene-5-carboxylic acid, 1,4-diaminobenzene-2-methylbenzene, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylurea-2,2'-disulfonic acid, 4,4'-diaminodiphenyloxyethane-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, 4,4'-diaminodiphenylethane-2,2'-disulfonic acid, 2-amino-5-aminomethylnaphthalene-1-sulfonic acid, 2-amino-5-aminomethylnaphthalene-1,7-disulfonic acid, 1-amino-4-methoxy-5-aminomethylbenzene-6-sulfonic acid.

If an aminoacetylamino compound instead of a diamine as the diazo component should be used from which subsequently saponified the acetyl group is split off again, as described above in the explanations of the process variants is described the monoacetyl compounds of the above diazo components in question, e.g. B. 1-acetylamino-3-aminobenzene-4-sulfonic acid or 1-acetylamino-4-aminobenzene-3-sulfonic acid.

If the two residues -B-N (R) -X and -B′-N (R ′) - Z in Formula (1) to the same component, e.g. B. the Coupling components are bound, like this above as diazo components can also be described are used in addition to the amino group to be diazotized contain no acylatable amino group, such as. B. Aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene,  1-amino-2-methoxy-4-nitrobenzene, 1-aminobiphenyl, 1-aminobenzene-2-, -3- or -4-carboxylic acid, 2-aminodiphenyl ether, 1-aminobenzene-2-, -3- or -4-sulfonic acid amide, 1-aminobenzene-2-, -3- or -4-sulfonic acid, 1-aminobenzene-2,4- and -2,5-disulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonic acid, 4-aminobenzene-3,4′-disulfonic acid, 3-methoxy-4-amino-6-methyl-azobenzene-2 ', 4'-disulfonic acid or 3-methoxy-4-amino-6-methylazobenzene-2 ', 5'-disulfonic acid.

Coupling components (K)

1-amino-3-methylbenzene, 1-amino-2-methoxy-5-methylbenzene, 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1-aminonaphthalene-6- or -8-sulfonic acid, 1-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid,  1-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N-methylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl- or 2-ethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4′-nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-aminobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2- (4'-amino-3'-sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 2,4,6-triamino-3-cyanopyridine, 1-β-aminoethyl-3-cyano-4-methyl-6-hydroxypyridone- (2), 1- γ-aminopropyl-3-sulfomethyl-4-methyl-6-hydroxypyridone- (2), 1,3-diaminobenzene.  

The diazotization of the diazo components or the one intermediates containing diazotizable amino group usually takes place through the action of nitrous acid in aqueous mineral acid solution at low temperature. The coupling to the coupling component takes place at strongly acidic, neutral to weakly alkaline pH Values.

The condensation of the reactive components with the diazo components and the coupling components and with the Amines or with acylated monoazo or disazo intermediates or with the dyes containing amino groups preferably take place in aqueous solution or Suspension, at low temperature and at weak acidic, neutral to weakly alkaline pH. Advantageous becomes the one released during the condensation Hydrogen halide continuously by adding aqueous alkali metal hydroxides, -carbonate or -bicarbonate neutralized.

The formulas given are those of the free acids. At the salts are generally obtained during production, especially the alkali salts such as sodium, potassium or lithium salts. The quaternization with pyridines resulting charge is, depending on the insulation conditions, by a counter ion e.g. B. chloride, Balanced fluoride or sulfate; or the dyes form inner salts with sulfo or carboxyl groups.

All dyes, especially those in the latter Level with pyridines can be implemented depending on Reaction conditions as mixtures of the β-sulfatoethylsulfonyl dyes and their eliminated form the  Vinyl sulfone are present. The dyes can also be used as concentrated solutions are used.

The dyes according to the invention are outstandingly suitable for dyeing and printing natural and synthetic materials containing OH or amide groups, especially those made of cellulose and polyamides. they are particularly suitable for dyeing cellulosic materials in exhaust and block cold dwell processes, as well for printing on cotton and rayon.

