CH536871A - Dyestuffs suitable for fibres - contg. hydroxyl groups of nitrogen - Google Patents

Abstract

Reactive dyestuffs are obtained by introducing into dyestuffs or dyestuff intermediates by known methods at leasts one 5-member heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a C atom of the ring, and in the case of the intermediates converting them into the desired end dyestuffs. The water-soluble dyestuffs obtained are suitable for dyeing fibres containing OH or nitrogen e.g. natural or regenerated cellulose, wool, silk, polyamides or polyurethanes. They are especially suitable for cellulose materials due to the reactive sulphonyl substituent. To fastness properties particularly the fastness to wet processing, are excellent.

Description

  

  
 



   The present invention relates to a process for the preparation of valuable new reactive dyes of the formula
EMI1.1
 wherein F for the radical of an organic dye, m for a number from 1 to 4, R for hydrogen or a substituent, A for a five-membered heterocyclic ring with at least one reactive sulfonyl substituent on a carbon atom of the heterocyclic ring and X for a bridge member of Formula -CO-, -SO2-, -CO-alkylene or -CO-arylene, where -XA reactive groups of the formula
EMI1.2
 are excluded in which Y, and Y2 stand for reactive substituents.



   The subject of this invention does not include the preparation of dyes which are used in the process according to patent no. 442 220; the dyes indicated there have one or more reactive groups of the formula
EMI1.3
 on, where Y1 and Y2 are reactive substituents.



   In the dyes of the formula (I), the radical A is by definition linked either in a direct bond with amino or amide groups of the dye radical F or bonded to these groups via one of the specified bridge members. The amino or amide groups can carry further substituents R, such as lower alkyl (preferably C 1 to C 5), aralkyl, cycloalkyl or aryl groups, but are preferably in the form -NH- which is not further substituted.

  The amino groups in turn can either be bonded directly to an aromatic ring of the dye on the one hand and to the radical A on the other hand, or via a further bridge member, such as -502- or -CO- (as in the case of the amide group already mentioned), or an alkylene group, a Arylene, arylene-SO2, arylene-CO, arylenamino or aralkyleneamino group or a triazine or diazine ring, an arylenamidosulfonyl group or other types of members can be linked to the aromatic radical of the dye F on the one hand and the radical A on the other. If such further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, then these too can still have reactive atoms or groups, such as halogen atoms or sulfonyl substituents.



   As reactive sulfonyl substituent in the radical A lower alkylsulfonyl come with preferably 1 to 5 C atoms, such as methylsulfonyl, or Äthylsulfonyl- Propylsulfonylreste, arylsulfonyl groups such as phenylsulfonyl, p-toluenesulfonyl, pChlor- phenylsulfonylreste, Aralkylsulphonyl as Benzylsulfonylund p-TolylmethylsulfonylresteX and also heterosulfonyl radicals, such as 2-benzothiazolesulfonyl, are possible.



   The S-membered heterocyclic ring A, which has at least one reactive sulfonyl substituent, does not contain any further fused rings. The ring system A can be, for example, an imidazole, thiazole, 1,2,4-triazole, 1,2,4-thiadiazole or 1,3,4-thiadiazole radical.



   The binding of the heterocyclic 5-ring A to X or



  in the event that X represents a direct bond, either a carbon atom of the heterocyclic 5-membered ring or a heteroatom of this ring, in particular a nitrogen atom, starts at -N (R) -F.



   The heterocyclic 5-ring A contains, as heteroatoms, preferably oxygen, sulfur and / or nitrogen atoms in the form of the groupings or atoms
EMI1.4
 where B represents hydrogen or a substituent, e.g. B.



  an alkyl, aralkyl or aryl radical, which in turn can have further substituents or links.



   The heterocyclic 5-ring A is preferably aromatic, but can also be hydroaromatic in nature. Groups of preferred heterocyclic rings A are those which have at least two heterocyclically bonded nitrogen atoms or which contain at least one heterocyclically bonded nitrogen atom and one heterocyclically bonded sulfur atom, although heterocyclic ring systems of the type disclosed in Patent No. 442 220 (isothiazole rings in position 4 via carbonamide bound) or dyes with these ring systems are excluded from the subject matter of the present invention.



   In addition to at least one reactive sulfonyl substituent and the direct bond or the bridge member via which the 5-ring is linked to the dye molecule, the heterocyclic 5-ring A can have other substituents, such as alkyl, e.g. B. methyl or ethyl, aralkyl; z. Benzyl, aryl, e.g. B. phenyl groups, which in turn may have any further substituents, also hydroxy, mercapto, amino, acylamino, substituted amino, alkyloxy, aralkyloxy, aryloxy, alkylthio, aralkylthio, arylthio, halogen and especially chlorine - or bromine, carboxy, carbalkoxy, carbonamido, alkylcarbonyl, aralkylcarbonyl, arylcarbonyl, sulfinic acid, sulfonic acid, sulfonamide, nitro or nitrile groups.



   Examples of suitable 5-membered heterocyclic radicals A are specifically as follows: 2-methylsulfonyl-1-methylimidazol-yl-5, 2-methylsulfonyl-1-phenyl-imidazol-yl-5, 2-methylsulfonyl-4-phenyl-thiazol-yl-5 , 1-Methyl-3-methylsulfonyl-1H-triazol-1, 2,4-yl-5, 3-methylsulfonyl-5-phenyl4H-triazol-1,2,4-yl4, 3,5-dimethylsulfonyl4H-triazol-1 , 2,4-yl4, 2-methylsulfonyl thiadiazol-1,3,4-yl-5, 1-ethyl-2-methylsulfonyl-4-methyl-imidazol-yl-5, 1,4-dimethyl-2-ethylsulfonyl-imidazole- yl-5, 3-methylsulfonyl-thiadiazol-i, 2,4-yl-S,

   5-methylsulfonyl-thiadiazol-1,2,4-yl-3, 3-methylsulfonyl-l, 2,4-thiadiazolyl-5, 3-hydroxy-5-methylsulfonyl-isothiazolyl-4, 2-M ethyl-5-methyl sulfonyl- isothiazolin-3-on-yl4, 2,5-bis-methylsulfonyl-4-methylH-imidazol-yl-4 or 4-methyl-2-methylsulfonyl-thiazolyl-5.



   Among the multitude of possible and synthetically useful types of binding of F to A, i. H. Limbs
EMI1.5
 optionally including further bridges between F and -N (R) -, the following examples should be mentioned: -NH-, -N (CH3) -, -N (C2H5) -, -N (C3H7) -, -CONH- , -HNOC-, -SO2NH-, -NHO2S-, -CON (CH3) -, - (CH3) NOC-, -SO2N (CH3) -, - (CH3) NO2S- and the corresponding N-ethyl and N- Propylamides, -NH-CO-NH-, -HN-CH2-CO-NH-, -N (CH3) -CH2-CONH-, -HN-CH2-CH2-NH-, -HN-CH2-CH2-NH- CO-,
EMI2.1
 and the corresponding N-alkyl (1-5 C) amides or amines
EMI2.2

EMI2.3
 and the corresponding N-alkyl (1-5 C) amides or amines of the compounds mentioned.



   The new dyes can belong to a wide variety of classes, e.g. B. the series of metal-free or metal-containing mono- or polyazo dyes, metal-free or metal-containing azaporphin dyes, such as copper or nickel phthalocyanine dyes, the anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone and dibenzanthrone dyes and the polycyclic Condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds. In the context of these dye classes, among other things, dyes of the general compositions are particularly valuable.



  1. Azo dyes
EMI2.4
 wherein B and D represent aromatic, carbocyclic or heterocyclic radicals, for example B the radical of a carbocyclic diazo component of the benzene or naphthalene series and D the radical of an enolic or phenolic coupling component, e.g. B. a 5-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene, etc .; B and D can also have any substituents customary in azo dyes, including further azo groups; R1 stands for a substituent or preferably for a hydrogen atom, Q for a direct bond or a group -CO- or -SO2- and m 'is an integer, preferably the number 1 or 2; A represents the remainder of a S-membered heterocyclic ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring.



   Particularly valuable dyes of this series are those which are water-soluble, and in particular those which have sulfonic acid and / or carboxylic acid groups. The azo dyes can be either metal-free or metal-containing, with the copper, chromium and cobalt complexes being of preferred interest among the metal complexes.

 

   Important azo dyes are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene series, the naphthalene-azo-1-phenylpyrazolone5- Series and the stilbene-azo-benzene series, the dyes containing sulfonic acid groups being preferred here too.



  In the case of metal complex azo dyes, the metal complex-bonded groups are preferably in the o- & ellungen to the azo group, e.g. B. in the form of o, o'-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino and o-hydroxy-o'-aminoazo groups.



  2. Anthraquinone dyes
EMI3.1
 Here, L denotes hydrogen or substituents, among these in particular the sulfonic acid group, p denotes the number 1, 2 or 3, R1 denotes a substituent or preferably hydrogen, Q denotes a direct bond or a grouping -CO- or -SO2- and A denotes the remainder of a heterocyclic member Ring containing at least one reactive sulfonyl substituent attached to a carbon atom of the heterocyclic ring.



   In the field of these dyes, too, the water-soluble products are preferred because of their excellent suitability for dyeing and printing cellulose-containing fibers, the dyes substituted by sulfonic acid groups proving to be particularly suitable.



  3. Azaporphine dyes
EMI3.2

In this formula, Pc stands for the remainder of a phthalocyanine, e.g. B. a copper or nickel phthalocyanine or a tetraphenyl copper or nickel phthalocyanine, L for hydrogen or a substituent, the sulfonic acid group being preferred as the substituent, r for the number 1 or 2, q for the number 0, 1 or 2, RX for a substituent or preferably hydrogen, Q for a direct bond or a -CO- or -SO2 group, A for the remainder of a S-membered heterocyclic ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring, and m "for a Number from 0.5 to 4. The phthalocyanine residue Pc can of course have further substituents, in particular sulfonic acid and sulfonamide groups.



   Water-soluble phthalocyanine dyes of the formula (V>, which are preferred for application to cellulose-containing materials, are, in particular, those which have sulfonic acid groups in the Pc radical and optionally also as a substituent L).



   Examples of suitable S-membered heterocyclic radicals A in dyes of the formulas (1), (in), (III), (IV) and (V) include:
EMI3.3

EMI3.4
 By definition, the heterocyclic 5-rings contain no fused rings.



   The above compilation of a selection of suitable azo, anthraquinone and azaporphin dyes and heterocyclic ring systems A does not represent any restriction of the above formulas, neither with regard to the preparative possibilities for the preparation of such dyes within the framework of the general formula (1), nor with regard to the valuable application properties of these products. The new dyes can also have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxy, alkoxy, thioether , Azo groups and the like.



  The dyes can also contain other fixable groups, such as mono- or dihalotriazinylamino, mono-, di- or trihalopyrimidinylamino, 2,3-dihaloquinoxaline-6-carbonyl or -6-sulfonylamino, 1,4-dihalophthalazine 6-carbonyl or -6-sulfonylamino, 2-halobenzthiazole, 5-carbonyl or -5-sulfonylamino, esterified sulfonic acid oxalkylamide and oxalkylsulfone groups, sulfofluoride, haloalkylamino, acryloylamino, haloacylamino groups and the like.



   The new dyes of the formula (I) are obtained according to the invention by starting dyes of the formula
EMI4.1
 with compounds of the formula
Y-X-A (VI) converts, wherein Y is an anionically removable radical
Among the reactive substituents Y which can be split off as anionic radicals, Cl, Br and sulfonyl substituents are of preferred interest. Further suitable anionically removable radicals are, for example, fluorine, SO3M (M = H or metal cation), quaternary ammonium groups, alkyl mercapto, nitrile, alkoxy or aryloxy groups.



   Suitable heterocyclic 5-ring compounds of the formula (VI) for the reaction are, for example, 2-methylsulfonyl.1-methyl.imidazole-5-carboxylic acid chloride
EMI4.2
 2-methylsulfonyl-1-phenyl-imidazole-5-carboxylic acid chloride
EMI4.3
   4 {2 ', 5'-bis-methylsulfonyl4-methyl-4'H-imidazolyl- (4')} benzoyl chloride
EMI4.4
   4 {1'-methyl-3'-methylsulfonyl-1 'H-1', 2 ', 4'-triazolyl45')} benzoyl chloride
EMI4.5
   4 + 3, -Methylsulfonyl-5'-phenyl-4'H-triazol.1 ', 2', 4'-yl4) iben-zoyl chloride
EMI4.6
   4 {3 ', 5'-bis-methylsulfonyl4'H-triazol- I', 2 ', 4'-yl44')} benzoyl chloride
EMI4.7
   3,5-bis-methylsulfonyl-1, 2,4-thiodiazole
EMI4.8
 2,5-bis-methylsulfonyl-1, 3,4-thiodiazole
EMI4.9
   [1

   -Ethyl4-methyl-2-methylsulfonyl-imidazolyl- (5) Iacetyl chloride
EMI4.10
   1,4-Dimethyl-2-ethylsulfonyl-imidazole-5-carboxylic acid chloride
EMI4.11
  3-methylsulfonyl-5-chloro-1, 2,4-thiodiazole
EMI5.1
   S-CS-methylsulfonyl-1,2,4-thiodiazolyl43)} mercapto-acetylchloride
EMI5.2
   3-Hydroxy-5-methylsulfonyl-isothiazole-4-carboxylic acid chloride
EMI5.3
   2-methyl-5-methylsulfonyl-isothiazolin-3-one-4-carboxylic acid chloride
EMI5.4
   4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride
EMI5.5

The implementation of amino resp.

