HK1058051B - Reactive azo dye, method for the production and use thereof - Google Patents

Description

Reactive azo dyes, process for their preparation and their use

The present invention relates to the field of fibre-reactive dyes. WO 9610610, WO 9725377, WO9947608 and EP-A922735 disclose dyes which are structurally similar to the dyes of the invention described below but which differ in the type of reactive group or coupling component. These prior art dyes have a number of technical disadvantages in dyeing textile materials.

It has now been found that, surprisingly, the dyes defined by the general formula (1) below are superior to the dyes of the prior art.

Accordingly, the present invention provides reactive dyes of the general formula (1):

wherein

Y is a heterocyclic reactive group of the general formula (2) or (3):

wherein

X₁-X₃Each independently is hydrogen, cyano or halogen, with the proviso that X₁-X₃At least one of which is a halogen, is,

X₄is chlorine, fluorine or X₅，

X₅Is a group of the general formula (4):

wherein

R₁Is hydrogen, alkyl or aryl;

b is alkylene, arylene or arylenealkyl, and alkylene B may be interrupted by oxygen atoms; and

R₂is SO₂CH₂CH₂Z or SO₂CH＝CH₂A group wherein Z is a base-eliminable fragment;

n is 0 or 1; and

m is hydrogen, ammonium, alkali metal or alkaline earth metal equivalent,

with the proviso that dyes in which Y is a group of the following formula (3) are excluded: wherein X₄Is chlorine, R₁Is hydrogen, B is p-phenylene, n is 0 and the Y-NH-group is in the meta position relative to the diazo group, dyes in which Y is a group of the following formula (3) are also excluded: wherein X₄Is chlorine, R is hydrogen, B is ethylene and the Y-NH-group is in para-or meta-position to the diazo group.

In the general formula (1)) The alkali metal M may be chosen in particular from: lithium, sodium and potassium, while the alkaline earth metal M may be in particular calcium. M is preferably hydrogen or sodium. Halogen X₁-X₃In particular fluorine or chlorine. X₄Preferably fluorine or X₅。

Alkyl radical R₁Preferably is (C)₁-C₈) Alkyl, particularly preferably (C)₁-C₄) An alkyl group. Examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Aryl radical R₁In particular phenyl, which may be substituted, for example, by one or more substituents selected from: (C)₁-C₄) Alkyl, (C)₁-C₄) Alkoxy, chloro, fluoro and SO₃H。

R₁Preferably hydrogen, methyl or phenyl.

Alkylene B is preferably (C)₁-C₈) Alkylene, particularly preferably (C)₁-C₄) An alkylene group. Examples of such alkylene groups are methylene, ethylene, n-propylene, isopropylene and butylene. Alkylene- (CH) interrupted by oxygen atoms is preferred₂)₂-O-(CH₂)₂。

Arylene B is in particular selected from phenylene and naphthylene, preferably m-phenylene and p-phenylene.

The arylenealkyl group B is preferably a group of the general formula (5a) or (5B):

wherein p is 1-4 and the free valences on the aromatic ring may be related to N or R₂Are connected.

Examples of Z groups which can be eliminated by the action of bases, i.e. under the dyeing conditions, are chlorine, bromine, sulfuric acid, thiosulfuric acid, phosphoric acid, (C)₂-C₅) Alkanoyloxy radicals such as acetoxy, benzoylOxy, sulfobenzoyloxy or p-tolylsulfonyloxy, of which the sulfuric acid group is preferred.

The terms "sulfate", "thiosulfate" and "phosphate" include not only the acid form but also the salt form. The thiosulphate group thus corresponds to the general formula-S-SO₃M, the phosphoric acid group corresponding to the formula-OPO₃M₂And the sulfuric acid group corresponds to the formula-OSO₃M, wherein M in each is as defined above.

When X is present₄When it is chlorine, it is preferred that R is₁Compounds other than hydrogen, in particular methyl or phenyl. When X is present₄Is chlorine and R₁When hydrogen, compounds in which B is not ethylene are also preferred. In these cases, B has in particular the other preferred meanings of B mentioned above.

n is particularly preferably 0.

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

wherein M is as defined above, Y¹Is one of the groups (2a) - (2i) or (3a) - (3 r):

wherein M is as defined above.

