EP1877495A2

EP1877495A2 - Reactive azo dyes, methods for the production thereof and their use

Info

Publication number: EP1877495A2
Application number: EP06806725A
Authority: EP
Inventors: Gunter GÖRLITZ
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 2005-04-26
Filing date: 2006-04-19
Publication date: 2008-01-16
Also published as: WO2007006594A2; DE102005019333A1; TW200637890A; WO2007006594A3; US20080289124A1; CN101142285A

Abstract

The invention relates to reactive dyes of general formula (I), in which R1 to R5 represent Ar, n, Y and D, which have the meanings cited in Claims 1 and 2, to methods for the production thereof, and to their use for dying and imprinting materials containing carbonamide groups, amino groups and hydroxy groups.

Description

DYSTAR TEXTILFARBEN GMBH & CO. GERMANY KG DYS 2005 / D 506 Dr. med. Ku

description

Reactive azo dyes, process for their preparation and their use

The present invention is in the field of fiber-reactive dyes. From the documents DE 3 025 904, EP 0 581 730 and EP 0 581 731 dyes are already known which have structural similarities with the dyes according to the invention described below, but differ with respect to the reactive anchor in the coupling component. These known dyes have a number of technical disadvantages in the dyeing of textile materials, which was to be improved.

Surprisingly, it has now been found that the following dyes of the general formula (1) stand out advantageously from the known dyes.

The present invention relates to reactive dyes of the general formula (1),

wherein

D is the radical of a diazo component of the benzene or naphthalene series, a heterocyclic radical or the radical of a mono- or disazo dye,

R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl, R ^3, R ⁴ and R ⁵ are independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato or vinylsulfonyl substituted and with the exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl, wherein R ⁷ is hydrogen or C _r C ₄ alkyl or R ³ and R ⁴ are part of heterocyclic groups,

Q is C _r C ₁₈ -alkylene which is optionally substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is interrupted, with the exception of methylene, optionally by oxygen or NR ⁷ , n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C _r C ₄ alkyl, C _r C ₄ alkoxy or halogen-substituted phenylene or naphthylene radical,

Y is -CH = CH ₂ or -CH ₂ CH ₂ Y ¹ , in which

Y ^{1 is} hydroxy or an alkali cleavable group. In the dyestuffs according to the invention D preferably represents a group of the general formula (DI) (D-II) or (D-XII),

wherein - ^* B represents the bond to the diazo group at the Diaminopyridingruppe, a direct chemical bond, an ethylene or a diazo group, R ^D1 and R ^D2 are independently hydrogen, (C _r _C4) alkyl, ( C _r C ₄ ) -alkoxy,

Hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X ^{m has} one of the meanings of R ^m or R D ² or for a group of

Formula -SO ₂ -Z is where

Z has one of the meanings of Y or D represents a naphthyl group of the general formula (D-III),

wherein

- ^* represents the bond to the diazo group at the Diaminopyridingruppe, R ^D3 and R ^D4 are independently hydrogen, (C _r _C4) alkyl, (C _r C ₄₎ -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, Amido, ureido or halogen; and X ^{D2 has} one of the meanings of X ^m ; or

D is a group of general formula (D-IV),

wherein

- ^{* stands} for the bond to the diazo group on the Diaminopyridinruppe, M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or organic monovalent cations, in particular alkylammonium, R ^D5 and R ^D6 independently one of the meanings of R ^m and Have R ^D2 ;

R ^D7 is hydrogen, (C ₁ - C ₄₎ alkyl, unsubstituted or substituted by (C ₁ -C ₄₎ - alkyl, (C _r _C4) -alkoxy, sulfo, halogen or carboxy substituted phenyl; and Z ^D2 is a group of general formula (DV) or (D-VI) or (D-VII), wherein

- ^{* represents} the bond to nitrogen, V is fluorine or chlorine;

U ^m , U ^{D2 are} independently fluorine, chlorine or hydrogen; and Q ^m , Q ^D2 independently of one another chlorine, fluorine, cyanamido, hydroxy, (C ₁ -

C ₆ ) -alkoxy, phenoxy, sulfophenoxy, mercapto, (C ₁ -C ₆ ) -alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (D-VIII) or (D-IX),

wherein

- ^{* represents} the bond to the heterocycle,

R ^D8 is hydrogen or (C _r C ₆₎ alkyl, sulfo (C _r _C6) alkyl, or phenyl which is unsubstituted or substituted by (C _r _C4) alkyl, (C ₁ - C4) alkoxy, Sulfo, halogen, carboxy, acetamido, ureido is substituted;

R ^D9 and R ^mo independently of one another have one of the meanings of R ^D8 , or form a cyclic ring system of the formula - (CH ₂ ) -, where j is 4 or 5, or alternatively - (CH ₂ ) ₂ -E- (CH ₂ ) ₂ -, wherein E is oxygen, sulfur, sulfo, -NR ^D11 and R ^mi (C _r C ₆ ) alkyl; W is phenylene which is unsubstituted or substituted by 1 or 2

Substituents, such as (C _r C ₄ ) alkyl, (C _r C ₄ ) alkoxy, carboxy, sulfo, chlorine, bromine, or W is (C _r C ₄ ) -alkylene-arylene or (C ₂ -C ₆ ) -alkylene, which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl,

Carbonamido, or

W is phenylene-CONH-phenylene which is unsubstituted or substituted by (C ₁ -C ₄₎ - alkyl, (C _r C ₄₎ -alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or

Halogen is substituted or W is naphthylene which is unsubstituted or substituted by one or two

Sulfo groups is substituted; and

Z has the abovementioned meaning; or

D is a group of general formula (D-X) or (D-Xl),

where - ^{* stands} for the bond to the diazo group on the diaminopyridine group,

R ^{D12 has} one of the meanings of R ^m , X ^{D3 has} one of the meanings of X ^m has X ^D4 -CN and COOR ⁰¹³ , wherein R ^{13 has} one of the meanings of R and R is C ₁ -C ₄ alkyl.

Alkali eliminable substituents Y ¹ which are in the β-position of the ethyl group of Y are, for example, halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkylcarboxylic acids, optionally substituted benzenecarboxylic acids and optionally substituted benzenesulphonic acids, such as the alkanoyloxy groups of 2 to 5 C atoms, thereof in particular acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluenesulfonyloxy, further acidic Ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), as well as dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino and diethylamino, optionally substituted pyridinium, nicotinato, isonicotinato.

Y is preferably β-sulfatoethyl, β-chloroethyl and particularly preferably vinyl.

The groups "sulfo", "carboxy", "thiosulfato", "phosphato", and "sulfato" include both their acid form and their salt form Accordingly, sulfo groups means groups corresponding to the general formula -SO ₃ M, thiosulfato groups corresponding to the general groups Formula -S-SO ₃ M, carboxy groups groups corresponding to the general formula -COOM, phosphato groups corresponding to the general formula -OPO ₃ M ₂ and sulfato groups corresponding to the general formula -OSO ₃ M, wherein M is hydrogen, an alkali metal, ammonium, a Equivalent to an alkaline earth metal or organic monovalent cations, in particular alkylammonium means.

Preferred reactive dyes according to the invention are those of the general formula (1 a)

wherein

(DI), Ar and R ¹ to R ^{5 have} the meanings given above and n is O or 1. Further preferred reactive dyes according to the invention are those of the general formula (1b),

(D-I

wherein (D-II), Ar and R ¹ to R ^{5 have} the meanings given above and n is 0 or 1.

Further preferred reactive dyes according to the invention are those of the general formula (1c),

wherein

(D-III), Ar and R ¹ to R ^{5 have} the meanings given above and n is 0 or 1.

Very particularly preferred reactive dyes according to the invention are those of the general formula (1 d),

wherein

X xD1 has one of the meanings of R or R and R and R, Ar, Q and Y are as defined above and R ^{5 is} hydrogen or C _r C _1β alkyl.

Furthermore, very particularly preferred reactive dyes according to the invention correspond to the formula (1 e),

wherein

R, 1 ¹ C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ^{4 are} independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato, or vinylsulfonyl-substituted and with

The exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl mean wherein R ⁷ is hydrogen or C _r C ₄ alkyl, or R ³ and R ⁴ are part of heterocyclic groups, R ⁵ are hydrogen or C _r C ₁₈ alkyl, Q is C _r C ₁₈ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR ⁷ , with the exception of methylene, and

D and Y have the meanings given above.

Furthermore, very particularly preferred reactive dyes according to the invention of the formula (1f) correspond to

wherein

R ¹ is C _r C ₄ alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ^{4 are} independently hydrogen or optionally

Are C ₇ cycloalkyl, wherein R ⁷ is hydrogen or C _r C ₄ - hydroxy, sulfo, sulfato, or vinylsulfonyl substituted and ⁷ broken, with the exception of methyl, may be interrupted by oxygen or NR C _r C ₁₈ alkyl or C ₄ - Is alkyl, or R ³ and R ^{4 are} heterocyclic groups, R ^{5 is} hydrogen or C _r C _1β alkyl, Q is optionally substituted by C ₁ - C ₄ _alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or NR ^{7 is} interrupted C _r C ₁₈ -alkylene and (D-XII) and Y have the meanings given above.