   Dyes containing amide groups with heterocyclic compounds of the formula (VI) can, depending on the nature of the starting compounds used, in an organic, organic-aqueous or aqueous medium at temperatures of -10 "C to 80" C, preferably in the presence of alkaline condensing agents such as pyridine, aqueous alkali carbonate or Alkali hydroxide solutions.



   In the dyes of the formula I obtained, further conversion reactions can be carried out subsequently, as are customary in azo dyes, for example. B. acylation, condensation, reduction and metallization reactions. Also in the representation of other dyes, in particular those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (VI) can initially take place with an intermediate product, e.g. B. with m-phenylenediamine or a m-phenylenediaminesulfonic acid, and the resulting reaction product then with z. B. bromamic acid (1-amino-4-bromo-anthraquinone-2-sulfonic acid) can be further condensed into a reactive anthraquinone dye or with copper or nickel phthalocyanine sulfonic acid halide to form a reactive phthalocyanine dye.



   It is sometimes also possible that dyes containing amino or amide groups or, in particular, dye intermediates which have an exchangeable hydrogen atom on the amino or amide group, with compounds of the general formula A '- (Z) 1 (VII) wherein A' has an S-member represents a heterocyclic ring, Z represents an anionically removable radical, with the exception of a sulfonyl radical, and t is the number 2 or a number greater than 2, replacing one of the anionically removable radicals Z, then converts the remaining Z radical or radicals in a manner known per se is converted into sulfonyl substituents and, if dye precursors are used, these are converted into the desired final dyes.



   The replacement of one or more anionically removable substituents Z, z. B. of halogen atoms, against sulfonyl substituents can be, for. This can be accomplished, for example, by reacting the compounds with alkyl or aryl sulfinates or, if Z is, for example, an anionically cleavable alkyl mercapto or aryl mercapto group, converting these into the corresponding sulfonyl radicals using suitable oxidizing agents such as hydrogen peroxide, hypohalites, chlorine or permanganates.



   The dyes obtainable by the process according to the invention can, as already mentioned for a few cases, be subjected to further reactions customary for dyes, for example by adding metallizable dyes with metal donating agents, in particular with chromium, cobalt, copper or nickel salts, treated, dyes that have reducible groups, in particular nitro groups, reduced, dyes that have acylable groups, in particular acylable amino groups, acylated, or by subsequently treating dyes with sulfonating agents, such as chlorosulfonic acid, thionyl chloride, oleum or SO3 in chlorinated hydrocarbons, to introduce more sulfonic acid groups into the products. The last-mentioned process is sometimes of particular importance in the series of anthraquinone and phthalocyanine dyes.



   Depending on the number of reactive -HNR groups in the dyestuff residue that are suitable for the conversion reaction, up to four groupings of the formula -X-A can be incorporated into the dyestuffs.



   If the dyes represented according to the method contain metal complex-forming groups, they can be removed by the action of metal-donating agents, e.g. B. of copper, nickel, chromium or cobalt salts are converted into their metal complex compounds. They can also be subjected to other conventional conversion reactions, such as diazotization, coupling, acylation and condensation reactions.



   The new dyes are extremely valuable products that are suitable for a wide variety of applications. Water-soluble dyes are of particular interest for dyeing hydroxyl-containing and nitrogen-containing textile materials, in particular textile materials made from native and regenerated cellulose, and also from wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive sulfonyl substituent or substituents in the heterocyclic ring A, the products are particularly suitable as reactive dyes for dyeing cellulose materials using the techniques that have recently become known for this purpose. The fastness properties obtained, especially wet fastness properties, are excellent.

 

   To dye cellulose, the dyes are preferably used in an aqueous solution to which alkaline substances, such as alkali hydroxide or alkali carbonate, or compounds that change into alkaline substances, such as alkali bicarbonate, can be added.



  Further auxiliaries can be added to the solution, but these should not react in an undesired manner with the dyes. Such additives are, for example, surface-active substances, such as alkyl sulfates or substances that prevent the migration of the dye, or dyeing auxiliary products, such as urea (to improve the solubility and fixation of the dyes), or indifferent thickeners such as oil-water emulsions, tragacanth, starch, alginate or methyl cellulose.



   The solutions or pastes produced in this way are applied to the material to be colored, for example by padding in a padder or by printing, and then heated for some time to an elevated temperature, preferably 40 to 150 ° C. The heating can be carried out in the hot flue, in the steamer heated rollers or by placing them in heated, concentrated alkaline salt baths, both individually and in any order one after the other.



   When using a padding or dye liquor without alkali, the dry goods are passed through an alkaline solution to which common salt or Glauber's salt is added. The addition of salt prevents the dye from migrating from the fiber.



   The material to be dyed can also be pretreated with one of the aforementioned acid-binding agents, then treated with the solution or paste of the dye and finally, as indicated, fixed at an elevated temperature.



   For dyeing from a long liquor, one goes into an aqueous solution of the dye at room temperature and dyeing for 40 to 90 minutes, optionally with increasing the temperature to 95 ° C., with partial addition of salt, e.g. sodium sulfate or sodium chloride, and then Alkali, for example sodium phosphates, sodium carbonate or alkali hydroxide, where the chemical reaction occurs
Dye and fiber. After chemical fixation, the material to be dyed is rinsed hot and then soaped, removing non-fixed residues of the dye. The dyeings obtained are extremely fast, in particular water, wash, perspiration, rubbing, solvent and lightfast dyeings.



   In the so-called cold padding process, subsequent heating of the padded fabric can be saved by the fact that the fabric is left for some time, e.g. B. 2 to 40 hours, stored at room temperature. In this process, a stronger alkali is used than in the dyeing process described above from a long liquor.



   For printing on those containing hydroxyl groups
Materials is a printing paste made from the dye solution, a thickener such as sodium alginate and an alkali reacting or splitting off alkali when heated
Compound, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium bicarbonate, used and the printed material rinsed and soaped.



   Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, sometimes a final increase in the pH of the dyebath, e.g. B. to pH 6.5 to pH 8.5 is advantageous.



   The dyes are applied, for example, to synthetic polyamide fabric as solutions or preferably in dispersed form and then post-treated, optionally together with (preferably smaller amounts) acid-binding agents such as sodium carbonate. Particularly favorable results are achieved with dyes which are insoluble or only sparingly soluble in water. These are processed into a dye dispersion according to conventional techniques and with the addition of the known auxiliaries and used as such in the dye and / or pad bath or in a printing paste. The auxiliaries suitable for this application are, among other things, compounds that prevent the migration of the dye on the fiber, such as cellulose ethers, alkali metal chlorides and sulfates, wetting agents, such as condensation products of ethylene oxide and fatty alcohols or

  Phenols, sulfonated fatty alcohols, solvents such as thiodiglycol, and thickeners such as starch, tragacanth, alginate thickener, gum arabic, etc.



   The aftertreatment of the dyeings, impregnations and prints obtained on polyamide fiber fabrics is preferably carried out at a temperature of 50 to 110 ° C. and for a duration of 5 to 60 minutes.



   The dyeings obtainable with the new dyes are generally distinguished by good to very good fastness properties, in particular excellent wet fastness properties.



   In the following examples, parts stand for parts by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kg relate to liters.



  example 1
To the solution of 34.7 parts of sodium 2-aminonaphthalene-4,8-disulphonic acid and 7 parts of sodium nitrite in 300 parts of water, 28 parts by volume of concentrated hydrochloric acid are added while cooling with ice and the mixture is stirred for half an hour at 0 to 10 ° C. After excess nitrous acid has been removed 10.7 parts of 3-aminotoluene, dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water, are added and the coupling is completed by blunting the mixture to pH 3 to 5. The aminoazo dye formed is salted out, filtered off with suction and washed and then again dissolved in 700 parts of water with the addition of sodium hydroxide solution at pH 7.

  The aqueous solution is then mixed with 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, which is made into a paste with a wetting agent and a little water, and stirred vigorously. The temperature of the reaction mixture is kept at about 20 ° C.; the mixture is blunted the released hydrochloric acid with soda solution until no free amino group can be detected any more The resulting dye of the formula
EMI6.1
 is salted out with 80 parts of common salt, pressed, washed and dried at 30 to 40 "C in a vacuum. It is a yellow powder that is soluble in water with a yellow color.



  Printing specification A
If you print on cellulose fabric with a printing paste containing 15 grams of the dye, 10 g of sodium m-nitrobenzenesulfonate, 100 g of urea, 300 ml of water, 500 g of alginate thickening (60 g of sodium alginate per kg of thickening), 2 g of sodium hydroxide and 10 g of soda and which has been made up to 1 kg with water, dries, steams at 105 ° C. for one minute, rinses with hot water and soaps at the boil, a strong, reddish-yellow print of good washing and lightfastness is obtained.



  Example 2
0.1 mole of the copper complex compound of the formula
EMI7.1
 (prepared according to the information in German patent specification 1 117 235) by coupling diazotized l-amino-8 (benzene-sulfonyloxytnaphthalene-disulfonic acid- (3, in a soda-alkaline medium with the equivalent amount of 2-acetylamino-5-hydroxynaphthalenedisulfonic acidX4.8) , Conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysis of the acetyl and benzenesulfonyl groups, are dissolved in 2500 parts by volume of water at 20 "C at pH 6 to 6.5 and at this temperature with 0.1 mol of 4-methyl-2 methylsulfonyl-thiazole-5-carboxylic acid chloride is added, which is made into a paste with a wetting agent and a little water.

  During the condensation, a pH of 6 to 6.5 is maintained by adding sodium carbonate solution. When the reaction has ended, the dye is salted out and isolated. When dried, the dye is a dark powder that dissolves in water with a blue color.



  Dyeing instruction B
A cotton fabric is padded with an aqueous solution of 20 "C, which contains 20 g / l of the dye, 10 g / l of sodium m-nitrobenzenesulfonic acid, 15 g / l of sodium hydrogen carbonate and 150 g / l of urea, at 60 to 70" C. Intermediate drying, heated to 140 ° C. for 10 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue tones, water-fast.



  Example 3
46 parts of the monoazo dye obtained analogously to the information in Example 1 by coupling diazotized 2-aminonaphthalene-4,8-disulfonic acid onto 3-methylamino-toluene are dissolved in 400 parts of water at 20 ° C. at pH 7 to 8 and in the presence of excess sodium acetate or Calcium carbonate was partially mixed with a total of 26.4 parts of 4-isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and stirred at this temperature until a sample no longer changed in color on acidification.



  The resulting dye of the formula
EMI7.2
 is salted out, suction filtered, washed and dried.



  Dyeing instruction C
Cotton fabric is impregnated with an aqueous solution of 20 to 25 "C which contains 20 g of the above dye, 10 g of sodium m-nitrobenzenesulfonate, 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g per liter of liquor Then the fabric is squeezed between two rubber rollers to a moisture content of about 80/0 of the fabric weight. After intermediate drying at 60 to 70 "C, it is heated to 140" C for 1 to 3 minutes and the dyeing obtained in this way rinsed thoroughly with hot water and boiled for 20 minutes with a solution containing 5 g of Marseille soap and 2 g of soda per liter.

  After rinsing and drying, a strong reddish yellow coloration with good wet, rub and lightfastness is obtained.



   The table below lists the diazo components, coupling components and the reactive components which can be linked to the amino group and from which dyes can be synthesized analogously to the information in Examples 1 to 3, the color shades of which - obtained by one of the application processes described - are also shown in the table .