Dyes of the general formulae (1b) to (1e) are particularly preferred according to the invention:

wherein R is hydrogen, methyl or ethyl, Hal is fluorine or chlorine, and M is as defined above.

The reactive dyes of the general formula (1) according to the invention in which Y is a reactive group of the general formula (2) may be present in a mixture of dyes which are mixed with one another, the dyes differing only in respect of the reactive group of the general formula (2). Preferred mixtures of this type contain, for example, reactive dyes of the general formula (1) in which Y ═ 2a and reactive dyes of the general formula (1) in which Y ═ 2c, or reactive dyes of the general formula (1) in which Y ═ 2b and reactive dyes of the general formula (1) in which Y ═ 2 d.

The reactive dyes of the general formula (1) according to the invention are generally present as preparations in solid or liquid (dissolved) form. They usually contain, in solid form, the electrolyte salts customary in water-soluble, in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may also further contain auxiliaries customary in commercial dyes, such as buffer substances capable of stabilizing the pH of aqueous solutions at from 3 to 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium citrate and disodium hydrogen phosphate, and small amounts of drying agents, or, when they are present as liquids or aqueous solutions (including thickeners of the type customary in printing pastes), they may also contain substances which ensure the durability of these preparations, for example antimildew agents.

The reactive dyes of the general formula (1) according to the invention are preferably present as dye powders or as dye granules, wherein from 10 to 80% by weight, based on the powder or granule, of electrolyte salts of the type known as standardizers are contained. In particular, the particles have a particle size of 50 to 500 m. These solid preparations may additionally contain the abovementioned buffer substances in a total amount of up to 10%, based on the preparation. When the dye is present in the form of aqueous solutions, the total dye content of these aqueous solutions is up to about 50% by weight, for example 5-50% by weight, based on the aqueous solution, in which case the electrolyte salt content of these aqueous solutions is preferably less than 10% by weight. The aqueous solutions (liquid preparations) may generally contain up to 10% by weight, preferably up to 2% by weight, of the abovementioned buffer substances.

The reactive dyes of the general formula (1) according to the invention in which Y is a radical of the general formula 3 may have the same chromophore, but a fibre-reactive radical R₂Has different structures. More particularly, for the same chromophore, R₂May be-SO₂CH＝CH₂or-SO₂CH₂CH₂Z, particularly preferably β -sulphatoethylsulphonyl. The dye moiety in the form of a vinylsulfonyl group can be up to about 30 mol%, based on the respective dye chromophore. Preferably, the molar ratio of vinylsulfonyl dye to β -ethyl substituted dye is from 5: 95 to 30: 70.

The invention further provides a process for preparing the reactive dyes of the general formula (1).

The dyes may be obtained by subjecting the compounds of formulae (6), (7) and (2 ') or (6), (7), (4') and trifluorotriazine or trichlorotriazine to conventional diazotisation, coupling and condensation reactions in any desired sequence,

wherein M, n, R₁、R₂、B、X₁、X₂、X₃Each is as defined above, and X₀Is fluorine or chlorine.

For example, a compound of the general formula (8) is diazotized and reacted with a compound of the formula (6),

wherein Y, M and n are each as defined above.

Alternatively, the compounds of the formula (9) can be condensed with halogenopyrimidines of the formula (2 ') or with triazines of the formula (3'),

wherein X₄And X₅Each is as defined above, and X₀Is fluorine or chlorine.

The compounds of the general formula (3 ') can be obtained in succession from trifluorotriazine or trichlorotriazine and one or two compounds of the general formula (4').

Wherein Y is a group of the formula (3) (wherein X₄Fluorine or chlorine) reactive dyes of the general formula (1) according to the invention can also be prepared as follows: the compounds of the general formula (9) are reacted with trifluorotriazine or trichlorotriazine and subsequently condensed with amines of the general formula (4').

Wherein Y is a group of the formula (3) (wherein X₄Is X₅) The reactive dyes of the general formula (1) according to the invention can be obtained as follows: wherein X₄Reactive dyes of the general formula (1) according to the invention which are fluorine or chlorine react with amines of the general formula (4').

