DE4231537A1 - REACTIVE DYES, THEIR PRODUCTION AND USE - Google Patents

Description

Reactive dyes have long been widely used for dyeing and printing of textiles made of fiber materials, and there are a large number of useful reactive dyes with different properties and for different Areas of application available. In view of the ever increasing requirements Reactive dyeing in terms of economy, application technology and authenticity level the technical level achieved is often not fully satisfactory.

So z. B. often find that the degree of fixation is too low, and the difference between Degree of exhaustion and degree of fixation is too large (high soap loss), so that a considerable part of the reactive dye is lost for the dyeing process. Furthermore, the build ability to be desired in many cases.

The present invention was based on the object of new improved reactive dyes to find, which have a high reactivity and a good build ability, with high fixing output can be colored, especially for the pull-out dyeing process are suitable, and the wet and lightfast dyeings on cellulose-containing fiber material surrender.

It has been shown that the new reactive dyes defined below have these Requirements met.

The invention relates to reactive dyes of the formula

wherein D is the residue of a diazo component, Q is hydrogen or an optionally  substituted alkyl, alkoxy, alkylthio or amino radical means and A₁ and A₂ independently of one another a radical of the formula

wherein R₁ and R₂ are independently hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted aryl, mean, or R₁ and R₂ together with the N atom an optionally further substituted heterocyclic 5- or 6-ring form, with the proviso that at least one of the radicals A₁, A₂ or D a has fiber-reactive group.

D is z. B. the rest of an aminobenzene, aminonaphthalene, phenylazo-aminobenzene, Naphthylazo-aminobenzene, phthalocyanine-aminobenzene, Phenylazo-aminonaphthalene or naphthylazo-aminonaphthalene, each of which unsubstituted or, preferably, substituted as described below. D is preferably an optionally substituted residue of an aminobenzene or Aminonaphthalene.

Suitable substituents on the radical D are e.g. B .: C₁-C₄ alkyl, which is generally methyl, ethyl, n- or iso-propyl or n-, sec- or tert-butyl is included; C₁-C₄ alkoxy, which generally includes methoxy, ethoxy, n- or iso-propoxy or n-, sec.- or tert.-butoxy is to be understood; Amino; N-mono- or N, N-Di-C₁-C₄-alkylamino, where the alkyl optionally z. B. by -OH, -OCOCH₃, -OSO₃H, -CN or halogen may be further substituted, e.g. B. methylamino, ethylamino, n- or iso-propylamino or n-, sec- or tert-butylamino, N, N-dimethyl- or -diethylamino, β-chloroethylamino, β-cyanoethylamino, β-acetyloxyethylamino, N- (β-hydroxyethyl), N-ethylamino, β-sulfatoethylamino, N, N-di- (β-hydroxyethyl) amino, N, N-di- (β-sulfatoethyl) amino or hydroxypropylamino; Phenylamino; C₁-C₄ alkanoylamino, especially acetylamino, propionylamino; Benzoxylamino; C₁-C₄ alkoxycarbonyl, e.g. B. methoxy or ethoxycarbonyl; Nitro; Cyano; Trifluoromethyl; Halogen, which generally means fluorine, chlorine and bromine; Hydroxy; Carboxy; Sulfo; Sulfomethyl; Sulfamoyl; N-mono- or N, N-di-C₁-C₄ alkyl sulfamoyl; N-phenylsulfamoyl; Carbamoyl; N-mono- or N, N-di-C₁-C₄-alkylcarbamoyl; Ureido; C₁-C₄ alkylsulfonyl, e.g. B. methyl or ethyl sulfonyl.  

D may also have a reactive residue, e.g. B. one by a cleavable Group or a removable atom substituted C₂-C₄-alkanoyl or C₂-C₄-alkylsulfonyl, one possibly by a cleavable atom or a cleavable atom Group substituted C₂-C₄-alkenoyl-C₂-C₄-alkenesulfonyl and / or one carbo- or substituted by a removable atom or a removable group heterocyclic 5- or 6-ring containing radical, said radicals directly or can be bound to the chromophore via a bridge member. The pontic can doing z. B. from a functional group, e.g. B. an amino, carbonyl, carbonylamino, Aminocarbonyl, sulfonyl, sulfonylamino or aminosulfonyl group or from one aliphatic, cycloaliphatic, aliphatic-heterocyclic, aromatic or mixed aliphatic-aromatic group, which is one of the functional groups mentioned bears, exist.

