CH371268A - Compass with a compass socket rotatably mounted in a holder - Google Patents

Description

  

  Process for dyeing or printing hydroxyl-containing textile materials with fluorine-containing reactive dyes The present invention relates to a process for dyeing or printing hydroxyl-containing textile materials, which is characterized in that one or more reactive dyes of the formula are applied to these textile materials in any order
EMI0001.0011
         auroringt;

      In this formula, D denotes the radical of an organic dye which does not contain the anthraquinone skeleton, R denotes hydrogen or a lower alkyl group, R denotes an amino group which can have mono-bonded substituents, an optionally etherified oxy

          optionally etherified @ thio group or an optionally substituted hydrocarbon radical, Q is an alkylene, aralkylene, arylene, -CO- or -S02- group, which is directly linked to a ring carbon of the dye D,

   m 1 or 2, n the number @l 0 or 1 and F a fluorine substituent.



  In the dyes of the formula (I) the -N (R) - group is linked directly to a carbon atom of the triazine ring.

   On the other hand, the -N (R) group is either directly (in the case of n = 0) or (in the case of n - 1) via one of the mentioned bridging members to a ring carbon of the dye D bound.



  Examples of substituents R in the triazine ring are: primary, secondary or tertiary amino groups, such as -NH2, -NHCH:

  s, -NHC2H5, -N (CH8) 2, -N (CjH5) 2, -NHCH2CH20H, -N (CH-, CH20H) 2, Morpholino-, Piperidina-, Hydrazino-, N-Methykhy- drazino-, N- Phenyl'amino-, N- (2-, 3- or 4-sulfophenyl) -amino-, N-toluidino-, N- (2,3- or 2,4- or 2,

  5- or 4,5-disulfophenyl) -amino-, -OH, -0C113, -OC2H5, phenyloxy-, sulfophenyloxy-, -SH, --SCHs, -SC2H5, phenyl-, oxyphenyl-, sulfophenylE-, methyl-, TricWor- methyl, 2-, 3- or 4-chlorophenyl radicals.



  Dyes in which R 1 stands for an optionally substituted alkoxy group or a mono- or disubstituted amino group, the substituents by definition being linked to the amino group by simple bonds, and <B> R </B> stands for hydrogen,

            belong to a preferred group of the dyes which can be used according to the invention.



  The new dyes can do the rest
EMI0002.0001
    have once or twice in the molecule. Suitable triazine compounds
EMI0002.0005
         are for example:

         2-fluoro-4-amino-6-triazinyl, 2-fluoro-4-methylamino-6-triazinyl, 2-fluoro-4-phenylamino-6-triazinyl, 2-fluoro-4- (o-, m- or p -sulfophenyl) -amino-6-triazinyl, 2-fluoro-4- (2,4- or 2,5- or 3,5- or 4,5-disulfophenyl) -amino-6-triazinyl, 2-fluoro-4 -dimethylamino-6-triazinyl, 2-fluoro-4-methoxy-6-triazinyl, 2-fluoro-4- (f-methoxy-ethoxy) -6-triazinyl, 2-fluoro-4-hydrazino-6-triazinyl,

            2-fluoro-4-phenoxy-6 "triazinyl, 2-fluoro-4- (2-, 3- or 4-sulfophenoxy) -6-triazinyl, 2-fluoro-4-benzyloxy-6-triazinyl, 2-fluoro- 4 - (/ 3-oxyethoxy) -6-triazinyl, 2-fluoro-4- (ss-oxyäthyhnercapto) -6-triazinyl, 2-fluoro-4-methyl-6-triazinyl, 2-fluoro-4-phenyl-6 -triazinyl, 2-fluoro-4- (2'-, 3'- or 4'-sulfophenyl) -6-triazinyl, 2-fluoro-4-diethylamino-6-triazinyl, 2-fluoro-4-0-bis- oxäthylamino) -6-triazinyl,

            2-fluoro-4-methylmercapto-6-triazinyl, 2-fluoro-4-phenylmercapto-6-triazinyl, 2-fluoro-4- (2'-, 3'- or 4'-chlorophenylmercapto) -6-triazinyl or 2 -Fluoro-4- (2'-, 3'- or 4'.sulfophenylmercapto) -6-triazinyl, 2-fluoro-4- (N-methyl-N-phenyl) -amino- 6-triazinyl, 2-fluoro- 4- (o-, m- or p-methylphenyl) -amino-6-triazinyl, 2-fluoro-4-benzylamino-6-triazinyl,

            2-fluoro-4- (o, o'-dimethylphenyl) -amino-6-triazinyl, 2-fluoro-4-n-butyl-amino-6-triazinyl, 2-fluoro-4- (N-methyl-N- / 3-cyanoethyl) -amino-6-triazinyl, 2-fluoro-4-N, N-bis-cyanoethyl, amino-6-triazinyl. Among the bonding possibilities of the radical (11) to D, the direct bonding of the -N (R) groups to a carbon atom of a carbocyclic ring of D is preferred.

   Suitable bridge members of this type and of the other type, including the -N (R) group, are, for example (A stands for the remainder of the formula 11I): -NH-A, -N (CH ;;) - A, -N ( C2H5) -A, -N (C; lH7) -A, -CONH-A, -SO2> NH-A, -CON (CH ;;) - A, SO "N (CH; 3) -A and the corresponding N-ethyl- and N-propylamides, -CH_-NH-A, -CH_-N (CH :;

  ) -A, -CH_-N (C2Hr,) - A, -CH -CONH-A,
EMI0002.0077
    The new dyes are non-anthraquinoid and can, for. 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 phihalocyanine dyes, oxazro, dioxazine,

          Triphen.ylmethane, nitro and azomethine series belong to. Of these, mono- and disazo dyes as well as copper and nickel phthalocyanine dyes are of outstanding interest. In the context of these dye classes, among others, dyes with the following general composition are particularly valuable:

        1. Azo dyes
EMI0003.0002
    where B and E represent aromatic, carboeyclic or heterocyclic radicals, in particular B the radical of a carbocyclic diazo component of the benzene or naphthalene series, and E the radical of an English or phenolic coupling component, e.g.

   B. a 5-pyrazolone, an acetoacetic arylamide, an oxynaphthalene or an aminonaphthalene; B and E can also have any substituents customary in azo dyes, including further azo groups;

      R 'stands for a —CH3 group or, preferably, for a hydrogen atom, F for a fluorine substituent. and R1 'for a preferably mono- or disubstituted amino group in which the substituents are linked to the amino group by a single bond,

       or Rj 'represents an optionally substituted alkoxy group.



  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 Benzol¯azo-l-phenyl-5-pyrazolone series, the Benztil 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 are also preferred here. 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-hydroxy-o'-carboxy, o-carboxy-o'-anrino and o-hydroxy-o'-amino-azo groups. Particularly outstanding types of monoazo dyes of the type that can be used at the end of the day are illustrated by the following formulas:

       
EMI0003.0094
  
EMI0003.0095
  
EMI0003.0096
    
EMI0004.0001
  
EMI0004.0002
  
EMI0004.0003
  
EMI0004.0004
         } (o) means the o position of the respective indicated radicals in the aryl nucleus, and A stands for the remainder of the formula
EMI0004.0010
    wherein R'1 and F have the meanings already given;

       Acyl stands for an acyl radical; the cores drawn in dashed lenses indicate that they are present or may be absent.

      2. Phthalocyanine dyes
EMI0004.0023
      In this formula, Pc stands for the radical of a nickel or copper phthalocyanine, L and L 'for substituents, in particular sulfonic acid groups, r for an integer from 0 to 2, q for the number 0 or 1, R' for a methyl group or preferably Hydrogen, R ', for a preferably mono- or disubstituted amino group,

      in which the substituents are linked to the amino group by single bonds, or for an optionally substituted alkoxy group and F for a fluorine substituent. The phthalocyanine residue Pc preferably has 1 to 2 sulfonic acid and / or 1 to 2 sulfonic acid amide groups, such as -SO,) as further substituents

  NH- "SO2NH-alkyl, -SO2N (alkyl) 2. And -SO2NH (aryl) groups, where alkyh stands for alkyl radicals with 1 to 3 carbon atoms.



  The above compilation of a selection of suitable azo and azaporphin dyes and fluorine-substituted triazine rings does not represent a restriction of the general formulas, neither in view of the preparative possibilities for the preparation of such dyes in the context of general formula (I) nor in terms of the valuable application technology properties of these products.

   The new dyes can also have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, sulfonamide and carbonamide groups, which can be further substituted on the amide nitrogen atom, sulfonic acid ester and carboxylic acid ester groups, alkyl, aralkyl and aryl, alkylamino,

          Aralkyl, imino, aryl, amino, acylamino, nitro, cyano, halogen, such as Cl, Br and F, hydroxy, alkoxy, thioether, azo groups and the like.

   The dyes can also contain other fixable groups, such as other mono- or dihalotriazinylamino-, other mono-, di- or trihalopyrimidinylamino-, 2,3-dihaloquinoxaline-6-carbonyl- or -6-sulfonylamino-, 1,4-dihalogen -phthal- azin-6-carbonyl- or @ -6-sulfonylamino-,

          2-halogen or 2-alkylsulfonyl or 2-arylsulfonylbenzthiazole-5-carbonyl or -5-sulfonylamino, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfonic acid, oxa-alkylamide and oxalkylsulfino groups, sulfofluoramido groups, , Acryloylamino,

          Have halogenoylamino groups or other reactive groups.



  The new dyes of formula (I) are z. B. obtained by converting at least one group of the formula into organic, non-anthraquinoid dyes or dye precursors
EMI0005.0107
    introduces.

   In the case of dye precursors, these can then be converted into the desired end dyes, in particular by diazotization and / or coupling and / or condensation reactions;

   in the formula (111a) denotes R, an amino group which may have single bonded substituents, an optionally etherified oxy group, optionally etherified thio group or an optionally substituted hydrocarbon radical, F a fluorine substituent,

      R is hydrogen or a lower alkyl group, Q is an alkylene, aralkylene, arylene, —CO or —SO2 group which is directly bonded to a ring carbon of the dye D, and n is the number 0 or 1.



  The introduction of the radical (111) via an amino or amide group - (Q) "- N (R) -, wherein Q, <B> 'R </B> and n have the meaning already given, in dyes or dye precursors generally takes place in such a way that non-anthraquinoid dyes or dye precursors which are bonded to a ring carbon have at least one group - (Q) "- N (R) H in which Q, R and n have the meaning given, have,

   with compounds of the general formula
EMI0005.0152
    where R and F have the meaning given and X stands for an anionically removable radical, and, in the case of dye precursors, converts these in a suitable manner into the desired final dyes.

   Among the reactive substituents X which can be split off as anionic radicals, the fluorine substituent is of preferred interest. Further radicals that can be removed from anionic form on a case-by-case basis are, for example, quaternary ammonium groups such as -N # (CH; s) 3 and -N- "(C, Hs): 3.



  According to a further method of preparation, the new dyes can be obtained in such a way that non-anthraquinoid dyes of the formula
EMI0005.0177
    where D, Q, R, F, X and n have the meanings already given, condensed with ammonia or with amino, oxy or thio compounds which have a reactive hydrogen atom, with elimination of HX.

      Triazine compounds suitable for the reactions mentioned are, for example, 2,4,6-sym.-trifluorotriazine, 2,4-difluoro-6-amino-sym.-triazine, 2,4-difluoro-6-methylamino-sym .-triazine, 2,4-difluoro-6-ethylamino-sym.-triazine, 2,4-difluoro-6-phenylamino-sym.-triazine, 2,4-difluoro-6- (2'- or 4'- or 6'-sulfophenyl) - amino-sym.-triazine, 2,4-difluoro-6- (2,4- or 3,4- or 2,5- or 4,

  5-disulfophenyl) -amino-sym.-triazine, 2,6-difluoro-4-dimethylamino-triazine, 2,6-difluoro-4-methoxy-triazine, 2,6-difluoro-4 - (/ j- methoxy-ethoxy) -triazine, 2, δ-difluoro-4-hydrazino-triazine, 2,6-difluoro-4-phenoxy-triazine, 2,6-difluoro-4- (2-, 3- or 4-sulfophenoxy ) -triazine, 2,6-difluoro-4-benzyloxy-triazine, 2,6-difluoro-4- (f-oxyethoxy) -trnazine, 2,6-difluoro-4- / 3-oxyethylmercapto-triazine, 2,6 -Difluoro-4-methyl-triazine,

            2,6-difluoro-4-phe, nyl-triazine, 2,6-difluoro-4- (2-, 3- or 4-sulfophenyl) -triazine, 2,6-difluoro-4-diethylmercapto-triazine, 2, 6-Difluoro-4 - (@ - bis-oxyäthylamino) -triazine, 2,6-Difluoro-4-methylmercapto-triazine, 2,6-Difluoro-4-phenylmercapto-triazine, 2,6-Difluoro-4- (2 -, 3- or 4-chloro-phenylmercapto) - triazine or 2,6-difluoro-4- (2-, 3- or 4-sul'fo-phenylmercapto) -triazine, 2,

  4-Difluoro-6- (N-methyl-N-phenyl) -amino- sym.-triazine, 2,4-difluoro-6- (o-, m- or p-methyl-phenyl) -amino-sym.- triazine, 2,4-difluoro-6- (o, o'-dimethyl-phenyl) -amino-sym.-triazine, 2,4-difluoro-6-n-butyl-amino-sym.-triazine, 2,4 -Difluoro-6-be.nzylamino-, sym.-triazine, 2,4-difluoro-6- (N-methyl-N- (3-cyanoethyl) -amino-sym.-triazine, 2,4 -Difluor-6-N,

  N-bis-cyanoethyl-amino-sym.-triazine. In the condensation reaction with the amino or amide group-containing non-anthraquinoid dyes or dye precursors, these triazine derivatives react with elimination of the radical X.