The compounds of formula (8) can be obtained in various ways. When Y is a radical of the formula (2), they are obtainable by reacting halogenopyrimidines of the formula (2') with aromatic diaminobenzenesulphonic acids, preferably 1, 3-diaminobenzene-4-sulphonic acid or 1, 4-diaminobenzene-2-sulphonic acid. When Y is a group of the formula (3), the compound of the formula (8) can be obtained by reacting the compound of the formula (3) with an aromatic diaminobenzenesulphonic acid, preferably 1, 3-diaminobenzene-4-sulphonic acid or 1, 4-aminobenzene-2-sulphonic acid.

The diazotisation, coupling and condensation reactions described above are well known to the person skilled in the art and can be carried out in a conventional manner, which is widely described in the literature of the art. The dyes of the general formula (1) according to the invention are obtained as solutions or suspensions from the preparation processes described above and can be isolated by salting out. It may also be spray dried, or the solution or suspension may be evaporated.

The reactive dyes of the general formula (1) according to the invention have useful application properties. They can be used for dyeing or printing hydroxyl-and/or carboxamido-containing materials, for example materials in the form of sheet-like structures, such as paper and leather, or materials in the form of films, such as films of polyamides, or in the form of blocks, such as those of polyamides and polyurethanes, but are particularly useful for dyeing or printing such materials in the form of fibers. They are preferably used for dyeing or printing cellulosic fibre materials of any type. They can also be used for dyeing or printing hydroxyl-containing fibres present in mixtures of mixed fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres. It is also possible to use them for printing textiles or paper by means of the ink-jet process.

The present invention therefore also provides the use of the reactive dyes of the general formula (1) according to the invention for dyeing and printing materials of this type, and also a process for dyeing or printing such materials in a conventional manner by using one or more reactive dyes of the general formula (1) according to the invention as colorant.

Advantageously, the synthetic solutions of the reactive dyes of the general formula (1) according to the invention can be used directly for dyeing as liquid preparations, if appropriate after addition of buffer substances, and likewise after concentration or dilution.

The material is preferably applied in the form of a fibrous material, in particular in the form of textile fibres, such as a woven fabric or yarn, such as in the form of bundles or rolls.

The hydroxyl-containing material is a natural or synthetic hydroxyl-containing material, such as a cellulosic fibrous material or a regenerated product thereof and polyvinyl alcohol. Preferred cellulosic fibre materials are cotton fibres and also other plant fibres, such as flax, hemp, jute and ramie fibres. Regenerated cellulose fibers are, for example, short viscose (staple viscose) and long viscose (filament viscose).

Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, nylon-6, nylon-11 and nylon-4.

The reactive dyes of the general formula (1) according to the invention can be applied and fixed to the substrates, in particular to the fibre materials, by known application techniques for water-soluble dyes, in particular for fibre reactive dyes. When a large bath ratio exhaust dyeing process using various acid binders and, if appropriate, neutral salts such as sodium chloride or sodium sulfate is carried out, they give dyeing marks on cellulose fibers with a very good tinctorial yield. The dyeing is preferably carried out in a water bath at temperatures of from 40 to 105 ℃ and, if appropriate, up to 130 ℃ and at pressures above atmospheric pressure, and in the presence or absence of customary dyeing auxiliaries. One possible method is to introduce the material into a warm water bath, gradually heating the bath to the desired dyeing temperature, and then completing the dyeing process at this temperature. If desired, the neutral salt which accelerates the exhaustion of the dye can also be added to the water bath only after the actual dyeing temperature has been reached.

Likewise, the fixing process provides good tinctorial yield and good colour build-up on the cellulose fibres, and the dyeing marks can be fixed on the material by steam processing in a conventional manner or batch treatment using dry-heat methods at room temperature or at elevated temperatures, for example up to about 60 ℃.

Likewise, conventional printing processes for cellulosic fibers can be carried out in a single phase, such as printing with a printing paste containing sodium bicarbonate or other acid-binding agent, followed by steam processing at 100-; or in two phases, for example with neutral or weakly acidic dyeing dyes, followed by fixing as follows: the printed material is fixed by passing it through a hot alkaline bath containing an electrolyte, or overcolouring (overprinting) with a fixing solution containing an alkaline electrolyte, followed by batch treatment of the alkali-overcoloured material, or followed by steam treatment or subsequent dry heat treatment, to give a strong printed trace with a clear outline and a white background. The effect of the printing and dyeing marks is not greatly influenced by the change of the fixation conditions.

