MXPA00003866A - Water-soluble disazo compounds with arylcarbonamide-containing diazo-components, process for their preparation and their use - Google Patents

Abstract

New reactive disazo dyes are 1-amino-2,7-bis(N-aryl- or -alkyl-aminocarbonylphenylazo)-8-naphthol-3(4),6-disulfonic acids or alkali metal salts (I), which contain at least one vinylsulfonyl (precursor) group. New reactive disazo dyes are 1-amino-2,7-bis(N-aryl- or -alkyl-aminocarbonylphenylazo)-1-naphthol-3(4),6-disulfonic acids o alkali metal salts of formula (I), which contain at least one vinylsulfonyl (precursor) group (-SO2Z). one of D<1>, D<2>=an N-aryl- or -alkyl-aminocarbonylphenyl group of formula (II);the other D<1>, D<2>=(II) or a phenyl group (III) or a naphthyl group (IV). The full definitions are given in the DEFINITIONS (Full Definitions) Field. An Independent claim is also included for the preparation of dyes (I).

Description

SOLUBLE POWDER COMPOUNDS IN WATER THAT HAVE COMPONENTS DIAZO DE ARILCARBOXAMIDA, PREPARATION OF THEM AND USE OF THEMSELVES DESCRIPTION OF THE INVENTION The present invention relates to the technical field of disazo reactive dyes in fibers. Various patent documents describe disazo dyes having reactive dyeing properties on fibers and dyeing for example cotton in dark blue to black shades. These include dyes containing a diazo component having a carboxamide function formed from an aromatic carboxylic acid derivative and an aliphatic amine. Examples are DE-A 39 05 074, DE-A 39 05 270, EP-A 221 013, EP-A 284 568, EP-A 309 406, EP-A 381 133 and EP-A 559 617. However, the Application properties of these dyes, for example color concentration and accumulation behavior as a function of the dyeing process, require improvements in some cases. It has now been found that disazo class reactive dyes based on 1-amino-8-hydroxy-naphthalenedisulfonic acids containing at least one diazo component having an N-arylcarboxamide function formed from an aromatic carboxylic acid derivative and an aromatic amine have improved application properties. The present invention then provides reactive dyes of the general formula I (i) where D1 and D2 each represent a group of general formula II wherein R 1 is hydrogen, C 1 -C 4 alkyl, aryl or substituted aryl; and R2 and R3 are independently hydrogen, C? -C alkyl, CrC4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; A is a phenylene group of the formula III wherein R 4 and R 5 are independently hydrogen, C 1 -C alkyl, CrC 4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; a naphthylene group of the general formula IV (IV) wherein R6 and R7 are independently hydrogen, C-t-C alkyl, CrC alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the general formula V - (CR8R9) k- (V) wherein k is an integer greater than 1; and R 8 and R 9 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X1 is hydrogen or -SO2-Z; or represent a phenyl radical of the general formula VI (VI) wherein R10 and R11 are independently hydrogen, CrC alkyl, C? -C alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X2 has one of the meanings of X1; or represent a naphthyl radical of the general formula VII wherein R, 12 and R "13 are independently hydrogen, CrC 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; X3 has one of the meanings of X1; Z is -CH = CH2, -CH2CH2Z1 or hydroxyl, wherein Z1 is hydroxyl or an alkali-releasable group; and M is hydrogen or an alkali metal; wherein at least one of D1 and D2 is a group of the general formula II; wherein, if A is a group of the general formula V, R is aryl or substituted aryl; and wherein the reactive dye of the general formula I contains at least one -SO2-Z group. The individual symbols in the general formulas can be identical or different from each other within the scope of their definitions. R C4 alkyl may be straight or branched chain, and is particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logic applies to the C 1 -C 4 alkoxy groups. R aryl is in particular phenyl. R1 substituted aryl is in particular phenyl substituted by one, two or three independent groups selected from the group consisting of CrC4 alkyl, C? -C alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen. R halogen is in particular fluorine, chlorine or bromine, and chlorine and bromine are preferred. Z1 removable by alkali in the β-position of the ethyl group of Z includes for example halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkylcarboxylic acids, substituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids, such as alkanoyloxy having 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy , also acid ester groups of inorganic acids such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphate, sulfate and thiosulfate groups), similarly dialkylamino groups having alkyl groups of 1 to 4 carbon atoms in each case, such as dimethylamino and diethylamine. Z is preferably vinyl, β-chloroethyl and particularly preferably β-sulfatoethyl. The groups "sulfo", "carboxyl", "thiosulfate", "phosphate" and "sulfate" include not only their acid form but also their salt form. Accordingly, the sulfo groups are groups having the general formula -SO3M, the thiosulfate groups are groups having the general formula -S- SO3M, the carboxyl groups are groups having the general formula -COOM, the phosphate groups are groups which they have the general formula -OPO3M2 and the sulphate groups are groups having the general formula -OSO3M, in each of which M is as defined above. The dyes of the general formula I can have different reactive fiber groups -SO2Z within the meaning of Z. Most particularly, the reactive -SO2Z groups in fiber can be on the one hand vinylsulfonyl groups and on the other groups -CH2CH2Z1, preferably β groups -sulfatoethylsulfonyl. If the dyes of the general formula I contain vinylsulfonyl groups in some cases, then the fraction of the respective dye with the vinylsulfonyl group is up to about 30 mol%, based on the respective amount of total dye. M alkali is in particular lithium, sodium or potassium. M is preferably hydrogen or sodium. k is preferably 2 or 3. R1 to R13 are each preferably hydrogen and R6, R7 and R13 are each preferably sulfo as well. When A is phenylene and X1 is -SO2Z, the group SO2Z is preferably arranged meta or para relative to the nitrogen atom. In the group of the general formula II, the carboxamide group is preferably arranged for or in relation to the diazo group. When A is naphthylene, the bond that leads to the nitrogen atom is preferably linked to the naphthalene nucleus in the β-position. When D1 or D2 is a group of the general formula VII, then the linkage leading to the diazo group is preferably linked to the naphthalene nucleus in the β position. When D1 or D2 is a group in the general formula VI and X2 is -SO2Z, then the group SO2Z is preferably arranged meta or para relative to the diazo group. Examples of substituents A are in particular 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1,5-phenylene, 2-bromo-1, 4-phenylene, 2-sulfo-1,4-phenylene, 2-sulfo-1,5-phenylene, 2-methoxy-1,5-phenylene, 2-ethoxy-1,5-phenylene, 2,5-dimethoxy- 1, 4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene, 1-sulfo-2,6- naphthylene, 6-sulfo-2,8-naphthylene or 1, 2-ethylene and 1,3-propylene. A is particularly preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene. , 2-methoxy-5-methyl-1,4-phenylene or 1,2-ethylene and 1,3-propylene, and in the case of the last two alkylene groups mentioned R1 is preferably phenyl or 2-sulphophenyl. Examples of groups D and D2 of the general formulas VI and VII are 2- (β-sulfatoethylsulfonyl) -phenyl, 3- (β-sulfatoethylsulfonyl) -phenyl, 4- (β-sulfato-ethylsulfonyl) -phenyl, 2-carboxyl- 5- (β-sulfatoethylsulfonyl) -phenyl, 2-chloro-4- (β-sulfatoethylsulfonyl) -phenyl, 2-chloro-5- (β-sulfatoethylsulfonyl) -phenyl, 2-bromo-4- (β-sulfatoethylsulfonyl) - phenyl, 2-sulfo-4- (β-sulfatoeti-sulphonyl) -phenyl-2-sulfo-5- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5- (β-suyfatoethylsulfonyl) -phenyl, 2-ethoxy-5- (β-sulfatoethylsulfonyl) -phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5 -methyl-4- (ß-suyfatoethylsulfonyl) -phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) -phenyl, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) -phenium, 2-methoxy-5- ( β-thiosulfatoethylsulfonyl) -phenyl, 2-sulfo-4- (β-phosphate-ethylsulfonyl) -phenyl-2- or 3- or 4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4- (β -chloro-ethylsulphonyl) -phenyl, 2-chloro-5- (ß-chloroethylsulfonyl) -phenyl, 3- or 4- (ß-acetoxyethylsulfonyl) -phenyl, 6- or 8- (ß-sulfatoethylsulfonyl) -naft-2- ilo, 6- (ß-sulfatoeti-sulfonyl) -1-sulfo-naphth-2-yl and 8- (ß-sulfatoethylsulfonyl) -6-sulfo-naphth-2-yl, preferably 3- (ß-sulfatoethylsulfonyl) -phenyl, - (β-sulfatoethylsulfonyl) -phenyl, 2-sulfo-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5- (β-sulfato-ethylsulfonyl) -phenyl, 2,5-dimethoxy-4- (β- sulfatoethylsulfonyl) -phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) -phenyl and 3- or 4-vinylsulfonyl- phenyl. The reactive dyes that are preferred according to the invention have the general formula wherein R1, A and Z are each as defined above. Particularly preferably, A is phenylene and Z is vinyl or β-sulfatoethyl in the general formula la. Most preferably, A is phenylene, R 1 is hydrogen and Z is vinyl or β-sulfatoethyl in the general formula la. The disazo dyes of the general formula I can be prepared, for example, by diazotizing an amine of the general formula VIII D 1 H 2 (VIII) wherein D 2 is as defined above, in a conventional manner, for example at -5 - + 15 ° C in an acidic aqueous medium by means of alkali metal nitrite at a pH of -1.5, and then reacting the resulting diazonium compound in an aqueous medium with 1-amino-8-hydroxy-3,6-disulfonic acid (acid H). ) or 1-amino-8-hydroxy-4,6-disulfonic acid (acid K) at a pH of 0 to 2 and at a temperature of 0 to 10 ° C to form the monoazo dye of the general formula IX (IX) wherein D2 and M are each as defined above, and subsequently diazotizing an amine of the general formula X D1-NH2 (X) wherein D1 is as defined above, in a conventional manner and then copulating the compound of diazonium resulting with the monoazo dye of the general formula IX at a pH of 4 to 7.5, preferably 5 to 6, and at a temperature of 5 to 20 ° C, preferably between 10 and 15 ° C to form the disazo dye of the general formula I: The compounds of the general formula I prepared according to the invention can be separated and isolated either from their synthesis solutions by generally known methods, for example either by precipitation from the reaction medium by means of electrolytes such as as sodium chloride or potassium chloride, or by the addition of an alcohol, or by evaporating the reaction solution, for example by spray drying, in which case a pH regulating substance can be added to the reaction solution. The amines of the general formulas VIII and X containing a group of the formula II can be prepared in a conventional manner (for example, DE-B-1 126 547), for example by condensing a suitably substituted primary or secondary aromatic amine with respect to R1 and A with a nitrobenzoyl chloride suitably substituted with respect to R2 and R3, in an aqueous medium in the presence of a base, for example sodium carbonate, at a pH between 7 and 1 1 and at temperatures of 50 to 95 ° C with the subsequent reduction of the nitro group to the amine at a higher temperature, preferably 60 to 95 ° C, using normal reducing agents, for example sodium acid sulfide solution, iron in acid solution or by catalytic hydrogenation. When X1 is -SO2Z where Z1 = hydroxyl, the corresponding amine of the general formula XI wherein R1 to R3 and A are as defined above, can be esterified, for example with monohydrate, oleate or using chlorosulfonic acid, and then diazotized or esterified and diazotized simultaneously with nitrosylsulfuric acid, preferably at temperatures of from 10 to 30 ° C. a conventional way The dyes of the general formula I according to the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form, they generally include the normal electrolyte salts for water-soluble dyes and especially fiber reagents, such as sodium chloride, potassium chloride and sodium sulfate, and may also include the normal auxiliaries in commercial dyes, such as buffer substances. pH capable of fixing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium acid diphosphate, sodium tricitrate and disodium hydrogen phosphate, or small amounts of siccatives; if they are present in an aqueous and liquid solution (including the presence of thickeners of the common type in printing pastes), they can also include substances that ensure a long life for these preparations, for example mold preventatives. In general, the dyes of the general formula I according to the invention are present as powder colorants containing 30 to 90% by weight, based on the weight of the dye powder or the dye preparation. These powder colorants may further include the pH regulating substances mentioned above in a total amount of up to 5% by weight, based on the powder colorant. If the dyes of the general formula I according to the invention are present in aqueous solution, the total dye content of these aqueous solutions will be up to about 50% by weight, for example between 5 and 50% by weight. Aqueous solutions (liquid preparations) may include the pH regulating substances mentioned above in an amount which is generally up to 10% by weight, preferably up to 2% by weight. The solutions obtained in the synthesis of the dyes of the general formula I, if appropriate after the addition of a pH regulating substance and if suitable after concentration, can also be used directly in dyeing, as liquid preparations. The reactive dyes of the general formula I according to the invention have reactive properties in fiber and have very suitable coloring properties. They can therefore be used to dye material containing hydroxyl and / or carboxamide, especially fiber material, and also skin. The present invention therefore also provides therefore the use of reactive dyes of the general formula I for dyeing or printing hydroxyl and / or carboxamide containing materials, or methods for their application on these substrates. This includes mass coloration, for example polyamide composite films, and printing. The materials are preferably used in the form of fiber materials, especially in the form of textile fibers, such as woven fabrics or yarns, such as in the form of hanks or winding packages. The hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. The cellulose fiber materials are preferably cotton, but other vegetable fibers such as flax, hemp, jute and ramia fibers can also be used; The regenerated cellulose fibers are for example viscose fiber cut and viscose filaments. Carboxamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal, silk, fur, nylon-6,6, nylon-6, nylon-1 1 and nylon coats. -4. The reactive dyes of the general formula I can be appland fixed on the said substrates, especially the mentioned fiber materials, by the application of known techniques for water-soluble dyes, especially dyes reactive in fibers. For example, on cellulose fibers produced by the depletion method from a large liquid using various acid binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, navy blue dyes having very good color yields. and excellent color build-up combined with high fixing performances. The staining is carrout in an aqueous bath at temperatures between 40 and 105 ° C, optionally at temperatures of up to 120 ° C under superatmospheric pressure, and optionally in the presence of common staining aids. One possible method is to introduce the material into the hot bath and gradually heat the bath to the desired dyeing temperature to complete the dyeing procedure at that temperature. The neutral salts which accelerate the depletion of the reactive dyes of the formula (general) I can also, if desired, be added only to the bath after the actual dyeing temperature has been reached. However, the reactive dyes of the general formula I are also very useful for salt-free or low-salt staining, and can then be appl for example, without any salt at a shallow depth of hue, with very little salt such as no more of 5 g / l of electrolyte salt at a depth of medium shade and with no more than 10 g / l of electrolyte salt at higher depths of hue, and in all cases strong stains are obtained. The shallow depths of hue for the purposes of this invention are shallow depths that include no more than 2% by weight of the colorant being used, based on the substrate. The mean hue depths will be understood as meaning more than two to not more than 4% by weight of dye, and higher hue depths will be understood as more than 4 to not more than 10% by weight of dye, based on the substrate .