The coupling component of the general formula (2) in the dyes of the invention are novel and also the subject of the invention.

The present invention accordingly furthermore relates to diaminopyridines of the general formula (2),

wherein

R ^{1 is} C ₁ -C ₄ -alkyl ₁

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ , R ⁴ and R ^{5 are} independently hydrogen or optionally substituted by hydroxy, sulfo, sulfato, or vinylsulfonyl-substituted and with

The exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl mean wherein R ⁷ is hydrogen or C _r C ₄ alkyl, or R ³ and R ⁴ are part of heterocyclic groups, Q is optionally substituted by C ₁ - C ₄ substituted _Alkyl, halogen or hydroxy and with the exception of methylene optionally interrupted by oxygen or NR ⁷ interrupted C _r C ₁₈ alkylene, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C _r C ₄ alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical

Y is -CH-CH ₂ or -CH ₂ CH ₂ Y ¹ , in which Y ^{1 is} hydroxy or an alkali cleavable group.

Preferred diaminopyridines of the general formula (2) are, for example, the abovementioned diaminopyridines which may be present as an isomer mixture.

Name Diaminopyridine

If a compound of the general formula (2) or the formulas P (1) to P (25) contains an acid group, such as a group SO ₃ H, this may also be in the form of a salt, for. B. with the group SO ₃ M, where M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or organic monovalent cations, in particular alkylammonium means.

The present invention furthermore relates to processes for preparing the diaminopyridines of the general formula (2).

In this case, a 2,6-dichloropyridine of the general formula (3),

wherein R ¹ and R ^{2 are} as defined above, reacted with one molar equivalent of an amine of the general formula (4), wherein

R ³ and R ^{4 are} independently hydrogen or optionally

Hydroxy-, sulfo-, substituted and with the exception of methyl optionally by

Oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ interrupted C _r C ₁₈ alkyl or

C ₄ - C _{7 are} cycloalkyl, wherein R ^{7 is} hydrogen or C _r C ₄ alkyl, or R ³ and

R ⁴ component of heterocyclic groups, wherein the monoaminopyridine of the general formula (5) is obtained as a mixture of isomers.

Alternatively, it is also possible first to prepare a compound of the general formula (6)

wherein R ^{1 is} C _r C ₄ alkyl, R ^{2 is} cyano, carbamoyl or sulfomethyl, R ^{5 is} hydrogen or optionally substituted by hydroxy-substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - ₇ cycloalkyl, wherein R ⁷ is hydrogen or C _r C ₄ alkyl, Q is C _r C ₁₈ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR ⁷ , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical,

Y means -CH ₂ CH ₂ OH, through

a) reacting dichloropyridine of the general formula (3) with one molar equivalent of an amine of the formula (7),

wherein Q, Ar, n and R ⁵ are as defined above and

Y is -CH ₂ CH ₂ OH, or

b) reacting dichloropyridine of the general formula (3) with one molar equivalent of an amine of the formula (8),

wherein R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ interrupted C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C _r C ₄ Alkyl,

Q is optionally substituted by C ₁ - C ₄ _Alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or

NR ^{7 is} interrupted C _r C ₁₈ -alkylene, n is 0 or 1, Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AlkVl, C _r C ₄ alkoxy or halogen-substituted phenylene or naphthylene radical and

Y is -CH ₂ CH ₂ Y ¹ , in which

Y ^{1 is} hydroxy to form the corresponding monochloropyridine derivative of the general

Formula (9),

wherein

R ¹ is C _r C ₄ alkyl, R ² is cyano, carbamoyl or sulfomethyl,

R ⁵ is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl mean wherein R ⁷

Is hydrogen or C _r C ₄ alkyl, Q is optionally substituted by C ₁ - C ₄ substituted _Alkyl, halogen or hydroxy and with the exception of methylene optionally interrupted by oxygen or

NR ^{7 is} interrupted C _r C ₁₈ -alkylene, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C _r C ₄ alkyl, C _r C ₄ alkoxy or halogen-substituted phenylene or naphthylene radical and

Y is -CH ₂ CH ₂ Y ¹ , in which

Y ^{1 is} hydroxy, followed by oxidation to form the monochloropyridine of general formula (6).

By further reaction of the monochloropyridine a) of the general formula (6) with an amine of the general formula (4) or b) by reacting the monochloropyridine of the general formula (5) with an amine of the general formula (7) or c) by reacting the monochloropyridine of the general formula (5) with an amine of the general formula (8) and subsequent oxidation of the resulting intermediate of the formula (10),

wherein R, 1 ¹ C ₁ -C ₄ alkyl ₁

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ⁴ independently of one another denote hydrogen or C _r C ₁₈ -alkyl which is optionally interrupted by hydroxyl or sulfo, substituted and, with the exception of methyl, optionally interrupted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ ₄ - C ₇ denote cycloalkyl, in which R ⁷

Is hydrogen or C _r C ₄ alkyl, or R ³ and R ⁴ are part of heterocyclic groups, R ⁵ is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ Alkyl or C ₄ -C ₇ cycloalkyl, in which R ⁷

Is hydrogen or C _r C ₄ alkyl,

Ar is an unsubstituted or substituted by sulfo, carboxy, C _r C ₄ alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ Y ¹ , in which

Y ^{1 is} hydroxy, or d) by reacting the monochloropyridine of the general formula (9) with an amine of the general formula (4) and subsequent oxidation of the resulting intermediate of the formula (10), a diaminopyridine of the formula (2) is obtained which is obtained as a mixture of isomers, wherein the ratio of the isomers of the trodden synthesis route depends.

The oxidation is preferably carried out in water, an organic solvent or in a mixture of water and organic solvent. Preferred organic solvents are, for example, acetic acid, dichloromethane or N-methylpyrrolidone. Preferred temperatures for said oxidation are temperatures of 10 to 80 ⁰ C, in particular from 30 to 50 ⁰ C. The said oxidation is advantageously carried out in the presence of a catalyst. Examples of such catalysts are salts which contain titanium, vanadium, manganese, molybdenum or tungsten or clays or clay mineral earths. Particularly advantageous catalysts are, for. As sodium tungstate, montmorillonite or kaolin. Suitable oxidizing agents are, for example, halogens or peroxides, such as. For example, chlorine, hydrogen peroxide, peroxodisulfates or peracids, such as. Eg

Chloroperbenzoic acid, peracetic acid or periodic acid or salts thereof, such as Oxone®. In strongly acidic medium, said oxidation step may also be carried out with e.g. Sulfur trioxide or oleum are carried out in the presence of iodine-containing catalysts. Another example of the oxidation step is the reaction with a halogen, e.g. B. with chlorine, the z. B. can be done in hydrochloric acid medium.

The preparation of the monoaminopyridines (5), (6) and (9) and the diaminopyridines (2) and (10) is usually carried out in water, an organic solvent such as toluene, butanol or N-methylpyrrolidone or without the use of a solvent temperatures of 30 to 150 ⁰ C, preferably at 40 to 80 ⁰ C, in the presence of a base, for example alkali metal carbonate, Alkali hydrogen carbonate, alkaline earth oxide, alkaline earth metal hydroxide, alkaline earth carbonate, or trialkylamine, preferably triethylamine or tributylamine.

Optionally, the desired secondary product can be prepared by reaction with the corresponding acid derivative or the corresponding acid, which can be converted in a conventional manner into the corresponding vinyl compound. The reaction of compounds of formula (2) or compounds of formula (10) wherein

R ¹ is C _r C ₄ alkyl, R ² is cyano, carbamoyl or sulfomethyl,

R ³ and R ⁴ independently of one another denote hydrogen or C _r C ₁₈ -alkyl which is optionally interrupted by hydroxyl or sulfo, substituted and, with the exception of methyl, optionally interrupted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ ₄ - C ₇ cycloalkyl, wherein R ⁷ is hydrogen or C _r C ₄ alkyl, or R ³ and R ⁴ are part of heterocyclic

Are groups,

R ⁵ is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl mean wherein R ⁷ is hydrogen or C _r C ₄ - Alkyl is,

Q is C _r C ₁₈ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR ⁷ , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C _r C ₄ alkyl, C _r C ₄ alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ Y ¹ in which

Y ¹ denotes hydroxy with an acid derivative or an acid to give compounds of the formula (2) or to compounds of the formula (10) in which

R ¹ is C _r C ₄ alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl, R ³ and R ^{4 are} independently hydrogen or optionally

Hydroxy, sulfato or sulfo, substituted and with the exception of methyl optionally interrupted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ interrupted C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C _r C ₄ alkyl, or R ³ and R ⁴ part of heterocyclic

Are groups,

R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfato, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ C _r C ₁₈ alkyl or C ₄ - C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C _r C ₄ alkyl is

Q is C _r C ₁₈ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR ⁷ , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C ₁ -C ₄ -AlkVl, C _r C ₄ alkoxy or halogen substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} a group which can be split off under the action of alkali, is preferably carried out in an organic solvent or without the use of solvents in the corresponding acid or the corresponding acid derivative. Preferred acids or acid derivatives are, for example, acetic anhydride, sulfuric acid, oleum or sulfur trioxide monohydrate. Preferred temperatures for said reaction are temperatures of -5 to 140 ° C, in particular from 5 to 40 ⁰ C. The said reaction with organic acid derivatives proceeds advantageously in the presence of a catalyst or dehydrating agent, wherein as catalysts pyridine or pyridine derivatives such. For example, 4-diaminopyridine, 4-pyrrolidinopyridine, nicotinic acid, or pyridonaphthyridine are particularly preferred.

