CH494266A - Process for the production of reactive dyes - Google Patents

Description

  

  
 



  Process for the production of reactive dyes
The present invention relates to a process for the preparation of valuable new reactive dyes of the general composition
EMI1.1
 In this formula, D is the radical of an organic dye, R is hydrogen or a lower alkyl group, R1 is hydrogen or a substituent, R2 is hydrogen, halogen, cyano, optionally substituted alkyl, alkenyl, aralkyl and aryl radicals or carboxylic acid ester, carboxamide, Alkylsulfone and arylsulfone groups and F is a fluorine substituent.



   In the dyes of the general formula (I) the -N (R) group is linked directly to a carbon atom of the pyrimidine ring in the 2- or 4-position. On the other hand, the N (R) group can either directly or via a further bridge member, such as -SOz or -CO-, as in the case of amide groups, or via an alkylene group, an alkylene-CO-, an arylene, arylene -SOr, arylene-CO- or a triazine or diazine ring, an arylenamidosulfonyl group to be bound to an aromatic ring of the dye D.

  If such further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, then these too can still have reactive atoms or groups, such as halogen atoms or other large numbers of known substituents.



   Examples of substituents R1 in the 5-position of the pyrimidine ring are: halogen, such as Cl, Br and F, alkyl radicals such as -CH3 and -C2H5, substituted alkyl radicals such as mono-, di- or trichloro- or tribromomethyl-, trifluoromethyl- , Alkenyl such as vinyl, halovinyl and allyl radicals, -NO2, -CN, carboxylic acid, carboxylic acid ester and optionally N-substituted carboxylic acid or sulfonic acid amide groups, sulfonic acid and sulfonic acid ester groups, alkylsulfonyl, aralkylsulfonyl or arylsulfonyl radicals.



   Examples of possible substituents R2 in the 6-position of the pyrimidine ring are: halogen, such as C1, Br and F, alkyl, such as methyl and ethyl, alkenyl, such as vinyl, halovinyl and allyl, and substituted alkyl, such as mono -, Di- or trichloro or bromomethyl or trifluoromethyl radicals, carboxylic acid ester, such as methyl and ethyl ester, carboxamide groups including the N-substitution products, alkylsulfonyl and arylsulfonyl radicals, such as CH: SOr, C2H5SO, CssHs-CG02 and p- -.



   Dyes in which R1 and R. denote hydrogen, halogen and / or alkyl radicals belong to a preferred group of the compounds according to the invention.



   The new dyes can do the rest
EMI1.2
     have one or more times in the molecule. Dyes with 1 to 2 such reactive radicals are preferred for economic reasons.



   Suitable pyrimidine rings
EMI2.1
 which have at least one removable (reactive) fluorine substituent are, for example, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5, 6-dichloro-4-pyrimidinyl, 2,6 difluoro-5-methyl-4-pyrimidinyl, 2,5W-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl, 2-fluoro -5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5methyl-4-pyrimidinyl, 2, 5, 6 -Trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6-difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl -4-pyrimidinyl, 2,6-difluoro-5-chloromethyl -4-pyrimidinyl,

   2,6-Difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2 -Fluoro-6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl , 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-phenyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 2-fluoro 5 -carbomethoxy-4-pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2 fluoro-6 -phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro 5-chloro-6 carbomethoxy-4-pyrimidinyl, 2,

   6-difluoro-5-trifluoromethyl-4-pyrimidinyl.



   Of the large number of possible bonding options for radical (II) 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 other types, including the -N (R) group, are for example (A stands for the remainder of the formula III): -NH-A, -N (CH3) -A, -N (C2H6) -A , -N (C3H7) -A, -CONH-A, -SO2NH-A, -CON (CH3) -A, -SO2N (CH3) -A and the corresponding N-ethyl- and N-propylamides, -HN-CO -NH-A, -HN-CH2-CO-NH-A, N (CH3) CHCONHA, -HN-CH2-CH2-NH-A, -NH-SO2- (CH2) 1-3-NH-A, - NH-CO- (CH) 11-NH-A, -CH2-NH-CO- (CH2) 1-2-NH-A,
EMI2.2
 as well as the corresponding N-alkyl (1-5C) amides or



  amine
EMI3.1
 as well as the corresponding N-alkyl (l-3 C) amides or



  -amines of the compounds mentioned.



   The new dyes can belong to a wide variety of classes, e.g. B. the series of metal-free or metal-containing mono- or polyazo dyes, metal-free or metal-containing azaporphin dyes, such as copper or nickel phthalocyanine dyes, the anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone and dibenzanthrone dyes and the polycyclic Condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds. In the context of these dye classes, among others, dyes of the following general compositions are particularly valuable 1.

  Azo dyes
EMI3.2
 wherein 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, e.g. B. a 5 pyrazolone, an acetoacetic acid 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 -CH group or preferably a hydrogen atom, and R'1 and R'2 independently of one another stand for hydrogen or halogen groups.



   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 both metal-free and metal-containing, the copper, chromium and cobalt complexes being of preferred interest among the metal complexes.

 

   Important azo dyes are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azonaphthalene series, the naphthalene-azo-1-phenylpyrazolone-5 series and the stilbene -azo-benzene series, the dyes containing sulfonic acid groups being preferred here too. In the case of metal complex azo dyes, the metal complex-bonded groups are preferably in the o positions relative to the azo group, e.g. B. in the form of o, o'-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino and o-hydroxy-o'-amino-azo groups.

  Particularly outstanding types of monoazo dyes of the type obtainable according to the invention are illustrated by the following formulas:
EMI3.3
  
EMI4.1


<tb> <SEP> H; <SEP> OCH3; <SEP> NH-aeyi
<tb> OH
<tb> = <SEP> = <SEP> -iJS "<SEP> (vi)
<tb> cE <SEP> 03H <SEP> 1-3
<tb> <SEP> Ocplle <SEP> -o
<tb> (HO3S) - <SEP> 3 <SEP> = <SEP> N (R '<SEP>) -A <SEP> (via)
<tb> <SEP> = <SEP> N <SEP> 0-3JC <SEP> Me = Cu; Cr; Co
<tb> <SEP> H; C1; N02
<tb> <SEP> H; OH;

  ; N02 <SEP> 2
<tb> (sO5H) <SEP> 0-2
<tb> <SEP> o <SEP> Cu <SEP> o
<tb> 8 <SEP> iti <SEP> = <SEP> N <SEP> - <SEP> wNH2 <SEP> (<SEP> or <SEP> NH-acyl)
<tb> (SO3H) 13 <SEP> (viii)
<tb> to
<tb> <SEP> NH-A
<tb> <SEP> NH,
<tb> <SEP> + N <SEP> = <SEP> N <SEP> - <SEP>? 2 <SEP> (ix)
<tb> <SEP> (S 3H) O-1 <SEP> w>
<tb> <SEP> (SG3H) 13
<tb> <SEP> or <SEP> NH-alkyl)
<tb> <SEP> RN <SEP> = <SEP> N <SEP> <
<tb> 50 <SEP> 5H <SEP> HO <SEP> * <SEP> IXa <SEP>)
<tb> <SEP> SO; 3H
<tb> <SEP> ofl <SEP> (NH-acyl) 0 <SEP> or <SEP> 1
<tb> <SEP> = <SEP> '0 <SEP> the <SEP> (
<tb> A-H119N <SEP> tJt (<SEP> SO, H) 1-3 <SEP> (x)
<tb> <SEP> (so3H) 01
<tb> (o) means the o position of the radicals indicated in the aryl nucleus, and A stands for the radical of the formula
EMI5.1
 wherein R'1 and R's have the meanings already given;

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



  2. Anthraquinone dyes
EMI5.2
 Here L and L 'denote substituents, among these in particular sulfonic acid groups, p an integer from 0 to 2, R "denotes a methyl or ethyl group or hydrogen, R'1 and Re independently of one another are hydrogen or halogen radicals.



  3. Phthalocyanine dyes
EMI5.3
 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'1 and R'2 independently of one another are hydrogen or halogen radicals.



  The phthalocyanine residue Pc preferably bears 1-2 sulfonic acid and / or 1-2 sulfonic acid amide groups as further substituents, such as SOoNH2, -SO; NH-alkyl, -SON (alkyl) 2 and SO2NH (aryl) groups, with alkyl for alkyl radicals 1-3 carbon atoms.



   The above compilation of a selection of suitable azo, anthraquinone and azaporphine dyes as well as fluorine-substituted pyrimidine rings does not constitute a restriction of the general formulas. The new dyes can also have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, sulfonamide and carbonamide groups, the can be further substituted on the amide nitrogen atom, sulfonic acid ester and carboxylic acid ester groups, alkyl, aralkyl and aryl radicals, alkylamino, aralkylamino, arylamino, 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 mono- or dihalotriazinylamino-, mono-, di- or trihalopyrimidinylamino-, 2,3-dihaloquinoxaline-6-carbonyl- or -6-sulfonylamino-, 1,4-dihalogenophthalazine-6 -carbonyl- or -6-sulfonylamino-, 2-halogen- or 2-alkylsulfonyl- or 2-arylsulfonylbenzthiazole- 5-carbonyl- or -5-sulfonylamino-, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfonic acid oxyalkylamide groups, sulfonic acid oxyalkylamide and oxyalkylsulfonylamino groups -, acryloylamino, haloacylamino groups or other reactive groups.



   The process according to the invention is characterized in that dyes D-N (R) H are used with compounds of the general formula
EMI5.4
  in which R1 and R2 have the meaning given (F stands for a fluorine substituent) and X stands for a radical which can be removed anionically, one or more of the reactive radicals contained in formula XIII being introduced. Among the reactive substituents X which can be split off as anionic radicals, the fluorine substituent is of preferred interest. Further radicals which can be removed anionically from case to case are, for example, quaternary ammonium groups, such as -N (CH3) 3 and -N (CiH5) 3.



   Heterocyclic pyrimidine compounds of the formula (XIII) which are suitable for the reaction are, for example, 2,4-difluoropyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine, 2,4,6-trifluoropyrimidine , 2, 4-Difluoropyrimidine- 5-ethylsulfone, 2,6-Difluor- 4-chloropyrimidine, 2, 4, 5, 6-tetrafluoropyrimidine, 2, 4, 6-trifluoro-5-chloropyrimidine, 2, 6 difluoro-4- methyl 5-bromopyrimidine, 2, 4-difluoro-5, 6-dichloro- or -dibromopyrimidine, 4, 6-difluoro-2, 5-dichloro- or -dibromopyrimidine, 4,6-difluoro-4-bromopyrimidine, 2,4, 6-trifluoro-5-bromopyrimidine, 2,4,6-trifluoro5-chloromethylpyrimidine, 2, 4, 6-trifluoro-5-nitropyrimidine, 2, 4, 6-trifluoro-5-cyanopyrimidine, 2, 4, 6-trifluoropyrimidine 5-carbonsÅallremethyl- or -äthylester or -5carbonsäureamid, 2,6-difluoro-5-methyl-4-chloropyrimidine, 2,6-difluoro-5-chloropyrimidine, 2, 4,

   6-trifluoro-5-methylpyrimidine, 2, 4, 5-trifluoro-6-methylpyrimidine, 2, 4-difluoro-5-nitro-6-chloropyrimidine, 2,4-difluoro-5cyanpyrimidine, 2,4-difluoro-5- methylpyrimidine, 6-trifluoromethyl-5-chloro-2, 4-difluoropyrimidine, 6-phenyl-2, 4-difluoropyrimidine, 6-trifluoromethyl-2, 4-difluoropyrimidine, 5-trifluoromethyl-2, 4, 6-trifluoropyrimidine, 5-trifluoromethyl -2, 4-difluoro-pyrimidine, 2, 4-difluoro-5-nitro-pyrimidine, 2, 4-difluoro-5-trifluoromethyl-pyrimidine, 2, 4-difluoro-5-methylsulfonyl-pyrimidine, 2, 4-difluoro-5-phenyl pyrimidine, 2,4-difluoro-5-carbonamido-pyrimidine, 2,4-difluoro-5-carbomethoxypyrimidine, 2,4-difluoro-6-trifluoromethyl-pyrimidine, 2,4-difluoro-5-bromo-6-trifluoromethyl-pyrimidine , 2, 4-difluoro-6-carbonamido-pyrimidine, 2, 4-difluoro-6-carbomethoxy-pyrimidine, 2, 4-difluoro-6-phenylpyrimidine, 2, 4-difluoro-6-cyanopyrimidine, 2, 4,

   6-trifluoro-5-methylsulfonyl-pyrimidine, 2,4-difluoro-5-chloro-6-carbomethoxypyrimidine.



  2,4-Difluoro-5-sulfonamido-pyrimidine.



   In the condensation reaction with the dyes or dye precursors containing amino or amide groups, these pyrimidine derivatives probably each react in the 4-position with elimination of the radical X.