  Said and other fluorotriazine compounds that can be used can generally be obtained by reacting the corresponding chlorine or bromine compounds with alkali metal fluorides, eg.

   B. with potassium fluoride, NaHF, KSO, 2F, SOF; i, AgFz, or by implementing appropriate OH compounds with SF4, COF_ "COCIF or cyanofluoride or by heating corresponding diazonium tetrafluoborates.



  The reaction of the dyes or dye precursors containing amino or amide groups with heterocyclic compounds of the formula (XII) and the reaction of dyes of the formula (XIII) with amino, oxy or thio compounds can be organic, depending on the type of starting compounds used , organic-aqueous or aqueous medium at temperatures from -10 to 100 C,

   preferably from 0 to 50 ° C. in the presence of alkaline condensing agents, such as aqueous alkali carbonate or alkali hydroxide solutions.



       Dye intermediates obtained can be converted into the desired end dyes in a customary manner. This method is of preferred interest for the preparation of azo dyes by, for example, a diazo and / or coupling component, which has a reactive amine-o- or amide group of the type indicated, first with the reactive component (XII)

      condensed and the intermediate product obtained is subsequently converted into an azo dye by diazotization and / or coupling and / or condensation. In this, further conversion reactions can be carried out afterwards, as are customary in azo dyes, eg. B. acylation, condensation, reduction and metallization reactions.



  Also in the representation of other dyes, especially those of the phthalocyanine series; the condensation of a reactive component (XII) can first be carried out with an intermediate product, e.g. B. with m-phenylenediamine or a m-phenylenediaminesulfonic acid, and the reaction product obtained then further condensed with a copper or nickel phthalocyanine sulfonic acid halide to form a reactive phthalocyanine dye.



  Another variant of the preparation of the new dyes of the formula (1), which can be used in some cases, is that in non-anthraquinoid dyes or, in particular, dye intermediates, the at least one group of the formula
EMI0006.0106
    in which R, R ,, Q and n have the meaning given and Z is an anionically removable radical, with the exception of a fluorine substituent, have,

   Z is exchanged for a fluorine substituent and, if dye precursors are used, these are then converted into the desired final dyes. The replacement of one or more anionically removable substituents Z, z. B. of Cl or Br atoms against fluorine substituents can be accomplished, for example, in the manner already explained.



  The non-anthraquinoid dyes obtainable according to the various procedures described can, as already mentioned for some cases, be subjected to other reactions customary for dyes, for example by treating metallizable dyes with metal donating agents, in particular with chromium, cobalt, copper or nickel salts , treated, dyes that have reducible groups, especially nitro groups, reduced, dyes,

   which have acylatable groups, in particular acylatable amino groups, acylated, or by treating dyes subsequently with sulfonating agents, such as with chlorosulfonic acid, oleum or SO,.; in chlorinated hydrocarbons to introduce (further) sulfonic acid groups into the products.

   The last-mentioned process is sometimes of particular importance in the series of phthalocyanine dyes. Dyes of the formula (I) containing sulfonic acid and / or carboxylic acid groups are preferred in the context of this invention.



  Depending on the number of reactive -NHR groups in the dyestuff radical or in the dyestuff precursors which are suitable for the conversion reaction, one or more groupings of the formula (1I) can be incorporated into the dyestuffs. In the majority of cases, the number m = 4 is not exceeded, but dyes, especially those with a higher molecular structure, with more than 4, z. B. to 8, groupings of the formula (1) to synthesize.



  If the dyes contain metal complex-forming groups, they can be released 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 conventional conversion reactions, such as diazotization, coupling, acylation and condensation reactions.



  In the reaction of amino group-containing non-anthraquinoid dyes with reactive components of the formula (XII), groups of particularly preferred dyes are obtained if the amino group-containing starting dyes on which the dyes of the formulas (1V) to (XI) are used, ie instead of the
EMI0007.0003
    or the -N (R ') - A group have the grouping -N (R') - H.



  In the production of phthalocyanine dyes, a diaminoaryl compound monocondensed with the reactive component (X11) can first be produced and this can then condense with preferably copper or nickel phthalocyanine sulfonic acid halides, with other amino compounds such as ammonia, aliphatic amino compounds, simultaneously or subsequently and / or aromatic amino compounds can also be used.

   In this way, phthalocyanine, preferably copper or nickel phthalocyanine-sulfonamide dyes are obtained which contain a certain proportion of sulfonarylamide groups which carry the reactive group and also a certain proportion of non-reactive sulfonamide groups and / or free sulfonic acid groups. You can also use copper or nickel phthalocyanine, sulfonic acid (aminoaryl) amides,

      which may additionally have optionally N-substituted sulfonamide groups of a different type and free sulfonic acid groups, condense on the amino group of the aminoaryl radical with reactive components (XII) to form the new dyes (1).



  From French patent specification No. 1 <B> 400833 </B> Reactive dyes have become known in which, unlike the present dyes, a halotriazinyl radical is bonded to a dye radical via a urea bridge.

   The reactive components required and specified for the preparation, namely 2-ethylamino-4-N-chloroformyl-N-ethylamino-6-flour, s-triazine and 2-methylamino-4-N-chloroformyl-N-ethylamino-6-flour s-triazine, have not been characterized and it is likely that they will be extremely difficult and expensive to manufacture, if at all.



  In French Patent No. 1 <B> 372905 </B> Reactive dyes are indicated which can contain a fluorine atom as a mobile atom. It is said that the mobility of the fluorine atom is due to the simultaneous presence of an SO2 group. Fluorotriazinyl radicals are neither explicitly nor implicitly mentioned as reactive radicals.



  The present fluorine-containing dyestuffs differ from the known reactive dyestuffs with mobile chlorine and / or bromine atoms in that they have better color yield and, in particular, higher reactivity. a. brings significant economic benefits.



  The new dyes used according to the invention are extremely valuable products which are suitable for a wide variety of applications. You will find fiction according to use for dyeing hydroxyl-containing textile materials,

          in particular of textile materials made from native and regenerated cellulose. Thanks to the reactive fluorine substituents in the triazine ring, the products are particularly suitable as reactive dyes for dyeing cellulosic textile materials according to the techniques that have recently become known. 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 carbonate, Cl; ZC-COONa, can be added.

   Further auxiliaries can be added to the solution, but they 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 auxiliaries, such as urea, or indifferent thickeners, such as oil-water emulsions, tranganth, starch, alginate or methyl cellulose.



  The solutions or pastes produced in this way are applied to the textile material to be dyed, for example by padding in a padder (short liquor) or by printing, and then heated to an elevated temperature, preferably 40 to 150 ° C., for some time. The heating can be carried out in the hot flue, in the steaming apparatus, on heated rollers or by placing in heated concentrated salt baths, either on its own or in any order.



  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 colored can also be treated 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 as 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 increasing the temperature to 20 to 60 ° C., with the partial addition of Salt, e.g. B. sodium sulfate, and then alkali, for example sodium phosphates, sodium carbonate, NaOH or KOH.



       This is where the chemical reaction occurs between the dye and the fiber. After chemical fixation has taken place, the material to be dyed is rinsed with hot water and then soaped, with non-fixed residues of the dye being removed. The dyeings obtained are excellent, particularly those which are fast to water and light.



  In the so-called block cold dwell 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 20 hours at room temperature. In this process, a stronger alkali is used than in the dyeing process described above from a long liquor.



  For printing, a printing paste composed of the dye solution, a thickening agent such as sodium alginate, and a compound which reacts alkaline or releases alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium hydrogen carbonate,

          used and the printed textile material ge rinsed and soaped.



  If the dyes contain groups which form metal complexes, the dyeings and prints can be treated with metal donating agents such as copper salts, e.g. B. copper sulfate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, can be improved in their fastness properties.



  In the following examples, parts stand for parts by weight, unless otherwise stated. Parts by weight and volume relate to each other like kg and liter.



   <I> Example 1 </I> a) To the solution of 34.7 parts of 2-aminonaphthalene-4,8-disulfonic acid sodium 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 at 0 to for half an hour 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, are added <B> 150 </B> Parts of water are added and the coupling is completed by blunting the mixture to pH 3 to 5. The resulting aminoazo dye is salted out, filtered off with suction, washed ge and then again in 1400 parts of water and <B> 100 </B> Parts of acetone dissolved at pH 7 with the addition of sodium hydroxide solution.

   22 parts of 2,4-difluoro-6- / 3-methoxyethoxy-triazine are added dropwise to this solution at 0 ° to 10 ° C. and a pH of 6 to 6.5 is maintained with 2N sodium hydroxide solution. When the reaction is complete, the resulting dye becomes the likely formula
EMI0008.0048
    salted out with sodium chloride and the product obtained in this way filtered off with suction and washed with NaCl solution and dried in vacuo at 50.degree.



  b) If you print cellulose fabric with a printing paste that contains 15 grams of the dye, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg thickening) and 20 g soda and which is based on W asseT 1 kilogram has been filled, dries, steams for 2 minutes at 100 C, rinsed with hot water and soaped at the boil,

    this gives a strong, reddish-yellow print of good fastness to washing and light. <I> Example 2 </I> a) 0.1 mol of the copper complex compound of the formula
EMI0008.0076
    (produced according to the information in German patent no.

   1 117 235 by coupling dianotated 1-Amirto-8- (benzene-sulfonyloxy) -naphthalene-disulfonic acid- (3.6) in a soda-alkaline medium with the equivalent amount of 2-acetylamino-5-hydroxynaphthalene-disulfonic acid- (4.8 ),

      Conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysis of the acetyl and benzenesulfonyl groups is dissolved in 2500 parts by volume of water at 60 to 65 C at pH 6 to 6.5 and at 10 to 20 C with 0.11 mol 2.4 -Difluoro-6-methylmercaptotriazine added. During the condensation, a pH of 6 to 7 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.



  b) 100 parts by weight of a cotton fabric are padded at room temperature with an aqueous solution containing 2% of the dye, 15 g / 1 sodium hydrogen carbonate and 150 g / 1 urea, dried, heated to 140 ° C. for 30 seconds, then rinsed and soaped at the boil . The fabric is dyed wetfast in very clear blue tones.



   <I> Example 3 </I> a) 46 parts of the monoazo dye obtained analogously to the details in Example 1 by coupling dianotated 2-aminonaphthalene-4,8-disulphonic acid onto 3-methylaminotoluene are dissolved in 400 parts of water and 100 parts of acetone at 20.degree dissolved, 22 parts of 2,4-difluoro-6-methoxy-triazine were added while maintaining a pH of 6 to 7 using 2N soda solution;

   the condensation continues until a sample no longer shows any color change on acidification. The resulting dye has the likely formula
EMI0008.0129
      and is salted out, filtered off with suction, washed and dried at 30 ° C. in vacuo, b) cotton fabric is impregnated with a solution of 20 to 25 ° C., which contains 20 g of the above dye and 0, per liter of liquor

  Contains 5 g of a night-time wetting agent (e.g. a polyoxyethylene oleyl alcohol) as well as 15.0 g of urea and 15 g of sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of about 100%.

   After intermediate drying at 50 to 60 C, the mixture is heated for 30 seconds at 140 C and the resulting dye is rinsed thoroughly with hot water and treated at the boil for 20 minutes with a solution containing 5 g Marsedler soap and 2 g soda per liter. After rinsing and drying, a strong reddish yellow color of good wet,

   Rub and light fastness.



  The table below lists the diazo components, coupling components and the reactive components that can be linked to the amino group, from which dyes can be synthesized analogously to the information in Examples 1 and 2,

   the colors of which - obtained using one of the application methods described - are also listed in the table.
EMI0009.0052
  
    Abbreviations <SEP> for <SEP> the <SEP> reactive components:

    <SEP> A <SEP> = <SEP> 2,4a-difluoro-6-methoxy-triarzine
 <tb> B <SEP> - <SEP> 2,4-iDifluoro-6-methylmercaptotriazine
 <tb> <U> D </U> ia <U> zo </U> k <U> omp </U> onente <SEP> coupling <U> s </U> ko <U> mp </U> onente <SEP> reactive component <SEP> hue
 <tb> 2-aminonaphthalene-4,8-disulfonic acid <SEP> 1 <SEP> "Amino-2-methoxy-5-methylbenzene <SEP> A <SEP> yellow
 <tb> <SEP> <B> B </B>
 <tb> 1 <SEP> aminonaphthalene-3,6-disulfonic acid <SEP> 1-amino-3, methylbenzene <SEP> A <SEP>
 <tb> B
 <tb> 2 <SEP> aminonaphthalene-5,7-disulfonic acid <SEP> A <SEP>
 <tb> <SEP> <B> B </B> <SEP>
 <tb> 2-aminonaphthalene-6, & disulfonic acid <SEP> <SEP> A <SEP>
 <tb> <SEP> <SEP> <B> B </B> <SEP>
 <tb> 4-Aminoazobenzene, 3,4'-disulfonic acid <SEP> <SEP> A <SEP> brownish yellow
 <tb> 1-aminobenzene-4-sulfonic acid <SEP> - *
 <tb> 1-aminonaphthalene-6-sulfonic acid <SEP> <SEP> B <SEP>
 <tb> 243'-sulfo-4'-aminophenyl)

  -6-methyl- <SEP> <SEP> A <SEP> yellow
 <tb> benzthiazole-7-sulfonic acid
 <tb> 2-aminonaphthalene-4,8-disulfonic acid <SEP> 1-methylamino-3-methoxybenzene <SEP> B <SEP>
 <tb> 1-Amino-3-acetylaminobenzene <SEP> A <SEP>
 <tb> <b> s </B> <SEP> aniline <SEP> A <SEP> <I> Example 4 </I> a) In the solution of 36.5 parts of the sodium salt of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 200 parts of water at 0 to 10 C 22 parts of 2,4-difluoro-6- f-methoxyethoxy-triazine given and a pH of 5 with constant blunting of the acid released,

  Maintain 5 to 6. The reaction is followed by chromatography. The resulting solution of the intermediate dye product is added to 900 parts of water and, at a pH of 7 to 8 at 0 to 5 ° C., is coupled with 17.5 parts of diazotized 2-amnobenzenesulfonic acid dissolved in 200 parts of water. At a final pH of 6.5, common salt is salted out,

      abge with suction and washed with 15% saline solution. It is dried in vacuo at 30 to 40 ° C. The dye
EMI0009.0078
    forms red needles.



  b) If fabrics made of cotton or regenerated cellulose are dyed or printed with this dye by one of the methods described in Examples 1 to 3, clear bluish red dyeings and prints of good wet, rub and light fastness are obtained.