Alternatively, the compound of the general formula (10) can be derivatized with an acid or an acid derivative first and then oxidized, wherein an oxidation can already take place during the derivatization with an acid or an acid derivative. In the described derivatizations with an acid or an acid derivative, it is also possible to derivatize substituents of R ¹ to R ⁵ or of the groups Q or Ar. Thus, at the groups mentioned z. As esterification, saponification or oxidation take place, for. B. hydroxy groups in R ³ to R ^{5 can} also be esterified, as is also the case in the examples described below. Furthermore, groups of R ¹ to R ⁵ or groups of Q or Ar or their substituents can be derivatized in the described oxidations.

The synthesis of the bis-reactive diaminopyridines of the general formula (2) is also carried out by stepwise introduction of the amino substituents by reacting a dichloropyridine of the general formula (3) with compounds of the general formula (8), wherein Y ^{1 is} hydroxy, followed by those described above Oxidation steps and optionally followed by the derivatization steps described above or by reacting a

Dichloropyridine of the general formula (3) with compounds of the general formula (7), wherein Y ^{1 is} hydroxy, optionally followed by the derivatization steps described above.

The dyes according to the invention can be obtained by reacting the corresponding diazonium salts with a coupling component of the general formula (2) or (10), optionally followed by the oxidation and derivatization steps described above for the coupling component analogously for the dye synthesis.

The diazonium salts are prepared in the usual way by diazotization of the corresponding amines D-NH ₂ . Preferred amines for diazotization are shown in Table 1

Table 1 :

The dyes of the general formula (1) according to the invention are obtained in the above-described preparation process as a solution or suspension and can be isolated by salting out. They can also be spray-dried, and evaporation of the solution or suspension is also possible. According to the invention, reactive dyestuffs of the general formula (1) according to the invention are present as isomer mixtures, unless the isomers were separated at one stage of the synthesis of the dyestuff or diaminopyridine or an isomerically pure coupler was used for the synthesis of the dyestuff. In addition, in the case of the reactive dyes of the general formula (1) according to the invention with the same chromophore SO ₂ Y on the one hand preferably - ß- sulfatoethylsulfonyl and on the other, particularly preferably -SO ₂ CH = CH ₂ . Preferably, the proportion of vinylsulfonyl dye to ß-ethyl-substituted dye in the molar ratio between 1: 99 and 99: 1.

The reactive dyes of the general formula (1) according to the invention are generally present as a preparation in solid or in liquid form. In solid form they generally contain the water-soluble and in particular fiber-reactive Dyes conventional electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate, and may further contain the usual in commercial dyes aids, such as buffer substances that can adjust a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate , Sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives or, if present in liquid form (including the level of thickening agents common in printing pastes), substances which ensure the shelf life of these preparations, such as mildewproofing agents.

Preferably, the reactive dyes of the general formula (1) according to the invention as a dye powder or dye granules with a content of 10 to 80 wt .-%, based on the powder or the granules, of an electrolyte salt, which is also referred to as an adjusting agent before. Granules have in particular grain sizes of 50 to 500 microns. These solid preparations may also contain the mentioned buffer substances in a total amount of up to 10 wt .-%, based on the preparation. If the dyes are present in liquid preparation, the total dye content in these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight. The electrolyte salt content in these aqueous solutions is preferably below 10% by weight. , based on the aqueous solution. The liquid preparations may contain the mentioned buffer substances usually in an amount of up to 10% by weight, preferably up to 2% by weight.

The reactive dyes of the general formula (1) according to the invention have valuable performance properties. They are used for dyeing and printing carbonamide and / or hydroxyl or amino-containing materials, for example in the form of fabrics, such as paper and leather or films, such as polyamide or in the mass, such as polyamide and polyurethane, but especially used in the form of fibers of the materials mentioned. They are used for dyeing and printing cellulosic fiber materials of all kinds. They are also preferably suitable for dyeing or printing polyamide fibers or blended fabrics Polyamide with cotton or with polyester fibers. It is also possible to use them to print textiles or paper using the inkjet process.

The present invention thus also relates to the use of the inventive reactive dyes of the general formula (1) for dyeing or printing said materials or processes for dyeing or printing such materials in per se conventional procedures, in which one or more inventive Reactive dyes of the general formula (1) used as a colorant.

Advantageously, the solutions of the reactive dyes of the general formula (1) according to the invention, optionally after addition of a buffer substance, optionally also after concentration or dilution, can be fed directly as liquid preparation to the dyeing use.

The materials mentioned are preferably used in the form of fiber materials, in particular in the form of textile fibers, such as fabrics or yarns, such as in the form of strands or wound bodies.

Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-1 and polyamide-4.

Hydroxy-containing materials are those of natural or synthetic origin such as cellulosic fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, rayon and viscose rayon.

The novel reactive dyes of the general formula (1) can be on the substrates mentioned, in particular on the fiber materials mentioned, apply and fix according to the application techniques known for water-soluble, in particular according to the application techniques known for fiber-reactive dyes.

Felt-free or low-felt wool (compare, for example, H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, especially the equipment according to the so-called Hercosett method (p Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-44) with very good fastness properties. The process of dyeing wool is carried out here in the usual and well-known Därbeweise from an acidic environment. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. In order to achieve a useful levelness of the dyeing, it is advisable to add conventional leveling agents, such as those based on a reaction product of cyanuric chloride with three times the molar amount of a

Aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or based on a reaction product of, for example, stearylamine with ethylene oxide. Thus, for example, the dye mixture according to the invention is preferably first subjected to the exhaustion process from acid dyebath having a pH of about 3.5 to 5.5 under the control of the pH, and the pH then, towards the end of the dyeing time, into the neutral and optionally weak shifted alkaline range to a pH of 8.5, especially to achieve high color depths, the full reactive binding between the dyes of the dye mixtures of the invention and the fiber bring about. At the same time, the non-reactively bound dye fraction is removed.

The procedure described here also applies to the production of dyeings on fiber materials from other natural polyamides or from synthetic polyamides and polyurethanes. For dyeing these materials, it is possible to use the customary dyeing and printing processes described in the literature and known to the person skilled in the art (see, for example, H. -K. Rouette, Handbuch der Textilveredlung, Deutscher Fachverlag GmbH, Frankfurt am Main). The dyeing liquors and printing pastes may contain other additives in addition to the dyes of the general formulas (I) and water. Additives are for example Wetting agents, anti-foaming agents, leveling agents and the properties of the textile material influencing agents, such as softening agents, additives for flameproofing and dirt, water and oil repellent or water-softening agents. In particular, printing pastes may also contain natural or synthetic thickeners, such as alginates and cellulose ethers. In dyeing baths and printing pastes, the amounts of dye can vary within wide limits depending on the desired color depth. In general, the dyes of the general formula (I) are present in amounts of from 0.01 to 15% by weight, in particular in amounts of from 0.1 to 10% by weight, based on the dyestuff or the printing paste.

On cellulose fibers obtained by the exhaust process from a long liquor using various acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, dyeings with very good, color yields. Preferably, the extraction process at a pH of 3 to 7, in particular at a pH of 4 to 6 dyed. The liquor ratio can be chosen within a wide range and is for example between 1: 3 and 1:50, preferably between 1: 5 and 1: 30. It is preferably dyed in an aqueous bath at temperatures between 40 and 105 ⁰ C, optionally at a temperature up to 130 ⁰ C under pressure, and optionally in the presence of conventional dyeing auxiliaries. To increase the wet fastness of the dyed material can be removed in a post-treatment unfixed dye. This aftertreatment is carried out in particular at a pH of 8 to 9 and at temperatures of 75 to 80 ^° C.

It is possible to proceed in such a way that the material is introduced into the warm bath and this is gradually heated to the desired temperature and the dyeing process is completed. If desired, the neutral salts which accelerate the removal of the dyes can also be added to the bath only after the actual dyeing temperature has been reached.

After the padding process cellulose fibers are also excellent color yields and a very good color composition obtained by staying at Room temperature or elevated temperature, for example up to about 60 " ¹ O, can be fixed by steaming or dry heat in a conventional manner.

Also according to the usual printing processes for cellulosic fibers, the single phase - for example, by printing with a sodium bicarbonate or other acid-binding agent-containing printing paste and subsequent steaming at

100 to 103 ⁰ C, - or two-phase - for example, by printing with neutral or weakly acidic ink and then fixing either by passing through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and then staying or steaming or treatment with dry heat of the alkaline padded material can be carried out, you get strong color prints with good contour and a clear white fund. The failure of the prints is only slightly dependent on changing fixing conditions.