  In the general formulas (I), (II) and (IV) to (XII), the pyrimidine ring is therefore likely and preferably bonded to the remainder of the N (R), N (R ') group-containing dye via the 4-position.



   Said and other fluoropyrimidine compounds which can be used according to the invention can generally be obtained easily by reacting the corresponding chlorine or bromine compounds with alkali metal fluorides, e.g. B. with potassium fluoride, NaHF2, KSO2F, SOF2, AgF.2 or by reacting appropriate OH compounds with SF4, COF2, COCIF or cyanuric fluoride, or by heating the corresponding diazonium tetrafluoborates.



   Those reactive components which have the formula are particularly preferred for the reaction according to the invention
EMI6.1
 correspond, where R'1 and R'2 are independently hydrogen or halogen radicals (Cl, Br or F) and Y represents an anionically removable radical, in particular a fluorine substituent.



   The reaction of the dyes or dye precursors containing amino or amide groups with heterocyclic compounds of the formula (XIII) is usually carried out, depending on the type of starting compounds used, in an organic, organic-aqueous or aqueous medium at temperatures from -10 ° C. to 100 ° C., preferably from 0 to 500C, in the presence of alkaline condensation agents such as aqueous alkali carbonate or alkali hydroxide solutions.



   When dye intermediates are used, the condensation products obtained are converted into the desired end dyes in a manner customary per se. This process is of preferred interest for the preparation of azo dyes, for example by first condensing a diazo and / or coupling component, which has a reactive amino or amide group, with the reactive component (XIII) or (XIV) and then condensing the intermediate product obtained Converts diazotization and / or coupling and / or condensation into an azo dye. 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, in particular those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (XIII) or (XIV) can initially take place with an intermediate product, e.g. B. with m-phenylenediamine or an m phenylenediaminesulfonic acid, and the resulting reaction product can then be further condensed with an anthraquinone sulfonic acid halide or with a copper or nickel phthalocyanine sulfonic acid halide to form a reactive phthalocyanine dye.



   Another variant for the preparation of the new dyes of the formula (I), which can be used in some cases, is that in dyes or, in particular, dye intermediates, the at least one group of the general formula
EMI6.2
  wherein R, R1 and R2 have the meaning given and Z is an anionically removable radical, except for a fluorine substituent, have, Z exchanges for a fluorine substituent in a manner known per se and, if dye precursors are used, these are then converted into the desired end 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 dyes obtainable by the various processes described can, as already mentioned for some cases, be subjected to further reactions customary for dyes, for example by treating metallizable dyes with metal donating agents, in particular with chromium, cobalt, copper or nickel salts, Dyes that have reducible groups, in particular nitro groups, are reduced, dyes that have acylable groups, in particular acylatable amino groups, acylated, or by treating dyes subsequently with sulfonating agents, such as chlorosulfonic acid, oleum or SOs in chlorinated hydrocarbons, in order to (further) Introduce sulfonic acid groups into the products.



  The last-mentioned process is sometimes of particular importance in the series of anthraquinone and 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 -HNR groups in the dyestuff radical or in the dyestuff precursors which are suitable for the conversion reaction, one or more groupings of the general formula (II) can be incorporated into the dyes. 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, e.g. B.



  to synthesize up to 8 groupings of the formula (II).



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



   When dyes containing amino groups are reacted with reactive components of the formula (XIII) or (XIV), groups of particularly preferred dyes are obtained if the amino group-containing starting dyes on which the dyes of the formulas (IV) to (XII) are based, ie instead of the
EMI7.1
 or the -N (R ') - A group have the grouping -N (R') - H or -N (R ") - H.



   In the preparation of phthalocyanine dyes, a diaminoaryl compound monocondensed with the reactive component (XIII) or (XIV) can be prepared and then condensed with preferably copper or nickel phthalocyanine sulfonic acid halides, with other amino compounds such as ammonia, aliphatic amino compounds and / or aromatic amino compounds can also be used. In this way, phthalocyanine, preferably copper or nickel phthalocyaninesulfonamide dyes are obtained which contain a certain proportion of sulfonarylamide groups which carry the reactive group and in addition a certain proportion of non-reactive sulfonamide groups and / or free sulfonic acid groups.



  Likewise, copper or nickel phthalocyaninesulfonic acid (aminoaryl) amides, which may additionally have optionally N-substituted sulfonamide groups of a different type and free sulfonic acid groups, can be added to the amino group of the aminoaryl radical with reactive components (XIII) or (XIV) to form the new dyes (I ) condense.



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



   To dye cellulose, the dyes are preferably used in an aqueous solution to which alkaline substances, such as alkali hydroxide or alkali carbonate, or compounds that change into alkaline substances, such as alkali bicarbonate, ClsC-COONa, can be added. Further auxiliaries can be added to the solution, but these should not react in an undesired manner with the dyes. Such additives are, for example, surface-active substances, such as alkyl sulfates, or substances that prevent the migration of the dye or auxiliary dye products, such as urea, or indifferent thickeners, such as oil-water emulsions, tragacanth, starch, alginate or methyl cellulose.

 

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



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



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



   For dyeing from a long liquor, one goes into an aqueous solution of the dye (liquor ratio 1: 5 to 1:40) at room temperature and dyeing for 40 to 90 minutes, optionally increasing the temperature to 20-90 ° C., preferably 30-50 ° C. , with partial addition of salt, e.g. sodium sulfate, and then alkali, e.g. sodium phosphates, sodium carbonate, NaOH or KOH, where the chemical reaction between dye and fiber occurs.



  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 cold padding process, subsequent heating of the padded fabric can be saved by the fact that the fabric is left for some time, e.g. B. 2 to 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 on materials containing hydroxyl groups, a printing paste consisting of the dye solution, a thickening agent such as sodium alginate, and a compound that reacts alkaline or releases alkali when heated, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium hydrogen carbonate, is used and the printed material is rinsed and soaped.



   If the dyes contain groups that form metal complexes, the dyeings and prints can often 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.



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



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

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



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



  Here, too, in the event that the dyes used contain groups forming metal complexes, the colorations can be carried out with metal donating agents, such as copper salts, e.g. Copper sulfate or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, can sometimes be improved in their fastness properties.



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



   The new products of the formula (I) have significant advantages in terms of application compared to known reactive dyes containing chlorine- or bromopyrimdinylamino-group-containing reactive dyes, as described for example in Belgian patents 572 973, 573 299 and 578 742. The new dyes, which have a 2,6-difluoro-5-chloropyrimidinylamino or a 2-fluoro-5,6-dichloropyrimidinylamino radical, surprisingly provide a better color yield compared to the next comparable trichloropyrimidinylamino dyes on cotton and regenerated fibers and are superior to these in terms of color strength when dyeing from a long liquor.

  In contrast to the known chloropyrimidine reactive dyes, the new fluoropyrimidine reactive dyes are also well suited for the so-called cold padding process for cotton and regenerated fibers. The new dyes can be used for quick fixation in the printing process. The bond between fibers and dye is much stronger in an alkaline medium than with known dyes.



   The new fluoropyrimidine reactive dyes are distinguished from the known chloropyrimidine dyes in that they produce valuable dyeings on wool with good fastness to washing, fulling and potting. Wet-fast dyeings can also be obtained on silk and synthetic superpolyamide and polyurethane fibers.



   In the following examples, parts stand for parts by weight, unless otherwise stated. These relate to parts of volume like kg to liter.

 

   example 1
To the solution of 34.7 parts of sodium 2-aminonaphthalene-4,8-disulfonic acid and 7 parts of sodium nitrite in 300 parts of water, 28 parts by volume of concentrated hydrochloric acid are added while cooling with ice and the mixture is stirred at 0-10 ° C. for 1/2 hour. After excess nitrous acid has been removed, 10.7 parts of 3-aminotoluene, dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water, are added and the coupling is completed by blunting the mixture to pH 3-5. The aminoazo dye formed is salted out, filtered off with suction, washed and then redissolved in 1400 parts of water and 200 parts of acetone with the addition of sodium hydroxide solution at pH 7.

  19.2 parts of 2,4,6 trifluoro-5-chloropyrimidine are added dropwise to this solution at 2 (r-30 "C) and a pH of 5.5-6 is maintained with 2N sodium carbonate solution. When the reaction is complete, the resulting dye of the likely formula
EMI9.1
 Salted out with 210 parts of saturated sodium chloride solution and the product which has crystallized in yellow needles is filtered off with suction and washed with 2% NaCl solution and dried at 500 ° in vacuo.

  If cellulose fabric is printed with a printing paste which contains 15 grams of the dye, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg thickening), 20 g soda and which has been made up to 1 kg with water, dried, steamed for 1 minute at 105 ° C., rinsed with hot water and soaped at the boil, a strong, reddish-yellow print of good fastness to washing and light is obtained.



   Example 2
0.1 mole of the copper complex compound of the formula
EMI9.2
 (prepared according to the information in German patent specification 1,117,235) by coupling diazotized 1-amino-8- (benzenesulfonyloxy) -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) are dissolved in 2500 parts by volume of water at 60-65 "C at pH 6-6.5 and at 20-300 with 0.12 mol of 2, 4, 6-trifluoro-5-chloropyrimidine were added.



   During the condensation, a pH of 6-6.5 is maintained by adding sodium carbonate solution.



  When the reaction has ended, the dye is salted out and isolated. When dried, the dye is a dark powder that dissolves in water with a blue color.



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



   Example 3
46 parts of the monoazo dye obtained analogously to the information in Example 1 by coupling diazotized 2-aminonaphthalene-4, 8-disulfonic acid onto 3-methylamino-toluene are dissolved in 400 parts of water, 100 parts of acetone at 20-30 ° C., 20 parts of 2 , 4,6-Trifluoro5-chloropyrimidine is added dropwise while maintaining a pH of 6-7 using 2N soda solution; the condensation is continued until a sample no longer shows any change in color when acidified. The resulting dye has the probable formula
EMI9.3
 and is salted out, filtered off with suction, washed and dried at 300 in a vacuum.



   Cotton fabric is impregnated with a solution of 20-25 ° C. which contains 20 g of the obligatory dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylene oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate per liter of liquor.



  The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50-60.degree. C., the mixture is heated to 140.degree. C. for 2 minutes 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 Marseille soap and 2 g of soda per liter. After rinsing and drying, a strong reddish yellow coloration with good wet, rub and lightfastness is obtained.



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



   Abbreviations for the reactive A = 2,4,6-trifluoro-5-chloropyrimidine components: B = 2,4,6-trifluoropyrimidine Example Diazo component Coupling component Reactive color no. Component
4 2-aminonaphthalene-4,8-1-amino-2-methoxy-5-A yellow disulfonic acid methylbenzene
5 2-aminonaphthalene-4,8-1-amino-2-methoxy-5-B yellow disulfonic acid methylbenzene
6 1-aminonaphthalene-3,6 disulfonic acid 1-amino-3-methylbenzene A yellow
7 1-aminonaphthalene-3,6-disulfonic acid 1-amino-3-methylbenzene B yellow
8 2-amino-naphthalene-5,7-disulfonic acid 1-amino-3-methylbenzene A yellow
9 2-aminonaphthalene-5,7 disulfonic acid 1-amino-3-methylbenzene B yellow 10 2-aminonaphthalene-6,8 disulfonic acid 1-amino-3-methylbenzene A yellow 11 2-aminonaphthalene-6,8 disulfonic acid <RTI

    ID = 10.7> 1-Ariino-3-methylbenzene B yellow 12 4-Aminoazobenzene-3,4'-disulphonic acid 1-Amino-3-methylbenzene A blue 13 1-aminobenzene-4-sulphonic acid <1-aminonaphthalene
6-sulfonic acid 1-Ammo-3-methylbenzene B brown-yellow 14 2- (3'Sulfo-4'-aminophenyl) -
6-methyl-benzothiazole-7-sulphonic acid 1-amino-3-methylbenzene A yellow 15 2-aminonaphthalene-4,8- 1-methylamino-3-disulfonic acid methoxybenzene B yellow 16 2-aminonaphthalene-4,8-1-amino 3-acetyl disulfonic acid aminobenzene A yellow 17 2-aminonaphthalene-4,8 disulfonic acid aniline A yellow
Example 18
51.6 parts of that obtained by diazotizing 1-hydroxy-2-aminobenzene-4-sulfonic acid and coupling

   2-Amino5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper-donating agent of the dye of the formula
EMI10.1
 are dissolved in 1500 parts of water at pH 7. With thorough stirring, 20.0 parts of 2, 4, 6-trifluoro-5-chloropyrimidine are added dropwise at 20-30 ° C. and the hydrofluoric acid liberated is continuously blunted with soda solution to a pH of 6-7. When free amino groups can no longer be detected, the reactive dye formed is of the formula
EMI10.2
 salted out, pressed out, washed and dried in vacuo at 30-40 ° C. Fabrics made of cellulosic materials can be dyed or printed with this dye using one of the above-mentioned methods in wet, rub and lightfast ruby tones.

