CH549087A - Reactive dyestuffs containing a sulphonyl group - suitable for dyeing synthetic polyamides and polyurethanes and regenerated cellulosic fibres - Google Patents

Abstract

Reactive dyestuffs have the formula F -(X - A) m where F = the residue of an organic dyestuff; X = NR, SO2, arylene, alkylene, or N=N, this group being either directly bonded to F, or being bonded to F via bridging group, and R is H or a substituent; A = the residue of a heterocyclic six-membered ring which contains at least one reactive sulphonyl substituent, and may be condensed with an aromatic ring; and m = 0.5-8.

Description

  

  
 



   The present invention relates to methods of preparing valuable new azo reactive dyes of the composition
EMI1.1
 In this formula, F is the radical of an azo dye, X is an -SO2-, -arylene- or -alkylene- group, t is O or 1, R is hydrogen or a substituent, arylene is an arylene radical and alkylene is a lower alkylene radical; A denotes the radical of a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring and which can have fused aromatic rings, and m is a number from 1 to 3.



   In the dyes of the general formula (1), the radical A is, by definition, linked to the dye radical F via an -N (R) - (X) t- radical; here the group -N (R) - can be connected either directly or via a further bridge member to a cyclic carbon atom of the dye.



   As a bridge member -N (R) - (X), - is the group
EMI1.2
 preferred, especially the groups -NH- and -N (CH3) -. The amino and Amide groups can carry further substituents, such as lower alkyl (preferably C1 to C5), aralkyl, cycloalkyl or aryl groups. For the case t = 0 amino groups -N (R) - are on the one hand linked directly to the radical A and on the other hand either directly or via a further bridge member, such as -SO2- or -CO- (amide group) or via an alkylene group, an alkylene-CO-, an arylene-. Arylene-SO-, arylene-CO-. Arylenamino or aralkylenamino group, a urea grouping or a triazine or diazine ring, an arylenamidosulfonyl group or other types of members bonded to an aromatic ring of the azo dye F.

  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.



   The following types of bond of the radical A may be mentioned, for example: - (R) N-alkylene-A; - (R) N-aralkylene-A; - (R) N-alkarylene-A; - (R) N-arylene-A; - (R) NO2S-alkylene-A; - (R) NO2S aralkylene-A; - (R) NO2S-alkarylene-A; - (R) NO2S-Arylene-A; - (R) N-OC-alkylene-A; - (R) N-OC-aralkylene-A; - (R) N-O C-alkarylene-A; - (R) N-OC-Arylene-A; - (R) NO2S-A; - (R) N-A; -Alkylene-N (R) -A; Arylene-N (R) -A; Aralkylene-N (R) -A; Alkarylene-N (R) -A.



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



   The 6-membered heterocyclic ring A, which has at least one reactive, i.e. H. Has sulfonyl substituents which can be split off under the known conditions of reactive dye use, is, for example, a monoazine, diazine or triazine ring, such as a pyridine; Pyrimidine, pyridazine, pyrazine, thiazine or as. Or sym. Triazine ring, or such a ring system with one or more fused aromatic rings, such as a quinoline, phthalazine, chinnoline, quinazoline, quinoxaline, acridine, Phenazine or phenanthridine ring. The heterocyclic ring A is preferably one which, as in the above-mentioned compounds, contains one or more ring nitrogen atoms. Fused-on rings are by definition aromatic in nature; they can be carbocyclic or heterocyclic. The fused rings can be 5- or 6-membered.

  Of particular interest are pyrimidine and sym.triazine rings A.



   The bond of the heterocyclic ring A to - (X), - N (R) either starts from the heterocyclic ring which carries the reactive sulfonyl substituent (s), or the bond starts from a fused-on carbocyclic or heterocyclic ring system. In the event that the bridge member (X) tN (R) starts from the heterocyclic ring which has the reactive sulfonyl substituent or substituents, the bridge member is either with a carbon atom or a heteroatom, among these generally with a nitrogen atom of the heterocyclic 6- Linked ring. (X) t -N (R) is preferably bonded to a carbon atom of the hetero ring A.



   Examples of suitable heterocyclic radicals A which have at least one reactive sulfonyl substituent and which can contain further rings fused are: 2-carboxymethylsulfonyl-4-pyrimidinyl, 2-methylsulfonyl-4-methyl-6-pyrimidinyl.



  2-phenylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-bis-methylsulfonyl-6-pyrimidinyl, 2,4-bis-methylsulfonyl -5-sulfamidyl-pyrimidinyl-, 3-phenylsulfonyl-6-pyridazinyl-, 3-methylsulfonyl-4-methyl-6-pyridazinyl-, 2,5-bis-methylsulfonyl-6-pyrazinyl-, 1-methylsulfonyl-3-triazinyl -,
1 -Methylsulfonyl-3- (3'-sulfophenylamino) -5-triazinyl-,
1 -Methylsulfonyl-3- (2'-hydroxyethylamino) -S4riazinyk
1 -Methylsulfonyl-3-amino-5-triazinyl-, 1 -Methylsulfonyl-3-methoxy-5-triazinyl-,
I -Methylsulfonyl-3- (2'-benzthiazolyl) -thio-5-triazinyl-, 1 - (4'-methylphenylsulfonyl) -3-phenyl-5-triazinyl-, also 2-methylsulfonyl-4-quinazolyl-, 2- Methylsulfonyl4-pyrimidinyl-2-phenylsulfonyl4 -pyrimidinyl-,

   2-methylsulfonyl-4-methyl-6-pyrimidinyl, 2-methylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2-carboxy-methylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 3- (4 '-Nitrophenyl) -sulfonyl-6-pyridaziny 5-chloro-6methylsulfonyl-4-pyridazinyl,
I-phenylsulfonyl-3-methoxy-5-triazinyl, 1,3-bis-phenylsulfonyl-5-triazinyl, 1-methylsulfonyl-3-phenoxy-5-triazinyl, 1-methylsulfonyl-3-phenyl-5-triazinyl.



   The reactive sulfonyl substituent or substituents in the core A can be further substituted in the aryl, alkyl or hetero radicals by ionogenic or non-ionogenic groups, e.g. B. by carboxy (for example in the form of carboxymethyl), sulfo, hydroxy, nitro or halogen (Cl, BrF radicals, such as those in carboxymethylsulfonyl, chloromethylsulfonyl, chloroethylsulfonyl, hydroxyäthylsulfonyl, nitrophenylsulfonyl , Sulfophenylsulfonyl groups are present.

 

   Among the large number of groups -N (R) - (X), - A (II), the following examples should be mentioned: -N HA, -N (CH3) -A, -N (C2H5) -A, -N ( C3H7) -A, -CON HA, -S02N HA, -N HO2S-A, -CON (CH3) -A, -SO2N (CH3) -A, - (CH3) -NO2S-A, as well as the corresponding N-ethyl - and N-Propylamides, -HN-CO-NH-A, -HN-CH2-CO-NH-A, -N (CH3) -CH2-CON HA, -HN-CH2-CH2-N HA,
EMI2.1
 and the corresponding N-alkyl (1-5 C) amides or amines
EMI2.2
 and the corresponding N-alkyl (1-5 C) amides or amines of the compounds mentioned.



   The new azo reactive dyes can be both metal-free and metal-containing mono- or polyazo dyes. Dyes of the following general composition are particularly valuable:
EMI2.3
  wherein B and D represent aromatic, carbocyclic or heterocyclic radicals, in particular B the radical of a carbocys metallic diazo component of the benzene or naphthalene series, and D the radical of an enolic or phenolic coupling component, eg.

  B. a 5-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene; 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 -SO2- and m 'denotes the number I or 2; A stands 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 which can have fused carbocyclic rings.



   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 of 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-positions to the azo group, e.g. B. in the form of o, o'-dihydroxy, o-hydroxyo'-carboxy, o-carboxy-o'amino and o-hydroxy-o'-amino-azo groups.



   The above compilation of a selection of suitable azo dyes and heterocyclic ring systems A does not represent any restriction of the general formulas, neither with regard to the preparative possibilities for the preparation of such dyes within the scope of general formula (I) nor with regard to the valuable application properties of these products. The new azo 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 ssulfonyl amines, 1, dihalophthalazine carbonyl or -6-sulfonylamino, 2-halobenzothiazole-5-carbonyl or -5sulfonylamino, esterified sulfonic acid oxalkylamide and oxalkylsulfone groups, sulfofluoride, haloalkylamino, acryloylamino, haloacylamino groups and the like.



   The new azo dyes of the formula (1) are obtained by combining a diazo component with a coupling component and choosing the components so that at least one of these has at least one group
EMI3.1
 in which X is a grouping -SO2-, -arylene or -alkylene-, arylene is an arylene radical and alkylene is a lower one. Alkylene radical, t denotes the number 0 or I, A represents the radical of a 6-membered heterocyclic ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring and which can have fused aromatic rings, and R represents hydrogen or a substituent stands.



   The coupling of the diazo and coupling components takes place in a manner customary per se in an aqueous or organically aqueous medium in an acidic, neutral or alkaline range.



   The azo dyes obtained in this way contain 1 to 3 groupings of the general formula - (R) N- (X) t-A.



   If the azo dyes represented according to the method contain metal complex-forming groups, these can be obtained by the action of metal-releasing agents, e.g. B. of copper, nickel, chromium or cobalt salts are converted into their metal complex compounds. Likewise, they can be subjected to other common conversion reactions such as acylation and condensation reactions.