A group of suitable reactive dyes according to the invention comprises compounds of the formula (I) given above, in which D is a reactive radical of the formula

wherein W is a functional group, e.g. B. -SO₂NR₃-, -CONR₃- or -NR₃CO-, R₃ is hydrogen, C₁-C₄ alkyl, optionally by hydroxy, sulfo, sulfato, carboxy  or cyano is substituted, or a residue

means R for hydrogen, Hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C₁-C₄ alkoxycarbonyl, C₁-C₄-alkanoyloxy, carbamoyl or represents the group -SO₂-Z, Z-CH = CH₂ or -CH₂-CH₂-Y and Y is a leaving group, E is -O- or -NR₄-, R₄ is hydrogen or C₁-C₄-alkyl, alk and alk 'independently of one another a C₁-C₆-alkylene radical represent and arylene z. B. for a phenylene or naphthylene radical which is unsubstituted or e.g. B. is substituted by sulfo, carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy and / or halogen, stands.

Suitable leaving groups Y are e.g. B. -Cl, -Br, -F, -OSO₃H, -SSO₃H, -OCO-CH₃, -OCO-C₆H₅, -OPO₃H₂, -OCO-CCl₃, -OCO-CHCl₂, -OCO-CH₂Cl, OSO₂-R *, where R * C₁-C₄-alkyl or phenyl optionally substituted by C₁-C₄-alkyl, or -OSO₂N (C₁-C₄-alkyl) ₂.

Preferably Y is a group -Cl, -OSO₃H, -SSO₃H, -OCOCH₃, -OCO-C₆H₅ or -OPO₃H₂.

When alk and alk 'are independently z. B. a methylene, Ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or the like branched isomers.

alk and alk 'independently of one another preferably represent a C₁-C₄ alkylene radical and particularly preferred for an ethylene radical.

R is preferably hydrogen or the group -SO₂-Z, where Z is the one specified above Has meaning. R particularly preferably represents hydrogen.

R₃ is preferably hydrogen, C₁-C₄-alkyl or a group -alk-SO₂-Z, wherein alk and Z each have the meaning given above.

arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or z. B. is substituted by sulfo, methyl, methoxy or carboxy.

E is preferably -NH- and particularly preferably -O-.  

W preferably denotes a functional group -CONH- or -NHCO-.

D preferably contains a reactive radical of the formula (2) or (2a) given above, where W is -CO-NH- or -NH-CO-, Z each has the meaning given above and alk represents a C₁-C₄ alkylene radical.

In a further group of suitable reactive dyes according to the invention Formula (1) contains D a reactive radical of the formula

wherein R₅ is hydrogen or C₁-C₄ alkyl, which may be carboxy, Cyano, hydroxy, sulfo or sulfato is substituted, X is a cleavable anion Group means and T either has the meaning of X independently or a grouping contains a further reactive radical or for a non-reactive Stands for substituents.

Here R₅, preferably a C₁-C₄ alkyl radical and particularly preferably Hydrogen.

X is e.g. B. for chlorine, bromine, sulfo, C₁-C₄-alkylsulfonyl or phenylsulfonyl and preferred for fluorine or chlorine.

T stands for a non-reactive substituent, this can e.g. B. a hydroxy, C₁-C₄ alkoxy, C₁-C₄-alkylthio-, amino-, N-C₁-C₄-alkylamino- or N, N-di-C₁-C₄-alkylamino-, wherein the alkyl optionally z. B. by sulfo, sulfato, hydroxy, carboxy or Phenyl is substituted, cyclohexylamino, morpholino, phenylamino, N-C₁-C₄-alkyl, N-phenylamino or naphthylamino radical, the phenyl or naphthyl optionally e.g. B. by C₁-C₄ alkyl, C₁-C₄ alkoxy, carboxy, sulfo and / or halogen is substituted.

Examples of suitable non-reactive substituents T are amino, methylamino, Ethylamino, β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino,  Cyclohexylamino, morpholino, o-, m- or p-methylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or p-chlorophenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl, N-phenylamino, N-methyl, N-phenylamino, Methoxy, ethoxy, n- or iso-propoxy, hydroxy.