This provides partially different reductions not only from the effluent load of wastewater in the colorant industries but also from the associated costs. Also, the impregnation process provides excellent color yields together with high fixing performances and very adequate color build-up on cellulose fibers, allowing the dyes to be fixed on the material by changing between room temperature or elevated temperature, for example up to about 60 ° C, by applying steam or using dry heat in a conventional manner. Similarly, normal printing processes for cellulose fibers, which can be carried out either individually, for example by printing with a printing paste comprising sodium carbonate or some other acid binder and the reactive dye of the formula General I and applying steam subsequently at 100-103 ° C, or two phases, for example by printing with printing paste comprising a dye for neutral or weakly acid printing and subsequent fixing either by passing the printed material through a bath hot alkaline comprising electrolytes or overprinting with an alkaline impregnation liquid comprising electrolytes with subsequent sampling of the overprinted material with alkali or subsequent vapor application or subsequent treatment with dry heat, produces strong impressions with well-defined contours and a clear white background . The performance of the prints is not greatly affected by variations in the fixing conditions. The binding yields obtained with the reactive dyes of the general formula I are very high not only in dyeing, but also in printing. When it is fixed by means of dry heat according to the normal thermofixation procedures, hot air of 120 to 200 ° C is used. In addition to the normal steam from 101 to 103 ° C it is also possible to use superheated steam and high pressure steam at temperatures up to 160 ° C. The acid binding agents which carry out the fixation of the reactive dyes of the general formula 1 on the cellulose fibers include, for example, water-soluble basic salts of the alkali metals and the alkaline earth metals of inorganic or organic acids and similar compounds that they release alkali in the heat. Especially suitable are the hydroxides of the alkali metal and alkali metal salts of inorganic or organic acids weak to medium, the alkali metal compounds which are preferred being the sodium and potassium compounds. Such acid binding agents include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium acid diphosphate, disodium hydrogen phosphate, sodium trichloroacetate, sodium or phosphate silicate. trisodium The treatment of the reactive dyes of the formula I with the acid binding agents with or without heating binds the dyes chemically to the cellulose fiber. Cellulose stains in particular, after the normal post-treatment rinsing to remove unfixed dye portions exhibit very adequate fixations, in particular since said unfixed dye portions are easily washed out due to their adequate solubility in cold water. Stains on polyurethane and polyamide fibers are usually carried out from an acidic medium. For example, the dye bath can include acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or sodium acetate to obtain the desired pH. In order to achieve uniformity useful for dyeing, it is advisable to add common leveling auxiliaries, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or aminonaphthalenesulfonic acid or based on a product of reaction of for example stearylamine with ethylene oxide. Generally the material to be dyed is introduced into the bath at a temperature of approximately 40 ° C, it is stirred there for some time, and the dye bath is then adjusted to the desired weakly acid pH, preferably with acetic acid, and the actual dyeing is carried out at a temperature between 60 and 98 ° C. However, the stains can also be brought to the boiling point or at temperatures up to 120 ° C (under pressure). The stains and prints prepared with the reactive dyes of the general formula I according to the invention are remarkable for bright shades. The stains and impressions on cellulose fiber materials in particular, as already mentioned, also have high color concentration, adequate resistances to light and moisture, and also suitable hot pressing fixings. Particularly noteworthy are the high fixation yields obtainable on cellulose fiber materials, which can be more than 90%, and also the very adequate color fixation, including the depletion method using reduced neutral salt quantities or supplying together with salt, depending on the hue depth, that is, depending on the amount of colorant used. An additional advantage of the reactive dyes of the general formula 1 is the ease with which the portions not fixed in the printing or dyeing processes are washed out, as a result of which the washing of the printed or dyed cellulose fiber materials also can be achieved with smaller amounts of washing liquid and, as the case may be, temperature control to save energy during washing. The following examples serve to illustrate the invention. The parts and percentages are by weight, unless otherwise indicated. Parts by weight refer to parts by volume in relation of kilogram to liter. The compounds described in the examples in terms of a formula are indicated in the form of the free acid. In general, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used to dye in the form of their salts. The starting compounds and the mentioned components in free acid form in the following examples can be used similarly in the synthesis as such or in the form of their salts, preferably alkali metal salts. The maximum visible absorption (in nm) reported for the dyes of the invention were determined in aqueous solutions of their alkali metal salts.