 

  Abbreviations for the reactive components: A = 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride B = 4-isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride In the case of diazo component, coupling component, reaction, color play tiv- tone no nent
4 2-Aminonaph- I-Amino-2-meth- A yellow thalin4,8-oxy-5-methyl disulfonic acid benzene
5 2-Aminonaph-I-Amino-2-meth-B Yellow thalin4,8-oxy-5-methyl disulfonic acid benzene
6 1-Aminonaph-I-Amino-3-A yellow thalin-3,6-methylbenzene disulfonic acid
7 I-Aminonaph- I-Amino-3-B yellow thalin-3,6-methylbenzene disulfonic acid
8 2-aminonaph- I-amino-3-A yellow thalin-5,7-methylbenzene disulfonic acid, diazo component, coupling component, reaction, color play tiv- tone no. <RTI

    ID = 8.1> component
9 2-aminonaph-1-amino-3-B yellow thalin-5,7-methylbenzene disulfonic acid 10 2-aminonaph-1-amino-3-A yellow thalin-6,8-methylbenzene disulfonic acid 11 2-aminonaph-I-amino -S B yellow thalin-6,8- methylbenzene disulfonic acid 12 4-aminoazol-amino-3-A brown benzene-3,4'-methylbenzene yellow disulfonic acid 13 I-aminobenzene-1-amino-3-B brown
4-sulfonic acid methylbenzene yellow
1-aminonaphthalene-6 sulfonic acid 14 2 <3'-sulfo4-1-Amino-3-A yellow aminophenyl) methylbenzene
6-methyl-benzothiazole-7-sulfonic acid 15 2-aminonaph-I-methylamino-3-B yellow thalin, 8-dimethoxybenzene sulfonic acid
16 2-Aminonaph-1-Amino-3-A yellow thalin4,8-di-acetylamino sulfonic acid benzene
17th

   2-aminonaph- aniline A yellow thalin4,8-disulfonic acid Example 18
51.6 parts of the dye of the formula obtained by diazotizing 1-hydroxy-2-amino benzene-sulfonic acid and coupling onto 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper-releasing agent
EMI8.1
 are dissolved in 1500 parts of water at pH 7. With thorough stirring, 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are introduced at 20 ° C. and the hydrochloric acid liberated is continuously blunted to a pH of 5 to 7 with soda solution.

  When free amino groups can no longer be detected, the reactive dye formed is of the formula
EMI8.2
 salted out, pressed out, washed and dried in vacuo at 30 to 40 ° C. Fabrics made of cellulose materials can be dyed or printed with this dye using one of the above-mentioned methods in ruby tones that are fast to wet, rub and lightfast.



   The following table lists the heavy metal complexes of other aminoazo dyes and the reactive components linked to the amino group, as well as the color tones of these dyes on cellulose materials. The aminoazo dyes, their metal complexes and their conversion with the reactive components can be prepared analogously to the information in Example 18.



  Abbreviations for the reactive components as in the table for example 3 for aminoazo dye com reac play of colors plexi- tive tone no
Heavy metal
19 1-Hydroxy-2-aminobenzene-Cu A ruby
4,6-disulfonic acid - 2 amino-5-hydroxynaphthalene-
7-sulfonic acid 20 1-hydroxy-2-aminobenzene-Cu A ruby
4-sulfonic acid - # 2 ethylamino-5-hydroxy naphthalene-7-sulfonic acid 21 1-amino-2-hydroxy-6-nitro- Cu A ruby naphthalene4-sulfonic acid -
2-amino-5-hydroxynaphthalene
7-sulfonic acid 22 1-amino-2-hydroxy-6-nitro- Cr A Green naphthalene4-sulfonic acid - pithy
2-Amino-5-hydroxynaphthalene gray
7-sulfonic acid 23 1-amino-2-hydroxy-6-nitro-Co B Rotsti naphthalene4-sulfonic acid - chig

     l-amino-8-hydroxynaphthalene black
4-sulfonic acid 24 1-amino-2-hydroxy-5-me-Cu A violet thylsulfonyl-benzene
1-amino-8-hydroxynaphthalene
3,6-disulfonic acid 25 1-amino-2-hydroxy-5-me- Co A greythylsulfonyl-benzene 1-amino-8-hydroxynaphthalene-
3,6-disulfonic acid 26 1-amino-2-hydroxy-5-me- Cr A green thylsulfonyl-benzene> tinged l-amino-8-hydroxynaphthalene- black
3,6-disulfonic acid 27 1-amino-2-methylbenzene- Cu B blue 4-sulfonic acid - l-amino-
2-hydroxy-5-methylbenzene b I-amino-8-hydroxynaphthalene-4,6-disulfonic acid 28 1-amino-2-methylbenzene-Co B gray
4-sulfonic acid l 1-amino
2-hydroxy-5-methylbenzene <I-amino-8-hydroxynaphthalene-4,6-disulfonic acid 29 1-amino-2-methylbenzene-Cr A green
4-sulfonic acid

     b l-amino-pricked
2-hydroxy-5-methylbenzene black 1-amino-8-hydroxynaphthalene4,6-disulfonic acid with- aminoazo dye com- reac- play of colors plex- tiv- tone no. Bound com
Heavy nent metal 30 (1-amino-2-chlorobenzene- Cu A Marine Li-sulfonic acid - l-hydroxy blue
2-acetylaminobenzene), saponified, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid 31 (1-amino-2-chlorobenzene-Co A gray 4-sulfonic acid - 1-hydroxy-
2-acetylaminobenzene),

   saponified, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid 32 1-amino-8-hydroxynaphthalene-Co A black
4-sulfonic acid - 1-hydroxy
2,6-diaminobenzene-4-sulfonic acid 1,3-dihydroxybenzene 33 1-amino-8-hydroxynaphthalene-3> A gray disulfonic acid - 1-hydroxy
2,6-diaminobenzene-4-sulfonic acid - 2-hydroxynaphthalene 34 1-amino-8-hydroxynaphthalene-Co A gray
4-sulfonic acid 1-hydroxy
2,6-diaminobenzene-4-sulfonic acid - 3-methylpyrazolone45) Example 35
96 parts (based on 10000 goods) of the copper phthalocyanine tetrasulfochloride freshly prepared in the usual way by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or the isomeric,

   Copper phthalocyanine tetrasulfochloride, built up from l-sulfobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid, is suspended in the form of the moist, well-washed suction cake in 500 parts of water and 500 parts of ice, the solution of 50 parts of sodium salt.



  zes of 1,3-diaminobenzene-sulfonic acid in 500 parts of water was added and the pH was adjusted to 8.5 with soda.



  The suspension is stirred for 24 hours at room temperature and the pH is always kept at 8.5 by continuously adding soda. The resulting condensation product is precipitated at pH 1 to 2 by adding sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral.



  A suspension of 72 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride in water is added to the blue solution using a wetting agent and the resulting hydrochloric acid is constantly blunted with soda solution to pH 5 to 7 and stirred at 20 ° C. for so long , until free amino groups can no longer be detected The reactive dye of the formula thus obtained
EMI9.1
 is salted out, washed and dried at 30 to 40 "C in a vacuum. It is a dark blue powder that is soluble in water with a blue color and dyes cotton and regenerated cellulose in clear blue tones with good wet, rub and rubbing properties using one of the above-mentioned dyeing or printing processes. and lightfastness.



   Instead of the 96 parts of copper phthalocyanine tetrasulfonyl chloride - with otherwise the same procedure as in Example 35 - 87 parts (based on 1000! Of the above goods) of the copper or nickel phthalocyanine trisulfonyl chloride obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine in the form of the moist can be used suction cake washed with ice water can be used; reactive dyes which also have a clear blue color are then obtained.



   Even if you work as indicated in Example 35, but start from 87 parts of copper phthalocyanine trisulfochloride and instead of 50 parts of the sodium salt of 1,3-diaminobenzene-sulfonic acid 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2,2 '-disulphonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulphonic acid is used to obtain reactive dyes which dye cellulose materials in wet, rubbing and lightfast, clear blue shades by one of the above processes.



   If you start from 4 ', 4 "W \ 4" "- tetraphenyl-Cu-phthalocyanine, sulfochlorination and reaction with 1,3-phenylenediamine-4-sulfonic acid and acylation with 4-methyl-2-methylsulfonylthiazole-5-carboxylic acid chloride are obtained a reactive dye that dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.



  Example 36
71 parts of the aminoanthraquinone dye obtained by reacting 1-amino-4-bromoanthraquinone-2-sulphonic acid with excess 4,4'-diamino diphenyl-2,2'-disulphonic acid are dissolved in 700 parts of water at 20 ° C. with thorough stirring Part 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and by continuously adding soda solution maintains a pH of 6 to 7. If no amino group can be detected, the resulting dye is of the formula
EMI9.2
 salted out, filtered off with suction, washed and dried at 30 to 40 ° C. in vacuo. It dyes cotton and regenerated cellulose using one of the processes listed above in wet, rub and lightfast blue tones.

 

   If the procedure given in Example 36 is followed, but instead of 71 parts of the starting dye used there, equivalent amounts of one of the following derivatives of l-amino-4-xaminoarylaminopanthraquinone-2-sulfonic acid are used, similar dyestuffs are obtained with blue colorations similar to those of the dyestuff obtained above exhibit:

  : I-Amino4- (4'amino-2'-sulfophenylaminoSanthraquinone-2-sulfonic acid, 1-Amino4- (4-aminophenylaminoVanthraquinone-2,6-disulfonic acid, mixture of isomers of 1-Amino444-aminophenylamino) -anthraquinone-2 , 5- and 2,8-disulfonic acid, isomer mixture of l-amino444'-amino-2'-sulfophenylaminotanthraquinone-2,5- and 2,8-disulfonic acid, isomer mixture of l-amino443'-aminophenylaminoSanthraquinone-2, 5- and -2,8-disulfonic acid, 1-amino443'-aminophenylaminoVanthraquinone-2,6-disulfonic acid,

   1-Amino4 <3'-amino-4'-sulfophenylaminotanthraquinone-2-sulfonic acid. With 1-amino-444 '{4 "- amino-2" -sulfophenyl} aminophenyl) -anthraquinone-2,6-disulfonic acid, reactive dyes with a bluish gray color are obtained.



  Example 37
If you proceed as indicated in Example 18, but instead of that. there used copper-containing aminomonoazo dye of the equivalent amount of the chromium complex of the l-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid obtained by coupling with 13 '(3 "-aminophenyl) isulfonylimido-sulfonyl-phenyl-3 -methylpyrazolone <5) aminoazo dye obtained from, a reactive dye is obtained which dyes cellulose materials in good wet, rub and lightfast yellow-brown shades by one of the processes given above.



   Example 38
0.1 mole of the copper complex compound of the formula
EMI10.1
 are dissolved in 3000 parts by volume of water at pH 6 and combined with 24 parts by weight (0.1 mol) of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride with stirring at a temperature of about 50 ° C. The mixture is stirred until the condensation is complete, the dye is deposited and isolated by adding a little sodium chloride. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained which dissolves in water with a green color and cotton after the in the Examples 1 to 3 indicated procedures in green tones.



  Dyeing instruction D
Cotton fabric is impregnated with a solution of 20 to 25 ° C. which contains 25 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate per liter of liquor the fabric is squeezed between two rubber rollers to a moisture content of about 100/0. After intermediate drying at 50 to 60 "C, it is heated to 140" C for 10 minutes and the resulting dye is rinsed thoroughly with hot water and boiled with a solution for 20 minutes which contains 5 g of Marseille soap and 2 g of soda per liter After rinsing and drying, a green dyeing of good wet, rub and lightfastness is obtained.



   Even after one of the dyeing or printing processes A to C, clear green tones with good fastness properties are obtained on cellulose materials.



  Example 39
0.1 mole of the paste of the aminoazo compound of the formula
EMI10.2
 which is obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene-4,8 disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex are dissolved in 2000 parts by volume of water at pH 6.5 and combined with 24 parts by weight of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride. The reaction mixture is stirred at 20 ° C. until the condensation has ended, the pH of the reaction solution being kept at 6 to 7 by adding soda.

  After the reaction has ended, the dye is salted out, isolated and dried in vacuo
The dried dye is a dark powder that dissolves in water with a violet color and colors cotton in the presence of alkali in bluish violet tones.



  Example 40
The aqueous solution of 0.1 mole of the copper complex of the formula
EMI10.3
 manufactured according to the information in German patent specification 1,061,460 or 1,085,988, is combined in a conventional manner with a solution of 23.6 parts by weight of trichloropyrimidino-pyrimidine in acetone. The pH is maintained at 6 to 7 by adding soda and the dye is isolated by salting out after the reaction has ended. When dried, it is a dark powder that dissolves in water with a purple color. Cotton fabric is dyed in lightfast and wetfast purple tones.



  Example 41
56.8 parts of the diaminoazo dye obtained by coupling diazotized 1-amino-3-acetylaminobenzene-6-sulfonic acid to 2-aminonaphthalene-5,7-disulfonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are 450 parts at pH 7 Dissolved in water. After adding 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, the mixture is stirred for about one hour at 50 ° C. with soda solution to pH 4 to 6, while constantly blunting the released hydrochloric acid.