       Equally good results are obtained using the following procedure: 50 g of cotton rope are in <B> 1 </B> liter of dye liquor containing 1.5 g of the above dye, dyed by adding within 30 minutes:

          at 20 to 30 C add 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 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 derived from the diazo components, coupling components and reactive components linkable to the amino group in the latter analogous to the information in Example 4 - or by reacting the corresponding aminoazo dyes with the reactive components - to be built up and after

  can be dyed or printed on cellulose materials using one of the processes described above: Abbreviations for the reactive components as in the table for example 3.
EMI0010.0017
  
    Diazo component <SEP> coupling component <SEP> reactive component <SEP> hue
 <tb> 1, aminobenzene-2-sulfonic acid <SEP> 1-amino-8-hydroxynaphthalene <SEP>.
 <tb> 3,6-disulfonic acid <SEP> B <SEP> red
 <tb> aminobenzene <SEP> 1, (3'-aminobenzoylamino) -8-hydroxy naphthalene-3,6-disulfonic acid <SEP> A <SEP>
 <tb> <SEP> <SEP> B <SEP>
 <tb> 1-Amino-2-carboxybenzene-4-sulfonic acid <SEP> 1-amino-8-hydroxynaphthalene 3,

  6-disulfonic acid <SEP> A <SEP>
 <tb> 1-Amino-4-methylbenzene-2-sulfonic acid <SEP> <SEP> A <SEP>
 <tb> 1-Amino-3-acetyl-aminobenzene 6-sulfonic acid <SEP> <SEP> B <SEP>
 <tb> 1-Amino-3- (2 '- [4 "-sulfophenylaminol 4-chlorotriazine-1', 3 ', 5'-yl-6') aminabenzene..6-sulfonic acid <SEP> <SEP> A <SEP>
 <tb> 1-aminobenzene-2-sulfonic acid <SEP> 2-amino-5 <SEP> hydroxynaphthalene 7-sulfonic acid <SEP> A <SEP> orange
 <tb> 1, Amino-3- (2 '- [4 "-sulfophenylaminol 4'-methylaminotriazin-1', 3 ', 5'-yl-6')

    aminobenzene-6-sulfonic acid <SEP> <SEP> A <SEP>
 <tb> 1-aminobenzene-2-sulfonic acid <SEP> 2-methylamino-5-hydroxynaph @ thaiin 7-sulfonic acid <SEP> A <SEP>
 <tb> 1-Amino-4-acetylamino-6-sulfomic acid <SEP> <SEP> A <SEP> scarlet fever
 <tb> <SEP> 2-amino-5-hydroxynaphthalene 7-sulfonic acid <SEP> A <SEP> <I> Example 5 </I> In the solution of 21 parts of the sodium salt of 1,3-diaminoberrzene-6-sulfonic acid in <B> 100 </B> Parts of water are mixed with 22 parts of 2,

  4-Difluoro-6- / 3- methoxyethoxy-triazine and stirred at 0 to 10 C with constant blunting of the hydrofluoric acid released to pH 6 to 6.5. Until a sample of diazotizing and coupling to 1-hydroxynaphthaHn- 4- sulfonic acid gives a clear, yellowish red color.

      The resulting intermediate dye product is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid after addition of ice and then with a solution of 47 parts of the sodium salt of 1-Be.nzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula
EMI0010.0043
    takes place, which is salted out, sucked off,

          washed and dried at 30 to 40 C in a vacuum. The dye dissolves easily in water with a red color and, by 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, analogously to the information in Example 5, are made 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. The above-mentioned processes can be used to dye and print cellulose materials with the dyes in the table.



  Abbreviations for the reactive components as in the table for example 3.
EMI0011.0001
  
    Reactive- <SEP> PH <SEP> des
 <tb> diazo component <SEP> coupling component <SEP> component <SEP> coupling <SEP> hue
 <tb> mediums
 <tb> 1,3-diaminobenzene <SEP> 2-aminonaphthalene 4-sulfonic acid <SEP> 5,7-disulfonic acid <SEP> A <SEP> 4-5 <SEP> orange
 <tb> <SEP> 2-aminonaphthalene 3,6-disulfonic acid <SEP> A <SEP> 4-5
 <tb> 2-aminonaphthalene 6-sulfonic acid <SEP> B <SEP> 4-5
 <tb> <SEP> 2-hT-methylamino-8 hydroxynaphthalene 6-sulfonic acid <SEP> A <SEP> 4-5 <SEP> a
 <tb> <SEP> 1- (3 ', 5'-dichloro 1', 2'-thiazole-4 'carbonamido) -8 hydroxynaphthalene 3,6-disulfonic acid <SEP> A <SEP> 7-8 <SEP> red
 <tb> <SEP> 1- (2 ', 4'-dihydroxy triazin-1', 3 ', 5' yl-6'-amino) -8 hydroxynaphthalene 3,

  6-disulfonic acid <SEP> B <SEP> 7-8
 <tb> <SEP> 2-hydroxynaphthalene 3,6-disulfonic acid <SEP> A <SEP> 8 <SEP> scarlet fever
 <tb> <SEP> 1- (3'-sulfophenyl) 3-methyl-pyrazolone-5 <SEP> A <SEP> 6 <SEP> yellow
 <tb> <SEP> 1- (2 ', 5'-dichloro 4'-su <SEP> lfophenyl) -3 methyl-pyrazolon-5 <SEP> A <SEP> 6 <SEP> a
 <tb> <SEP> 1- (5 ', 7'-disulfonaphthyl-2') -3 methyl-pyrazolone-5 <SEP> A <SEP> 6
 <tb> <SEP> 1- (3'-sulfophenyl) 3-methyl-5-amino pyrazole <SEP> B <SEP> 6
 <tb> 1,4-diaminobenzene <SEP> 2-amino-8-hydroxy 3-sulfonic acid <SEP> naphthalene-6 sulfonic acid <SEP> A <SEP> 4-4.5 <SEP> red
 <tb> <SEP> 2-acetylamino-5 hydroxynaphthalene 7-sulfonic acid <SEP> A <SEP> 6-7 <SEP> scarlet fever
 <tb> <SEP> 1-acetylamino-5 hydroxynaphthalene 7-sulfonic acid <SEP> B <SEP> 6-7 <SEP> red <I> Example 6 </I> 51,

  6 parts of the by diazotizing 1-hyd, roxy-2- aminobenzene-4 @ sulfonic acid and coupling on 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper donor obtained dye of the formula
EMI0011.0013
      are dissolved in 1500 parts of water at pH 7. With thorough stirring, add 20 to 30 ° C.

  Part 2,4-difluoro-6-methoxy-triazine and blunt the released hydrofluoric acid with soda solution continuously to a pH of 6-6.5. When free amino groups can no longer be detected, the reactive dye formed is of the formula
EMI0012.0012
    carrion salted, pressed, washed and dried in vacuo at 30 to 40 ° C.

   Fabrics made from cellulose materials can be dyed or printed with this dye using one of the above-mentioned processes 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 shades 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 6.



  Abbreviations for the reactive components as in "Table for Example 3.
EMI0012.0027
  
    Aminoazo dye <SEP> complex-bound <SEP> reactive <SEP> hue
 <tb> heavy metal <SEP> component
 <tb> 1-Hydroxy-2-amine, benzene-4,6-disulfonic acid <SEP> <U> - </U>
 <tb> 2-Amino-5-hydroxynaphthalene-7-sulfonic acid <SEP> Cu <SEP> A <SEP> ruby
 <tb> 1-Hydroxy-2-aminobenzene-4 = sulfonic acid <SEP> - +
 <tb> 2-Ethylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP> Cu <SEP> A <SEP>
 <tb> 1-Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid
 <tb> 2-Amino-5-hydroxynaphthalene-7-sulfonic acid <SEP> Cu <SEP> A <SEP>
 <tb> <SEP> Cr <SEP> A <SEP> green.
 <tb> gray
 <tb> 1-Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid <SEP> -> <SEP> Co <SEP> B <SEP> rotst.
 <tb> l,

  Amino - $ - hydroxynaphthalene-4-sulfonic acid <SEP> black
 <tb> 1-Amino-2-hydroxy-5-methylsulfonylbe @ nzol <SEP> ->
 <tb> 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> Cu <SEP> A <SEP> purple
 <tb> <SEP> Co <SEP> A <SEP> gray
 <tb> <SEP> Cr <SEP> A <SEP> green.
 <tb> black
 <tb> 1-Amino-2-me, ethylbenzene-4-sulfonic acid <SEP>, <SEP> 1-amino 2-hydroxy-5-methylbenzene <SEP> -, <SEP> 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP> Cu <SEP> B <SEP> blue
 <tb>%> <SEP> Co <SEP> B <SEP> gray
 <tb> <SEP> Cr <SEP> A <SEP> green.
 <tb> black
 <tb> (1 <SEP> amino-2-chlorobenzene-4-sulfonic acid <SEP> -a <SEP> 1 <SEP> Hydroxy 2-aeetylaminobenzene), <SEP> saponified, <SEP> - <B> -> </B> <SEP> 1-amino 8-hydroxynaphthalene-3,6-disulfonic acid <SEP> Cu <SEP> A <SEP> navy blue
 <tb> (1-Aminoo-2-chlorobenzene-4-sulfonic acid <SEP> -> <SEP> 1-hydroxy 2-acetylamino-benzene),

    <SEP> saponified <SEP> -> <SEP> 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid <SEP> Co <SEP> A <SEP> gray
 <tb> 1-Amino-8-hydroxynaphthalene-4-sulfonic acid <SEP> <U>, </U>
 <tb> 1-Hydroxy-2; 6-diaminobenzene-4-sulfonic acid <SEP> <U> -a </U>
 <tb> 1,3-i-Dihydroxybenzene <SEP> Co <SEP> A <SEP> black
 <tb> 1-. Amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> E 1 <SEP> Hydroxy-2,6-diaminobenzene-4-sulfonic acid <SEP> <U> -. @ </U>
 <tb> 2-hydroxynaphthalene <SEP> Co <SEP> A <SEP>
 <tb> 1-Amino-8-hydroxynaphthalene-4-sulfonic acid <SEP> E-1-hydroxy-2,6-diaminobenzene-4-sulfonic acid <SEP> ->
 <tb> 3-methyl-pyrazolone- (5) <SEP> Co <SEP> A <SEP> <I> Example 7 </I> 96 parts (based on 100% goods)

   the copper phthalocyanine tetrasulfochloride freshly prepared in the usual manner by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or the isomeric, from 1-sulfobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid on copper phthalocyanine tetrasulfochloride built up well in the form of the moist washed suction cake suspended in 500 parts of water and 500 parts of ice, the solution of 50 parts 1,

  3-diaminobenzene 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 adding soda. The. The resulting condensation product is precipitated at pH 1 to 2 by adding sodium chloride, filtered off with suction, washed and then dissolved again in 100 parts of water until neutral.

   65 parts of 2,4-difluoro-6- / i-methoxyethoxy-triazine are added to the blue solution with vigorous stirring and the mixture is stirred at 0 ° to 10 ° C., continuously blunting with soda solution to pH 6, until free amino groups are no longer detectable . The reactive dye of the formula obtained in this way
EMI0013.0029
    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 shades of good wet, rub and lightfastness using one of the above-mentioned dyeing and printing processes.



  Instead of the 96 parts of copper phthalocyanine tetrasulfochloride - with otherwise the same procedure as in Example 7 - 87 parts (based on 100% strength goods) of the copper or nickel phthalocyanine trisulfochloride obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine in the form of the moist th, well-washed suction cake with ice water can be used;

   then likewise clear blue coloring reactive dyes are obtained.



  If you work as indicated in Example 7, but starting from 87 parts of Kupferphthalocyan.in-trisulfo- chloride and instead of 50 parts of the sodium salt of 1,3-diaminobenzene 90 parts of the sodium salt of 4,4'-diaminod'iphenyl 2,2'-disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulfonic acid is used, one obtains reactive dyes, wel che cellulose materials by one of the above-mentioned processes in wet,

       Dye clear blue tones that are fast to rub and light.



  If you start from 4 ', 4 ", 4"', 4 "" - tetraphenyl-Cu-phthalocyanine, after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with 2,4-difluoro-6- methoxy-triazine a reactive dye which dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.



   <I> Example 8 </I> 38.9 parts of the dye obtained from 6-nitro-2-diazo-1-hydroxybenzene-4-sulfonic acid and 2-hydroxynaphthalene by alkaline soda coupling are dissolved in 200 parts of water at pH 8 at a temperature of 70 to 80.degree touched.