   A particularly preferred group of reactive dyes within the scope of the compounds of the formula (I) has the composition
EMI3.2
 In this formula, F is the radical of an azo dye, A is the radical of a pyrimidine ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring, R 'is hydrogen or a CH3 group and m' is a number from I to 2.



   In the dyes of the general formula (IX), the radical A is linked, by definition, to the azo dye radical F via an amino group -N (R). The amino group is preferably in the non-substituted -NH- form. The amino groups are in turn bound directly to an aromatic ring carbon atom or a lower alkylene group of the azo dye.



   As reactive sulfonyl substituents in the pyrimidine ring A; there are lower alkylsulfonyl radicals with preferably 1 to 5 carbon atoms, such as methylsulfonyl, ethylsulfonyl or propylsulfonyl radicals, arylsulfonyl radicals. such as phenylsulphonyl, p-toluenesulphonyl, p-chlorophenylsulphonyl radicals, aralkylsulphonyl radicals, such as benzylsulphonyl and p-toluylmethylsulphonyl radicals, and also heterosulphonyl radicals, such as 2-benzothiazolesulphonyl, in question.



   Examples of suitable pyrimidine rings A ,, which have at least one reactive sulfonyl substituent are: 2-carboxymethylsulfonyl-4-pyrimidinyl, 2-methylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-6-pyrimidinyl, 2- Phenylsulfonyl-4-methyl-5.chlor-6-pyrimidinyl, 2,4-bis-methylsulfonyl-6-pyrimidinyl, 2-methylsulfonyl4-methyl-5-nitro-6-pyrimidinyl, 2-methylsulfonyl-5-cyano4-pyrimidinyl, 2-methylsulfonyl4-carboxy-6-pyrimidinyl or 2-ethylsulfonyl-5-sulfo4-pyrimidinyl and other compounds already mentioned in column 2.

 

   The reactive sulfonyl substituent or substituents in the core Al can be further substituted by ionic or non-ionic groups, e.g. B. by carboxy (for example in the form of carboxymethyl), hydroxy, nitro, Halogen4Cl, Br), sulfonic acid or sulfone radicals, or other groups already mentioned in column 3/4.



   From an application point of view, particularly valuable dyes are those of the general formula (IV) in which the remainder
EMI4.1
 corresponds to the following specified formula:
EMI4.2
 where R'I stands for a lower alkyl radical containing 1 to 3 carbon atoms or hydrogen, one of the radicals R3 or R4 stands for the group -SO2M, where M stands for an alkyl, aralkyl or aryl radical, the other of the radicals R3 or R4 likewise a group -SO2M or hydrogen, alkyl, aralkyl, aryl, -SO3H, -COOH, -COO-alkyl, -Cl, -Br or -CN and R5 is hydrogen or a substituent, such as alkyl, aralkyl, aryl, - SO3H, -COOH.



  -COO-alkyl, -Cl, -Br, -CN, nitro, carbonamide or sulfonamide.



   Those dyes of the formula (IV) in which the remainder
EMI4.3
 is a 2-methylsulfonyl-5-chloro-6-methylpyrimidinyl-4 radical.



  This residue is introduced by reacting a diazo or coupling component containing amino groups with, for example, 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine.



   The new dyes of the formula (IV) are obtained in a completely analogous manner to the dyes of the formula (I).



   A particularly valuable type of reactive dyes within the scope of the new dyes of the formula (1) corresponds to the formula
EMI4.4

In this formula, F is the residue of an azo dye, X is an amino group, R'5 is a halogen atom, R'4 is hydrogen or an optionally substituted alkyl substituent, R is an aliphatic, carbocyclic or heterocyclic substituent and m 'is a number from 1 to 2 .



   In the dyes of the general formula (VI), the pyrimidine radical is, by definition, linked to the dye radical F via an amino group. The amino group can carry further substituents, such as lower alkyl (preferably C1 to C5), aralkyl, cycloalkyl or aryl groups, but is preferably in the form -NH- which is not further substituted.



   The amino group is in turn bound directly to an aromatic ring carbon atom of the dye or to an alkylene group of the dye.



   The reactive sulfonyl substituents -SO2R, in the 2-position of the pyrimidine ring, are lower alkylsulfonyl radicals with preferably 1 to 5 carbon atoms, such as methylsulfonyl, ethylsulfonyl or propylsulfonyl, arylsulfonyl, such as phenylsulfonyl, p-toluenesulfonyl, p-toluenesulfonyl, p-toluenesulfonyl, p-toluenesulfonyl such as benzylsulphonyl and p-toluylmethylsulphonyl radicals, and also heterosulphonyl radicals, such as 2-benzothiazolesulphonyl, are possible.



   The reactive sulfonyl substituents can be further substituted by ionic or non-ionic groups, e.g. B. by carboxy, nitro, halogen (CI, Br), sulfonic acid or sulfone radicals. As halogen atoms R'5, chlorine and bromine are of preferred interest, as substituents R'4, in addition to hydrogen, preferably lower alkyl radicals such as methyl, ethyl, and substituted lower alkyl radicals such as halomethyl, e.g. B. monochloromethyl, bromomethyl, dichloromethyl and trichloromethyl, carboxymethyl, carboalkoxymethyl, such as carbomethoxymethyl and carboethoxymethyl, and cyanomethyl groups.



   The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds they are of particular interest for dyeing textile materials containing hydroxyl groups and nitrogen, in particular textile materials made from native and regenerated cellulose, and also from wool, silk, synthetic polyamide and polyrethane fibers.



  Thanks to the reactive sulfonyl substituent or substituents in the pyrimidine ring, 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 (short liquor) 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, on heated rollers or by placing them in heated concentrated 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 reduces the migration of the dye from the fiber.



   The material to be colored 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 elevated temperature.



   For dyeing from a long liquor, one goes into an aqueous solution of the dye (liquor ratio 1: 5 to 1:40) at room temperature and dyeing for 40 to 90 minutes, optionally with increasing the temperature to 85 ° C, with partial addition of salt, For example sodium sulphate, followed by alkali, for example sodium phosphates, sodium carbonate, NaOH or KOH. This is where the chemical reaction between dye and fiber occurs. After chemical fixation, the dyed material is rinsed with hot water and then soaped off, removing non-fixed residues of the dye The dyeings obtained are extremely fast, in particular wetfast and lightfast.



   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. 20 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 materials containing hydroxyl groups, a printing paste composed of the dye solution, a thickening agent such as sodium alginate and a compound that reacts alkaline or releases alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium carbonate, is used and the printed material is 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, with a subsequent increase in the pH of the dye tape, 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 dyeing and / or padding tape or in a printing paste. The auxiliaries suitable for this application include compounds that prevent the dye from migrating 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 specified.



  Example I.
In the solution of 36.5 parts of the sodium salt of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts of water, 25 parts of 2,4-bis-methylsulfonyl-6- added methylpyrimidine and stirred while constantly blunting the released hydrochloric acid to pH 6-7 until no free amino group can be detected. The intermediate dye product obtained in this way, after dilution with 600 parts of water and addition of 12 parts of soda at 5-10 ° C., is 17 , 5 parts of diazotized 2-aminobenzenesulfonic acid. dissolved in 200 parts of water, coupled. The dye of the formula which is formed at a final pH of approx. 7
EMI5.1
 is salted out with 100 parts of sodium chloride, filtered off with suction, washed and dried at 30-40 "C in a vacuum.

  The dye forms shiny red needles that dissolve easily in water with a red color.



   When printing cellulosic fabric with a printing paste that contains 15 grams of dye per kilogram, 100 g
Urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate per kg thickening), 2 g sodium hydroxide and
Contains 10 g of soda and which has been made up to 1 kilogram with water, dries, steams for 8 minutes at 105 ° C., rinses with hot water and soaps at the boil, this gives a strong, reddish-yellow print of good fastness to washing and light.



   100 parts by weight of a cotton fabric are used in
Room temperature with an aqueous solution containing 2% des
Dye, 15 g / l sodium hydrogen carbonate and 150 g / l urea. fouladed, dried in between, heated to 140 C for 10 minutes, then rinsed and soaped at the boil. The fabric is dyed wetfast in very clear blue tones.



   Cotton fabric is impregnated with a solution of 20-25 ° C., which contains 20 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g of urea and 15 g per liter of liquor
Contains sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50-60 oC, the mixture is heated to 140 "C for 10 minutes and the coloration thus obtained is rinsed thoroughly with hot water and treated at the boil for 20 minutes with a solution that pro
Liter contains 5 g of Marseille soap and 2 g of soda. After rinsing and drying, a strong reddish yellow coloration with good wet, rub and lightfastness is obtained.

 

   If fabric made of cotton or regenerated cellulose is dyed or printed with this dye according to one of the processes described above, clear, bluish red dyeings and prints of good quality are obtained
Wet, rub and light fastness.



   The following procedure gives equally good results:
50 g of cotton hank are dyed in 1 liter of a dye liquor containing 1.5 g of the above dye by increasing the temperature from 20 "C to approx.



  80 "C increases, with a total of 50 g of table salt in several
Add portions, then add 20 g of soda and treat for 60 minutes at this temperature. After rinsing, boiling soaps and drying, a bluish red dyeing of good wet, rub and lightfastness is obtained.