As a non-reactive substituent, T preferably has the meaning amino, N-C₁-C₄-alkylamino, wherein the alkyl is unsubstituted or substituted by hydroxy, sulfato or sulfo is, morpholino, phenylamino or N-C₁-C₄-alkyl, N-phenylamino, wherein the phenyl is in each case unsubstituted or substituted by sulfo, carboxy, methyl or methoxy.

If T has the meaning of X independently, it preferably means chlorine or fluorine.

If T is a group which contains a further reactive radical, this can, for. B. the formula

correspond, wherein R, R₃, R₅, E, W, Z, alk, alk 'and arylene the aforementioned Meanings and preferences apply and p is 0 or 1.  

T corresponds to a group which contains a further reactive radical, preferably one of the formulas given below

wherein W '-CONR₅'- or -NR₅'CO-, R' is hydrogen or the group -SO₂-Z, R₃ 'is hydrogen, C₁-C₄-alkyl or the group -alk-SO₂-Z, R₅ ′ hydrogen or C₁-C₄-alkyl, E′-O- or -NH- and R₆ is hydrogen, sulfo, carboxy, chlorine, methoxy or methyl, alk and alk 'independently of one another represent a C₁-C₄ alkylene radical, and for Z the previously meanings and preferences mentioned apply.

D has a reactive residue, it can be z. B. also a pyrimidine or Chionoxaline residue, each of which has at least one group which can be split off as an anion decrees, act. Examples are the 2,3-dichloroquinoxaline-6-carbonylamino radical, 2,4-dichloropyrimidine-5-carbonylamino radical or a radical of the formula  

wherein one of the radicals X₁, preferably that in the 2-position, is a cleavable anion Group and the other radical X₁ has the meaning given for T under the formula (3) X₂ is a negative substituent and R₅ is independently those of the formula (3) has the meaning given.

The meanings and preferences given above apply to R₅ and T; at the radical X 1 which can be split off as an anion is preferably fluorine or chlorine. Examples of suitable radicals X₂ are nitro, cyano, C₁-C₄-alkylsulfonyl, carboxy, chlorine, Hydroxy, C₁-C₄-alkoxysulfonyl, C₁-C₄-alkylsulfinyl, C₁-C₄-alkoxycarbonyl or C₁-C₄ alkanoyl, where the meanings chlorine, cyano, formyl and methylsulfonyl for X₂ are preferred.

Examples of preferred reactive radicals of the formula (5) at radical D are 2,4,5-trichloropyrimidine-6-amino, 2,4-difluoro-5-chloropyrimidine-6-amino, 2,4-dichloro-5-methylsulfonylpyrimidine-6-amino or a residue of the formula

wherein R₅ ', E', W ', R₆ and Z have the meaning given above, X₂ chlorine, cyano or  Is methylsulfonyl, p represents the number 0 or 1 and alk and alk ′ independently of one another represent a C₁-C₄ alkylene radical.

If the radical D has no fiber-reactive group, D preferably represents the radical one Aminobenzene or aminonaphthalene, which is unsubstituted or by sulfo, carboxy, C₁-C₄-alkoxy, C₁-C₄-alkyl, C₁-C₄-alkanoylamino and / or halogen is substituted.

If D has a fiber-reactive group, it preferably means the remainder of an aminobenzene or aminonaphthalene, which is unsubstituted or by sulfo, acetylamino, Methyl, methoxy, chlorine or bromine is substituted and also a reactive radical of the formula (2), (2a) or (3) given above.

R₁ and / or R₂ in formula (1a) represent an optionally substituted C₁-C₆ alkyl radical, so it is z. B. a methyl, ethyl, n- or iso-propyl, n-, sec- or tert-butyl or a straight-chain or branched pentyl or hexyl radical, where these residues z. B. by hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C₁-C₄ alkoxycarbonyl, C₁-C₄ alkanoyloxy, cabamoyl and / or a reactive radical substituted can be and the alkyl radical, with the exception of methyl optionally z. B. can be interrupted by a group -O- or -NR₄-; here R₄ has the previous one given meaning.