  When the acylation has ended, the reactive dye formed is of the formula
EMI10.4
 salted out, filtered off, redissolved in 4000 parts of water at 30 ° C., filtered and separated out in completely pure form from the filtrate by adding 400 parts of common salt.



  The dye is dried in a vacuum as usual at 35 ° C. It dyes cellulose materials in true yellowish orange tones by one of the processes mentioned above.



  Example 42
24 parts of 4-methyl-2-methylsulfonyl-thiazole are added to a neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8trisulfonic acid with 3-acetylamino-aniline in an acetic acid medium in 500 parts of water -5-carboxylic acid chloride and stirred for one hour at 45 ° C., a pH of about 6 being maintained by the constant addition of sodium hydroxide solution. The partially precipitated acylation product is completely separated off at pH 6.5 by adding 100 parts of sodium chloride For purification, the reactive dye thus obtained can be dissolved again in 2500 parts of water at 30 ° C., clarified and separated out again by salting out the filtrate with 350 parts of common salt.



  The dye has the formula
EMI11.1
 After filtering off, drying at 35 "C and grinding, it is a yellow powder that easily dissolves in water with a yellow color and dyes cellulose fibers in very real reddish-yellow tones using one of the above-mentioned dyeing processes in the presence of acid-binding agents. Also on wool and Real yellow dyeings are obtained from polyamide fibers.



   Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4-amino-2'-acetylamino-phenyl {l '> azo-naphthaleneX2> 3,6,8-trisulphonic acid sodium corresponding amounts of the in column 2 indicated amino compounds and the coupling components indicated in column 3 in the usual manner by diazotization and coupling in an acetic acid medium used aminoazo dyes and acylated with 4-methyl-2-methylsulfonylthiazole-5-carboxylic acid chloride.



  Example Diazo component Coupling component shade play on No. Cotton 43 2-aminonaphthalene-1-amino-3-methyl-6-strong
1,5-disulfonic acid methoxybenzene reddish
Yellow 44 2-aminonaphthalene-1-amino-3-methyl yellow
1,5-disulfonic acid benzene 45 2-aminonaphthalene-1-aminonaphthalene-rotsti
1,5-disulfonic acid 6-sulfonic acid chiges
Yellow 46 2-aminonaphthalene-1-amino-3-acetyl-rotsti
1,5-disulfonic acid aminobenzol chiges
Yellow 47 2-aminonaphthalene-3-aminophenyl rotsti
1,5-disulfonic acid urea chiges
Yellow 48 2-aminonaphthalene-1-amino-3-hydroxy rotsti
1,5-disulfonic acid acetyl-aminobenzol chiges
Yellow 49 2-aminonaphthalene-1-amino-3-methyl-strong
5,7-disulfonic acid 6-methoxybenzene rotsti chiges
Yellow 50 2-aminonaphthalene-1-aminonaphthalene rotsti
5,7-disulfonic acid 7-sulfonic acid

   chiges
Yellow 51 2-aminonaphthalene-1-amino-3-acetyl-rotsti
5,7-disulfonic acid aminobenzol chiges
Yellow 52 2-aminonaphthalene-3-aminophenyl rotsti
5,7-disulfonic acid urea chiges
Yellow example diazo component coupling component color match on No. cotton
53 2-aminonaphthalene-I-amino-3-hydroxy rotsti
5,7-disulfonic acid acetylaminobenzol chiges
yellow
54 I-Aminonàphthalin-1-Amino-3-methyl-6 Stark
3,7disulfonic acid methoxybenzene reddish
yellow
55 I-aminonaphthalene-I-amino-3-methyl-rotsti
3,7-disulfonic acid benzene chiges
yellow
56 I-aminonaphthalene- I-aminonaphthalene rotsti
3,7disulfonic acid 6-sulfonic acid chiges
yellow
57 2-aminonaphthalene-I-amino-3-methyl-rotsti
3,6-disulfonic acid benzene chiges
yellow
58 2-Aminonaphthalene-I-Amino-3-methyl-6-Strong
3,6-disulfonic acid methoxybenzene reddish
yellow
59

   2-aminonaphthalene-I-amino-3-acetyl-rotsti
3,6-disulfonic acid aminobenzol chiges
yellow
60 2-aminonaphthalene-3-aminophenyl rotsti
3,6-disulfonic acid urea chiges
yellow
61 2-aminonaphthalene-I-amino-3-hydroxy rotsti
3,6-disulfonic acid acetylaminobenzol chiges
yellow
62 2-aminonaphthalene-I-aminonaphthalene rotsti 3,6-disulfonic acid 6-sulfonic acid chiges
yellow
63 2-A minonaphthalene-I-amino-3-acetyl-rotsti
6,8-disulfonic acid aminobenzol chiges
yellow
64 2-aminonaphthalene-1-amino-2-methoxy-Stark
6,8-disulfonic acid naphthalene-6-sulfon-rotsti acidic
yellow
65 2-aminonaphthalene-I-aminonaphthalene rotsti
6,8-disulfonic acid 6-sulfonic acid chiges
yellow
66 2-aminonaphthalene-1-aminonaphthalene yellow
4,8-disulfonic acid 6-sulfonic acid
67 2-aminonaphthalene-I-aminonaphthalene yellow 4,8-disulfonic acid 7-sulfonic acid
68

   2-aminonaphthalene-1-amino-2-methoxy-strong
4,8-disulfonic acid naphthalene-6-sulfon- rotsti Bei- Diazo component Coupling component Color shade play on no. Cotton acid-like
yellow
69 2-aminonaphthalene-1-methylamino-3-yellow
4,8-disulfonic acid methylbenzene
70 2-aminonaphthalene-1-ethylamino-3-yellow
4,8-disulfonic acid methylbenzene
71 2-Aminonaphthalene-N-Methylaniline Yellow
4,8-disulfonic acid
72 2-Aminonaphthalene-N-Ethylaniline Yellow
4,8-disulfonic acid
73 2-aminonaphthalene- N- (p-hydroxyethyl) - yellow
4,8-disulfonic acid aniline
74 2-aminonaphthalene-N-butylaniline yellow
4,8-disulfonic acid
75 2-aminonaphthalene aniline rotsti
3,6,8-trisulfonic acid yellow
76 2-aminonaphthalene-I-amino-3 methyl rotsti
3,6,8-trisulfon-benzene acid yellow
77 2-aminonaphthalene- 3-aminophenyl-

   rotsti
3,6,8-trisulfonic urea acidic yellow
78 2-aminonaphthalene-1-amino-3-hydroxy rotsti
3,6,8-trisulfonacetylaminobenzene acidic yellow
79 2-aminonaphthalene-1-amino-3-acetyl yellow yellow
3,6,8-trisulfonic-amino-6-methoxy-chiges acid benzene orange
80 2-aminonaphthalene-1-amino-3-acetyl-rotsti
3,6,8-trisulfon-amino-6-methyl-acid benzene yellow
81 2-aminonaphthalene-1-amino-3-methanotesti
3,6,8-trisulfonsulfonylaminobenzene acidic yellow
82 2-aminonaphthalene-2,5-dimethoxyaniline yellowish
3,6,8-trisulfonic acid orange
83 2-aminonaphthalene-3-methyl-6-methoxy yellow yellow
3,6,8-trisulfon-aniline acidic orange
84 2-aminonaphthalene-N-methylaniline rotsti
3,6,8-trisulfonic acid yellow
85 2-aminonaphthalene-N-ethylaniline rotsti
3,6,8-trisulfonic acid yellow
86 2-aminonaphthalene-N-butylaniline

   rotsti
3,6,8-trisulfonic acid yellow
87 2-Aminonaphthalin- NA-HydroxyäthylS rotsti
3,6,8-trisulfonaniline acidic yellow
88 2-aminonaphthalene- 3- (N-ethylaminor rotsti
3,6,8-trisulfon-toluene acidic yellow
89 2-aminonaphthalene-2-aminotoluene rotsti
3,6,8-trisulfonic acid yellow
90 2-aminonaphthalene-1-amino-2,5-di-Stark
3,6,8-trisulfonmethylbenzene rotsti acidic
Yellow example diazo component coupling component color match on No.

  Tree wool
91 2-Aminonaphthalene-1-Amino-2-meth Stark
3,6,8-trisulfonoxybenzene rotsti acid chiges
yellow
92 2-aminonaphthalene-1-amino-3-meth- rotsti
3,6,8-trisulfonoxybenzene acidic yellow
93 2-aminonaphthalene-1-ethylamino-3-rotsti
3,6,8-trisulfon-methoxybenzene acidic yellow
94 2-aminonaphthalene-1-aminonaphthalene rotsti
3,6,8-trisulphone-6-sulphonic acid yellow
95 2-aminonaphthalene-1-aminonaphthalene rotsti
3,6,8-trisulphone-7-sulphonic acid yellow
96 2-aminonaphthalene-1-amino-3-methyl-rotsti
4,6,8-trisulfon-benzene acid yellow
97 2-aminonaphthalene-1-amino-3-acetyl-rotsti
4,6,8-trisulfonaminobenzene acidic yellow
98 1-Aminonaphthalene- 1-Amino-3-methyl- yellow
2,4,7-trisulfonic benzene acid
99

   1-aminonaphthalene-1-aminonaphthalene yellow
2,4,7-trisulfonic-6-sulfonic acid
100 4-Nitro4'-amino-1-amino-3-acetyl-rotsti stilbene-2,2'-aminobenzene chiges disulfonic acid yellow
101 4-Nitro-4'-amino-3-aminophenyl rotsti stilbene-2,2'-urea-like disulfonic acid yellow
102 4-Nitro4-amino-1-amino-3-hydroxy-rotsti stilbene-2,2'-acetylaminobenzene chiges disulfonic acid yellow
103 4-Nitro-4-amino-N-methylaniline reddish stilbene-2,2'-disulfonic acid yellow 104 4-Nitro-4'-amino-N-ethylaniline reddish stilbene-2,2'-disulfonic acid yellow 105 4-Nitro-4'-amino-N-butylanilaniline rotsti stilbene-2,2'disul- chiges phonic acid yellow
106 4-Nitro4-amino-N- (ss-HydroxyäthylS rotsti stilbene-2,2'-disulaniline chiges fonsäure Yellow 107

   4-Nitro-4'-amino- 1- (N-ethylamino) - rotsti stilbene-2,2'-disul- 3-methylbenzene acidic yellow
108 aniline-2,5-disul- I-aminonaphthalene rotsti fonsäure 6-sulfonic acid chiges
yellow
109 Aniline-2,5-disul- 1-aminonaphthalene rotsti fonsäure 7-sulfonic acid chiges
Yellow 110 aniline-2,5-disul- 1-amino-3-methyl-rotsti fonsäure benzol chiges
Yellow 111 aniline-2,5-disul- 1-amino-3-acetyl-rotsti fonsäure aminobenzol chiges
Yellow example diazo component coupling component color match on No.

  Baumwolle 112 aniline-2,5-disul- 1-amino-2-methoxy-rotsti fonsäure methylbenzol chiges
Yellow 113 aniline-2,5-disul- 1-amino-2,5-dimeth-rotsti fonsäure oxybenzol chiges
Yellow 114 aniline-2,4-disul- 1-amino-2-methoxy-rotsti fonsäure 5-methylbenzene chiges
Yellow example 115
65 parts of the dye of the formula
EMI13.1
 (produced by coupling diazotized 1-hydroxy-2-aminobenzene-4,6-disulfonic acid to 2-amino-8-hydroxynaphthalene-6sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water until neutral.

  24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are added and the mixture is stirred at 20 ° C. while constantly blunting the liberated hydrochloric acid with soda solution to pH 5 to 6 until no free amino group can be detected any longer. The reactive dye formed the formula
EMI13.2
 is salted out, filtered off, washed and dried at 30 to 40 ° C. It dyes cellulose materials in very real ruby tones according to one of the processes specified above.