When the fixation is carried out by a dry heat method according to a conventional hot fixation method, the hot air used is 120-200 ℃. In addition to the use of conventional steam at 101-103 deg.C, superheated steam and high pressure steam at temperatures up to 160 deg.C may also be used.

Acid binders which affect the fixation of the dyes of the invention on cellulose fibres include, for example, alkali metal and alkaline earth metal basic salts of water-soluble inorganic or organic acids, or compounds which liberate alkali on heating. Particularly suitable are alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being sodium and potassium compounds. Such acid binders include, 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 reactive dyes of the general formula (1) according to the invention have a high reactivity, excellent fastness properties, very good build-up and high light and perspiration/light fastness. Therefore, they can be used for exhaustion dyeing at low dyeing temperature, and only short steam processing is required in the steam-fixing process (pad-steam process). The fixation rate is high, unfixed parts are easy to wash away, and the difference between the degree of exhaustion and the degree of fixation is very small, namely the loss caused by hydrolysis is very small. They are also particularly useful for printing, in particular not only on cotton, but also on nitrogen-containing fibres, such as wool or silk or mixed fabrics containing wool or silk.

In addition, the reactive dyes of the general formula (1) according to the invention make it very easy to wash the unfixed dye fraction from the fibre material after the dyeing process and the removed dye does not stain the white fraction of the articles washed, which is also significant. This provides convenience to the dyeing process as it saves wash cycles and thus costs.

Dyeings and prints produced using the reactive dyes of the general formula (1) according to the invention have high color strength and high fiber-dye binding stability not only in the acidic but also in the alkaline range, in particular on cellulosic fibre materials, and they also have excellent light fastness and very good wetfastness properties, such as fastness to washing, to water, to seawater, to cross-dyeing and to perspiration, and also excellent fastness to pleating and to dry heat setting and to rubbing.

The following examples illustrate the invention. Unless otherwise indicated, parts and percentages are by weight. Parts by weight relate to parts by volume like kilograms relate to liters.

The various compound moieties described in the examples according to the formulae are shown in the form of the free acids. However, in general these compounds are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and are used for dyeing in the form of their salts. Likewise, the starting compounds mentioned in the following examples, in particular in the table examples, can be used for the synthesis in the form of the free acids or their salts, alkali metal salts being preferred.

The dye of the present invention has a maximum absorption value (. lamda.) in the visible light region_max) As measured in aqueous solution with its alkali metal salt.

Example 1

18.8 parts of 1, 3-diaminobenzene-4-sulfonic acid are suspended in 150 parts of water and converted into a neutral solution by addition of lithium hydroxide. After cooling to 10 ℃, 17.4 parts of 2, 4, 6-trifluoropyrimidine were added dropwise over 1 hour while maintaining the pH at 5.5 with a 15% sodium carbonate solution. After the addition was complete, the batch was allowed to warm to 20-25 ℃ and stirred for an additional 1 hour. Followed by filtration and addition of 6.9 parts of sodium nitrite.

The filtrate was cooled to 10 ℃ by adding ice and added dropwise over 30 minutes to 100 parts of ice and 60 parts of concentrated hydrochloric acid (31%) prepared beforehand. After stirring for 1 hour, excess nitrite was destroyed by addition of amidosulfuric acid.

23.9 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid are dissolved in 300 parts of water by addition of aqueous sodium hydroxide solution. This neutral solution was heated to 50 ℃ and 13.4 parts of formaldehydized bisulfite (sodium salt) were added. After stirring for 30 minutes the solution was cooled to 20 ℃ and added dropwise to the cold diazotization batch over 30 minutes at 10 ℃.

The pH value obtained is 2.0-2.5. After stirring for 1 hour, the pH is adjusted to 5.5 with sodium carbonate solution and then with NaH₂PO₄/Na₂HPO₄The solution was buffered. The resulting solution was evaporated to dryness.

The resulting dye has the formula:

the dye is used for dyeing and printing cotton products into neutral red color tone, and has good fastness, especially high light fastness.

The dyes of the following examples 2 to 26 were obtained in a similar manner. The pyrimidine compound is reacted with a condensation component, diazotized and coupled onto the compound of formula (7).