If the alkyl radical R₁ and / or R₂ is substituted by a reactive radical, it can be e.g. B. is a radical -SO₂-Z, where Z has the meaning given above.

In a preferred embodiment of the reactive dyes according to the invention mean R₁ and R₂ independently of one another are hydrogen or a C₁-C₄-alkyl radical which unsubstituted or by hydroxy, sulfo, sulfato, carboxy, cyano or the group -SO₂-Z is substituted and / or interrupted by -O-; preferably means one of the radicals R₁ or R₂ is hydrogen.

Examples of particularly preferred non-reactive alkylamino radicals A₁ and A₂ are:

Examples of preferred reactive alkylamino radicals A₁ and A₂ are those mentioned above Residues of formulas (4) and (4a) and in particular the residues of formulas (4 ') or (4a').

Form R₁ and R₂ together with the nitrogen atom, to which both are bound, one heterocyclic radical, this can e.g. B. a piperidinyl, piperazinyl or pyrrolidinyl radical be unsubstituted or z. B. by a reactive radical of the formula

wherein alk, p and Z each have the meaning given above, substituted is. The piperidinyl radical is a non-reactive radical and one is a reactive radical The rest of the formula (4d) given above is preferred.

If R₁ or R₂ is an aryl radical, this can, for. B. a phenyl or Be naphthyl, which is unsubstituted or z. B. by sulfo, carboxy, C₁-C₄-alkyl, C₁-C₄ alkoxy, halogen, a reactive radical and / or a group -N = N-K is substituted, wherein K is the rest of a coupling component of the benzene or naphthalene series or heterocyclic series means.

Here, K preferably represents the rest of a benzene, naphthalene, pyrazolone, 1-phenyl-5-pyrazolone or pyridons, which e.g. B. by one or more identical or different of the substituents mentioned above for D is substituted.

K particularly preferably corresponds to one of the formulas listed below

R₁ or R₂ as aryl have a reactive group, it can be z. B. a rest of the aforementioned formula (2), (2a), (3) or (5) or the 2,3-dichloroquinoxaline-6-carbonylamino or 2,4-dichloropyrimidine-5-carbonylamino radical.

A₁ and / or A₂ mean a non-reactive aryl radical, this corresponds to z. B. the formula

wherein R₆ is hydrogen, sulfo, chlorine, methoxy or carboxy and R₆ 'independently the R₆ has meaning or represents a group of the formula (8) given above.

Preferred reactive aryl radicals A₁ and A₂ are the groups of the formula given above (4b ′) or (4c ′) or a group of the formula

wherein R₅, R₆, X and T each have the meaning given above and B

and in particular -N = means.

A preferred group of reactive dyes according to the invention comprises compounds of the formula (1), in which A₁ and A₂ independently of one another are amino, N-C₁-C₄-alkylamino, wherein the alkyl is unsubstituted or substituted by hydroxy, sulfato or sulfo  or phenylamino, in which the phenyl is unsubstituted or by sulfo, carboxy, Methyl, methoxy, chlorine and / or by a radical of the formula

is substituted.

Another group of preferred reactive dyes according to the invention comprises Compounds of formula (1), wherein A₁ is a radical of formula (1a), (4 ′) or (4a ′), wherein R₁ is hydrogen and R₂ is hydrogen or unsubstituted or by Hydroxy, sulfo or sulfato are substituted C₁-C₄-alkyl, R ', R₃' and R₅ 'each Are hydrogen, E 'is -O-, and alk, alk' and Z are each the previously specified Have meaning is and A₂ independently has the meaning of A₁ or unsubstituted or by sulfo, chlorine, methoxy, carboxy or a residue of the above Formula (2), (2a) or (3) is substituted phenylamino.

Q in the meaning of an alkyl radical can be unsubstituted or z. B. by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, Act sulfo or trihalomethyl substituted C₁-C₆ alkyl. The alkyl radical is preferably unsubstituted.

Q in the meaning of an alkoxy radical can be unsubstituted or z. B. by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano, C₁-C₄-alkoxycarbonyl, C₁-C₄ alkylsulfonyl, sulfo or trihalomethyl substituted C₁-C₆ alkoxy act. The alkoxy radical is preferably unsubstituted.

