Reactive dyestuffs, their preparation and their use.

0001Reactive dyes are widely used for dyeing and printing textile fiber materials. Although a large number of usable reactive dyes with different properties and for different areas of application are available today, the technical status achieved, in view of the high requirements with regard to suitability for certain dyeing processes and fastness level of the dyeings, can in many cases not fully satisfy.

0002This also applies to reactive dyes in the exhaust dyeing process, especially at low dyeing temperatures. The provision of improved reactive dyes is therefore urgently desired. The object of the present invention was to find new reactive dyes which are particularly suitable for the exhaust dyeing process. It has been shown that the new reactive dyes defined below largely meet the requirements.

0003The invention relates to reactive dyes of the formula<chemistry id="chem0001" num="0001"><img file="EP0074928A2_D0001.tif" /></chemistry>wherein D is the residue of an organic dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, Naphthoquinone, pyrenequinone or perylene tetracarbimide series, R is hydrogen or optionally substituted C _1-4 -Alkyl, AC_2-6-Alkylene, Z hydrogen, optionally substituted alkyl or aryl or a radical of the formula<chemistry id="chem0002" num="0002"><img file="EP0074928A2_D0002.tif" /></chemistry>and X halogen, SO₃H, OH, OR₁₃ SH or SR₁ where R₁ is an optionally substituted aliphatic residue.

0004Preferred subgroups are:<ul id="ul0001" list-style="none"><li>a) reactive dyes of the formula (1), in which D, R, A and Z have the meanings given under formula (1), and X is chlorine or fluorine.</li><li>b) reactive dyes of the formula (1), in which D, R, A and Z have the meanings given under formula (1), and X is OH or C._1-4-Alkoxy is.</li><li>c) reactive dyes of the formula (1), in which D, R and X have the meanings given under formula (1), A is ethylene and Z is hydrogen.</li><li>d) reactive dyes of the formula (1), in which D is the remainder of a mono- or disazo dye.</li><li>e) reactive dyes of the formula (1), in which D is the remainder of a metal complex azo or formazan dye.</li><li>f) reactive dyes of the formula (1)., wherein D is the residue of an anthraquinone dye.</li><li>g) reactive dyes according to e), wherein D is the remainder of a metal complex azo dye of the benzene or naphthalene series.</li><li>h) reactive dyes according to g), wherein D is the remainder of a 1: 1 copper complex azo dye of the benzene or naphthalene series, and the copper atom is bonded to a metallizable group in the ortho position to the azo bond.</li><li>i) reactive dyes according to d) of the formula<chemistry id="chem0003" num="0003"><img file="EP0074928A2_D0003.tif" /></chemistry>wherein D1 is the remainder of a diazo component of the benzene or naphthalene series, K is the remainder of a coupling component of the benzene or naphthalene series or the heterocyclic series, R is hydrogen or optionally substituted C_1-4Alkyl, and X is chlorine, fluorine, OH or C_1-4Is alkoxy, and the reactive radical is bound to the diazo component or to the coupling component, or one reactive radical is bound to both the diazo component and the coupling component.</li><li>j) reactive dyes according to i) wherein R is hydrogen or methyl and X is chlorine or fluorine.</li></ul>

0005The radical D in formula (1) can be substituted in the customary manner, in particular the radical D contains one or more sulfonic acid groups.

0006Examples of further substituents on the radical D are alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups with 1 to 6 carbon atoms, such as acetylamino and propionylamino, benzoylamino, amino, alkylamino with 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, nitro, cyano, Trifluoromethyl, halogen such as fluorine, chlorine and bromine, sulfamoyl, carbamoyl, ureido, hydroxy, carboxy, sulfomethyl and sulfo.

0007Those reactive dyes in which D is the residue of an azo dye contain, as substituents, in particular methyl, ethyl, methoxy, _Benzoylamino, amino, acetylamino, ureido, sulfomethyl, hydroxy, carboxy, halogen and sulfo.

0008The alkyl radical for R in formula (1) is a straight-chain or branched alkyl radical, which can also be substituted, for example by halogen, hydroxyl, cyano or sulfo. Examples of R are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, β-chloroethyl, β-hydroxyethyl, β-hydroxybutyl, β-cyanoethyl and sulfomethyl.

0009As C_2-6Alkylene radicals for A in formula (1) are a straight-chain or branched alkylene radical, for example ethylene, n-propylene, isopropylene, n-butylene, n-pentylene and n-hexylene. The ethylene residue is preferred.

0010The radical of an optionally substituted alkyl or aryl Z is, for example, an alkyl radical which is straight-chain or branched, which preferably has 1 to 6 carbon atoms and which can be further substituted, for example by halogen, hydroxy, cyano, alkoxy, carboxy or sulfo, or a unsubstituted alkyl radical with 7 to 20 carbon atoms, a cyclohexyl radical, or a phenyl radical, for example can be substituted by methyl, ethyl, methoxy, ethoxy, chlorine, bromine, carboxy, sulfo or sulfomethyl.

0011The following substituents may be mentioned as examples of Z:<ul id="ul0002" list-style="none"><li>Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, nonyl, dodecyl, hexadecyl, pentadecyl, carboxymethyl, β-carboxyethyl, ß-carboxypropyl, methoxycarbonylmethyl, aethoxycarbonylmethyl, ß- Methoxyethyl, β-ethoxyethyl, β-methoxypropyl, β-chloroethyl, y-chloropropyl, y-bromopropyl, sulfomethyl, ß-sulfoethyl, aminosulfonylmethyl, β-sulfatoethyl, cyclohexyl, phenyl, o-, m- or p-chlorophenyl, o- , m- or p-methylphenyl, p-ethylphenyl, p-methoxyphenyl, o-, m- or p-sulfophenyl, p-carboxyphenyl and p-</li></ul>

0012Sulfomethylphenyl. Unsubstituted alkyl radicals having 1 to 4 carbon atoms are preferred.

0013In particular, Z is hydrogen or a radical of the formula<chemistry id="chem0004" num="0004"><img file="EP0074928A2_D0004.tif" /></chemistry>wherein A has the meaning given under formula (1).

0014If Z is a radical of the formula (2), the radicals of the formula (2) which are bonded to the nitrogen atom of the external radical in formula (1) can be identical or different. Both radicals of the formula (2) are preferably identical.

0015If X is a substituent OR₁or SR₁ where R₁ is an optionally substituted aliphatic radical, come for R₁ for example, the same radicals which are mentioned above in the explanation of the radical Z, with the exception of aryl radicals and a radical of the formula (2).

0016The dyes of the formula (1) are fiber-reactive since they contain at least one leaving group on the triazine residue.

0017Fiber-reactive compounds are to be understood as those which are able to react with the hydroxyl groups of cellulose or with the amino groups of natural or synthetic polyamides to form covalent chemical bonds.

0018The preparation of the reactive dyes of the formula (1) is characterized in that an organic dye of the formula<chemistry id="chem0005" num="0005"><img file="EP0074928A2_D0005.tif" /></chemistry>or a dye precursor, at least one equivalent of one

0019Connection of the forms<chemistry id="chem0006" num="0006"><img file="EP0074928A2_D0006.tif" /></chemistry>where Ha1 is halogen, and X is halogen, SO₃H, OH, OR, SH or SR₁ and at least one equivalent of an amine of the formula<chemistry id="chem0007" num="0007"><img file="EP0074928A2_D0007.tif" /></chemistry>where Y is hydrogen or SO₃H is and Z 'is hydrogen, optionally substituted alkyl or aryl or a radical of the formula<chemistry id="chem0008" num="0008"><img file="EP0074928A2_D0008.tif" /></chemistry>is, in which Y has the meaning given above, condensed and, if X is halogen, this may be subsequently against S0₃H, OH or SH exchanged, and, if Y is hydrogen, reacted with sulfuric acid, where D, R and A in the above formulas and radicals have the meanings given under formula (1), and that in the case of the use of dye precursors , converts them into the desired final dyes.

