CH510092A - Process for the production of reactive dyes - Google Patents

Description

  

  
 



  Process for the preparation of reactive dyes
The present invention relates to a process for the preparation of valuable new reactive dyes of the formula
EMI1.1
 In this formula, D is the radical of an organic dye, R is hydrogen or a lower alkyl group, m is a number from 1 to 8, R1 is hydrogen or a substituent, R2 is hydrogen or optionally substituted alkyl, alkenyl, aralkyl or aryl radicals and F is a Fluorine substituents.



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

  If such 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 andC2H5, substituted alkyl radicals such as mono-, di- or trichloro- or tribromomethyl-, trifluoromethyl-, alkenyl - Such as vinyl, halovinyl and allyl radicals, -NOe, -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 groups.



   Examples of possible substituents R2 in the 2-position of the pyrimidine ring are: alkyl, such as methyl and ethyl, alkenyl, such as vinyl, halovinyl and allyl, and substituted alkyl, such as mono-, di- or trichloro- or tribromomethyl- or trifluoromethyl radicals.



   Dyes in which R2 is hydrogen and R1 is halogen or -CF3 and m is the number 1 belong to a preferred group of the compounds of the formula I which can be prepared according to the invention.



   In the context of the new dyes (I), a preferred group of products corresponds to the formula
EMI1.2
 where D 'is the radical of an azo, anthraquinone or azaporphine dye containing sulfonic acid groups and R1, R2 and F have the meanings already given.



   The new dyes can do the rest
EMI2.1
 have one or more times in the molecule.



  Dyes with 1 to 2 such reactive radicals are preferred for economic reasons.



   Suitable pyrimidine rings
EMI2.2
 which have a removable (reactive) fluorine substituent in the 6-position are, for example: 6-fluoro-5-chloropyrimidinyl4, 6-fluoro-5-trifluoromethyl-pyrimidinyl-4, 6-fluoro-2-methylpyrimidinyl4, 6-fluoro-5- chloro-2-methyl-pyrimidinyl-4, 5,6-difluoro-pyrimidinyl-4, 6-fluoro-5-chloro-2-trifluoromethyl-pyrimidinyl-4, 6-fluoro-2phenyl-pyrimidinyl-4, 6-fluoro-5- cyano-pyrimidinyl-4, 6-fluoro-5-nitro-pyrimidinyl-4, 6-fluoro-5-methylsulfonyl-pyrimidinyl-4, 6-fluoro-5-phenylsulfonyl-pyrimidinyl-4.



   Of the large number of possible bonding options for radical (III) 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 (C2H5) -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) -CH2-CONH -A, -HN-CH2-CH2-NH-A,
EMI2.3
 and the corresponding N-alkyl (1-5 C) amides or amines
EMI3.1
 as well as the corresponding N-alkyl (1-3 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 this class of dyes, dyes of the following general compositions, inter alia, 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 -Clla group or preferably a hydrogen atom, R'1 stands for halogen (F, Cl, Br) or -CF3 and R'2 stands for hydrogen.



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



   Important azo dyes are, for example, those of the benzene-azo-naphthalene series, the benzene-azo-1-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene series, the naphthalene-azo-1-phenylpyrazolone series 5 series and the stilbenazo-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-acyl
<tb> (HO, S <SEP>) o = jf3 <SEP>; 4- <SEP> OH
<tb> (HO3 <SEP>) 0 <SEP> 3 <SEP> | <SEP> - <SEP> N? - '"<SEP> 1-3 <SEP> (VI)
<tb>
EMI4.2

EMI4.3


<tb> <so3H) <SEP> 0-2
<tb> <SEP> Ow <SEP> O
<tb> <SEP> N-N <SEP> 2 (or <SEP> NH-acyl)
<tb> <SEP> (v <SEP> (S03H) <SEP> 1-3 <SEP> (VIII)
<tb> <SEP> Y
<tb> <SEP> NH-A
<tb>
EMI4.4

EMI4.5


<tb> <SEP> NH2 <SEP> (or <SEP> NH-alkyl <SEP>)
<tb> <SEP>,

   > <SEP> NNX <SEP> (IXa)
<tb> A-NH <SEP> SOnH <SEP> HO <SEP> (iXa)
<tb> <SEP> SO, H
<tb> <SEP> XO <SEP> (NH-aCYl <SEP>) <SEP> o <SEP> or
<tb> <SEP> (o) <SEP> (<SEP> -acy1) 0 <SEP> or <SEP> 1
<tb> <SEP> A-HN + <SEP> N (S03H) <SEP> 1-3 <SEP> (x)
<tb> <SEP> (so3n) 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
 2. Anthraquinone dyes in which R'1 and R'2 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.
EMI5.2




  L and L 'here denote substituents, among these in particular sulfonic acid groups, p an integer from 0 to 2, R "a methyl or ethyl group or hydrogen, R's hydrogen and R'1 halogen or CF3.



   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' Hne methyl group or preferably hydrogen, R'2 for hydrogen and R'1 for halogen or -CFa '. The Phthal Öcyaninrest Pc preferably carries as further substituents 1-2 sulfonic acid and / or 1-2 sulfonic acid amide groups, such as -SONH2-, -SO2NH-alkyl-, -SO2N (alkyl) 2- and -SO2NH (aryl) groups, where alkyl represents alkyl radicals with 1-3 C atoms.



   The above compilation of a selection of suitable azo, anthraquinone and azaporphine dyes and fluorine-substituted pyrimidine rings does not represent any restriction on the general formulas; namely neither with regard to the preparative possibilities for the preparation of such dyes in the context of the general formula (I), nor with regard to the valuable application properties of these products.

  The new dyes can also have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, sulfonamide and carbonamide groups, which can be further substituted on the amide nitrogen atom, sulfonic acid ester and carboxylic acid ester groups, alkyl, aralkyl and aryl 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-di hçlogen-phthalazine 6-carbonyl- or -6-sulfonylamino-, 2-halogen- or 2-alkylsulfonyl- or 2-arylsulfonylbenzthiazole-5-carbonyl- or -5-sulfonylamino, alkylsulfonylpyrimidinyl, arylsulfonylpyrimidinyl, esterified sulfonic acid oxyalkylulfamide and oxalkylsulfonylsulfonylamido groups , Haloalkylamino, acryloylamino, haloacylamino groups or other reactive groups.



   The new dyes of the formula (I) are obtained by adding the dyes to at least one pyrimidine ring containing the reactive fluorine substituent in the 6-position
EMI5.4
 introduces which is linked directly to the amino group -N (R) -.



   The introduction of the radical or radicals (III) via an amino group N (RF into dyes or dye precursors is carried out according to the invention by adding dyes containing amino or amide groups which have a reactive hydrogen atom on the amine or amide nitrogen with compounds of the formula
EMI6.1
 in which X is a radical which can be removed anionically, azinylated. 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 (C2H5) 3.



   Heterocyclic pyrimidine compounds of the formula (XIII) suitable for the reaction are, for example:
4,6-Difluoro-5-chloro-pyrimidine, 4,6-Difluoro-5-trifluoromethyl-pyrimidine, 4,6-Difluoro-2-methyl-pyrimidine, 4,6-Difluoro-5-chloro-2-methyl-pyrimidine , 4,5,6-trifluoro-pyrimidine, 4,6-difluoro-5-chloro-2-trifluoromethyl-pyrimidine, 4,6-difluoro
2-phenyl-pyrimidine, 4,6-difluoro-5-cyano-pyrimidine, 4,6-difluoro-5-nitro-pyrimidine, 4,6-difluoro-5-methylsulfonyl-pyrimidine, 4,6-difluoro-5 -phenyl sulfonyl-pyrimidine.



     -Bti-cterndensation reaction with the amino resp.



   Dyes or dye precursors containing amide groups react with these pyrirnidine derivatives, splitting off the radical X in the 4-position.



   The gennnntenüiirWeere - according to the invention ver usable fluoropyrimidine compounds can generally be obtained by reacting the corresponding chlorine or bromine compounds with alkali metal fluorides, e.g. B. with potassium fluoride, NaHF, KSO2F,
SOFT, AgF2, or by converting the appropriate OH
Compounds with SF4, COF2, COClF or cyanuric fluoride, or by heating the corresponding diazonium tetrafluoroborate.



   Particularly preferred for the inventive reaction are those reactive components which are the
formula
EMI6.2
 correspond, where R'2 is hydrogen and R'1 is halogen or -CF3- groups and Y is an anionically removable radical, in particular a fluorine substituent.



   The reaction of the amino or amide group-containing dyes or dye precursors with heterocyclic compounds of the formula (XIII) or (XIV) can, depending on the nature of the starting compounds used, in an organic, organic-aqueous or aqueous medium at temperatures from -10.degree. C. to 100.degree , preferably at 0 to 50 ° C., 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 can be converted into the desired final dyes. This process is of particular interest for the production of, for example, dyes 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 a m-phenylenediaminesulfonic acid, and the reaction product obtained 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.



   The dyes obtainable according to the invention can, as already mentioned for a few cases, be subjected to other reactions customary for dyes, for example by treating metallizable dyes with metal donating agents, in particular with chromium, cobalt, copper or nickel salts, dyes , which have reducible groups, in particular nitro groups, are reduced, dyes that have acylable groups, in particular acylable amino groups, acylated, and / or by subsequently treating dyes with sulfonating agents, such as with chlorosulfonic acid, oleum or SO3 in chlorinated hydrocarbons, 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 formula (III) can be incorporated into the dyes. In the majority of cases the number m = 4 is not exceeded, but dyes, in particular those with a higher molecular weight structure, with more than 4 and with up to 8 groupings of the formula (III) can also be synthesized.