Q in the meaning of an alkylthio radical can be unsubstituted or z. B. by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano, C₁-C₄-alkoxycarbonyl, C₁-C₄ alkylsulfonyl, sulfo or trihalomethyl substituted C₁-C₆ alkylthio act. The alkylthio radical is preferably unsubstituted.

Q in the meaning of an amino radical can be the radical -NH₂ or a unsubstituted or e.g. B. by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, nitro, cyano,  C₁-C₄ alkoxycarbonyl, C₁-C₄ alkylsulfonyl, sulfo or trihalomethyl substituted Act C₁-C₆ alkylamine. The alkylamino radical is preferably unsubstituted.

Q is preferably a methyl, methoxy or methylthio radical.

A particularly preferred embodiment of the dyes according to the invention relates Compounds of formula (1) wherein Q is methyl.

The compounds of the formula (1) can be prepared in a manner known per se, e.g. B. by using a diazo component of the formula

D-NH₂ (10)

or their precursor with a compound of the formula

or their precursor by diazotization and coupling to reactive dyes Reacts formula (1), or the intermediates obtained in the desired end dyes transferred, and optionally a further conversion reaction follows; the above meanings and preferences apply to D, A₁, A₂ and Q.

The diazotization of the compounds of formula (10) and the coupling with the compounds Formula (11) is carried out in each case by the customary methods.

The compounds of the formula (10) which have no reactive radical are known or can be produced by methods known per se. Connections of the Formula (10) which have a reactive radical are, for. B. from European patent applications No. 1 44 766, 1 74 909, 2 08 655 or 2 14 093 known or can be analog to be manufactured.

Some of the compounds of the formula (11) are new; they can be made e.g. B.,  by using a compound of formula

with an amine of the formula

to connect the formula

reacted and then with another amine of formula (1a *) to the compound of the formula (11). In the formulas (12), (1a *) and (13) have Q, R₁, R₂ and A₁ each has the meaning given above and Hal represents halogen, for. B. for bromine and especially chlorine.

The reaction of compounds (12) and (1a *) is preferably in a polar Solvent carried out, z. B. C₁-C₄ alkanols, e.g. B. methanol or ethanol, Glycols and glycol ethers such as ethylene glycol or ethylene glycol mono- or dimethyl ether, Formamides such as N, N-dimethylformamide and in particular water are suitable; Mixtures of several solvents are also suitable. The reaction temperature is about 50 to 150 ° C and preferably 60 to 100 ° C.

The components of formulas (12) and (1a *) can be used in a stoichiometric ratio are used, but an excess of component (1a *) often proves to be cheaper.  

The reaction of the compounds of formula (13) with a further amine Formula (1a *) is preferably carried out in one of the solvents mentioned above in a Temperature above 100 ° C. The temperature is usually between 120 and 250 ° C and preferably between 140 and 200 ° C. The reaction step can take place in the open Vessel under normal pressure or, preferably, in a closed vessel (autoclave) be carried out under autogenous pressure. Components (13) and (1a *) can be in stoichiometric Quantities are used; however, the amine is preferably the Formula (1a *) in an up to 5-fold excess, based on the compound of Formula (13), present.

The amines of the formula (1a *) on which the radicals A₁ and A₂ in formula (11) are based can be the same or different.

Are A₁ and A₂ residues of different amines, one is preferably the above select the two-step route described for the synthesis of the compounds of the formula (11) and use the components in approximately stoichiometric amounts; often turns out however, an excess of amine of the formula (1a *) is more favorable.

A₁ and A₂ each represent the rest of an identical amine, the compounds of formula (11) advantageously in one step by the compound of formula (10) with a corresponding excess of amine of formula (1a *) implements.

The compounds of formula (12) are e.g. B. from EP-A 55 693 or can can be produced analogously.

Compounds of the formula (1a *) which have no reactive radical are also known or can be produced in a manner known per se. Amines the Formula (1a *) which have a reactive radical are, for. B. from the aforementioned EP-A 1 44 766, 1 74 909, 2 08 655 or 2 14 093 are known or can be prepared analogously will.