   67.9 parts of the chromium complex compound of the azo dye of 4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3 are carried into this suspension , 6-disulfonic acid, the pH being kept between 7 and 9 by adding soda solution. After 20 minutes at 70 to 80 C a dark blue solution has formed.

   The paper chromatogram shows that a uniform mixed complex has been created. The Mischkom plex is acylated within one hour at 20 C and pH 6 to 7 with 25 parts of 2,4-difluoro-6- / 3-methoxyethoxy-triazine, 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.degree. A dark powder is obtained which dissolves in water with a blue-gray color.



       The pentasodium salt of the dye corresponds to the formula
EMI0014.0001
    Obtained substances 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.

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



  The output components given in the following table can also be used to produce valuable color
EMI0014.0016
  
    1 <SEP>: <SEP> 1-chromium complex <SEP> metal-free <SEP> dye <SEP> hue <SEP> on
 <tb> cotton
 <tb> 4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> - @ <SEP> 4-nitro-2-amino-1-hydroxybenzene <SEP> ->
 <tb> 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> 2-hydroxynaphthalene <SEP> black
 <tb> 4nitro-2-amino-1-hydroxybenzene <SEP> - @
 <tb> 2-hydroxynaphthalene-6-sulfonic acid <SEP>
 <tb> 4-nitro-2-amino-1-hydroxybenzene <SEP> - *
 <tb> 1, hydroxynaphthalene-4-sulfonic acid <SEP> navy blue
 <tb> 6-nitro-2-amino-1-hydroxybenzene 4-sulfonic acid <SEP> <B> -.> </B> <SEP> 2-hydroxynaphthalene <SEP> black
 <tb> <SEP> 4,

  Nitro-2-amino-1-hydroxybenzene <SEP> .-- *
 <tb> 1-acetylamino-7-hydroxynaphthalene <SEP>
 <tb> 6rNitro-1-amino-2-hydroxynaphthalene 4-sulfonic acid <SEP> - <B> -> </B> <SEP> 2-hydroxynaphthalene <SEP>
 <tb> 4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> -> <SEP> 4-nitro-2-amino-1-hydroxynaphthalene 1-amino-8-hydroxynaphthalene-4,6-diisulfonic acid <SEP> 6-sulfonic acid <SEP> - + <SEP> 2-hydroxynaphRhalin <SEP>
 <tb> 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> - @ <SEP> 4 - nitro-2-amino-1-hydroxybenzene
 <tb> 1-amino-8 <SEP> hydroxynaphthalene-3,6-disulfonic acid <SEP> 2-hydroxynaphthalene <SEP> blue-black
 <tb> <SEP> 4-nitro-2-amino-1-hydroxybenzene
 <tb> 2-hydroxynaphthalene-6-sulfonic acid <SEP>
 <tb> <b> </B> <SEP> 4-chlorine,

  2-amino-1-hydroxybenzene
 <tb> 2 <SEP> hydroxynaphthalene <SEP> navy blue
 <tb> <b> s </B> <SEP> 4-nitro-2-amino-1-hydroxybenzene <SEP> ->
 <tb> 1-acetylamino-8-hydroxynaphthalene 3,6-disulfonic acid <SEP> blue
 <tb> <SEP> 4-nitro-2-amino-1-hydroxybenzene <SEP> - @
 <tb> l, amino-8-hydroxynaphthalene 2,4-disulfonic acid <SEP> navy blue
 <tb> <b> </B> <SEP> 6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid <SEP> - * <SEP> 2-hydroxynaphthalene <SEP> blue tail
 <tb> <b> </B> <SEP> 2-aminobenzene-1-carboxylic acid, 5-sulfonic acid <SEP> -> <SEP> 1-phenyl-3-methyl 5-pyrazolone <SEP> gray-green
EMI0015.0001
  
    1 <SEP>:

    <SEP> 1-chromium complex <SEP> metal-free <SEP> dye <SEP> hue <SEP> on
 <tb> cotton
 <tb> 4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> - @ <SEP> 6-nitro-1-amino-2-hydroxynaphthalene 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> 4-sulfonic acid <SEP> <U> -, </U> <SEP> 2-hydroxynaphthalene <SEP> black
 <tb> 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> 4-chloro-2-amino-1-hydroxyb, -nzene <SEP> <U> - </U>
 <tb> 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone <SEP> purple
 <tb> 4-methyl-2-amino-1-hydroxy'benzene-6-sulfonic acid <SEP> 4-chloro-2-amino-1-hydroxybenzene
 <tb> 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> 2-hydroxynaphthalene-6-sulfonic acid <SEP> rotst.

    <SEP> blue
 <tb> 4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid <SEP> 5-nitro-2-amino-1 = hydroxybenzene <SEP> -3 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> 2-hydroxynaphthalene-6-sulfonic acid <SEP> black
 <tb> <SEP> 4-nitro-2-amino-1-hydroxybenzene <SEP>,
 <tb> 2-hydroxynaphthalene-8-sulfonic acid <SEP>
 <tb> <SEP> 4-nitro-2-amino-1-hydroxybenzene <SEP> ->
 <tb> 1-hyd <SEP> roxynaphthal <SEP> in-5-sulfonic acid <SEP>
 <tb> <SEP> 6-nitro-2-amino-1-hydroxybenzene <SEP> --->
 <tb> 1-hydroxynaphthalene-5-sulfonic acid <SEP> right <SEP> <I> Example 9 </I> If you proceed as indicated in example 6,

   but instead of the copper-containing amino monoazo dye used there is based on the equivalent amount of the chromium complex of the 1-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid obtained by coupling with 1- [3 '- (3 "-aminophenyl) ] -sulfonylimido-sulfonyl-phenyl-3-methylpyrazolone- (5) obtained aminoazo dye, a reactive dye is obtained, which cellulose materials by one of the above-mentioned processes in good wet,

         rubbing and lightfast yellow-brown tones.



   <I> Example 10 </I> a) 0.1 mol of the copper complex compound of the formula
EMI0015.0015
    is dissolved in 3000 parts by volume of water at pH 6 and combined with 20 parts of 2,4-difluoro-6-methoxy-triazine with stirring at a temperature of 20 to 30 ° C. and a pH of 6 is maintained with 2N potassium carbonate solution. The mixture is maintained stirred until the condensation has ended, the dye 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 dyes cotton in green shades according to the procedures given in Examples 1 to 3.



  b) Cotton fabric is impregnated with a solution at 20 to 25 C which contains 25 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate per liter of liquor. The fabric is then squeezed between two rubber rollers to a moisture content of about 100 / '0.

   After intermediate drying at 50 to 60 C, the mixture is heated to 140 C for 15 seconds and the resulting dye is rinsed thoroughly with hot water and treated at the boil for 20 minutes with a solution containing 5 g of Mareins soap and 2 g of soda per liter. After rinsing and drying, a green dyeing of good wet, rub and light fastness is obtained.

      One of the other dyeing or printing processes described in Examples 1 to 5 also gives clear green tones of good fastness properties on cellulose materials.



   <I> example <B> 11 </B> 0.1 mol of the paste of the ananoazo compound of the formula
EMI0015.0050
    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 is obtained in 2000 parts by volume of water at pH 6 , 5 solved and with 26 parts 2,

  4-Difluoro-6-phenylamino-triazine combined. The reaction mixture is stirred at 20 to 30 ° C. until the condensation has ended, the pH of the reaction solution being kept at 6 to 7 by adding soda solution. 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.



   <I> Example 12 </I> The aqueous solution of 0.1 mol of the copper complex of the formula
EMI0016.0013
         manufactured according to the information in German patent specification no. <B> 1061 </B> 460 or <B> 1085 </B> 988, is reacted in the usual way with 0.1 part of 2,4-difluoro-6- (4'-sulfophenylamino) triazine.

   The pH is kept at 6-7 by adding soda and the dye is isolated by salting out after the reaction has ended. When dry, it is a dark powder that dissolves in water with a purple color. Cotton fabric is dyed in lightfast and wetfast purple tones.

       <I> Example 13 </I> 27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid sodium are dissolved in 150 parts of water, mixed with 20 parts of 2,4-difluoro-6-dimethylamino-triazine and at 20 ° C. under Blunt the resulting hydrogen fluoride with a total of 34 parts by volume of 16% soda solution, stirred to pH 6 to 7. After a short time, the acylation is complete, the pH is 7 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 was formed immediately
EMI0016.0046
    is completely separated after stirring for one hour by adding 80 parts of common salt, filtered off,

      Washed with dilute sodium chloride solution and dried at 35 ° C. in vacuo. It dyes cellulose materials in reddish orange tones of very good wet fastness and good resistance to chlorine by the above-mentioned processes ,

  4-Difluoro-6-ethoxytriazine and coupling of the acylamino naphthotsulfonic acids formed with the orange to red reactive dyestuffs mentioned in column 1.
EMI0016.0071
  
    Diazo component <SEP> aminonaphtholsulfonic acid <SEP> hue <SEP> on
 <tb> cotton
 <tb> 2-aminonaphthalene <SEP> 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP> orange
 <tb> 1,7-disulfonic acid
 <tb> <SEP> 2- (ss-hydroxyethylamino) -5-hydroxynaphthalene 7-sulfonic acid <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene-1,

  7-disulfonic acid <SEP>
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-6-sulfonic acid <SEP> scarlet fever
 <tb> <B> b </B> <SEP> 2-amino-8-hydroxy-naphthalene-3,6-disulfonic acid <SEP>
 <tb> 2-aminonaphthalene <SEP> 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP> orange
 <tb> 1,5-disulfonic acid
 <tb> <SEP> 2-Ethylam @ ino-5-hydroxynaphthalene-7-sulfonic acid
 <tb> <SEP> 2- (ss-hydroxyethylamino) -5 <SEP> hydroxynaphthalene 7-sulfonic acid <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene, 1,7-disulfonic acid <SEP>
 <tb> <SEP> 2-amino-8-hydroxynaphthalene. # 6-sulfonic acid <SEP> scarlet fever
 <tb> r <SEP> 2-amino-8-hydroxynaphthalene-3,

  6-disulfonic acid <SEP>
EMI0017.0001
  
    Diazo component <SEP> aminonaphtholsulfonic acid <SEP> hue <SEP> on
 <tb> construction <U> m </U> w <U> ol </U> l <U> e </U>
 <tb> 2-aminonaphthalene <SEP> 2-amino-5-hydroxynaphthalene-7-sulfonic acid <SEP> orange
 <tb> 1,5,7-trisulfonic acid
 <tb> <SEP> 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-6-sulfonic acid <SEP> scarlet fever
 <tb> 2-aminobenzene <SEP> 24f-hydroxyethylamino) -5-hydroxynaphthalene- <SEP> orange
 <tb> sulfonic acid <SEP> 7-sulfonic acid
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-6-sulfonic acid <SEP> scarlet fever
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene @ 1,7-disulfomic acid <SEP> orange
 <tb> 2-aminonaphthalene <SEP> 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> bluish.

    <SEP> red
 <tb> 1-sulfonic acid
 <tb> <SEP> 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP>
 <tb> 2-aminonaphthalene <SEP> 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> 1,5-disulfonic acid
 <tb> <SEP> 1 <SEP> -, amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP>
 <tb> <SEP> 1-amino-8-hydroxynaphthalene- @ 6-sulfonic acid <SEP>
 <tb> 2-aminonaphthalene <SEP> l, amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> 1,7-disulfonic acid
 <tb> <SEP> 1-A @ mino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP>
 <tb> <SEP> 1-amino-8-hydroxynaphth, alin-6-s, sulfonic acid <SEP>
 <tb> 2-aminonaphthalene <SEP> <SEP>
 <tb> 1,5,7-trisulfonic acid, right
 <tb> 1-amino-4-chloro- <SEP> 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> benzene-2-sulfonic acid
 <tb> l, amino-2-methoxy- <SEP> <SEP>
 <tb> benzene-5-sulfonic acid
 <tb> 1-A:

  minobenzene-2-car- <SEP> <SEP>
 <tb> bonsäure-4-sulfonic acid
 <tb> 1-amino-4-acetylamino- <SEP> <SEP> purple
 <tb> benzene-2-sulfonic acid
 <tb> <B> a: </B> <SEP> 1 <SEP> amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP> mouse. <SEP>, red <I> Example 14 </I> 56.8 parts of the by coupling of diazotized 1 - amino - 3 - acetylaminobenzene - 6 - sulfonic acid to 2- aminonaphthalene-5,

  7-disulfonic acid in acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group obtained diaminoazo dyes are dissolved at pH 7 in 450 parts of water. After the addition of 20 parts of 2,4-difluoro-6-methoxy-triazine, the hydrofluoric acid released is stirred with soda solution from pH 6 to 7 for about one hour at 20 ° C. while constantly blunting the hydrofluoric acid released.

   When the acylation has ended, the reactive dye formed is presumably of the formula
EMI0017.0023
         salted out, filtered off, again dissolved in water at 30 ° C., filtered and separated from the filtrate in a completely pure form by adding sodium chloride. The dye is dried in vacuo as usual at 35 ° C. It dyes cellulose materials according to one of the above-mentioned Process in real yellowish orange tones.

       <I> example <B> 15 </B> 25 parts of 2 are added to the neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-amino-naphthalene-3,6,8-trisulfonic acid with 3-acetylaminoanal in an acetic acid medium in 500 parts of water , 4-Difluoro-6-fl-ethoxyethoxy-triazine and stir for one hour at 10 C,

        A pH value of 6 is maintained by constantly adding sodium hydroxide solution. The partially precipitated acylation product is completely separated off at pH 7 by adding 100 parts of common salt and filtered off. For purification, the reactive dye thus obtained can again be dissolved in 2500 parts of water of 30%

  C dissolved, clarified and deposited again by salting out the filtrate with 350 parts of common salt. The dye has the formula
EMI0018.0019
    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 shades using one of the above-mentioned dyeing processes in the presence of acid-binding agents. Real yellow dyeings are also obtained on wool and polyamide fibers.



  Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4'-amino-2'-acetylaminophenyl- (1 ') -azonaphthalene- (2) -3,6,8-trisulfonic acid sodium corresponding amounts of the the amino compounds indicated in column 1 and the coupling components indicated in column 2 are used in the usual manner by diazotization and coupling in an acetic acid medium and with 2,

  4- Difluoro-6-f-methoxyethoxy-triazine acylated.
EMI0018.0040
  
    Diazo component <SEP> coupling component <SEP> hue <SEP> on <SEP> cotton
 <tb> 2-aminonaphthalene-1,5-disulfonic acid <SEP> 1-A @ mino-3-methyl-6-methoxybenzene <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-amino-3-methylbenzene <SEP> yellow
 <tb> <SEP> 1-aminonaphthalene-: 6-sulfonic acid <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-amino-3-acetyl <SEP> aminobenzene <SEP>
 <tb> <SEP> 3. Aminophenylurea <SEP>
 <tb> <SEP> 1-amino-3-hydroxyacetylaminobenzene <SEP>
 <tb> 2-aminonaphthalene-5,7-disulfonic acid <SEP> 1-amino-3-methyl-6-me:

  thoxybenzene <SEP> strong <SEP> rots.t. <SEP> yellow
 <tb> <SEP> 1-aminonaphthalene-7-sulfonic acid <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-amino-3-acetylaminobenzene <SEP>
 <tb> <SEP> 3-aminophenylurea <SEP>
 <tb> <SEP> 1-amino-3-hydroxyacetylaminobenzene <SEP>
 <tb> 1-aminonaphthalene-3,7-disulfonic acid <SEP> 1- @ Amino-3-methyl-6-methoxybenzene <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1 <SEP>, amino-3-methylbenzene <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-aminonaphthalene-6-sulfonic acid <SEP>
 <tb> 2-aminonaphthalene-3,6-disulfonic acid <SEP> 1-amino-3-methyllbenzene <SEP>
 <tb> <SEP> 1-amino-3-methyl-6-methoxybenzene <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-amino-3-acetylaminobenzene <SEP> rotst.

    <SEP> yellow
 <tb> <SEP> 3-aminophenylurea <SEP>
 <tb> <b> </B> <SEP> 1-amino-3-hydroxyacetylaminobenzene <SEP>
 <tb> <SEP> 1 <SEP>, aminone, aphthalene-6-sulfonic acid <SEP>
 <tb> 2-aminonaphthalene-6,8-disulfonic acid <SEP> 1-amino-3-acetylaminobenzene <SEP>
 <tb> <SEP> 1-amino-2-methoxynaphthalene-6-sulfonic acid <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-aminonaphthalene-6-sulfonic acid <SEP> rotst. <SEP> yellow
 <tb> 2-aminonaphthalene-4,8-disulfonic acid <SEP> <SEP> yellow
 <tb> <SEP> 1-, aminonaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 1-amino-2-methoxynaphthalene-6-sulfonic acid <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <SEP> aniline <SEP> yellow
 <tb> <SEP> 1-ethylamino-3-: methylbenzene <SEP>
 <tb> <SEP> N-methylaniline <SEP>
 <tb> <SEP> N-ethylaniline <SEP>
 <tb> N - (/ 3-:

  Hydroxyethyl) anil <SEP> in <SEP>
 <tb> <SEP> N-butylaniline <SEP>
EMI0019.0001
  
    Diazo component <SEP> coupling component <SEP> hue <SEP> on <SEP> cotton
 <tb> 2-aminonaphthalene-3,6,8-trisulfonic acid <SEP> aniline <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-amino-3-methylbenzene <SEP> <b> </B>
 <tb>> <SEP> 3-aminophenylurea <SEP> <b> </B>
 <tb> <SEP> I <SEP> -amino-3-hydroxyacetylamine benzene
 <tb> <SEP> 1 <SEP> Amino-3-acetylamino-6-methoxybenzene <SEP> yellow orange
 <tb> <SEP> 1-amino-3-acetylamino-6-methylbenzene <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1 <SEP> -amino-3-methanesulfonylaminobenzene <SEP> <B>> </B>
 <tb> <SEP> 2,5-i-dimethoxyaniline <SEP> yellow. <SEP> orange
 <tb> 2-aminonaphthalene-3,6,8-trisulfonic acid <SEP> 3-methyl-6-methoxyaniline <SEP> <b> </B>
 <tb> <SEP> N-methylaniline <SEP> rotst.

    <SEP> yellow
 <tb> <SEP> N-ethylaniline <SEP> <b> </B>
 <tb> <SEP> N-butylaniline <SEP> <B>> </B>
 <tb> <SEP> N4 / 3-hydroxyethyl) anil <SEP> in <SEP> <b> </B>
 <tb>> <SEP> 3- (N-ethylamino) toluene <SEP> <B>> </B>
 <tb> <SEP> 2, aminotoluene <SEP> <B>> </B>
 <tb> <SEP> 1-amino-2,5-dimethylbenzene <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> <B>> </B> <SEP> 1-amino-2-methoxybe <SEP> nzol <SEP> <B>> </B>
 <tb>> <SEP> 1-amino-3-methoxybeneol <SEP> rotst. <SEP> yellow
 <tb> <SEP> 1-ethyl <SEP> amino-3-methoxybenzene <SEP> <B>> </B>
 <tb>> <SEP> 1-aminonaphthalene - 6-sulfonic acid <SEP> <B>> </B>
 <tb> <SEP> 1-aminonaphRhalin-7-sulfonic acid <SEP>
 <tb> 2-aminonaphthalene-4,6,8-trisulfonic acid <SEP> 1-amino-3-methylbenzene <SEP> <B>> </B>
 <tb>> <SEP> aminobenzene <SEP> <B>> </B>
 <tb>> <SEP> aniline <SEP> yellow
 <tb>> <SEP> 1-amino-3-acetylaminobenzene <SEP> rotst.

    <SEP> yellow
 <tb> 1-aminonaphthalene-2,4,7-trisulfonic acid <SEP> 1-amino-3-methylbenzene <SEP> yellow
 <tb> <SEP> 1, aminonaphthalene-6-sulfonic acid <SEP> <b> </B>
 <tb> 4-nitro-4'-am <SEP> inostilbene 2,2'-lisulfonic acid <SEP> 1-amino-3-acetylaminobenzene <SEP> rotst. <SEP> yellow
 <tb> <SEP> 3 "aminophenylurea <SEP> <B>> </B>
 <tb> <SEP> 1 <SEP> -, amino-3-hydroxyacetylaminobenzene <SEP> <b> </B>
 <tb>> <SEP> N-methylaniline <SEP> <B>> </B>
 <tb> <B>> </B> <SEP> N, ethylaniline <SEP> <b> </B>
 <tb> <b> </B> <SEP> N-butylaniline <SEP> <B>> </B>
 <tb> <B>> </B> <SEP> N- (f <SEP> hydroxyethyl) aniline <SEP> <b> </B>
 <tb>> <SEP> 1- (N-Ethyl'amino) -3-methylbenzene <SEP>>
 <tb> aniline-2,

  5-d <SEP> isulfonic acid <SEP> 1-atninonaphthalene-6-sulfonic acid <SEP> <B>> </B>
 <tb> <B>> </B> <SEP> 1-aminonaphthalene-7-sulfonic acid <SEP> <B>> </B>
 <tb>> <SEP> 1-amino-3-methylbenzene <SEP> yellow
 <tb> <SEP> 1-amino-3-acetyl <SEP> aminobenzene <SEP> <B>> </B>
 <tb> <B>> </B> <SEP> 1-amino-2-methoxy-5 @ methylbenzene <SEP> rotst.

    <SEP> <b> yellow </B>
 <tb> <SEP> 1-amino-2,5-dimethoxybenzene <SEP> <B>> </B>
 <tb> A <SEP> nil <SEP> in-2,4-disulfone <SEP> säu <SEP> right <SEP> 1, amino-2-methoxy-5-methylbenzene <SEP> <B>> </B> <I> Example 16 </I> 65 parts of the dye of the formula
EMI0020.0002
    (produced by coupling diazotized 1-hydroxy-2-aminobenzene-4,6-disulphonic acid to 2-amino-8-hydroxynaphthalene-6-sulphonic acid and coppering of the azo dye obtained)

      are dissolved neutral in 700 parts of water. 20 parts of 2,4-difluoro-6-methoxy-triazine are added and the mixture is stirred at 0 ° to 10 ° C. with constant blunting of the acid released to pH 6 to 7 with solo solution until no free amino group can be detected. The resulting reactive dye of the formula
EMI0020.0019
    is salted out, filtered off, washed and dried at 30 to 40 C.

   It colors cellulose materials in very real ruby tones using one of the methods given above. Dyes with similar properties are obtained analogously to the procedure outlined above from the copper complexes of the azo dyes prepared from the diazo and azo components listed in the table below.
EMI0020.0031
  
    Diazo component <SEP> coupling component <SEP> hue <SEP> on
 <tb> cotton
 <tb> 1-Hydroxy-2-aminobenzene-4-sulfonic acid <SEP> 2 = methylamino-5-hydroxynaphthalene-7-sulforic acid <SEP> ruby
 <tb> <SEP>

  2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 2 - (/ i-hydroxyethylamino) -5-hydroxynaphthalene- <SEP>
 <tb> 7-sulfonic acid
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> 1-Hydroxy-2-aminobenzene-4,6-disulfonic acid <SEP> 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid <SEP>
 <tb> <SEP> 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> <SEP> 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid <SEP>
 <tb> <SEP> 2-ethylamino-5-hydroxynaphth @ aline-7-sulfonic acid <SEP>
 <tb> <SEP> 2- (ss-Hydroxyäthylamino) -5-hydroxynaphthalene- <SEP>
 <tb> 7-sulfonic acid
 <tb> <SEP> 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid <SEP> purple
 <tb> <SEP> 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP>
 <tb> 1-Hydroxy-2-aminobenzene-5-sulfonic acid <SEP> 1-amino-8-hydroxynaphthalene-3,

  6-disulfonic acid <SEP>
 <tb> <SEP> 1, amino-8-hydroxynaphthalene-4,6-disulfonic acid <SEP>
 <tb> 1-Hydroxy-2-amino-4-acetylaminobenzene- <SEP> 1-amino-8-hydroxynaphthalene-3,6, disulfonic acid <SEP> bluish.
 <tb> 6-sulfonic acid <SEP> purple
 <tb> <SEP> 1-ethoxy-8-hydroxynaphthalene-3,6-disulfonic acid <SEP>
 <tb> (4 permanent <SEP> acetylamino group <SEP> then <SEP> saponified)
 <tb> 1-Hydroxy-2-amino-4-acetylaminobenzene- <SEP> 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid <SEP> blue
 <tb> 6-sulfonic acid
 <tb> <SEP> 1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid <SEP>
EMI0021.0001
  
    Diazo component <SEP> coupling component <SEP> hue <SEP> on
 <tb> cotton
 <tb> 1-Hydroxy-2-amino-4-acetylamino @ benzene- <SEP> 1-amino-8-hydroxynaphthalene-2,

  4-disulfonic acid <SEP> blue
 <tb> 4-sulfonic acid
 <tb> (6 employees <SEP> acetylamino group <SEP> saponified)
 <tb> 1-amino - 2-hydroxy-6-nitronaphth @ alin- <SEP>
 <tb> 4, sulfonic acid <SEP>
 <tb> (6 employees <SEP> nitro group <SEP> then <SEP> reduced <SEP> to <SEP> -NH2)
 <tb> 1-Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid <SEP> 1-amino-8-hydroxynaphthalene-2,4,6-t-trisulfonic acid <SEP>
 <tb> (6 employees <SEP> nitro group <SEP> reduced <SEP> to <SEP> -NH.2)
 <tb> 1-Hydroxy-2-amino-6-acetylaminobenzene 4-sulfonic acid <SEP> 1-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid <SEP>
 <tb> (6 employees <SEP> acetylamino group <SEP> saponified) <I> Example 17 </I> Proceed as indicated in example 5,

   however, instead of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid, the diazotized intermediate product containing reactive groups couples in a soda-alkaline medium with 40 parts of the sodium salt of 1-acetylamino-8-hydroxynaphthalene-3 , 6-disulphonic acid and isolates the resulting dye of the formula
EMI0021.0011
    in the manner indicated in Example 5.

   The water-soluble dye dyes cellulose materials by the pad-steaming or pad-thermofixing process (at 140 ° C.) in white-etchable, wet, rub-fast and lightfast bluish red shades.

       <I> Example 18 </I> The solution of 19.5 parts of the sodium salt of 1-aniinobenzene-4-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 excess nitrous acid is then removed. The solution of 26, which has cooled and thereby partially crystallized out again, is added at 0 to 10 ° C. to the diazo suspension thus obtained.

  2 parts of the potassium salt of 1-aminonaphthalene-8-sulfonic acid in 250 parts of hot water and the strongly acidic coupling mixture is blunted to pH 4 at 10 to 20 ° C. by careful addition of sodium hydroxide solution.