   In the table below, the hues of other dyes are listed which are built up from the diazo components, coupling components and reactive components that can be linked to the amino group in the latter analogous to the information in Example 1 - or by reacting the corresponding aminoazo dyes with the reactive components - and are built up from the diazo components, coupling components also listed can be dyed or printed on cellulosic materials using one of the methods described above:
Abbreviations for the reactive components:

  :
A = 2-methylsulfonyl-4-chloro-6-methylpyrimidine
B = 2,4-bis-methylsulfonyl-6-methylpyrimidine diazo component coupling component reactive color component l-aminobenzene-2- 1-amino-8-hydroxy- B red sulfonic acid naphthalene-3,6 disulfonic acid aminobenzene 1- (3'-aminobenzoyl - A red amino) -8-hydroxy naphthalene-3,6-disulfonic acid aminobenzene 1- (3'-aminobenzoyl- B red amino) -8-hydroxy naphthalene-3,6-disulfonic acid l-amino-2-carboxy- 1-Amino-8-hydroxynaph- A Red benzene-4-sulfonic acid thalin-3,6-disulfonic acid l-Amino4-methylben-1-Amino-8-hydroxynaph- A Red zol-2-sulfonic acid thalin-3,6-disulfonic acid l-Amino-3-acetylamino- 1-Amino-8-hydroxynaph- B Red benzene-6-sulfonic acid thalin-3,6-disulfonic acid 1-Amino-3- (2 '- [4 "- 1-Amino-8- hydroxynaph- A red <RTI

    ID = 6.6> sulfophenylamino] -4-thalin-3,6-disulfonic acid chlorotriazine-l ', 3', 5'-yl- 6 ') - aminobenzene-6-sulfonic acid l-aminobenzene-2-sulfone- 2-amino- 5-hydroxy- A orange acid naphthalene-7-sulfonic acid l-amino-3- (2'- 2-amino-5-hydroxy- A orange [4 "-sulfophenyl- naphthalene-7-sulfonamino] 4'-methyl- acid amino-triazin-1 ', 3', 5'-yl-6 ') - aminobenzene-6-sulfonic acid 1-aminobenzene- 2-methylamino-5-hy- A Orange 2-sulfonic acid hydroxy-naphthalene-7 sulfonic acid l- Amino4-acetyl- 2-methylamino-5-hy- A scarlet amino-6-sulfonic acid droxy-naphthalene-7 sulfonic acid l-amino-4-acetyl- 2-amino-5-hydroxy- A scarlet amino-6-sulfonic acid naphthalene- 7-sulphonic acid
If cellulose fabric is printed with a printing paste containing 30 g of the dye described in Example 1, 100 g of urea,

   300 g water, 500 g alginate thickener (60 g sodium alginate per kilogram thickener), 10 g soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was made up to 1 kilogram with water, then dried and then put in a suitable steamer 30 Seconds at 103 to 115 "C, a strong bluish red print of good wet, rub and lightfastness is obtained after rinsing and boiling soaps.



  Example 2
25.0 parts of 2-methylsulfonyl-4-chloro-6methylpyrimidine are introduced into the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 100 parts of water with thorough stirring and at 60-65 ° C. with constant blunting the released hydrochloric acid is stirred to pH 7-8 until a sample gives a clear, yellowish red color when diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid.

  After ice has been added, the resulting intermediate dye is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then with a solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula
EMI7.1
 takes place, which is salted out, filtered off with suction, washed and dried at 30-40 C in a vacuum. The dye dissolves easily in water with a red color and, according to one of the processes described above, gives clear bluish red dyeings and prints on cellulose materials.



   The following table lists the color shades and the pH of the coupling medium of dyes which are prepared analogously to the information in Example 2 from a diazo component which contains a further, preferably acylatable amino group, from a coupling component and from a reactive component that can be linked to the diazo component will. For dyeing and printing cellulosic materials with the dyes in the table, the above-mentioned methods can be used.



   Abbreviations for the reactive components as in the table for example 1 Diazo component Coupling component Reactive pH of the color component Coupling medium 1,3-diaminoben- 2-aminonaphthalene-A 4-5 orange zol4-sulfonic acid 5,7-disulfonic acid 1, 3-diaminoben- 2-aminonaphthalene- A 4-5 orange zene-4-sulfonic acid 3,6-disulfonic acid 1,3-diaminoben- 2-aminonaphthalene- B 4-5 orange zene-4-sulfonic acid 6-sulfonic acid 1,3- Diaminoben- 2-N-Methylamino-8- A 4-5 Orange zol4-sulfonic acid hydroxynaphthalene
6-sulfonic acid 1,3-diaminobenzene- 1- (3 ', 5'-dichloro-1', A 7-8 red 4-sulfonic acid 2'-thiazol4-carbon amido) -8-hydroxynaphtha lin-3,6- disulfonic acid 1,3-diaminobenzene- 1- (2 ', 4'-dihydroxy- B 7-8 red 4-sulfonic acid triazine-l', 3 ', 5', - yl-6'-amino) -8-hydroxynaphtha lin -3,6-disulfonic acid 1,3-diaminobenzene- 1- (3 ', 5'-dichloro-l',

   A 7-8 Red 4-sulfonic acid 2'-thiazole-4'-carbon amido) -8-hydroxynaphtha lin-3,6-disulfonic acid 1,3-diaminobenzene-2-hydroxynaphthalene-3,6- A 8 Scarlet 4-sulfonic acid disulfonic acid 1,3-diaminobenzene-1-acetylamino-8-hydroxy-B 7-8 red 4-sulfonic acid naphthalene-3,6-disulfonic acid 13-diaminobenzene-I 43'-sulfophenyl) -3- A 6 yellow 4-sulfonic acid methyl-pyrazolone-5 1,3-diaminobenzene- 1- (2 ', 5'-dichloro-4'- A 6 yellow 4-sulfonic acid sulfophenyl) -3-methyl pyrazolone-5 1,3-diaminobenzene- l (5' , 7'-Disulfonaphthyl A 6 yellow 4-sulfonic acid -2 '-) - 3-methyl pyrazolone-5 1,3-diaminobenzene-143'-sulfophenylS3- B 6 yellow 4-sulfonic acid methyl-5-aminopyrazole 1,4-diaminobenzene - 2-Amino-8-hydroxy- A 4-4.5 Red 3-sulfonic acid naphthalene
6-sulfonic acid 1,4-diaminobenzene

   2-Acetylamino-5-hydroxy-A 6-7 scarlet 3-sulfonic acid naphthalene-7-sulfonic acid 1,4-diaminobenzene-1-acetylamino-5-hydroxy-B 6-7 red 3-sulfonic acid naphthalene-7-sulfonic acid Example 3
27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid sodium are dissolved in 150 parts of water, mixed with 25 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine and kept at 50-55 ° C The methanesulfinic acid formed is blunted with a total of 34 parts by volume of 160 / ciger soda solution, stirred to pH 6-7. After a short time, the acylation is complete, the pH is 6 and no longer changes.



   30 parts of sodium bicarbonate are then added and the diazo suspension of 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulfonic acid in 200 parts of water is added dropwise at 20 ° C. over the course of 15 minutes. The orange-colored reactive dye of the formula which is formed immediately
EMI8.1
 is completely separated after stirring for one hour by adding 80 parts of sodium chloride, filtered off, washed with dilute sodium chloride solution and dried at 35 C in a vacuum. It dyes cellulose materials in reddish orange tones with very good wet fastness properties and good chlorine resistance using the above-mentioned processes.



   If, in this example, instead of 25 parts by weight of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine, equivalent amounts of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine are used, an orange reactive dye is obtained, whose coloring behavior corresponds to the reaction product of the
Bis-methylsulfonylderivates corresponds.



   In an analogous manner, acylation of the in
Column 2 of the following table listed aminonaphtholsulfonic acids with 2,4-bis-methylsulfonyl-6-methyl-pyrimi dine and coupling of the acylamino-naphtholsulfonic acids with the diazo components mentioned in column 1 orange to red reactive dyes.



  Diazo component aminonaphthol shade on sulfonic acid cotton 2-aminonaphthalene- 2-ethylamino-5-orange 1,7-disulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene- 2- (p-hydroxyethyl orange 1,7-disulfonic acid amino) -5-hydroxy naphthalene-7 sulfonic acid 2-aminonaphthalene- 2-amino-5-hydroxy- orange 1,7-disulfonic acid naphthalene- 7 sulfonic acid 2-aminonaphthalene- 2-amino-5-hydroxy- orange 1,7-disulfonic acid naphthalene-1,7 disulfonic acid 2-aminonaphthalene- 2-amino-8-hydroxy- scarlet 1,7-disulfonic acid naphthalene-6 sulfonic acid 2- Aminonaphthalene-2-amino-8-hydroxy-scarlet 1,7-disulfonic acid naphthalene
3,6-disulfonic acid 2-aminonaphthalene-2-methylamino-5-orange
1,5-disulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene-2-ethylamino-5-orange Id-disulfonic acid hydroxynaphthalene
7-sulfonic acid diazo component <RTI

    ID = 8.7> Aminunaphthol- color shade on sulphurous cotton 2-aminonaphthalene- 2- (ss-hydroxyethyl-orange 15-disulfonic acid amino) -5-hydroxy naphthalene-7-sulfonic acid 2-aminonaphthalene- 2-amino-5-hydroxy-orange 1 , 5-disulfonic acid naphthalene-7 sulfonic acid 2-aminonaphthalene-2-amino-5-hydroxy-orange 1,5-disulfonic acid naphthalene-1,7 disulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet 1, 5-disulfonic acid naphthalene-6 sulfonic acid 2-aminonaphthalene- 2-amino-8-hydroxy- scarlet 1,5-disulfonic acid naphthalene-3,6 disulfonic acid 2-aminonaphthalene- 2-amino-5-hydroxy- orange 1,5,7-trisulfonic acid naphthalene- 7 sulfonic acid 2-aminonaphthalene-2-methylamino-5-orange 1,5,7-trisulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet

   1,5,7-trisulfonic acid naphthalene-6-sulfonic acid 2-aminobenzene-2-methylamino-5-orange sulfonic acid hydroxynaphthalene-7 sulfonic acid 2-aminobenzene-2- (ss-hydroxyethyl-orange sulfonic acid amino) -5-hydroxy naphthalene-7 sulfonic acid 2-aminobenzene-2-amino-8-hydroxy-scarlet sulfonic acid naphthalene-6 sulfonic acid 2-aminobenzene-2-amino-8-hydroxy-scarlet sulfonic acid naphthalene-3,6 disulfonic acid 2-aminobenzene-2-amino-5-hydroxy - Orange sulfonic acid naphthalene-1,7 disulfonic acid 2-aminonaphthalene- l-amino-8-hydroxy- blue
1-sulphonic acid naphthalene-3,6-thrown disulphonic acid red 2-aminonaphthalene- 1-amino-8-hydroxy-blue 1 -sulphonic acid naphthalene-4,6-thrown disulphonic acid red 2-aminonaphthalene- l-amino-8-hydroxy-blue
1,5-disulfonic acid naphthalene-3,6-pricked

   disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue
1,5-disulfonic acid naphthalene-4,6-tipped disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue Id-disulfonic acid naphthalene-6-tipped sulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue
1,7-disulfonic acid naphthalene-3,6- tinged disulfonic acid red 2-aminonaphthalene- 1-amino-8-hydroxy-blue
1,7-disulfonic acid naphthalene-4,6-tinged disulfonic acid red
2-aminonaphthalene-1-amino-8-hydroxy blue
1,7-disulfonic acid naphthalene-6- tipped sulfonic acid red diamkt, rllpc> nente aminonaphthol color on sulfonic acid cotton 2-aminonaphthalene- l-amino-8-hydroxy- blue 1,5,7-trisulfonic acid naphthalene-6-

   pithy sulfonic acid red l-amino4-chlorobenzene- 1-amino-8-hydroxy-bluuzol-2-sulfonic acid naphthalene-3,6- pungent disulfonic acid red l-amino-2-methoxy- 1-amino-8-hydroxy- blue benzene- 5-sulfonic acid, 3,6-naphthalene disulfonic acid, red, 1-amino-benzene-2-1-amino-8-hydroxy-blue carboxylic acid, 4-sulfonic acid, 3,6-naphthalene-3,6- disulfonic acid, red, I-amino-4-acetyl-1 -Amino-8-hydroxy- violet aminobenzene-2-sulfone- naphthalene-3,6 acid disulfonic acid l-amino4-acetyl- 1-amino-8-hydroxy- blue aminobenzene-2-sulfone- naphthalene, 6-prick acid disulfonic acid red Example 4
The procedure is as indicated in Example 2, but the diazotized,

   intermediate product containing reactive groups in a soda-alkaline medium instead of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid with 40 parts of the sodium salt of l-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid and isolated the formed dye of the formula
EMI9.1
 in the manner indicated in Example 2. The water-soluble dye dyes cellulose materials by the steaming or thermosetting process (at 140 ° C.) in white-etchable, wet, rubbing and lightfast bluish red shades.



  Example 5
If you proceed according to the instructions in Example 1, but not the intermediate dye obtained with the
Diazo compound from 17.5 parts of 2-aminobenzenesulfonic acid but with the diazo compound from 20.8 parts of 3-Chlorani lin-6-sulfonic acid in the presence of 12 parts of soda in a
The final pH of 7 is coupled, a reactive dye of the formula is obtained
EMI9.2
 with the cellulose materials from a long liquor at 40 "C or according to one of the padding or printing processes customary for reactive dyes with soda as an acid-binding agent in wet-fast, brilliant red tones can be dyed or printed.



   In an analogous manner, the coupling components listed in the table below give valuable reactive dyes by acylating their amino group with 2-methylsulfonyl4-chloro-6-methyl-pyrimidine and coupling the dye intermediates with the specified diazo components, with which cellulose materials in the shades listed - preferably in Presence of soda - can be colored or printed:

  : Diazo component coupling component coupling color pH l-amino-4-methoxy- 1-amino-8-hydroxy- 7-8 violet benzene-6-sulfonic acid naphthalene-3,6 disulfonic acid l-amino4-methoxy- 1 -amino-8- hydroxy- 7-8 redbenzene-6-sulfonic acid naphthalene4,6- tinged disulfonic acid violet l-amino-4-methoxy- 2-amino-5-hydroxy- 7 scarlet benzene-6-sulfonic acid naphthalene-1,7 disulfonic acid l-amino- 5-chloro-ben- 2-amino-5-hydroxy-7 orange zol-2-sulfonic acid naphthalene-1,7 disulfonic acid 1-aminobenzene-2-amino-5-hydroxy-7 orange
3-sulfonic acid naphthalene-1,7 disulfonic acid
1-aminobenzene-2-amino-5-hydroxy-7 orange
4-sulfonic acid naphthalene-1,7 disulfonic acid
1-aminobenzene-2-amino-8-hydroxy-7-8 scarlet
4-sulfonic acid <RTI

    ID = 9.24> naphthalene-3,6-disulfonic acid
4-aminobenzoic acid- I-amino-8-hydroxy- 7-8 red (p-sulfonaphthalene-3,6 ethyltamide disulfonic acid diazo component coupling component coupling color pH l-amino-4-sulfo- 1-amino-8-hydroxy- 7-8 Violet acetylamino-benzene-naphthalene-3,66-sulfonic acid disulfonic acid l-amino-3-sulfo- 2-amino-5-hydroxy- 7 Orange acetylamino-benzene-naphthalene-1,76-sulfonic acid disulfonic acid l-amino- 4-sulfo- 2-amino-5-hydroxy- 7 scarlet acetylamino-benzene naphthalene-1,7 disulfonic acid l-aminobenzene-2,4- 1- (2'-methyl-3'- 6 yellow disulfonic acid amino-5'- sulfophenyl)
3-methyl-pyrazolon- (5) 2-amino-naphthalene- 1- (2'-methyl-3'- 6 yellow 4,8-disulfonic acid amino-5'-sulfophenyl)
3-methyl-pyrazolone- (5) example

   6th
If one proceeds according to the instructions in Example 2, but the intermediate dye product obtained from 1,3-diaminobenzene-6-sulfonic acid and 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine after diazotization at 10 ° C. and pH 7.5 Coupling 6.5 with the solution of 40.5 parts of the disodium salt of 2-sulfoacetylamino-5-hydroxynaphthalene-7-sulfonic acid gives a reactive dye of the formula
EMI10.1
 the cellulose materials after the usual application process with soda as an acid-binding agent in real orange tones.



  Example 7
30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 300 parts of water, heated to 60-65 ° C. and 20 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine are added. Over the course of one hour, 40 parts of 150 / above sodium carbonate solution are added so that the pH is between 6-7.5 The acylation product partially precipitates out.



   A freshly prepared diazonium salt solution of 13.6 parts of p-aminobenzylsulfonic acid is added dropwise at 0-5 ° C. to the suspension of the acylation product to which 12.5 parts of soda have been added. After stirring for five hours at ice bath temperature, the mixture is salted out with sodium chloride, suction filtered, washed with dilute sodium chloride solution and dried at 30 ° C. in a vacuum drying cabinet.

  The dye obtained corresponds to the formula
EMI10.2

If one proceeds as indicated above, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid, 30.4 parts of 2-amino-5-oxynaphthalene-1,7-disulfonic acid with 2-methylsulfonyl-4 -chlor-6-methyl-pyrimidine acylated and the coupling component containing reactive groups is coupled with diazotized p-aminobenzylsulfonic acid, a readily soluble reactive dye is obtained which dyes tissue containing cellulose fibers in brilliant reddish orange tones.



   Cotton or cellulose fabric is impregnated on a padder at 20-25 "C with a solution containing 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezed to a moisture content of 100% off and the moist fabric rolls up again.After standing for 24 hours at room temperature, the fabric is rinsed, soaped at the boil in the usual way and dried. A brilliant scarlet dyeing of good wet and light fastness is obtained.



   Cotton or cellulose fabric is impregnated on a padder at 20-25 "C with a solution containing 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezed to a moisture content of about 100 o / o and steams for 30 seconds at 103 "C. After rinsing, boiling soaps and drying, a brilliant scarlet coloration with good wet and light fastness is also obtained.



   Cotton fabric is impregnated with a solution at 20-25 ° C., containing 20 g of the dye obtainable according to this example, paragraph 1, and 0.5 g of a non-ionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g per liter of liquor Contains urea and 15 g sodium bicarbonate.



  The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100/0. After intermediate drying at 50-60 "C it becomes 10
Minutes to 140 ° C. and the resulting dye is rinsed thoroughly with hot water and treated with a boiling solution for 10 minutes containing 5 g of Marseille soap and 2 g of soda per liter. After rinsing and drying, a strong one is obtained scarlet color with good wet and light fastness.