When fixing by means of dry heat according to the usual thermofixing hot air is used from 120 to 200 ⁰ C. In addition to the usual water vapor of

101 to 103 ⁰ C can also superheated steam and pressure steam of temperatures up to 160 ⁰ C are used.

The acid-binding and the fixing of the dyes on the cellulose fibers causing agents are, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat. In particular, the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids may be mentioned, of the alkali metal compounds preferably the sodium and potassium compounds are meant. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.

The novel reactive dyes of the general formula (1) are characterized by high reactivity, good fixability, very good build-up capacity, as well as high light and perspiration light fastness. They can therefore be used by the Ausziehfärbeverfahren at low dyeing temperatures and require Pad-Steam process only short steaming times. The degrees of fixation are high, and the unfixed portions can be easily washed out, the difference between the degree of exhaustion and the degree of fixation remarkably small, ie the Seifverlust is very low. They are also particularly suitable for printing, especially on cotton, but also for printing on nitrogen-containing fibers, eg. As wool or silk or blended fabrics containing wool or silk.

The reactive dyes of the general formula (1) according to the invention are characterized in that non-fixed dye components can be washed out very easily on the fiber material after the dyeing process, without whitening, which is involved in the washing process, being soiled by the detaching dye. This results in advantages for the dyeing process, in which washing cycles and thus costs are saved.

The dyeings and prints prepared with the dyes of the general formula (1) according to the invention have, in particular on polyamides, high color strength and high fiber-dye binding stability in both the acidic and the alkaline range, furthermore good fastness to light and very good Wet fastness properties, such as washing, water, seawater, over-dyeing and perspiration fastness, as well as good plushing fastness, ironing fastness and rub fastness.

Furthermore, the present invention relates to the use of the abovementioned dyes of the general formula (1) in printing inks for digital textile printing by the ink-jet process.

The printing inks of the invention comprise one or more of the reactive dyes mentioned, for example in amounts of from 0.1% by weight to 50% by weight, preferably in amounts of from 1% by weight to 30% by weight and more preferably in amounts of 1 wt .-% to 15 wt .-% based on the total weight of the ink. It may also contain combinations of said reactive dyes with other reactive dyes used in textile printing. For the use of inks in the continuous flow process, a conductivity of 0.5 to 25 mS / m can be set by addition of electrolyte. Suitable electrolytes are, for example: lithium nitrate, potassium nitrate.

The dye inks according to the invention can be organic solvents with a

Total content of 1-50%, preferably from 5-30 wt .-% included.

Suitable organic solvents are, for example

Alcohols, e.g. As methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert. Butanol, pentyl alcohol, polyhydric alcohols z. B, 1, 2-ethanediol, 1, 2,3-propanetriol,

Butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-propanediol, 2,3-propanediol, pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, hexanediol, D, L-1, 2- Hexanediol, 1,6-hexanediol, 1, 2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols, e.g. B.: Polyethylene glycol, polypropylene glycol, alkylene glycols having 2 to 8 alkylene groups, eg. For example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, lower alkyl ethers of polyhydric alcohols, e.g. B .: ethylene glycol monomethyl ether, ethylene glycol, diethylene glycol, diethylene, diethylene, diethylene glycol monohexyl ether, triethylene, triethylene or tripropylene, tetraethylene glycol monomethyl ether, tetraethylene, tetraethylene, propylene glycol, propylene glycol, propylene glycol, Tripropylenglykolisopropylether, polyalkylene such. B.: Polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, Polyethylenglykoltridecylether, Polyethylenglykolnonylphenylether, amines, such as. Example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-formylethanolamine, ethylenediamine,

Urea derivatives, such as. For example, urea, thiourea, N-methylurea, N, N'-epsilon, dimethylurea, ethyleneurea, 1,1,3,3-tetramethylurea, N- acetyl ethanolamine,

Amides, such as For example: dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as. B.: Acetone, diacetone alcohol, cyclic ethers, such as. B .; Tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma-butyrolactone, epsilon-caprolactam, also sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadienesulfone, dimethylsulfoxide, dibutylsulfoxide, N-cyclohexylpyrrolidone , N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1- (3-hydroxypropyl) -2-pyrrolidone, 1, 3-dimethyl-2 - Imidazolidinone, 1, 3-dimethyl-2-imidazolinone, 1, 3-bismethoxymethylimidazolidine, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2 -Propoxyethoxy) ethanol, pyridine, piperidine, butyrolactone, trimethylolpropane, 1, 2-dimethoxypropane, dioxane, ethyl acetate, ethylenediaminetetraacetate, ethyl penthyl ether, 1, 2-dimethoxypropane, trimethylpropane. Furthermore, the printing inks of the invention may contain the usual additives, such as viscosity moderators to adjust viscosities in the range of 1, 5 to 40.0 mPas in a temperature range from 20 to 50 ⁰ C. Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas. Suitable viscosity moderators are rheological additives, for example:

Polyvinylcaprolactam, polyvinylpyrrolidone and their co-polymers polyether polyol, associative thickener, polyurea, polyurethane, sodium alginates, modified galactomannans, polyether urea, polyurethane, nonionic cellulose ethers. As further additives, the inks of the invention can surface-active substances for the adjustment of surface tensions of 20 to 65 mN / m, which are optionally adjusted depending on the method used (thermal or piezo technology).

Suitable surface-active substances are, for example: surfactants of all kinds, preferably nonionic surfactants, butyldiglycol, 1,2-hexanediol. Further, the inks may still contain conventional additives such as fungicidal and bacterial growth inhibiting agents in amounts of from 0.01 to 1% by weight based on the total weight of the ink. The inks can be conveniently prepared by mixing the components in water getting produced.

The dye inks according to the invention are suitable for use in inkjet printing processes for printing a wide variety of preprepared materials, such as silk, leather, wool, cellulosic fiber materials of all kinds and polyurethanes, and in particular polyamide fibers. The invention

Printing inks are also suitable for printing pretreated hydroxyl-containing or amino-containing fibers contained in blend fabrics, z. As mixtures of cotton, silk, wool with polyester fibers or polyamide fibers. In contrast to conventional textile printing, in which the printing ink already contains all fixing chemicals and thickeners for a reactive dye, in the case of ink-jet printing the auxiliaries must be applied to the textile substrate in a separate pretreatment step. The pretreatment of the textile substrate, such as, for example, cellulose and cellulose regenerated fibers, as well as silk and wool, takes place before printing with an aqueous alkaline liquor. Alkali, such as sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as sodium chloroacetate, sodium formate, hydrotropes such as urea, reduction inhibitors such as sodium nitrobenzenesulfonates, as well as thickening agents, the flow of the To prevent motifs when applying the ink, these are, for example, sodium alginates, modified polyacrylates or highly etherified galactomannans. These pre-preparation reagents are coated with suitable applicators, such as a 2- or 3-roll pad, with non-contact

Spray technologies, applied by foam application or with appropriately adapted inkjet technologies in a defined amount evenly on the textile substrate and then dried. After printing, the textile fiber material is dried at 120 to 150 ° C and then fixed.

The fixation of the ink jet prints prepared with reactive dyes can be carried out at room temperature, or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or electron beams or with other suitable types of energy transfer.

One distinguishes one- and two-phase fixation processes:

In single-phase fixation are the necessary for fixation

Chemicals already on the textile substrate. In the case of two-phase fixation, this pretreatment can be omitted. For fixing only alkali is needed, which is applied after the ink-jet printing before the fixing without intermediate drying. Other additives such as urea or thickener can be dispensed with. After the fixation, the post-treatment is carried out, which is the prerequisite for good fastness, high brilliance and a perfect white foundation.

The prints produced with the dye inks according to the invention have, especially on polyamide, a high color strength and a high fiber-dye bond stability in both the acidic and in the alkaline range, furthermore good light fastness and very good wet fastness properties, such as washing, water, seawater -, over-dyeing and perspiration, as well as a good pleating, ironing and rubbing fastness.

The following examples serve to illustrate the invention. The parts are by weight, the percentages are by weight unless otherwise stated. Parts by weight refer to parts by volume such as kilograms to liters.

The compounds described by formula in the examples are given in the form of the free acid. In general, however, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used in the form of their salts for dyeing. Likewise, the starting compounds and components mentioned in the following examples, in particular table examples, in the form of the free acid and components as such or in the form of their salts, preferably alkali metal salts, can be used in the synthesis.

example 1 In a mixture of 400 ml of toluene and 100 ml of triethylamine are 187 g of 2,6-dichloro-4-methyl-nicotinonitrile (3-cyano-2,6-dichloro-4-methyl-pyridine) and 89 g of 3-methoxy-propylamine entered. The mixture is heated to 50 ⁰ C, and stirred for 16 hours at this temperature.

The reaction mixture is cooled to 0 ^° C. The resulting crystals are filtered off with suction, washed with ether, dried, stirred in 1, 5 l of water, adjusted to pH 1 with hydrochloric acid, filtered off with suction, washed neutral with water, filtered off with suction and dried. Only one isomer of the formula (5-1) is obtained.

while the other isomer remains in solution. In 50 ml of 2- (2-amino-ethylsulfanyl) - ethanol 12 g of the product obtained are added and heated to 1 10 ⁰ C. After 4 hours, allowed to cool, the reaction mixture is poured onto 200 g of ice, filtered off with suction, washed with water and dried the filter cake. The product of the formula (10-1) is obtained.