 

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



   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'HH or -N (R ") - H.



   When preparing phthalocyanine dyes, a diaminoaryl compound monocondensed with the reactive component (XIII) or (XIV) can first be produced and this can then be 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.

  It is also possible to use copper or nickel phthalocyanine sulfonic acid (aminoaryl) amides, which may additionally have N-substituted sulfonamide groups of another type and free sulfonic acid groups, on 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 other 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, Cl3C-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.



   Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, sometimes a final increase in the pH of the dyebath, e.g. B. to pH 8 to pH 9 is advantageous.



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



   In the following examples, parts stand for parts by weight, unless otherwise stated. Parts by volume are related to parts by weight in the ratio of liters to kg.



   example 1
To the solution of 34.7 parts of 2-aminonaphthalene-4, 8-disulphonic acid and 7 parts of sodium nitrite in 300 parts of water, 28 parts by volume of concentrated hydrochloric acid are added while cooling with ice, and the mixture is stirred at 0-10 ° C. for half an 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 resulting aminoazo dye 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.

  18 parts of 4,6-difluoro-5-chloropyrimidine, dissolved in 10 parts of acetone, are added dropwise to this solution at 30 to 40 ° C. and a pH of 6 to 7 is maintained with 2N sodium hydroxide solution. After the reaction has ended, the resulting dye becomes the probable formula
EMI7.2
 salted out with 210 parts of saturated sodium chloride solution and the product thus obtained is filtered off with suction and washed with 2 O / above NaCl solution and dried in vacuo at 50 ° C.



  Printing specification
If cellulose fabric is printed with a printing paste that contains 15 grams of the dye, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg thickening) and 20 g soda and which has been made up to 1 kg with water, dried, steamed for 8 minutes at 100 ° 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
EMI8.1
 (prepared according to the information in German patent specification 1 117 235 by coupling diazotized 1-amino-8- (benzene-sulfonyloxy) -naphthalene-disulfone re (3,6) in a soda-alkaline medium with the equivalent amount of 2-acetylamino-5- hydroxynaphthalene disulfonic acid (4.8), conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysis of the acetyl and benzenesulfonyl groups) is dissolved in 2500 parts by volume of water at 60 to 65 "C at pH 6 to 6.5 and at 40 to 50 "C with 1.4 mol of 4,6-difluoro-5-chloropyrimidine, dissolved in 150 parts of acetone, added. During the condensation, a pH of 6 to 7 is maintained by adding sodium carbonate solution.

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



  Staining instructions
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, heated to 140 ° C. for 5 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-methylaminotoluene are dissolved in 400 parts of water, 100 parts of acetone at 20 to 30 ° C., 18 parts 4.6 -Difluoro-5chlorpyrimidine, dissolved in 10 parts of acetone, added while maintaining a pH of 6 to 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
EMI8.2
 and is salted out, filtered off with suction, washed and dried at 30 ° C. in vacuo.



  Coloring prescription
Cotton fabric is impregnated with a solution of 20 to 25 ° C. which contains 20 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate per liter of liquor. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100ovo. After intermediate drying at 50 to 60 "C, the mixture is heated at 140 OC for 5 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 gives a strong reddish yellow coloration of good wet, rub and light fastness.

 

   The table below lists the diazo components, coupling components and the reactive components which can be linked to the amino group and from which dyes can be synthesized analogously to the information in Examples 1 and 2, the hues of which are obtained by one of the application methods described - are also shown in the table.



   Abbreviations for A = 4,6-difluoro-5-chloropyrimidine
Reactive components:
B = 4,6-difluoro-5-chloro-2-methyl pyrimidine diazo component, coupling component, reactive color component
EMI9.1


<tb> 2-aminonaphthalene- <SEP> 1-amino-2-methoxy- <SEP> A <SEP> yellow
<tb> 4,8-disulfonic acid <SEP> 5-methylbenzene
<tb> <SEP> "<SEP>" <SEP> B
<tb> 1 <SEP> -aminonaphthalene- <SEP> 1-amino-3-methyl- <SEP> A <SEP> II
<tb> 3,6-disulfonic acid <SEP> benzene
<tb> <SEP> "<SEP> B <SEP>"
<tb> 2-aminonaphthalene- <SEP> n <SEP> A <SEP> 1
<tb> 5,7-disulfonic acid
<tb> <SEP> "<SEP>" <SEP> B <SEP> "
<tb> 2-aminonaphthalene- <SEP> n <SEP> A <SEP> I1
<tb> 6,

   <SEP> 8-disulfonic acid
<tb> <SEP> n <SEP> "<SEP> B <SEP> <SEP> 1 <SEP>
<tb> 4-Aminoazobenzene- <SEP> "<SEP> A <SEP> Brown-yellow
<tb> 3,4 '<SEP> -disulfonic acid
<tb> 1-aminobenzene-4- <SEP> n <SEP> B <SEP> n
<tb> sulfonic acid <SEP> #
<tb> 1-aminonaphthalene
<tb> 6-sulfonic acid
<tb> 2- (3'-Sulfo-4'- <SEP> "<SEP> A <SEP> yellow
<tb> aminophenyl) -6
<tb> methyl-benzothiazole
<tb> 7-sulfonic acid
<tb> 2-aminonaphthalene- <SEP> 1-methylamino-3- <SEP> B <SEP> "<SEP>
<tb> 4,8-disulfonic acid <SEP> methoxybenzene
<tb> <SEP> "<SEP> 1-Amino-3-acetyl- <SEP> A <SEP>"
<tb> <SEP> aminobenzene
<tb> <SEP> II <SEP> aniline <SEP> A <SEP> n
<tb>
Example 4
51.6 parts of the by diazotizing 1-hydroxy-2aminobenzene-4-sulfonic acid and coupling to 2-amino5-hydroxynaphthalene-7-sulfonic acid in water / pyridine

   Presence of soda and subsequent treatment with a copper releasing agent obtained dye of the formula
EMI10.1
 are dissolved in 1500 parts of water at pH 7. With thorough stirring, 20 parts of 4,6 difluoro-5-chloropyrimidine are added at 30 to 40 ° C. and the hydrofluoric acid released is continuously blunted to a pH of 6 to 7 with soda solution. 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 to 40 OC. 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 shades of these dyes on cellulose materials. The aminoazo dyes, their metal complexes and their conversion with the reactive components can be prepared analogously to the information in Example 4.



   Abbreviations for the reactive components as in the table for example 3 aminoazo dye complex-bound reactive shade
Heavy metal component
EMI10.3


<tb> 1-Hydroxy-2-aminobenzene- <SEP> Cu <SEP> A <SEP> ruby
<tb> 4,6-disulfonic acid <SEP> A <SEP>
<tb> 2-Amino-5-hydroxy
<tb> naphthalene-7 <SEP> sulfonic acid
<tb> 1-Hydroxy-2-amlnobenzene- <SEP> Cu <SEP> A <SEP> ruby
<tb> 4-sulronic acid <SEP>> <SEP>
<tb> 2-Xthylamino-5-hydroxy- <SEP>
<tb> <SEP> naphthahlin-7-sulfonic acid
<tb> <SEP> 1-amino-2-hydroxy-6- <SEP> Cu <SEP> A <SEP> "
<tb> nitronaphthalene-4
<tb> sulfonic acid <SEP>> <SEP>
<tb> <SEP> 2-amino-5-hydroxy
<tb> <SEP> naphthalene-7-sulfonic acid
<tb> <SEP> Cr <SEP> Cr <SEP> A <SEP> <RTI

    ID = 10.10> lowest. <SEP>
<tb>



   <SEP> gray
<tb> 1-Amlno-2-hydroxy-6- <SEP> Co <SEP> B <SEP> rotst.
<tb> nitronaphthalene-4- <SEP> black
<tb> sulronic acid <SEP> -----) <SEP>
<tb> 1-amino-8-hydroxy- <SEP>
<tb> naphthalene-4-sulfonic acid
<tb> Aminoazo dye complex-bound reactive shade
Heavy metal component
EMI11.1


<tb> (l-amino-2-chlorobenzene- <SEP> Co <SEP> A <SEP> gray
<tb> 4-sulfonic acid
<tb> 1-Hydroxy-2-acetylamine- <SEP>
<tb> benzene),

   <SEP> saponified, #
<tb> 1-amino-8-hydroxy
<tb> naphthalene-3,6-di
<tb> sulfonic acid
<tb> 1-Amino-8-hydroxy- <SEP> Co <SEP> A <SEP> Black
<tb> naphthalene- <SEP> -sulfone
<tb> acid <SEP> <
<tb> 1-hydroxy-2,6-diamino
<tb> benzene-4-sulfonic acid <SEP> #
<tb> 1,3-dihydroxybenzene
<tb> 1-Amino-8-hydroxy- <SEP> Co <SEP> A
<tb> naphthalene-3,6-di
<tb> sulfonic acid <SEP> <
<tb> 1 <SEP> -Hydroxy-2,6-diamino- <SEP>
<tb> benzene-4-sulfonic acid <SEP> #
<tb> 2-hydroxynaphthalene
<tb> 1-Amino-2-hydroxy-5- <SEP> Cu <SEP> A <SEP> violet
<tb> methylsulfonyl-benzene <SEP> #
<tb> 1 <SEP> -amino-8-hydroxy- <SEP>
<tb> naphthalene-3,6-di
<tb> sulfonic acid
<tb> 1-Amino-8-hydroxy- <SEP> Co <SEP> A <SEP> n
<tb> naphthalene-4-sulfone
<tb>

   acid
<tb> 1-hydroxy-2,6-diamino
<tb> benzene-4-sulfonic acid <SEP> #
<tb> 3-methyl-pyrazolone- (5)
<tb> <SEP> Co <SEP> A <SEP> gray
<tb> <SEP> Cr <SEP> A <SEP> green. <SEP>
<tb>