0020In the method described in the foregoing, the individual method steps can be carried out in a different order, possibly partially at the same time. Different process variants are possible. In general, the implementation is carried out step by step.

0021However, it depends on the structure of the starting materials, for example the type of halogen Hal in formula (5), and on the special reaction conditions, for example the condensation temperature, which of the possible process variants are the most advantageous.

0022If, as described below, one does not start from an organic dye of the formula (4) but from its components, for example from the diazo and coupling component, the number of possible design variants (reaction sequences) becomes even greater. However, these can easily be specified on the basis of the description given.

0023Reactive dyes of the formula (1) in which X is chlorine can thus be prepared smoothly and in good yield by condensing an organic dye of the formula (4) with cyanuric chloride, the dichlorotriazine dye obtained with an amine of the formula (6) , wherein Y is hydrogen, ie the hydroxyamine in question, condenses, and the resulting monochlorotriazine dye of the formula<chemistry id="chem0009" num="0009"><img file="EP0074928A2_D0009.tif" /></chemistry>finally reacted with sulfuric acid.

0024However, the dichlorotriazine dye can also be used directly with the already sulfated amine of the formula (6), in which Y = S0₃H is condense. The corresponding vinyl compound can in some cases be formed by elimination of sulfuric acid. A special choice of the reaction conditions must therefore ensure that on the one hand the condensation of the dichlorotriazine dye with the amine of the formula (6) is as complete as possible, and on the other hand that the yield is reduced as little as possible by the formation of the vinyl compound.

0025If the procedure is as described above, but the cyanuric fluoride is used instead of the cyanuric chloride, the corresponding monofluorotriazine compound is obtained by reacting the difluorotriazine dye with the hydroxyamine. In the subsequent sulfation, the terminal free hydroxyl group is esterified smoothly, ie into the group -OS0₃H transferred, at the same time the fluorine atom still remaining on the triazine ring is replaced by a hydroxyl group, so that a dye of the formula (1) is obtained, in which X = OH.

0026Conversely, if the difluorotriazine dye is reacted with an already sulfated amine of the formula (6), the monofluorotriazine dye, ie a dye of the formula (1), in which X = fluorine, is obtained in good yield.

0027Instead of condensing a halotriazine of the formula (5) first with an amino dye of the formula (4), then condensing the condensation product with an amine of the formula (6) and optionally sulfating the compound obtained, a halotriazine of the formula ( 5) condense with an amine of the formula (6), then condense the primary condensation product with an amino dye of the formula (4), and if necessary sulfate last.

0028The explanations given above for the different process variants also apply if one starts from amines of the formula (6), in which Z 'is a radical of the formula (2a), where Y is hydrogen or S0₃H can be. It should be borne in mind that, if Y = H, the consumption of sulfuric acid during sulfation is twice as high.

0029Furthermore, if one starts from a trihalotriazine of the formula (5), a halogen atom on the triazine ring can subsequently be substituted by a radical OH, SH or S0₃H can be replaced by the dihalotriazine dye or the monohalotriazine dye present after condensation with an amine of formula (6), in which Y is hydrogen, or by condensation of a trihalotriazine with an amine of formula (6), in which Y is hydrogen or S0₃H, the resulting dihalotriazine compound is reacted with water or a hydrolyzing agent, hydrogen sulfide or sulfurous acid or salts thereof, and optionally sulfated.

0030Those reactive dyes of the formula (1) in which D is the remainder of an organic dye composed of two or more than two components can also be prepared by a process variant which starts from dye precursors. This is done by condensing a component of the dye of the formula (4) which contains a group -N (R) H and a compound of the formula (5), and in a suitable stage of the process, if appropriate also beforehand , with an amine of the formula (6) and with the other (or the other) component (s) of the dye of the formula (4), and if appropriate with water, hydrogen sulfide or sulfurous acid or salts thereof and optionally sulfated last .

0031Examples of such organic dyes composed of two or more than two components are: monoazo, disazo, trisazo, tetrazo, metal complexazo, formazan and azomethine dyes.

0032The process variant described above is particularly important for the production of reactive dyes of the formula (1), in which D is the remainder of an azo dye containing sulfo groups. In these the part of the azo dye residue to which the reactive residue is directly attached can be either the rest of the diazo component or the rest of the coupling component. This results in two important embodiments of the method variant described above.

0033One of the two variants is characterized in that a diazo component of the dye, which contains a group -N (R) H, is condensed with a compound of the formula (5), the resulting condensation product is diazotized and coupled to a coupling component, and after that Condensation or after coupling with an amine of formula (6) and optionally with water, hydrogen sulfide or sulfurous acid or their salts are reacted and, if appropriate, lastly sulfated.

0034The second variant is characterized in that a coupling component of the dye, which contains a group -K (R) H, is condensed with a compound of the formula (5), and a diazotized diazo component is coupled to the condensation product thus obtained, and after the condensation or after coupling with an amine of formula (6) condensed and optionally reacted with water, hydrogen sulfide or sulfurous acid or salts thereof and optionally sulfated last.

0035According to these process variants, reactive dyes of the formula (1) which contain two reactive radicals can be prepared by condensing a diazo component which contains a group -N (R) H with a compound of the formula (5), that furthermore a coupling component , which contains a group -N (R) H, condensed with a compound of the formula (5) and that the condensation product of the diazo component is diazotized and coupled to the condensation product of the coupling component, wherein the R in the condensation product of the diazo component is independent of the R in the condensation product of the coupling component, and that before or after coupling both triazine residues are condensed with an amine of the formula (6) and optionally reacted with water, hydrogen sulfide or sulfurous acid or salts thereof and optionally sulfated in the last stage.

0036Dyes of the formula (1) which contain two reactive radicals can also be prepared by using dyes of the formula (4) which contain a further group -N (R) H in D, this with a corresponding amount of a compound of the formula (5) condensed so that two halotriazine residues are introduced into the dye molecule, then condensed with a corresponding amount of an amine of the formula (6) and optionally sulfated, etc.

0037Organic dyes of the formula (4) in which D is the remainder of a mono- or disazo dye are preferably used as starting materials.

0038Amines of the formula (6) in which AA is ethylene are also preferably used.

0039A preferred embodiment is characterized in that organic dyes of the formula<chemistry id="chem0010" num="0010"><img file="EP0074928A2_D0010.tif" /></chemistry>where D₁the rest of a diazo component of the benzene or naphthalene series and K the rest of a coupling component of the benzene or naphthalene series or the heterocyclic series are used as starting materials.

0040According to a further preferred method of preparation, compounds of the formula (4) are used in which D is the remainder of a metal complexazo or formazan dye.

0041According to a further preferred method of preparation, compounds of the formula (4) are used in which D is the residue of an anthraquinone dye.

0042The dyes of the formula (4) used as starting materials can be substituted in the radical D as described above. Organic dyes of the formula (4) are preferably used, in which D is the residue of an azo dye which may contain methyl, ethyl, methoxy, benzoylamino, amino, acetylamino, ureido, sulfomethyl, hydroxy, carboxy, halogen and sulfo as substituents.

0043In the method described in the foregoing, the individual method steps can be carried out in a different order, possibly partially at the same time. Different process variants are possible. In general, the reactions are carried out step by step.

0044If, as described above, one does not start from an organic dye of the formula (4) but from its components, for example from the diazo and coupling components, the number of possible design variants (reaction sequences) becomes even greater. However, these can easily be specified on the basis of the description given.

0045A preferred procedure is characterized in that an organic dye of the formula (4) is condensed with 2,4,6-trichloro-1,3,5-triazine, the condensation product with an amine of the formula (6), in which Y is hydrogen , condensed, and reacting the secondary condensation product with sulfuric acid.