 

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



     Abbreviations for the reactive components as in the table for example 3 Example aminoazo dye complex reactive color no. Bound component
Heavy metals 19 1-Hydroxy-2-aminobenzene-Cu A Ruby
4,6-disulfonic acid # 2-amino
5-hydroxynaphthalene-7-sulfonic acid 20 1-hydroxy-2-aminobenzene-Cu A ruby
4-sulfonic acid # 2-ethylamino
5-hydroxynaphthalene-7 sulfonic acid 21 1-amino-2-hydroxy-6-nitro-Cu A ruby naphthalene-4-sulfonic acid
2-amino-5-hydroxynaphthalene
7-sulfonic acid 22 1-amino-2-hydroxy-6-nitro-Cr A greenish naphthalene-4-sulfonic acid # gray
2-amino-5-hydroxynaphthalene
7-sulfonic acid 23 1-amino-2-hydroxy-6-nitronaphtha- Co B reddish tinged lin-4-sulfonic acid + 1-amino black
8-hydroxynaphthalene-4-sulfone

   Acid 24 1-Amino-2-hydroxy-5-methylsul- Cu A Violet phonyl-benzene # 1-Amino-8-hydroxy-naphthalene-3,6-disulphonic acid 25 1-Amino-2-hydroxy-5-methylsul- Co A gray fonyl-benzene # 1-amino-8-hydroxy naphthalene-3,6-disulphonic acid 26 1-amino-2-hydroxy-5-methylsul- Cr A greenish fonyl-benzene # 1-amino-8-hydroxy- black naphthalene- 3,6-disulphonic acid 27 1-amino-2-methylbenzene-4-sul-Cu B bluefinic acid o 1-amino-2-hydroxy
5-methylbenzene # 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid 28 1-amino-2-methylbenzene-4eul-Co B gray acid # 1-amino-2-hydroxy
5-methylbenzene o 1-amine-8-hydroxynaphthalene-4,

   6-disulfonic acid 29 1-Amino-2-methylbenzene-4-sul- Cr A greenish tinged acid # 1-Amino-2-hydroxy- Black
5-methylbenzene # 1-amino-8 hydroxynaphthalene-4,6-disulfonic acid 30 (1-amino-2-chlorobenzene-4-sulfone-Cu A marine acid # 1-hydroxy-2-acetylaminobenzene), blue saponified, # 1 -Amino-8-hydroxy naphthalene-3,6-disulfonic acid 31 (1-amino-2-chlorobenzene-4-sulfone- Co A gray acid # hydroxy-2-acetylaminobenzene), fonsäure 1 -hydroxy-2,6MDIAMINORENZOL 32 1- Amino-8-hydroxynaphthalene-4-sul Co A Black -4-sulfonic acid # 1,3-dihydroxybenzene 33 1-Amino-8-hydroxynaphthalene-3,

   6-di- Co A black sulfonic acid t -hydroxy-2,6-diamino benzene-4-sulfonic acid # 2-hydroxy naphthalene 34 1-amino-8-hydroxynaphthalene-4- Co A black sulfonic acid + 1-hydroxy-2, 6-dia monobenzene-4-sulfonic acid o 3-methyl pyrazolone- (5)
Example 35
96 parts (based on 100% goods) of the copper phthaloxyanine tetrasulfochloride freshly prepared in the usual manner by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or of the isomeric copper built up from 1-sulfobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid phthalocyanine-tetrasulfochloride are in the form of the moist,

   Well washed suction cake suspended in 500 parts of water and 500 parts of ice, the solution of 50 parts of 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 continuously adding soda. The resulting condensation product is precipitated at pH 1-2 by adding sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral.



  57 parts of 2, 4, 6-trifluoro-5-chloropyrimidine are added to the blue solution with vigorous stirring and the mixture is stirred at 20-30 ° C. with constant blunting with soda solution to pH 6 until no more free amino groups can be detected. The reactive dye of the formula obtained in this way
EMI12.1
 is salted out, washed and dried at 30-400C 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 or printing processes.



   Instead of the 96 parts of copper phthalocyanine tetrasulfonyl chloride, with otherwise the same procedure as in Example 35, 87 parts (based on 100% of the above goods) of the copper or nickel phthalocyanine trisulfonyl chloride obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine in the form of the moist can be used suction cake washed with ice water can be used; reactive dyes which also have a clear blue color are then obtained.



   Even if you work as indicated in Example 35, but start from 87 parts of copper phthalocyanine trisulfochloride and instead of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonic acid 90 parts of the sodium salt of 4,4'-diaminodiphenyl2,2'- disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulfonic acid, reactive dyes are obtained which dye cellulose materials in wet, rubbing and lightfast, clear blue tones by one of the above processes.



   If you start from the 4 ', 4 ", 4'", 4 "" - tetraphenyl-cuphthalocyanine, after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with 2,4,6-trifluoro-5-chloropyrimidine one gets Reactive dye that dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.



   Example 36
63 parts of 1-amino-4- (4'-aminophenyl) -amino-anthraquinone-2, 5, 8-trisulfonic acid are dissolved in 630 parts of water, the pH is adjusted to 6 with sodium hydroxide solution, then 18 parts are added dropwise at 0-5 ° C 2, 4, 6-Trifluor-5chlorpyrimidin and maintains a pH of 66.5 with soda solution. After the reaction has ended, it is re-salted with 7 parts of potassium chloride, filtered off with suction and washed with 3 ole potassium chloride solution. The dye, which is obtained in blue-green needles, is dried in vacuo at 30-40 ° C. It probably has the following formula
EMI12.2
 and dyes cotton in greenish blue tones.

 

   Example 37
If one proceeds as indicated in Example 18, but instead of the copper-containing aminomonoazo dye used there, 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-sulfouyl-phenyl-3-methylpyrazolone- (5) obtained aminoazo dye, a reactive dye is obtained, which cellulose materials by one of the processes given above in good wet, rub- and lightfast yellow-brown tones colors.



   Example 38
0.1 mole of the copper complex compound of the formula
EMI12.3
  are dissolved in 3000 parts by volume of water at pH 6 and combined with stirring at a temperature of 20-30 ° C. with 16.8 parts by weight (0.1 mol) of 2,4,6-trifluoro-5-chloropyrimidine and a pH of 2N potassium carbonate solution 6 complied with. The mixture is stirred until the condensation has ended, and the dye is precipitated 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 1-3.



   Cotton fabric is impregnated with a solution at 20-25 ° C. which contains 25 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate per liter of liquor the fabric is squeezed between two rubber rollers to a moisture content of approx. 100 o / o.



  After intermediate drying at 50-60 ° C., the mixture is heated to 140 ° C. for 2 minutes 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 Marseille soap and 2 g of soda per liter. After rinsing and drying, a green dyeing of good wet, rub and light fastness is obtained.



   Other customary dyeing or printing processes also give clear green tones with good fastness properties on cellulose materials.



   Example 39
0.1 mole of the paste of the aminoazo compound of the formula
EMI13.1
 which is obtained by coupling the diazonium compound from 6 acetamino-2-aminonaphthalene-4,8Xdisulfonic acid with 2 oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex are dissolved in 2000 parts by volume of water at pH 6.5 and with 20 parts by weight of 2, 4, 6-trifluoro-5-chloropyrimidine combined. The reaction mixture is stirred at 20-30 ° C. until the condensation has ended, the pH of the reaction solution being kept at 6-7 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.



   Example 40
The aqueous solution of 0.1 mole of the copper complex of the formula
EMI13.2
 manufactured according to the information in German patent specification 1,061,460 or 1,085,988, is reacted in the customary manner with 22 parts by weight of 2,4,6-trifluoro-5-chloropyrimidine. The pH is kept at W7 by adding soda and the dye is isolated by salting out after the reaction has ended. When dried, it is a dark powder that dissolves in water with a purple color. Cotton fabric is dyed in lightfast and wetfast purple tones.



   Example 41
56.8 parts of the diaminoazo dye obtained by coupling diazotized 1-amino-3-acetylaminobenzene-6-sulfonic acid to 2-aminonaphthalene-5, 7-disulfonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are dissolved in 450 parts of water at pH 7 solved. After adding 20 parts of 2, 4, 6-trifluoro-5-chloropyrimidine, the hydrofluoric acid released is constantly blunted with soda solution to pH 6-7 approx.



  Stirred for one hour at 30 ° C. When the acylation is complete, the reactive dye formed is presumably of the formula
EMI13.3
 salted out, filtered off, redissolved in 4000 parts of water at 30 ° C., filtered and separated out in completely pure form from the filtrate by adding 400 parts of common salt. The dye is dried in a vacuum as usual at 35 ° C. It dyes cellulose materials in true yellowish orange tones by one of the processes mentioned above.



   Example 42
To a neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminnaphthalene-3, 6, 8-trisulfonic acid with 3-acetylaminoaniline in an acetic acid medium in 500 parts of water are added 2q parts of 2, 4, 6 trifluorine 5-chloropyrimidine and stir for one hour at 30.degree. C., a pH of 6 being maintained by constant addition of sodium hydroxide solution. The partially precipitated acylation product is completely separated out at pH 7 by adding 100 parts of sodium chloride and filtered off. For purification, the reactive dye obtained in this way can be dissolved again in 2500 parts of water at 30 ° C., clarified and separated out again by salting out the filtrate with 350 parts of common salt.



  The dye has the formula
EMI14.1
 After filtering off, drying at 35 "C and grinding, it is a yellow powder that easily dissolves in water with a yellow color and dyes cellulose fibers in very real reddish yellow tones using one of the above-mentioned dyeing processes in the presence of acid-binding agents. Also on wool and polyamide fibers, true yellow dyeings are obtained.



   Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4'-amino2'-acetylamino-phenyl- (1 ') -azonaphthalene- (2) -3, 6, 8-trisulfonic acid sodium corresponding amounts of the amino compounds indicated in column 2 and the coupling component indicated in column 3 are used in the usual manner by diazotization and coupling in an acetic acid medium aminoazo dyes and acylated with 2, 4, 6-trifluoro-5-chloropyrimidine.



  Example diazo component coupling component color shade on play cotton no.



   43 2-aminonaphthalene-1-amino-3-methyl-6-methoxy-strong red
1,5-disulfonic acid benzene
yellow
44 2-Aminonaphthalene-1-Amino-3-methylbenzene Yellow 1,5isulfonic acid
45 2-aminonaphthalene-1-aminonaphthalene-6- reddish
1,5-disulfonic acid sulfonic acid yellow
46 2-aminonaphthalene-1-amino-3-acetylamino-rusty
1,5-disulfonic acid benzene yellow
47 2-aminonaphthalene-3-aminophenylurea reddish
1,5-disulfonic acid yellow
48 2-aminonaphthalene-1-amino-3-hydroxyacetyl reddish
1,5-disulfonic acid aminobenzene yellow
49 2-aminonaphthalene-1-amino-3-methyl-6-methoxy strongly rotsti
5,7-disulfonic acid benzene yellow
50 2-aminonaphthalene-1-aminonaphthalene-7-sulfone reddish.