   Dyes with similar properties are obtained analogously to the procedure outlined above from the copper complexes of the azo dyes produced from the diazo and azo components listed in the table below: Example diazo component coupling component color shade play on No. Cotton 116 1 -hydroxy-2-amino- 2- Methylamino-5-ruby benzene4-sulfonic acid hydroxynaphthalene
7-sulfonic acid 117 1-hydroxy-2-amino-2-ethyl-amino-5-ruby benzene-4-sulfonic acid hydroxynaphthalene
7-sulfonic acid 118 1-hydroxy-2-amino-24ss-hydroxyethyl ruby benzene 4-sulfonic acid aminot5-hydroxynaphthalene-7 sulfonic acid 119 1-hydroxy-2-amino-2-amino-8-hydroxy-ruby benzene 4-sulfonic acid naphthalene -3,6 disulfonic acid 120 1-hydroxy-2-amino-2-amino-5-hydroxy-ruby

   benzene-4,6-disulfon- naphthalene-1,7- acid disulfonic acid 121 1 -hydroxy-2-amino- 2-amino-8-hydroxy- ruby benzene4,6-disulfon- naphthalene-3,6 acid disulfonic acid 122 1 -hydroxy- 2-amino-2-methylamino-5-ruby benzene4,6-disulfonic hydroxynaphthalic acid 7-sulfonic acid 123 1-Hydroxy-2-amino-2-ethylamino-5 ruby benzene4,6-disulfonic-hydroxynaphthalic acid 7-sulfonic acid 124 1 -Hydroxy-2-amino- 24ss-hydroxyethyl- ruby benzene4,6-disulfon- aminop5-hydroxy- acid naphthalene-7 sulfonic acid example- diazo component coupling component shade match on no.

  Cotton 125 1 -hydroxy-2-amino- 1-amino-8-hydroxy- violet benzene-4,6-disulfonic naphthalene-3,6 acid disulfonic acid 126 1 -hydroxy-2-amino- 1 -amino-8-hydroxy- Violet benzene-4,6-disulphon-naphthalene, 6-acid disulphonic acid 127 1-hydroxy-2-amino-1-amino-8-hydroxy-violet benzene-5-sulphonic acid naphthalene-3,6 disulphonic acid 128 1-hydroxy-2-amino - 1 -amino-8-hydroxy violet benzene-5sulphonic acid naphthalene4,6-disulphonic acid 129 1 -hydroxy-2-amino-1-amino-8-hydroxy blueust.



   4-acetylaminobenzene-naphthalene-3,6-violet
6-sulfonic acid disulfonic acid 130 1 -hydroxy-2-amino 1 -ethoxy-8-hydroxy bluust.



   4-acetylaminobenzene-naphthalene-3,6-violet
6-sulfonic acid disulfonic acid (4-position acetylamino group then saponified) 131 1 -hydroxy-2-amino-1-amino-8-hydroxy blue
4-acetylaminobenzene-naphthalene-3,6
6-sulfonic acid disulfonic acid 132 1-hydroxy-2-amino-1-amino-8-hydroxy blue
4-acetylaminobenzene-naphthalene-2,4,6-
6-sulfonic acid trisulfonic acid 133 1-hydroxy. 2-amino-1-amino-8-hydroxy blue
6-acetylaminobenzene naphthalene
4-sulfonic acid 2,4-disulfonic acid (6-position acetylamino group saponified) 134 1-amino-2-hydroxy-1-amino-8-hydroxy blue
6-nitronaphthalene naphthalene
4-sulfonic acid 2,4-disulfonic acid (6-position nitro group then reduced to -NH2) 135 <RTI

    ID = 13.37> 1-amino-2-hydroxy-1-amino-8-hydroxy blue
6-nitronaphthalene naphthalene
4-sulfonic acid 2,4,6-trisulfonic acid (6-position nitro group subsequently reduced to -NH2) with diazo component, coupling component, color shade play on No. Cotton 136 1-hydroxy-2-amino-1-amino-8-hydroxy blue
6-acetylaminobenzene naphthalene
4-sulfonic acid 2,4,6-trisulfonic acid (6-position acetylamino group saponified) Example 137
The solution of 19.5 parts of the sodium salt of l-aminobenzene-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is allowed to run into a mixture of 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid; then the mixture is stirred for half an hour at 0 to 10 ° C., and then excess nitrous acid is removed.

  The solution of 26.2 parts of the potassium salt of 1-aminonaphthalene-8-sulfonic acid in 250 parts of hot water, which has cooled and thereby partially crystallized out again, is added to the diazo suspension thus obtained at 0 to 10 ° C. and the strongly acidic coupling mixture is blunted at 10 to 20 "C by carefully adding sodium hydroxide solution to pH 4. The coupling is completed quickly; the aminoazo dye formed is completely salted out with 100 parts of sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 10 ° C. and pH 6 to 7.

  24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are added to the aqueous solution and the mixture is stirred for one hour at 10 ° C. with soda solution to pH 5 while the hydrochloric acid released is continuously blunted. When no more aminoazo dye can be detected, is the partially precipitated reactive dye of the formula
EMI14.1
 Salted out with 40 parts of sodium chloride, filtered off and dissolved again in 800 parts of warm water for cleaning. After the solution has been clarified, the pure dye is separated out from the filtrate by adding 80 to 100 parts of common salt.



  After filtering off, drying at 35 ° C. and grinding, a yellow powder is obtained which easily dissolves in water with a yellow color and dyes the cellulose fibers in very good wet, light and chlorinefast yellow shades using one of the above dyeing processes in the presence of acid-binding agents .



  True yellow colorations are also obtained on wool and polyamide fibers.



   If one proceeds as indicated above, but instead of the 19.5 parts of the sodium salt of l-aminobenzene-sulfonic acid, equivalent amounts of the diazo components listed in the table below are coupled to the 1-amino-naphthalene-8-sulfonic acid, acylation with 4-methyl gives -2-methylsulfonyl-thiazole-5-carboxylic acid chloride are also valuable yellow to brown reactive dyes.



  Diazo component shade on
Cellulose fiber l-aminobenzene-2,5-disulfonic acid Reddish yellow 2-Amino-naphthalene4,8-disulfonic acid Very reddish
Yellow 2-amino-naphthalene-5,7-disulfonic acid Strongly red tinged
Yellow 2-amino-naphthalene-6,8-disulfonic acid strong red tinged
Yellow 2-amino-naphthalene-3,6,8-trisulfonic acid Strongly red tinged
Yellow 2-Amino-naphthalene-4,6,8-trisulfonic acid Yellowish brown 4-Amino-2-acetylamino-azobenzene-Orange2 ', 5'-disulfonic acid brown Diazo component color
Cellulose loose fiber
EMI14.2
 Reddish brown (I-aminobenzene-2,5-disulfonic acid acidic to l-amino-naphthalene-6-sulfonic acid coupled)
EMI14.3
 Reddish brown (I-aminobenzene-2,5-disulfonic acid acidic to the technical mixture of 1-aminonaphthalene-6- and -7-sulfonic acid coupled)
EMI14.4

   
 Violet brown (1-amino-naphthalene-2,5,7-trisulfonic acid acidic to l-amino-naphthalene-6-sulfonic acid coupled)
EMI14.5
 Reddish brown (1-amino-naphthalene-2,5,7-trisulfonic acid, acidic on l-amino-2-methoxy-5-methylbenzene, coupled) Example 138
A mixture of the solutions of 65.5 parts each of the chromium 2: I complex ice and the cobalt 2 l complex of the dye of the formula
EMI15.1
 in 400 parts of water each is stirred with 48 parts of finely powdered 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride for about 2 hours at 20 C while maintaining pH 4.5 to 5.5.

  If the aminoazo dye (Co complex: blue; Cr complex: blue-green) can no longer be detected by chromatography, the resulting mixture of the two reactive dyes is salted out with potassium chloride, filtered off and dried.



   The dye produces strong, very good wet and lightfast black tones on cellulose materials by the pad dyeing process or in printing in the presence of acid-binding agents.



   If one proceeds accordingly, but the mixture of the chromium-2: 1 and cobalt-2: 1 complex of the following aminoazo dyes is used, valuable black dyes are also obtained: Diazo component, coupling component, coupling pH 1-hydroxy-2-amino4-1 -hydroxy- 8-amino-9 nitrobenzene naphthalene
3,6-disulfonic acid 1-hydroxy-2-amino4-1-hydroxy-8-amino-9 nitronaphthalene-7-naphthalenesulfonic acid 3,6-sulfonic acid Example 139
To the neutral solution of 53.15 parts of the disodium salt is added by coupling diazotized l-amino4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5'-sulfophenyl) -3-methylpyrazoloneX5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye

   in 300 parts of water 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and the mixture is stirred for one hour at 25 ° C., the hydrochloric acid liberated being continuously brought to a pH of 4 to 4 with soda solution 6. The deposited dye of the formula
EMI15.2
 is filtered off, dissolved in 3000 parts of warm water at pH 6 to 7 and reprecipitated from the filtered solution by adding sodium chloride. After filtering off, drying and powdering, a yellow, readily water-soluble powder is obtained, which colors cellulose materials from a long liquor at 85 ° C. or with soda (in the cold padding process) as an acid-binding agent in clear, washable, rub-fast and lightfast yellow tones .



   If the above procedure is followed, but instead of the aminoazo dye used there, equivalent amounts of the aminoazo dyes made up of the components listed in the table below are used, valuable new reactive dyes are likewise obtained.



   In the table, the expression saponified means that an acylamino group contained in the aminoazo dye has been subsequently saponified, while the expression reduced means that a nitro group contained in the diazo component is reduced to the amino group after coupling, with the desired aminoazo dye being formed.



  Example Diazo component Azo component pH of the color match Kupp- auf Nr. Lun s- Cel medululose ums 140 1-Amino4-nitro- 144'-sulfophe- 5-6 yellow benzene-2-sulfon-nylS3-methyl-acid pyrazolone- ( 5) (4-position nitro group subsequently reduced) 141 1-Amino4-nitro- 1 {4'-sulfophe- 5-6 Rotsti benzene-2-sulfon- nylS3-carboxy acid pyrazolone- (5) yellow by-diazo component azo component H of the color upp-auf Nr. l-Cel medululose ums 142 1-Amino-4-nitro- 13'-sulfophe- 6-7 yellow benzene-2-sulfon- nylS3-methyl-acid 5-aminopyrazole 143 1-amino-3 -ace- 1 <3-sulfophe-

   6-7 yellow tylamino-benzene-nylS3-methyl-
6-sulfonic acid 5-aminopyrazole (3-position acetylamino group then saponified) 144 1-Amino-3-ace- I {ss-hydroxy- 5-6 yellow tylamino-benzene- ethylS3-methyl-
6-sulfonic acid pyrazolone <5) 145 2 mol l-amino-3- 1 mol bis-pyr- 5-6 yellow acetyl-amino-azolone from 4.4:

  : benzene-6-sulfone-bis-hydrazino acid (saponified) dibenzyl-2,2'-disulfonic acid and
Acetoacetic ethyl ester 146 1 mol of 1-amino-3- 1- (4'-sulfophe- 5-6 yellow acetyl-amino-nyl) -3-carboxy-benzene-6-sulfone-pyrazolone <5) acid (saponified) 147 1 Amino-5-acetyl- 1 <4'-sulfophe- 5-6 Rotsti amino-naphthanylS3-carboxy- chiges lin-3,7disulfon- pyrazolon <5) yellow acid (saponified) 148 1-amino-2-methyl- 2-Acetylamino- 7-8 orange benzene4,6-di- 5-naphthol-7 case- diazo component azo component pH desFarnish play Kupp- on r. l- Cel medululose ums sulfonic acid sulfonic acid (saponified) 149 1-amino-2-methyl- 2-acetylamino- 7-8 red benzene4,6-di- 8-naphthol-6 sulfonic acid sulfonic acid (saponified) 150 1-amino- 2-methyl- 1-chloro-2-ace-

   7-8 Orange benzene-4,6-di- tylamino-5 sulfonic acid naphthol-7-sulfonic acid (saponified) 151 I-aminobenzene-1-acetylamino-7-8 red
2-sulfonic acid 8-hydroxy-naphthalene-4,6-disulfonic acid (saponified) 152 2-aminonaphtha- 1 -acetylamino-7-8 bluesti lin-3,6-disulfonic-8-hydroxy-naphthous acid thalin4,6 -di-red sulfonic acid (saponified) 153 2-aminonaphtha- 1 -acetylamino- 7-8 Blausti lin-3'7-disulfonic- 8-hydroxy-naphthous acid thalin4,6-di- red sulfonic acid (saponified) 154 2 -Aminonaphtha- 1-Acetylamino- 7-8 Blausti lin4,8-disulfonic- 8-hydroxy-naphthous acid thalin4,6-di- Red sulfonic acid (saponified) 155 2-Aminonaphtha- 1-Acetylamino- 7-8 Blausti lin -3,6-disulfone-8-hydroxynaph- chiges

   acid thalin-3,6-disulphonic acid (saponified) 156 2-aminonaphtha- I-acetylamino- 7-8 bluesti lin4,8-disulphone- 8-hydroxynaph- chiges acid thalin-3,6-di- red sulphonic acid ( saponified) 157 1-Amino4-meth- 2 (N-Acetyl-N- 7-8 Yellow stoxybenzene-2-methylamino) -chiges sulfonic acid 5-hydroxy-naph- red thalin-7-sulfonic acid (saponified) 158 1-Amino4 -meth- 2 (N-acetyl-N- 7-8 red oxybenzene-2- methylamino) sulfonic acid 8-hydroxy-naphthalin-6-sulfonic acid (saponified) 159 1-aminobenzene-2- 2- (N-acetyl- N- 7-8 red sulfonic acid methylamino) 8-hydroxy-naphthalin-6-sulfonic acid (saponified) with- diazo component azo component pH of the color match coupling on no.