    The coupling is completed quickly; the amino azo 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 6.5. The aqueous solution is partially with 20 parts of 2,

  4- Difluoro-6-methylamino-triazine is added and the mixture is stirred for one hour at 10 to 20 ° C. with soda solution to pH 6 to 7, while baptizing the acid that is released. When the aminoazo dye is no longer detectable, the partially precipitated reactive dye is of the formula
EMI0021.0062
    Salted out with common salt, filtered off and dissolved again in 800 parts of warm water for cleaning.

   After the solution has been clarified, the pure dye is deposited from the filtrate by adding sodium chloride. After filtering off, drying at 35 ° C. and grinding, a yellow powder is obtained that dissolves easily in water with a yellow color and the cellulose fibers have very good wet, light and chlorine fastness according to one of the above-mentioned dyeing processes in the presence of acid-binding agents Shades of yellow. True yellow colorations are also obtained on wool and polyamide fibers.



  If the above procedure is followed, but instead of 19.5 parts of the sodium salt of 1-aminobenzene'-4-sulfonic acid, equivalent amounts of the diazo components listed in the table below are coupled to the 1-aminonaphthalene-8-sulfonic acid Acylation with 2,

  4-Difluoro-6-methylmercaptotriazine also valuable yellow to brown reactive dyes.
EMI0022.0014
  
    Diazo component <SEP> hue <SEP> on
 <tb> cellulose fiber
 <tb> 1-aminobenzene-2,5-disulfonic acid <SEP> rotst. <SEP> yellow
 <tb> 2-aminonaphthalim-4,8-disulfonic acid <SEP> strong <SEP> rotst. <SEP> yellow
 <tb> 2-aminonaphthalene-5,7-disulfonic acid <SEP>
 <tb> 2-aminonaphth <SEP> alin-6, <SEP> 8-disulfone <SEP> acid <SEP>
 <tb> 2-aminonaphthalene-3;

  6,8-trisulfonic acid <SEP>
 <tb> 2-aminonaphthalene-4,6,8-trisulfonic acid <SEP>
 <tb> 4-Aminoazobenzene-3,4'-disulfonic acid <SEP> yellow. <SEP> brown
 <tb> 4-amino-2-acety <SEP> laminoazobenzo <SEP> l-2 ', <SEP> 5'-disu <SEP> Lfonic acid <SEP> orange brown
EMI0022.0015
  
     <b> <I> SO </I> </B> <SEP> 3Na
 <tb> <B> N = N </B> <SEP> NH2 <SEP> rough.

    <SEP> brown
 <tb> <b> <I> SO </I> </B> <SEP> 3Na
 <tb> <b> <I> SO </I> </B> <SEP> 3Na
 <tb> <B> (1-aminobenzene-2,5-disulfonic acid <SEP> angry <SEP> on </B>
 <tb> <B> 1-aminonaphthalene-6-sulfonic acid <SEP> coupled) </B>
 <tb> <b> <I> SO </I> </B> <SEP> 3Na
 <tb> i @ <b> <I> N = N </I> </B> <SEP> @ \ NH2
 <tb> <B> SO </B> <SEP> 3Na <SEP>
 <tb> S03 <SEP> Well <SEP> (in <SEP> 6- <SEP> or <SEP> 7 position)
 <tb> (1-aminobenzene-2,5-disulfonic acid <SEP> angry <SEP> on
 <tb> the <SEP> technical <SEP> mixture <SEP> from <SEP> 1-aminonaphthalene-6 and <SEP> -7-sulfonic acid <SEP> coupled)
 <tb> 03 <SEP> Well
 <tb> <b> <I> <U> N </U> </I> <SEP> _ <I> <U> N </U> </I> </B> <SEP> \ <SEP> <B> H2 </B>
 <tb> Na03S <SEP> \ <SEP> # <SEP>. \ <SEP> @ 1
 <tb> violet.

    <SEP> brown
 <tb> o3Na <SEP> or similar <SEP> 3 <SEP> Well
 <tb> <B> (1-aminonaphthalene-2,5,7-trisulfonic acid <SEP> angry </B>
 <tb> <b> on </B> <SEP> 1-aminonaphthalene-6-sulfonic acid <SEP> coupled)
EMI0023.0001
  
    Diazo component <SEP> hue <SEP> on
 <tb> cellulose fiber
 <tb> <B> 0 <SEP> <I> 3 </I> </B> <SEP> Well <SEP> ocH3
 <tb> <B> N <SEP> .N- <SEP> NH2 </B> <SEP> rotst.

    <SEP> brown
 <tb> Nao3s
 <tb> <B> CH </B> 3
 <tb> S03 <SEP> Well
 <tb> (1-aminonaphthalene-2,5,7-trisulfonic acid <SEP> angry
 <tb> <b> on </B> <SEP> 1-amino-2-methoxy-5-methylbenzene <SEP> coupled) <I> Example 19 </I> If cellulose fabric is printed with a printing paste containing 30 g of the dye described in Example 4, 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 intermediate drying and then in a suitable steamer for 45 seconds at 103 bis <B> 115'C </B> steams, so after rinsing and boiling soaps you get a strong bluish red print of good wet, rub and lightfastness. <I> Example 20 </I> A mixture of the solutions of 65.5 parts each of the chromium-2: 1 complex and the cobalt-2:

          1 complex of the dye of the formula
EMI0023.0017
    in 400 parts of water, the mixture is stirred with 40 parts of 2,4-difluoro-6-methoxy-triazine for about 2 hours at 20 to 30 ° C. while maintaining the pH 6 to 7.

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



       The dye provides strong, very good wet and lightfast black tones on cellulose materials after the Kletz dyeing process or when printed in the presence of acid-binding agents.



  If one proceeds accordingly, but the mixture of the chromium 2: 1 and cobalt 2: 1 complexes of the following aminoazo dyes is used, valuable black dyes are also obtained:

       
EMI0023.0040
  
    Diazo component <SEP> coupling component <SEP> coupling pH
 <tb> 1-Hydroxy-2-amino-4-nitrobenzene <SEP> 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid <SEP> 9
 <tb> 1-Hydroxy-2-amino-4-nitro-naphthalene-7-sulfonic acid <SEP> a <SEP> 9 <I> Example 21 </I> Add to the neutral solution of 53.1 parts of the disodium salt obtained by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5'-sulfoph, enyl) -3-methyl -pyrazolone- (5)

          and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye in 300 parts of water 30 parts of 2,4-difluoro-6-f-methoxyethoxy-triazine and the mixture is stirred for 1 hour at 20 ° C., the acid released being continuously added to a solution : pH value of 6 blunted.

   The deposited dye of the formula
EMI0024.0001
    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, water-soluble powder is obtained,

   the cellulose materials from a long liquor at 30 C or using the cold pad process with soda as an acid-binding agent dyes in clear, washable, rubbing and lightfast yellow tones.



       If one proceeds as indicated above, but instead of the aminoazo dye used there, equivalent amounts of the aminoazo dyes built up from the components listed in the table below are used, valuable new reactive dyes are likewise obtained. In the table means

      Unless otherwise stated, the expression saponified 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 .

    
EMI0024.0052
  
    pH <SEP> des <SEP> hue <SEP> on
 <tb> <B> Diazo component </B> <SEP> azo component <SEP> coupling <SEP> cellulose
 <tb> mediu <U> ms </U>
 <tb> 1-Amino-4-nitrobenzene-2-sulfonic acid <SEP> 1- (4 '= sulfophenyl) -3-methyl-pyrazolone- (5) <SEP> 5-6 <SEP> yellow
 <tb> (4 permanent <SEP> nitro group <SEP> then <SEP> reduced)
 <tb> 1-Amino-4-nitrobenzene-2-sulfonic acid <SEP> 1- (4'-sulfophenyl) -3-carboxy-pyrazolone- (5) <SEP> 5-6 <SEP> rotst.

    <SEP> yellow
 <tb> <SEP> 1- (3'-sulfophenyl) -3-methyl-5-amino-pyrazole <SEP> 6-7 <SEP> yellow
 <tb> 1-Amino-3-acetylaminobenzene 6-sulfonic acid <SEP> <SEP> 6-7 <SEP>
 <tb> (3 part <SEP> acetylamino group <SEP> then <SEP> saponified)
 <tb> 1 <SEP> -amino-3-acetylaminobenzene- <SEP> 1- (ss-hydroxyethyl) -3-methyl 6-sulfonic acid <SEP> J <SEP> pyrazolone- (5) <SEP> 5-6 <SEP>
 <tb> 2 <SEP> moles <SEP> 1-amino-3-acetylaminobenzene <SEP> 1 mole <SEP> bis-pyrazolone <SEP> off <SEP> 4,4'-bis-hydrazino δ-sulfonic acid <SEP> (saponified) <SEP> dibenzyl-2,2'-disulfonic acid <SEP> and
 <tb> Acete.sigäthylester <SEP> 5-6 <SEP>
 <tb> 1 <SEP> moles <SEP> 1-amino-3-acetylaminobenzene <SEP> 1 <SEP> 44 ', sulfophenyl) -3-carboxy 6-sulfonic acid <SEP> (saponified) <SEP> pyrazolone- (5) <SEP> 5-6 <SEP>
 <tb> 1-Amino-5-acetylantinonaphthalener
 <tb> 3,7-disulfonic acid <SEP> (saponified)

    <SEP> <SEP> 5-6 <SEP> rotst. <SEP> yellow
 <tb> 1-amino-2-methylbenzene <SEP> 2-acetylamino-5-naphthol-7-sulfonic acid
 <tb> 4,6-disulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP> orange
 <tb> <b> </B> <SEP> 2-acetylamino-8-naphthol-6-sulfonic acid
 <tb> (saponified) <SEP> 7-8 <SEP> red
 <tb> <b> </B> <SEP> 1, chloro-2-acetyl <SEP> amino-5-naphthol 7-sulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP> orange
 <tb> 1-aminobenzene-2-sulfonic acid <SEP> 1-acetylamino-8-hydroxynaphthalene 4,6-disulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP> red
 <tb> 2-kaminonaphthalene-3; 6-disulfonic acid <SEP> <SEP> 7-8 <SEP> bluish. <SEP> red
 <tb> 2 @ aminonaphthalene-3,7-disulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 2-aminanaphthalene-4,8-disulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 2, aminonaphthalene-3; 6-disulfonic acid <SEP> 1-acetylamino-8-hydroxyn:

  aphthalene 3,6-disulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP>
 <tb> 2-aminonaphfhalin-4,8-disulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 1-Amino-4-methoxybenzene-2-sulfonic acid <SEP> 2- (N-Acetyl @ N-methylamino) -5-hydroxy naphthalene-7-sulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP> tanned. <SEP> red
EMI0025.0001
  
    PH <SEP> (les <SEP> hue <SEP> on
 <tb> diazo component <SEP> azo component <SEP> coupling <SEP> cellulose
 <tb> mediums
 <tb> 1-Amino-4-methoxybenzene-2-sulfonic acid <SEP> 24N-Acetyl-N-methylaniino) -8-hydroxy naphthalene-6-sulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP> red
 <tb> 1-aminobenzene-2-sulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 1-aminobenzene-3-sulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 1-aminobenzene-4-sulfonic acid <SEP> <SEP> 7-8 <SEP>>
 <tb> 1-Amino-4-methylbenzene-2-sulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> 1-amino-2,

  4-dimethyl @ benzene 6-sulfonic acid <SEP> <SEP> 7-8 <SEP>
 <tb> <SEP> 2-acetylamino-8-hydroxynaphth <SEP> a1 <SEP> in 6-sulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP>
 <tb> <SEP> 2-acetylamino-8-hydroxyn, aphthalene 3,6-disulfonic acid <SEP> (saponified) <SEP> 7-8 <SEP>
 <tb> 4-Aminoazobenzene-3,4'-disulfonic acid <SEP> 1-amino-3-acetylaminobenzene <SEP> 5-6 <SEP> yellow-brown
 <tb> <SEP> 1-amino-3-hydroxyacetylaminobenzene <SEP> 5-6 <SEP>
 <tb> <SEP> 1-aminonaphthalene-6-sulfonic acid <SEP> 5-6 <SEP>
 <tb> <SEP> 1-aminonaphthalene-7-sulfonic acid <SEP> 5-6 <SEP>
 <tb> <SEP> 1-amino-2- (4'-amino-2'-sulfophenyl- (1 ') azo) -8-hydroxynaphthalene-3;

  6-disulfonic acid <SEP> 8 <SEP> black <I> Example 22 </I> 52.4 parts of the disodium set of 4 - ([4 "-aminophenyl] -amino) - 2'-nitrodiphenylamine-3,4-disulfonic acid are dissolved in 1000 parts of water and 20 parts of 2,4- Difluoro-6-methoxy-triazine is stirred for one hour at 0 ° to 10 ° C. The acid released is continuously blunted to a pH of 6 to 7 with soda.

   The reactive nitro dye formed of the formula
EMI0025.0011
    is salted out, filtered off, washed and dried. It dyes cellulose fibers from a long liquor or using one of the customary padding processes in the presence of soda as an acid-binding agent in deep violet-brown shades that are fast to wet and rub. <I> Example 23 </I> 0,

  1 mole of the aminoazo dye of the formula
EMI0025.0022
    - prepared according to the information in German Patent No. 1 115 865 by coupling the diazonium compound from 2-aminonaphthalene-4,8-disulfonic acid with 1-aminonaphthalene-6-sulfonic acid, further diazotizing the aminoazo dye obtained, coupling with the equivalent amount 2 5-diaminonaphthalene-4,

  8-disulfonic acid and conversion into the aminotriazole - is dissolved in 1000 parts by volume of water at pH 6 and 22 parts of 2,4-difluoro-6-methylmercapto-triazine are added while stirring at a temperature of 20 to 30 ° C. The hydrofluoric acid that is slowly released is blunted with soda solution until the reaction has ended.