One obtains with good building ability and high fixing yields Dyes with good general fastness properties, in particular Wet fastness properties.

Example 1

a) 0.2 mol of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 350 ml of water at pH 6.5 and cooled to 0 ° C with 350 g of ice. 0.21 mole 2,4,6- Trifluoro-1,3,5-triazine (cyanuric fluoride) are added and the pH with Na₂CO₃ solution between 3.5 and 4 held. After 5 minutes, 0.2 mol of morpholine is added and adjust the pH to 7 with soda solution a. The temperature rises to approx. 10 ° C.

b) 0.2 mol of 6-fluoro-5-chloro-4- (3'-amino-4'-sulfophenyl) pyrimidine (from 2,4-diaminobenzenesulfonic acid and 4,6-difluoro-5-chloropyrimidine) are suspended in water and with 65 ml 30% Hydrochloric acid and 300 g of ice added. After that 46 ml of 30% sodium nitrite solution are added and Stirred for 1 hour at 0 ° C. Excess sodium nitrite is destroyed with sulfamic acid and the diazotization thus obtained to dissolve the coupling component a) given. With soda solution a pH set from 6-7.

After the coupling has ended, the dye is salted out, isolated, dried and ground. The way dye of the formula obtained  

dyes cotton in clear red tones.

Example 2

a) 0.2 mol of 1,4-diaminobenzenedisulfonic acid 2.5 in 500 ml of water with conc. Sodium hydroxide solution dissolved neutral. The mixture is heated to 50 ° C. and 0.3 mol of 4.6 Difluoro-5-chloropyrimidine too. By simultaneous The addition of soda solution (20 g / 100 ml) is kept at pH 7. The reaction is complete after 3 hours. Man cools to 0 ° C and adds 55 ml of 30% HCl. Drops are made at 0 ° C-5 ° C within 30 minutes 47 ml of sodium nitrite solution (30 g / 100 ml). The Diazotization is stirred for 30 minutes at 0-5 ° C. Subsequently becomes excess nitrite with amidosulfonic acid destroyed.

b) 0.2 mol of 6-amino-1-naphthol-3-sulfonic acid are in 600 ml of water with the addition of 38 ml of 11% Lithium hydroxide solution dissolved at pH 7-7.5. In  0.21 mol of cyanuric fluoride is added dropwise over 30 minutes. You stop by simultaneously dropping in 11% lithium hydroxide solution has a pH of 3.7-4.1. The mixture is stirred for 5 minutes and 0.2 mol Morpholine too. With soda solution (20 g / 100 ml) to pH 7. T = 5 ° -8 ° C. Stir for 15 minutes and drips the above diazotization within 1 hour a) to. With 1molar sodium hydrogen carbonate solution a pH of 5.5-6.5 is maintained. To completed coupling is salted out with CaCl, isolated and dries. The dye of the formula

dyes cotton in red tones.

The dyes of Examples 3-31 below general formula

X D N = N K Z

can be produced in an analogous way under Use of the listed diazo or coupling components and amines. They dye cotton in the listed shades.

X has the meaning given in formula (1).

Example 32

0.2 mole of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 450 ml of water with sodium hydroxide solution at pH 8-9 and 0.22 mol of 4,6-difluoro-5-chloropyrimidine were added. The condensation takes place at 35-40 ° C, the pH is maintained with soda solution.

Coupled with the diazotization described in Example 1 under the same conditions, you get after Salt out, isolate, dry the dye of the formula

of cotton in red tones.

Example 33

0.2 mol of 8- (4'-amino-benzoylamino) -1-naphthol-3,6-disulfonic acid are in 800 ml of water with soda solution (20 g / 100 ml) dissolved at a pH of 7. With 10% HCl solution is adjusted to pH 4.5. You give  2.2 mol of 4,6-difluoro-5-chloropyrimidine and heats up 30 ° C. The soda solution (20 g / 100 ml) becomes a pH kept from 4.5-6. The reaction is complete after 4 hours.