   5,7-disulfonic acid yellow
51 2-aminonaphthalene-1-amino-3-acetylaminobenzene reddish 5,7zisulfonic acid yellow
52 2-aminonaphthalene-3-aminophenylurea reddish
5,7-disulfonic acid yellow
53 2-aminonaphthalene-1-amino-3-hydroxyacetyl reddish
5,7-disulfonic acid aminobenzene yellow
54 1-aminonaphthalene-1-amino-3-methyl-6-meth- strongly rotsti
3.7 disulfonic acid oxybenzene yellow
55 1-aminonaphthalene-1-amino-3-methylbenzene reddish
3,7-disulfonic acid yellow
56 1-aminonaphthalene-1-aminonaphthalene-6-sulfone reddish
3,7-disulfonic acid yellow
57 2-aminonaphthalene-1-amino-3-methylbenzene reddish
3,6-disulfonic acid yellow
58 2-aminonaphthalene-1-amino-3-methyl-6-methoxy strongly rotsti
3,6-disulfonic acid benzene-like yellow
59 2-aminonaphthalene- <RTI

    ID = 14.14> 1-amino-3-acetylamino reddish
3,6-disulfonic acid benzene yellow
60 2-aminonaphthalene-3-aminophenylurea reddish
3,6-disulfonic acid yellow
61 2-aminonaphthalene-1-amino-3-hydroxyacetyl-reddish 3,6aisulfonic acid aminobenzene yellow
62 2-aminonaphthalene-1-aminonaphthalene-6-sulfone reddish
3,6-disulfonic acid yellow
63 2-aminonaphthalene-1-amino-3-acetylaminobenzene reddish
6,8-disulfonic acid yellow
64 2-aminonaphthalene-1-amino-2-methoxynaphthalene-stark rosti
6,8-disulfonic acid 6-sulfonic acid-like yellow 65 2-Amionaphthalin-1-Aminonaphthalin-6-Sul- reddish
6,8-disulfonic acid yellow 66 2-aminonaphthalene-1-aminonaphthalene-6-sulfone yellow
4,8-disulfonic acid 67 2-aminonaphthalene-1-aminonaphthalene-7-sulfonic acid

   yellow
4,8-disulfonic acid 68 2-aminonaphthalene-1-amino-2-methoxynaphthalene- strongly rotsti
4,8-disulfonic acid 6-sulfonic acid yellow 69 2-aminonaphthalene-1-methylamino-3-methylbenzene yellow
4,8-disulfonic acid 70 2-aminonaphthalene-1-ethylamino-3-methylbenzene yellow
4,8-disulfonic acid 71 2-aminonaphthalene-N-methylaniline yellow
4,8-disulfonic acid 72 2-aminonaphthalene-N-ethylaniline yellow
4,8-disulfonic acid 73 2-aminonaphthalene-N- (ss-hydroxyethyl) -aniline yellow
4,8-disulfonic acid 74 2-aminonaphthalene-N-butylaniline yellow
4,8-disulfonic acid 75 2-aminonaphthalene-aniline reddish
3,6,8-trisulfonic acid yellow 76 2-aminonaphthalene-1-amino-3-methylbenzene reddish
3,6,8-trisulfonic acid yellow 77 2-aminonaphthalene-3-aminophenylurea reddish
3,6,8-trisulfonic acid yellow 78 2-aminonaphthalene- 1-amino-3-hydroxyacetyl-

   reddish
3,6,8-trisulfonic acid aminobenzene yellow 79 2-aminonaphthalene-1-amino-3-acetylamino-6-yellow tinge
3,6,8-trisulfonic acid methoxybenzene sat. Orange 80 2-aminonaphthalene-1-amino-3-acetylamino-6-reddish
3,6,8-trisulfonic acid methylbenzene yellow 81 2-aminonaphthalene-1-amino-3-methane-sulfonyl-reddish
3,6,8-trisulfonic acid aminobenzene yellow 82 2-aminonaphthalene-2,5-dimethoxyaniline yellowish
3,6,8-trisulfonic acid sat. Orange 83 2-aminonaphthalene-3-methyl-6-methoxyaniline yellowish
3,6,8-trisulfonic acid sat. Orange 84 2-aminonaphthalene-N iMethylanilin reddish
3,6,8-trisulfonic acid yellow 85 2-aminonaphthalene-N-ethylaniline reddish
3,6,8-trisulfonic acid yellow 86 2-aminonaphthalene-N-butylaniline reddish
3,6,8-trisulfonic acid yellow 87 2-aminonaphthalene-N- (ss-hydroxyethyl) -aniline reddish
3,6,8-trisulfonic acid yellow

   88 2-aminonaphthalene- 3- (N-ethylamino) toluene reddish
3,6,8-trisulfonic acid yellow 89 2-aminonaphthalene-2-aminotoluene reddish
3,6,8-trisulfonic acid yellow 90 2-aminonaphthalene-1-amino-2,5-dimethyibenzene strongly reddish
3,6,8-trisulfonic acid-like yellow 91 2-aminonaphthalene-1-amino-2-methoxybenzene very reddish
3,6,8-trisulfonic acid-like yellow 92 2-aminonaphthalene-1-amino-3-methoxybenzene reddish
3,6,8-trisulfonic acid yellow 93 2-aminonaphthalene-1-ethylamino-3-methoxybenzene reddish
3.6,

   8-trisulfonic acid yellow 94 2-aminonaphthalene-1-aminonaphthalene-6-sulfonic acid reddish
3,6,8-trisulfonic acid yellow 95 2-aminonaphthalene-1-aminonaphthalene-7-sulfonic acid reddish
3,6,8-trisulfonic acid yellow 96 2-aminonaphthalene-1-amino-3-methylbenzene reddish
4,6,8-trisulfonic acid yellow 97 2-aminonaphthalene-1-amino-3-acetylaminobenzene reddish
4.6,

   8-trisulfonic acid yellow
98 1-Aminonaphthalene-1-Amino-3-methylbenzene Yellow
2,4,7-trisulfonic acid
99 1-aminonaphthalene-1-aminonaphthalene-6-sulfonic acid yellow
2,4,7-trisulfonic acid 100 4-nitro-4'-aminostil- 1-amino-3-acetylaminobenzene reddish ben-2,2'-disulfonic acid yellow 101 4-nitro-4'-aminostil- 3-aminophenylurea reddish ben- 2,2'-disulfonic acid yellow 102 4-nitro-4'-aminostil- 1-amino-3-hydroxyacetylamino reddish ben-2,2'-disulfonic acid benzene yellow 103 4-nitro-4'-amino-N-methylaniline reddish stilbene-2,2'-disulfonic acid 104 4-nitro-4'-amino-N-ethylaniline reddish stilbene-2,2'-disulfonic acid 105 4-nitro-4'-amino-N-butylaniline reddish stilbene-2,2'-disulfonic acid 106 4-nitro-4'-amino-N- (ss-hydroxyethyl) aniline

   reddish-tinged stilbene-2,2'-disulfonic acid 107 4-nitro4'-amino- 1- (N-ethylamino) -3-methylbenzene reddish-tinged stilbene-2,2'-disulfonic acid 108 aniline-2,5isulf- 1-aminonaphthalene-6-sulphonic acid yellow 109 aniline-2,5-disul- 1-aminonaphthalene-7-sulphonic acid red-tinged fonic acid yellow 110 aniline-2,5-disul- 1-amino-3-methylbenzene yellow fonsäure 111 Aniline-2,5-disul- 1-amino-3-acetylaminobenzene yellow fonsäure 112 aniline-2,5-disul-1-amino-2-methoxy-5-methyl-reddish fonsäure benzene yellow 113 aniline-2,5-disul - 1-Amino-2,5-dimethoxybenzene reddish acidic acid yellow 114 Aniline-2,4-disulfone-1-amino-2-methoxy-5-methyl-reddish acidic acid benzene yellow Example 115
65 parts of the dye of the formula
EMI16.1
 (made by domes

   of diazotized 1-hydroxy2-aminobenzene-4,6-disulfonic acid to 2-amino-8-hydroxynaphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water until neutral. 20 parts of 2,4,6-trifluoro-5-chloropyrimidine are added and the mixture is stirred at 20-30 ° C. while constantly blunting the liberated acid with soda solution to p 6-7, until no free amino group can be detected any longer. The resulting reactive dye of the formula
EMI16.2
 is salted out, filtered off, washed and dried at 30-40 0C. It dyes 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: No. Diazo component Coupling component Color shade
Cotton 116 1-hydroxy-2-amino coupling component ruby benzene-4-sulfonic acid naphthalene-7-sulfonic acid 117 1-hydroxy-2-amino 2-irthyl-amino-5-hydroxy ruby benzene-4-sulfonic acid naphthalene-7- sulfonic acid 118 1-hydroxy-2-amino 2- (ss-hydroxyethylamino) - ruby benzene-4-sulfonic acid 5-hydroxynaphthalene-7-sulfonic acid 119 1-hydroxy-2-amino-2-amino-8-hydroxynaphthalene ruby benzene4 sulfonic acid 3,6-disulfonic acid 120 1-hydroxy-2-amino 2-amino-5-hydroxynaphthalene ruby benzene-4,6-disulfonic 1,7-disulfonic acid 121 <RTI

    ID = 17.4> 1-Hydroxy-2-amino-2-amino-8-hydroxynaphthalene-ruby benzene-4,6-disulfonic-3,6-disulfonic acid 122 1-hydroxy-2-amino 2-methylamino-5-hydroxy - Rubin benzene-4,6-disulfonic acid-naphthalene-7-sulfonic acid 123 1 -Hydroxy-2-amino-2-ethylamino-5-hydroxy- Rubin benzene-4,6-disulfonic-naphthalene-7-sulfonic acid 124 1 -Hydroxy-2-amino- 2- (ss-hydroxyethylamino) -5-hy- ruby benzene-4,6-disulfonic-droxynaphthalene-7-sulfonic acid 125 1-hydroxy-2-amino-1-amino-8-hydroxynaphthalene - Violet benzene-4,6-disulfonic-3,6-disulfonic acid 126 1-Hydroxy-2-amino-1-amino-8-hydroxynaphthalene- Violet benzene-4,6-disulfonic-4,6-disulfonic acid 127 1-Hydroxy -2-amino-1-amino-8-hydroxynaphthalene violet benzene-5-sulfonic acid 3,6-disulfonic acid 128

   1-Hydroxy-2-amino-1-amino-8-hydroxynaphthalene violet benzene-5-sulfonic acid 4,6 disulfonic acid 129 1-Hydroxy-2-amino-4-1-amino-8-hydroxynaphthalene violet.



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



   acetylaminobenzene-6- 3,6-disulfonic acid violet sulfonic acid (4-position acetylamino group then saponified) 131 1-hydroxy-2-amino-4- 1-amino-8-hydroxynaphthalene blue acetylaminobenzene-6,2,4-disulfonic acid sulfonic acid 132 1-Hydroxy-2-amino-4-1-amino-8-hydroxynaph- blue acetylaminobenzene-6-thalin sulfonic acid 2,4,6-trisulfonic acid 133 1-hydroxy-2-amino-1-amino-8-hydroxynaphthalene blue
6-acetylaminobenzene-2,4-disulfonic acid
4-sulfonic acid (6-position acetylamino group saponified) 134 1-amino-2-hydroxy-6- 1-amino-8-hydroxynaphthalene blue nitronaphthalene-4- 2,4-trisulfonic acid sulfonic acid (6-position nitro group subsequently reduced to -NH2 ) 135 1-Amino-2-hydroxy-6- 1-amino-8-hydroxynaphthalene blue nitronaphthalene-4- 2,4,6-trisulfonic acid sulfonic acid (6-position nitro group subsequently reduced to

   -NH2) 136 1-Hydroxy-2-amino-6- 1-Amino-8-hydroxynaphthalene blue acetylaminobenzene-4- 2,4,6-trisulfonic acid sulfonic acid (6-position acetylamino group saponified)
The solution of 19.5 parts of the sodium salt of 1-aminobenzene-4-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is concentrated in a mixture of 100 parts of ice and 28 parts by volume. Let in hydrochloric acid; then the mixture is stirred for half an hour at 0-10 ° C., and then excess nitrous acid is removed.

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

  20 parts of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise to the aqueous solution and the mixture is stirred for one hour at 20-30 ° C. with soda solution to pH W7 while the acid released is continuously blunted. When the aminoazo dye is no longer detectable, the partially precipitated reactive dye becomes of the formula
EMI18.1
 Salted out with 40 parts of sodium chloride, filtered off and dissolved again in 800 parts of warm water for cleaning. After the solution has been clarified, the pure dye is separated out from the filtrate by adding 80 to 100 parts of common salt.

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



   If you proceed as indicated above, but instead of the 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-amino-naphthalene-8-sulfonic acid, one obtains according to Acylation with 2,4,6-trifluoro-5-chloropyrimidine also valuable yellow to brown reactive dyes.



  Diazo component shade on
Cellulose fiber 1-aminobenzene-2,5-disulfonic acid reddish yellow 2-amino-naphthalene-4,8-disulfonic acid strongly reddish yellow 2-amino-naphthalene-5,7-disulfonic acid strongly reddish yellow 2-amino-naphthalene-6,8- disulfonic acid very reddish yellow 2-amino-naphthalene-3,6,8-trisulfonic acid very reddish
Yellow 2-amino-naphthalene-4, 6,

   8-trisulfonic acid strongly reddish
Yellow 4-Amino-azobenzene-3,4-disulfonic acid yellowish brown 4-Amino-2-acetylamino-azobenzene-2 ', 5'-disulfonic acid Orange brown
EMI18.2
 reddish brown (1-aminobenzene-2,5-disulfonic acid acidic to 1-aminonaphthalene-6-sulfonic acid coupled) diazo component color shade on cellulose fiber
EMI19.1
 reddish brown (1-aminobenzene-2,5-disulfonic acid acidic to the technical mixture of 1-aminonaphthalene-6- and -7-sulfonic acid coupled)
EMI19.2
 violet-tinged brown (1-amino-naphthalene-2,5,7-trisulfonic acid acidic to t-amino-naphthalene-6-sulfonic acid coupled)
EMI19.3
 reddish brown (1-amino-naphthalene-2,5 7-trisulfonic acid acidic to 1-amino-2-methoxy-5-methylbenzene coupled)
Example 138
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
EMI19.4
 in 400 parts of water, the mixture is stirred with 40 parts of 2,4,6 trifluoro-5-chloropyrimidine for about 2 hours at 30-40 ° C. while maintaining pH 6-7. When the aminoazo dye (Co complex: blue; Cr complex: blue-green) can no longer be detected by chromatography, the resulting mixture of the two reactive dyes is salted out with potassium chloride, filtered off and dried
The dye produces strong, very good wet and lightfast black tones on cellulose materials by the pad dyeing process or in printing in the presence of acid-binding agents.