0046A further preferred procedure is characterized in that 2,4,6-trichloro-1,3,5-triazine is condensed with an amine of the formula (6) in which Y is hydrogen, the condensation product with an organic dye of the formula ( 4) condensed, and the secondary condensation product treated with sulfuric acid.

0047Another preferred method is characterized in that an organic dye of the formula (4) is condensed with 2,4,6-trifluoro-1,3,5-triazine, the condensation product with an amine of the formula (6), in which Y is hydrogen is condensed, and the secondary condensation product is reacted with sulfuric acid.

0048Another preferred method is characterized in that 2,4,6-trifluoro-1,3, S-triazine is condensed with an amine of the formula (6), in which Y is hydrogen, the condensation product with an organic dye of the formula ( 4) condenses, and the secondary condensation product is reacted with sulfuric acid.

0049Another preferred method is characterized in that an organic dye of the formula (4) is condensed with 2,4,6-trifluoro-1,3,5-triazine, and the condensation product with an amine of the formula (6), in which Y S0₃H is condensed.

0050Another preferred method is characterized in that 2,4,6-trifluoro-1,3,5-triazine with an amine of the formula (6), in which Y is S0₃H is condensed, and the condensation product is condensed with an organic dye of the formula (4).

0051The compound of the formula is preferably used as the amine of the formula (6)<chemistry id="chem0011" num="0011"><img file="EP0074928A2_D0011.tif" /></chemistry>or the compound of the formula<chemistry id="chem0012" num="0012"><img file="EP0074928A2_D0012.tif" /></chemistry>

0052The condensations of the compound of formula (5) with the organic dyes of formula (4) or the diazotizable and / or couplable components containing a group -N (R) H are preferably carried out in aqueous solution or suspensions, with weakly acidic, neutral to weakly alkaline pH, and between 0 to 5 ° C if X is a halogen atom and between 5 and 40 ° C if X is not a halogen atom. The hydrogen fluoride, chlorine or bromine released during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates.

0053For the further reaction of the halotriazine dyes thus obtained or for the reaction of the compounds of the formula (5) with the amines of the formula (6), the amines are expediently used in the form of a salt, preferably in the form of the hydrochloride. The reaction of the compounds of formula (5) with the amines of formula (6) is carried out at temperatures between about 0 and 5 ° C when X is a halogen atom and at about 40 ° C when X is not a halogen atom. The reaction of the halotriazine dyes mentioned, in which X is a halogen atom, takes place approximately between 5 and 40 ° C., preferably between 5 and 25 ° C. The reactions mentioned are carried out with the addition of acid-binding agents, preferably sodium carbonate, and in a pH range from 2 to 6.5, preferably 5 to 6.5, if Y SO₃Is H, or in a pH range of 6 to 8 if Y is hydrogen.

0054The sulfation of the hydroxyl group in an amine of the formula (6), in which Y = H, or in one of the residues of such a condensation product containing amine, for example with a dihalotriazine dye, is preferably carried out by reaction with concentrated sulfuric acid at from 0 ° to moderately elevated temperature. This sulfation can also be carried out by reacting the hydroxy compound with 2 equivalents of chlorosulfonic acid per hydroxyl group in a polar organic solvent such as N-methylpyrrolidone at 10 to 80 ° C.

0055The sulfation is preferably carried out by introducing the compound in question into sulfuric acid monohydrate at temperatures between 5 and 15.degree.

0056The introduction of a rest OH, OR₁, SH or SR₁ for X in a compound of formula (5) instead of a halogen atom, is carried out by condensation of a halotriazine with a hydroxy or mercapto compound. This can be done before or, if X is OH or SH, after the condensation of the halotriazine with a dye of the formula (4) and / or an amine of the formula (6). The condensation of the halotriazine with a hydroxy or mercapto compound is preferably carried out in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline pH, or, if X is OH or SH, and only one replaceable halogen atom on Triazine ring is left, in which case Y must be hydrogen, or if there are still two interchangeable halogen atoms on the triazine ring, at elevated temperature, for example between 50 and 100 ° C. Here, too, the hydrogen fluoride, chlorine or bromine released during the condensation is advantageously neutralized by the continuous addition of aqueous alkali metal hydroxides, carbonates or bicarbonates.

0057The introduction of a sulfo group S0₃H for X in a compound of formula (5) instead of a halogen atom, is carried out by reacting a halotriazine with an alkali sulfite in aqueous solution at low temperature and at a weakly acidic, neutral to weakly alkaline pH. A trihalotriazine is preferably used, for example Cyanuric chloride, with sodium or potassium sulfite, before or after additional condensation of the triazine with a dye of formula (4) or an amine of formula (6), wherein Y is hydrogen.

0058Possible starting materials which can be used to prepare the reactive dyes of the formula (1) are to be mentioned individually below.

0059Dyes of the following structure types are particularly suitable as dyes of the formula (4):<chemistry id="chem0013" num="0013"><img file="EP0074928A2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP0074928A2_D0014.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP0074928A2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP0074928A2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP0074928A2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP0074928A2_D0018.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP0074928A2_D0019.tif" /></chemistry>wherein acyl is, for example, acetyl or optionally substituted benzoyl.

0060Metal complexes of dyes of the formulas:<chemistry id="chem0020" num="0020"><img file="EP0074928A2_D0020.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP0074928A2_D0021.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP0074928A2_D0022.tif" /></chemistry>Cu (1: 1 complex) or Cr and Co (1: 2 complex) are preferred as the metal atom. Cr and Co complexes can contain the azo compound of the formula given above once or twice, ie they can be symmetrical or unsymmetrical with any other ligand groups.

0061<chemistry id="chem0023" num="0023"><img file="EP0074928A2_D0023.tif" /></chemistry>

0062The condensed rings indicated by dashed lines represent alternative naphthalene systems.<chemistry id="chem0024" num="0024"><img file="EP0074928A2_D0024.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP0074928A2_D0025.tif" /></chemistry>

0063In this formula, Pc represents the Cu or Ni phthalocyanine residue. The total number of substituents on the Pc framework is 4.<chemistry id="chem0026" num="0026"><img file="EP0074928A2_D0026.tif" /></chemistry>

0064The dyes of the formulas given above can be further substituted in the alkyl or aryl radicals, in particular by the substituents mentioned in the explanation of D in formula (1).

0065The following are particularly important azo dyes of the formula (9):<chemistry id="chem0027" num="0027"><img file="EP0074928A2_D0027.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP0074928A2_D0028.tif" /></chemistry><chemistry id="chem0029" num="0029"><img file="EP0074928A2_D0029.tif" /></chemistry>and<chemistry id="chem0030" num="0030"><img file="EP0074928A2_D0030.tif" /></chemistry>wherein K is the residue of a coupling component of the benzene, naphthalene or heterocyclic series, acyl is a low molecular weight, aliphatic acyl radical containing at most 3 carbon atoms or an aromatic radical containing at most 8 carbon atoms, and R is the meaning given in the explanation of formula (1) has, as well as the metal complex azo dyes of the formulas<chemistry id="chem0031" num="0031"><img file="EP0074928A2_D0031.tif" /></chemistry>and<chemistry id="chem0032" num="0032"><img file="EP0074928A2_D0032.tif" /></chemistry>wherein R and acyl have the meanings given above and Me stands for Cu, Cr or Co.

Compounds of formula (5)

0066<ul id="ul0003" list-style="none"><li>2,4,6-trichloro-1,3,5-triazine (cyanuric chloride),</li><li>2,4,6-trifluoro-l, 3,5-triazine (cyanuric fluoride),</li><li>2,4,6-tribromo-1,3,5-triazine (cyanuric bromide),</li><li>2,4-dichloro-6-sulfo-1,3,5-triazine,</li><li>2,4-dichloro-6-hydroxy-1,3,5-triazine,</li><li>2,4-difluoro-6-hydroxy-l, 3,5-triazine,</li><li>2,4-dichloro-6-methoxy-1,3,5-triazine,</li><li>2,4-dichloro-6-methylmercapto-l, 3,5-triazine,</li><li>2,4-dichloro-6-isopropoxy-1,3,5-triazine,</li><li>2,4-dichloro-6-ß-ethoxyethoxy-1,3,5-triazine</li></ul>and primary condensation products of the three trihalotriazines mentioned above with the hydroxy or mercapto compounds mentioned below.