0.2 mol of the diazonium salt from Example is now added 1 and stops at the same time by adding soda solution (20 g / 100 ml) pH 7.5-8. After finished Coupling is salted out with NaCl, isolated and dries. The dye of the formula

dyes cotton in red tones.

Examples 34-52 of the formula

can be prepared as described in Examples 32 and 33, if the corresponding intermediates are used. They dye cotton in the specified colors.

Example 53

0.2 mole of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are in 650 ml of water and with sodium hydroxide solution at pH 6.5 dissolved and heated to 35 ° C. Become this solution 0.21 mol of 2,3-dichloroquinoxaline-6-carboxylic acid chloride added and the pH adjusted to 6-7 with soda solution and condensed at 35 ° C for about 6 h.

Then with 6-fluoro-5-chloro-4- (3'-amino-4'-sulfophenylamine) - pyrimidine diazotization coupled analogously to Example 1.

The dye is salted out, isolated, dried and ground. It has the following formula

and dyes cotton in red tones.  

As described above, the dyes of the Examples 54-64 of the formula

with the listed diazo and coupling components (K) are produced, X has the formula given in formula (1) Importance,

Example 65

0.26 mol of 3- (2-sulfatoethyl) sulfonyl-aniline are in 250 ml of water with 1 molar sodium hydrogen carbonate solution solved neutral. 250 g of ice are added and 0.27 mol are added dropwise Cyanuric fluoride. With 1molar sodium hydrogen carbonate solution a pH of 4-5 is maintained.

Stir for 10 minutes.

0.2 mol of 8- (4'-amino-benzoylamino) -1-naphthol-3,6-disulfonic acid are stirred in 300 ml of water and with 11% lithium hydroxide solution dissolved neutral. These Solution is added to the above condensation solution. With Soda solution is kept at a pH of 6.5-7, the temperature rises to approx. 10 ° C. After the reaction is over 0.2 mol of the diazonium salt from Example 1 is added and maintained simultaneously by adding sodium carbonate solution (20 g / 100 ml) a pH of 7.5-8. After 3 hours, salt with NaCl from, insulates and dries. The dye obtained formula  

dyes cotton in red tones.

The dyes of Examples 66-75 are obtained analogously using the appropriate diazo components Coupling components and amines. You own the general formula

X D N = N K Z

Example 76

a) 0.2 mol of 2-amino-4- (aminomethyl) benzenesulfonic acid are in 500 ml of water with conc. Sodium hydroxide solution a pH of 8 dissolved. 0.25 mol of 4.6- Difluoro-5-chloropyrimidine too. By simultaneous Add 11% lithium hydroxide solution pH kept at 8-8.5. T = 30 ° C-40 ° C. Man cools to 0 ° C and gives 56 ml of 30% hydrochloric acid to.

47 ml are added dropwise at 0-5 ° C. within 1 hour Sodium nitrite solution (30 g / 100 ml). The diazotization stir for 1 hour at 0-5 ° C. Subsequently becomes excess nitrite by adding amidosulfonic acid destroyed.

b) 0.2 mol of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid are added in 300 ml of water from conc. Sodium hydroxide solution dissolved at pH = 5-7. You give 300 g of ice and sprinkle in 0.21 mol of cyanuric chloride. With soda solution (20 g / 100 ml) a pH of 4-4.5 kept at 0 ° C. After condensation has ended 0.2 mol of a neutral solution of 4- Chloraniline in about 200 ml of water. You heat up 20 - 30 ° C and holds with soda solution (20 g / 100 ml) pH 6-7. After about 1 hour, cool to 10 ° C and admits the above diazotization a).  

Simultaneously hold with soda solution (20 g / 100 ml) pH 7-7.5.

When coupling is complete, salt out with NaCl, insulates and dries. The dye obtained formula

dyes cotton in red tones.