   If one proceeds accordingly, but using a mixture of the chromium 2: 1 and cobalt 2: 1 complexes of the following aminoazo dyes, valuable black dyes are also obtained: diazo component, coupling component, coupling pH 1-hydroxy-2-amino-4 1 -hydroxy-8 -amino-naphthalene- 9 nitrobenzene 3,6-disulfonic acid 1 -hydroxy-2-amino-4- 1-hydroxy-8-amino-naphthalene- 9 nitronaphthalene-3,6-disulfonic acid 7-sulfonic acid
Example 139
Add to the neutral solution of 53.15 parts of the disodium salt of the by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2 '<chloro-5'sulfophenyl) -3-methyl-pyrazolone- (5) and then Reduction of the nitro group with sodium sulfide obtained NEN aminoazo dye in 300 parts of water 20 parts <RTI

    ID = 20.2> 2,4,6-trifluoro-5-chloropyrimidine and the mixture is stirred for one hour - at 30 ° C., and the released
Acid continuously with soda solution to a pH of
6.0 dulls. The deposited dye of the formula
EMI20.1
 is filtered off, dissolved in 3000 parts of warm water at pH 6-7 and reprecipitated from the filtered solution by adding sodium chloride. After filtering off, drying and powdering, a yellow, readily water-soluble powder is obtained, the cellulosemateria lien from a long liquor at 300C or after the block
Cold dwell process with soda as an acid-binding agent colors in clear, washable, rub- 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 ones are also obtained
Reactive dyes.



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



  Example diazo component azo component pH of the shade on play coupling cellulose no. Mediums
140 1-Amino-4-nitro- 1- (4'-sulfophenyl) - 5-6 yellow benzene-2-sulfonic acid 3 -methyl-pyrazolone- (5) (4-position nitro group then reduced)
141 l-Amino-4-nitro- 1- (4'-sulfophenyl) - 56 reddish benzene-2-sulfonic acid 3-carboxy-pyrazo yellow ion- (5)
142 1-Amino-4-nitro-1- (3'-sulfophenyl) - 6-7 yellow benzene-2-sulfonic acid 3-methyl-5-aminopyrazole
143 1-Amino-3-acetyl- 1- (3, -Sulfophenyl) - 6-7 yellow amino-benzene-6- 3-methyl-5-amino sulfonic acid pyrazole (3-position acetylamino group subsequently saponified)
144 1-Amino-3-acetyl- l4ss-hydroxyethyl) - 56 yellow amino-benzene-6- 3-methyl-pyrazolone sulfonic acid (5)
145 2 moles

   1-Amino-3- 1 mole bis-pyrazolone 56 yellow acetyl-amino-benzene- from 4,4'-bis-hydrazino
6-sulfonic acid (dibenzyl-2,2'-disulfonic soap) acid and acetoacetic ethyl ester)
146 1 mole of 1-amino-3- 1- (4'-sulfophenyl) - 56 yellow acetyl-amino-benzene-3-carboxy-pyrazolone
6-sulfonic acid (soaped (5))
147 1-Amino-5-acetyl- 1- (4'-sulfophenyl) - 56 rotst.



     amino-naphthalene-3; 7-3-carboxy-pyrazolone-yellow disulfonic acid (soaped (5)
148 1-Amino-2-methyl-2-Acetylamino-5- 7-8 Orange benzene-4,6-disulfonic naphthol-7-sulfonic acid (saponified)
149 1-Amino-2-methyl-2-Acetylamino-8- 7-8 Red benzene4 6 -lisulphonic naphthol-6-sulphonic acid (saponified) 150 1-Amino-2-methyl-1-chloro-2-acetyl - 7-8 Orange benzene-4,6-disulphonic-amino-5-naphtholic acid 7-sulphonic acid (saponified) 151 1-aminobenzene-2- 1-acetylamino-8-hydroxy-7-8 red sulphonic acid naphthalene-4,6 disul - fonsäure (saponified) 152 2-aminonaphthalene- 1-acetylamino-8-hydroxy-7-8 bluust.



   3,6-disulfonic acid naphthalene-4,6-disulfonic acid (saponified) 153 2-aminonaphthalene-1-acetylamino-8-hydroxy-7-8 bluust.



   3,7-disulfonic acid naphthalene-4,6-disulfonic acid (saponified) 154 2-aminonaphthalene-1-acetylamino-8-hydroxy-7-8 bluust.



   4,8-disulfonic acid naphthalene-4,6-disulfonic acid (saponified) 155 2-aminonaphthalene-3,6-1-acetylamino-8- 7-8 bluust.



   disulfonic acid hydroxynaphthalene red
3,6-disulfonic acid (saponified) 156 2-aminonaphthalene-1-acetylamino-8- 7-8 bluust.



   4,8-disulfonic acid hydroxynaphthalene red
3,6-disulfonic acid (saponified) 157 1-amino-4-methoxy-2- (N-acetyl-N-methyl-7-8 yellow.



   benzene-2-sulfonic acid amino) -5-hydroxy- red naphthalene-7-sulfonic acid (saponified) 158 1-amino-4-methoxy- 2- (N-acetyl-N-methyl- 7-8 red benzene-2- sulfonic acid amino) -8-hydroxy naphthalene-6-sulfonic acid (saponified) 159 1-aminobenzene-2- 2- (N-acetyl-N-methyl- 7-8 red sulfonic acid amino) -8-hydroxy naphthalenex-sulfone- acid (saponified) 1'60 1-aminobenzene-3- 2- (N-acetyl-N-methyl- 7-8 red sulfonic acid amino) -8-hydroxy naphthalene-6-sulfonic acid (saponified) 161 1-aminobenzene- 4- 2- (N-Acetyl-N-methyl-7-8 Red sulfonic acid amino) -8-hydroxy naphthalene-6sulfonic acid (saponified) 162 1-Amino-4-methyl-24N-acetyl-N-methyl-7 -8 Red benzene-2-sulfonic acid amino) -8-hydroxy naphthalene-6-sulfonic acid (saponified) 163

   1-Amino-2,4-dimethyl-2- (N-acetyl-N-methyl-7-8 red benzene-6-sulfonic acid amino) -8-hydroxy naphthalene-6-sulfonic acid (saponified) 164 1-amino -2,4-dimethyl-2-acetylamino-8- 7-8 red benzene-6-sulfonic acid hydroxynaphthalene
6-sulfonic acid 1 (saponified) 165 1-amino-2,4-dimethyl-2-acetylamino-8- 7-8 red benzene-6-sulfonic acid hydroxynaphthalene
3,6-disulfonic acid (saponified) 166 4-aminoazobenzene- 1-amino-3cetyl- 5-6 yellow-
3,4'-disulfonic acid aminobenzene brown 167 4-aminoazobenzene-1-amino-3-hydroxy-56 yellow
3,4'-disulfonic acid acetylaminobenzene brown 168 4-aminoazobenzene-1-amino-naphthalene-56 yellow
3, 4'-disulfonic acid 6-sulfonic acid brown 169 4-aminoazobenzene- 1-amino-naphthalene-5-6 yellow
3,4'-disulfonic acid 7-sulfonic acid brown 170 4-aminoazobenzene-

   1-amino-2- (4'-amino-8 black
3,4'-disulfonic acid, 2'-sulfophenyl- (1 ') azo) -8-hydroxynaphthalin-3,6-disulfonic acid
Example 171
52.4 parts of the disodium salt of 4 - ([4 "-amino phenyl] -amino) -2'-nitro-diphenylamine-3,4'-disulfonic acid are dissolved in 1000 parts of water and 20 parts of 2, 4, 6- Trifluoro-5-chloropyrimidine stirred at 20-30 ° C. for one hour. The acid released is continuously blunted with soda to a pH value of 5.5-6. The reactive nitro dye formed of the formula
EMI22.1
 is salted out, filtered off, washed and dried. sung. Clear blue dyeings are obtained on cotton. It dyes cellulose fibers from a long liquor or from good wet fastness properties and good light fastness.



  one of the usual Klotz processes in the presence of the dye obtained corresponds to the probable soda as an acid-binding agent in wet and rub-fast, chen formula deep purple-brown shades.



   Example 172
52 parts of 1-amino-4- (4'-N-methylaminomethylanilino) -anthraquinone-2,2'-disulfonic acid are dissolved in 550 parts of water and adjusted to pH 6 with sodium hydroxide solution. 18 parts of 2,4,6-trifluoro-5-chloropyrimidine are then added dropwise at room temperature and a pH of 6 is maintained with 2N sodium carbonate solution. The conversion is followed by chromatography. The reaction product crystallized in blue needles is filtered off with suction and the filter residue is washed with 3 O / above sodium chloride solution
EMI22.2
 Example of a water-soluble amino-anthraquinone derivative shade no.



  173 1 -Amiuo-4 (4'-Nmethylaminomethylanilino) - green.



     anthraquinone-2,6,2'-trisulfonic acid blue 174 1-Amino-4- (4'-N-methylaminomethylanilino) - green.



     anthraquinone-2,5,8-trisulfonic acid blue 175 1 amino-4- (4'-N-methylaminomethylanilino) - blue anthraquinone-2,8-disulfonic acid 176 1-amino4- (4'-aminoanilino) -anthraquinone- blue green
2,6-disulfonic acid 177 1-amino-4- (4'-aminoanilino) anthraquinone green.



   2,5-disulfonic acid blue 178 1-Amino-4- (3'-aminoanilino) anthraquinone blue
2,6-disulfonic acid 179 1-amino-4- (3'-aminoanilino) anthraquinone blue
2,5-disulfonic acid 180 1-amino-4- (3'-aminoanilino) -anthraquinone- something
2,4'-disulfonic acid rotst. Blue 181 1-Amino-4- (3'-aminoanilino) anthraquinone red.



   2,4'-6'-trisulfonic acid blue 182 1-Amino-4- (4'-aminocyclohexylamino) - clear anthraquinone-2,5,8-trisulfonic acid blue 183 1-Amino-4- (4'-N-methylaminomethylanilino) - Blue anthraquinone-2,3'-disulfonic acid 184 1-Amino-4- (4'- [4 "-aminobenzoylamino] -anilino) - Blue-green anthraquinone-2,5,8-trisulfonic acid 185 1-Amino-4- (4 '- [4 "-aminobenzenesulfamido] - green.



     anilino) anthraquinone-2,5,8-trisulfonic acid Blue 186 1-Amino-4- (4 "-aminostilbenamino) -anthraquinone- Green
2,2 ', 2 "trisulfonic acid
EMI23.1
 clear rotst. blue
Example 188
If one proceeds as indicated in Example 139, but instead of the aminoazo dye used there, 53.15 parts of the disodium salt of the 1-amino-4-nitrobenzene-2-sulfonic acid obtained by coupling with 1- (2'-chloro-5'-sulfophenyl) ) - 3-methyl-pyrozolone- (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye with the 2,4,6 trifluoro-5-chloropyrimidine acylated, one also obtains a valuable reactive dye, with which cellulose materials according to the usual Dyeing and printing processes can be printed in real yellow tones.



   Similar reactive dyes are obtained if, instead of the above-mentioned aminoazo dye, one of the aminoazo dyes made up of the components listed in the table below is acylated with 2,4,6-trifluoro-5-chloropyrimidine: Example diazo component azo component shade no.



  189 1-Amino-4-nitro- 1- (2'-methyl-4'-sulfo- yellow benzene-2-sulfon-phenyl) -3-methyl-pyraic acid (reduced) zolone45) 190 1-Amino-4- nitro- 1- (2 ', 5'-disulfophenyl) - yellow benzene-2-sulfonic 3-methyl-pyrazolon- (5) acid (reduced) 191 1-amino-4-nitro- 1 <2'-methyl- 4'-sulfo- yellow benzene-2-sulfone- 6'-chlorophenyl) -3-methyl acid (reduced) pyrazolone- (5) 192 1-amino-4-nitro- 1- (2 ', 5'-dichloro- 4'- yellow benzene-2-sulfon-sulfophenyl) -3-methyl- acid (reduced) pyrazolone (5) 193 1-amino-3-acetylamino- 1- (2'-methyl-4'-sulfo- green-tinged benzene- 6-sulfonic acid phenyl) -3-methyl-pyrazo yellow (saponified) ion- (5) 194 1 -amino-3-acetylamino- 1- (4'-sulfophenyl) -3- green-tinged benzene-6-sulfonic acid methyl-pyrazolone (5) yellow

   (saponified) 195 1-Amino-3-acetylamino- 1- (2'-methyl-4'-sulfo-green-tinged benzene-6-sulfonic acid phenyl) -3-carboxy-pyrazo-yellow (saponified) ion- (5) 196 1-Amino-3-acetylamino- 1- (2'-chloro-4'-sulfo- green-tinged benzene-6-sulfonic acid phenyl) -3-carboxypyrazo yellow (saponified) ion- (5)
Example 197 58 parts of the dye of the formula
EMI24.1
 (produced by coupling diazotized 1-hydroxy2-amino-4-chlorobenzene-5-sulfonic acid to 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved in 700 parts of water under neutral conditions.