Amines of the formula (6)

0067<ul id="ul0004" list-style="none"><li>ß- (ß-Hydroxyethyl-sulfonyl) -ethyl-amine (2-taurylethanol),</li><li>γ- (β-hydroxyethyl sulfonyl) propyl amine,</li><li>α- (β-hydroxyethyl-sulfonyl) -isopropyl-amine,</li><li>δ- (β-hydroxyethyl sulfonyl) butyl amine,</li><li>ß- (ß-hydroxyethyl-sulfonyl) -isobutyl-amine,</li><li>ε- (β-hydroxyethylsulfonyl) pentylamine,</li><li>β- (β-hydroxyethylsulfonyl) hexylamine,</li><li>N-methyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-ethyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-propyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-butyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-pentyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-hexyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-nonyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>N-dodecyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-hexadecyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>N-octadecyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>N-carboxymethyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>N-sulfatomethyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>N-β-carboxyethyl-N-γ- (β-hydroxyethylsulfonyl) propylamine,</li><li>N-β-sulfatoethyl-N-γ- (β-hydroxyethylsulfonyl) propylamine,</li><li>N-β-sulfatoethyl-N-δ- (β-hydroxyethylsulfonyl) butylamine,</li><li>N-β-ethoxyethyl-N-δ- (β-hydroxyethylsulfonyl) butylamine,</li><li>N-γ-chloropropy1-N-β- (β-hydroxyethyl-sulfonyl) ethyl-amine,</li><li>N-phenyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>Np-chlorophenyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>No-methylphenyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>Np-methoxyphenyl-N-β- (β-hydroxyethylsulfonyl) ethylamine,</li><li>Nm-sulfophenyl-N-ß- (ß-hydroxyethyl-sulfonyl) -ethyl-amine,</li><li>Np-sulfophenyl-N-ß- (ß-hydroxyethyl-sulfonyl) ethyl amine,</li><li>Bis- [ß- (ß-hydroxyethylsulfonyl) ethyl] amine,</li><li>Bis- [y- (β-hydroxyethylsulfonyl) propyl] amine,</li><li>Bis- [δ- (β-hydroxyethylsulfonyl) butyl) amine,</li></ul>as well as the corresponding sulfated compounds.

0068Preferred are the low molecular weight amines such as the β- (β-hydroxyethylsulfonyl) ethyl amine and its N-methyl derivative. Also preferred is the bis- [β- (β-hydroxyethylsulfonyl) -athyl] amine and the corresponding sulfated compounds.

0069Hydroxy and mercapto compounds, which with halotriazines, for the purpose of exchanging a halogen atom for a residue OH, OR₁, SH or SR₁, can be condensed, for example water, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, hexanol, cyclohexanol, β-methoxyethanol, β-ethoxyethanol, y-methoxypropanol, y -Ethoxypropanol, β-ethoxy-β-ethoxy-ethanol, glycolic acid, hydrogen sulfide, methanethiol, ethanethiol, propanethiol, isopropanethiol, n-butanethiol, thioglycolic acid.

0070If one goes for the preparation of the preferred reactive dyes of the formula (1), in which D is the remainder of an azo dye, not from the finished amino dyes, for example those described above, but from dye precursors, ie the diazo and coupling components, for example consider the following:

Diazo components:

0071<ul id="ul0005" list-style="none"><li>Aminobenzene, 1-amino-2-, -3- or -4-methylbenzene,</li><li>1-amino-2-, -3- or -4-methoxybenzene,</li><li>1-amino-2-, -3- or -4-chlorobenzene,</li><li>1-amino-2,5-dichlorobenzene, 1-amino-2,5-dimethylbenzene, 1-amino-3-methyl-6-methoxybenzene, 1-amino-2-methoxy-4-nitrobenzene, 4-aminobiphenyl, 1- Aminobenzene-2-, -3- or -4-carboxylic acid, 2-aminodiphenyl ether, 1-aminobenzene-2-, -3- or -4-sulfonic acid amide, -N-methylamide, -N-ethylamide, -N, N -dimethylamide or -N, N-diethylamide, dehydrothiopotoluidine sulfonic acid, 1-amino-3-trifluoromethyl-6-sulfonic acid, 1-amino-3- or -4-nitrobenzene, 1-amino-3- or -4- acetylaminobenzene, 1-aminobenzene-2-, -3- or -4-sulfonic acid, 1-aminobenzene-2,4- and</li><li>-2,5-disulfonic acid, 1-amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-methylbenzene-6-sulfonic acid, 1-amino-6-methylbenzene-3- or -4-sulfonic acid, 1-amino -2-carboxybenzene-4-sulfonic acid, l-amino-4-carboxybenzene-2-sulfonic acid, 1-amino-4- or -5-chlorobenzene-2-sulfonic acid, 1-amino-6-chlorobenzene-3- or -4 -sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, l-amino-2,5-dichlorobenzene-6-sulfonic acid, 1-amino-2,5-dichlorobenzene-4-sulfonic acid, 1-amino-4 -methyl-5-chlorobenzene-2-sulfonic acid, 1-4mino-5-methyl-4-chlorobenzene-2-sulfonic acid, l-amino-4- or</li><li>-5-methoxybenzene-2-sulfonic acid, 1-amino-6-methoxybenzene-3- or -4-sulfonic acid, 1-amino-6-ethoxybenzene-3- or -4-sulfonic acid, 1-amino-2,4-dimethoxybenzene -6-sulfonic acid, 1-amino-2,5-dimethoxybenzene-4-sulfonic acid, 1-amino-3-acetylaminobenzene-6-sulfonic acid, 1-amino-4-acetylaminobenzene-2-sulfonic acid, 1-amino-3-acetylamino -4-methylbenzene-6-sulfonic acid, 2-amino-l-methylbenzene-3,5-disulfonic acid, 1-amino-4-methoxybenzene-2,5-disulfonic acid, 1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-3-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonic acid, 1-amino-3- or -4-nitrobenzene-6-sulfonic acid, 1-aminonaphthalene, 2-aminonaphthalene, 1-aminonaphthalene 2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-aminonaphthalene-1-, -3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 2-amino-naphthalene-3,6- or -5,7-disulfonic acid, 1-aminonaphthalene-3,6- or -5,7-disulfonic acid, 2-aminonaphthalene-1,5-,</li><li>-1,7-, -3,6-, -5,7-, -4,8- ​​or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 2-aminonaphthalene-1,5 , 7-, -3.6.8_- or -4,6,8-trisulfonic acid, 1-hydroxy-2-aminobenzene-4-sulfonic acid, 1-hydroxy-2-aminobenzene-5-sulfonic acid, 1-hydroxy-2-aminobenzene-4,6-disulfonic acid, 1- Hydroxy-2-amino-4-acetylaminobenzene-6-sulfonic acid, l-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid, 1-hydroxy-2-amino-4-chlorobenzene-5-sulfonic acid, 1-hydroxy- 2-amino-4-methylsulfonylbenzene, 1-amino-2-hydroxy-6-nitronaphthalene-6-sulfonic acid, 2-amino-l-hydroxynaphthalene-4,8-disulfonic acid, 4-aminoazobenzene-3,4'-disulfonic acid, 3-methox-y-4-amino-6-methylazobenzene-2 ​​', 4'-disulfonic acid, 3-methoxy-4-amino-6-methylazobenzene-2', 5'-disulfonic acid.</li></ul>