Examples	Pyrimidines	Condensation component	Color tone	λmax
					2	5-chloro-2, 4, 6-trifluoropyrimidine	1, 3-diaminobenzene-4-sulfonic acid	Red wine	521
3	4, 5, 6-trifluoro-pyrimidines	1, 3-diaminobenzene-4-sulfonic acid	Red wine	520
					4	5-chloro-4, 6-difluoropyrimidine	1, 3-diaminobenzene-4-sulfonic acid	Red wine	520
5	4, 6-difluoropyrimidine	1, 3-diaminobenzene-4-sulfonic acid	Red wine	521
					6	2, 4, 5, 6-tetrachloropyrimidine	1, 3-diaminobenzene-4-sulfonic acid	Red wine	520
7	5-cyano-2, 4, 6-trichloropyrimidines	1, 3-diaminobenzene-4-sulfonic acid	Red wine	520
					8	5-chloro-2, 4, 6-trifluoropyrimidine	1, 4-diaminobenzene-2-sulfonic acid	Red wine	526
9	4, 5, 6-trifluoro-pyrimidines	1, 4-diaminobenzene-2-sulfonic acid	Red wine	525
					10	5-chloro-4, 6-difluoropyrimidine	1, 4-diaminobenzene-2-sulfonic acid	Red wine	526
11	4, 6-difluoropyrimidine	14-diaminobenzene-2-sulfonic acid	Red wine	526
					12	2, 4, 5, 6-tetrachloropyrimidine	1, 4-diaminobenzene-2-sulfonic acid	Red wine	525
13	5-cyano-2, 4, 6-trichloropyrimidines	1, 4-diaminobenzene-2-sulfonic acid	Red wine	527
					14	4, 5, 6-trifluoro-pyrimidines	1, 4-diaminobenzene-2-sulfonic acid	Red wine	527
15	5-chloro-2, 4, 6-trifluoropyrimidine	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	521
					16	4, 5, 6-trifluoro-pyrimidines	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	521
17	5-chloro-4, 6-difluoropyrimidine	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	520
					18	2, 4, 6-trifluoro-pyrimidines	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	521
19	2, 4, 5, 6-tetrachloropyrimidine	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	521
					20	5-cyano-2, 4, 6-trichloropyrimidines	1, 3-diaminobenzene-4, 6-disulfonic acid	Red wine	521
21	5-chloro-2, 4, 6-trifluoropyrimidine	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	525
					22	4, 5, 6-trifluoro-pyrimidines	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	525
23	5-chloro-4, 6-difluoropyrimidine	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	526
					24	2, 4, 6-trifluoro-pyrimidines	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	526
25	2, 4, 5, 6-tetrachloropyrimidine	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	526
					26	5-cyano-2, 4, 6-trichloropyrimidines	1, 4-diaminobenzene-2, 5-disulfonic acid	Red wine	525

Example 27

21.8 parts of 4-nitroaniline-2-sulfonic acid are suspended in 400 parts of water and neutralized with aqueous NaOH solution. 6.9 parts of sodium nitrite are added and the mixture is stirred until all the material is dissolved.

The obtained solution was added dropwise to 80 parts of ice and 30 parts of hydrochloric acid (31%) prepared in advance at 0 to 5 ℃ and stirred for 60 minutes. Excess nitrite is removed by addition of an amino sulphuric acid solution. N-sulfomethylene gamma acid was prepared separately and cooled to 10 ℃ as described in example 1. The solution was then added to a suspension of the diazonium salt and the pH adjusted to 2.0 by the addition of sodium carbonate solution.

This gives a dye solution containing the compound of formula (10) in free acid form,

the solution of the compound of formula (10) is then warmed to 35-40 ℃ and adjusted to pH 8.5 with aqueous NaOH. While the pH was kept constant at 8.5 by adding hydrochloric acid, a solution of 5.6 parts NaHS in 50 parts water was added dropwise.

The resulting compound was precipitated by adding 150 parts of sodium chloride, filtered and washed with aqueous sodium chloride solution. The resulting compound corresponds to formula (9a) in the free acid form.

53.2 parts of compound (9a) are dissolved in 500 parts of water. After cooling to 15 ℃, 13.4 parts of 2, 4, 6-trifluoropyrimidine were added dropwise at 15 ℃ over 1 hour. The pH was maintained at 6.5 by the addition of aqueous sodium carbonate. After the addition was complete, the batch was stirred at 30-35 ℃ for 1 hour. The end point of the reaction was determined by thin layer chromatography. The dye from example 14 is precipitated by addition of sodium chloride, filtered off with suction and dried.