  20.0 parts of 2,4,6 trifluoro-5-chloropyrimidine are added dropwise and the mixture is stirred at 20-30 ° C. while constantly blunting the hydrofluoric acid released with soda solution to pH 6.0-6.5 until there are no more free amino groups - is demonstrable. The reactive dye formed of the formula
EMI24.2
 is salted out, filtered off, washed and dried at 30-40 ° 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 oxidizing copper plating of the mono- and disazo dyes produced from the diazo and azo components listed in the table below: Example diazo component azo component coupling color tone play pH No.



  198 1-Hydroxy-2-amino-2-amino-8-hydroxy-10 rotst.



   4-chlorobenzene-5-naphthalm-3,6-violet sulfonic acid disulfonic acid 199 1-hydroxy-2-amino-1-amino-8-hydroxy-10 bluust.



   4-chlorobenzene-5-naphthalene-3,6-violet sulfonic acid disulfonic acid 200 2-amino-naphthalene-2-hydroxy-6-ace- 8-9 rotst.



   4,6,8-trisulfonic acid tylamino-naphtha- blue (oxidizing copper-plated) lin-4-sulfonic acid (saponified) 201 1-amino-2-hydroxy-1-hydroxy-8-ether-10 blue
6-nitronaphthalenoxy-naphthalene
4-sulfonic acid (re-3,6-disulfonic acid reduced) 202 1-hydroxy-2-amino- 2-hydroxy-3-amino- 10 red benzene-4,6-disulfonic-naphthalene-5,7 acid disulfonic acid 203 2- Amino-naphthalene-2-hydroxy-3-amino-8-9 blue
4,8-disulfonic acid naphthalene-5,7 (oxidizing copper-plated) disulfonic acid 204 2-aminonaphthalene-2-hydroxy-3-amino-8-9 blue
4,6,8-trisulfonic acid naphthalene-7-sulfonic (oxidizing copper-plated) acid 205 3-methoxy-4-amino-6- 2-methylamino-5- 10 marine methyl-azobenzene-2 ', hydroxynaphthalene blue
4'-disulfonic acid (methylated copper-7-sulfonic acid) 206 3-methoxy-4-amino-6- 2-amino-8-hydroxy-10 marine methyl-azobenzene-2 ',

   naphthalene-3,6-di-blue
4'-disulfonic acid (desulfonic acid methylating copper-coated) 207 3-methoxy-4-amino-6-2-amino-5-hydroxy-10 marine methyl-azobenzene-2 ', naphthalene-1,7-di-blue
4'-disulfonic acid (methylated copper-containing desulfonic acid) 208 3-methoxy-4-amino-2-methylamino-5- 10 marine
6-methyl-azobenzene-hydroxynaphthalene-blue
2 ', 5'-disulfonic acid 7-sulfonic acid (demethylating copper-plated) 209 3-methoxy-4-amino-2-amino-8-hydroxy-10 marine
6-methyl-azobenzene-naphthalene-3,6-di-blue
2 ', 5'-disulfonic acid sulfonic acid (demethylating copper-plated) 210 3-methoxy-4-amino-2-amino-5-hydroxy-10 marine
6-methyl-azobenzene-naphthalene-1, 7-di-blue
2 ', 5'-disulfonic acid sulfonic acid (demethylating copper-plated)
Example 211
62.0 parts of trisodium salt of 4-chloro-2-amino-1-hydroxybenzene-6- diazotized by soda-alkaline coupling

   sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are obtained in 300 parts of water at 70-80 ° C. and a pH of 8-9 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 were added. After 10 minutes a deep blue solution has formed.



   The mixed complex is acylated with 20 parts of 2,4,6-trifluoro-5-chloro-pyrimidine in about one hour at 30 10 C and a pH of 6.5-7.5. The pH value is kept constant by adding soda solution. The acylated dye is precipitated with 200/0 sodium chloride, filtered off with suction and dried at 30.degree
EMI25.1
 The process given in Example 3 gives a blue-black print of excellent lightfastness and washfastness on cotton.



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



   The coppered amino-diazo dye is then acylated in aqueous solution at pH 6-7 at a temperature of 20-30 ° C. with 20 parts of 2,4,6-trifluorochloropyrimine, the pH being in the specified range by adding soda is held. 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:
EMI25.2
     tr dyes cellulose fabric using the methods known for reactive dyes in wet and lightfast navy blue tones.



   In a similar way, further dyes according to the invention can be prepared if the above-mentioned monoazo dye is obtained from Z-amino-1-methylbenzene-3,5-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene with the aminonaphtholsulfonic acids listed in the table below and 2,4,6-trifluoro-5-chloropyrimidine combined in accordance with the instructions given above.



   Coupling component 2-amino-5-hydroxynaphthalene
1,7-disulfonic acid
2-amino-8-hydroxynaphthalene
3,6-disulfonic acid
The dyes obtained are blue in color.



   Example 213
0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid are diazotized and coupled with 0.1 mol of 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid in an alkaline form. 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 4-6 and after 30 minutes at pH 97 and temperatures of 20-30 ° C. with 0.1 mol of 2.4, 6-trifluoro-5-chloro-pyrimidine acylated. The obtained dye of the formula
EMI26.1
 is salted out.

  A blue color is obtained on cotton.



   Example 214
A neutral paste of copper phthalocyanine-3,3 ', 3 "-trisulphonic acid chloride made from 600 g of technical 96% copper phthalocyanine is stirred with a little water, adjusted to 4 liters and at a pH of 3.5-6.0 with 216 g N-methyl-N- (4-amino-2'sulfobenzyl) -amine at initially 0-3 "C, finally 20-35 ° C, with the addition of 300 ml (= 295 g) of pyridine and then the pyridine at pH 9 , 0 distilled off with steam from the resulting solution of copper phthalocyanine disulfonic acid monosulfonic acid (3 'sulfo-4'-methyl-aminomethyl-anilide).

  In the brought to 20-30 ° C. solution, 300 g of 2,4,6-trifluoro-5-chloro-pyrimidine are partially added dropwise over the course of 1 to 2 hours and. maintain a pH of 6-7 by adding dilute sodium hydroxide solution. At the same time, if necessary, the reaction mixture is diluted with water to such an extent that the dye always remains dissolved.



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



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



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



   Example 215
0.1 mole of the aminoazo dye of the formula
EMI26.2
 prepared according to the information in German patent specification 1,115,865 (application F 27466 IV b / 22 a) by coupling the diazonium compound from 2-aminonaphthalene-4,8-disulfonic acid with 1-aminonaphthalene-6sulfonic acid, further diazotizing the resulting aminoazo dye, coupling with the equivalent amount of 2.5 diaminonaphthalene-4,8- disulfonic acid and conversion into the aminotnazole - are dissolved in 1000 parts by volume of water at pH 6 and, with stirring at a temperature of 20-30 ° C, with 21 parts of 2,4,6-trifluoro- 5-chloro-pyrimidine was added. The slowly liberated hydrofluoric acid is blunted with soda solution until the reaction has ended.

  The dye is then deposited by adding sodium chloride, isolated and dried at about 50 ° C. in vacuo.



  It is a yellow powder that is soluble in water with a yellow color.



   Example 216
38.9 parts of the dye obtained by coupling with alkaline soda from 6-nitro-2-diazo-1-hydroxybenzene-4-sulfonic acid and 2-hydroxynaphthalene are stirred in 200 parts of water at pH 8 at a temperature of 70-80 ° C. 67.9 parts of the chromium complex compound of the azo dye composed of 4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6 and containing 1 chromium atom per molecule of dye are carried into this suspension - Disulfonic acid, the pH being kept between 7 and 9 by adding soda solution. After 20 minutes at 70-80 Cc a dark blue solution has formed.



  The paper chromatogram shows that a uniform mixed complex has arisen. The mixed complex is acylated within one hour at 40 ° C. and pH 6.5-7.5 with 22.0 parts of 2,4,6-trifluoro-5-chloropyrimidine, the pH being kept in the specified range by adding a soda solution dropwise . 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
EMI27.1
 It dyes cotton in gray to black shades using the method given in Examples 1-3.



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



     l: l chromium complex metal-free dye hue on
Cotton 217 4-Nitro-2-amino-1-hydroxybenzene-6-sul- 4-nitro-2-amino-1-hydroxybenzene black (fonsäure o 1-amino-8-hydroxynaphthalene-) 2-hydroxynaphthalene
3,6-disulfonic acid 218 4-nitro-2-amino-1-hydroxybenzene-6-sul-4-nitro-2-amino-1-hydroxybenzene black fonic acid e l-amino-8-hydroxynaphthalene- # 2-hydroxynpahthalene
3,6-disulfonic acid 219 4-Nitro-2-amino-1-hydroxybenzene-6-sul- 4-nitro-2-amino-1-hydroxybenzene black acid # 1-amino-8-hydroxynaphthalene- # 2-hydroxynaphthalene
3,6-disulfonic acid 220 4-Nitro-2-amino-1-hydroxybenzene-6-sul-4-nitro-2-amino-1-hydroxybenzene black acidic acid <RTI

    ID = 27.12> # 1-Amino-8-hydroxynaphthalene- # 2-hydroxynaphthalene-6-sulfonic acid
3,6-disulfonic acid 221 4-nitro-2-amino-1-hydroxybenzene-6-sul-4-nitro-2-amino-1-hydroxybenzene black fonsäure e l-amino-8-hydroxynaphthalene-o 2-hydroxynaphthalene-6 sulfonic acid
3,6-disulfonic acid 222 4-nitro-2-amino-1-hydroxybenzene-6-sul-4-nitro-2-amino-1-hydroxybenzene navy blue phonic acid # 1-amino-8-hydroxynaphthalene-# 1-hydroxynaphthalene-4 sulfonic acid
3,6-disulfonic acid 223 4-nitro-2-amino-1-hydroxybenzene-6-sul-6-nitro-2-amino-1-hydroxybenzene-4-black phonic acid # 1-amino-8-hydroxynaphthalene-sulfonic acid # 2 -Hydroxynaphthalene
3,6-disulfonic acid 224 4-nitro-2-amino-1-hydroxybenzene-6-sul-

   4-nitro-2-amino-1-hydroxybenzene black fonsäure # 1-amino-8-hydroxynaphthalene- # 1-acetylamino-7-hydroxynaphthalene
3,6-disulfonic acid 225 4-nitro-2-amino-1-hydroxybenzene-6-sul-6-nitro-1-amino-2-hydroxynaphthalene-black acid # 1-amino-8-hydroxynaphthalene-4-sulfonic acid # 2 -Hydroxynaphthalene
3,6-disulfonic acid 226 4-nitro-2-amino-1-hydroxybenzene-6-sulfone-4-nitro-2-amino-1-hydroxynaphthalene-black acid # 1-amino-8-hydroxynaphthalene-4,6- 6 -sulfonic acid # 2-hydroxynaphthalene disulfonic acid 227 4-chloro-2-amino-1-hydroxybenzene-6-sulfone- 4-nitro-2-amino-1-hydroxybenzene blue-black acid # 1-amino-8-hydroxynaphthalene-3,6- # 2-hydroxynaphthalene disulfonic acid 228

   4-chloro-2-amino-1-hydroxybenzene-6-sulfone- 4-nitro-2-amino- 1 -hydroxybenzene blue-black acid # 1-amino-8-hydroxynaphthalene-3,6- # 2-hydroxynaphthalene disulfonic acid 229 4- Chloro-2-amino-1-hydroxybenzene-6-sulfone-4-nitro-2-amino-1-hydroxybenzene blue-black acid # 1-amino-8-hydroxynaphthalene-3,6- # 2-hydroxynaphthalene-6-sulfonic acid disulfonic acid 230 4-chloro-2-amino-1-hydroxybenzene-6-sulfone- 4-chloro-2-amino-1-hydroxybenzene navy blue acid # l-amino-8-hydroxynaphthalene-3,6- o 2-hydroxynaphthalene disulfonic acid 231 4- Chloro-2-amino-1-hydroxybenzene-6-sulfone-4-nitro-2-amino-1-hydroxybenzene blue acid # 1-amino-8-hydroxynaphthalene-3,6- # 1-acetylamino-8-hydroxynaphthalene disulfonic acid 3 , 6-disulfonic acid 232 <RTI