The diaminopyridine of the formula (10-1) thus obtained is introduced into 100 ml of water together with 0.165 g of sodium tungstate dihydrate and 1 ml of ethanol and heated to 50 ⁰ C. 15 ml of 35% hydrogen peroxide solution are added to this mixture within 6 hours. The diaminopyridine of the formula (2-1) is obtained. The isolation is carried out after cooling by suction.

The diaminopyridine of formula (2-1 a) is stirred with methanol and added to a reaction mixture of a diazonium salt which is prepared from 8.9 g of 2-amino-5- (4-sulfophenylazo) -benzenesulfonic acid (D-44) by conventional Diazotization was obtained. With soda solution, the pH of the mixture is kept at 3.5 to 4.5 for about 2 hours and then adjusted to 6.5. It is isolated in the usual way by salting out with sodium chloride and suction and dried the resulting presscake. The product of the formula (1 -1 a) is obtained in the form of the disodium salt, written as the free acid:

10 g of the product thus obtained are added at a temperature of 10 - 15 ⁰ C in 30 ml of 100% sulfuric acid (monohydrate) and stirred for 30 minutes at this temperature. The reaction mixture is discharged onto 200 g of ice and adjusted to a pH of 6 with 50 g of calcium carbonate at a temperature of 0-5 ° C. and filtered. Evaporation of the filtrate gives dye (1 -1 b) in the form of the trisodium salt, written as the free acid,

which polyamide colors in red shades. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness. Alternatively, the filtrate is adjusted to a pH of 10 to 11 with 20% sodium hydroxide solution, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated. The residue contains the product of (1 -1 c) in the form of the disodium salt, written as the free acid,

which polyamide colors in red shades. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness.

Example 2

12 g of the product of the formula (5-1) obtained in Example 1, 15 ml of 15% sodium carbonate solution and 13 g of 2- (2-methylaminoethylsulfanyl) ethanol are introduced into 100 ml of N-methylpyrolidone. The mixture is heated to 140 ^° C until completion of the reaction. The reaction mixture contains the product of formula (10-2).

To the resulting reaction mixture is added 100 ml of water, 0.165 g of sodium tungstate dihydrate, heated to 50 ° C, dropwise at this temperature for about 2 hours 19 ml of a 35% hydrogen peroxide solution, heated to 70 to 75 ⁰ C and stirred 3 hours at this temperature. The reaction mixture contains the product of formula (2-2a).

The reaction mixture can be used without further workup for the coupling with diazonium salts. To isolate the product, 20% saline solution is added and the precipitated solid is filtered off with suction, washed and dried.

10 g of the product of the formula (2-2a) thus obtained are added at a temperature of 10-15 ° C in 30 ml of 100% sulfuric acid (monohydrate) and stirred at this temperature for 5 hours. The reaction mixture is discharged onto 200 g of ice, adjusted at a temperature of 0-5 ⁰ C with about 60 g of calcium carbonate to a pH of 6 and filtered.

The filtrate contains the compound of formula (2-2b) in the form of the sodium salt, written as the free acid.

The solution thus obtained (the filtrate) is adjusted to a pH of 10 to 1 l with 20% sodium hydroxide solution, stirred for 60 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and the precipitated solid is filtered off with suction, washed and dried. There is thus obtained a product containing the compound of the formula (2-2c).

Preparation of the dye starting from (2-2a):

The product of formula (2-2a) is added at a temperature of 15 to 20 ^0C to a reaction mixture of a diazonium salt which is composed of 12.5 g of 2-amino 5- (4-sulfo-phenylazo) -benzenesulfonic acid (D-44) was obtained by conventional diazotization.

With soda solution, the pH of the mixture is kept at 1.5 for about 2 hours and then adjusted to 6. It is heated to 35 ⁰ C by salting out with sodium thiocyanate and suction isolated. The obtained press cake is digested with acetone until no more rhodanide is detectable in acetone and dried. A product of the formula (1 -2a) in the form of the disodium salt, written as the free acid, is obtained.

The product thus obtained is added at a temperature of 10-15 ° C in 45 ml of 100% sulfuric acid (monohydrate) and stirred for 16 hours at this temperature. The reaction mixture is discharged onto 300 g of ice, adjusted at a temperature of 0-5 ⁰ C with 85 g of calcium carbonate to a pH of 6 and filtered. The filtrate contains the product of the formula (1 -2b) in the form of the trisodium salt, written as the free acid,

which polyamide colors in red shades. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness. The filtrate thus obtained is adjusted to a pH of 10 to 1 l with 20% strength sodium hydroxide solution, stirred for 1 hour at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and concentrated by evaporation. This gives the product of the formula (1 -2c) in the form of the disodium salt, written as the free acid,

The dye of formula (1-2c) may also be obtained by coupling the diazonium salt of diglybaic acid (D44) to the coupler of formula (2-2c).

Example 3

In 400 ml of toluene at 75 ⁰ C 187 g of 2,6-dichloro-4-methyl-nicotinonitrile (3-cyano-2,6-dichloro-4-methyl-pyridine) and 121 g of 2- (2-amino-ethylsulfanyl ) ethanol. Is added dropwise 101 g of triethylamine, stirred for 24 hours at 75 ⁰ C, filtered, washed with water, the toluene, the toluene phase is separated off and the solvent evaporated in vacuo. A product mixture of the following compounds (formula 9-3a) is obtained:

Half of the product thus obtained is dissolved in a mixture of 500 ml of N-methylpyrrolidone, 250 ml of water and 1.65 g of sodium tungstate dihydrate. The mixture is heated to 30 ⁰ C and 200 ml of 30% hydrogen peroxide solution are added dropwise, the temperature may rise to 75 ⁰ C. The product mixture obtained corresponds to the following formulas (6-3):

Is added to the reaction mixture with 62 g of ethanolamine (2-aminoethanol) and heated to 105 to 120 ⁰ C. At the end of reaction, the reaction mixture (820 g of solution A) The following compounds (2-3a):

The product (2-3a) can also be obtained in the following manner: Half of the product Example 3, Formula (9-3) is introduced into 62 g of ethanolamine (2-aminoethanol) and heated to 105 to 120 ⁰ C. At the end In the reaction, the reaction mixture contains the following compounds (Formula 10-3):

To the thus obtained reaction mixture are added 50 ml of water, 100 ml of N-methylpyrrolidone, heated to 50 ^° C., are added to the mixture 1.65 g of sodium tungstate. Dihydrate, 240 ml of 30% hydrogen peroxide solution is added dropwise so that the temperature does not rise above 75 ° C and stirred at this temperature until completion of the reaction, about 5 hours. At the end of the reaction, the reaction mixture (406 g solution B) contains the compounds (2-3a). The reaction mixture can without further workup for the coupling with

Diazonium salts are used. For the isolation of the product is with 20%

Brine is added and the precipitated solid is filtered off with suction, washed and dried.

10 g of the product thus obtained are added at a temperature of 10 - 15 ⁰ C in 30 ml of 100% sulfuric acid (monohydrate) and stirred for 9 hours at this temperature. The reaction mixture is discharged onto 200 g of ice, adjusted to a pH of 6 with about 65 g of calcium carbonate at a temperature of 0-5 ° C. and filtered. The filtrate contains the compounds of formula (2-3b) in the form of disodium salts, written as free acids.

The solution thus obtained (the filtrate) is adjusted to a pH of 10 to 11 with 20% sodium hydroxide solution, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated. A product is thus obtained which contains the compounds of formula (2-3c) in the form of the sodium salts, written as free acids.

93.5 g of the reaction mixture of compounds of the formula (2-3a) are added to a reaction mixture of the diazonium salt which is diazotised from 26.9 g of 2-amino-5- (4-sulfophenylazo) -benzenesulfonic acid (diglybaic acid, D44) was obtained in the usual way. With sodium carbonate solution, the pH of the mixture is maintained at 2 to 2.5 for about 4 hours. The reaction mixture is concentrated in vacuo, taken up with 400 ml of water, filtered and poured into 3 l of ethanol. The precipitated dye is filtered off with suction and dried. The product thus obtained contains the dyes of the formula (1 -3a) in the form of disodium salts, written as free acids:

The product thus obtained is added at a temperature of 10 - 15 ⁰ C in 60 ml of 100% sulfuric acid (monohydrate) and stirred for 9 hours at this temperature. The reaction mixture is discharged onto 400 g of ice, adjusted at a temperature of 0 - 5 ⁰ C with 1 15 g of calcium carbonate to a pH of 6 and filtered. The filtrate contains the dyes of the formula (1 -3b) in the form of the tetrasodium salts, written as free acids,

which color polyamide in red shades. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness. Dyes of the formula (1-3b) can also be obtained by coupling the diazonium salt of the diglybaic acid to couplers of the formula (2-3b).