EXAMPLE OF PREPARATION 1 80 parts of concentrated sulfuric acid are mixed with 7 parts of sodium nitrite at no more than 10 ° C with cooling, stirred briefly and then heated at 70 ° C for 30 minutes until the nitrite has dissolved. At 20 ° C, an additional 90 parts of concentrated sulfuric acid and also 32 parts of 4-amino-N- (4 - ((β-hydroxyethyl) sulfonyl) phenyl) benzamide are added up to a maximum temperature of 30 ° C and the The mixture is subsequently stirred at 20-25 ° C for 3 hours. The suspension of the product obtained by simultaneous esterification and diazotization is cooled and poured slowly onto ice while the temperature is maintained at minus 20 ° C with additional ice, and subsequently the excess of nitrite is reduced with amidosulfonic acid. The diazonium salt is filtered on a suction filter, suspended in 75 parts of water and added slowly at 15-20 ° C and at a pH between 4.5 and 5.5 to a solution in 100 parts of water of 56 parts of a red monoazo dye prepared at pH 0.7-1.5 in a conventional manner by coupling diazotized 1-aminophenyl-4-β-sulfatoethyl sulfone on 1-amino-8-naphthol-3,6-disulfonic acid (H-acid), while establishing the pH from 4.5 to 5.5 mentioned above and maintained with sodium carbonate. Stirring is continued at about 20 ° C until the pH remains constant. The dark blue bisazo dye resulting from the formula with an absorption maximum of 608 nm, it can be isolated from the reaction mixture in a conventional manner, for example by misaligning with potassium chloride or by precipitating by the addition of ethanol or by evaporating the dye solution at 50 ° C under reduced pressure or by spray drying. The dye has very suitable fiber reactive dyeing properties and when applied by standard methods in the art for reactive dyes in fibers, including the exhaustion method under low salt or unsalted tinsion conditions, to the materials mentioned in The description, produces stains and impressions in deep navy blue shades that have adequate fixing properties.