   <SEP> black
<tb> <SEP> 1-amino-2-methylbenzene- <SEP> Cu <SEP> B <SEP> blue
<tb> <SEP> 4-sulfonic acid
<tb> <SEP> 1-amino-2-hydroxy-5- <SEP>
<tb> <SEP> methylbenzene
<tb> <SEP> 1 <SEP> -Amino-8-hydroxy- <SEP>
<tb> <SEP> naphthalene-4,6-di
<tb> <SEP> sulfonic acid
<tb> <SEP> "<SEP> Co <SEP> B <SEP> gray
<tb> <SEP> Cr <SEP> A <SEP> green. <SEP>
<tb>



   <SEP> black
<tb> <SEP> (1-amino-2-chlorobenzene- <SEP> Cu <SEP> A <SEP> navy blue
<tb> <SEP> 4-sulfonic acid <SEP> #
<tb> <SEP> 1-Hydroxy-2-acetylamine- <SEP>
<tb> <SEP> benzene), <SEP> saponified, <SEP>
<tb> <SEP> 1-amino-8-hydroxy- <SEP>
<tb> <SEP> naphthalene-3,6-di
<tb> <SEP> sulfonic acid
<tb>
Example 5
96 parts (based on 100% goods) of the copper phthalocyanine tetrasulfochloride freshly prepared in the customary manner by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine or of the isomeric copper phthalocyanine built up from 1-sulfobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid -tetrasulfochlorids are in the form of the moist,

   The well-washed suction cake was 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 to 2 by adding sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral.



  60 parts of 4,6-difluoro-5-chloropyrimidine are added to the blue solution with vigorous stirring and stirred at 20 to 30 ° C. with constant blunting with soda solution to pH 7 until free amino groups can no longer be detected. The reactive dye of the formula obtained in this way
EMI12.1
 is salted out, washed and dried at 30 to 40 "C in a vacuum. It is a dark blue powder that is soluble in water with a blue color and dyes cotton and regenerated cellulose in clear blue tones with good wet and rub properties using one of the above-mentioned dyeing or printing processes - and lightfastness.



   Instead of the 96 parts of copper phthalocyanine tetrasulfochloride - with otherwise the same procedure as in Example 5 - 87 parts (based on 100/0 goods) of the copper or nickel phthalocyanine trisulfochloride obtainable by the action of chlorosulfonic acid on copper or nickel phthalocyanine in the form of the moist can be used suction cake washed with ice water can be used; reactive dyes which also have a clear blue color are then obtained.



   If you work as indicated in Example 5, but start from 87 parts of copper phthalocyanine trisulfochloride and instead of 50 parts of the sodium salt of 1,3-diaminobenzene 90 parts of the sodium salt of 4,4'-diaminodiphenyl-2,2'-disulfonic acid or 90 parts Using parts of the sodium salt of 4,4'-diaminostilbene 2,2'-disulfonic acid, reactive dyes are obtained which dye cellulosic materials in wet, rub and lightfast clear blue shades by one of the above processes.



   If you start from 4 ', 4 ", 4"', 4 "" - tetraphenyl-cuphthalocyanine, a reactive dye is obtained after sulfochlorination and conversion with 1,3-phenylenediamine and acylation with 5-trifluoromethyl-4,6-difluoropyrimidine, which dyes cellulose materials in the presence of acid-binding agents in clear, wet and lightfast green tones.

 

   Example 6
63 parts of 1-amino-4- (4'-aminophenyl) -amino-anth rachinon-2,5,8-trisulfonic acid are dissolved in 630 parts of water and adjusted to pH 6 with sodium hydroxide solution; 16 parts of 4,6-difluoro-2methylpyrimidine are then added dropwise at 20 to 30 ° C. and a pH of 6 to 7 is maintained with soda solution. After the reaction has ended, the mixture is salted out with 50 parts of potassium chloride, filtered off with suction and washed with 10% potassium chloride solution. The dye, which is obtained in blue-green needles, is dried in vacuo at 30 to 40 ° C. It probably has the following formula
EMI12.2
 and dyes cotton in greenish blue tones.



   Example 7
If one proceeds as indicated in Example 4, 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 diazotized by coupling with 1 [3 '- (3 "-Aminophenyl)] -sulfonylimido-sulfonyl-phenyl3-methyl-pyrazolone- (5) obtained from the aminoazo dye, a reactive dye is obtained which dyes cellulose materials in good wet-, rub- and lightfast yellow-brown shades by one of the processes given above.



   Example 8
0.1 mole of the copper complex compound of the formula
EMI13.1
 is dissolved in 3000 parts by volume of water at pH 6 and combined with 20 parts of 4,6-difluoro-5-chloropyrimidine while stirring at a temperature of 30 to 40 ° C. and a pH of 7 is maintained with 2N potassium carbonate solution. 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 to 3.



  Staining instructions
Cotton fabric is impregnated with a solution of 20 to 25 ° C. which contains 25 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylene oleyl alcohol), 150 g of urea and 20 g of sodium carbonate per liter of liquor. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 1000 / o.



  After intermediate drying at 50 to 60 ° C., the mixture is heated to 140 ° C. for 5 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.



   One of the other dyeing or printing processes described in Examples 1 to 3 also gives clear green tones with good fastness properties on cellulose materials.



   Example 9
0.1 mole of the paste of the aminoazo compound of the formula
EMI13.2
 which is obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene-4,8-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex, is in 2000 parts by volume of water at pH 6.5 dissolved and combined with 20 parts of 4,6-difluoro5-chloropyrimidine. The reaction mixture is stirred at 30 to 40 ° C. until the condensation has ended, the pH of the reaction solution being kept at 6 to 7 by adding soda solution. When 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 shades of blue.



   Example 10
The aqueous solution of 0.1 mole of the copper complex of the formula
EMI13.3
  prepared according to the information in German patent specification 1061460 or 1,085,988, is reacted in the customary manner with 20 parts of 4,6-difluoro-5-chloropyrimidine. The pH is maintained at 6 to 7 by adding soda and the dye is isolated by salting out after the reaction has ended. When dried, it is a dark powder that dissolves in water with a purple color. Cotton fabric is dyed in lightfast and wetfast purple tones.



   Example 11
56.8 parts of the diaminoazo dye obtained by coupling diazotized 1-amino-3-acetyl-aminobenzene-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 obtained at pH 7 dissolved in 450 parts of water.



  After 20 parts of 4,6-difluoro-5-chloropyrimidine have been added, the hydrofluoric acid liberated is constantly blunted with soda solution to pH 6 to 7 and stirred at 30 ° C. for about one hour. After the acylation has ended, the reactive dye formed is presumably of the formula
EMI14.1
 salted out, filtered off, redissolved in water, filtered and separated from the filtrate in a completely pure form by adding sodium chloride. The dye is dried as usual at 35 ° C. in vacuo. It dyes cellulose materials in true yellowish orange tones using one of the processes mentioned above.



   Example 12
20 parts of 4,6-difluoro-5chloropyrimidine are added to a neutral solution of 60 parts of the trisodium salt of the aminoazo dye obtained by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 3-acetylaminoaniline in an acetic acid medium in 500 parts of water and stir for one hour at 40 ° C., a pH value of 7 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
EMI14.2
 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'-amino 2'-acetylaminophenyl- (l ') -azonaphthalene- (2) -3, 6, 8-trisulfonic acid sodium corresponding amounts of the Amino compounds indicated in column 1 and the coupling components indicated in column 2 are used in the usual manner by diazotization and coupling in an acetic acid medium and azinylated with 5-trifluoromethyl-4,6-difluoropyrimidine.



  Diazo component, coupling component hue
Cotton 2-aminonaphthalene- l-amino-3-methyl- strong red.



     1,5-disulronic acid 6-methoxybenzene yellow 1? 1-amino-3-methylbenzene yellow "1-aminonaphthalene redst.



   6-sulfonic acid yellow n 1-amino-3-acetyl-1I aminobenzene 2-aminonaphthalene-3-aminophenylurea redst.



  1,5-disulfonic acid yellow "1-amino-3-hydroxy-" acetylaminobenzene 2-aminonaphthalene-1-amino-3-methyl- strongly reddish.



  5,7-disulfonic acid 6-methoxybenzene yellow n -aminonaphthalene redst.



   7-sulfonic acid yellow
1-Amino-3-acetyl aminobenzene "3-aminophenylurea" 1-amino-3-hydroxy-acetylaminobenzene
1-aminonaphthalene-1-amino-3-methyl- strongly rotst.



  3,7-disulfonic acid 6-methoxybenzene yellow n 1-Amino-3-methylbenzene redst.



   Yellow "1-aminonaphthalene-" 6-sulfonic acid 2-aminonaphthalene-1-amino-3-methylbenzene n 3, 6-disulfonic acid
1-Amino-3-methyl strongly rotst.