   If cellulose fabric is printed with a printing paste containing 30 g of the dye described in this example, paragraph 1, 100 g of urea, 300 g of water, 500 g of alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of soda and contains 10 g of the sodium salt of nitrobenzenesulfonic acid and that with water
1 kilogram was filled, then net between drying and then in a suitable steamer for 30 seconds
103-115 "C, a strong, scarlet dyeing with good fastness properties is obtained after rinsing and boiling soaps.



   100 parts of wool are placed in a bath at 40 "C, which is dissolved in 5000 parts of water, 1.5 parts of the dye described in this example, paragraph 1, and 6 parts of 300 / Die acetic acid and 0.5 part of a polyoxyethylene hydroxyl-containing stearylamine derivative The dyebath is brought to the boil in 30 minutes, then it is dyed at the boil for one hour. After rinsing and drying, a brilliant scarlet dyeing that is washable, millfast and lightfast is obtained.



  Example 8
In the solution of 36.5 parts of the sodium salt of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts
Water are added with good stirring at 50-60 "C 29 parts 2, bis-methylsulfonyl-5chloro-6methyl-pyrimidine and stirred with constant blunting of the hydrochloric acid released to pH 6-7 until no free amino group can be detected The intermediate dye product obtained in this way is, after dilution with 600 parts of water and addition of 12 parts of soda, coupled at 5-10 ° C. with 17.5 parts of diazotized 2-aminobenzenesulfonic acid dissolved in 200 parts of water.

  The dye of the formula which is formed at a final pH of approx. 7
EMI11.1
 is salted out with 100 parts of table salt, suctioned off, washed and dried at 30-40 "C in a vacuum. The dye forms shiny red needles that are in
Easily dissolve water with red paint.



   If fabric made of cotton or regenerated cellulose is dyed or printed with this dye by one of the processes described in Example 1, then clear blue-tinged red dyeings and prints of good water are obtained; Rub and light fastness.



   The following procedure gives equally good results:
50 grams of cotton rope are dyed in 1 liter of a dye liquor containing 1.5 g of the above dye by increasing the temperature from 20 ° C. to about 80 ° C. within 30 minutes, adding a total of 50 g of table salt in several portions , then add 20 g of soda and treat for 60 minutes at this temperature.

  After rinsing, boiling soap and drying, a bluish red dyeing of good wet, rub and lightfastness is obtained
The following table shows the other colors
Dyestuffs listed, which from the also listed dia zo components, coupling components and with the amino group in the latter linkable reactive components analogous to the information in Example 8 - or by reacting the corresponding aminoazo dyes with the reactive components - are built up and by one of the processes described above Cellulosic materials can be dyed or printed:
Abbreviations for the reactive components:

  :
A = 2-methylsulfonyl-4,5-dichloro-6-methyl-pyrimidine B = 2,4-bis-methylsulfonyl-chloro-6-methyl-pyrimidine
Diazo component Coupling component Reactive color component l-aminobenzene-2- 1-amino-8-hydroxy- B red sulfonic acid naphthalene-3,6 disulfonic acid
1-aminobenzene- 13'-aminobenzoyl- A red
2-sulfonic acid amino> 8hydroxynaphthalene-3,6 disulfonic acid
Aminobenzene 143'-aminobenzoyl- B red amino8hydroxynaphthalene-3,6 disulfonic acid l-amino-2-carboxy-1-amino-8-hydroxy- A red benzene-sulfonic acid naphthalene-3.6-disulfonic acid l-amino4methylben-1-amino- & ydroxy - A

   Red zol-2-sulfonic acid naphthalene-3,6 disulfonic acid I-amino-3acetylamino- 1-amino-8-hydroxy- B red benzene-6-sulfonic acid naphthalene-3,6 disulfonic acid diazo component coupling component reactive shade component l-amino-3 - (2 '- [4 "- 1-Amino-8-hydroxy- A red sulfophenylamino] 4'-naphthalene-3,6chlorotriazine-1', 3 ', 5'-yl-disulfonic acid 6') - aminobenzene-6- sulfonic acid l-aminobenzene-2-sulfone- 2-amino-5-hydroxy- A orange acid naphthalene-7 sulfonic acid 1-amino-3- (2'- 2-amino-5-hydroxy- A orange [4 "-sulfophenyl- naphthalene-7 amino] -4'-methyl-sulfonic acid aminotriazine-1 ', 3', 5'-yl-6 ') -amino-benzene-6-sulfonic acid 1-aminobenzene-2-methylamino-5-A Orange

   2-sulfonic acid hydroxy-naphthalene-7 sulfonic acid l-amino4-acetyl- 2-methylamino-5- A scarlet amino-6-sulfonic acid hydroxy-naphthalene-7 sulfonic acid l-amino-4-acetyl- 2-amino-5-hydroxy- A scarlet amino-6-sulfonic acid naphthalene-7 sulfonic acid Example 9
In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 100 parts of water, 24.0 parts of 2-methylsulfonyl-4,5-dichloro-6-methyl-pyrimidine are added with thorough stirring and at 60- 65 "C with constant blunting of the hydrochloric acid released to pH 7-8 until a sample gives a clear, yellowish red color when diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid.

  After adding ice, the resulting intermediate dye is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then with a solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula
EMI12.1
 takes place, which is salted out, filtered off with suction, washed and dried at 30-40 "C in a vacuum. The dye dissolves easily in water with a red color and gives clear bluish red dyeings and prints on cellulose materials according to one of the processes described above.



  The following table lists the color shades and the pH of the coupling medium of dyes which are prepared analogously to the information in Example 9 from a diazo component containing a further, preferably acylatable amino group, from a coupling component and from a reactive component that can be linked to the diazo component will. For dyeing and printing cellulosic materials with the dyes in the table, the above-mentioned methods can be used.



   Abbreviations for the reactive components as in table for Example 8 Diazo component Coupling component Reactive pH of the color component Coupling medium 1,3-diaminoben- 2-aminonaphthalene-A 4-5 orange zene-4-sulfonic acid 5,7-disulfonic acid 1 , 3-diaminoben- 2-aminonaphthalene-A 4-5 orange zol-4-sulfonic acid 3,6-disulfonic acid 1,3-diaminoben- 2-aminonaphthalene-B 4-5 orange zol-4-sulfonic acid 6-sulfonic acid 1,3-diaminob - 2-N-Methylamino-8- A 4-5 Orange zol4-sulfonic acid hydroxynaphthalene
6-sulfonic acid diazo component coupling component reactive pH of the color component coupling medium 1,3-diaminobenzene 143 ', 5'-dichloro-1', A 7-8 red 4-sulfonic acid 2¯thiazole-4'-carbon- amido) -8-hydroxy naphthalene-3,6 disulfonic acid 1,3-diaminobenzene- 1- (2 ', 4'-dihydroxy- B 7-8 red 4-sulfonic acid triazin-1', 3 ', 5', - yl

   6'-aminof8-hydroxynaphthalene-3,6 disulfonic acid 1,3-diaminobenzene-1- (3 ', 5'-dichloro-l'. A 7-8 red 4-sulfonic acid 2'-thiazole-4'-carbon amido) X8-hydroxynaphthalene-3,6-disulfonic acid 1,3-diaminobenzene-2-hydroxynaphthalene-A 8 scarlet 4-sulfonic acid 3,6-disulfonic acid 1,3-diaminobenzene-I-acetylamino-8- B 7-8 red 4-sulfonic acid hydroxynaphthalene
3,6-disulfonic acid 1,3-diaminobenzene- I- (3'-sulfophenyl) -3- A 6 yellow 4-sulfonic acid methylpyrazolone-5 1,3-diaminobenzene- 1- (2 ', 5'-dichloro-4' - A 6 yellow 4-sulfonic acid sulfophenyl) -3-methyl pyrazolone-5 1,3-diaminobenzene- 1- (5 ', 7'-disulfo- A 6 yellow 4-sulfonic acid naphthyl-2'-) -3-methyl- pyrazolone-5 1,3-diaminobenzene-1 (3'-sulfophenyl) -3- B 6 yellow 4-sulfonic acid methyl-5-aminopyrazole 1,4-diaminobenzene- <RTI

    ID = 13.9> 2-Amino.8-hydroxy- A 4-4.5 red 3-sulfonic acid naphthalene-6-sulfonic acid 1,4-diaminobenzene-2-acetylamino-5- A 6-7 scarlet 3-sulfonic acid hydroxynaphthalene-7 sulfonic acid 1 , 4-Diaminobenzene- I-Acetylamino-5- B 6-7 Red 3-sulfonic acid hydroxynaphthalene-7 sulfonic acid Example 10
27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid sodium are dissolved in 150 parts of water, 29 parts of 2,4-bis-methylsulfonyl-5-chloro-6-methyl-pyrimidine are added and 55 "C with constant blunting of the methanesulfinic acid formed with a total of 34 parts by volume of 160 / above soda solution to pH 6-7. After a short time, the acylation is complete, the pH is 6 and does not change any more.



   30 parts of sodium bicarbonate are then added and the diazo suspension of 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulfonic acid in 200 parts of water is added dropwise at 20 ° C. over the course of 15 minutes. The orange-colored reactive dye of the formula which is formed immediately
EMI13.1
 is completely separated after stirring for one hour by adding 80 parts of sodium chloride, filtered off, washed with dilute sodium chloride solution and dried in vacuo at 35 ° C. It dyes cellulose materials in reddish orange shades of very good wet fastness and good chlorine resistance according to the above processes.



   If in this example, instead of 29 parts by weight of 2,4-bis-methylsulfonyl-5-chloro-6-methyl-pyrimidine, equivalent amounts of 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine are used, an orange color is obtained Reactive dye whose coloring behavior corresponds to the reaction product of the bis-methylsulfonyl derivative.