EXAMPLE OF PREPARATION 2 32 parts of 4-amino-N- (4 - ((β-hydroxyethyl) sulfonyl) phenyl) benzamide are introduced in 184 parts of concentrated sulfuric acid at a temperature of up to 30 ° C and stirred for 5 hours. The esterification suspension is poured gradually onto ice, and more ice is added to keep the temperature below 20 ° C. The precipitated product is filtered, and the wet press cake is suspended 200 parts of water and adjusted to pH 6 with 15.6 parts of sodium carbonate and mixed with 7.6 parts of sodium nitrite (in the form of a 5N aqueous solution) . The suspension obtained is gradually added dropwise to a mixture of 100 parts of ice and 22.1 parts of concentrated sulfuric acid, and the resulting mixture is stirred at a temperature of 5 to 10 ° C for 1 hour. The excess nitrite is then removed with aqueous solution of 1 N aminosulphonic acid, and the diazonium salt suspension is reacted in the manner of Preparation Example 1 by coupling on the indicated red monoazo dye 2- (4- (β-sulfatoethylsulfonyl ) -phenyl) -azo-3,6-disulfur-1-amino-8-hydroxy-naphthalene to form the dark blue bisazo dye which can be isolated as indicated in Preparation Example 1 and has coloring properties similar to those of the compound disazo of the preparation example 1 according to the invention.

EXAMPLE OF PREPARATION 3 32 parts of 4-amino-N- (3 - ((β-hydroxyethyl) sulfonyl) phenylbenzamide are introduced in 202 parts of concentrated sulfuric acid at a temperature between 20 and 30 ° C, and the mixture is subsequently stirred at room temperature for 3 hours.The esterification mixture is cooled to 0-10 ° C and a mixture of 50 parts of ice and 50 parts of water is gradually added while adding 250 more parts of ice to keep the temperature below 15 ° C. The precipitated aminosulfone ester is filtered after an additional 30 minutes of stirring and washed with 50 parts of ice-water.The wet press cake is suspended in 200 parts of water and 100 parts of ice, and diazotized with 7.6 parts of sodium nitrite (in the form of a 5N aqueous solution) at a pH of less than 1.5 and at a temperature of 5 to 10 ° C within 2 hours. The excess nitrite is then decomposed with 1 N aqueous aminosulfonic acid solution, and the diazonium salt is added to a solution in 100 parts by weight of 58 parts of the conventionally prepared monoazo red dye 2- (4- (β-suyfatoethylsulfonyl)) phenyl) -azo-3,6, -disulfo-1-amino-8-hydroxy-naphthalene and copulate at a pH of 4.5 to 5.5 and at a temperature of 10 to 20 ° C to form bisazo dye. The indicated pH scale is established and maintained by the addition of solid sodium carbonate. The dark blue bisazo dye resulting from the formula with a maximum absorption of 609 nm, it can be isolated from the reaction solution in a conventional manner, for example by desalting with potassium chloride or evaporating the dye solution under reduced pressure at 50 ° C.