It dyes cotton to a blue red shade.

In a similar manner, the compounds of the formulae in examples 8 to 13 can be prepared by condensing the compound of (9a) with the appropriate pyrimidine derivative.

Example 28

53.2 parts of compound (9a) are dissolved in 500 parts of water. 4.2g of sodium fluoride are added and the batch is cooled to 5 ℃. 13.5 parts of 2, 4, 6-trifluorotriazine are then added dropwise over 5 minutes. The pH is first lowered and then stabilized at about 4.5-5.0. After the completion of the addition, the reaction solution was stirred for 15 minutes. Then it was mixed with a neutral aqueous solution of N-methylaminoethyl 2-sulfatoethylsulfone added dropwise, and then it was warmed to 20-25 ℃ while keeping the pH constant at 6.5-7.0 by adding an aqueous solution of sodium carbonate.

The end point of the reaction was determined by thin layer chromatography. After the reaction has ended, the dye is salted out by addition of sodium chloride, filtered off with suction and dried. Which conforms to the formula:

the dye is used for dyeing cotton products into heavy bluish red shade, and has good fastness, especially high light fastness.

Examples 29 to 35 shown in the tables below were obtained in an analogous manner by first reacting the dye radical (9a) with trifluorotriazine or trichlorotriazine and then condensing the product obtained with an amine of the general formula (4').

Example 36

28.1 parts of 4- (2' -sulphatoethylsulphonyl) aniline are dissolved in 250 parts of water and neutralised with solid sodium bicarbonate. To this solution was added 4.2 parts of sodium fluoride, followed by cooling to 0-5 ℃ by adding ice. Then, 13.5 parts of trifluorotriazine are added dropwise over 5 minutes, the pH value of which first decreases rapidly and then stabilizes at 4.5 to 5.0. After the addition was complete, the batch was stirred for a further 15 minutes. A solution of 53.2 parts of the compound of the formula (9a) in 500ml of water is then added dropwise, the pH being adjusted to 6.0-6.5. The batch was warmed to 30-35 ℃ and then stirred for 60 minutes to complete the reaction. The dye is precipitated by addition of sodium chloride, filtered off with suction and dried. This gives a deep red dye powder whose structure corresponds to the formula:

the dye dyes cotton products into heavy bluish red shade with good fastness, especially high light fastness.

Examples 37 to 40 shown in the tables below were obtained in an analogous manner by first reacting the amine of the general formula (4') with trifluorotriazine or trichlorotriazine and then condensing the product obtained with the compound of the formula (9 a).

EXAMPLE 41

28.1 parts of 4- (2' -sulphatoethylsulphonyl) aniline are dissolved in 250 parts of water and neutralised with solid sodium bicarbonate. To this solution was added 4.2 parts of sodium fluoride, followed by cooling to 0-5 ℃ by adding ice. Then, 13.5 parts of trifluorotriazine are added dropwise over 5 minutes, the pH value of which first decreases rapidly and then stabilizes at 4.5 to 5.0. After the addition was complete, the batch was stirred for a further 15 minutes. Then, a neutralized solution of 18.8 parts of 1, 3-diaminobenzene-4-sulfonic acid in water was added dropwise to adjust the pH to 6.0 to 6.5. The batch was warmed to 30-35 ℃ and then stirred for 60 minutes to complete the reaction. The resulting solution was filtered and mixed with 6.9 parts of sodium nitrite.

The resulting solution was cooled to 10 ℃ by adding ice and added dropwise over 30 minutes to 100 parts of ice and 60 parts of concentrated hydrochloric acid (31%) prepared in advance. After stirring for 1 hour, excess nitrite was destroyed by addition of amidosulfuric acid.

23.9 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid are dissolved in 300 parts of water by addition of aqueous sodium hydroxide solution. This neutral solution was heated to 50 ℃ and 13.4 parts of formaldehydized bisulfite (sodium salt) were added. After stirring for 30 minutes the solution (compound of formula (b)) was cooled to 20 ℃ and added dropwise to the cold diazotization batch over 30 minutes at 10 ℃.

