HK1003228B - Reactive dyes, process for their preparation and their use - Google Patents

Description

Reactive dyes are widely used for dyeing and printing textile fibre materials. e current state of the art often does not fully satisfy the high requirements for suitability for certain dyeing processes and the level of authenticity of the dyes, although a large number of usable reactive dyes with different properties and for different applications are available today.

The Commission has also proposed a number of measures to improve the quality of the printing process, in particular by improving the quality of the printing process and by improving the quality of the printing process.

Copper formats with the basic structure of formula (1) are already known from US-A-4024123, but other substitutes are provided in the chlorotriazine residue Y of formula (2), e.g. 2,4-dichloro-6-methylamino-s-triazine, from which the substituent Y can be formed.

Finally, copper formasan dyes are already known from EP-A-210951 which contain reactive groups with a sulphone bridging compound (-SO2-) and are bound to the formasan structure by a carbonyl group (-CO-) and not by an amino group (-NH-).

The present invention is based on the task of finding new reactive dyes particularly suitable for printing textile fibre materials. The dyes should have a high degree of fixation and at the same time a good washability of the unfixed parts, and generally have good authenticity and in particular blue hues.

The invention relates to reactive dyes of the formula: Other where Y is a remainder of the formula Other or Other -CO-A-SO2-X (3), Other Other R1 and R2 are independently hydrogen or C1−4 alkyl, substituted by halogen, cyan, C1−4 alkoxy, N,N-Di-C1−4 alkylamine, hydroxy, carboxy, sulphate or sulphate; A is an aliphatic or aromatic constituent, if any, substituted and X is β-sulphate ethyl, β-thiosulphate ethyl, β-phosphatyl, β-acyloxyethyl, β-halogenethyl or vinyl, the benzene residues I, II and III may contain 2 to 4 sulphate groups or the -NH-Y residue in benzene II may contain additional substituents; and the reactive residue of the forrest (1) contains only a single fibre residue.

The following are suitable substitutes R1 and R2 in the chlorine-1,3,5-triazine residues Y of formula (2): hydrogen, C1−4 alkyl substituted with halogens such as fluorine, chlorine and bromine, cyan, C1−4 alkoxy, N,N-Di-C1−4 alkylamino, hydroxy, carboxy, sulfo or sulphate. Examples of such amino groups are: -NH2, β-methoxyethylamino, γ-methoxypropylamino, β-aethoxyethylamino, β-chlorophylamino, β-cyanpropylamino, γ-cyanpropylamino, β-hydroxylamino, β-hydroxylamino, sulfolamino, β-boxylhelamino, β-methoxylamino, β-methylamino, β-methylamino, β-methylamino, β-methylamino, β-carboxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxylamino, β-methoxy, β-methoxylamino, β-methoxy,

The aliphatic or aromatic bridge link A in the remainder of formula (3) is preferably an alkyl or aryl residue. Thus, A can be a long (e.g. with 10 or more carbon atoms) or shorter, straight-chain or branched, cyclic or bicyclic alkyl residue; in particular, an alkyl residue with 2 to 6 carbon atoms is considered, e.g. ethylene, propylene, butylene, hexylene, cyclohexylene or endomethylenohylohexylene.

The β-acetoxyethyl residue in particular and the β-chlorethyl residue in particular may be considered as β-acyloxyethyl for X.

Other examples of substituents for benzene residues I, II and III are alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, aethoxy, propopxy, isopropoxy or butyxy, acylamine groups with 1 to 8 carbon atoms, in particular C2−6 alkanoyl groups such as acetylamino, propionylamino or benzoylamino, amine, alkylamine with 1 to 4 carbon atoms, such as methyl sulphate, propylamino, propylamino, benzoylamino, isopropyl sulphate or butylamino, up to and including phenol, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl, n-methyl,

The following are preferred: (a) Reactive dyes of formula (1) wherein Y is a residue of formula Other The following substances are to be classified as: Other (b) Reactive dyes of formula (1) in which the benzene residues I, II and III do not contain any other substituents.