   6-methoxybenzene yellow 1 -Amlno-3-acetylamino redst.



   benzene yellow ft 3-aminophenylurea "1-amino-3-hydroxy-" acetylaminobenzene diazo component coupling component hue on
Cotton 1-Aminonaphthalene
6-sulfonic acid 2-aminonaphthalene-1-amino-3-acetylamino rotst.



  6,8-disulfonic acid benzene yellow
1-Amino-2-methoxynaphthalene strongly rotst.



   6-sulfonic acid yellow n 1-aminonaphthalene red.



   6-sulfonic acid yellow 2-aminonaphthalene-? 1 yellow 4,8-disulfonic acid n -aminonaphthalene- n 7-sulfonic acid
1-Amino-2-methoxynaphthalene strongly rotst.



   6- sulfonic acid yellow n aniline yellow "1-ethylamino
3-methylbenzene "N-methylaniline" lt N-thylaniline
N- (ss-hydroxyethyl) aniline "
N-butylaniline "2-aminonaphthalene-aniline rotst.



  3,6,8-trisulfonic acid yellow "1-amino-3-methylbenzene" "3-aminophenylurea" "1-amino-3-hydroxy-" acetylaminobenzene n 1 -amino-3-acetylamino- yellow.



   6-methoxybenzene orange "1-amino-3-acetylamino rotst.



   6-methylbenzene yellow diazo component coupling component color shade
cotton
1-Amino-3-methanesulfonylaminobenzene "2,5-dimethoxyaniline yellow.



   Orange 2-aminonaphthalene-3-methyl-6-methoxyaniline yellow.



  3,6,8-trisulfonic acid orange "N-methylaniline rotst
Yellow "N-ethylaniline" "N-butylaniline" "N- (ss-hydroxyethyl) aniline" "3- (N-ethylamino) toluene" "2-aminotoluene" n 1-amino-2,5-dimethylbenzene very red .



   Yellow n 1-amino-2-methoxybenzene n n 1 -amino-3-methoxybenzene redst.



   Yellow "1-ethylamino-3-methoxybenzene" n 1 -aminonaphthalene- lt
6-sulfonic acid "1-aminonaphthalene-"
7-sulfonic acid 2-aminonaphthalene-1-amino-3-methylbenzene "4,6,8-trisulfonic acid aminobenzene lt n aniline yellow 1-amino-3-acetylaminobenzene redst.



   Yellow 1-aminonaphthalene-1-amino-3-methylbenzene gel 2,4,7-trisulfonic acid II 1-aminonaphthalene- n
6-sulfonic acid diazo component coupling component color shade on
Cotton 4-nitro-4'-amino-1-amino-3-acetylaminobenzene rotst.



  stilbene-2,2'-yellow disulfonic acid "3-aminophenylurea"
4-nitro-4'-amino-1-amino-3-hydroxy rotst.



     stilbene-2,22- acetylaminobenzene yellow disulfonic acid "N-methylaniline" "N-ethylaniline" "N-butylaniline" "N- (ss-hydroxyethyl) -aniline" "1- (N-ethylamino) -" 3 @@ é @ @lb @@@@@
3-methylbenzene
Aniline-2,5-1-aminonaphthalene- "disulfonic acid 6-sulfonic acid" 1-aminonaphthalene- "
7-sulfonic acid
1-Amino-3-methylbenzene yellow n 1 "Amino-3-acetyleminobenzene n 1-amino-2-methoxy redst.



   5-methylbenzene yellow "1-amino-2,5-dimethoxybenzene" aniline-2,4-1-amino-2-methoxy-n-disulfonic acid 5-methylbenzene
Example 13 65 parts of the dye of the formula
EMI19.1
 (prepared by coupling 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 in a neutral manner. 20 parts of 4,6-difluoro-5-chloropyrimidine are added and the mixture is stirred at 30 to 40 ° C. while constantly blunting the liberated acid with soda solution to pH 6 to 7, until no more free amino groups can be detected. The resulting reactive dye der
formula
EMI19.2
 is salted out, filtered off, washed and dried at 30 to 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 diazo and azo components listed in the table below
Azo dyes.



  Diazo component, coupling component, color shade on cotton
1-hydroxy-2-amino- 2-methylamino-5-hydroxy- ruby benzene -4-sulfonic acid naphthalene-7-sulfonic acid n-thylamino-5-hydroxy-naphthalene-7-sulfonic acid "2- (ss-hydroxyethylamino) -"
5-hydroxynaphthalene
7-sulfonic acid 1- hydroxy-2 -amino- 2-amino-8 -hydroxynaphthal in ruby benzene-4-sulfonic acid 3,6-disulfonic acid 1 -hydroxy-2-amino- 2-ajnino-5-hydroxynaphthalene- n benzene- 4,6- 1,7-disulfonic acid disulfonic acid n 2-amino-8-hydroxynaphthalene-
3,6-disulfonic acid n 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid 1l 2-X thylamino-5-hydroxynaphthalene-7-sulfonic acid "

   2- (ss-hydroxyethylamino)
5-hydroxynaphthalene
7-sulfonic acid diazo component coupling component color shade on
Cotton n 1-Amino-8-hydroxynaphthalene violet
3, 6-disulfonic acid
1-Amino-8-hydr-oxynaphthalene-
4,6-disulfonic acid 1 hydroxy-2-amino- 1 n benzene-5-sulfonic acid 3, 6-disulfonic acid "1-amino-8-hydroxynaphthalene-"
4,6-disulfonic acid 1-hydroxy-2-amino-1-amino-8-hydroxynaphthalene bluust.



  4-acetylaminobenzene-3,6-disulfonic acid violet 6-sulfonic acid 1-hydroxy-2-amino-1-ethoxy-8-hydroxynaphthalene 4-acetylaminobenzene-3,6-disulfonic acid 6-sulfonic acid (4-position acetylamino group subsequently saponified) 1-hydroxy -2-amino- 1-amino-8-hydroxynaphthalene blue 4-acetylaminobenzene- 2,4-disulfonic acid 6-sulfonic acid "1-amino-8-hydroxynaphthalene-"
2,4,6-trisulfonic acid 1-hydroxy-2-amino-1-amino-8-hydroxynaphthalene- "6-acetylaminobenzene-2,4-disulfonic acid 4-sulfonic acid (6-position acetylamino group saponified) l-amino-2-hydroxy - l-amino-8-hydroxy blue
6-nitronaphthalene-naphthalene-2, 4-disul
4-sulfonic acid (6-position nitro group then reduced to
1-amino-2-hydroxy-1-amino-8-hydroxy
6-nitronaphthalene-naphthalene-2,

   4.6
4-sulfonic acid trisulfonic acid (6-position nitro group reduces to -NH2)
1-hydroxy-2-amino-1-amino-8-hydroxy
6-acetylaminobenzene-naphthalene-2,4,6
4-sulfonic acid trisulfonic acid (6-position acetylamino group saponified)
Example 14
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 allowed to run into a mixture of 100 parts of ice and 28 parts by volume of concentrated hydrochloric acid; then the mixture is stirred for half an hour at 0 to 10 C and then excess nitrous acid is removed.

  The solution of 26.2 parts of the potassium salt of 1-aminonaphthalene-8-sulfonic acid in 250 parts of hot water, which has cooled and thereby partially crystallized out again, is added to the diazo suspension obtained in this way at 0 to 10 ° C. and the strongly acidic coupling mixture is blunted at 10 to 20 ° C "C by carefully adding sodium hydroxide solution to pH 4. The coupling is completed quickly; the aminoazo dye formed is completely salted out with 100 parts of sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 30 ° C. and pH 6 to 7. The aqueous solution is partially mixed with 20 parts of 4,6-difluoro-5-chloropyrimidine and Stirred with soda solution to pH 6 to 7 for one hour at 30 to 40 ° C. while continuously blunting the liberated acid.

  If no more amino azo dye can be detected, the partially precipitated reactive dye becomes of the formula
EMI21.1
 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 one proceeds as stated 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-aminonaphthalene-8-sulfonic acid, after azinylation with 4, 6-Difluoro-5-chloropyrimidine likewise valuable yellow to brown reactive dyes.



  Diazo component shade on cellulose fiber l-aminobenzene-2,5-disulronic acid red.



   Yellow 2-aminonaphthalene-4,8-disulfonic acid very reddish.



   Yellow 2-aminonaphthalene-5,7-disulfonic acid II 2-aminonaphthalene-6,8-disulronic acid n 2-aminonaphthalene-3, 6,8-trisulfonic acid tt 2-amnonaphthalene-4,6,8-trisulronic acid 4-aminoazobenzene-3, 4 "-disulfonic acid dissolved.



   Brown 4-Amino-2-acetylamlnoazobenzol-2 ', 5o-dlsulfonic acid Orange brown Diazo component shade on
Cellulose fiber
EMI22.1
   otst.



  Brown (1-aminobenzene-2,5-disulfonic acid acidic to 1-aminonaphthalene-6-sulfonic acid coupled)
EMI22.2


<tb> <SEP>, SONa
<tb> NIM <SEP> 8 <SEP> tl
<tb> S03Na <SEP> Ç;
<tb> <SEP> SO3Na <SEP> (in <SEP> 6- <SEP> or <SEP> 7-position)
<tb> (1-aminobenzene-2,5-disulfonic acid acidic to the technical mixture of 1-aminonaphthalene-6- and -7-sulfonic acid coupled)
EMI22.3
 violetest.



  Braun (1-aminonaphthalene-2,5,7-trisulfonic acid acidic to 1-aminonaphthalene-6-sulfonic acid coupled)
EMI22.4
 rotst.