    ID = 28.10> 4-chloro-2-amino-l-hydroxybenzene-6-sulfone 4-nitro-2-amino-1-hydroxybenzene navy blue acid # l-amino-8-hydroxynaphthalene-3,6- e 1-amino- 8-hydroxynaphthalene disulfonic acid 2,4-disulfonic acid 233 4-chloro-2-amino-1-hydroxybenzene-6-sulfone-6-nitro-1-amino-2-hydroxynaphthalene blue-black acid # 1-amino-8-hydroxynaphthalene- 3,6-4-sulfonic acid # 2-hydroxynaphthalene disulfonic acid 234 4-chloro-2-amino-1-hydroxybenzene-6-sulfone-2-aminobenzene-1-carboxylic acid-5-sulfonic acid gray-green acid # 1-amino-8-hydroxynaphthalene -3,6- # 1-phenyl-3-methyl-5-pyrazolon disulfonic acid 235 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid- 6-nitro-1-amino-2-hydroxynaphthalene- black re #

   1-Amino-8-hydroxynaphthalene-3,6-di- -4-sulfonic acid # 2-hydroxynaphthalene sulfonic acid 236 4-chloro-2-amino-1-hydroxybenzene-6-sulfone- 4-chloro-2-amino-1- hydroxybenzene violet acid # 1-amino-8-hydroxynaphthalene- # 1- (4'-sulfophenyl) -3-methyl
3,6-disulfonic acid 5-pyrazolone 237 4-methyl-2-amino-1-hydroxybenzene-6-sulfone-4-chloro-2-amino-1-hydroxybenzene reddish acid # 1-amino-8-hydroxynaphthalene-3,6 - # 2-hydroxynaphthalene-6-sulfonic acid blue disulfonic acid 238 4-nitro-2-amino-1-hydroxybenzene-6-sulfone- 5-nitro-2-amino-1-hydroxybenzene black acid # 1-amino-8-hydroxynaphthalene- 3,6- # 2-Hydroxynaphthalene-6-sulfonic acid disulfonic acid 239 4-Nitro-2-amino-1-hydroxybenzene-6-sulfone-4-nitro-2-amino-1-hydroxybenzoI

   black acid # 1-amino-8-hydroxynaphthalene-3,6- # 2-hydroxynaphthalene-8-sulfonic acid disulfonic acid 240 4-nitro-2-amino-1-hydroxybenzene-6-sulfone-4-nitro-2-amino-1 -hydroxybenzene black acid # 1-amino-8-hydroxynaphthalene-3,6- # 1-hydroxynaphthalene-5-sulfonic acid disulfonic acid 241 4-nitro-2-amino-1-hydroxybenzene-6-sulfone-6-nitro-4-chloro -1-hydroxybenzene blue black acid # 1-amino-8-hydroxynaphthalene-3,6- # 1-hydroxynaphthalene-5-sulfonic acid disulfonic acid
Example 242
8.2 parts of 1-amino-4- [3'-amino-anilino] -anthraquinone-2-sulfonic acid are dissolved in a mixture of 160 parts of water and 80 parts of dioxane with the addition of 1.05 parts of sodium carbonate.

  3.8 parts of 2,4,6-trifluoro-5-chloro-pyrimidine are added dropwise at 0 C. and a Pn of 66.5 is maintained by adding 2N soda solution. When the acylation is complete, the dye is salted out at 20 ° C. with 25 parts of sodium chloride and the crystalline product is filtered off with suction, washed with 2% sodium chloride solution and dried in vacuo at 30 ° C.



   The dye dyes wool in very wetfast blue tones.
EMI28.1




   Example 243
8.3 parts of 1-amino4- [4'-aminocyclohexylamino] anthraquinone-2-sulfonic acid are dissolved in 160 parts of water and 80 parts of dioxane with the addition of 1.3 parts of the above sodium hydroxide solution and at W5 C 3.8 Parts of 2,4,6-trifluoro-5-chloropyrimidine were added dropwise. A pH of 9-10 is maintained by adding 2N soda solution.



  When the acylation is complete, the pH is adjusted to 4.5 by adding hydrochloric acid. The crystalline product is filtered off with suction and washed with 2 of the above sodium chloride solution until it is colorless. The dye obtained is dried in vacuo at 30 ° C. and dyes wool in clear, washable blue tones.
EMI29.1




   Example 244
8.2 parts of 1-amino-4- (p-amino-anilino) -anthraquinone-2-sulfonic acid are dissolved in a mixture of 160 parts of water and 80 parts of dioxane and mixed with 3.8 parts of trifluorochloropyrimidine at 0 and a pH of 6 -7 implemented. The pH is maintained with 2N sodium hydroxide solution. When the reaction has ended, it is filtered off with suction at 20 ° C. and washed with 2% sodium chloride solution. Dry at 60. The dye
EMI29.2
 dyes wool in greenish blue tones with good wet fastness properties.



   Example 245
9.5 parts of 1-amino-4- (p-aminophenylamino) -an thrachinon-2.6.2'-trisulfonic acid are dissolved in 95 parts of water and at 20-250 5.0 parts of 2.4.6-trifluoro-5-chloro pyrimidine was added dropwise. The PH is kept between 6 and 7. After the reaction has ended, the precipitated reaction product becomes
EMI29.3
 suctioned off and washed with 5% saline solution.



  It is dried in vacuo at 60.



   Example 246
57 parts of 1-amino-4- (p-aminophenylamino) - to thrachinone-2.6. 3'-trisulfonic acid are dissolved in 600 parts of water and mixed with 18 parts of trifluorochloropyrimidine. A pH of 6-7 is maintained with caustic soda. Working up is carried out according to Example 331.



  The blue-green dye is obtained
EMI29.4

Example 247
12.2 parts of 1-amino-4- (p-aminophenylamino) anthraquinone-2.2'-disulfone-6-carboxylic acid are dissolved in 360 parts of water and acylated at pH 6 with 3.7 parts of difluorodichloropyrimidine. The resulting dye
EMI29.5
 is salted out with 10 g of sodium chloride, filtered off with suction and washed with 10% sodium chloride solution. It dyes wool a greenish blue with very good mill and potting fastness.



   Example 248
10 parts of 1-amino-4- (3'- [2 ", 6" -difluoro-5 "-chloropyrimidinyl-amino] -anilino) -anthraquinone-2-sulfonic acid are introduced into 70 parts of 13% strength oleum at 0. Against At the end of the reaction, the temperature is brought to 20 ° C. and, when the sulfonation is complete, is introduced into a mixture of 220 parts of ice water and 30 parts of potassium chloride The very well crystallized product is filtered off with suction and washed neutral with saturated potassium chloride solution
EMI29.6
 dyes cotton and wool in reddish blue shades with good wet fastness properties.



   Example 249
10 parts of 1-amino-4- (3'- [2 ".6" -difluoro-5 "- chloropyrimidinyl] anilino) - anthraquinone-2,6-disulfonic acid are dissolved in 65 parts of 13% oleum at OC and after the sulfation has ended registered in a mixture of 220 parts of ice and 30 parts of potassium chloride.



  It is filtered off with suction, washed with saturated potassium chloride solution and dried at 60 ° C. in vacuo. Blue prints with good wet fastness properties are obtained on cotton.



   Example 250
6 parts of l-amino-4- (4'-N-methylaminomethyl-anilino) -anthraquinone-2, 6, 2'-trisulfonic acid are dissolved in 160 parts of water and at 0-5 ° C. with 2 parts of 5-nitro-2, 4 acylated difluoropyrimidine. A pH of 6.5-7 is maintained with sodium hydroxide solution. When the reaction is complete, it is salted out with common salt, filtered off with suction and dried in vacuo. On wool results in the dye
EMI30.1
 blue shades.



   Example 251
10.0 parts of 1-amino-4- (2 '. 6'-dimethyl-anilino-3' suifonamido) -anthraquinone-2-sulfonic acid are dissolved in 150 parts of water and adjusted to pH 12. It is acylated with 3.7 parts of trifluorochloropyrimidine and, when the reaction has ended, is adjusted to pH 5, salted out with 25 parts of potassium chloride, filtered off with suction and washed with ice-cold 15% strength potassium chloride solution. The dye
EMI30.2
 is dried in vacuo at 60C and dyes wool in clear blue tones.



   Example 252
26 parts of 1-amino-4- (4'-N-methylaminomethyl-anilino) -anthraquinone-2. 2'-disulfonic acid is dissolved in 560 parts of water and acylated at 0-5 ° C. with 10.2 parts of difluorodichloropyrimidine. A pEr of 6-6.5 is maintained with 2N sodium hydroxide solution. It is by adding 10 parts of conc. Hydrochloric acid to pH 1.5, suction filtered and washed with 5% sodium chloride solution. The dye dried in vacuo at 60C
EMI30.3
 dyes cotton in real, clear blue tones.



   Example 253
13.3 parts of 1-Amino4- (4'-N-methylaminomethyl anilino) -anthraquinone-2. 6. 2'-trisulfonic acid is dissolved in 360 parts of water and acylated at 20-25 "with 6 parts of 2,4,6-trifluoropyrimidine. The pH is maintained at 6-7 by adding 2N sodium hydroxide solution. After the reaction has ended is quickly salted out with 65 parts of sodium chloride and dried at 60C in a vacuum.

 

  The dye obtained
EMI30.4
 gives a greenish blue color on wool.



   In an analogous manner, valuable dyes can be obtained from the following components:
Dye reactive component shade 254 1-Amino-4- (4'-N-methylaminomethyl- 2.4-difluoro-6-chloro-green-anilino) -anthraquinone-2.6.2'-pyrimidine chig blue trisulfonic acid 255 1-Amino-4- (4 '-N-methylaminomethyl-2.4-difluoro-5-chloro-blue anilino) -anthraquinone-2.7.2'-pyrimidine trisulfonic acid 256 1-amino-4- (4'-amino-anilino) - 2.4-difluoro-6-blue-green anthraquinone-2.7-disulfonic acid difluoromethyl-5 chloropyrimidine 257 1-Amino-4- (4'-N-methylaminomethyl-2.4-difluoro-6-blue anilino) -anthraquinone-2.6.2'-trifluoromethyl-5 trisulfonic acid chloropyrimidine
Example 258
6.1 parts of 1-amino-4- (3'-aminomethyl-2 '. 6'-dimethyl-anilino) -anthraquinone-2. 6th

   5'-trisulfonic acid is dissolved in 65 parts of water and acylated at a pH of 6 with 2 parts of chlorotrifluoropyrimidine. The pH value is adjusted with 2N sodium hydroxide solution. The resulting dye is salted out with 10 parts of potassium chloride and washed with 20% of the above potassium chloride solution. It is dried in vacuo at 60. The dye
EMI31.1
 dyes wool in clear blue tones with good fullness and perspiration fastness.



   Example 259
10.6 parts of 1-amino-4- (3'-aminomethyl-2 '. 6'-dimethyl-anilino) -anthraquinone-2. 5'-disulfonic acid are used in
Dissolved 110 parts of water. It is acylated with 4.4 parts of trifluorochloropyrimidine at 20-25 "and a pH of 6-6.5. The pn value is maintained with 2N sodium hydroxide solution. When the reaction has ended, the dye obtained is obtained
EMI31.2
 salted out with 20 parts of sodium chloride, filtered off with suction and washed with 10% sodium chloride solution. The dye, dried in vacuo at 60 ° C., provides wet-fast, clear, reddish blue dyeings on cotton or wool.



   Example 260
7.8 parts of 1-amino-4- (3'-N-methylaminomethyl-2 '.



  6'-dimethyl-anilino) -anthraquinone-2. 6. 5'-trisulfonic acid is acylated in 85 parts of water at 20-25 "with 2.3 parts of 2.4.6-trifluoro-5-chloro-pyrimidine. During the reaction, a pH of 6-6 is maintained with 2N soda solution, 5. Before the rapid addition of 20 parts of sodium chloride, 1 part of concentrated hydrochloric acid is used to adjust the pH to 3.5 and the mixture is washed with saturated sodium chloride solution
EMI31.3
 dyes wool or cotton in wet-fast clear blue tones.



   Example 261
7.6 parts of 1-amino-4- (3'-N-methylaminomethyl-2 '.



  6'-dimethyl-anilino) - anthraquinone-2. 6-disulfonic acid are dissolved in 250 parts of water and acylated with 3.1 parts of trifluorochloropyrimidine under the following conditions: pH 6-6.5, temperature 2W25. Ma maintains the pH by adding 2N sodium hydroxide solution. When the reaction has ended, the batch is salted out with 10 parts of sodium chloride and washed with 2% sodium chloride solution. On cotton or wool, you get wet-fast clear blue shades.



   Analogous to the procedures described in Examples 258 to 261, when using the components given in the table below, valuable dyes are also obtained which dye cotton and wool in clear red-tinged to green-tinged blue shades:
Dye reactive component 262 1-Amino-4- (3'-N-methylaminomethyl-2'.6'-di-2.4-difluoro-5.6 methyl-anilino-) anthraquinone-2. 7-disulfon-dichloro-pyrimidine acid 263 1-Amino-4- (3'-N-methylaminomethyl-2 '.