The reaction dye of formula Other where Y has the value given in formula (1), m is 1 or 2, n is 0, 1 or 2, and m+n = 2, 3 or 4.

The most preferred reagents are those of formula (4) Other where the 2, 3 or 4 sulphuric acid groups in the benzene rings I and III are bound as follows: 1,3,3'-Trisulf; 1,2'-Disulf; 1,3-Disulf; 3,2'-Disulf; 1,3,2',4'-Tetrasulf; 1,3,4'-Trisulf; 1,2',4'-Trisulf; 3,2',4'-Trisulf; 1,3'-Disulf; or 1,3,2'-Trisulf.

The most preferred reagent is the formula Other

The reaction dye of formula

The remainder of the formula contained in the colouring matter of formula (1) Other The remainder of the formula (3) has a residual, the -SO2-X group, which contains a residual, e.g. if X is β-chlorethyl, or may be active according to the type of the fibres, e.g. if X is vinyl.

The process of preparation of the reagents of formula (1) is characterised by the use of a compound of formula Other condensed with 2,4,6-trichloro-s-triazine and the resulting primary condensation product with an amine of the formula Other where R1 and R2 have the values given, condensed, or condensed with a 2-amino-4,6-dichlor-s-triazine; or condensed with an acyl halidescorresponding to the remainder of formula (3) and followed by a further conversion reaction, if necessary.

The preferred embodiments of the invention are characterized by the fact that the (a) an amine of the formula (9) or a 2-amino-4,6-dichlorosulf-triazine is used, Other The following shall be added to the list of active substances: Other (c) uses a compound of formula (8) in which the benzene residues I, II and III do not contain any other substituents.

A particularly favourable embodiment of the process of the invention is characterized by the use of a compound of the formula where m is the number 1 or 2 and n is the number 0, 1 or 2 and m+n = 2, 3 or 4 is used.

The most preferred embodiments of the method of the invention are characterised by condensation of a compound of formula (11) with 2,4,6-trichloro-s-triazine and condensation of the resulting primary condensation product with an amine of formula (9) or with a 2-amino-4,6-dichloro-s-triazine.

The important compounds of the formulas 6 and 7 are obtained by taking a compound of the formula Other Condensed with 2,4,6-trichloro-s-triazine and the resulting primary condensation product condensed with ammonia or β-sulphoethylamine or condensed with 2-amino-4,6-dichloro-s-triazine or 2- ((β-sulphoethylamino) -4,6-dichloro-s-triazine.

Compounds of formula (8) are e.g. the copper complexes of The following substances are to be classified in the same heading as the active substance: The following substances are to be classified in the same heading as the active substance: a width of not more than 30 mm, a width of not more than 30 mm, The following substances are to be classified in the same heading as the active substance: The following substances are to be classified in the same heading as the active substance: a width of not more than 30 mm, a width of not more than 30 mm, a width of not more than 30 mm, The following substances are to be classified in the same heading as the active substance: The following substances are to be classified in the same heading as the active substance: a width of not more than 30 mm, a width of not more than 30 mm, The following substances are to be classified in the same category as the active substance:

The following are examples of amines of formula (9): ammonia, methoxyethylamine, aethoxyethylamine, methoxypropylamine, chlorophylamine, hydroxyethylamine, dihydroxyethylamine, aminomethanesulfonic acid, hydroxypropylamine, glycine, aminoethylamine sulfonic acid, N-methylaminoethylamine, N-ethylaminoethylamine, β-sulfatoethylamine, γ-N,N-dimethylpropylamine, N-methyl-N-β-hydroxyethylamine, hydroxylethylamine, hydroxyl sulphonyl.

In the manufacture of such triazine dyes, the individual steps of the process may be carried out in different sequences, or even simultaneously, if necessary. Different process variants are possible. The implementation is generally carried out in succession. It depends on the structure of the starting materials which of the possible process variants gives the best results or under which special conditions, e.g. at which condensation temperature, the reaction is most advantageous to carry out.