  Braun (1-aminonaphthalene-2,5,7-trisulfonic acid, acidic to 1-amino-2-methoxy-5-methylbenzene, coupled)
Example 15
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
EMI23.1
 in 400 parts of water, the mixture is stirred with 45 parts of 4,6-difluoro-5-chloropyrimidine for about 3 hours at 40 to 50 ° C. while maintaining the pH 6 to 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, Xupplungs-pH 1 -hydroxy-2-amino-1 -Hydroxy-8-aminonaphthalene- 9 4-nitrobenzene 3,

   6-disulfonic acid 1-hydroxy-2-amino-n 9 4-nitronaphthalene-7-sulfonic acid
Example 16
Add to the neutral solution of 53.1 parts of the disodium salt obtained by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with 1- (2'-chloro-5'sulfophenyl) -3-methyl-pyrazolone- (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye in 300 parts of water 18 parts of 4,6-difluoro-5-chloro-pyrimidine and the mixture is stirred for 2 hours at 30 "C, the acid liberated continuously with soda solution to a pH Value of 6.5 dulls The deposited dye of the formula
EMI23.2
 is filtered off, dissolved in 3000 parts of warm water at pH 6 to 7 and reprecipitated from the filtered solution by adding sodium chloride.

  After filtering off, drying and powdering, a yellow, readily water-soluble powder is obtained which dyes cellulose materials from a long liquor at 30 ° C. or according to the Klotz cold batch process with soda as an acid-binding agent in clear, washable, rub-fast and lightfast yellow tones.

 

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



     Diazo component Azo component pH of the hue
Coupling cellulose mediums 1-amino-4-nitro- 1- (4'-sulfophenyl) - 5 - 6 yellow benzene-2-sulfonic acid 3-methyl-pyrazolone (4-position nitro group then reduced) 1-amino-4-nitro - 1- (4t-sulfophenyl) - 5 - 6 rotst.



     benzene-2-sulfonic acid 3-carboxy-pyrazolone- yellow (5)
1- (3'-sulfophenyl) - 6-7 yellow
3-methyl-5-amino pyrazole 1-amino-3-acetylamino- 1- (3'-sulrophenyl) - 6 - 7 benzene-6-sulfonic acid 3-methyl-5-amino pyrazole (3-position acetylamino group then saponified) 1 -Amino-3-acetylamino- 1- (ss-hydroxyethyl) - 5-6 benzene-6-sulfonic acid 3-methyl-pyrazolone (5) 2 moles 1-amino-3- 1 mole bis-pyrazolone 5-6 acetylaminobenzene- from 4,4'-bis-hydra-6-sulfonic acid zlnodlbenzyl-2,22- (saponified) disulfonic acid and
Ethyl acetoacetate 1 mol l-amino-3- 1- (4'-sulfophenyl) - 5-6 acetylaminobenzene- 3-carboxy-pyrazolone-6-sulfonic acid (5) (saponified) 1-amino-5-acetyl- 5 5 - 6 rotst.



  aminonaphthalene yellow 3,7-disulfonic acid (saponified) 1-amino-2-methyl-2-acetylamino-5- 7 - 8 Orange benzene-4,6-di- naphthol-7-sulfonsulfonic acid (saponified) "2- Acetylamino-8- 7-8 red naphthol-6-sulfonic acid (saponified) diazo component azo component pH of the shade
Coupling cellulose mediums 1-amino-2-methyl-1-chloro-2-acetyl- 7-8 Orange benzene-4,6-amino-5-naphthol disulfonic acid 7-sulfonic acid (saponified) l-aminobenzene-l-acetylamino-7 - 8 red 2-sulfonic acid 8-hydroxynaphthalene
4,6-disulfonic acid (saponified) 2-aminonaphthalene- "7 - 8 bluust.



  3,6-disulfonic acid red 2-aminonaphthalene- 7 7 - 8 n 3,7 -disulfonic acid 2-aminonaphthalene- 7 7-8 n 4,8-disulfonic acid 2-aminonaphthalene- l-acetylamino-8- 7 - 8 n 3, 6-disulfonic acid hydroxynaphthalene
3,6-disulfonic acid (saponified) 2-aminonaphthalene-7 7-8 n 4,8-disulfonic acid 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) n 2- (N-acetyl-N-methyl- 7 - 8 red amino) -8-hydroxy naphthalene-6-sulfone- acid (saponified) 1-aminobenzene- "7-8" 2-sulfonic acid 1-aminobenzene- "7-8" 3- sulfonic acid 1-aminobenzene- "7-8" 4-sulfonic acid 1-amino-4-methyl- " 7 - 8 "benzene-2-sulfonic acid diazo component azo component pH of the shade
Coupling cellulose mediums 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) n 2-acetylamino-8-7-8 II hydroxynaphthalene
6-sulfonic acid (saponified) n 2-acetylamino-8- 7 - 8 II hydroxynaphthalene
3,6-disulfonic acid (saponified) 4-aminoazobenzene-i-amino-3-acetyl-5 - 6

   Yellow-brown 3,41-disulfonic acid aminobenzene "1-Amino-3-hydroxy-5-6 acetylaminobenzene
1-aminonaphthalene-5-6 II 6- sulfonic acid
1-aminonaphthalene- 5 - 6 II
7-sulfonic acid "1-Amino-2- (4'-amino-8 Black
2'-sulfophenyl- (1 ') azo) -8-hydroxy naphthalene-3,6 disulfonic acid
Example 17
52.4 parts of the disodium salt of 4 - ([4 "-aminophenyl] -amino) -2'-nitrodiphenylamine-3, 4'-disulfonic acid are dissolved in 1000 parts of water and 20 parts of 4,6-difluoro-5 -chlorpyrimidine stirred for two hours at 30 to 40 ° C. The acid released is continuously blunted with soda to a pH of 6 to 6.5 The reactive nitro dye of the formula that is formed
EMI26.1
 is salted out, filtered off, washed and dried.



  It dyes cellulose fibers from a long liquor or using one of the customary padding processes in the presence of soda as an acid-binding agent in deep violet-brown tones that are fast to wet and rub-resistant.



   Example 18
52 parts of 1-amino-4- (4'-N-methylaminomethylanilino) anthraquinone-2,2'-disulfonic acid are dissolved in 1550 parts of water and the pH is adjusted to 6 with sodium hydroxide solution. Then 20 parts of 4,6-difluoro-5-chloropyrimidine are added dropwise at room temperature and a pH of 7 is maintained with 2N sodium hydroxide solution. The conversion is followed by chromatography. The reaction product is salted out, filtered off with suction and the filter residue is washed with 10% sodium chloride solution. Clear blue dyeings of good wet fastness and good light fastness are obtained on cotton.



   The resulting dye corresponds to the likely formula
EMI27.1

In basically the same way, the amino-anthraquinone derivatives listed in the table below can be converted into valuable reactive dyes, the hues of which are given on cotton.



  Water-soluble amino-anthraquinone derivative hue on
Cotton 1-Amino-4- (4'-N-methylaminomethylanilino) - green.



  anthraquinone-2,6,2'-trisulfonic acid blue 1-Amino-4- (4'-N-methylaminomethylanilino) - "anthraquinone-2, 5, 8-trisulfonic acid) 1-amino-4- (4'-N-methylaminomethylanilino ) - blue anthraquinone-2, 8-disulfonic acid 1-amino-4- (4'-aminoanilino) -anthraquinone- blue-green 2,6-disulfonic acid 1-amino-4- (4'-aminoanilino) -anthraquinone- green.



  2,5-disulfonic acid blue 1-amino-4- (3'-aminoanilino) -anthraquinone- blue 2,6-disulfonic acid 1-amino-4- (3'-aminoanilino) -anthraquinone- "2,5-disulfonic acid 1 - Amino-4- (3 '-aminoanilino) -anthraquinone- a little red.



  2,4'-disulfonic acid blue 1-amino-4- (31 -aminoanilino) -anthraquinone red.



     2,4 ', 6' -trisulfonic acid blue 1-Amino-4- (4'-aminocyclohexylamino) - clear anthraquinone-2,5,8-trisulfonic acid blue 1-Amino-4- (4'-N-methylaminomethylanilino) - blue anthraquinone-2,31-disulfonic acid 1-amino-4- (4 '- [4 "-aminobenzoylamino] -anilino) - blue-green anthraquinone-2,5,8-trisulfonic acid 1-amino-4- (4' - [4" -aminobenzolsulfamido] -anilino) - green.



  anthraquinone-2,5,8-trisulfonic acid blue 1-amino-4- (4 "-aminostilbenamino) -anthraquinone-green 2, ', 2" -trisulfonic acid
Water-soluble amino-anthraquinone derivative hue on
cotton
EMI28.1


<tb> <SEP> NR2
<tb> <SEP> O <SEP> 1 \ JH,
<tb> C1H3 <SEP> k} {urS <SEP> rotst.
<tb>