   In an analogous manner, acylation of the aminonaphtholsulfonic acids listed in column 2 of the table below with 2, SBis-methylsulfonyl-5-chlorosmethylpyrimidine or 2-methylsulfonyl-4,5-dichloro-6-methyl-pyrimidine also gives the acylaminonaphtholsulfonic acids formed the diazo components mentioned in column 1 orange to red reactive dyes.



  Diazo component aminonaphthol shade on sulfonic acid cotton 2-aminonaphthalene- 2-ethylamino-5-orange 1,7-disulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene- 2- (ss-hydroxyethyl-orange 1,7-disulfonic acid amino) -5-hydroxy naphthalene-7-sulfonic acid 2-aminonaphthalene-2-amino-5-hydroxy-orange 1,7-disulfonic acid naphthalene
7-sulfonic acid 2-aminonaphthalene-2-amino-5-hydroxy-orange 1,7-disulfonic acid naphthalene I, 7-disulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet 1,7-disulfonic acid naphthalene
6-sulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet fever 1,7-disulfonic acid naphthalene
3,6-disulfonic acid 2-aminonaphthalene-2-methylamino-5-orange 1,5-disulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene-2-ethylamino-5-orange 1,5-disulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene- <RTI

    ID = 14.3> 2- (ss-hydroxyethyl-orange 1,5-disulfonic acid amino) -5-hydroxy-naphthalene-7-sulfonic acid 2-aminonaphthalene-2-amino-5-hydroxy-orange 1,5-disulfonic acid naphthalene
7-sulfonic acid 2-aminonaphthalene-2-amino5-hydroxy-orange 1,5-disulfonic acid naphthalene
1,7-disulfonic acid 2-aminonaphthalene-2-amino8-hydroxy-scarlet fever 1,5-disulfonic acid naphthalene
6-sulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet fever 1,5-disulfonic acid naphthalene
3,6-disulfonic acid 2-aminonaphthalene-2-amino-5-hydroxy-orange 1,5,7-trisulfonic acid naphthalene
7-sulfonic acid 2-aminonaphthalene-2-methylamino-5-orange 1,5,7-trisulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminonaphthalene-2-amino-8-hydroxy-scarlet 1,5,7-trisulfonic acid naphthalene sulfonic acid 2-aminobenzene-2-methylamino-5-orange

   sulfonic acid hydroxynaphthalene
7-sulfonic acid 2-aminobenzene- 2- (ss-hydroxyethyl- orange sulfonic acid amino) -5-hydroxy naphthalene-7 sulfonic acid 2-aminobenzene-2-amino8-hydroxy-scarlet sulfonic acid naphthalene
6-sulfonic acid 2-aminobenzene-2-amino8-hydroxy-scarlet sulfonic acid naphthalene
3,6-disulfonic acid 2-aminobenzene- 2-amino5-hydroxy-orange sulfonic acid naphthalene I, 7-disulfonic acid di.lzocomponent ammonaphthoi- color on sulfonic acid cotton 2-aminonaphthalene- I-amino-8-hydroxyblue1-sulfonic acid naphthalene-cast
3,6-disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1-sulfonic acid naphthalene-tinged
4,6-disulfonic acid red 2-aminonaphthalene

   1-amino-8-hydroxy-blue 1,5-disulfonic acid naphthalene-tinged
3,6-disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue Id-disulfonic acid naphthalene-pricked
4,6-disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1,5-disulfonic acid naphthalene-tinged
6-sulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1,7-disulfonic acid naphthalene-tinged
3,6-disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1,7-disulfonic acid naphthalene-tinged
4,6-disulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1,7-disulfonic acid naphthalene-tinged
6-sulfonic acid red 2-aminonaphthalene-1-amino-8-hydroxy-blue 1,5,7-trisulfonic acid naphthalene-pricked
6-sulfonic acid red 1-amino-4-chlorobenzo-1-amino-8-hydroxy-bluuzol-2-sulfonic acid naphthalene-pricked
3,6-disulfonic acid red <RTI

    ID = 14.18> l-Amino-2-methoxy-1-amino-8-hydroxy-bluebenzene-5-sulfonic acid naphthalene-pricked
3,6-disulfonic acid red 1-amino-benzene-2-1-amino-8-hydroxy-blue-carboxylic acid-4-sul- naphthalene-spicy acid 3,6-disulfonic acid red l-amino-4-acetyl-1-amino- 8-hydroxy violet aminobenzene-2-sulfon naphthalic acid 3,6-disulfonic acid 1-amino-4-acetyl-1-amino-8-hydroxy-blue-aminobenzene-2-sulfon-naphthalene-acidic acid 4,6-disulfonic acid red Example 11
The procedure is as indicated in Example 9, but the diazotized,

   intermediate product containing reactive groups in a soda-alkaline medium instead of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene-3'6-disulfonic acid with 40 parts of the sodium salt of 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid and isolates the resulting Dye of the formula
EMI14.1
 in the manner indicated in Example 9. The water-soluble dye dyes cellulose materials by the steaming or thermosetting process (at 140 ° C.) in white-etchable, wet, rubbing and lightfast bluish red shades.



  Example 12
If you proceed according to the instructions in Example 8, but the dye intermediate obtained is not with the diazo compound from 17.5 parts of 2-aminobenzenesulfonic acid but with the diazo compound from 20.8 parts of 3-chloroaniline-6-sulfonic acid in the presence of 12 parts of soda in a The final pH of 7 is coupled, a reactive dye of the formula is obtained
EMI15.1
 with the cellulose materials from a long liquor at 40 "C or according to one of the padding or printing processes customary for reactive dyes with soda as an acid-binding agent in wet-fast, brilliant red tones can be dyed or printed.



   In an analogous manner, the coupling components listed in the table below give valuable reactive dyes by acylating their amino group with 2-methylsulfonyl-4,5-dichloro-6methyl-pyrimidine and coupling the dye intermediates with the indicated diazo components, with which cellulose materials in the listed shades - preferably in the presence of soda - can be colored or printed:

  : Diazo component Coupling component Coupling color pH l-amino4-methoxy- 1-amino-8-hydroxy- 7-8 violet benzene-6-sulfonic acid naphthalene-3,6 disulfonic acid l-amino4-methoxy- 1 -amino-8-hydroxy- 7-8 red benzene-6-sulfonic acid naphthalene46- tinged disulfonic acid violet l-amino-4-methoxy- 2-amino-5-hydroxy- 7 scarlet benzene-6-sulfonic acid naphthalene-1,7 disulfonic acid l-amino-5-chloro-ben- 2-Amino-5-hydroxy- 7 Orange zol-2-sulfonic acid naphthalene-1,7 disulfonic acid 1-aminobenzene- 2-amino-5-hydroxy- 7 Orange 3-sulfonic acid naphthalene-1,7 disulfonic acid 1 -aminobenzene 2- Amino-5-hydroxy-7 orange 4-sulfonic acid naphthalene-1,7 disulfonic acid 1-aminobenzene-2-amino-8-hydroxy-7-8 scarlet

   4-sulfonic acid naphthalene-3,6 disulfonic acid 4-aminobenzoe- I-amino-8-hydroxy- 7-8 red acidQp-sulfonaphthalene-3,6 ethyl) amide disulfonic acid l-amino4-sulfo- 1 -amino-8- hydroxy- 7-8 violet acetylamino-benzene-3,6zene-6-sulfonic acid disulfonic acid 1-amino-3-sulfo-2-amino-5-hydroxy- 7 orange acetylamino-benzene-naphthalene-1.7- 6-sulfonic acid disulfonic acid l-Amino4-sulfo-2-amino-5-hydroxy-7 scarlet acetylamino-benzene naphthalene-1,7 disulfonic acid l-aminobenzene-2,4-142'-methyl-3'- 6 yellow disulfonic acid amino-5'-sulfophenylS
3-methyl-pyrazolone- (5) 2-amino-naphthalene-1 (2'-methyl-3'- 6 yellow

   4,8-disulfonic acid amino-5'-sulfophenyl)
3-methyl-pyrazolone- (5) Example 13
If you proceed according to the instructions in Example 9, but the intermediate dye product obtained from 1,3-diaminobenzene-6-sulfonic acid and 2-methylsulfonyl4,5-dichloro-6-methyl-pyrimidine after diazotization at 10 "C and pH 7, Coupling 5 to 6.5 with the solution of 40.5 parts of the disodium salt of 2.Sulfoacetylamino-5-hydroxynaphthalene-7-sulfonic acid gives a reactive dye of the formula
EMI16.1
 of the cellulose materials according to the usual application methods with soda as acid-binding agent in true orange tones, Example 14
30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 300 parts of water, heated to 60-65 "C and 25 parts,

   2,4-bis-methylsulfonyl-5-chloro-6-methyl-pyrimidine was added. In the course of one hour, 40 parts of 150 / above soda solution are added so that the pH is between 6-7.5. The acylation product partially precipitates.



   A freshly prepared diazonium salt solution of 13.6 parts of p-aminobenzylsulfonic acid is added dropwise at 0-5 ° C. to the suspension of the acylation product mixed with 12.5 parts of soda dried at 30 "C in a vacuum drying cabinet.