The pH value obtained is 2.0-2.5. After stirring for 1 hour, the pH is adjusted to 5.5 with sodium carbonate solution and then with NaH₂PO₄/Na₂HPO₄The solution was buffered. The resulting solution was evaporated to dryness.

This gives a red dye powder whose structure corresponds to the formula:

the dye is used for dyeing cotton products into heavy bluish red shade, and has good fastness, especially high light fastness.

Examples 42 to 51 shown in the tables below were obtained in an analogous manner by first reacting the amine of the general formula (4') with trifluorotriazine and then condensing the product obtained with 1, 3-diaminobenzene-4-sulfonic acid or 1, 4-diaminobenzene-2-sulfonic acid. The dye is obtained after diazotization and coupling to the compound of formula (6).

The dye structures of examples 46, 47, 48, 49 and 51 are identical to the dyes of examples 36, 37, 38, 39 and 40.

Example 52

28.1 parts of 4- (2' -sulphatoethylsulphonyl) aniline are dissolved in 250 parts of water and neutralised with solid sodium bicarbonate. To this solution was added 92.4 parts of the dye of example 46 and the pH was adjusted to 5.5-6.0. The solution was heated to 80-90 ℃ and its pH was maintained within the set range by the addition of aqueous sodium carbonate. The progress of the reaction was monitored by thin layer chromatography.

After the reaction is finished, the dye solution is cooled, buffered and dried. This gives a dark red powder whose structure corresponds to the formula:

the cotton product is dyed with blue red color, and has excellent fastness, especially high light fastness.

The examples 53 to 59 shown in the table below were obtained in a similar manner by condensation of the starting dyes shown in the table below with amines of the formula (4').

Claims (10)

1. A compound of the general formula (1):

wherein

Y is a heterocyclic reactive group of the general formula (3):

wherein

X₄Is fluorine or X₅，

X₅Is a group of the general formula (4):

wherein

R₁Is hydrogen, C₁-C₈Alkyl or phenyl;

b is C₁-C₈Alkylene, phenylene or naphthylene, in which C₁-C₈The alkylene group may be interrupted by an oxygen atom; and

R₂is SO₂CH₂CH₂Z or SO₂CH＝CH₂A group in which Z is chlorine, bromine, a sulfate group, a thiosulfate group, a phosphate group, (C)₂-C₅) -an alkanoyloxy, benzoyloxy, sulphobenzoyloxy or p-toluenesulfonyloxy group;

n is 0 or 1; and

m is hydrogen, ammonium, an alkali metal or an equivalent of an alkaline earth metal.

2. The compound of claim 1, wherein n is 0.

3. The compound of claim 1 or 2, wherein

Y is a heterocyclic reactive group of the general formula (3),

R₁is hydrogen, (C)₁-C₄) An alkyl group or a phenyl group, or a substituted or unsubstituted alkyl group,

b is ethylene, propylene or phenylene, and

R₂is-SO₂CH₂CH₂A Z group, wherein Z is a sulfate group.

4. A compound according to claim 1 or 2, which corresponds to general formula (1 a):

wherein

Y¹Is one of the groups (3a) to (31):

wherein M is as defined in claim 1.

5. The compound of claim 1 or 2, which conforms to one of the formulae (1c) to (1 e):

wherein R is hydrogen, methyl or ethyl and M is as defined in claim 1.

6. The compound of claim 1 or 2, wherein M is hydrogen or sodium.

7. A process for the preparation of a compound according to claim 1, which comprises obtaining said compound by subjecting each of the compounds of formulae (6), (7), (4') and trifluorotriazine to conventional diazotization, coupling and condensation reactions in any desired order,

wherein M, n, R₁、R₂And B are each as defined in claim 1.

8. The process of claim 7, wherein the compound of formula (8) is diazotized and reacted with the compound of formula (6),

wherein Y, M and n are each as defined in claim 1.

9. The process of claim 7, wherein the compound of the formula (9) is condensed with a triazine of the formula (3'),

wherein M and n are each as defined in claim 1,

wherein X₄And X₅Each as defined in claim 1, and X₀Is fluorine.

10. Use of a compound according to any one of claims 1 to 6 for dyeing or printing hydroxyl-and/or carboxamido-containing fibre materials.