0072Coupling components:<ul id="ul0006" list-style="none"><li>Phenol, 1-hydroxy-3- or -4-methylbenzene, l-hydroxybenzene-4-sulfonic acid, 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxynaphthalene-6-or -7-sulfonic acid, 2-hydroxynaphthalene-3,6- or -6,8-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-4,6- or 4,7-disulfonic acid, l-amino-3-methylbenzene, 1-amino-2-methoxy-5-methylbenzene , 1-amino-2,5-dimethylbenzene, 3-aminophenylurea, 1-amino-3-acetylaminobenzene, 1-amino-3-hydroxyacetylaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, l-aminonaphthalene-6- or -8-sulfonic acid, l-amino-2-methoxynaphthalene-6-sulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 1-amino-8- hydroxynaphthalene-6-sulfonic acid, l-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 2-hydroxy-3-aminonaphthalene-5,7-disulfonic acid, l-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid, 1-hydroxy-8-acetylaminonaphthalene-3-sulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-methyl- or 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid, 2- (N-acetyl-N -methylamino) -5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-l, 7-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-methyl or -Aethylamino-8-hydroxynaphthalene-6-sulfonic acid, 2- (N-acetyl-N-methylamino) -8-hydroxynaphthalene-6-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene -3,6-disulfonic acid, 2-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-3,6- or -4, 6-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-aninobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (4'-nitrobenzoyl-amino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 1- (3'-amino-benzoylamino) -8-hydroxyanphthaline 3,6- or -4,6-disulfonic acid, 1- (3'-nitrobenzoylamino) -8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, 2- (4'-amino-3'- sulfophenylamino) -5-hydroxynaphthalene-7-sulfonic acid, 3-methylpyrazolone- (5), l-phenyl-3-methyl-5-pyrazolone, 1- (4'-sulfo</li></ul> phenyl) -3-methyl-5-pyrazolone, 1- (4'-sulfophenyl) pyrazolone (5) -3-carboxylic acid, 1- (3'-aminophenyl) -3-methyl-5-pyrazolone, 1- ( 2 ', 5'-disulfophenyl) -3-methyl-5-pyrazolone, 1- (2'-methyl-4'-sulfophenyl) -5-pyrazolone-3-carboxylic acid, 1- (4', 8'-disulfonaphthyl- [2 ']) - 3-methyl-5-pyrazolone, 1- (5', 7'-disulfonaphthyl- [2 ']) - 3-methyl-5-pyrazolone, 1- (2', 5'-dichloro- 4'-sulfophenyl) -3-methyl-5-pyrazolone, 3-aminocarbonyl-4-methyl-6-hydroxypyridone- (2), 1-ethyl-3-cyan- or -3-chloro-4-methyl-6-hydroxy-pyridone- (2), 1-ethyl-3- sulfomethyl-4-methyl-6-hydroxypyridone- (2), 2,4,6-triamino-3-cyanopyridine, 2- (3'-sulfophenylamino) -4,6-diamino-3-cyanopyridine, 2- ( 2'-hydroxyethylamino) -3-cyan-4-methyl-6-aminopyridine, 2,6-bis (2'-hydroxyethylamino) -3-cyan-4-methylpyridine, 1-ethyl-3-carbamoyl-4-methyl -6-hydroxypyridone- (2), 1-ethyl-3-sulfomethyl-4-methyl-5-carbamoyl-6-hydroxypyridone- (2): N-acetoacetylaminobenzene, 1- (N-acetoacetylamino) -2-methoxybenzene-5-sulfonic acid, 4-hydroxyquinolone- (2), 1-amino-8-hydroxy-2- (phenylazo) -naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-2- (4'-sulfophenylazo) naphthalene-3,6-disulfonic acid, 1-amino-8-hydroxy-2- (2 ', 5'-disulfophenylazo) naphthalene-3,6 -disulfonic acid.

0073If one starts from dye precursors, at least one of the two components, the diazo component or the coupling component, must have an acylatable amino group. The intermediate products containing a diazotizable amino group are generally diazotized by the action of nitrous acid in aqueous mineral acid solution at low temperature, and the coupling is carried out at weakly acidic, neutral to weakly alkaline pH values.

0074The reactive dyes of the formula (1) are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyamide urethanes, but in particular cellulosic materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the pad dyeing process, according to which the goods are impregnated with aqueous and optionally also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat. They are particularly suitable for the so-called cold residence process, after which the dye is applied to the foulard together with the alkali and is then fixed by storage at room temperature for several hours.

0075The reactive dyes of the formula (1) are notable for high reactivity and good fixing power. They can therefore be used at low dyeing temperatures using the pull-out dyeing process and only require short steaming times with the padsteam process. They result in dyeings with good wet and light fastness and high color strength and remarkably high fiber-dye binding stability, both in the acidic and in the alkaline range.

0076The reactive dyes of the formula (1) are particularly suitable for dyeing cotton using the exhaust dyeing process, the difference between the degree of exhaust and the degree of fixation being remarkably small, ie the soap loss is very low.

0077The reactive dyes of the formula (1) are also suitable for printing, in particular on cotton, but also for printing nitrogen-containing fibers, for example blended fabrics containing wool, silk or wool.

0078It is advisable to subject the dyeings and prints to a thorough rinsing with cold and hot water, if appropriate with the addition of a dispersing agent and promoting the diffusion of the unfixed portions.

0079The preparation of the monoazo or disazo intermediate compound is not described in all cases in the following exemplary embodiments, but is readily derived from the above.

0080In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

Example 1: 10.9 parts of the dye of the formula

0081<chemistry id="chem0033" num="0033"><img file="EP0074928A2_D0033.tif" /></chemistry>

0082are dissolved neutral in 200 parts of water, cooled to 0 to 5 ° C. by adding ice and at this temperature with a solution of 3.9 parts of 2,4,6-trichloro-l, 3,5-triazine in 15 parts of acetone transferred. Until the condensation is complete, the pH of the reaction mixture is kept at 6-7 by constant addition of 2N sodium hydroxide solution. After adding 4.6 parts of 2-taurylethanol, the temperature is slowly raised to 25 to 30 ° C., and the pH of the reaction mixture is kept at 7.5 to 8 by the constant addition of 2N sodium hydroxide solution. After the reaction is complete, the reactive dye formed is salted out at pH 6.5 by sprinkling in sodium chloride, filtered, washed and dried in vacuo. It is an orange powder and dyes cotton in reddish yellow tones, especially as a hot dye.

0083Elemental analysis of a 63.2 percent batch:<tables id="tabl0001" num="0001"><img file="EP0074928A2_D0034.tif" /></tables>

0084* Difference: total chlorine minus inorganic chlorine

0085EXAMPLE 2 6 parts of the dyestuff of the formula which can be prepared according to Example 1 are converted into the sulfuric acid monoester without hydrolysis of the chlorine atom on the triazine<chemistry id="chem0034" num="0034"><img file="EP0074928A2_D0035.tif" /></chemistry>

0086finely ground and introduced into 12 parts of sulfuric acid monohydrate cooled to 5 to 10 ° C. After complete homogenization, it is poured onto 50 parts of ice and the pH of the reaction mixture is carefully adjusted to 6.0 with dilute potassium hydroxide solution. The reactive dye formed is salted out by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It is an orange powder and dyes cotton in reddish yellow tones, as a cold dye as well as a hot dye.

0087Elemental analysis of a 74.3 percent batch:<tables id="tabl0002" num="0002"><img file="EP0074928A2_D0036.tif" /></tables>

0088Example 3: Analogous to Example 1, the reactive dye of the formula<chemistry id="chem0035" num="0035"><img file="EP0074928A2_D0037.tif" /></chemistry>

0089obtained, which dyes cotton in particular as a hot dye in scarlet tones.

0090Elemental analysis of a 46.8 percent batch:<tables id="tabl0003" num="0003"><img file="EP0074928A2_D0038.tif" /></tables> Example 4: Analogously to example 2, the dye which can be prepared according to example 3 is converted into the sulfuric acid monoester. This dyes cotton in scarlet tones, as a cold dye as well as a hot dye.