   The dyestuff is then deposited by adding sodium chloride, isolated and dried at about 50.degree. C. in a vacuum. It is a yellow powder that is soluble in water with a yellow color.



   <I> Example 24 </I> If you proceed as in Example 4, but the dye intermediate obtained 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 Presence of 12 parts of soda at a final pH of 7,

   a reactive dye of the formula is obtained in this way
EMI0026.0010
    with the cellulose materials from a long liquor at 40 C or by one of the padding and printing processes customary for reactive dyes with soda as an acid-binding agent, the agent can be dyed or printed in wet-fast brilliant red tones.



  In an analogous manner, the coupling components listed in the table below are obtained by acylating their amino group with 2,4-dif @ uor-6-methoxy-triazine and coupling the resulting dye intermediates with the specified diazo components valuable reactive dyes with which Cellulose materials in the listed shades - preferably in the presence of soda - can be colored or printed:

    
EMI0026.0028
  
    pH <SEP> des
 <tb> shade <SEP> diazo component <SEP> coupling component <SEP> coupling <SEP> on
 <tb> cellulose
 <tb> mediums
 <tb> 1-Amino-4-methoxybenzene-4-sulfonic acid <SEP> 1-amino-8-hydroxyruaphthalene 3,6-d.isulfonic acid <SEP> 7-8 <SEP> purple
 <tb> <SEP> 1-amino-8-hydroxynaphthalene <SEP> rotst.
 <tb> 4,6-disulfonic acid <SEP> 7-8 <SEP> purple
 <tb> <SEP> 2-amino-5-hydroxynaphtha1 <SEP> in 1,7-disulfonic acid <SEP> 7 <SEP> scarlet fever
 <tb> 1-Amino-5-chlorobenzene-2-sulfonic acid <SEP> <SEP> 7 <SEP> orange
 <tb> 1-aminobenzo1-3-sulfonic acid <SEP> 7 <SEP>
 <tb> 1-aminobe, nzene-4-sulfonic acid <SEP> <SEP> 7
 <tb> <SEP> 2-amino-8-hydroxy <SEP> naphthal <SEP> in 3,6-disulfonic acid <SEP> 7-8 <SEP> scarlet fever
 <tb> 4-aminobenzoic acid - (/ l-sulfoiithyl) -amide <SEP> 1-amino-8-hydroxynaphthalene 3,

  6-disulfonic acid <SEP> 7-8 <SEP> red
 <tb> 1-Amino-4-sulfoacetylamine benzene 6-sulfonic acid <SEP> <SEP> 7-8 <SEP> purple
 <tb> 1-Amino-3-sulfoacetylaminobenzene- <SEP> 2, amino-5-hydroxynaphthalene 6-sulfonic acid <SEP> 1,7-disulfonic acid <SEP> 7 <SEP> orange
 <tb> 1-Amino-4-sulfoacetylaminobenzene <SEP> <SEP> 7 <SEP> scarlet fever
 <tb> 1-aminobenzene-2,4-disulfonic acid <SEP> 1- (2'-Pvlethyl-3'-amino-5'-sulfophenyl) 3-methylpyrazolone- (5) <SEP> 6 <SEP> yellow
 <tb> 2-aminonaphthalene-4,8-disulfonic acid <SEP> <SEP> 6 <SEP> <I> Example 25 </I> 0.1 mol of 4-ureido-2-amino-1-hydoxybenzene-5, sulphonic acid is diazotized and sodaallcal with 0,

  1 mol of 1-amino-8-hydroxynaphthane-2,4-disulfonic acid gekup pelt. The coupling solution is adjusted to a content of 2 mol / liter with caustic soda 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 6 to 7 and temperatures of 20 to 30 ° C. with 0.1 mol of 2, 4-Difluoro-6-methoxy-triazine acylated. The obtained dye of the formula
EMI0027.0001
    is salted out. A blue color is obtained on cotton.



   <I> Example 26 </I> If one proceeds as indicated in Example 21, but instead of the aminoazo dye used there, 53.1 parts of the disodium salt of the by coupling of diazotized 1-amino-4-nitrobenzal-2-sulfonic acid with 1- (2'-chloro 5'-sulfopheny1) -3-methyl-pyrazolon- (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye with the 2,4-difluoro-6-phenylamino-triazine acylated,

      this also gives a valuable reactive dye with which cellulose materials can be printed in true yellow tones by the usual dyeing and printing processes.



       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 using 2,4-difluoro-6-methoxy-triazine:

       
EMI0027.0034
  
    Diazo component <SEP> azo component <SEP> hue
 <tb> 1-Amino-4-nitrobenzene-2-sulfonic acid <SEP> 1- (2'-methyl-4'-sulfophenyl) -3, methyl-pyrazolone. (5) <SEP> yellow
 <tb> (reduced)
 <tb> <SEP> 1- (2 ', 5', disulfophenyl) -3-nlethyl-pyrazolone- (5) <SEP>>
 <tb> <SEP> 1 .- (2'-methyl-4'-sulfo-6'-chlorophenyl) 3-methyl-pyrazolone- (5) <SEP> <b> </B>
 <tb> <SEP> 1- (2 ', 5'1-dichloro-4'-sulfophenyl) -3-methyl-pyrazolone- (5) <SEP> <B>> </B>
 <tb> 1 <SEP> Amino-3-acetylaminabenzene-6-sulfonic acid <SEP> 1 "(2'-methyl-4'-sulfophenyl) -3-methyl-pyrazolone- (5) <SEP> green.
 <tb> (saponified) <SEP> _ <SEP> yellow
 <tb> <SEP> 1- (4'-sulfophenyl) -3-methyl-pyrazolone- (5) <SEP> <B>> </B>
 <tb> <SEP> 1- (2 '- iMethyl-4'-sulfophenyl) -3-carooxy-pyrazolone- (5) <SEP>>
 <tb> <SEP> 1- (2'-chloro-4'-sulfophenyl) -3-carboxy-pyrazolone, (5)

    <SEP> <B>> </B> <I> Example 27 </I> 58 parts of the dye of the formula
EMI0027.0036
    (produced by coupling diazotized 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid to 2-methyl @ amino-8-hydroxynaphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water under neutral conditions. 20 parts 2 are dripped in,

  4-Difluoro-6-ethoxytriazine is added and the mixture is stirred at 0 to 100 ° C. while constantly blunting the hydrofluoric acid released with soda solution to pH 6 to 7, until no free amino group can be detected any longer. The reactive dye formed of the formula
EMI0027.0059
      is salted out, filtered off, washed and dried at 30 to 40 C.

   It dyes cellulose materials in very real violet tones using one of the methods given above.



       Dyes with similar properties are obtained analogously to the procedure described above from the copper complexes obtained by simple demethylating or oxylnating copper of the mono and disazo dyes prepared from the diazo and azo components listed in the table below:

       
EMI0028.0016
  
    pH <SEP> des
 <tb> shade <SEP> on
 <tb> diazo component <SEP> azo component <SEP> coupling cellulose
 <tb> mediums
 <tb> 1-hydroxy-2-amino-4-chlorobenzene- <SEP> 2-amino-8-hydroxynaphthalene <SEP> rotst.
 <tb> 5-sulfonic acid <SEP> 3,6-disulfonic acid <SEP> 10 <SEP> purple
 <tb> <SEP> 1-amino-8-hydroxynaphthalene <SEP> bluish.
 <tb> 3,6-disulfonic acid <SEP> 10 <SEP> purple
 <tb> 2-aminonaphthalene-4,6,8-trisulfonic acid <SEP> 2-hydroxy-6-acetylaminonaphthalene (oxidizing <SEP> coppered) <SEP> 4-sulfonic acid <SEP> (saponified) <SEP> 8-9 <SEP> rotst.

    <SEP> blue
 <tb> 1-amino-2-hydroxy-6-nitronaph, ghalin- <SEP> 1-hydroxy-8-ethoxynaphthalene-4-sulfonic acid <SEP> (reduced) <SEP> 3,6-disulfonic acid <SEP> 10 <SEP> blue
 <tb> 1-hydroxy-2-aminobenzene- <SEP> 2-hydroxy-3-aminonaphthatin 4,6-disulfonic acid <SEP> 5,7-disulfonic acid <SEP> 10 <SEP> red
 <tb> 2-aminonaphthalene-4,8-disulfonic acid <SEP> 2-hydroxy-3-aminonaphthalin (oxidizing <SEP> coppered) <SEP> 5,7-disulfonic acid <SEP> 8-9 <SEP> blue
 <tb> 2-aminonaphfhalin-4,6,8-trisulfonic acid <SEP> 2-hydroxy-3-aminonaphthalene (oxidizing <SEP> coppered) <SEP> 7-sulfonic acid <SEP> 8-9 <SEP>
 <tb> 3-methoxy-4-amino-6-methyl-azobenzene 2 ', <SEP> 4'-disulfonic acid <SEP> 2-methylam <SEP> ino-5-hyd <SEP> roxyn <SEP> aph <SEP> thalin (demethylating <SEP> coppered) <SEP> 7-sulfonic acid <SEP> 10 <SEP> navy blue
 <tb> <SEP> 2-amino-8-hydroxynaphthalene 3,

  6-disulfonic acid <SEP> 10 <SEP>
 <tb> <SEP> 2-amino-5-hydroxynaphthalene 1,7-disulfonic acid <SEP> 10 <SEP>
 <tb> 3-Methoxy-4-amino-6-methyl-azobenzene 2 ', 5'-disulfonic acid <SEP> 2-methyl <SEP> amino-5-hydroxynaphthalene <SEP> in (demethylating <SEP> coppered) <SEP> 7-sulfonic acid <SEP> 10 <SEP>
 <tb> <SEP> 2-amino-8-hydroxynaphthalene 3,6-disulfonic acid <SEP> 10 <SEP>
 <tb> <SEP> 2-amino-5-hydroxyn <SEP> aphth @ al <SEP> i <SEP> n 1,7-disulfonic acid <SEP> 10 <SEP> <I> Example 28 </I> 62 parts of trisodium salt of 4-chloro-2-amine diazotized by soda-alkaline coupling;

  ino-l-hydroxybenzen-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6-lisulfonic acid are obtained 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-1-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene added. After 10 minutes a deep blue solution has formed.



  The mixed complex is acylated with 20 parts of 2,4-difluoro-6-methoxy-triazine for about 2 hours at 20 to 30 ° C. and a pH of 6 to 7. Here, the pH value is kept constant by adding dropwise solo solution. The acylated dye is deposited with 20% sodium chloride, filtered off with suction and dried at 30.degree.
EMI0029.0001
    The process given in Example 3 gives a blue-black print of excellent lightfastness and washfastness on cotton.

       <I> Example 29 </I> a) 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 300 parts of water, heated to 20 to 30 C and 20 parts of 2,4-difluoro-6- methoxy-triazine added. Over the course of an hour, 40 parts of 15% soda solution are added so that the pH is 6 to 7.



  A freshly prepared diazonium salt solution from 13.6 parts of p-aminobenzylsulfonic acid is at 0 to <B> 51C </B> added dropwise to the suspension of the acylation product mixed with 12.5 parts of soda. After stirring for 5 hours at ice bath temperature, the mixture is salted out with sodium chloride, filtered off with suction, washed with dilute sodium chloride solution and dried at 30 ° C. in a vacuum drying cabinet.

   The dye obtained corresponds to the formula
EMI0029.0028
    If you proceed 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 2,4-difluoro -6-methoxy-triazine acylated and the coupling component containing reactive groups is coupled with diazotized p-aminobenzylsulfonic acid,

   it is a readily soluble reactive dye that dyes cellulose fiber-containing fabrics in brilliant red-tinged orange tones.



  * b) Cotton or cellular wool fabric is impregnated on a padder at 20 to 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 onto one Moisture content of about 100% and rolls up the moist tissue again.

   After standing for 2 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.



  c) Cotton or rayon fabric is impregnated on a padder at 20 to 25 C with a solution containing 30 g of the dye described in this example, paragraph 1, per liter of liquor <B> 100 </B> contains g urea and 20 g soda, squeezes to a moisture content of about 100% and steams for 15 seconds at 103 C.

   After rinsing, boiling soaps and drying, a brilliant scarlet coloration with good wet and light fastness is also obtained.



  d) Cotton fabric is impregnated with a solution of 20 to 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 Contains 150 g urea and 15 g sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of about 100%.

   After intermediate drying at 50 to 60 ° C., the mixture is heated to 140 ° C. for 30 seconds and the resulting dye is rinsed thoroughly with hot water and treated at the boil for 10 minutes with a solution containing 5 g of Marseille soap and 2 g of soda per liter. After rinsing or drying, a strong, scarlet coloration with good wet and light fastness is obtained.



  e) 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 Contains soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was made up to 1 kilogram with water,

       then intermediate drying and then in a suitable steamer for 30 seconds at 103 bis <B> 115'C </B> steams, so you get a strong scarlet color with good fastness properties after rinsing and boiling soaps.



   <I> Example 30 </I> 28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is also coupled <B> 13.7 </B> g of 1-amino-2-methoxy-5-methylbenzene in a weakly acidic medium.

   The monoazo dye obtained is isolated and then or immediately diazotized in solution without isolation and coupled with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid under alkaline conditions. The disazo dye obtained is salted out by adding sodium chloride, filtered off with suction and the isolated product with about 50 parts of crystallized copper sulfate, 40 parts of diethanolamine, 50 parts of ammonia (D:

   0.88) metallized in 5 hours at 95 to 100 C. The dye is isolated from the copper solution by adding salt and carefully acidifying it.