By varying the diazo components, coupling components and amines, the dyes of the following are obtained Examples 77-96 of the general formula

X D N = N K Z

They dye cotton in the specified tones.

Example 97

0.2 mol of 2-aminonaphthalenesulfonic acid in 280 ml Water dissolved with lithium hydroxide at pH 7 and 250 g ice admitted. Then 0.21 mol of cyanuric fluoride is added and the pH was kept at about 4 with soda solution. To the resulting suspension becomes a neutral solution of 2,4-diaminobenzenesulfonic acid and the pH 7-7.5 raised. The reaction temperature is raised to 20 ° C raised and stirred for about 1 hour. The reaction mixture is cooled to 0 ° C and with HCl and sodium nitrite solution diazotized at pH 2-2.2. After annihilation of the excess nitrite couples with amidosulfonic acid one on the coupling component described in Example 32 at pH 7-8 and 10-15 ° C. Salting out, isolating and Drying gives the dye of the formula

of cotton in red tones.

The dyes of Examples 98-110 of the general formula

Z D N = N K X

can be produced in an analogous manner using of the specified diazo and coupling components.

In some cases, however, it is cheaper to do that first Synthesize azochromophore and then the reactive components or to condense one of them (Z). they dye cotton in the specified colors.

X has the meaning given in formula (1).

Example 111

0.22 mol of N-ethylaniline are in 200 ml of water at pH 7 solved. 200 g of ice are added and 0.24 mol is sprinkled on Cyanuric chloride. Hold with soda solution (20 g / 100 ml) a pH of 6-7. After about 1 hour at 0 ° C Condensation ended. 0.2 mol of 2,4-diamino-benzenesulfonic acid are in 250 ml of water by adding conc. Dissolved sodium hydroxide solution and added to 1 stage of the condensation. With soda solution (20 g / 100 ml) a pH of Held 6-7. The mixture is heated to 25-35 ° C. After finished Condensation is cooled to 0 ° C. It becomes 56 ml 30% hydrochloric acid added. 47 ml of sodium nitrite solution are added dropwise (30 g / 100 ml) and stir for 1 hour 0 ° C. Sodium nitrite is destroyed with sulfamic acid and the diazotization thus obtained to the coupling component given from Example 32. With soda solution (20 g / 100 ml) a pH of 7-8 is maintained. T = 10- 15 ° C. When coupling is complete, salt out with NaCl, insulates and dries. The dye obtained formula

dyes cotton in red tones.  

The dyes of 112-117 of the general formula

Z D N = N K X

can be used using the corresponding diazo, Manufacture coupling components and amines analogously. In in some cases it is cheaper to use the condensation Cyanuric chloride and amine at the end of the synthesis frequency deliver.

X has the meaning given in formula (1).

Other valuable dyes of the formula

are those of Examples 118-134, which can be prepared by known methods, such as Shown above, have it made and dye cotton in the specified tones.

The dyes of Examples 135-149 can be obtained analogously to the production processes described above or by customary processes, using the corresponding starting components.

Claims (9)