The solution of the dyes (the filtrate) is adjusted with 20% sodium hydroxide solution to a pH of 10 to 1 1, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated. This gives a product which contains the dyes of (1 -3c) in the form of trisodium salts, written as free acids,

which color polyamide in red shades. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness. Dyes of the formula (1-3c) may also be obtained by coupling the diazonium salt of the diglybaic acid to couplers of the formula (2-3c).

Example 4

81 g of the reaction mixture Example 3 Formula (2-3a) become a reaction mixture of the diazonium salt which consists of 25 g of 2- (4-amino-3-sulfophenyl) -2H-naphtho [1,2-d] [1, 2,3] triazole-6,8-disulfonic acid (Formula D48) was obtained by diazotizing in the usual manner.

With soda solution, the pH of the mixture is kept at 2 to 2.5 for about 1 hour. The reaction mixture is filtered and poured into 1, 5 l of ethanol. The precipitated dye is filtered off with suction and dried. The product thus obtained contains the dyes of the formula (1-4a) in the form of the trisodium salts, written as free acids:

20 g of the product thus obtained are added at a temperature of 10 - 15 ⁰ C in 60 ml of 100% sulfuric acid (monohydrate) and stirred for 6 hours at this temperature. The reaction mixture is discharged to 400 g of ice, placed at a temperature of 0-5 ° C with 110 g of calcium carbonate to a pH of 5.5 and filtered. The filtrate contains the dyes of the formula (1 -4b) in the form of the pentasodium salts, written as free acids,

which polyamide color in clear orange tones. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness.

The solution of the dyes (the filtrate) is adjusted with 20% sodium hydroxide solution to a pH of 10 to 1 1, stirred for 30 minutes at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid and evaporated. This gives a product which contains the dyes of the formula (1 -4c) in the form of tetrasodium salts, written as free acids,

which polyamide color in clear orange tones. The dyeings are characterized by good fastness properties, in particular by good light and wet fastness. Analogously to the preceding examples, the compounds can be prepared in the following table:

Example 42

In 150 ml of 2- (2-amino-ethylsulfanyl) -ethanol 47 g of 2,6-dichloro-4-methyl-nicotinonitrile (3-cyano-2,6-dichloro-4-methyl-pyridine) at a temperature of 50 ⁰ C entered. The mixture is heated to 120 ⁰ C, and stirred for 6 hours at this temperature. The reaction mixture is diluted with 500 ml of water, treated with 70 g of sodium chloride and stirred for about 1 hour. When the mixture is standing, an oily phase precipitates, which is added to ice. The mixture thus obtained is adjusted to a pH of from 3 to 3.5 with hydrochloric acid, allowed to stand for about 16 hours, filtered off with suction, the resulting presscake is washed with water, suspended in water, filtered off with suction again and washed with water. The obtained press cake contains the product of the following formula (11 -11).

)

The obtained press cake is dispersed in 300 ml of ice water. The mixture is warmed to 30 ⁰ C and treated with 1.65 g of sodium tungstate dihydrate. To the

Mixture at a temperature of 30 ⁰ C within 30 minutes 15 ml of 35% hydrogen peroxide solution is added, further 15 ml of a 35% hydrogen peroxide solution are added within 30 minutes, the reaction mixture heated to 50 ⁰ C. It is stirred for 3 hours at this temperature. In the following, the oxidation is completed by dropping a total of 68 ml of a 35% hydrogen peroxide solution and simultaneously raising the temperature to 75 ° C. The reaction mixture (634 g) contains the product of formula (12-1).

315 g of the reaction mixture thus obtained are added to a reaction mixture of the diazonium salt obtained from 8.93 g of 2-amino-5- (4-sulfophenylazo) benzenesulfonic acid (diglybaic acid) by diazotizing in the usual manner. With soda solution, the pH of the mixture is kept at 3.5 to 4.5 for about 4 hours and then adjusted to 6.5. The reaction mixture is filtered and evaporated. The residue thus obtained contains the product of formula (13-1a) in the form of the disodium salt, written as the free acid:

The product thus obtained is added at a temperature of 10-15 ° C in 90 ml of 100% sulfuric acid (monohydrate) and stirred for 2 hours at this temperature. The reaction mixture is discharged onto 600 g of ice, adjusted at a temperature of 0-5 ⁰ C with 170 g of calcium carbonate to a pH of 6 and filtered. Half of the filtrate is evaporated. The residue contains the product of formula (13-1b) in the form of the tetrasodium salt, written as the free acid,

The remaining half of the filtrate is adjusted to a pH of 10 to 1 l with 20% sodium hydroxide solution, stirred for 1 hour at this pH, adjusted to a pH of 6 to 6.5 with hydrochloric acid, to conventional Were isolated by salting out with sodium chloride and the resulting presscake dried. This gives the product of the formula (13-1 c) in the form of the disodium salt, written as the free acid,

Analogously to the preceding example, the compounds can be prepared in the following table:

Table 2

Further examples of dyes according to the invention are listed in the following table:

Dyeing Example 1

1 part of the dyestuff according to formula (1 -1 c) are dissolved in 2000 parts of water and 5 parts of sodium sulphate, 1 part of a leveling agent (based on a higher aliphatic amine condensation product and ethylene oxide) and 5 parts of sodium acetate are added.

Then the pH is adjusted to 4.5 with acetic acid (80%). The dyebath is heated to 50 ^° C. for 10 minutes and then 100 parts of a wool fabric are added. The mixture is heated within 50 minutes to a temperature of 100 ⁰ C and colored for 60 minutes at this temperature. Then allowed to cool to 90 ⁰ C and removes the Färbegut. The wool fabric is washed with warm and cold water, then spun and dried. It will get a red color with good light and wet fastness, as well as good Faseregalität.

Dyeing Example 2

1 part of the dyestuff according to formula (1 - 2c) is dissolved in 2000 parts of water and 1 part of a leveling agent (based on a condensation product of a higher aliphatic amine and ethylene oxide and 5 parts of sodium acetate is added.) The pH is then adjusted with acetic acid (80 %) is set to a value of 5. The dyebath is heated for 10 minutes at 50 ⁰ C., and then 100 parts of a polyamide fabric was added. The mixture is heated over 50 minutes to a temperature of 1 10 ⁰ C, and dyeing is 60 minutes This temperature is then allowed to cool to 60 ^° C. and the product is removed.The polyamide fabric is washed with warm and cold water, soaped and then spun and dried.

It will get a red color with good light and wet fastness, as well as good Faseregalität.

Dyeing Example 3 2 parts of a dye obtained according to formula (1 -3b) and 50 parts

Sodium chloride is dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent added. In this dyebath there One 100 g of a cotton fabric. The temperature of the dyebath is initially maintained at 25 ^° C. for 10 minutes, then raised to final temperature (40-80 ^° C.) in 30 minutes, and this temperature is maintained for a further 60-90 minutes. Thereafter, the dyed fabric is first rinsed with drinking water for 2 minutes and then with e-water for 5 minutes. Neutralize the dyed fabric at 40X; in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid for 10 minutes. With E-water is rinsed at 70 ⁰ C and then soaped for 15 minutes with a detergent, rinsed again and dried. This gives a strong red color with very good fastness properties.

Dyeing Example 4

A textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried. The fleet intake is 70%.

An aqueous ink containing 2% of the dye according to Example (1 -3c) 20% sulfolane 0.01% Mergal K9N 77.99% water with a drop-on-demand (bubble jet) ink is applied to the textile pretreated in this way. Jet print head printed. The print is completely dried. The fixation takes place by means of saturated steam at 102 ⁰ C for 8 minutes. Subsequently, the pressure is rinsed warm, subjected to hot water at 95 ⁰ C a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.

Claims

claims

1. reactive dyes of the general formula (1),

residential

R ^{1 is} C ₁ -C ₄ -alkyl, R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ , R ⁴ and R ^{5 are} independently hydrogen or optionally

Hydroxy, sulfo, sulfato or vinylsulfonyl-substituted and with

In which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl or R ³ and R ^{4 are} heterocyclic group-derived radicals, C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl which is interrupted by oxygen or NR ⁷ Q is optionally substituted by C ₁ -C ₄ -alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or

NR ^{7 is} interrupted C 1 -C 4 -alkylene, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -AIKoXy or halogen-substituted phenylene or naphthylene radical, Y is -CH = CH ₂ or -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} hydroxy or a group cleavable by AlKali effect.