Acyl halides corresponding to the rest of formula (3) are known, examples being: a width of not more than 30 mm, a thickness of not more than 0,05 mm, a width of not more than 30 mm, The 'Chemical' is a chemical compound containing a chemical element with a chemical structure which is a chemical element.

A modified embodiment of the process is to first produce a dye containing a precursor of the reactive residue and then convert it to the final stage, e.g. by esterification or an addition reaction. For example, one can produce a dye in which X is a residue HO-CH2CH2 and convert the intermediate product to sulphuric acid before or after acylation, so that the hydroxy group is transferred to the sulphate group; or one can use an analogue dye in which X is the group H2C=SS-CH and deposit thiosulphuric acid to the intermediate product, leaving a residue HO3CH2CH2.[1] The hydrolysis of the sulphate group is carried out in a precursor or formula of the formula (1):B. by translocation with concentrated sulphuric acid at 0°C to moderately elevated temperature. Sulphation can also be achieved by reaction of the hydroxy compound with two equivalent chlorosulphonic acids per hydroxy group in a polar organic solvent such as N-methylpyrrolidone at 10 to 80°C. Preferably, sulphation is achieved by introduction of the compound in sulphuric acid monohydrate at 5 to 15°C. The introduction of another residue for X in a compound of formula (1) or an intermediate in place of a halogen atom or sulphate group, such as a sulphate thiosulfate or phosphatase, is known to be the most effective way.

For example, reactive dyes of formula (1) containing chlorethyl sulphonyl or sulphate ethyl sulphonyl residues may be treated with acid-dissociating agents such as sodium hydroxide, leaving the chlorethyl sulphonyl or sulphate ethyl sulphonyl residues in vinyl sulphonyl.

Condensation of 2,4,6-trichloro-s-triazine with a compound of formula (8) is preferably carried out in aqueous solution or suspension, at low temperatures, preferably between 0° and 5°C, and at a slightly acidic, neutral to slightly alkaline pH. It is advantageous to gradually neutralize the hydrochloride released by condensation by adding aqueous alkali hydroxides, carbonates or bicarbonates. For further transformation of the resulting chlorotriazine dyes or for transformation of 2,4,6-trichloro-s-triazine with the amines of the formulas (9), the free amine or its salts, preferably in the form of hydrochloride, is removed. The initial binding is carried out at temperatures of between 0° and 25°C, preferably between 5° and 10°C, preferably in a sodium amine additive, preferably in a sodium amine solution, preferably in the form of hydrochloride.

The condensation of an acyl halides with a compound of formula (8) is also preferably carried out in aqueous solution or suspension, at room temperature and at a pH of slightly acidic to neutral.

The reagents of formula (1) can be isolated and processed into usable dry dye preparations. The isolation is preferably at the lowest possible temperature by salinization and filtration. The filtered dyes can be dried, if necessary, after addition of coupling agents and/or buffering agents, e.g. by addition of a mixture of equal parts of monosodium and disodium phosphate or sodium tripolyphosphate; the drying is preferably carried out at not too high temperatures and under reduced pressure.

The invention also relates to the storage-stable, concentrated liquid dye preparations of the reactive dyes of formula (1) and their use in the manufacture of block flots, dye baths and, in particular, printing pastes used for dyeing and printing of fibre materials, in particular cellulose-containing fibre materials.

Liquid dye preparations have advantages over the powder form, e.g. no dust formation when applying printing pastes and from blocks and dye floats, no wetting problems due to clumping, no stained stains due to undissolved dye particles.

The aqueous solution or suspension obtained directly from the synthesis, containing solvent if necessary, or a aqueous sludge of the wet press or filter cake of the raw dyes, of varying content of undesirable low molecular weight dissolved substances, especially of by-products of the synthesis of the dye and dissolved inorganic and organic salts, may be used as starting solution or suspension for the preparation of the dye preparations. In cases where the condensation product cannot or is difficult to desalinate, the raw condensation or neutralisation solution may also be used directly. Process solutions containing up to 50% of the dyes are used.

However, the raw dye powder can also be assumed to be dry if it is first smeared with water.