   l- cel medululose ums 160 1 -aminobenzene-3- 2- (N-acetyl-N- 7-8 red sulfonic acid methylamino)
8-hydroxy-naphthalene-6-sulfonic acid (saponified) 161 1-aminobenzene-4- 2 (N-acetyl-N- 7-8 red sulfonic acid methylamino)
8-hydroxy-naphthalene-6-sulfonic acid (saponified) 162 1-Amino4-me- 2- (N-acetyl-N- 7-8 red ethylbenzene-2- methylamino) sulfonic acid 8-hydroxy-naphthalene-6- sulfonic acid (saponified) 163> r1-amino-2,4-di- 2 (N-acetyl-N- 7-8 red methylbenzene-methylamino)
6-sulfonic acid 8-hydroxynaphthalene-6-sulfonic acid (saponified) 164 1-amino-2,4-di- 2-acetylamino- 7-8 red methylbenzene- 8-hydroxynaph-
6-sulfonic acid thalin-6-sulfonic acid (saponified) 165 1-amino-2,4-di- 2-acetylamino-7-8

   Red methylbenzene- 8-hydroxynaph-
6-sulfonic acid thalin-3,6-disulfonic acid (saponified) 166 4-Aminoazoben- I-Amino-3-ace- 5-6 yellow zol-3,4'-disultylaminobenzene brown fonsäure 167 4-Aminoazoben- I- Amino-3-hydr- 5-6 yellow zol-3,4'-disul- oxyacetylamino- brown fonsäure benzene 168 4-aminoazoben- 1-amino-naphtha- 5-6 yellow zol-3,4'-disul- lin- 6-sulfonic acid brown fonsäure 169 4-Aminoazoben- 1-Amino-naphtha- 5-6 yellow zol-3'4'-disul- lin-7-sulfonic acid brown fonsäure 170 4-Aminoazoben- 1-Amino-2- (4 ' - 8 Black zol-3,4'-disulamino-2'-sulfonic acid phenyl {l'S azo-8-hydroxynaphthalene-3,6 disulfonic acid Example 171
52.4 parts of the disodium salt of 44 "-Aminophenyli amino>

   2 "-nitro-diphenylamine-3,4'-disulfonic acid are dissolved in 1000 parts of water and stirred at 20" C. for one hour with 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride. The hydrochloric acid released is continually blunted with soda to a pH value of 4 to 6.



  The reactive nitro dye formed of the formula
EMI16.1
  is salted out, filtered off, washed and dried. It dyes cellulose fibers from a long liquor or using one of the usual padding processes in the presence of soda as an acid-binding agent in deep purple-brown tones that are fast to wet and rub-resistant.



  Example 172
The neutral solution of 54.7 parts of the disodium salt of 1-amino-4 <2'-methyl-3'-aminophenylYamino-anthraquinone-2, S-disulfonic acid in 1000 parts of water is with 24.0 parts of 4-methyl -2-methylsulfonyl-thiazole-5-carboxylic acid chloride is stirred for one hour at 20 ° C. The hydrochloric acid released is continuously blunted with soda solution to a pH of 6.5 to 7. After the reaction has ended, the resulting reactive dye of the formula
EMI17.1
 salted out, filtered off, washed and dried at 30 to 40 ° C. It dyes cellulose materials in very good wet, rubbing and lightfast clear blue tones.



   Blue dyes of similar properties are obtained if one proceeds as above, but instead of the water-soluble aminoanthraquinone derivative mentioned there, equivalent amounts of the aminoanthraquinone-sulfonic acid derivatives listed below are acylated with 4-methyl-2-methylsulfonylthiazole-5-carboxylic acid chloride: When water-soluble amino- anthraquinone derivative game no.



  173 1-Amino4 {3'-aminophenylFamino-anthraquinone-
2,5-disulfonic acid 174 1-amino442'-chloro-3'-aminophenylpamino-anthraquinone-2,5'-disulfonic acid 175 1-Amino4 {2'-methyl-3'-methylaminophenylpamino-anthraquinone-2,5'-disulfonic acid 176 1 -Amino4 {4'-aminophenylFamino-anthraquinone- 2,6,3¯trisulfonic acid 177 1 -Amino443'-aminophenylpamino-anthraquinone-
2,6,4'-trisulfonic acid 178 1-amino44'-aminophenylamino-anthraquinone-2,5,3'-trisulfonic acid 179 1-amino4 {3'-aminophenylpamino-anthraquinone-2,5,4-trisulfonic acid 180 mixture of l-amino4 {3 '-aminophenylpamino-

       anthraquinone-2,4,5- and 2,4 ', 8-trisulfonic acid, furthermore the derivatives post-sulfated with 5% oleum at 20 to 30 C: 181 1-Amino4 {4 {4'-aminobenzylSphenyl} amino-anthraquinone-2- sulfonic acid 182 1-amino4 {4'-methylaminophenylpamino-anthraquinone-2-sulfonic acid 183 1-amino4 {3'-methylaminophenylfamino-anthraquinone-2-sulfonic acid 184 1-amino42'-methylaminophenyl> amino-anthraquinone-2-sulfonic acid 185 1-amino4 {7'-amino-naphthyl {21pamino-anthraquinone-2-sulfonic acid 186 condensation product of 1 mol of cyanuric chloride with 1 mol of 1,4-diamino-anthraquinone-2-sulfonic acid, 1 mol of aniline-2,5-disulfonic acid and 1 mol of ethylenediamine ( half-sided),

   gives after acylation with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride a violet reactive dye.



  Example 187
A solution of 107 g of a mixture of equal molar proportions of copper phthalocyanine trisulfonic acid {3.3 ', 3 "S mono (m-amino-p-sulfophenyl) amide and copper phthalocyanine trisulfonic acid (3.3', 3") di- (m-amino -p-sulfophenyl) amide is adjusted to 1.3 liters and pH 6; 37.1 g of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are introduced at 10 ° C. The temperature is increased by 5 ° C. per hour with stirring and then left at 20 to 25 ° C. for several hours. At the same time, a pH of about 6.1 to 6.9 is maintained by adding 3N NaOH. until, on average, every dye molecule is provided with at least one 4-methyl-2-methylsulfonyl-thiazole-5-carbonamido radical, which can easily be determined on the one hand by the consumption of sodium hydroxide and on the other hand by determining the amino groups.



  The 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride can also be introduced in solution in acetone. For work-up, the dye solution can also be warmed up slightly at the specified pH without the reactivity of the dye with the cellulose being significantly reduced. Unreacted thiazole-carboxylic acid chloride and the saponification products formed therefrom are separated off by filtration or in a separator. The reaction product is precipitated by adding 150 g of table salt per liter of dye solution. It is suctioned off and dried in vacuo or at about 30 ° C. under normal pressure. 195 to 200 g of crude dye are obtained, which still contains about 30% common salt. The common salt can largely be removed by stirring the raw dye with 250 ml of water and again suctioning it off.



   The dye dyes cellulose materials using the Klotz thermosetting process at 140 C and using the Klotz steaming process in turquoise tones that are fast to wet, rub and light.



   The dye mixture used as starting material can be obtained by methods known per se, e.g. B. by adding 3 mol of 2,4-diaminobenzenesulfonic acid at a pH of about 6.5 to an aqueous suspension of copper phthalocyanine trisulfonic acid chloride free from sulfonic acid groups at 0 to 20 C and at the same time catalyzing the saponification with 3 mol of pyridine, the above-mentioned mixture of Pc sulfonamides arises.



   A similar product is obtained if a mixture is used as the starting material which contains the components mentioned in a molar ratio of 4: 1. This mixture is obtained from the same copper phthalocyanine trisulfonic acid chloride and 2 mol of 2,4-diaminobenzenesulfonic acid by the same process.

 

   Instead of the starting materials mentioned, it is also possible to use those which contain nickel as the central atom instead of copper or which are made from copper phthalocyanine trisulfonic acid chloride <4,4 ', 4') or from phthalocyanine tetrasulfonic acid chlorides X3,4 ', 4 ", 4 ") or {4,4 ', 4", 4 "') or using other arylenediaminesulfonic acids, such as toluenediamine (2,4> sulfonic acid5); 4,4'-diamino-dibenzyl-disulfonic acid X2,2 '), naphthylenediamine {1,5-disulfonic acid {3,7).



  Such products and their manufacture are widely described in the patent literature. Your reaction with 4-methyl-2-methylsulfonyl-thiazole-carboxylic acid chloride can always be carried out in the same way.



   This also applies to the conversion of 4-methyl-2-methylsulfo nyl-thiazole-5-carboxylic acid chloride with the reactive dyes leading to green copper and nickel phthalocyanine inter mediate products such as z. B. by polysulfochlorination of tetra {3.3: 3 ", 3" ') (p-tolylmercaptoScupferphthalocyanin with
Chlorosulfonic acid, condensation of 1 to 2 sulfochloride groups per molecule with 1,3-phenylenediamine - 1-sulfonic acid or 1, phenylenediamine-3-sulfonic acid and saponification of the remaining sulfochloride groups are available;

   the uniform or mixed amino and sulfo groups arylation and alkylation products of tramercapto copper (or nickel) phthalocyanine can be prepared in an analogous manner by acylation of their amino group with 4Methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride in valuable green reactive dyes are transferred.



  Example 188
If you proceed as indicated in Example 139, but instead of the aminoazo dye used there 53.15 parts of the disodium salt of the by coupling of diazotized 1-amino4nitrobenzene-2-sulfonic acid with 12'-chloro-5'-sulfophenylt3-methyl-pyrazolone- ( 5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye with the 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated, one also obtains a valuable reactive dye with which cellulose materials after the usual dyeing and printing processes in real yellow
Tones can be printed.



   Similar reactive dyes are obtained if, instead of the above-mentioned aminoazo dye, one of the aminoazo dyes made up of the components listed in the table below is acylated with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride: Example diazo component azo component shade game no.



   189 1-Amino4nitro- 1 (2'-methyl4- yellow benzene-2-sulfone-sulfophenylS3- acid (reduced) methyl-pyrazolone- (5) 190 1-amino-4nitro-1 (2 ', 5-disulfo yellow benzene -2-sulfon- phenyl) -3-methyl- acid (reduced) pyrazolon- (5) 191 1-amino4nitro- 142'-methyl4- yellow benzene-2-sulfon- sulfo-6-chloric acid (reduced) phenylS3- methyl pyrazolone <5)
Example diazo component azo component color match
No.



   192 1-Amino4nitro-12 ', 5-dichloro-yellow benzene-2-sulfone-4'-sulfophenyl acid (reduced) 3-methyl-pyrazolone- (5) 193 l-amino-3-acetyl-1- (2 'Methyl-4'- green aminobenzol-6- sulfophenyly3- sti sulfonic acid methyl-pyr- chiges (saponified) azoles- (5) yellow 194 1-amino-3-acetyl- 1-84'-sulfophe- green aminobenzol-6- nylS3-methyl-pyr- sti sulfonic acid azolon- (5) chiges (saponified) yellow 195 1-Amino-3-acetyl- l (2'-methyl4- green aminobenzene-6-sulfophenylS3- sti sulfonic acid carboxy-pyr- chiges (saponified ) azolon- (5) yellow 196 l-amino-sacetyl- 1 {2'-chloro-4'-green aminobenzene-6- <RTI

    ID = 18.40> sulfophenylS3- sti sulfonic acid carboxypyrchiges (saponified) azoloen- (5) yellow Example 197
58 parts of the dye of the formula
EMI18.1
  (produced by coupling diazotized 1-hydroxy-2-amino4-chlorobenzene-5-sulfonic acid to 2-methylamino-8-hydroxy naphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water in a neutral manner are 24.0 parts of finely powdered 4-methyl-2-methylsulfonyl-thia zol-5-carboxylic acid chloride and stirred at 20 C with constant blunting of the hydrochloric acid liberated with soda solution to pH 5 to 6 until no free amino group can be detected formed reactive dye of the formula
EMI18.2
 is salted out, filtered off,

   washed and dried at 30 to 40 ° C. It dyes cellulose materials in very true violet tones according to one of the above methods.