   6'- 2.4-Difluoro-6-chloro (dimethyl-anilino) -anthraquinone-2.7.5'-pyrimidine trisulfonic acid 264 1-Amino-4- (4'-N-methylaminomethyl-2'.6'-2.4.6-trifluoro dimethyl-anilino) -anthraquinone-2.6.5'- pyrimidine trisulfonic acid 265 1-Amino-4- (3'-N-methylaminomethyl-2'.6 '2.4-difluoro-5.6 dimethyl-anilino) -anthraquinone-2.6.4' - dichloropyrimidine trisulfonic acid
266 1-Amino-4- (3'-aminomethyl-4'-methyl-2,4,6-trifluoro-5 anilino) -anthraquinone-2,

   6,6'-difluoromethyl-pyrimidine trisulfonic acid
267 1-Amino-4- (3'-aminomethyl-4'-methyl-2,4,6-trifluoro-5 anilino) -anthraquinone-2,6'-disulfonic-trifluoromethyl acid pyrimidine
268 1-Amino-4- (3'-aminomethyl-4'-methyl-2,4-difluoro-5-tri anilino) -anthraquinone-2,7,6'-fluoromethyl-pyrimidine trisulfonic acid
269 1-Amino-4- (3'-methylamino-4'-methoxy-2,4'-difluoro-5 anilino) -anthraquinone-2,7,6'-tricarbonamido-pyrimidine sulfonic acid
270 1-Amino-4- (4'-amino-anilino} 2,4-difluoro-5-chloro-anthraquinone-2, 3 ', 6-trisulfonic acid 6-phenyl-pyrimidine
271 l-Amino-4- (3 '- amino-anilino) - 2,4-difluoro-5-cyano anthrachonone-2,6-disulfonic acid pyrimidine
272 1-amine o-4- (4'-amino-anilino) -2, 4-difluoro-5-anthraquinone-2,

   6-disulfonic acid carbonethyl ester pyrimidine
273 1-Amino-4- (4'-amino-anilino) - 2,4-Difluoro-5-methyl anthraquinone-2,7-disulfonic acid sulfonyl-pyrimidine 274 1-Amino-4- (3'-amino-anilino) - 2,4,6-Trifluoro-5 anthraquinone-2,7-disulfonic acid bromo-pyrimidine 275 1-Amino-4- (2 ', 4', 6'-trimethyl-2,4,6-trifluoro-5
3'-amino-anilino) -anthraquinone-chloro-pyrimidine
2,5'-disulfonic acid

 

Claims (1)

PATENT CLAIM Process for the preparation of reactive dyes of the formula EMI32.1 wherein D is the residue of an organic dye, R Hydrogen or a lower alkyl group, R1 hydrogen or a substituent, R hydrogen, halogen, Cyano, an optionally substituted alkyl, alkenyl, Aralkyl or aryl group or a carboxylic acid ester, Carboxamide, alkylsulphone or arylsulphone group and F is a fluorine substituent, characterized in that compounds of the formula D - NH R (Ia) with compounds of the formula EMI32.2 converts, in which X is an anionically removable radical, one or more of the in formula XIII containing reactive radicals introduces. SUBCLAIMS 1. The method according to claim, characterized in that one uses preferably sulfonic acid and / or carboxylic acid group-containing starting dyes. 2. The method according to claim, characterized in that one of the reactants of the formula XIII uses the following fluoropyrimidine compounds: 2,4-difluoropyrimidine, 2,4-difluoro-6-methylpyrimidine, 2,6-difluoro-4-methyl-5-chloropyrimidine, 2, 4, 6 Trifluoropyrimidine, 2,4-difluoropyrimidine-5-ethylsulfone, 2,6-Difluoro-4-chloropyrimidine, 2, 4, 5, 6-tetrafluoropyrimidine, 2, 4, 6-trifluoro-5-chloropyrimidine, 2,6-difluoro-4-methyl-5-bromopyrimidine, 2, 4-difluoro-5, gdichloro- or -dibromopyrimidine, 2,6-difluoro-5-bromopyrimidine, 2,6-difluoro-4bromopyrimidine, 2,4,6-trifluoro-5-bromopyrimidine, 2, 4, 6- Trifluoro-5-chloromethylpyrimidine, 2, 4, 6-trifluoro-5-nitropyrimidine, 2, 4, 6-trifluoro-5-cyanopyrimidine, 2, 4, 6-trifluoropyrimidine-5-carboxylic acid methyl or ethyl ester or -5-carboxamides, 2,6-Difluoro-5-methyl-4-chloropyrimidine, 2,6-difluoro-5-chloropyrimidine, 2, 4, 6-trifluoro-5-methylpyrimidine, 2, 4, 5-trifluoro-6-methylpyrimidine, 2, 4- Difluoro-5-nitro-6 chloropyrimidine, 2, 4-difluoro-5-cyanopyrimidine, 2, 4-di fluoro-5-methylpyrimidine, 6-trifluoromethyl-5-chloro-2, 4 difluoropyrimidine, 6-phenyl-2, 4-difluoropyrimidine, strifluoromethyl-2, 4-difluoropyrimidine, 5-trifluoromethyl-2, 4, 6-trifluoropyrimidine, 5-trifluoromethyl-2, 4-difluoropyrimidine, 2, 4-difluoro-5-nitropyrimidine, 2,4 -Difluoro-5trifluoromethyl-pyrimidine, 2, 4-Difluoro-5-methylsulfonyl pyrimidine, 2, 4-Dinuor-5-phenylpyrimidine, 2, 4-Difluoro-5-carbonamido-pyrimidine, 2, 4-Difluoro-5-carbomethoxy-pyrimidine, 2, 4-Difluoro-6-trifluoromethyl-pyrimidine, 2, 4-Difluoro-6-bromo-6-trifluoromethyl-pyrimidine, 2, 4 difluoro-6-carbonamido-pyrimidine, 2, 4-difluoro-6 carbomethoxypyrimidine, 2, 4-difluoro-6-phenyl-pyrimidine, 2, 4-difluoro-6-cyanopyrimidine, 2, 4, 6-trifluoro-5-methylsulfonyl pyrimidine, 2,4-difluoro-5-chloro-6-carbomethoxy-pyrimidine or 2,4-difluoro-5-sulfonamido-pyrimidine. 3. The method according to dependent claim 2, characterized in that with 2,4-difluoro-5, 6-dichloropyrimidine, 2, 4, 6-trifluoropyrimidine, 6-methyl-2, 4-difluoropyrimidine or 6-trifluoromethyl-2 , 4-difluoropyrimidine or preferably condensed with 2, 4, 6-trifluoro-5-chloropyrimidine as reactive component. 4. The method according to claim, characterized in that the starting compound of the formula Ia is aminoazo dyes of the formula EMI33.1 is used in which B and E represent aromatic, carbocyclic or heterocyclic radicals and R 'represents the methyl group or preferably a hydrogen atom. 5. The method according to dependent claim 4, characterized in that B is the remainder of a carbocyclic diazo component of the benzene or naphthalene series and E is the remainder of an enolic or phenolic coupling component, preferably a 5-pyrazolone, an oxynaphthalene or an aminonaphthalene, which also has other substituents, may also have further azo groups among them. 6. The method according to claim, characterized in that the starting compound of the formula Ia is aminoanthraquinone dyes of the formula O NH2 (L) P # O HN # (CH2) a-NH (L ') PR @ "is used in which L and L' are substituents, in particular sulfonic acid groups, R" is hydrogen, a methyl or ethyl group, p is the number 0.1 or 2 and a is the number Mean 0 or 1. 7. The method according to claim, characterized in that the starting compound of the formula Ia is azoporphine dyes of the formula EMI33.2 used, where Pc for the radical of a nickel or copper phthalocyanine, L and L 'for substituents, especially sulfonic acid groups, r for the number 0, 1 or 2, a for 0 or 1, R' for a methyl group or preferably hydrogen, Ru for Hydrogen, an alkyl or aryl radical, R4 represents hydrogen, an alkyl or aryl radical, r 'represents a number from 0 to 3 and r ″ represents a number from 0 to 2. 8. The method according to claim or one of the subclaims 1-7, characterized in that one with a reactive component of the formula EMI33.3 where R'1 and R's independently of one another denote hydrogen or halogen radicals and Y represents a radical which can be removed anionically, in particular a fluorine substituent, condenses with elimination of the anionic radical Y. 9. The method according to claim and dependent claims 1-7, characterized in that such starting components are used which have one or more sulfonic acid groups. 10. The method according to claim and dependent claim 1, characterized in that such dyes are produced in which the radical D contains one or more sulfonic acid groups. 11. The method according to claim and dependent claim 4, characterized in that reactive azo dyes of the formulas EMI33.4 EMI34.1 <tb> <SEP>; <SEP> OCH <SEP> 5 <SEP> NH-acyl <tb> (H03S <SEP> O-3 <SEP> N <SEP> = <SEP> N <SEP> NX (S03H) <SEP> 1 <SEP> 3 <tb> <SEP> o <SEP> - <SEP> Me <SEP> - <SEP> 0 <tb> (<SEP> H <SEP> O <SEP> 3S <SEP> <1 <SEP>. <SEP> NO <SEP> &commat; <SEP> S <SEP> OH <SEP>) <SEP> 1 <SEP> 3 <tb> <SEP> N <SEP> SO, K) 1-3 <tb> <SEP> 1I; OH; N02 <SEP> 2 <tb> (S03H) O¯2 <tb> <SEP> O <SEP> - <SEP> Cu <SEP> <tb> <SEP> = <SEP> wj <SEP> N <SEP> = <SEP> N <SEP> - <SEP> N112 (or <SEP> NH-cy1) <tb> 9 <SEP> 0 <SEP> (SO3H) l3 <tb> <SEP> NH-A <tb> <SEP> 22 <tb> <SEP> ¯N <SEP> = <SEP> N <SEP> h <tb> A-HN <SEP> \ $ / <SEP>> <SEP> <tb> <SEP> (s <SEP> 031 '<SEP>) 0-. <tb> <SEP> (SO, H) i-9 <tb> <SEP> NH2 <SEP> (or <SEP> NH-alkyl <SEP>) <tb> A-NH <SEP> N <SEP> = <tb> <SEP> 50311 <tb> <SEP> 0311 <SEP> or <tb> <SEP> OH <SEP> or <tb> <SEP> (NH¯aCYl) o <SEP> or <SEP> 1 <tb> A-11N-N <SEP> = <SEP> N% hSO! iH) <SEP> or <SEP> 1 <tb> <SEP> (S 3H) 0-1 <tb> where A is the remainder EMI35.1 EMI35.2 R 'represents a -CH3 group or preferably a hydrogen atom and R'1 and R'r independently represent hydrogen or halogen radicals, in which (o) {indicates the ortho position of the respective substituents in the aryl nucleus and Me represents Cu, Cr or Co, and F represents a fluorine substituent. 12. The method according to claim and sub-claims 1-11, characterized in that reactive dyes are prepared in which the reactive component is the 2,6-difluoro-5-chloropyrimidin4-yl radical. 13. The method according to claim, characterized in that reactive dyes of the formula in which D1 is the radical of an azo, anthraquinone or phthalocyanine dye containing sulfonic acid groups, q is the number 0 or 1, R 'is hydrogen or CH: and F represents a fluorine substituent. 14. The method according to dependent claim 4, characterized in that dyes are prepared in which the radicals B and / or E have one or more sulfonic acid groups. 15. The method according to dependent claims 6 and 8, characterized in that one reactive anthrachi non-dyestuffs of the formula EMI35.3 where L and L 'are substituents, including sulfonic acid groups, p is a number from 0 to 2, R "is a methyl or ethyl group or hydrogen, R'1 and R'2 are independently hydrogen or halogen and F is a fluorine substituent. 16. The method according to dependent claim 15, characterized in that such dyes are produced which have one or more sulfonic acid groups. 17. The method according to subclaims 7 and 8, characterized in that reactive Antrhachianin dyes of the formula EMI35.4 where Pc stands 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' for a methyl group or preferably hydrogen, R'1 and R'2 independently represent hydrogen or halogen radicals and the phthalocyanine radical Pc is preferably used as further substituents 1-2 sulfonic acid and / or 1-2 sulfonic acid amide groups, such as SO2NH2, -SO2NH-alkyl, -SOzN (alkyl) e and Carries SONH (aryl) groups, where alkyl stands for alkyl radicals with 1-3 carbon atoms, and F stands for a fluorine substituent. 18. The method according to dependent claim 17, characterized in that such dyes are produced which have one or more sulfonic acid groups. 19. The method according to claim, characterized in that the dyes obtained are acylated and / or sulfated.