EXAMPLE OF PREPARATION 4 32 parts of 4-amino-N- (3 - ((β-hydroxyethyl) sulfonyl) phenyl) benzamide are esterified and isolated in 202 parts of concentrated sulfuric acid as described in preparation example 3. The wet pressing cake it is introduced into 100 parts of water, pH 6 is adjusted with 7.8 parts of sodium carbonate, stirred briefly and mixed with 7.6 parts of sodium nitrite (in the form of a 5N aqueous solution). The excess nitrite is then decomposed with aqueous solution of 1 N aminosulfonic acid, and the diazonium salt is reacted in the manner described in Preparation Example 3 by coupling the monoazo red dye 2- (4- (β-sulfatoethylsulfonyl) - phenyl) -azo-3,6-disulfo-1-amino-8-hydroxy-naphthalene mentioned above to form the dark blue bisazo dye, which can be isolated as indicated in the preparation example 3.

EXAMPLE OF PREPARATION 5 32 parts of 3-amino-N- (4 - ((β-hydroxyethyl) sulfonyl) phenyl) benzamine are introduced in 202 parts of concentrated sulfuric acid at a temperature between 20 and 30 ° C, and the mixture is subsequently stirred at room temperature for 3 hours. The esterification mixture is cooled to 0 ° C - 10 ° C and gradually added to 85 parts of ice while adding an additional 250 parts of ice to keep the temperature below 20 ° C. The precipitated aminosulfone ester is filtered after briefly stirring and introduced into 165 parts of water, adjusted to pH 5 with 40 parts of sodium carbonate and mixed with 8 parts of sodium nitrite (in the form of a 5N aqueous solution). ). The resulting suspension is added slowly by dropping to a mixture of 85 parts of ice and 42 parts of concentrated sulfuric acid, and the mixture is stirred at a temperature of 5-10 ° C for 1.5 hours. The excess nitrite is then decomposed with 1 N aqueous aminosulfonic acid solution, and the diazonium salt suspension is gradually added at 10-20 ° C and at a pH between 4.5 and 5.5 to a solution of 56 parts of a red monoazo dye. prepared at pH 0.7-1.5 in a conventional manner by coupling diazotized 1-amino-8-naphthol-3,6-disulfonic acid (H acid) 1-aminophenyl 4- (β-sulfatoethyl) -sulfone acid, while setting the pH from 4.5 to 5.5 mentioned above and maintained with sodium carbonate. Stirring is continued at approximately 20 ° C until the pH remains constant. The dark blue bisazo dye resulting from the formula with a maximum absorption of 604 nm, it can be isolated from the reaction mixture in conventional manner, for example by desalting with potassium chloride or by precipitating by the addition of ethanol or by evaporating the dye solution at 50 ° C under reduced pressure by drying by aspesión.

EXAMPLE OF PREPARATION 6 80 parts of concentrated sulfuric acid are mixed with 7 parts of sodium nitrite at no more than 10 ° C with cooling, stirred briefly and then heated at 70 ° C for 30 minutes until the nitrite has dissolved. At 20 ° C an additional 90 parts of concentrated sulfuric acid are added and also 35 parts of 4-amino-N- (2 - ((β-hydroxyethyl) sulfonyl) ethyl) -N-phenyl-benzamide are introduced up to a maximum temperature of 30 ° C and the mixture is subsequently stirred at 20-25 ° C for 2 hours. The suspension of the product obtained by simultaneous esterification and diazotization is cooled and slowly poured over 50 parts of ice while maintaining the temperature at less than 20 ° C with the addition of 200 more parts of ice, and subsequently the excess of nitrite is reduced with amidosulfonic acid. The resulting suspension is gradually added at 12-20 ° C and at a pH between 4.5 and 5.5 to a solution in 100 parts of water of 55 parts of a red monoazo dye conventionally prepared by coupling 1-aminophenyl 4-β-sulfatoethylsulfone on acid 1- amino-8-naphthol-3, 6-disulfonic acid (acid H) at pH 0.7-1.5, the aforementioned pH of 4.5 to 5.5 being established and maintained with a total of 174 parts of sodium carbonate. Stirring is continued at about 20 ° C until the pH remains constant. The sodium sulfate precipitated from the dye solution is filtered and then any additional sodium sulfate is frozen and filtered. The dark blue bisazo dye resulting from the formula with a maximum absorption of 612 nm, it can be isolated from the reaction mixture in a conventional manner, for example by evaporating the dye solution at 50 ° C under reduced pressure or by spray drying.