   Dyes with similar properties are obtained analogously to the procedure described above from the copper complexes - obtained by simple, demethylating or oxidizing coppering - of the mono and disazo dyestuffs prepared from the diazo and azo components listed in the table below: with diazo component azo component coupling Shade play no. PH 198 1-Hydroxy-2- 2-Amino-8-10 Rotst.



   amino4-chloro-hydroxy-naphtha- violet benzene-5-lin-3,6-disulphonic acid sulphonic acid 199 1-hydroxy-2- 1-amino-8-10 Blaust.



     amino4-chloro-hydroxy-naphtha- violet benzene-5-lin-3,6-disulfonic acid sulfonic acid 200 2-amino-naphtha- 2-hydroxy-6-ace-8-9 Rotst.



   lin-4,6,8-trisultylamino-naphtha- blue fonic acid (oxydi- lin4-sulfonic acid rend coppered) (saponified) 201 1-amino-2- 1-hydroxy-8-eth- 10 blue hydroxy-6-nitro - oxy-naphthalene naphthalene-4-sul- 3,6-disulfonic acid (reduced) 202 1 -hydroxy-2- 2-hydroxy-3- 10 red aminobenzene-aminonaphthalene
4,6-disulfonic-5,7-disulfonic acid 203 2-amino-naphtha- 2-hydroxy-3- 8-9 blue lin4,8-disulfonic-amino-naphthalenic acid (oxidized-5,7-disulfonic acid rend coppered) 204 2-aminonaphtha- 2-hydroxy-3- 8-9 blue lin4,6,8-trisul-amino-naphthalenic acid (oxydi- 7-sulfonic acid rend-coppered) 205 3-methoxy4-2-methylamino-5-10 marine amino -6-methyl-hydroxynaphtha- blue azobenzene-2'-lin-7-sulfonic acid 4 ,;

  ; disulfonic acid (demethylating coppered) 206 3-methoxy4-2-amino-8-10 marine amino-6-methyl-hydroxy-naphtha- blue azobenzene-2'-lin-3,6-di
4-disulfonic acid sulfonic acid (demethylating coppered) 207 3-methoxy4- 2-amino-5- 10 marine amino-6-methyl-hydroxy-naphtha- blue azobenzene-2'-lin-1, 7-di-
4-disulfonic acid sulfonic acid (demethylating coppered) 208 3-methoxy4- 2-methylamino-5- 10 marine amino-6-methyl-hydroxynaphtha- blue azobenzene-2 ', 5'-lin-7-sulfonic acid disulfonic acid (demethylating coppered) by- Diazo component Azo component Kupp shade play no.

   pH 209 3-methoxy4-2-amino-8-10 marine amino-6-methyl-hydroxy-naphtha- blue azobenzene-2 ', 5'-lin-3,6-dj disulfonic acid sulfonic acid (demethylating coppered) 210 3-methoxy4 - 2-Amino-5- 10 marine amino-6-methyl-hydroxy-naphtha- blue azobenzene-2 ', 5'-lin-1,7-di-disulfonic acid sulfonic acid (demethylating copper-plated) Example 21 t
If the procedure is as in Example 172, but instead of the 54.7 parts of the disodium salt mentioned there, 63.5 parts of l-amino4 {(2'-methyl-3'-aminophenylpamino} anthraquinone-2,5-disulfonic acid are used of the trisodium salt of l-Amino4 {3'-aminophenylpamino} anthraquinone-2,4 ', 6'- (or 2,2', 6'-ytrisulfonic acid), a reactive dye is obtained, the cellulose fibers in one of the usual dyeing processes good wetfast, clear,

   reddish blue tones.



   When using equivalent amounts of l-amino-4 (3'.aminophenylaminoSanthraquinone-2,5,8-trisulfonic acid, a valuable reactive dye is also obtained which dyes cotton in real grayish blue tones.



  Example 212
28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The monoazo dye obtained is isolated and then, or even without isolation, immediately diazotized in solution and coupled under alkaline conditions with 25.3 parts of 2-methylamino5-hydroxynaphthalene-7-sulfonic acid. The disazo dye obtained is salted out by adding sodium chloride, filtered off with suction and the isolated product is metallized with about 50 parts of crystallized copper sulfate, 40 parts of diethanolamine, 50 parts of ammonia (D: 0.88) in 5 hours at 95 to 100 ° C. From the coppering solution the dye is isolated by adding salt and careful acidification.



   The coppered amino-disazo dye is then acylated in aqueous solution at pH 4 to 6 at a temperature of 20 ° C. with 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, the pH value being increased by adding soda When the acylation is complete, the dye is isolated with sodium chloride and dried at 35.degree. In the form of the free sulfonic acid, the dye corresponds to the formula:
EMI19.1
 he dyes cellulose fabric using the methods known for reactive dyes in wet and lightfast navy blue tones.

 

   In a similar way, other dyes can be produced if the above-mentioned monoazo dye is made from 2-amino-1-methylbenzene-3,5-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene with the ones listed in the table below Aminonaphtholsulfonic acids and 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride combined according to the instructions given above, coupling component 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid
2-amino-8-hydroxynaphthalene-3,6-disulfonic acid
The dyes obtained are blue in color.



  Example 213
0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5-sulphonic acid are diazotized and coupled with 0.1 mol of 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid using alkaline soda The coupling solution is mixed with caustic soda to a content of 2 Set mol / liter and then refluxed for 3 hours to saponify the ureido group. After cooling, it is neutralized with hydrochloric acid. By adding 25 parts of copper sulfate and 100 parts of 2N sodium hydroxide solution, the dye is metallized at 45 "C and a pH of 4 to 6 and after 30 minutes at pH 4 to 6 and temperatures of 20" C with 0.1 mol of 4- Acylated methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride. The obtained dye of the formula
EMI20.1
 is salted out. A blue color is obtained on cotton.



  Example 214
A neutral paste of copper phthalocyanine3.3: 3 "trisulfonic acid chloride made from 600 g of technical 96/0 copper phthalocyanine is mixed with a little water, adjusted to 4 liters and at a pH of 3.5 to 6.0 with 216 g of N-methyl-NX4 -amino-2'-sulfobenzyl) amine at initially 0 to 3 "C, finally 20 to 35" C, with the addition of 300 ml (= 295 g) of pyridine and then the pyridine at pH 9.0 with steam from the resulting solution of copper phthalic acid monosulfonic acid <3'-sulfo4-methyl-aminomethyl-anilide) distilled off.

  Partly 305 g of finely powdered 4-methyl-2methylsulfonyl-thiazole-5-carboxylic acid chloride are sprinkled into the solution, which has cooled to 10 ° C., over the course of 1 to 2 hours and a pH of 7.5 to 8.5 is maintained by adding dilute sodium hydroxide solution At the same time, if necessary, the reaction mixture is diluted with water to such an extent that the dye always remains dissolved.



   10 l of dye solution are obtained, which is separated off from the excess acylating agent, adjusted to pH 7.0 by adding acetic acid and precipitated by stirring in 2.5 l of concentrated sodium chloride solution.



   After suctioning off and drying at 30 "C, a clear turquoise-blue dye is obtained which is fixed to cotton from a solution in a soda-alkaline solution at 40 to 60" C with very good yield and wash fastness.



   If the NiPc-3,3 ', 3 "-trisulphonic acid chloride is used as the starting material, one obtains an only slightly greener turquoise blue with equally valuable properties.



  Example 215
12.5 parts of 3-amino-4-sulfobenzyl-N-methylamine are dissolved in 150 parts by volume of concentrated hydrochloric acid. 4 parts of sodium nitrite in 20 parts by volume of water are added dropwise to the solution. The resulting clear diazonium salt solution is added dropwise at 30 to 35 ° C. to an aqueous solution of the equimolar amount of 1-N-benzoyl-amino-8-oxynaphthalene-4,6-disulfonic acid, 16 parts of sodium bicarbonate in 200 parts by volume of water.



   The dye partially precipitates and is redissolved by adding 2000 parts by volume of water.



  17.6 parts of 4-methyl-2-methylsulfonylthiazole-5-carboxylic acid chloride are then added at 20 ° C. The pH value is maintained between 6 and 7 by adding a soda solution dropwise. When the acylation is complete, as can be seen from the consumption of soda, the mixture is separated remove the dye with 10 percent cooking salt, vacuum and press and dry in a vacuum oven at 30 "C. The bluish red dye obtained corresponds in the form of the free acid of the formula
EMI20.2
 Example 216
38.9 parts of the dye obtained by the soda-alkaline coupling of 6-nitro-2-diazo-1-hydroxybenzenesulfonic acid and 2-hydroxynaphthalene are mixed in 200 parts of water at pH 8 at a temperature of 70 to 80.degree.

  67.9 parts of the chromium complex compound of the azo dye composed of 4-chloro-2-diazo-1-hydroxybenzene-6-sulphonic acid and 1-amino-8-hydroxynaphthalene-3,6 are carried into this suspension -disulfonic acid, the pH being kept between 7 and 9 by adding soda solution. A dark blue solution has formed after 20 minutes at 70 to 80 ° C. The paper chromatogram shows that a uniform mixed complex has formed. The mixed complex is mixed with 24.0 parts of 4-methyl within 30 minutes at 5 ° C. and pH 4 to 6 -2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated, the pH being kept in the specified range by adding dropwise a soda solution.

  The acylated dye is salted out with 20% potassium chloride, filtered off and dried at 30 ° C. A dark powder is obtained which dissolves in water with a blue-gray color.



   The pentasodium salt of the dye corresponds to the formula
EMI21.1

It dyes cotton in gray to black shades according to the method given in Examples 1 to 3.



   Valuable dyes can also be obtained from the starting components indicated in the table below in the manner indicated in this example. For the production of these dyes, the azo dye, which carries the reactive group in the 2: 1 mixed complex, was always used as a 1: 1 chromium complex.



      Example 1: 1 (chromium complex metal-free dye color match on No. Baum wolle 217 4-Nitro-2-amino-4-Nitro-2-amino-Black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid 2-hydroxy - # 1-amino-8-naphthalene hydroxynaphthalene
3,6-disulfonic acid 218 4-nitro-2-amino-4-nitro-2-amino-black, 1-hydroxybenzene-1-hydroxybenzene
6-sulfonic acid 2-hydroxy 1-amino-8-naphthalene hydroxynaphthalene
3.6-disulfonic acid 219 4-nitro-2-amino-4-nitro-2-amino-black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid 2-hydroxy 1-amino8-naphthalene hydroxynaphthalene
3,6-disulfonic acid 220 4-nitro-2-amino-4-nitro-2-amino-black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid - # 2-hydroxy- <RTI

    ID = 21.11> 1-amino8-naphthalene-6 hydroxynaphthalene sulfonic acid
3,6-disulfonic acid 221 4-nitro-2-amino-4-nitro-2-amino-black, 1-hydroxybenzene-1-hydroxybenzene
6-sulfonic acid - # 2-hydroxy-1-amino-8-naphthalene-6 hydroxynaphthalene-sulfonic acid
3,6-disulfonic acid 222 4-nitro-2-amino-4-nitro-2-amino-marine
I-hydroxybenzene- I-hydroxybenzene blue
6-sulfonic acid 1-hydroxy 1-amino-8-naphthalene-4-hydroxynaphthalene sulfonic acid
3,6-disulfonic acid 223 4-nitro-2-amino-6-nitro-2-amino-black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid 4-sulfonic acid Example- 1-1 chromium complex metal-free dye color match on no.

  Cotton 1-amino-8- - # 2-hydroxy-hydroxynaphthalene-naphthalene
3,6-disulfonic acid 224 4-nitro-2-amino-4-nitro-2-amino-black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid - # 1-acetyl-1-amino-8-amino4-hydroxy-hydroxynaphthalene-naphthalene
3,6-disulfonic acid 225 4-nitro-2-amino-6-nitro-1-amino-black 1-hydroxybenzene-2-hydroxynaphtha
6-sulfonic acid lin4-sulfone 1-amino-8-acid 2-hydroxynaphthalene-droxynaphthalene
3,6-disulfonic acid 226 4-nitro-2-amino- 4-nitro-2-amino- black l-hydroxybenzene- 1 -hydroxynaphtha-
6-sulfonic acid lin-6-sulfone 1-amino8- acid 2-hydroxynaphthalene-

   droxynaphthalene
4,6-disulfonic acid 227 4-chloro-2-amino-4-nitro-2-amino blue
I-hydroxybenzene- I-hydroxybenzene black
6-sulfonic acid 2-hydroxy-1-amino-8-naphthalene hydroxynaphthalene
3,6-disulfonic acid 228 4-chloro-2-amino-4-nitro-2-amino blue
I-hydroxybenzene- I-hydroxybenzene black
6-sulfonic acid 2-hydroxy 1-amino-8-naphthalene hydroxynaphthalene
3,6-disulfonic acid 229 4-chloro-2-amino-4-nitro-2-amino blue
I-hydroxybenzene- I-hydroxybenzene black
6-sulfonic acid 2-hydroxy 1-amino8-naphthalene-6 hydroxynaphthalene sulfonic acid
3,6-disulfonic acid 230 4-chloro-2-amino-4-chloro-2-amino-marine 1-hydroxybenzene-1-hydroxybenzene blue
6-sulfonic acid 2-hydroxy-1-amine-8-

   naphthalene hydroxynaphthalene
3,6-disulfonic acid 231 4-chloro-2-amino-4-nitro-2-amino-blue, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid - # 1-acetylamino- example 1: l-chromium complex metal-free dye shade match on no.