0091Elemental analysis of a 60.4 percent batch:<tables id="tabl0004" num="0004"><img file="EP0074928A2_D0039.tif" /></tables>

0092Example 5: Analogous to Example 1, the reactive dye of the formula<chemistry id="chem0036" num="0036"><img file="EP0074928A2_D0040.tif" /></chemistry>

0093obtained, which dyes cotton in particular as a hot dye in bluish red tones.

0094Elemental analysis of a 73.0 percent batch:<tables id="tabl0005" num="0005"><img file="EP0074928A2_D0041.tif" /></tables>

0095Example 6: Analogously to example 2, the dye which can be prepared according to example 5 is converted into the sulfuric acid monoester. This dyes cotton in bluish red tones, as a cold dye as well as a hot dye.

0096Elemental analysis of a 62.9 percent batch:<tables id="tabl0006" num="0006"><img file="EP0074928A2_D0042.tif" /></tables>

0097Example 7: Analogous to Example 1, the reactive dye of the formula<chemistry id="chem0037" num="0037"><img file="EP0074928A2_D0043.tif" /></chemistry>obtained, which dyes cotton in particular as a hot dye in bluish red tones.

0098Elemental analysis of a 76.0 percent batch:<tables id="tabl0007" num="0007"><img file="EP0074928A2_D0044.tif" /></tables>

0099Example 8: Analogously to example 2, the dye which can be prepared according to example 7 is converted into the sulfuric acid monoester. This dyes cotton in bluish red tones, as a cold dye as well as a hot dye.

0100Elemental analysis of a 68.3 percent batch:<tables id="tabl0008" num="0008"><img file="EP0074928A2_D0045.tif" /></tables>

0101Example 9: Analogous to Example 1, the reactive dye of the formula

0102<chemistry id="chem0038" num="0038"><img file="EP0074928A2_D0046.tif" /></chemistry>obtained, which dyes cotton in particular as a hot dye in scarlet tones.

0103Elemental analysis of a 41.7 percent batch:<tables id="tabl0009" num="0009"><img file="EP0074928A2_D0047.tif" /></tables> Example 10: Analogously to example 2, the dye which can be prepared according to example 9 is converted into the sulfuric acid monoester. This dyes cotton in scarlet tones, as a cold dye as well as a hot dye.

0104Elemental analysis of a 64.9 percent batch:<tables id="tabl0010" num="0010"><img file="EP0074928A2_D0048.tif" /></tables>Further reactive dyestuffs, which dye cotton in particular as a hot dye in the shades given in Table 1, column 3, are obtained if the chromophores containing amino groups given in column 2 are first given 2,4,6-trichloro-1 as described in Example 1 , 3,5-triazine and then reacted with 2-taurylethanol. The reactive dyes obtained in this way are converted into the sulfuric acid monoesters as described in Example 2. These are reactive dyes that dye cotton in the colors shown in Table 1, column 3, as good as a cold dye as well as a hot dye.

0105<tables id="tabl0011" num="0011"><img file="EP0074928A2_D0049.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP0074928A2_D0050.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP0074928A2_D0051.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP0074928A2_D0052.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP0074928A2_D0053.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP0074928A2_D0054.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP0074928A2_D0055.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP0074928A2_D0056.tif" /></tables><tables id="tabl0019" num="0019"><img file="EP0074928A2_D0057.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP0074928A2_D0058.tif" /></tables><tables id="tabl0021" num="0021"><img file="EP0074928A2_D0059.tif" /></tables><tables id="tabl0022" num="0022"><img file="EP0074928A2_D0060.tif" /></tables>

0106Example 11: 31.9 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 100 parts of water until neutral. This solution is added dropwise over a period of 10 minutes to a mixture of 200 parts of ice and water, 18.5 parts of 2,4,6-trichlor-l, 3,5-triazine and 10 parts of 37% hydrochloric acid. Until the condensation is complete, the pH of the reaction mixture is kept at 1.0 by the constant addition of 2N sodium hydroxide solution. After adding 15.3 parts of 2-taurylethanol, the temperature of the reaction mixture is slowly increased from 5 ° C to 30 ° C. The pH of the reaction mixture is initially maintained at 3.0 by continuously adding 2N sodium hydroxide solution and 5.0 at the end of the condensation. After the reaction is complete, this intermediate dye is coupled at 0 to 10 ° C. and pH 5.0 with 30.3 parts of diazotized 2-aminonaphthalene-1,5-disulfonic acid. After the coupling reaction is complete at pH 6.5, the reaction mixture is clarified and the reactive dye of the formula formed<chemistry id="chem0039" num="0039"><img file="EP0074928A2_D0061.tif" /></chemistry>Salted out by sprinkling sodium chloride, filtered and dried in vacuo. It dyes cotton in bluish red tones, especially as a hot dye.

0107Example 12: Analogously to example 2, the dye which can be prepared according to example 11 is converted into the sulfuric acid monoester. This dyes cotton in bluish red tones, as a cold dye as well as a hot dye.

0108Further reactive dyestuffs, which dye cotton in particular as a hot dye in the shades given in Table 2, column 4, are obtained if, according to the information in Example 11, the coupling component given in column 2, which is first identified with 2,4,6- Trichlor-1,3,5-triazine and then reacted with 2-taurylethanol, which couples the diazotized diazo component indicated in column 3. The reactive dyes obtained in this way are converted into the sulfuric acid monoesters as described in Example 2. These are reactive dyes that dye cotton in the shades given in Table 2, column 4, as good as a cold dye as well as a hot dye.<tables id="tabl0023" num="0023"><img file="EP0074928A2_D0062.tif" /></tables>

0109Example 13: 10.9 parts of the dye of the formula<chemistry id="chem0040" num="0040"><img file="EP0074928A2_D0063.tif" /></chemistry>are dissolved neutral in 400 parts of water, and the solution is cooled to 0 to 5 ° C. At this temperature, 2.8 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise within 15 minutes, the pH of the reaction mixture being kept at 6.0 to 6.5 by the simultaneous addition of 2N sodium hydroxide solution. After adding 4.6 parts of 2-taurylethanol, the temperature is raised to 20 to 25 ° C. within 2 to 3 hours and the pH of the reaction mixture is kept at 7.0 to 7.5 by constant addition of 2N sodium hydroxide solution. After the reaction is complete, the reactive dye formed is salted out at pH 6.5 by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It is an orange powder and dyes cotton in reddish yellow tones, especially as a cold dye.

0110Elemental analysis of a 47.9 percent batch:<tables id="tabl0024" num="0024"><img file="EP0074928A2_D0064.tif" /></tables>^** Difference: total fluorine minus inorganic fluorine

0111Example 14: 7 parts of the dye of the formula which can be prepared according to Example 113<chemistry id="chem0041" num="0041"><img file="EP0074928A2_D0065.tif" /></chemistry>are finely ground and introduced into 12 parts of sulfuric acid monohydrate cooled to 5 to 10 ° C. After complete homogenization, it is poured onto 50 parts of ice and the pH of the reaction mixture is carefully adjusted to 6.0 with dilute potassium hydroxide solution. The reactive dye of the formula formed<chemistry id="chem0042" num="0042"><img file="EP0074928A2_D0066.tif" /></chemistry>is salted out by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It is an orange powder and dyes cotton in reddish yellow tones, especially as a cold dye.

0112Elemental analysis of a 67.6 percent batch:<tables id="tabl0025" num="0025"><img file="EP0074928A2_D0067.tif" /></tables>

0113Example 15: The reactive dye of the formula is analogous to Example 13<chemistry id="chem0043" num="0043"><img file="EP0074928A2_D0068.tif" /></chemistry>obtained, which dyes cotton in particular as a cold dye in scarlet tones.