  The dye obtained corresponds to the formula
EMI16.2

If the above procedure is followed, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid, 30.4 parts of 2-amino-5-oxynaphthalene-1,7-disulfonic acid with 2-methylsulfonyl-4 , Acylating 5-dichloro-6-methyl-pyrimidine and coupling the coupling component containing reactive groups with diazotized p-aminobenzylsulphonic acid, a readily soluble reactive dye is obtained which dyes tissue containing cellulose fibers in brilliant reddish orange tones.



   Cotton or cellulose fabric is impregnated on a padder at 20-25 "C with a solution containing 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezed to a moisture content of 100/0 and the moist fabric is rolled up again.After standing for 24 hours at room temperature, the fabric is rinsed, soaped at the boil in the usual way and dried to give a brilliant, scarlet dyeing of good wet and light fastness.



   Cotton or cellulose fabric is impregnated on a padder at 20-25 "C with a solution containing 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g of soda per liter of liquor, squeezed to a moisture content of 100% off and dampens for 30 seconds at 103 "C. After rinsing, boiling soaps and drying, a brilliant scarlet coloration with good wet and light fastness is also obtained.



   Cotton fabric is impregnated with a solution of 20-25 "C, the per liter of liquor 20 g of the dye available according to this example, paragraph 1, and 0.5 g of a nonionic wetting agent (z. B. a polyoxyethylene oleyl alcohol) and 150 g of urea and contains 15 grams of sodium bicarbonate.



  The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100/0. After intermediate drying at 50-60 "C, the mixture is heated to 140" C for 10 minutes and the resulting dye is rinsed thoroughly with hot water and boiled for 10 minutes with a solution containing 5 g of Marseille soap and 2 g of soda per liter. After rinsing and drying, a strong scarlet coloration with good wet and light fastness is obtained.



   If cellulose fabric is printed with a printing paste containing 30 g of the dye described in this example, paragraph 1, 100 g of urea, 300 g of water, 500 g of alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was made up to 1 kilogram with water, then dried in between and then steamed in a suitable steamer for 30 seconds at 103-115 "C, a strong scarlet color with good results after rinsing and boiling soaps Fastnesses.



   100 parts of wool are placed in a bath at 40 "C, which is dissolved in 5000 parts of water, 1.5 parts of the dye described in this example, paragraph 1, and 6 parts of 300 / above acetic acid and 0.5 parts of a polyoxyethylated, hydroxyl-containing stearylamine derivative The dyebath is brought to the boil in 30 minutes, then it is dyed at the boil for an hour.After rinsing and drying, a brilliant scarlet dyeing that is washable, millfast and lightfast is obtained.



  Example 15
In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 100 parts of water 50.1 parts by weight of 2,4,6-tris-phenylsulfonyl-triazine- (1,3,5) in Added aqueous-methanolic solution and stirred at 0-5 C with constant blunting of the acid released to pH 5-6 until a sample gives a clear, yellowish red color when diazotizing and coupling on 1-hydroxynaphthalene-4-sulfonic acid.

  After ice has been added, the resulting intermediate dye is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then with a solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula
EMI17.1
 takes place, which is salted out, filtered off with suction, washed and dried at 20-30 C in a vacuum. The dye dissolves in water with a red color and provides clear, bluish red dyeings and prints on cellulose materials
Fastnesses.



   In an analogous manner, dyes of the specified shades can be obtained from the combinations indicated in the table for Example 2.



  Example 16
If the dyes or dye precursors containing amino groups described in Examples 3-7, as indicated in Example 15, are condensed with 2,4,6-tris-phenylsulfonyl-triazineql, 3,5) and optionally further reacted analogously, then fixing dyes become obtained which give dyeings with excellent wet fastness properties.



  Example 17
If the dyes described in Examples 15-16, each with two phenylsulfonyl groups per triazine ring in a molar ratio of 1: 1, are reacted with colorless amino, hydroxyl or mercapto derivatives, for example N-methylaniline, aminobenzene, at 20-70 ° C. while blunting the acid released -3-sulfonic acid, aminobenzene4-sulfonic acid, aminobenzene-3-carboxylic acid, ethylamine, B-hydroxyethylamine, B, B¯dihydroxydiethylamine, N, N-dimethylhydrazine, methyl alcohol, ethyl alcohol, trichloroethyl alcohol, phenol, phenolsulfonic acid, methyl mercaptan, or so that only one phenylsulfonyl group remains per triazine ring, reactive dyes are also obtained which give dyeings with excellent wet and acid fastness properties.



   The 2,4,6-tris-phenylsulfonyl-triazine41,3,5) used as the active component is nylmefcapto-triazine- (1.3,5) by oxidation of the 2,4,6-tris-phenyl, for example by chlorine in aqueous -methanolic solution at -10 to +10 "C, accessible.



   Example 18
If in Examples 8-14 the 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine is replaced by the 2-methylsulfonyl4-chloro-5 -bromo-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-5-bromo-methylpyrimidine replaced, so dyes with similarly good ones
Properties preserved.



   Example 19
If in Examples 1-7 the 2-methylsulfonyl-4-chloro-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-6-methylpyrimidine by the 2-methylsulfonyl4-chloro-6-phenylpyrimidine or the 2,4 -Bis-methylsulfonyl-6-phenylpyrimidine replaced, dyes with similarly good properties are obtained.



   Example 20
If in Examples 8-14 the 2-methylsulfonyl-4,5-dichloromethylpyrimidine or the 2,4-bis-methylsulfonyl-5chloro-6-methylpyrimidine is replaced by the 2-methylsulfonyl4,5-dichloropyrimidine or the 2,4 -Bis-methylsulfonyl-5-chloropyrimidine replaced, dyes with similarly good properties are obtained.



  Example 21
If, in Examples 1-7, the 2-methylsulfonyl-4-chloro-6methylpyrimidine is replaced by the 2-carboxymethylsulfonyl-4-chloro-6methylpyrimidine, then similar dyes with better solubility properties are obtained.



   PATENT CLAIM 1
Process for the preparation of azo reactive dyes of the formula
EMI17.2
 where F is the radical of an azo dye, X is -SO2-, -arylene or -alkylene-, t is the number 0 or 1, R is hydrogen or a substituent, arylene is an arylene radical, alkylene is a lower alkylene radical and A is the radical of a 6-membered heterocyclic ring , which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring and which may have fused aromatic rings, and where m is a number from 1 to 4, characterized in that a diazo is coupled with a coupling component and the components so chooses that at least one of these at least one group
EMI17.3
 having.



      PATENT CLAIM 11
Use of azo reactive dyes obtained by the process according to claim 1 for the production of metallized azo reactive dyes, characterized in that metal complexing dyes of the formula I are treated with metal donating agents.

 

   SUBCLAIMS
1. The method according to claim I, characterized in that such diazo and / or coupling components are used in which the radical A of the grouping A- (X) tN (R) - is one of the following radicals: 2-carboxymethylsulfonyl- 4-pyrimidinyl, 2-methylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-bis-methylsulfonyl-6- pyrimidinyl, 2,4-bis-methylsulfonvl-5-sulfamidvl-Dvrimidinvl.



     2-methylsulfonyl-4-pyrimidinyl-2-phenylsulfonyl-4-pyrimidinyl, 2-M ethyl sulfonyl4-m ethyld-pyrimidinyl, 2-methylsulfonyl4-methyl-5-chloro-6-pyrimidinyl,