   <SEP> O <SEP> NO
<tb> <SEP> SO2NH <SEP> 502 <SEP> iH2
<tb> <SEP> CH3
<tb>
Example 19
If one proceeds as indicated in Example 16, but instead of the aminoazo dye used there 53.1 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 subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye with the 4,6 difluoro-5-chloro-pyrimidine azinylated, so you also get a valuable reactive dye, with which cellulose materials after the usual dyeing and Printing process 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 composed of the components listed in the table below is azinylated with 4,6-difluoro-5-chloropyrimidine: Diazo component azo component shade 1 -amino-4-nitrobenzene- l- (2'-methyl-4 "-sulfophenyl) - yellow 2-sulfonic acid 3-methyl-pyrazolone- (5) (reduced)" 1- (2 ', 5'-disulfophenyl) - "
3-methyl-pyrazolone- (5) "1- (2'-methyl-4'-sulfo-" 6 '-chlorophenyl) -3-methyl-pyrazolone- (5) "1- (2', 5'-dichloro -4'- "sulfophenyl) -3-methyl-pyrazolone- (5) diazo component azo component shade 1 -amino-3-acetylamino- 1- (2 | -Methyl-42-sulfo green.



  benzene-6-sulfonic acid phenyl) -3-methyl- yellow (saponified) pyrazolon- (5) "1- (4'-sulfophenyl) -3-" methyl-pyrazolon- (5)
II l- (2'-methyl-4'-sulfophenyl) -3-carboxy pyrazolone- (5) 1- (2'-chloro-42-sulfo- nphenyl) -3-carboxy pyrazolone- (5)
Example 20
58 parts of the dye of the formula
EMI29.1
 (prepared by coupling diazotized 1-hydroxy 2-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 in a neutral manner. 20 parts of 4,6-difluoropyrimidine are added dropwise and the mixture is stirred at 40 to 50 ° C. with constant blunting of the hydrofluoric acid released with soda solution to pH 6 to 7 until no free amino group can be detected.

  The reactive dye formed of the formula
EMI29.2
 is salted out, filtered off, washed and dried at 30 to 40 CC. It dyes cellulose materials in very true violet tones using one of the methods given above.



   Dyes with similar properties are obtained analogously to the procedure outlined above from the copper complexes obtained by simple demethylating or oxidizing copper plating of the mono and disazo dyes prepared from the diazo and azo components listed in the table below: diazo component azo component pH of the shade
Coupling mediums l-hydroxy-2-amino-2-amino-8-hydroxy-10 rotst.



  4-chlorobenzene-5-naphthalene-3,6-violet sulfonic acid disulfonic acid "1-amino-8-hydroxy-10 bluust.



   naphthalene-3,6- violet disulfonic acid 2-aminonaphthalene- 2-hydroxy-6-acetyl- 8 - 9 rotst.



  4,6,8-trisulfonic acid aminonaphthalene blue (oxidizing coppery) 4-sulfonic acid (saponified) 1-amino-2-hydroxy-1-hydroxy-8-ethoxy-10 blue 6-nitronaphthalene-3,64-sulfonic acid disulfonic acid (reduced) 1-hydroxy-2-amino-2-hydroxy-3-amino-10 red benzene-4,6-naphthalene-5,7 disulfonic acid disulfonic acid
2-aminonaphthalene-2-hydroxy-3-amino-8-9 blue
4,8-disulfonic acid naphthalene-5,7 (oxidizing copper-plated) disulfonic acid
2-aminonaphthalene-2-hydroxy-3-amino-8-9 n
4,6,8-trisulfonic acid naphthalene-7 (oxidizing copper-plated) sulfonic acid
3-methoxy-4-amino-6- 2-methylamino-5- 10 navy blue methyl-azobenzene-2 ', 4L hydroxynaphthalene disulfonic acid (methylating copper-7-sulfonic acid) "2-amino-8-hydroxy- 10" naphthalene- 3,6 disulfonic acid "2-amino-5-hydroxy-

   10 "naphthalene-1,7 disulfonic acid
3-methoxy-4-amino-2-methylamino-5- 10 1 '6-methyl-asobenzene-hydroxynaphthalene
2 ', 5'-disulfonic acid 7-sulfonic acid (demethylating copper-plated) "2-amino-8-hydroxy-10" naphthalene-3,6-disulfonic acid "2-amino-5-hydroxy-10" naphthalene-1,7 disulfonic acid
Example 21
62 parts of the trisodium salt of the dye obtained by soda-alkaline coupling from diazotized 4-chloro-2-amino-1-hydroxy-benzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 300 parts of water at 70 up to 80 "C and a pH of 8 to 9 with 54.2 parts of 1:

   1-chromium complex of the dye from 6-nitro-1-diazo-2-hydroxynaphtbalin-4 sulfonic acid and 2-hydroxynaphthalene added. After 10 minutes a deep blue solution has formed.



   The mixed complex is azinylated with 20 parts of 4,6-difluoro-5-chloropyrimidine at 50 to 60 ° C. and a pH of 6.5 to 7.5 in about 2 hours. 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 300C.
EMI31.1




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



   Example 22
28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The monoazo dye obtained is isolated and then, or even without isolation, immediately diazotized in solution and coupled with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid under alkaline conditions. The disazo dye obtained is salted out by adding sodium chloride, filtered off with suction and the isolated product is metallized with about 50 parts of crystallized copper sulfate, 40 parts of diethanolamine, 50 parts of ammonia (D: 0.88) at 95 to 100 ° C. in 5 hours. The dye is isolated from the coppering solution by adding salt and carefully acidifying it.



   The coppered aminodisazo dye is now azinylated in aqueous solution at pH 6 to 7 at a temperature of 40 to 50 ° C. with 20 parts of 4,6-difluoro-5-chloropyrimidine, the pH being kept in the specified range by adding soda. When the acylation has ended, the dye is isolated with sodium chloride and dried at 35.degree. In the form of the free sulfonic acid, the dye corresponds to the formula
EMI31.2
 he dyes cellulose fabric using the methods known for reactive dyes in wet and lightfast navy blue tones.



   In a similar way, other dyes can be prepared if the above-mentioned monoazo dye from 2-amino-1-methylbenzene-3,5-disulfonic acid and 1-atnino-2-methoxy-5-methylbenzene with the aminonaphthol sulfonic acids and listed in the table below 4,6-Difluoro-5-chloropyrimidine combined according to the instructions given above: Coupling component 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid
The dyes obtained are blue in color.



   Example 23
0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5sulphonic acid is diazotized and coupled with 0.1 mol of 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid using alkaline soda. The coupling solution is adjusted to a content of 2 mol / liter with caustic soda and then refluxed for 3 hours to saponify the ureido group. After cooling, it is neutralized with hydrochloric acid. By adding 25 parts of copper sulfate and 100 parts of 2N sodium hydroxide solution, the dye is metallized at 45 ° C. and a pH of 4 to 6 and, after 30 minutes, at pH 6 to 7 and temperatures of 30 to 40 ° C. with 0.12 mol of 4 , 6 Difluoro-5-chloropyrimidine azinylated.Del obtained dye of the formula
EMI32.1
 is salted out. On cotton you get a blue one
Coloring.



   Example 24
A neutral paste of copper phthalocyanine-3, 3 ', 3 "-trisulfonic acid chloride produced from 600 g of technical 96 above copper phthalocyanine is stirred with a little water, adjusted to 4 liters and at a pH of 3.5 to 6 with 216 g of N-methyl -N- (4 'amino-2'-sulfobenzyl) -amine at initially 0 to 3 C, finally 20 to 35 aC, with the addition of 300 ml (=
295 g) pyridine reacted and then the pyridine at pH
9 distilled off with steam from the resulting solution of copper phthalocyanine disulfonic acid monosulfonic acid (3'-sulfo-4'-methylaminomethylanilide).

  300 parts of 4,6-difluoro-5-chloropyrimidine are added over the course of 1 to 2 hours to the solution, which has been brought to 20 to 30 ° C., and a pH of 6 to 7 is maintained by adding dilute sodium hydroxide solution 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 are separated off from the excess acylating agent. adjusts to pH 7 by adding acetic acid and precipitates by stirring in 2.5 1 of concentrated sodium chloride solution.



   After suctioning off and drying at 30.degree. C., a clear turquoise-blue dye is obtained, which is fixed on cotton from a solution in alkaline soda at 50 to 80.degree. C. with very good yield and washing fastness, giving turquoise colorations.



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



   Example 25
0.1 mol of the aminoazo dye of the formula
EMI32.2
 - prepared according to the information in German Patent 1,115,865 by coupling the diazonium compound from 2-aminonaphthalene-4,8-disulfonic acid with 1-aminonaphthalene-6-sulfonic acid, further diazotizing the resulting aminoazo dye, coupling with the equivalent amount of 2,5-diaminonaphthalene-4 , 8-disulfonic acid and conversion into the aminotriazole - is dissolved in 1000 parts by volume of water at pH 6 and mixed with 25 parts of 4,6-difluoro-5-chloropyrimidine with stirring at a temperature of 40 to 50 ° C. The slowly released hydrofluoric acid 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 26
38.9 parts of the dye obtained by the soda-alkaline coupling of 6-nitro-2-diazo-1-hydroxybenzene-4-sulfonic acid and 2-hydroxynaphthalene are stirred in 200 parts of water at pH 8 and a temperature of 70 to 80.degree. 67.9 parts of the chromium complex compound of the azo dye of 4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-8-hydroxynaphthalene-3,6 are carried into this suspension -disulfonic acid, the pH being kept between 7 and 9 by adding soda solution. After 20 minutes at 70 to 80 sC, a dark blue solution has formed. The paper chromatogram shows that a uniform mixed complex has arisen.

  The mixed complex is azinylated with 25 parts of 4,6-difluoro-5-chloropyrimidine at 60 ° C. and pH 6.5 to 7.5 over the course of one hour, the pH being kept in the specified range by adding a soda solution dropwise. The azinylated dye is salted out with 20% potassium chloride, filtered off and dried at 30.degree. A dark powder is obtained that dissolves in water with a blue-gray color.