0114Elemental analysis of a 53.8 percent batch:<tables id="tabl0026" num="0026"><img file="EP0074928A2_D0069.tif" /></tables>

0115Example 16: Analogously to example 14, the dye which can be prepared according to example 15 is converted into the reactive dye of the formula<chemistry id="chem0044" num="0044"><img file="EP0074928A2_D0070.tif" /></chemistry>

0116transformed. This dyes cotton especially as a cold dye in scarlet tones.

0117Elemental analysis of a 62.4 percent batch:<tables id="tabl0027" num="0027"><img file="EP0074928A2_D0071.tif" /></tables>Further reactive dyes, which dye cotton in particular as a cold dye in the shades given in Table 3, column 3, are obtained if the chromophores containing amino groups given in column 2 are first given 2,4,6-trifluoro-1 according to the information in Example 13 , 3,5-triazine and then reacted with 2-taurylethanol. The reactive dyes obtained in this way are converted into the sulfuric acid monoesters as described in Example 14, the fluorine atom also being replaced by a hydroxyl group. These are reactive dyes which dye cotton, in particular as a cold dye, in the colors shown in Table 3, column 3.

0118<tables id="tabl0028" num="0028"><img file="EP0074928A2_D0072.tif" /></tables><tables id="tabl0029" num="0029"><img file="EP0074928A2_D0073.tif" /></tables><tables id="tabl0030" num="0030"><img file="EP0074928A2_D0074.tif" /></tables><tables id="tabl0031" num="0031"><img file="EP0074928A2_D0075.tif" /></tables><tables id="tabl0032" num="0032"><img file="EP0074928A2_D0076.tif" /></tables><tables id="tabl0033" num="0033"><img file="EP0074928A2_D0077.tif" /></tables><tables id="tabl0034" num="0034"><img file="EP0074928A2_D0078.tif" /></tables><tables id="tabl0035" num="0035"><img file="EP0074928A2_D0079.tif" /></tables><tables id="tabl0036" num="0036"><img file="EP0074928A2_D0080.tif" /></tables><tables id="tabl0037" num="0037"><img file="EP0074928A2_D0081.tif" /></tables><tables id="tabl0038" num="0038"><img file="EP0074928A2_D0082.tif" /></tables><tables id="tabl0039" num="0039"><img file="EP0074928A2_D0083.tif" /></tables>

0119Example 17: 16.0 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 400 ml of water until neutral and the solution is cooled to 0 to 5 ° C. At this temperature and pH 4.5, 7.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise within 15 minutes, the pH of the reaction solution being kept slightly Congo acid by the simultaneous addition of 2N sodium hydroxide solution. After adding a mixture of 8.0 parts of 2-taurylethanol in 50 ml of water adjusted to pH 5.0, the pH of the reaction mixture is first kept slightly Congo acidic for a short time and then kept at 5.0 by constant addition of 2N sodium hydroxide solution. The temperature is increased to 20 to 25 ° C within 2 to 3 hours. After the reaction is complete, this intermediate dye is coupled at 0 to 10 ° C. and pH 5.0 with 15.2 parts of diazotized 2-aminonaphthalene-1,5-disulfonic acid. After the coupling reaction is complete at pH 6.5, the reaction mixture is clarified and the reactive dye of the formula formed<chemistry id="chem0045" num="0045"><img file="EP0074928A2_D0084.tif" /></chemistry>Salted out by sprinkling sodium chloride, filtered and dried in vacuo. It dyes cotton in bluish red tones, especially as a cold dye.

0120The reactive dye obtained in this way is converted into the sulfuric acid monoester as described in Example 14, the fluorine atom also being replaced by a hydroxyl group. This is a reactive dye that dyes cotton, especially as a cold dye, in bluish red tones.

0121Further reactive dyes, which dye cotton, in particular as cold dye, in the shades given in Table 4, column 4, are obtained if, according to the information in Example 17, the coupling component indicated in column 2, first with 2,4,6-trifluor -1,3,5-triazine and then reacted with 2-taurylethanol, which couples the diazotized diazo component indicated in column 3. The reactive dyes obtained in this way are converted into the sulfuric acid monoesters as described in Example 14, the fluorine atom also being replaced by a hydroxyl group. These are reactive dyes which dye cotton, in particular as a cold dye, in the colors shown in Table 4, column 4.

0122<tables id="tabl0040" num="0040"><img file="EP0074928A2_D0085.tif" /></tables>

0123Example 18: 10.9 parts of the dye of the formula<chemistry id="chem0046" num="0046"><img file="EP0074928A2_D0086.tif" /></chemistry>are reacted in 400 parts of water with 2.8 parts of 2,4,6-trifluoro-I, 3,5-triazine as described in Example 13. 6.9 parts of bis- [ß- (ß-hydroxyethylsulfonyl) ethyl] amine are added to the ice-cold reaction mixture. The temperature is raised to 20 ° C. within 2 to 3 hours and the pH of the reaction mixture is kept at 6.0 to 6.5 by the constant addition of 2N sodium hydroxide solution. After the reaction is complete, the reactive dye of the formula<chemistry id="chem0047" num="0047"><img file="EP0074928A2_D0087.tif" /></chemistry>Salted out by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It dyes cotton especially as a cold dye in reddish yellow tones.

0124The reactive dye obtained in this way is, as described in Example 14, in the double sulfuric acid monoester of the formula<chemistry id="chem0048" num="0048"><img file="EP0074928A2_D0088.tif" /></chemistry>transformed. This is a reactive dye that dyes cotton, especially as a cold dye, in reddish yellow tones.

0125Further reactive dyes, which dye cotton, in particular as cold dyes, in the hues given in Table 5, column 3, are obtained if the chromophores containing amino groups given in column 2 are first given 2,4,6-trifluoro-1 as described in Example 18 , 3,5-triazine and then reacted with bis- [ß- (ß-hydroxyethylsulfonyl) ethyl] amine. The reactive dyes thus obtained are converted into the double sulfuric acid monoesters as described in Example 14, the fluorine atom also being replaced by a hydroxyl group. These are reactive dyes, which dye cotton in particular as a cold dye in the colors shown in Table 5, column 3.<tables id="tabl0041" num="0041"><img file="EP0074928A2_D0089.tif" /></tables><tables id="tabl0042" num="0042"><img file="EP0074928A2_D0090.tif" /></tables><tables id="tabl0043" num="0043"><img file="EP0074928A2_D0091.tif" /></tables><tables id="tabl0044" num="0044"><img file="EP0074928A2_D0092.tif" /></tables>

0126Example 19: 10.9 parts of the dye of the formula<chemistry id="chem0049" num="0049"><img file="EP0074928A2_D0093.tif" /></chemistry>are reacted in 400 parts of water with 2.8 parts of 2,4,6-trifluoro-l, 3,5-triazine as described in Example 13. 7.0 parts of the 2-taurylethanol-sulfuric acid monoester described below are added to the ice-cold reaction mixture. The temperature is raised to 20 ° C. within 2 to 3 hours and the pH of the reaction mixture is kept at 6.0 to 6.5 by the constant addition of 2N sodium hydroxide solution. After the reaction is complete, the reactive dye of the formula<chemistry id="chem0050" num="0050"><img file="EP0074928A2_D0094.tif" /></chemistry>Salted out by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It is an orange powder and dyes cotton in reddish yellow tones, especially as a cold dye.

0127Elemental analysis of a 70.5 percent batch:<tables id="tabl0045" num="0045"><img file="EP0074928A2_D0095.tif" /></tables>For the conversion into the sulfuric acid monoester, 153 parts of 2-taurylethanol are added dropwise to 380 parts of sulfuric acid monohydrate and the temperature of the reaction mixture is kept between 10 and 15 ° C. by external cooling. After 2 hours, it is poured onto 1600 parts of ice and the pH of the reaction mixture is adjusted to 5.0 by sprinkling in calcium carbonate. The calcium sulfate is filtered off and the 2-taurylethanol-sulfuric acid monoester is isolated by gently evaporating the filtrate in vacuo or by freeze-drying. According to this specification, the bis- [ß- (ß-sulfatoethylsulfonyl) ethyl] amine mentioned below is prepared from bis- [ß- (ß-hydroxyethylsulfonyl) ethyl] amine.