The concentrated liquid preparations of the invention are generally real or colloidal solutions. They are thin (viscosity of about 5 to 300 cp/20°C) and well-stable, i.e. they remain in a usable condition for at least several months at temperatures of -20 to +60°C, in particular -10 to +40°C. These preparations can be water-based or colloidal, without the dye being dissolved or other inhomogeneities. The above-mentioned dyes, inks and printing materials can be dyed in a natural or synthetic way.

The stable concentrated liquid dye preparations of the invention are particularly suitable for the production of printing pastes for printing cellulose fibre materials.

A method for the production of a liquid preparation of the invention is described in the examples.

The reactive dyes of formula (1) are new, they are highly reactive and give good water and light-tight colours. The main features are that they are highly soluble and have a high fixation rate, diffuse well in cellulose fibre and are easy to remove unfixed parts.

The reagent dyes of formula (1) are suitable for the dyeing and printing of a wide variety of materials, such as silk, leather, wool, polyamide fibres and polyurethanes, but in particular of cellulosic materials of a fibrous structure, such as linen, pulp, regenerated cellulose and, in particular, cotton. They are suitable for both extrusion and dyeing using the foil dyeing process, whereby the product is impregnated with aqueous and, where appropriate, saline dye solutions and the dyes are fixed after an alkali treatment or in the presence of alkali, where appropriate, under heat.

They are particularly suitable for printing, particularly on cotton, but also for printing nitrogen-containing fibres, e.g. wool, silk or mixed fabrics containing wool.

It is recommended to rinse the colouring and printing thoroughly with hot and cold water, if necessary with the addition of a dispersing agent to promote the diffusion of the unfixed parts.

In practical use, the dyes of the invention are useful as liquid dyes or printing preparations.

The formulae of the formase compound used as the starting product in the following examples are: Other

Example 1: Cyanuric chloride is given at 0-5°C to a neutral solution of 33.8 parts by volume of the formate of formula (100) in 400 parts by volume of water. During condensation, the pH is first reduced to 4.0 and maintained there by adding 21 parts by volume of 2n sodium salts. Then 16 parts by volume of ammonia at 30% is added. At the initial pH of 10.5 is now condensed at 40°C until complete implementation, the pH is reduced to 9.0. The resulting dark blue dye powder can be used to dye or print cotton in neutral blue tones.

Other colours are obtained by using equivalent amounts of the amines listed below instead of ammonia. Other

Manufacture of concentrated liquid dye preparation

Err1:Expecting ',' delimiter: line 1 column 375 (char 374)

(a) Desalination:

After adding 40 l of water and then removing 40 l of permate (average flow rate of about 20 l/h), a solution of dye with a salinity of 0,43% is obtained.

(b) Concentration:

After desalination, 33.1 l of permeate (mean flow rate of about 12 l/h) are removed to obtain 10.9 kg of a concentrated dye solution with a dry matter content of 23.6% and a sodium chloride content of less than 0.01%.

94,4 parts of the dye solution obtained are mixed with 1,5 parts sodium tripolyphosphate at 40°C for 10 minutes and diluted with 4,2 parts water to obtain a liquid formulation with a pH of 7,0 with the following composition: 22,3% by weight of colour 1,5% by weight of sodium tri-polyphosphates Approximately 76.3% by weight of water < 0,1% by weight of sodium chloride

The resulting real solution is a thin liquid (about 6 cP at 20°C Brookfield, spindle No. 2) and is stable for several months at -10°C to +40°C. (Chemical and physical storage stability)

An equivalent amount of the neutralised synthetic solution (if appropriate after adjusting the concentration) may be used instead of the press cake used in the above example.

The liquid commercial form thus obtained can be used instead of the powdered dye in all dyeing and printing recipes, with the same results.

Example 13: In 500 ml of water, 33.8 parts w/w of the formasan chromophore of formula (100) are slurred and dissolved by adding baking soda at pH 7. Now a solution of 14.5 parts w/w β-Chlorethyl-4-benzoyl chloride sulphone is dripped into 50 parts w/w acetone. Further adding 2 parts w/w baking soda keeps the pH between 5 and 6. After about 4 hours of stirring at the same pH and room temperature, no free amino group is detected. The resulting dye of the formula is Other It's a neutral blue, very real color.