   The pentasodium salt of the dye corresponds to the formula
EMI33.1
 It dyes cotton in gray to black shades according to the methods given in Examples 1 to 3.



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



  1: 1 chromium complex metal-free dye hue on
cotton
EMI33.2


<tb> 4-Nitro-2-amino-1- <SEP> 4-Nitro-2-amino-1-hydroxy- <SEP> Black
<tb> hydroxybenzo1-6- <SEP> benzene
<tb> sulfonic acid <SEP> -------> <SEP> 2-hydroxynaphthalene
<tb> 1-Amino-8-hydroxy- <SEP>
<tb> naphthalene-3,6- <SEP>
<tb> disulfonic acid
<tb> <SEP> 4-nitro-2-amino-1-hydroxy- <SEP> n
<tb> <SEP> benzene
<tb> <SEP> 2-hydroxynaphthalene-6
<tb> <SEP> sulfonic acid
<tb> 1:

  : 1-chromium complex metal-free dye hue on
cotton
EMI34.1


<tb> 4-Nitro-2-amino-1 <SEP> - <SEP> 4-Nitro-2-amino-1 <SEP> - <SEP> Navy blue
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP> #
<tb> sulfonic acid <SEP> # <SEP> 1-hydroxynaphthalene
<tb> l-amino-8-hydroxy- <SEP> 4-sulfonic acid
<tb> naphthalene-3,

   <SEP> 6- <SEP>
<tb> disulfonic acid
<tb> <SEP> "<SEP> 6-Nitro-2-amino-1- <SEP> Black
<tb> <SEP> hydroxybenzene-4
<tb> <SEP> sulfonic acid <SEP> #
<tb> <SEP> 2-hydroxynaphthalene
<tb> <SEP> "<SEP> 4-Nitro-2-amino-1- <SEP>"
<tb> <SEP> hydroxybenzene <SEP>
<tb> <SEP> 1-acetylamino-7- <SEP>
<tb> <SEP> hydroxynaphthalene
<tb> <SEP> according to <SEP> 6-Nitro-1 <SEP> -amino-2- <SEP>
<tb> <SEP> hydroxynaphthalene
<tb> <SEP> 4-sulfonic acid
<tb> <SEP> 2-hydroxynaphthalene
<tb> 4-Nitro-2-amino-1- <SEP> 4-Nitro-2-amino-1- <SEP> "
<tb> hydroxybenzene-6- <SEP> hydroxynaphthalene-6
<tb> sulfonic acid <SEP> # <SEP> <SEP> sulfonic acid <SEP> #
<tb> 1-amino-8-hydroxy- <SEP> 2-hydroxynaphthalene
<tb>

   naphthalene-4,6
<tb> disulfonic acid
<tb> 4-chloro-2-amino-1 <SEP> 4-nitro-2-amino-1- <SEP> blue-black
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP> #
<tb> sulfonic acid <SEP> # <SEP> <SEP> 2-hydroxynaphthalene
<tb> 1-amino-8-hydroxy
<tb> naphthalene-3,6
<tb> disulfonic acid
<tb> <SEP> "<SEP> 4-Nitro-2-amino-1 <SEP>"
<tb> <SEP> hydroxybenzene <SEP> - <SEP>
<tb> <SEP> 2-hydroxynaphthalene
<tb> <SEP> 6- <SEP> sulfonic acid
<tb> <SEP> "<SEP> 4-chloro-2-amino-1- <SEP> navy blue
<tb> <SEP> hydroxybenzene <SEP> #
<tb> <SEP> 2-hydroxynaphthalene
<tb> <SEP> "<SEP> 4-Nitro-2-amino-1- <SEP> Blue
<tb> <SEP> hydroxybenzene <SEP> #
<tb> <SEP> 1-acetylamino-8
<tb> <SEP> hydroxynaphthalene
<tb> <SEP> 3,6-disulfonic acid
<tb> 1:

  : 1-chromium complex metal-free dye hue on
cotton
EMI35.1


<tb> 4-chloro-2-amino-1- <SEP> 4-nitro-2-amino-1- <SEP> navy blue
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP> #
<tb> sulfonic acid <SEP> # <SEP> 1-amino-8-hydroxy
<tb> 1-amino-8-hydroxy- <SEP> naphthalene-2,4
<tb> naphthalene-3,6- <SEP> disulfonic acid
<tb> disulfonic acid
<tb> <SEP> "<SEP> 6-Nitro-1-amino-2 <SEP> blue-black
<tb> <SEP> hydroxynaphthal <SEP> in- <SEP>
<tb> <SEP> 4-sulfonic acid <SEP> #
<tb> <SEP> 2-hydroxynaphthalene
<tb> <SEP> 2-aminobenzene-l- <SEP> gray-green <SEP>
<tb> <SEP> carboxylic acid-5- <SEP>
<tb> <SEP> sulfonic acid <SEP> #
<tb> <SEP> <RTI

    ID = 35.10> 1-phenyl-3-methyl- <SEP>
<tb> <SEP> 5-pyrazolone
<tb> 4-Nitro-2-amino-1- <SEP> 6-Nitro-1-amino-2- <SEP> Black
<tb> hydroxybenzene-6- <SEP> hydroxynaphthalene
<tb> sulfonic acid <SEP> # <SEP> <SEP> 4-sulfonic acid <SEP> #
<tb> 1-amino-8-hydroxy- <SEP> 2-hydroxynaphthalene
<tb> naphthalene-3,6
<tb> disulfonic acid
<tb> 4-chloro-2-amino-1 <SEP> 4-chloro-2-amino-1- <SEP> Viclett
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP> #
<tb> sulfonic acid <SEP> # <SEP> <SEP> 1- (4'-sulfophenyl)
<tb> 1-Amino-8-hydroxy- <SEP> 3-methyl-5-pyrazolone
<tb> naphthalene-3,6
<tb> disulfonic acid
<tb> 4-methyl-2-amino-1- <SEP> 4-chloro-2-amino-1- <SEP> rotst.
<tb>

 

  hydroxybenzene-6- <SEP> hydroxybenzene <SEP> # <SEP> <SEP> blue
<tb> sulfonic acid <SEP> # <SEP> <SEP> 2-hydroxynaphthalene
<tb> l-amino-8-hydroxy- <SEP> 6-sulfonic acid
<tb> naphthalene-3, <SEP> 6- <SEP>
<tb> disulfonic acid
<tb> 4-Nitro-2-amino-1 <SEP> - <SEP> 5-Nitro-2-amino-1 <SEP> - <SEP> Black
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP> #
<tb> sulfonic acid <SEP> # <SEP> <SEP> 2-hydroxynaphthalene
<tb> 1-amino-8-hydroxy- <SEP> 6-sulfonic acid
<tb> naphthalene-3,6
<tb> disulfonic acid
<tb> 1:

  : 1-chromium complex, metal-free dye hue
cotton
EMI36.1


<tb> 4-Nitro-2-amino-1- <SEP> 4-Nitro-2-amino-1- <SEP> Black
<tb> hydroxybenzene-6- <SEP> hydroxybenzene <SEP>> <SEP>
<tb> sulfonic acid # <SEP> <SEP> 2-hydroxynaphthalene
<tb> l-amino-8-hydroxy- <SEP> 8-sulfonic acid
<tb> naphthalene-3,

   <SEP> 6- <SEP>
<tb> disulfonic acid
<tb> <SEP> 4-Nitro-2-amino-1- <SEP> n
<tb> <SEP> hydroxybenzene <SEP>> <SEP>
<tb> <SEP> 1-hydroxynaphthalene
<tb> <SEP> 5-sulfonic acid
<tb> <SEP> n <SEP> 6-Nitro-4-chlor-1 <SEP> - <SEP> n
<tb> <SEP> hydroxybenzene <SEP> #
<tb> <SEP> 1-hydroxynaphthalene
<tb> <SEP> 5-sulfonic acid
<tb>
Example 27
8.2 parts of l-amino-4- [3'-aminoanilino] 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. 4.0 parts of 4,6-difluoro-5-chloropyrimidine are added dropwise at 0 C. and a pH of 6.5 to 7 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 5% sodium chloride solution and dried in vacuo at 30 ° C.



   The dye dyes wool in very wetfast blue tones.
EMI36.2




   Example 28
8.3 parts of l-amino-4- [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 45% sodium hydroxide solution and, at 5 to 10 "C., 4 parts of 4 , 6-Difluoro-5-chloropyrimidine was added dropwise, and a pH of 9 to 10 is maintained by adding 2N sodium hydroxide solution.



  After the acylation has ended, the pH is adjusted to 4.5 by adding hydrochloric acid. The crystalline product is filtered off with suction and washed with 5% strength sodium chloride solution until it is colorless. The dye obtained is dried in vacuo at 30 to 40 ° C., it dyes wool in clear, washable blue tones.
EMI36.3




   Example 29
12.2 parts of l-amino-4- (p-aminophenylamino) -anthraquinone-2,2'-disulfonic acid-6-carboxylic acid are dissolved in 360 parts of water and at a pH of 6 with 5 parts of 5-chloro-4 , 6-difluoro-2-phenyl-pyrimidine. dissolved in acetone, acylated at a temperature of 30-50 C. The resulting dye is salted out with 5 parts of sodium chloride, filtered off with suction and washed with 5% sodium chloride solution. It dyes cotton in greenish blue tones with good wet fastness properties.