2. A reactive dye according to claim 1, wherein D is a group of the general formula (DI) (D-II) or (D-XII) ₁

where the bond to the diazo group is the diaminopyridine group, B is a direct chemical bond, an ethylene or a diazo group, R ^D1 and R ^D2 are each independently hydrogen, (C ₁ -C ₎ -alkyl (C ₁ CJ-AIkOXy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen, and X ^{D1 has} one of the meanings of R ^D1 or R ^D2 or for a group of

Formula -SO ₂ -Z is where

Z has one of the meanings of Y or

D represents a naphthyl group of the general formula (D-III),

in which the bond to the diazo group is at the diaminopyridine group, R ^D3 and R ^D4 independently of one another are hydrogen, (C ₁ -C) -cycloalkyl, (C ₁ -C) -alkoxy, hydroxyl, sulfo, carboxy, cyano, nitro, amido, Ureido or halogen; and X ^{D2 has} one of the meanings of X ^D1 ; or D is a group of general formula (D-IV),

wherein

- ^{* is} the bond to the diazo group on the diaminopyridine group, M is hydrogen, an alkali metal, ammonium, one equivalent of a

Means alkaline earth metal or organic monovalent cations, in particular alkylammonium, R ^D5 and R ^D6 independently of one another have one of the meanings of R ^D1 and R ^D2 ; R ^D7 is hydrogen, (C ₁ - C ₄₎ alkyl, unsubstituted or substituted by (C ₁ -C ₄₎ - alkyl,

(C ₁ -CJ -alkoxy, sulfo, halogen or carboxyl substituted phenyl; and Z ^D2 is a group of the general formula (DV) or (D-VI) or (VII-D),

wherein is the bond to nitrogen, V is fluorine or chlorine;

IT, U ^{D2 are} independently fluorine, chlorine or hydrogen; and

Q ^D1, Q ^D2 is independently chlorine, fluorine, cyanamido, hydroxyl, (C ₁ - C ₆₎ alkoxy, phenoxy, sulfophenoxy, mercapto, (C ₁ -C ₆₎ - alkylmercapto, pyridino, carboxypyridino, or a group of Carbamoylpyhdino mean general formula (D-VIII) or (D-IX), wherein - ^{* represents} the bond to the heterocycle,

_! FT hydrogen or (C.-CJ alkyl, sulfo (C ₁ -C ₆₎ -alkyl or phenyl which is unsubstituted or substituted by (0, -CJ alkyl, (C ₁ - C4) -alkoxy, sulfo, Halogen, carboxy, acetamido, ureido is substituted;

R ^D9 and R ^D1 ° independently of one another have one of the meanings of

R ^D8 , or form a cyclic ring system of the formula - (CHJ ₁ -, wherein j is 4 or 5, or alternatively - (CH ₂ ) ₂ -E- (CH ₂ ) ₂ -, where E is oxygen, sulfur, sulfo, - NR ^D11 and R ^{D11 is} (C 1 -C 6 alkyl;

W is phenylene, which is unsubstituted or substituted by 1 or 2 substituents, such as (C.-CJ-alkyl, (C ₁ -CJ-alkoxy, carboxy, sulfo, chlorine,

Bromine, or

W is (O, CJ -alkylene-arylene or (C ₂ -C ₆ ) -alkylene, which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carbonamido, or W is phenylene-CONH-phenylene which is unsubstituted or is substituted by (C ₁ -C ₎ -alkyl, (C ₁ -C) -alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen, or

W is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and

Z has the abovementioned meaning; or

D is a group of the general formula (DX) or (D-XI),

in which

- ^{* stands} for the bond to the diazo group on the diaminopyridine, R ^{D12 has} one of the meanings of R ^D1 , X ^{D3 has} one of the meanings of X ^D1

X ^D4 -CN and COOR ⁰¹³ wherein R ¹³ has one of the meanings of R and R stands for C ₁ -C ₄ alkyl.

3. reactive dye of the general formula (1 a) according to at least one of claims 1 or 2,

wherein (DI), Ar and R ¹ to R ^{5 have} the meanings given in claims 1 and 2 and n is O or 1.

4. A reactive dye of the general formula (1 b) according to claim 1 or claim 2

wherein

(D-II), Ar and R ¹ to R ^{5 have} the meanings given in claims 1 and 2 and n is 0 or 1.

5. A reactive dye of the general formula (1 c) according to claim 1 or claim 2,

wherein (D-III), Ar and R ¹ to R ^{5 have} the meanings given in claims 1 and 2 and n is 0 or 1.

6. A reactive dye of the general formula (1 d) according to claim 1 or claim 2, wherein

X ^{D1 has} one of the meanings of R ^D1 or R ^D2 and R ³ and R ⁴ , Ar, Q and Y have the meanings given in claims 1 and 2 and R ^{5 is} hydrogen or C ₁ -C ₁₈ alkyl.

7. A reactive dye of the general formula ( ^' I e) according to claim 1 or claim 2,

residential

R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ^{4 are} independently hydrogen or optionally

C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl which is unsubstituted or interrupted by oxygen or NR ⁷ , with the exception of methyl, where R ^{7 is} C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl; Is hydrogen or C ₁ -C ₄ -alkyl or R ³ and R ^{4 are} constituents of heterocyclic groups, R ^{5 is} hydrogen or C ₁ -C ₁₈ -alkyl,

Q is optionally substituted by C ₁ - C ₄ _AIKyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or

NR ⁷ interrupted C ^ C ^ alkylene, and D and Y have the meanings mentioned in claims 1 and 2.

Reactive dye of the general formula ( ^" I f) according to Claim 1 or Claim 2,

wherein R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ^{4 are} independently hydrogen or optionally

C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl which is unsubstituted or interrupted by oxygen or NR ⁷ , with the exception of methyl, where R ^{7 is} C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl;

Is hydrogen or C ₁ -C ₄ -alkyl or R ³ and R ^{4 are} constituents of heterocyclic groups, R ^{5 is} hydrogen or C ₁ -C ₁₈ -alkyl,

NR ⁷ interrupted C ^ C ^ alkylene and (D-XII) and Y have the meanings mentioned in Anyprüchen 1 and 2.

9. Diaminopyridines of the general formula (2),

wherein

R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl, R ³ , R ⁴ and R ⁵ independently of one another are hydrogen or C ₁ - optionally substituted by hydroxyl, sulfo, sulfato or vinylsulfonyl and optionally interrupted by oxygen or NR ⁷ , with the exception of methyl. C ₁₈ -AIKyI or C ₄ -C ₇ cycloalKyl, in which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl, or R ³ and R ^{4 are} heterocyclic group constituents,

NR ^{7 is} interrupted C 1 -C 4 -alkylene, n is 0 or 1,

Y ^{1 is} hydroxy or a group cleavable by AlKali effect.

10. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3), wherein R ¹ and R ² are defined as defined in claim 1, with one molar equivalent of an amine of the general formula (4),

wherein

R and R independently of one another denote hydrogen or optionally C ₁ -C ₁₈ -alkyl or C ₄ interrupted by hydroxyl, sulfo, substituted and, where appropriate, by methyl, unsubstituted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ - C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C ₁ -C ₄ -AIKyI, or R ³ and R ^{4 are} heterocyclic group components, wherein the monoaminopyridine of the general formula (5) is obtained as a mixture of isomers

and reacting the monochloropyridine of the general formula (5) with an amine of the general formula (7),

wherein

Q, Ar, n and R ⁵ are as defined in claim 1 and Y is -CH ₂ CH ₂ OH or

Reaction of the monochloropyridine of the general formula (5) with an amine of the general formula (8), wherein R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ -C ₇ cycloalkyl, wherein R ⁷

Is hydrogen or C ₁ -C ₄ -alkyl,

Q is C ₁ -C ₄ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and is optionally interrupted by oxygen or NR ⁷ , with the exception of methylene, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical and Y is -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} hydroxy and subsequent oxidation of the compound of formula (10) formed from compound (5) and compound (8),

wherein R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ^{4 are} independently hydrogen or optionally substituted by hydroxy or sulfo, substituted and with the exception of methyl optionally interrupted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ -C _{7 is} cycloalKyl, wherein R ⁷ Is hydrogen or C ₁ -C ₄ alkyl, or R ³ and R ^{4 are} heterocyclic constituents

Groups are, R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfo, substituted and with

Exception of methyl optionally interrupted by oxygen or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ -C ₇ cycloalKyl, wherein R ⁷

Is hydrogen or C ₁ -C ₄ -alkyl, Q is optionally substituted by C ₁ - C ₄ substituted _AIKyl, halogen or hydroxy and with the exception of methylene optionally interrupted by oxygen or NR ⁷ interrupted C ^ C ^ alkylene, n is 0 or 1 is

Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -AIKoXy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} hydroxy, optionally followed by reaction with the corresponding

Acid derivative or the corresponding acid to a desired secondary product (2), which can be converted into the corresponding vinyl compound in a conventional manner.