0128Example 20: The reactive dye of the formula is analogous to Example 19<chemistry id="chem0051" num="0051"><img file="EP0074928A2_D0096.tif" /></chemistry>obtained, which dyes cotton especially as a cold dye in shades of blue.

0129Elemental analysis of a 66.6 percent batch:<tables id="tabl0046" num="0046"><img file="EP0074928A2_D0097.tif" /></tables>Further reactive dyes, which dye cotton, in particular as cold dyes, in the hues given in Table 6, column 3, are obtained if the chromophores containing amino groups indicated in column 2 are first given 2,4,6-trifluoro-l as described in Example 19 , 3,5-triazine and then reacted with 2-taurylethanol-sulfuric acid monoester.

0130<tables id="tabl0047" num="0047"><img file="EP0074928A2_D0098.tif" /></tables><tables id="tabl0048" num="0048"><img file="EP0074928A2_D0099.tif" /></tables><tables id="tabl0049" num="0049"><img file="EP0074928A2_D0100.tif" /></tables><tables id="tabl0050" num="0050"><img file="EP0074928A2_D0101.tif" /></tables><tables id="tabl0051" num="0051"><img file="EP0074928A2_D0102.tif" /></tables><tables id="tabl0052" num="0052"><img file="EP0074928A2_D0103.tif" /></tables><tables id="tabl0053" num="0053"><img file="EP0074928A2_D0104.tif" /></tables><tables id="tabl0054" num="0054"><img file="EP0074928A2_D0105.tif" /></tables><tables id="tabl0055" num="0055"><img file="EP0074928A2_D0106.tif" /></tables><tables id="tabl0056" num="0056"><img file="EP0074928A2_D0107.tif" /></tables><tables id="tabl0057" num="0057"><img file="EP0074928A2_D0108.tif" /></tables><tables id="tabl0058" num="0058"><img file="EP0074928A2_D0109.tif" /></tables>

0131Example 21: 16.0 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 400 ml of water until neutral and the solution is cooled to 0 to 5 ° C. At this temperature and pH 4.5, 7.1 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise within 15 minutes, the pH of the reaction solution being kept slightly Congo acid by the simultaneous addition of 2N sodium hydroxide solution. After adding a mixture of 16.3 parts of 2-taurylethanol-sulfuric acid monoester adjusted to pH 5.0 in 50 ml of water, the pH of the reaction mixture is first kept slightly Congo acidic for a short time and then kept at 5.0 by constant addition of 2N sodium hydroxide solution. The temperature is increased to 20 to 25 ° C within 2 to 3 hours. After the reaction is complete, this intermediate dye is coupled at 0 to 10 ° C. and pH 5.0 with 15.2 parts of diazotized 2-aminonaphthalene-1,5-disulfonic acid. After the coupling reaction is complete at pH 6.5, the reaction mixture is clarified and the reactive dye of the formula formed<chemistry id="chem0052" num="0052"><img file="EP0074928A2_D0110.tif" /></chemistry>Salted out by sprinkling sodium chloride, filtered and dried in vacuo. It dyes cotton in bluish red tones, especially as a cold dye.

0132Further reactive dyes, which dye cotton in particular as cold dye in the shades given in Table 7, column 4, are obtained if, according to the information in Example 21, the coupling component indicated in column 2, first with 2,4,6-trifluor -1,3,5-triazine and then reacted with 2-taurylethanol-sulfuric acid monoester, which couples the diazotized diazo component indicated in column 3.

0133<tables id="tabl0059" num="0059"><img file="EP0074928A2_D0111.tif" /></tables>

0134Example 22: 10.9 parts of the dye of the formula<chemistry id="chem0053" num="0053"><img file="EP0074928A2_D0112.tif" /></chemistry>are reacted in 400 parts of water with 2.8 parts of 2,4,6-trifluoro-l, 3,5-triazine as described in Example 13. 13.5 parts of bis- [ß- (ß-sulfatoethyl-sulfonyl) ethyl] amine are added to the ice-cold reaction mixture. The temperature is raised to 20 ° C. within 2 to 3 hours and the pH of the reaction mixture is kept at 6.0 to 6.5 by the constant addition of 2N sodium hydroxide solution. After the reaction is complete, the reactive dye of the formula<chemistry id="chem0054" num="0054"><img file="EP0074928A2_D0113.tif" /></chemistry>Salted out by sprinkling in potassium chloride, filtered, washed and dried in vacuo. It dyes cotton especially as a cold dye in reddish yellow tones.

0135Further reactive dyes, which dye cotton, in particular as cold dyes, in the color tones shown in Table 8, column 3, are obtained if the chromophores containing amino groups specified in column 2 are first given 2,4,6-trifluoro-l as described in Example 22 , 3,5-triazine and then reacted with bis- [ß- (ß-sulfatoethyl-sulfonyl) -ethyl] amine.<tables id="tabl0060" num="0060"><img file="EP0074928A2_D0114.tif" /></tables><tables id="tabl0061" num="0061"><img file="EP0074928A2_D0115.tif" /></tables><tables id="tabl0062" num="0062"><img file="EP0074928A2_D0116.tif" /></tables><tables id="tabl0063" num="0063"><img file="EP0074928A2_D0117.tif" /></tables>

Dyeing Instructions I

01362nd Parts of the dye obtained in Example 2 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the solution obtained so that it increases by 75% of its weight, and then dried.

0137Then the fabric is impregnated with a 20 ° C warm solution containing 4 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezed to 75% weight gain, the dye is dampened for 30 seconds at 100 to 102 ° C, rinsed, soaped during one Quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, rinses and dries.

Staining instructions II

01382nd Parts of the dye obtained in Example 2 are dissolved in 400 parts of water, and 1500 parts of a solution containing 53 g of sodium chloride per liter are added. This dye bath is mixed with 100 parts of a cotton fabric at 40 ° C. After 45 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of soda ash per liter are added. The temperature of the dyebath is kept at 40 ° C. for a further 45 minutes. The dyed goods are then rinsed, soaped at the boil with a nonionic detergent for a quarter of an hour, rinsed again and dried.

Staining instructions III

01394th Parts of the dye obtained in Example 2 are dissolved in 50 parts of water. 50 parts of a solution are added, which contains 5 g of sodium hydroxide and 20 g of calcined soda per liter. A cotton fabric is padded with the solution obtained so that it increases by 70% of its weight, and then wound onto a drum. The cotton fabric is stored for 3 hours at room temperature.

0140The dyed goods are then rinsed, soaped at the boil with a nonionic detergent for a quarter of an hour, rinsed again and dried.

Staining instructions IV

01412nd Parts of the dye obtained in Example 2 are dissolved in 400 parts of water; 1500 parts of a solution containing 53 g of sodium chloride per liter are added. This dye bath is mixed with 100 parts of a cotton fabric at 35 ° C. After 20 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of soda ash per liter are added. The temperature of the dyebath is kept at 35 ° C. for a further 15 minutes. The temperature is then raised to 60 ° C within 20 minutes. The temperature is held at 60 ° C for a further 35 minutes. It is then rinsed, soaped at the boil with a nonionic detergent for a quarter of an hour, rinsed again and dried.

Printing instruction

01423rd Parts of the dye obtained in Example 2 are sprinkled with rapid stirring into 100 parts of a stock thickener containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. A cotton fabric is printed with the printing paste thus obtained, and the printed material obtained is dried and steamed in saturated steam at 102 ° C. for 2 minutes. The printed fabric is then rinsed, if necessary soaped at the boil and rinsed again, and then dried.