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



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. EMI17.1 takes place, which is salted out, filtered off with suction, washed and dried at 20-30 C in a vacuum. The dye dissolves in water with a red color and provides clear, bluish red dyeings and prints on cellulose materials Fastnesses. In an analogous manner, dyes of the specified shades can be obtained from the combinations indicated in the table for Example 2. Example 16 If the dyes or dye precursors containing amino groups described in Examples 3-7, as indicated in Example 15, are condensed with 2,4,6-tris-phenylsulfonyl-triazineql, 3,5) and optionally further reacted analogously, then fixing dyes become obtained which give dyeings with excellent wet fastness properties. Example 17 If the dyes described in Examples 15-16, each with two phenylsulfonyl groups per triazine ring in a molar ratio of 1: 1, are reacted with colorless amino, hydroxyl or mercapto derivatives, for example N-methylaniline, aminobenzene, at 20-70 ° C. while blunting the acid released -3-sulfonic acid, aminobenzene4-sulfonic acid, aminobenzene-3-carboxylic acid, ethylamine, B-hydroxyethylamine, B, B¯dihydroxydiethylamine, N, N-dimethylhydrazine, methyl alcohol, ethyl alcohol, trichloroethyl alcohol, phenol, phenolsulfonic acid, methyl mercaptan, or so that only one phenylsulfonyl group remains per triazine ring, reactive dyes are also obtained which give dyeings with excellent wet and acid fastness properties. The 2,4,6-tris-phenylsulfonyl-triazine41,3,5) used as the active component is nylmefcapto-triazine- (1.3,5) by oxidation of the 2,4,6-tris-phenyl, for example by chlorine in aqueous -methanolic solution at -10 to +10 "C, accessible. Example 18 If in Examples 8-14 the 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-5-chloro-6-methylpyrimidine is replaced by the 2-methylsulfonyl4-chloro-5 -bromo-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-5-bromo-methylpyrimidine replaced, so dyes with similarly good ones Properties preserved. Example 19 If in Examples 1-7 the 2-methylsulfonyl-4-chloro-6-methylpyrimidine or the 2,4-bis-methylsulfonyl-6-methylpyrimidine by the 2-methylsulfonyl4-chloro-6-phenylpyrimidine or the 2,4 -Bis-methylsulfonyl-6-phenylpyrimidine replaced, dyes with similarly good properties are obtained. Example 20 If in Examples 8-14 the 2-methylsulfonyl-4,5-dichloromethylpyrimidine or the 2,4-bis-methylsulfonyl-5chloro-6-methylpyrimidine is replaced by the 2-methylsulfonyl4,5-dichloropyrimidine or the 2,4 -Bis-methylsulfonyl-5-chloropyrimidine replaced, dyes with similarly good properties are obtained. Example 21 If, in Examples 1-7, the 2-methylsulfonyl-4-chloro-6methylpyrimidine is replaced by the 2-carboxymethylsulfonyl-4-chloro-6methylpyrimidine, then similar dyes with better solubility properties are obtained. PATENT CLAIM 1 Process for the preparation of azo reactive dyes of the formula EMI17.2 where F is the radical of an azo dye, X is -SO2-, -arylene or -alkylene-, t is the number 0 or 1, R is hydrogen or a substituent, arylene is an arylene radical, alkylene is a lower alkylene radical and A is the radical of a 6-membered heterocyclic ring , which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring and which may have fused aromatic rings, and where m is a number from 1 to 4, characterized in that a diazo is coupled with a coupling component and the components so chooses that at least one of these at least one group EMI17.3 having. PATENT CLAIM 11 Use of azo reactive dyes obtained by the process according to claim 1 for the production of metallized azo reactive dyes, characterized in that metal complexing dyes of the formula I are treated with metal donating agents. SUBCLAIMS 1. The method according to claim I, characterized in that such diazo and / or coupling components are used in which the radical A of the grouping A- (X) tN (R) - is one of the following radicals: 2-carboxymethylsulfonyl- 4-pyrimidinyl, 2-methylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-6-pyrimidinyl, 2-phenylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-bis-methylsulfonyl-6- pyrimidinyl, 2,4-bis-methylsulfonvl-5-sulfamidvl-Dvrimidinvl. 2-methylsulfonyl-4-pyrimidinyl-2-phenylsulfonyl-4-pyrimidinyl, 2-M ethyl sulfonyl4-m ethyld-pyrimidinyl, 2-methylsulfonyl4-methyl-5-chloro-6-pyrimidinyl, 2-carboxy-methylsulfonyl-4-methyl-5-chloro-6-pyrimidinyl, 2-methyl-sulfonyl4-methyl-5-nitro-6-pyrimidinyl, 2-methylsulfonyl-5-cyano-4-pyrimidinyl, 2-methylsulfonyl- 4-earboxy-6-pyrimidinyl, 2-ethylsulfonyl-5-sulfo-4-pyrimidinyl, 2-methylsulfonyl-5-chloro-4-pyrimidinyl, 2-methylsulfonyl-5-bromo-4-pyrimidinyl, 2-methylsulfonyl-5- chloro-6-methyl-4-pyrimidinyl '2-M ethylsulfonyl-5-bromo-6-methyl-4-pyrimidinyl, 2-methylsulfonyl-5-chloro-6-chloromethyl-4-pyrimidinyl' 2-benzenesulfonyl-5-chloro4 -pyrimidinyl, 2-benzenesulfonyl-5-chloro-6-methyl-4-pyrimidinyl, 2-benzenesulfonyl-5-bromo-6-methyl-4-pyrimidinyl, 2-methylsulfonyl-5-chloro-6-carboxymethyl-4-pyrimidinyl or 2 -Carboxymethylsulfonyl-5-chloro-6-methyl-4-pyrimidinyl, 3- (4'-Nitrophenyl) -sulfonyl-6-pyridazinyl, 5-chloro-6-methylsulfonyl-4-pyridazinyl, 3-phenylsulfonyl-6-pyridazinyl, 3-methylisulfonyl-4-methyl-6-pyridazinyl, 2,5-bis -methylsulfonyl-6-pyrazinyl. 2. The method according to claim 1, characterized in that such diazo and / or coupling components are used in which the radical A of the grouping A- (X), - N (R) - 2-methylsulfonyl-4-quinazolyl. 3. The method according to claim 1, characterized in that such diazo and / or coupling components are used in which the radical A of the grouping A- (X), - N (R) - is one of the following radicals: I -Methylsulfonyl- 3-triazinyl-, 1-methylsulfonyl-3- (3'-sulfophenylamino) -5-triazinyl- 'I -methylsulfonyl-3- (2'-hydroxyethylamino) -5-triazinyl, 1-methylsulfonyl-3-amino-5- triazinyl-, I -methylsulfonyl-3-methoxy-5-triazinyl-, I -methylsulfonyl-3- (2'-benzthiazolyl) -thio-5-triazinyl-, 1- (4'-methylphenylsulfonyl) -3-phenyl-5 -triazinyl-, 1-phenylsulfonyl-3-methoxy-5-triazinyl, 1,3-bis-phenylsulfonyl-5-triazinyl, I-methylsulfonyl-3-phenoxy-5-triazinyl, 1-methylsulfonyl-3-phenyl-5- triazinyl. 4. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up EMI18.1 wherein B is an optionally substituted aromatic radical and D is an optionally substituted aromatic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and Ri is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number 1 or 2. 5. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up in which .B is an optionally substituted aromatic radical and D is an optionally substituted carbocyclic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and Rl is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number or 2. 6. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up, wherein B is an optionally substituted aromatic radical and D is an optionally substituted heterocyclic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and Rl is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number 1 or 2. 7. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up, wherein B is an optionally substituted carbocyclic radical, in particular a carbocyclic diazo component of the benzene or naphthalene series, and D is an optionally substituted carbocyclic radical of an enolic or phenolic coupling component, where B and D e.g. B. can have azo groups as substituents and Rl represents a substituent or preferably hydrogen, Q means a direct bond or a group -SO2 and m 'represents the number 1 or 2. 8. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up in which B is an optionally substituted carbocyclic radical, in particular a carbocyclic diazo component of the benzene or naphthalene series, and D is an optionally substituted aromatic radical of an enolic or phenolic coupling component, where B and D e.g. B. can have azo groups as substituents and R 1 is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number 1 or 2. 9. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up in which B is an optionally substituted carbocyclic radical, in particular a carbocyclic diazo component of the benzene or naphthalene series, and D is an optionally substituted heterocyclic radical of an enolic or phenolic coupling component, where B and D e.g. B. can have azo groups as substituents and R1 is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2 and m 'is the number 1 or 2. 10. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up, wherein B is an optionally substituted heterocyclic radical and D is an optionally substituted heterocyclic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and R1 for a Sub substituents or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number 1 or 2. 11. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up, wherein B is an optionally substituted heterocyclic radical and D is an optionally substituted carbocyclic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and R, is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number I or 2. 12. The method according to claim 1, characterized in that azo reactive dyes of the formula III are built up, wherein B is an optionally substituted heterocyclic radical and D is an optionally substituted aromatic radical of an enolic or phenolic coupling component, where B and D are z. B. can have azo groups as substituents and R 1 is a substituent or preferably hydrogen, Q is a direct bond or a group -SO2- and m 'is the number 1 or 2. 13. The method according to claim I, characterized in that such diazo and / or coupling components are used which have at least one sulfonic acid group. 14. The method according to claim 1, characterized in that such a diazo and / or coupling component is used which has at least one group EMI19.1 wherein A represents the remainder of a pyrimidine ring containing at least one reactive sulfonyl substituent attached to a carbon atom of the heterocyclic ring. 15. The method according to claim 1, characterized in that such a diazo and / or coupling component is used which has at least one group EMI19.2 wherein Al represents the residue of a pyrimidine ring which contains at least one reactive sulfonyl substituent bonded to a carbon atom of the heterocyclic ring. 16. The method according to claim 1, characterized in that a diazo and / or coupling component is used which has at least one group EMI19.3 in which one of the radicals R3 or R4 is the group -SO2M, in which M is an alkyl, aralkyl or aryl radical, the other of the radicals R3 or R4 is also a group -SO2M or hydrogen, alkyl, aralkyl, aryl, - SOjH, -COOH, -COO-alkyl, -Cl, -Br or -CN and R5 stands for hydrogen or a substituent. 17. The method according to claim 1, characterized in that a diazo and / or coupling component is used which has at least one group EMI19.4 in which R'l is a lower alkyl radical containing 1 to 3 carbon atoms, one of the radicals R3 or R4 is the group -SO2M, in which M is an alkyl, aralkyl or aryl radical, the other of the radicals R3 or R4 is also a group -SO2M or hydrogen, alkyl, aralkyl, aryl, -SO3H, -COOH, -COO-alkyl, -Cl, -Br or -CN and R5 stands for hydrogen or a substituent. 18. The method according to claim 1, characterized in that a diazo and / or coupling component is used which has at least one group EMI19.5 wherein X is an amino group, R'5 is a halogen atom, R'4 is hydrogen or an optionally substituted alkyl substituent and Ro is a carbocyclic substituent. 19. The method according to claim 1, characterized in that a diazo and / or coupling component is used which has at least one group EMI19.6 where X is an amino group, R'5 is a halogen atom, R'4 is hydrogen or an optionally substituted alkyl substituent and Ro is a heterocyclic substituent. 20. The method according to claim I, characterized in that a diazo and / or coupling component is used which has at least one group EMI19.7 where X is an amino group, R's is a halogen atom, R'4 is hydrogen or an optionally substituted alkyl substituent and Ro is an aliphatic substituent. 21. The method according to claim 1, characterized in that such diazo and / or coupling components are used which have at least one 2-methylsulfonyl-5-chloro-6-methylpyrimidinylamino group.