   The following dyes can be prepared in an analogous manner: Table of starting material, reactive component, color shade 1-amino-4- (4'-N-methylaminomethyl-anilino) -anthra- 4,6-difluoro-5-bromopyrimidine greenish blue quinone-2.6.2'- trisulfonic acid 1-amino-4- (4'-N-methylaminomethyl-anilino) -anthra- 4,6-difluoro-5-chloro-2-sulfophenyl-pyrimidine greenish blue quinone-2.7.2'-trisulfonic acid 1-amino-4- ( 4'-amino-anilino) -anthraquinone-2.7- 4.6-difluoro-5-chloro-2-trichloromethyl-pyrimidine blue-green disulfonic acid 1-amino-4- (3'-aminomethyl-2'.6'-dimethyl-anilino) - 4.6-Difluoro-5-chloro-2-trifluoromethyl-pyrimidine clear blue anthraquinone-2.6.5'-trisulfonic acid 1-amino-4- (3'-aminomethyl-2'.6'-dimethyl-anilino) - 4.6-Difluor- 5-trifluoromethyl-pyrimidine redstic klaanthraquinone-2.5'-disulfonic acid res blue 1-Amino-4- (3'-N-methylaminomethyl-2'.6'-dimethyl-

   4.6-Difluoro-5-methylsulfonyl-pyrimidine clear, somewhat anilino) anthraquinone-2.7-disulfonic acid, greenish blue 1-Amino-4- (3'-N-methylaminomethyl-2'.6'-dimethyl-4.6-Difluoro-5- chloro-pyrimidine clear, somewhat anilino) -anthraquinone-2.7.5'-trisulfonic acid green-tinged balu 1-amino-4- (4'-N-methylaminomethyl-2'.6'-dimethyl-4.5.6-trifluoropyrimidine clear,

   some anilino) anthraquinone-2.6.5'-trisulfonic acid greenish blue 1-Amino-4- (3'-aminomethyl-4'-methyl-anilino) -anthra- 4,6-difluoro-5-chloro-2- (3'- chlorophenyl) - blue quinone-2.6.6'-trisulfonic acid pyrimidine 1-amino-4- (3'-methylamino-4'-methoxy-anilino) - 4.6-difluoro-5-chloro-2- (3'-trifluoromethyl blue anthraquinone-2.7.6'-trisulfonic acid (phenyl) pyrimidine 1-amino-4- (4'-amino-anilino) -anthraquinone-2.6.3'-4.6-difluoro-5-carbethoxy-pyrimidine blue trisulfonic acid 1-amino-4 - (3'-aminomethyl-4'-methyl-anilino) -anthra- 4.5.6-trifluoropyrimidine blue quinone-2.7.6'-trisulfonic acid 1-amino-4- (3'-amino-anilino) -anthraquinone- 2.6- 4.6-Difluoro-2-trifluoromethyl-pyrimidine blue disulfonic acid 1-amino-4- (4'-amino-anilino) -anthraquinone-2.6- 4.6-difluoro-5-trifluoromethyl-pyrimidine greenish blue disulfonic acid

 

Claims (1)

PATENT CLAIM Process for the preparation of reactive dyes of the formula EMI38.1 where D is the residue of an organic dye, R is hydrogen or a lower alkyl group, m is a number from 1 to 8, R1 is hydrogen or a substituent. R. is hydrogen or an optionally substituted alkyl, alkenyl, aralkyl or aryl radical and F is a fluorine substituent, and where the group, respectively. the groups -N (R) - is bonded directly or via a bridge member to an aromatic ring of said organic dye residue, characterized. that one amino or amide-containing organic dyes of the formula EMI38.2 with compounds of the formula EMI38.3 azinylated, where X is an anionically removable radical. SUBClaims @. Method according to patent claim, characterized. that the reactive components are 4,6-difluoro-5-chloro-pyrimidine, 4,6-difluoro-5-trifluoromethyl-pyrimidine, 4,6-difluoro-2-methyl-pyrimidine, 3.6-difluoro-5-chloro-2- methyl pyrimidine. 4,5,6-trifluoropyrimidine. 4,6-Difluoro-5-chloro-2-trifluoromethyl-pyrimidine, 4,6-Difluoro-2-phenyl-pyrimidine. 4,6-difluoro-5-cyano-pyrimidine. 4,6-Di-fluoro-5-nitro-pyrimidine, 4,6-difluoro-5-methyl-sulfonyl-pyrimidine or 4,6-difluoro-5-phenylsulfonyl-pyrimidine is used. 2. The method according to dependent claim 1. characterized. that one azinylated with 4,6-difluoro-5-chloropyrimidine and 4,6-difluoro-5-chloro-2-methylprimidine as reactive components. 3. Method according to claim. characterized. that as the starting dye of the formula 11 aminoazo dyes of the formula EMI38.4 is used, in which B and E represent aromatic, carbocyclic or heterocyclic radicals and R stands for a -CH: 1 group or preferably a hydrogen atom. 4. Method according to claim. characterized in that the starting dyes of the formula 11 are aminoanthraquinone dyes of the formula EMI38.5 is used in which L and L 'are substituents, among them in particular sulfonic acid groups, p is an integer from 0 to 2 and R "is a methyl or ethyl group or hydrogen and, if appropriate, sulfonates the reactive dyes obtained. 5. Method according to claim. characterized in that the starting dyes of the formula II are azaporphine dyes of the formula EMI39.1 is used, where Pc for the remainder of a nickel or copper phthalocyanine, L and L 'for substituents, in particular sulfonic acid groups, r for an integer from 0 to 2, q for the number 0 or 1, R' for a methyl group or preferably hydrogen, R; represents 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 and the reactive dyes obtained may be sulfated. 6. The method according to claim, characterized in that with a reactive component of the formula EMI39.2 where R 'is hydrogen and R'1 is halogen or CF3 and Y is an anionically removable radical. in particular represents a fluorine substituent, azinylated with elimination of the anionic radical Y. 7. The method according to claim, characterized in that such dyes are built up. which have one or more sulfonic acid groups. 8. The method according to claim, characterized. that one reactive dyes of the formula EMI39.3 produces, in which D represents the residue of an azo, anthraquinone or azaporphin dye containing sulfonic acid groups. 9. The method according to claim and dependent claim 3, characterized in that reactive azo dyes of the formula EMI39.4 manufactures. where B and E represent aromatic, carbocyclic or heterocyclic radicals, in particular B the radical of a carbocyclic diazo component of the benzene or naphthalene series, and E the radical of an enolic or phenolic coupling component, preferably a 5-pyrazolone, an oxynaphthalene or an aminonaphthalene, the substituents, including further azo groups, R 'represents a -CH: group or preferably a hydrogen atom, R1 represents halogen or -CF :, and R'- represents hydrogen, and F represents a fluorine substituent. 10. The method according to claim and dependent claim 3, characterized in that one reactive Azo compounds of the formulas EMI39.5 EMI40.1 <tb> <SEP> (HO <SEP> OH <SEP> N ('<SEP>) -A <tb>) -A <SEP> r <tb> <SEP> H: (SO3H) <SEP> 1-3 <tb> EMI40.2 EMI40.3 <tb> (s03R) ō2 <tb> <SEP> I <SEP> N = W <SEP> the <SEP> NH-acyl) <tb> e <SEP> H) i-3 <tb> <SEP> NH-A <tb> EMI40.4 EMI40.5 <tb> A-KN <SEP> C \ <SEP> or <SEP> 1 <tb> A-HNN- <SEP> N <SEP> N <S <SEP> 03H <SEP>) <SEP> 1 <SEP> -3 <tb> <SEP> or <tb> <SEP> (S 3E ^) 0¯1 <tb> <SEP> NH2 <SEP> (or <SEP> NH-alkyl) <tb> <SEP> A-NH <SEP> NHO / \ <tb> <SEP> 3 <SEP> < <tb> <SEP> SO3H <tb>, where A is the remainder EMI41.1 stands, R 'for a -CH3 group or preferably for a hydrogen atom and R'1 for halogen or -CF-J and R'2! are hydrogen, in which (o) {indicates the ortho position of the respective substituents in the aryl nucleus and Me is Cu, Cr or Co, and F is a fluorine substituent, it being possible for the nuclei drawn in broken lines to be present or absent. 11. The method according to claim and dependent claim 4, - characterized in that reactive anthraquinone dyes of the formula EMI41.2 where L and L 'are substituents, among them in particular sulfonic acid groups, p is a number from 0 to 2, R "is a methyl or ethyl group or hydrogen, R'1 is halogen or -CF and R'2 is hydrogen and F is a fluorine substituent . 12. The method according to claim, characterized in that reactive phthalocyanine dyes of the formula EMI41.3 where 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 stands for halogen or -CF: 1 and R 'for hydrogen, and the phthalocyanine residue Pc preferably as further substituents 1-2 sulfonic acid and / or 1-2 sulfonic acid amide groups, such as SOeNHr, -S09NH-alkyl-, -SOeN ( alkyl) r and -5O2NH (aryl) groups, where alkyl stands for alkyl radicals with 1-3 C atoms, and F stands for a fluorine substituent. 13. The method according to dependent claim 9, characterized in that such dyes are prepared in which B and / or E have one or more sulfonic acid groups. 14. The method according to dependent claims 11 or 12, characterized. that one produces such dyes which have one or more sulfonic acid groups. 15. The method according to claim, characterized in that the dyes obtained are acylated and / or sulfated.