  Cotton 1-amino-8- 8-hydroxynaphtha hydroxynaphthalene-lin-3,6-disulfone
3,6-disulfonic acid
232 4-chloro-2-amino-4-nitro-2-amino-marine 1-hydroxybenzene-1-hydroxybenzene blue
6-sulfonic acid 1-amino-8-hy- -l-amino8-hydroxynaphthalene hydroxynaphthalene-2,4-disulfonic acid
3,6-disulfonic acid
233 4-chloro-2-amino-6-nitro-1-amino-blue I-hydroxybenzene-2-hydroxynaphtha- black
6-sulfonic acid lin4-sulfone -I-amino8- acid 2-hydroxynaphthalene-hydroxynaphthalene
3,6-disulfonic acid
234 4-chloro-2-amino-2-aminobenzene-1-gray
1-hydroxybenzenecarboxylic acid-5-sul- green
6-sulfonic acid 1-Phe-1-amino-8-nyl-3-methyl-5

   hydroxynaphthalene pyrazolone
3,6-disulfonic acid
235 4-nitro-2-amino-6-nitro-1-amino- black
1-hydroxybenzene-2-hydroxynaphtha
6-sulfonic acid lin4-sulfone 1-amino-8-acid 2-hydroxynaphthalene-droxynaphthalene
3,6-disulfonic acid
236 4-chloro-2-amino-4-chloro-2-amino-violet 1-hydroxybenzene-1-hydroxybenzene
6-sulfonic acid - # 1- (4'-sulfo-1-amino-8-phenylS3-methyl-hydroxynaphthalene-5-pyrazolone
3,6-disulfonic acid
62.0 parts of the trisodium salt of the dye obtained by soda-alkaline coupling from diazotized 4-chloro-2-amino-1-hydroxybenzene-6-sulphonic acid and 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are dissolved in 300 parts of water at 70 to 80 C and a pH of 8

   to 9 with 54.2 parts of the
1: 1 chromium complex of the dye from 6-nitro-l-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene. Example: 1: I-chromium complex metal-free dye shade matched to No. Cotton 237 4-methyl-2- amino-4-chloro-2-amino-Rotsti l-hydroxybenzene-I-hydroxybenzene chig
6-sulfonic acid 2-hydroxynaph-blue-1-amino8-thalin-6-sulfone hydroxynaphthalic acid
3,6-disulfonic acid 238 4-nitro-2-amino-5-nitro-2-amino-black, 1-hydroxybenzene-1-hydroxybenzene
6-sulfonic acid 2-hydroxynaph-1-amino-8-thalin-6-sulfone hydroxynaphthalic acid
3,6-disulfonic acid 239 4-nitro-2-amino-

   4-nitro-2-amino- black, l-hydroxybenzene- I-hydroxybenzene
6-sulfonic acid 2-hydroxynaph-1-amino-8-thalin-8-sulfone hydroxynaphthalic acid
3,6-disulfonic acid 240 4-nitro-2-amino-4-nitro-2-amino-black 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid ¯ 1 -hydroxynaph 1-amino-8-thalin-5-sulfone hydroxynaphthalic acid
3,6-disulfonic acid 241 4-nitro-2-amino-6-nitro-4-chloro-black, 1-hydroxybenzene-I-hydroxybenzene
6-sulfonic acid-1-hydroxynaph-1-amino-8-thalin-5-sulfone hydroxynaphthalic acid
3,6-disulfonic acid sets. After 10 minutes a deep blue solution has formed.



   The mixed complex is acylated in about 15 minutes at 0 to 5 C and a pH of 4 to 6 with 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride. The pH value is kept constant by adding soda solution. The acylated dye is precipitated with 20/0 sodium chloride, filtered off with suction and dried at 30.degree.
EMI22.1




  The process given in Example 3 gives a blue-black print of excellent lightfastness and washfastness on cotton.



  Example 242
6 g of 1-amino444'-aminophenylamino-santhraquinone-2,5,8-trisulfonic acid are dissolved as the Na salt in 180 ml of water at 40 ° C., the solution is adjusted to pH 8 and at 5 to 10 ° C. 2.4 g of 4 -Methyl-2-methylsulfonyl.thiazole-carboxylic acid chloride added in small portions. At the same time, dilute sodium hydroxide solution is added dropwise in such a way that a pH of 6 to 7 is maintained during the reaction. Stirring is continued at 20 ° C. until all of the starting material has disappeared is, sucks off excess thiazolecarboxylic acid chloride and salt out at 10 "C with so much solid sodium chloride that about a 10% sodium chloride solution is present.

  It is filtered off with suction, washed with a little sodium chloride solution and the resulting dye of the formula is dried
EMI23.1
 below 40 ° C. in a vacuum. About 8.5 g of the dye are obtained in the form of blue-green needles.



   The dye dyes cotton by methods customary for reactive dyes in strong blue-green shades of good wet and light fastness.



   The 1-amino-444-aminophenylaminopanthraquinone-2,5,8-trisulfonic acid used as starting material was obtained as follows: 31.2 g of p-phenylenediamine are dissolved under nitrogen in a solution of 62 g of 1-amino-4-bromo- anthraquinone-2,5,8-trisulphonic acid sodium and 12 g soda and stirred at 40 ° C. with the addition of CuCl paste until no more disulphated bromamic acid can be detected. Dilute hydrochloric acid is then added to the solution Dye is suctioned off, washed with dilute hydrochloric acid, enough dilute sodium hydroxide solution is added to 300 ml of water so that solution occurs and the dye is precipitated in the warm as Na salt; the product is then washed and dried.



  Example 243
50.3 g of the dye obtained by coupling 1-acetylamino-3-amino-benzene-4-sulfonic acid onto 2-hydroxynaphthalene-6,8-disulfonic acid and saponification are dissolved in 160 ml of water until neutral. 25.6 g of 3,5-bismethylsulfonyhhio diazole-1,2,4, made into a paste with a wetting agent and water, are added.



  The mixture is stirred at 55 to 60 ° C. at pH = 5 to 6 until no more soda solution is consumed until the methylsulfinic acid split off is neutralized. The orange dye of the formula
EMI23.2
 is suctioned off and dried at 40 "C in a vacuum.



   PATENT CLAIM 1
Process for the preparation of reactive dyes of the formula
EMI23.3
 wherein F stands for the residue of an organic dye, m for a number from 1 to 4, R for hydrogen or a substituent, A for a five-membered heterocyclic ring with at least one reactive sulfonyl substituent on a carbon atom of the heterocyclic ring and X for a bridge member of the Formula -CO-, -SO2-, -CO-alkylene- or -CO-arylene, where -XA is reactive groups of the formula
EMI23.4
 are excluded in which Y1 and Y2 stand for reactive substituents, characterized in that starting dyes of the formula
EMI23.5
 with compounds of the formula
Y-X-A (VI) converts, wherein Y is an anionically removable radical.

 

   SUBCLAIMS
1. The method according to claim 1, characterized in that the compounds of the formula YXA are 3,5-bismethylsulfonyl-1,2,4-thiodiazole, 2,5-bis-methylsulfonyl-1,3,4-thiodiazole, 4-Isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride or 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride is used.



   2. The method according to claim 1, characterized in that a dye of the formula 1 obtained which has nitro groups is then reduced.



   3. The method according to claim 1, characterized in that one aminoazo dyes of the formula

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. dissolved, the solution is adjusted to pH 8 and 2.4 g of 4-methyl-2-methylsulfonyl.thiazolecarboxylic acid chloride are introduced in small portions at 5 to 10 ° C. At the same time, dilute sodium hydroxide solution is added dropwise in such a way that a pH of 6 to 7. Stirring is continued at 20 "C. until all the starting material has disappeared, excess thiazolecarboxylic acid chloride is suctioned off and salted out at 10" C. with so much solid sodium chloride that about a 10% sodium chloride solution is present. It is filtered off with suction, washed with a little sodium chloride solution and the resulting dye of the formula is dried EMI23.1 below 40 ° C. in a vacuum. About 8.5 g of the dye are obtained in the form of blue-green needles. The dye dyes cotton by methods customary for reactive dyes in strong blue-green shades of good wet and light fastness. The 1-amino-444-aminophenylaminopanthraquinone-2,5,8-trisulfonic acid used as starting material was obtained as follows: 31.2 g of p-phenylenediamine are dissolved under nitrogen in a solution of 62 g of 1-amino-4-bromo- anthraquinone-2,5,8-trisulphonic acid sodium and 12 g soda and stirred at 40 ° C. with the addition of CuCl paste until no more disulphated bromamic acid can be detected. Dilute hydrochloric acid is then added to the solution Dye is suctioned off, washed with dilute hydrochloric acid, enough dilute sodium hydroxide solution is added to 300 ml of water so that solution occurs and the dye is precipitated in the warm as Na salt; the product is then washed and dried. Example 243 50.3 g of the dye obtained by coupling 1-acetylamino-3-amino-benzene-4-sulfonic acid onto 2-hydroxynaphthalene-6,8-disulfonic acid and saponification are dissolved in 160 ml of water until neutral. 25.6 g of 3,5-bismethylsulfonyhhio diazole-1,2,4, made into a paste with a wetting agent and water, are added. The mixture is stirred at 55 to 60 ° C. at pH = 5 to 6 until no more soda solution is consumed until the methylsulfinic acid split off is neutralized. The orange dye of the formula EMI23.2 is suctioned off and dried at 40 "C in a vacuum. PATENT CLAIM 1 Process for the preparation of reactive dyes of the formula EMI23.3 wherein F stands for the residue of an organic dye, m for a number from 1 to 4, R for hydrogen or a substituent, A for a five-membered heterocyclic ring with at least one reactive sulfonyl substituent on a carbon atom of the heterocyclic ring and X for a bridge member of the Formula -CO-, -SO2-, -CO-alkylene- or -CO-arylene, where -XA is reactive groups of the formula EMI23.4 are excluded in which Y1 and Y2 stand for reactive substituents, characterized in that starting dyes of the formula EMI23.5 with compounds of the formula Y-X-A (VI) converts, wherein Y is an anionically removable radical. SUBCLAIMS 1. The method according to claim 1, characterized in that the compounds of the formula YXA are 3,5-bismethylsulfonyl-1,2,4-thiodiazole, 2,5-bis-methylsulfonyl-1,3,4-thiodiazole, 4-Isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride or 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride is used. 2. The method according to claim 1, characterized in that a dye of the formula 1 obtained which has nitro groups is then reduced. 3. The method according to claim 1, characterized in that one aminoazo dyes of the formula EMI24.1 a carbocyclic diazo component of the benzene or naphthalene series and D, in particular, the remainder of an enolic or phenolic coupling component, B and D can otherwise have any further substituents, including azo groups, Rs is a substituent or preferably hydrogen and m 'is the number 1 or 2 means with compounds of the formula A-X-Y wherein B and D represent carbocyclic or heterocyclic radicals of aromatic nature, B in particular converts a radical. 4. The method according to claim I, characterized in that one aminoanthraquinone dyes of the formula EMI24.2 where L denotes hydrogen or a substituent, among these in particular a sulfonic acid group, p denotes the number 1, 2 or 3 and Rl denotes a substituent or preferably hydrogen, with compounds of the formula A-X-Y implements. 5. The method according to claim I, characterized in that azaporphine dyes of the formula EMI24.3 where Pc is the radical of a phthalocyanine, in particular a copper or nickel phthalocyanine or a tetraphenyl copper or nickel phthalocyanine, L is hydrogen or a substituent, among these in particular a sulfonic acid group, r is the number 1 or 2, q is the number 0, 1 or 2 and R1 is a substituent or preferably hydrogen and m "is a number from 1 to 4, with compounds of the formula A-X-Y implements. 6. The method according to claim 1, characterized in that reactive azo dyes are prepared which have one or more sulfonic acid groups. 7. The method according to claim I, characterized in that obtained dyes of the formula I which have metal complex-forming groups, in particular azo dyes, are metallized prior to use for dyeing Use of reactive anthraquinone or phthalocyanine dyes, prepared by the process according to claim I, for the preparation of sulfonated dyes, characterized in that those dyes are treated with sulfonating agents. SUBClaim 8. Use according to claim II, characterized in that the sulfonating agent used is chlorosulfonic acid, thionyl chloride, oleum or SO3.