EXAMPLE OF PREPARATION 7 32 parts of 4-amino-N- (3 - ((β-hydroxyethyl) sulfonyl) phenyl) benzamide are esterified with 202 parts of concentrated sulfuric acid and isolated, both steps being carried out as described in Preparation Example 3 The wet press cake is introduced into 200 parts of water and mixed with 7.6 parts of sodium nitrite (in the form of a 5N aqueous solution). The resulting suspension is gradually added dropwise to a mixture of 100 parts of ice and 11.6 parts of hydrochloric acid at 31% concentration, and the resulting mixture is stirred at 5-10 ° C for 2 hours. The excess nitrite is then removed with 1 N aqueous amidosulfonic acid solution and 31 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid (H acid) are added to the diazonium salt suspension in the 10 minutes. A pH between 0.7 and 1.5 is established and it is maintained with a total of 1.6 parts of sodium bicarbonate and it is continued stirring overnight at a temperature between 10 and 20 ° C. The red monoazo compound obtained in this way is subsequently dripped at a pH between 4.5 and 5.5 and at a temperature between 10 and 20 ° C with a diazonium salt suspension prepared from 28.4 parts of aminophenyl-4-ß- sulfatoethylsulfone by diazotization in a conventional manner with sodium nitrite in an acid aqueous medium at a temperature between 5 and 10 ° C. The reported pH scale is established and maintained by the addition of a total of 23 parts of sodium carbonate. The mixture is stirred overnight and the dark blue bisazo dye resulting from the formula with an absorption maximum of 587 nm, it is then isolated in a conventional manner, for example by desalting with potassium chloride or precipitating by the addition of ethanol or by evaporating the dye solution at 50 ° C under reduced pressure or by spray drying.

EXAMPLES OF PREPARATION 8-25 The following table examples describe additional disazo compounds according to the invention in terms of general formula 1b (Ib) They can be prepared in a manner according to the invention, for example similarly to the preparation examples 1-6 mentioned above, from the diazo component D-NH2, 1-amino-8-hydroxy-naphthalen-3 acid, 6-disulfonic acid and an amine having an appropriately substituted carboxamide function as an additional diazo component. They possess very suitable fiber reactive dye properties and dye the aforementioned materials, especially cellulose fiber materials, in navy blue shades having high color concentration and suitable fixings. 31 EXAMPLES OF PREPARATION 26-46 The following table examples describe additional reactive dyes according to the invention in terms of the general formula 1c (le) They can be prepared in a manner according to the invention, for example similarly to the preparation example 7 mentioned above, from an amine having an appropriately substituted carboxamide function as a diazo component coupled to acid, 1- amino acid 8-hydroxy-naphthalene-3,6-disulfonic acid and the additional diazo component D1-32 NH2. They have very suitable reactive dye properties in fiber and dye the materials mentioned in the description, especially cellulose fiber materials, in navy blue shades that have high color concentration and suitable fixings. 33 EXAMPLES OF PREPARATION 47-68 The following table examples describe additional disazo compounds according to the invention in terms of the formula Id (Id) They can be prepared in a manner according to the invention, for example similarly to the above-mentioned preparation examples 1-6 above, from the diazo component of D2-NH2, 1-amino-8-hydroxy-naphthalene. -3,6-disulfonic and an amine having an appropriately substituted carboxamide function as an additional diazo component. They possess very suitable fiber reactive dyeing properties and dye the materials mentioned in the description, especially cellulose fiber materials, in navy blue shades having high color concentration and suitable fixings.

EXAMPLES OF PREPARATION 69-90 The examples in the table below describe additional disazo compounds according to the invention in terms of the general formula 36 They can be prepared in a manner according to the invention, for example similar to the preparation example 7 mentioned above, from an amine having an appropriately substituted carboxamide function such as a diazo component coupled to acid, 1-amino-8- acid hydroxy-naphthalene-3,6-disulfonic acid and the additional diazo component D1-NH2. They possess very suitable reactive dyeing properties in fibers and dye the materials mentioned in the description, especially cellulose fiber materials, in navy blue tones which have high color concentration and suitable fixings. 37 38 EXAMPLE OF USE 1 2 parts of the dye obtained according to Preparation Example 1 or 2 are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and added optionally a part of a wetting agent. 100 g of a cotton cloth are placed in this dye bath. The temperature of the dye bath is first maintained at 25 ° C for 10 minutes, then raised for 30 minutes to the final temperature (40-60 ° C) and maintained at that level for an additional 60-90 minutes. Subsequently the dyed material is rinsed initially with tap water for 2 minutes and then with ion-free water for 5 minutes. The stained material is neutralized at 40 ° C in 1000 parts of an aqueous solution containing one part of 50% acetic acid for 10 minutes. It is subsequently rinsed with deionized water at 70 ° C and subsequently washed in the container with a detergent for 15 minutes, rinsed once more and dried. This gives a strong navy blue staining that has very suitable fixing properties.