Dyes of similar properties and of the same nuance can be produced by using equivalent amounts of the following acid chlorides for acylation: Other

Example 17: For a finely ground suspension of 9.4 parts cyanurchloride in 25 parts water, a neutral solution of 33.8 parts cyanurchloride of the formulation (100) in 400 parts water is allowed to run in such a way that the pH can be maintained at 4.5 by simultaneous addition of 1 part sodium. The temperature is maintained at 0-5 °C by cooling. When the end of the first condensation has been chromatographically determined, a solution of 6.25 parts taurine in 65 parts water is added. By adding sodium the pH is maintained at 8.5 and after heating at 40 °C at 8.5 °C. (approximately 165 parts 1 vol. of sodium). Other The cotton can be printed and dyed in very real clear neutral blue tones.

If the procedure described in examples 1 to 17 is followed and a combination of the following formulae (104) to (112) is used instead of the formamate of formula (100): Other This gives you dyes with similar properties and similar nuance.

Colouring rule 1

2 parts of the dye obtained in the manner described in example 1 are dissolved in 100 parts of water at 20 to 50 °C, with the addition of 5 to 20 parts of urea and 2 parts of calcined soda. The resulting solution is impregnated with a cotton fabric so that it increases by 50 to 80% of its weight and then dried.

Colouring rule 2

2 parts of the dye obtained in the manner described in example 1 are dissolved in 2000 parts of water with 120 parts of table salt or calcined chalk salt at 75°C. 100 parts of cotton cloth are placed in this dye bath and kept at a constant temperature for 30 to 60 minutes.

Colouring rule 3

2 parts of the dye obtained in the manner described in example 1 are dissolved in 100 parts of water with the addition of 0,5 parts of m-nitrobenzolsulfonic acid sodium. The resulting solution is impregnated with a cotton fabric, increasing it by 75% of its weight, and then dried. The fabric is then impregnated with a 20°C solution containing 5 g of sodium hydroxide and 300 g of sodium chloride per litre, squeezed to 75% by weight, dried for 30 seconds at 100 to 101°C, rinsed, soaked for a quarter of an hour in a 0,3% solution of an ion-free detergent, rinsed and dried.

Colouring rule 4

2 parts of the dye obtained in the first example are dissolved in 100 parts of water. The solution is added to 1900 parts of cold water, 60 parts of sodium chloride is added and 100 parts of cotton fabric are added to this dye bath. The temperature is raised to 60°C, after 30 minutes 40 parts of calcined soda and 60 parts of sodium chloride are added. The temperature is maintained at 60°C for 30 minutes, the dye is rinsed and soaked for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

Pressure requirement 1

Two parts of the dye produced in accordance with example 1 are sprinkled, by rapid agitation, in 100 parts of a stock thickening agent containing 45 parts 5% sodium alginate thickening agent, 32 parts water, 20 parts urea, 1 part m-nitrobenzene sulphonic acid sodium and 2 parts sodium carbonate. The resulting paste is then used to print a cotton fabric on a roll-out press and steam the resulting printed fabric in saturated steam for 4 to 8 minutes at 100 °C. The printed fabric is then thoroughly rinsed in cold and hot water, with the non-chemically fixed parts being very easily removed from the fibres and then dried.

Pressure requirement 2

(a) A stock thickening is prepared as follows: 500 kg of a 5% high viscosity Na-alginate solution are obtained by 125 kg of urea 12,5 kg Na salt of nitrobenzene sulphonic acid 75 kg of a 25% solution of soda and 287,5 kg of water (b) In 800 g of this stock thickness, 200 g of the liquid formulation of the reagent indicated in example 1 are now manually stirred to obtain a usable homogeneous printing ink. A part of this printing ink is used to print a fabric of mercerised bleached cotton.

The remaining ink is weighed at 20 g and mixed manually with 980 g of the above-mentioned stock thickness to produce a fabric of mercerised bleached cotton.