  The copper-plated aminodisazo dye is then acylated in aqueous solution at pH 6 to 7 at a temperature of 20 to 30 ° C. with 20 parts of 2,4-difluoro-6-methoxitriazine, the pH being kept in the specified range by adding soda. When the acylation has ended, 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
EMI0030.0041
    He dyes Cel'lulosegewebe according to the methods known for reactive dyes in wet and lightfast marine blue tones.



  In a similar way, other dyes can be prepared if the above-mentioned monoazo dye from 2-amino-1-methylbenzene-3,5-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene with the in the fol The aminonaphthalenesulfonic acids and 2,4-difluoro-6-methylmercapto-triazine listed in the table are combined in accordance with the instructions given above:

       <I> coupling component </I> 2-Annino-5-hydroxymaphthalene-1,7-disulfonic acid 2-Amino-8-hydroxynaph @ thal, in-3,6-d @ isulfonic acid The dyes obtained are blue in color.

       <I> Example 31 </I> In the solution of 36.5 parts of the sodium salt of 1-Anuno-8 = hydroxynaphthalene-3,6-disulfonic acid in 200 parts of water, 23 parts of 2,4-difluoro-6-phenylamino- given triazine and maintained a pH of 8 to 8.5 while constantly blunting the acid released. The reaction is followed by chromatography.

   The resulting solution of the intermediate dyestuff is added to 900 parts of water and, at a pH of 7 to 8 at 0 to 5 ° C., is coupled with 17.5 parts of diazotized 2-aminobenzenesulphonic acid dissolved in 200 parts of water. At a final pH of 6.5 it is salted out with sodium chloride, suction filtered and washed with 15% sodium chloride solution. It is dried in vacuo at 30 to 40 C.

   The dye
EMI0030.0084
    forms red needles.



  If fabrics made of cotton or regenerated cellulose are dyed or printed with this dye by one of the processes described above, clear bluish red dyeings and prints of good wet, rub and lightfastness are obtained.



  In the table below, the hues of other dyes are listed which are based on the diazo components, coupling components and reactive components linkable to the amino group in the latter analogous to the information in Example 31 or through conversion of the corresponding aminoazo dyes build up the reactive components and after one of the

  The methods described above can be dyed or printed on cellulose materials in the specified tones:
EMI0030.0111
  
    Diazo component <SEP> coupling component <SEP> reactive component <SEP> hue
 <tb> 1-aminobenzene <SEP> 1-amino-8-hydroxy- <SEP> 2,4-difluoro-6- (N 2-sulfonic acid <SEP> naphthalene-3,6-disulfone- <SEP> methyl) phenyl acid <SEP> amino-triazine <SEP> red
 <tb> 1- (4'-aminobenzoyl- <SEP>
 <tb> amino) -8-hydroxy naphthalene-3,6-disulfonic acid
EMI0031.0001
  
    Diazo component <SEP> coupling component <SEP> reactive component <SEP> hue
 <tb> 1-aminobenzene <SEP> 1- (4'Aminobenzoyl- <SEP> 2,4-difluoro-6-n 2-sulfonic acid <SEP> amino) -8-hydroxy- <SEP> butyl-amino-triazine <SEP> red
 <tb> naphthalene-3;

  6-disulfonic acid
 <tb> 2-amino-naphthalene- <SEP> <SEP> 2,4-difluoro-6-phenyl- <SEP>
 <tb> 1,5-disulfonic acid <SEP> amino-triazine
 <tb> 1-aminobenzene <SEP> 1-amino-8-hydroxy- <SEP> 2; 4-Difl @ uor-6-benzyl- <SEP>
 <tb> 2-sulfonic acid <SEP> naphthalene-3,6-disulfone- <SEP> amino-triazine
 <tb> acid
 <tb> 1-amino-2-earboxy- <SEP> <SEP> 2,4-difluoro-6-phenyl- <SEP>
 <tb> benzene-4-sulfonic acid <SEP> amino-triazine
 <tb> 1-amino-4-methyl- <SEP> <SEP> <SEP>
 <tb> benzene-2-sulfonic acid
 <tb> 1-amino-3-acetylamino- <SEP> <SEP> <SEP>
 <tb> benzene-6-sulfone, acid
 <tb> 1-aminobenzene <SEP> 2-amino-5-hydroxy-2-sulfonic acid <SEP> naphthalene-7-sulfonic acid <SEP> <SEP> orange <I> Example 32 </I> In the solution of 21 parts of the sodium salt of 1,

  3-Diaminobenzene-4-sulfonic acid in 200 parts of water, 24 parts of 2,4-difluoro-6-phenylamino-triazine are introduced with thorough stirring and at 0 to 5 ° C. with constant blunting of the hydrofluoric acid released to pH 7.0 8.0 stirred until a sample gives a clear, yellowish red color when diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid.

   The resulting intermediate dye product is filtered off with suction, washed with 10% sodium chloride solution and dried at 60.degree.



  39.8 parts of the sodium salt of the 1-amino-3- (2'-fluoro-4'-phenylamino-triazinyl-6 ') -aminobenzene-6-sulfonic acid obtained above are dissolved in 350 parts of water and 700 parts of dimethylformamide and after addition of 6.9 parts of sodium nitrite, slowly added dropwise to a solution, cooled to 0 C, of 60 parts of concentrated hydrochloric acid in 100 parts of water.

   After half an hour any excess nitrite is destroyed with sulfamic acid and the resulting diazosuspensnon is added to a solution of 29.8 parts of 1- (4'-sulfo-2'-methylphenyl) pyrazolone-5-carboxylic acid (3) in 350 Parts of water given. The pH of the solution is adjusted to 5.0 to 5.5.

   After coupling has ended, the dye is salted out with sodium chloride
EMI0031.0038
    is filtered off with suction, washed with saturated sodium chloride solution and dried at 60 ° C. in vacuo. The dye easily dissolves in water with a yellow color and, according to one of the processes described above, produces yellow dyeings and prints on cellulose materials.



  The following table lists the hues and the pH of the coupling medium of dyes which, analogously to the information in Example 32, consist of a diazo component containing a further acylatable amino group, a coupling component and one with an amino group of the diazo component linkable reactive component produced who the.

       Cellulose materials are colored or printed in the specified colors. Reactive components: A: 2,4-Difluoro-6-phenylamino-triazine B: 2,4-Difluoro-6-n-butylamino-triazine C: 2,4-Difluoro-6- (o-methyl-phenyl) -amino- triazine D:

       2,4-difluoro-6-benzylamino-triazine
EMI0032.0001
  
    Reaction <SEP> pH <SEP> des
 <tb> diazo component <SEP> coupling component <SEP> component <SEP> coupling <SEP> hue
 <tb> mediums
 <tb> 1,3-diaminobenzene <SEP> 2-amino-naphthalene-5,7-disudfonic acid <SEP> A <SEP> 4-5 <SEP> orange
 <tb> 4-sulfonic acid
 <tb> <b> </B> <SEP> 2-amino-naphthalene-3,6-disulfonic acid <SEP> C <SEP> 4-5 <SEP>
 <tb> <SEP> 1-aoetyl, amino-3-hydroxy-naphthalene- <SEP> D <SEP> 7-8 <SEP> red
 <tb> 3,6-disulfonic acid
 <tb> <SEP> 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl- <SEP> A <SEP> 5-6 <SEP> yellow
 <tb> pyrazolone-5
 <tb> <SEP> 1- (3'-sulfophenyl) -3-methyl-5-am, ino-pyrazole <SEP> A <SEP> 6 <SEP>
 <tb> 1,4-diaminobenzene <SEP> 2-amino-8-hydroxynaphthalene-6-sulfonic acid <SEP> A <SEP> 4--4,

  5 <SEP> red
 <tb> 3-sulfonic acid
 <tb> <SEP> 2-acetylamino-5-hydroxy-naphthalene- <SEP> B <SEP> 6-7 <SEP> scarlet fever
 <tb> 7-sulfonic acid
 <tb> <b> </B> <SEP> 1-acetylamino-5-hydroxy-naphthalene- <SEP> D <SEP> 6-7 <SEP> red
 <tb> 7-sulfonic acid <I> Example 33 79.6 parts of 1-amino48-hyd @ roxy-naphthalene-3,6-disulphonic acid are dissolved in 500 parts of water and a suspension of the diazo salt of 1-amino-3- (2'-fluoro 4'-phenylamino-triazinyl-6 ') - aminobenzene-6-sulfonic acid (from 47 parts 1,

  3-diamino-benzenesulfonic acid prepared according to Example -32) given. A pH of 3.0 is set with sodium acetate solution, salted out with sodium chloride after the coupling is complete and the crystalline reaction product is filtered off with suction and washed with 10% strength sodium chloride solution. The dye is dried at 60 ° C. in vacuo. <I> Example 34 </I> 38,

  6 parts of the monoazo dye from Example 33 are dissolved in 460 parts of water and 6.7 parts of soda, and the diazonium solution of 4.7 parts of aniline is added at 0 to 5 ° C. while maintaining a pH of 8 to 8.5.

    The mixture is left to stir for about 3 hours, the pH is adjusted to 5.5 with hydrochloric acid, and the mixture is filtered off with suction and washed with 5% sodium chloride solution. The dye
EMI0032.0041
         is dried at 60 C in a vacuum and produces a black color on cotton and rayon at 8 to 10 3ö iger coloration.



  If, in this example, the diazo components given in the table below are used in an equivalent amount instead of aniline, valuable dyes are likewise obtained which dye cotton in the color shades given.

    
EMI0032.0055
  
    Diazo component <SEP> hue
 <tb> 2 <SEP> amino-benzene-il-sulfonic acid <SEP> black
 <tb> 2-Amino-5-chloro-benzene-l-sulfonic acid <SEP>
 <tb> 2-Amino-5-methyl-abenzene-lrsulfons: acid <SEP>
EMI0032.0056
  
    Diazo component <SEP> hue
 <tb> 2-Am @ ino-5-nitro-benzene-1-sulfonic acid <SEP> black
 <tb> 2, amino-naphthalene-1-sulfonic acid <SEP>
 <tb> dihydro-p-toluidine-disulfonic acid <SEP>
 <tb> 2 "Amino-naphthalene-1; 5-disulfonic acid <SEP>

 

Claims (1)

A process for dyeing or printing textile materials containing hydroxyl groups, characterized in that one or more reactive dyes of the formula are applied to these textile materials in any order EMI0032.0066 applies, where D is the remainder of an organic dye which does not contain the anthraquinone skeleton, Q is an alkylene, Represents aralkylene, arylene, -CO- or -SO- group, R for hydrogen or a lower alkyl group, R for an amino group which can have simply bonded substituents, an optionally etherified oxy or optionally etherified thio group or an optionally substituted hydrocarbon radical, F for a fluorine substituent, m for 1 or 2 and n for the number 0 or 1, and where the group - (Q) ,,- NO) - Is bound directly to a ring carbon atom of the dye residue D. SUBClaims 1. The method according to claim I, characterized in that reactive dyes are used whose radical D has one or more sulfonic acid groups. 2. Process according to patent claim 1, characterized in that reactive azo dyes of the formula EMI0033.0043 used in which B and E represent aromatic, carbocyclic or heterocyclic radicals, in particular B the radical of a carbocyclic diazo component of the benzene or naphthalene series, and E the radical of an enolic or phenolic coupling component, preferably a single 5-pyrazole, an oxynaphthalene or an aminonaphthalene, the substituents, including further azo groups, can have, R 'for a -CH: 3 group or preferably represents a hydrogen atom, R 'represents a preferably mono or disubstituted amino group in which the substituents are bonded to the amino group with single bonds, or in which R' represents an optionally substituted alkoxy group and F a fluorine substituent. n means. 3. The method according to claim 1, characterized in that reactive azo dyes of the formulas EMI0033.0078 EMI0033.0079 EMI0034.0001 used, where A is the remainder EMI0034.0003 R 'represents a -CHs group or preferably a hydrogen atom and R' represents a preferably mono- or disubstituted amino group, in which the substituents with single bonds to the amino group are bonded, or in which R'1 is an optionally substituted alkoxy group, F is a fluorine substituent and in which (o) 1 indicates the ortho position of the respective substituents in the aryl nucleus and Me stands for Cu, Cr or Co. 4, The method according to claim 1, characterized in that reactive phthalocyanine dyes of the formula EMI0034.0037 used, where Pc for the remainder of a nickel or copper phthalocyanine, L and L 'for substituents, in particular sulfonic acid groups, r for an integer from 0 to 2, q for the number 0 or 1, R 'stands for a methyl group or preferably hydrogen and R' stands for a preferred mono- or disubstituted amino group in which the substituents are bonded to the amino group with single bonds, or in which R'1 stands for an optionally substituted alkoxy group, F denotes a fluorine substituent, R:, hydrogen, an alkyl or aryl group and R., denotes hydrogen, an alkyl or aryl group, r 'denotes a number from 0 to 3 and r ″ denotes a number from 0 to 2. 5 . Process according to dependent claim 2, characterized in that reactive dyes are used which have one or more sulfonic acid groups in the radical B and / or E. 6. The method according to dependent claim 4, characterized in that such reactive dyes are used which have one or more sulfonic acid groups. 7th Method according to claim I or one of the preceding sub-claims, characterized in that that the textile material treated with the dye is exposed to the action of elevated temperature. PATENT CLAIMS <B> 11. </B> Dye liquor or printing paste for carrying out the process according to patent claim I, characterized in that that it contains a dye of the formula I. <B> 111. </B> Cellulose-containing textile materials dyed or printed according to the method according to patent claim I. SUBClaim B. Textile materials according to claim III, characterized in that 'they contain native or regenerated cellulose. French <I> Patent Specifications </I> Nos. <I> 137290S, 1400833 </I>