1 1. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3),

wherein R ¹ and R ² are defined as defined in claim 1, with one molar equivalent of an amine of formula (8),

wherein

R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally by oxygen or NR ⁷ interrupted C ₁ -C ₁₈ alkyl or C ₄ -C ₇ cycloalkyl, in which R ^{7 is} hydrogen or C ₁ -C ₄ alkyl, Q is optionally substituted by C ₁ - C ₄ _Alkyl, halogen or hydroxy and with the exception of Methyl is optionally interrupted by oxygen or NR ⁷ interrupted C ^ C ^ alkylene, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical and Y is -CH ₂ CH ₂ Y ¹ , wherein Y ^{1 is} hydroxy, under Formation of the corresponding monochloropyridine derivative of the general formula (9),

wherein R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ^{5 is} hydrogen or C ₁ -C ₁₈ -alkyl or C ₄ -C ₇ -cycloalkyl which is optionally interrupted by hydroxyl, sulfo, substituted and, with the exception of methyl, optionally interrupted by oxygen or NR ⁷ , in which R ^{7 is} hydrogen or C ₁ -C _{4 is} -alkyl,

Q is optionally substituted by C ₁ -C ₄ -alkyl, halogen or hydroxy and, with the exception of methylene, optionally substituted by oxygen or

NR ^{7 is} interrupted C ₁ -C ₄ -alkylene, n is 0 or 1, Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -AIKoXy or halogen-substituted phenylene or naphthylene radical, and Y is -CH ₂ CH ₂ Y ¹ in which

Y ^{1 is} hydroxy, followed by oxidation of the compound (9) to form the monochloropyridine of the general formula (6),

wherein R ^{1 is} C ₁ -C ₄ -alkyl ₁

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ^{5 is} hydrogen or optionally substituted by hydroxy and with

The exception of methyl optionally interrupted by oxygen or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ - C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C ₁ -C ₄ -AIKyI,

Q is C ₁ -C ₄ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and which is optionally interrupted by oxygen or NR ⁷ , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ OH and further reaction of the monochloropyridine of the general formula (6) with an amine of the general formula ( 4)

wherein

R ³ and R ⁴ are each independently hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, optionally interrupted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ -C ₇ cycloalkyl, wherein R ^{7 is} hydrogen or C ₁ -C ₄ alkyl, or R ³ and

R ^{4 are} constituents of heterocyclic groups,

- followed, if appropriate, by an implementation with the corresponding

Acid derivative or the corresponding acid to a desired secondary product

(2), which can be converted in a conventional manner into the corresponding vinyl compound.

12. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3),

are C ₇ cycloalkyl, wherein R ⁷ is hydrogen or C ₁ - daytime R ⁵ is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl, may be interrupted by oxygen or NR ⁷ C ₁ -C ₁₈ -alkyl or C ₄ - C ₄ -alkyl is

NR ^{7 is} interrupted C ₁ -C ₁₈ -alkyl, n is 0 or 1,

Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI ₁ C ₁ -C ₄ -AIKoXy or halogen-substituted phenylene or naphthylene radical and Y is -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} hydroxy to give the corresponding monochloropyridine derivative of general formula (9), wherein

R ^{1 is} C ₁ -C ₄ -alkyl ₁

R ² is cyano, carbamoyl or sulfomethyl, R ⁵ is hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ C ₁ -C ₁₈ -alkyl or C ₄ -, C ₇ cycloalkyl wherein mean R ⁷

Is hydrogen or C ₁ -C ₄ -alkyl,

NR ^{7 is} interrupted C 1 -C 4 -alkylene, n is 0 or 1,

Y ^{1 is} hydroxy, and further reaction of the monochloropyridine of the general formula (9) with an amine of the general formula (4),

wherein

R and R independently of one another denote hydrogen or C ₁ -C ₁₈ -alkyl which is optionally interrupted by hydroxyl, sulfo, substituted and, where appropriate, by methyl, oxygen, sulfonyl (-SO ₂ -) or NR ⁷ , or C ₄ -C ₇ Cycloalkyl in which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl or R ³ and R ^{4 are} constituents of heterocyclic groups, and subsequent oxidation of the compound of formula (10) resulting from compound (9) and compound (4),

wherein R ^{1 is} C ₁ -C ₄ -alkyl ₁

R ^{2 is} cyano, carbamoyl or sulfomethyl,

R ³ and R ⁴ are independently hydrogen or optionally substituted by hydroxyl or sulfo, substituted and with the exception of methyl, may be interrupted by oxygen, sulfonyl (-SO ₂ -), or NR ⁷ interrupted C ₁ -C ₁₈ -alkyl or C ₄ - C _{7 is} cycloalkyl, where R ^{7 is} hydrogen or C ₁ -

C ₄ alkyl, or R ³ and R ^{4 are} heterocyclic group, R ^{5 is} hydrogen or optionally substituted by hydroxy, sulfo, substituted and with the exception of methyl optionally interrupted by oxygen or NR ⁷ C ₁ -C ₁₈ -AIKyI or C ₄ -C _{7 is} cycloalkyl, in which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl,

Q is C ₁ -C ₄ -alkylene which is unsubstituted or substituted by C ₁ -C ₄ -alkyl, halogen or hydroxyl and which is optionally interrupted by oxygen or NR ⁷ , n is 0 or 1, Ar is an unsubstituted or by sulfo, carboxy, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ Y ¹ , where Y ^{1 is} hydroxyl, optionally followed by reaction with the corresponding acid derivative or the corresponding acid to a desired secondary product (2), which can be converted in a conventional manner into the corresponding vinyl compound.

13. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3),

wherein R ¹ and R ² are defined as defined in claim 1, with one molar equivalent of an amine of the formula (7),

wherein

Q, Ar, n and R ⁵ are as defined in claim 12 and Y is -CH ₂ CH ₂ OH, to give the monochloropyridine of the general formula (6),

wherein

R ^{1 is} C ₁ -C ₄ -alkyl,

R ^{2 is} cyano, carbamoyl or sulfomethyl, R ^{5 is} hydrogen or optionally substituted by hydroxy and with

In which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl, optionally interrupted by oxygen or NR ⁷ interrupted C ₁ -C ₁₈ -AIKyI or C ₄ -C ₇ cycloalKyl,

NR ^{7 is} interrupted C 1 -C 4 -alkylene, n is 0 or 1, Ar is an unsubstituted or substituted by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -alkoxy or halogen-substituted phenylene or naphthylene radical, Y is -CH ₂ CH ₂ OH and further reaction of the monochloropyridine of the general formula ( 6) with an amine of the general formula (4),

wherein

R and R independently of one another denote hydrogen or optionally C ₁ -C ₁₈ -alkyl or C ₄ interrupted by hydroxyl, sulfo, substituted and, where appropriate, by methyl, unsubstituted by oxygen, sulfone or sulfonyl (-SO ₂ -), or NR ⁷ C _{7 is} cycloalkyl, in which R ^{7 is} hydrogen or C ₁ -C ₄ -alkyl, or R ³ and R ^{4 are} constituents of heterocyclic groups,

optionally followed by reaction with the corresponding acid derivative or the corresponding acid to give a desired secondary product (2).

14. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3),

wherein R ¹ and R ^{2 are} as defined in claim 1, with two molar equivalents of an amine of the formula (8),

wherein

R is hydrogen or unsubstituted or hydroxy- sulfo, substituted and interrupted with the exception of methyl, may be interrupted by oxygen or NR ⁷ C ₁ -C ₁₈ -alkyl or C ₄ - C ₇ cycloalkyl mean wherein R ⁷ is hydrogen or C ₁ -C ₄ -AikyI is, Q is optionally substituted and, except for methylene, optionally interrupted by oxygen or NR ⁷ interrupted C ^ C ^ alkylene, n is 0, Ar is an unsubstituted or by sulfo, carboxy, C ₁ -C ₄ -AIKyI, C ₁ -C ₄ -Alkoxy or halogen substituted phenylene or naphthylene radical and Y is -CH ₂ CH ₂ Y ¹ , wherein

Y ^{1 is} hydroxy, followed by oxidation of the resulting intermediate, optionally followed by reaction with the corresponding

Acid derivative or the corresponding acid to a desired secondary product (2), which can be converted in a conventional manner into the corresponding vinyl compound.

15. A process for preparing the diaminopyridines of the general formula (2), by reacting a 2,6-dichloropyridine of the general formula (3),

wherein R ¹ and R ^{2 are} as defined in claim 1, with two molar equivalents of an amine of the formula (7),

residential

Q, Ar, n and R ⁵ are as defined in claim 14 and Y is -CH ₂ CH ₂ OH,

optionally followed by reaction with the corresponding acid derivative or the corresponding acid to give a desired secondary product (2) which can be converted into the corresponding vinyl compound in a conventional manner.

16. The method according to claims 10 and 15, wherein the oxidation is carried out in water, an organic solvent or in a mixture of water and organic solvent in the presence of a catalyst.

17. The method according to claims 10 and 15, wherein the preparation of the monoaminopyridines (5), (6) and (9) is carried out in water, an organic solvent, or without solvent at temperatures of 30 to 150 ° C in the presence of a base.

18. The method according to claim 9, wherein the dehvation takes place in an organic solvent or without solvents in the corresponding acid or the corresponding acid derivative.

19. A process for the preparation of the dyes according to claim 1 by reacting the corresponding diazonium salts by conventional diazotization of

Amines D-NH ₂ , wherein D has the meaning given in claim 2, can be obtained with a coupling component of the general formula (2).

20. dye preparations containing one or more reactive dyes according to one or more of claims 1 to 8 for dyeing and printing carbonamidgruppenhaltigem and / or amino-containing and / or hydroxyl-containing material, in particular fiber material.

21. Aqueous printing inks for textile printing by the ink-jet process, characterized in that they contain one or more reactive dyes from the

Claims 1-8 in amounts of 0.01 wt.% To 40 wt.% Based on the total weight of the inks.

22. A process for dyeing, for conventional printing and for printing by the ink-jet process of textile fiber materials, characterized in that one or more reactive dyes used in claims 1 to 8.