After drying, the two pressures are fixed in saturated water vapour and then rinsed in cold and hot water.

The first printing results in a bright, evenly colored motif, the second printing in a pastel, spark-free and evenly colored motif.

Claims (10)

1. A process for the preparation of a reactive dye of formula in which Y is a radical of formula or         -CO-A-SO₂-X   (3) R₁ and R₂ are each independently of the other hydrogen or C₁₋₄alkyl substituted by halogen, cyano, C₁₋₄alkoxy, N,N-di-C₁₋₄alkylamino, hydroxyl, carboxyl, sulfo or sulfato; A is an unsubstituted or a substituted aliphatic or aromatic bridging group, and X is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acetoxyethyl, β-haloethyl or vinyl; the benzene radicals, I, II and III may contain further substituents in addition to 2 to 4 sulfo groups and, in the benzene radical II, to the radical -NH-Y; and the reactive dye of formula (1) contains only a single fibre-reactive radical which comprises condensing a compound of formula with 2,4,6-trichloro-s-triazine, and condensing the resultant primary condensate with an amine of formula in which R₁ and R₂ are as defined above, or with a 2-amino-4,6-dichloro-s-triazine, or with an acyl halide corresponding to the radical of formula (3), and carrying out a further optional conversion.
2. A process according to claim 1, which comprises using an acyl halide of formula         Hal-CO-A-SO₂-CH₂CH₂Cl   (10) in which Hal is halogen and A is n-propylene, phenylene or endomethylenecyclohexylene.
3. A process according to claim 1, which comprises using a compound of formula (8) in which the benzene radicals, I, II and III do not contain further substituents.
4. A process according to any one of claims 1 to 3, which comprises using a compound of formula in which m is the number 1 or 2, and n is the number 0, 1 or 2, and m + n is 2, 3 or 4.
5. A process according to claim 4 which comprises condensing a compound of formula (11) with 2,4,6-trichloro-s-triazine, and condensing the resultant primary condensate with an amine of formula (9), or with a 2-amino-4,6-dichloro-s-triazine in which the radical is -NH₂, β-methoxyethylamino, γ-methoxypropylamino, β-ethoxyethylamino, N,N-dimethylamino, N,N-diethylamino, β-chloroethylamino, β-cyanoethylamino, γ-cyanopropylamino, β-carboxyethylamino, sulfomethylamino, β-sulfoethylamino, N-methyl-N-β-sulfoethylamino, N-ethyl-N-β-sulfoethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfatoethylamino, γ-hydroxypropylamino, 3-(N,N-dimethylamino)-propylamino, carboxymethylamino, or β-hydroxyethylsulfonylethoxyethylamino.
6. A process according to claim 5, which comprises condensing a compound of formula with 2,4,6-trichloro-s-triazine, and condensing the resultant primary condensate with ammonia, or with 2-amino-4,6-dichloro-s-triazine.
7. A process according to claim 6, which comprises condensing a compound of formula with 2,4,6-trichloro-s-triazine, and condensing the resultant primary condensate with β-sulfoethylamine, or with 2-(β-sulfoethylamino)-4,6-dichloro-s-triazine.
8. Use of a reactive dye obtained according to claim 1 for dyeing or printing cellulosic fibre materials.
9. Use according to claim 8 for dyeing or printing cotton.
10. A storage-stable, concentrated, liquid dye formulation of a water-soluble reactive dye of formula in which Y is a radical of formula or         -CO-A-SO₂-X   (3) R₁ and R₂ are each independently of the other hydrogen or C₁₋₄alkyl substituted by halogen, cyano, C₁₋₄alkoxy, N,N-di-C₁₋₄alkylamino, hydroxyl, carboxyl, sulfo or sulfato; A is an unsubstituted or a substituted aliphatic or aromatic bridging group, and x is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acetoxyethyl, β-haloethyl or vinyl; the benzene radicals, I, II and III may contain further substituents in addition to 2 to 4 sulfo groups and, in the benzene radical II, to the radical -NH-Y; and the reactive dye of formula (1) contains only a single fibre-reactive radical.