1. Reactive dyes of the formula in particular dyes of the formula wherein
FB = the rest of a dye or the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl , Naphthoquinone, pyrenequinone or perylene tetracarbimide series,
B or B ′ = direct bond or bridge member to a ring C atom of an aromatic carbocyclic ring or to a ring C or N atom of an aromatic heterocyclic ring in FB, Z = heterocyclic fiber-active radical,
R, R '= H, optionally substituted C₁-C₆ alkyl with the exception of the dye of the formula 2. Dyes of claim 1 of the formula wherein
-K- in formulas (1d) and (1e) stands for the remainder of a double coupling coupling component,
D, D₁, D₂ = residue of a diazo component of the benzene or naphthalene series,
K = residue of a coupling component of the benzene, naphthalene, acetoacetic acid acrylide or heterocyclic series; preferably a pyrazolone or pyridone radical in the heterocyclic series. 3. Dyes of claim 1 with Z = fiber reactive fluorine-containing pyrimidyl-4 radical, in particular X. 4. dyes of claim 1 with wherein R₄ and R₅ independently of one another are hydrogen, C _1-4 -alkyl which is optionally substituted by halogen, cyano, C _1-4 -alkoxy, hydroxy, carboxy, sulfo or sulfato, benzyl, phenethyl, cyclohexyl, phenyl or -NHCH₂CH₂OCH₂CH₂- SO₂M (M = -CH = CH₂ or -CH₂CH₂V with V = alkali-eliminable residue), phenyl which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C _1-4 alkyl, C _1-4 - Alkoxy, C _1-4 alkanoylamino, benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo or naphthyl, which is optionally substituted by halogen, nitro, C _1-4 alkoxy, C _1-4 alkanoylamino, hydroxy, carboxy or Sulfo is
or in which R₄ and R₅ together with the amino nitrogen atom form a morpholino, piperidino or piperazino radical, and in which Y = Cl, F or optionally substituted pyridinium radical. 5. Dyes of claim 4
wherein R₄ and R₅ independently of one another hydrogen, C _1-4 -alkyl, which is optionally substituted by halogen, cyano, C _1-4 -alkoxy, hydroxy, carboxy, sulfo or sulfato, benzyl, phenethyl, cyclohexyl, phenyl or -NHCH₂CH₂OCH₂CH₂- SO₂M (M = -CH = CH₂ or -CH₂CH₂V with V = alkali-eliminable residue), phenyl, which is optionally substituted by halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C _1-4 alkyl, C _1-4 - Alkoxy, C _1-4 alkanoylamino, benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or naphthyl, which is optionally substituted by halogen, nitro, C _1-4 alkoxy, C _1-4 alkanoylamino, hydroxy, carboxy or sulfo, is
or in which R₄ and R₅ together with the amino nitrogen atom form a morpholino, piperidino or piperazine radical, and in which Y = Cl. 6. Dyes of claim 1, wherein stands in what
Y = Cl, F or optionally substituted pyridinium radical,
M = CH = CH₂ or CH₂CH₂-V, wherein
V = alkaline eliminable residue, e.g. B. OSO₃H, SSO₃H, OCOCH₃, OPO₃H₂, OSO₂CH₃, SCN, NHSO₂CH₃, Cl, Br, F, OCOC₆H₅, OSO₂- C₆H₄, N (CH₃) ₃] ⁺anion ^- or optionally substituted pyridinium radical (substituents, in particular optionally substituted C₁- C₄-alkyl, COOH, SO₃H, CN, carbonamide) and
R₂ = H, Cl, Br, C₁-C₄-alkyl, C₁-C₄-alkoxy, CO₂H or SO₃H. 7. dyes of claim 1 of the formulas wherein Pc stands for a Cu or Ni phthalocyanine residue and the total number of substituents on the Pc skeleton is at most 4; in which
T = Cl, Br, OCH₃,
R₃ = H, CH₃ or C₂H₅,
R₆ = H, C₁-C₄-alkyl, C₁-C₄-alkoxy, acylamino, especially C₁-C₄-alkylcarbonylamino, C₁-C₄-alkylsulfonylamino, aminocarbonylamino, optionally substituted phenylcarbonylamino Cl, Br,
R₇ = H, C₁-C₄-alkyl, C₁-C₄-alkox, OH, SO₃H,
W = aliphatic bridge member, in particular C₂- C₄ alkylene,
Alk = optionally heteroatoms or heteroatoms such as groups containing N, O or S, interrupted, straight-chain or branched C₁-C₆alkylene, and either either A = X or one A is X and the other A is Z and the benzene rings E are optionally further substituted. 8. Use of the dyes of claims 1-6 for Dyeing and printing of hydroxyl groups and Materials containing amide groups. 9. Dyed with the dyes of claims 1-6 or printed hydroxyl or amide groups containing materials.