EXAMPLE OF USE 2 4 parts of the dye obtained according to the preparation example 1 or 2, and 5 parts of sodium chloride are dissolved in 999 parts of 39 water and 5 parts of sodium carbonate, 0.7 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) are added and a part of wetting agent is optionally added. To this dye bath, 100 g of a cotton cloth are put. The rest of the processing is as indicated in the use example 1. This gives a strong dark blue color staining that has very suitable fixing properties.

EXAMPLE OF USE 3 Eight parts of the dye obtained according to the preparation example 1 or 2 and 10 parts of sodium chloride are dissolved in 997 parts of water and 5 parts of sodium carbonate, 1.3 parts of sodium hydroxide (in the form of a aqueous solution at 32.5%) and optionally a part of a wetting agent. 100 g of a cotton cloth are placed in this dye bath. The rest of the processing is as indicated in the use example 1. This gives a strong navy blue staining which has very suitable fixing properties.

Wherein R 4 and R 5 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, sulfo, carbpxyl, amido or halogen; a naphthylene group of the general formula IV (IV) wherein R 6 and R 7 are independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the general formula V where k is an integer of more than 1; and R8 and R9 are independently hydrogen, C1-C4 alkyl, C? -C alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X1 is hydrogen or -S02-Z; or represents a phenyl radical of the general formula VI X2 (VI) wherein R) 1? 0u and R11 are independently hydrogen, C -? - C4 alkyl, C -? - C4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X2 has one of the meanings of X1; or represent a naphthyl radical of the general formula VII

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - A reactive dye of the general formula I (I) where D1 and D2 each represent a group of the general formula (II) wherein R 1 is hydrogen, C 1 -C 4 alkyl, aryl or substituted aryl; and R 2 and R 3 are independently hydrogen, C 1 -C alkyl, C 1 -C 4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; A is a phenylene group of the general formula III (III) wherein R4 and R5 are independently hydrogen, C1-C4 alkyl, C1-C4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; a naphthylene group of the general formula IV (IV) wherein R6 and R7 are independently hydrogen, C? -C4 alkyl, C? -C4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the general formula V - (CR8R9) k- (V) wherein k is an integer of more than 1; and R8 and R9 are independently hydrogen, C-- C alkyl, C - - C4 alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X1 is hydrogen or -SO2-Z; or represents a phenyl radical of the general formula VI X2 (VI) wherein R10 and R11 are independently hydrogen, C -? - C4 alkyl, C? -C4 alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X2 has one of the meanings of X1; or represent a naphthyl radical of the general formula VII . 12" (vii) wherein R12 and R13 are independently hydrogen, C - - C alkyl, C - - C alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; X3 has one of the meanings of X1; Z is -CH = CH2, -CH2CH2Z1 or hydroxyl, wherein Z1 is hydroxyl or an alkali-releasable group; and M is hydrogen or an alkali metal; wherein at least one of D1 and D2 is a group of the general formula II; wherein, if A is a group of the general formula V, R1 is aryl or substituted aryl; and wherein the reactive dye of the general formula I contains at least one -SO2-Z group.

2. A reactive dye according to claim 1, further characterized in that R1 to R5 and R8 to R11 are each hydrogen and R6, R7, R12 and R13 are each hydrogen or sulfo.

3. A reactive dye according to claim 1 and / or 2, further characterized in that Z is vinyl, ß-chloroethyl or ß-sulfatoethyl.

4. A reactive dye according to one or more of claims 1 to 3, having the general formula (a) wherein A, Z and R are each as defined in claim 1.

5. A reactive dye according to claim 4, further characterized in that A is phenylene and Z is vinyl or β-sulfatoethyl.

6. A process for preparing a reactive dye according to one or more of claims 1 to 5, which comprises diazotizing an amine of the general formula VIII D2-NH2 (VIII) wherein D2 is as defined in the claim 1, in a conventional manner, then reacting the resulting diazonium compound in an aqueous medium with 1-amino-8-hydroxy-3,6-disulfonic acid (acid H) or 1-amino-8-hydroxy-4 acid, 6-disulfonic acid (acid K) to form the monoazo dye of the general formula IX (IX) and subsequently diazotizing an amine of the general formula X D1-NH2 (X) wherein D1 as defined in claim 1, in a conventional manner, and then coupling the resulting diazonium compound with the monoazo dye of the formula IX to form the disazo dye of the general formula I.

7. - A method for using a reactive dye of the general formula I according to one or more of claims 1 to 5 for dyeing fiber materials containing hydroxyl and / or carboxamido.