If appropriate, one uses in the preparation of the compounds of formula (1) instead of the diazo component of the formula (10) and / or the coupling component of the Formula (11) corresponding precursors and represents the final dye by another Diazotization and / or coupling or other conversion reactions with the  Intermediate finished.

A modified embodiment of the method is first a dye to produce that contains a precursor of the reactive radical and this subsequently in the Convert power amplifier, e.g. B. by esterification or an addition reaction. For example you can produce a dye in which Z is a radical HO-CH₂CH₂- and that React intermediate with or before the acylation with sulfuric acid so that the Hydroxyl group is converted into the sulfato group; or you use one analog dye, wherein Z is the group H₂C = CH-, and stored on the intermediate Thiosulfuric acid, whereby a residue HO₃SS-CH₂CH₂- is formed. The sulfation of the Hydroxyl group in a dye of formula (1) or a suitable precursor, z. B. by reaction with concentrated sulfuric acid at 0 ° C to moderate elevated temperature. Sulfation can also be accomplished by reaction of the hydroxy compound with two equivalents of chlorosulfonic acid per hydroxy group in a polar organic Solvents such as N-methylpyrrolidone take place at 10 to 80 ° C. The sulfation is preferably carried out by entering the compound in question in Sulfuric acid monohydrate at temperatures between 5 and 15 ° C. The introduction of similar Groups such as B. a thiosulfato or phosphato group takes place in itself known way.

Elimination reactions can also be connected to the synthesis. For example, reactive dyes of the formula (1), which sulfatoethylsulfonyl radicals contain, with halogen-hydrogen splitting agents, such as sodium hydroxide, treat, whereby the sulfatoethylsulfonyl residues are converted into vinylsulfonyl residues.

Another object of the invention relates to compounds of the aforementioned Formula (11) in which Q, A₁ and A₂ each have the meaning given above, with the Provided that A₁ and / or A₂ contain a reactive radical. Suitable reactive residues are e.g. B. from the explanations given above.

The dyes of the formula (1) according to the invention are fiber-reactive. Taking fiber reactive Dyes are to be understood as those with the hydroxyl groups of cellulose or with the reactive centers of natural or synthetic polyamides with formation covalent chemical bonds are able to react.

The reactive dyes of the formula (1) according to the invention are suitable for dyeing and  Printing on various materials, such as silk, leather, wool, polyamide fibers and especially cellulosic fiber materials of all kinds. Such fiber materials are for example the natural cellulose fibers such as cotton, linen and hemp, as well Pulp and regenerated cellulose. The reactive dyes of the invention are also suitable for dyeing or printing fibers containing hydroxyl groups in mixed fabrics are included, e.g. B. of mixtures of cotton with polyester fibers or Polyamide fibers.

The dyes of the invention can be applied to the fiber material in various ways apply and fix on the fiber, especially in the form of aqueous Dye solutions and printing pastes. They are suitable for both the pull-out process and also for dyeing according to the foulard dyeing process, after which the goods are mixed with aqueous optionally impregnated with salt-containing dye solutions, and the dyes after an alkali treatment or in the presence of alkali, optionally under the action of heat be fixed. They are particularly suitable for the so-called cold retention process, after which the dye together with the alkali is applied to the padder and is then fixed by storing for several hours at room temperature. After this The dyeings or prints are fixed with cold and hot water, if necessary with the addition of a dispersing and the diffusion of the unfixed Proportional agent thoroughly rinsed.

The reactive dyes according to the invention are notable for high reactivity, good Fixing ability and a good build ability. You can therefore use the pull-out dyeing process are used at low dyeing temperatures and require at Pad steam process only short steaming times. The degrees of fixation are high and not fixed portions can be easily washed out, the difference between Degree of exhaustion and degree of fixation remarkably small, d. H. the soap loss is very low. The Reactive dyes according to the invention are also particularly suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. B. from Wool or silk or of blended fabrics containing wool or silk.

The dyeings and prints produced with the dyes according to the invention Cellulose fiber materials have a high color strength and a high fiber-dye binding stability, both in acidic and in alkaline range, still a good one Light fastness and very good wet fastness properties, such as washing, water, sea water, Overdye and sweat fastness, as well as good pleating fastness, ironing fastness  and rub fastness. The very good chlorine fastness of the reactive dyes according to the invention; the compounds of formula (1) also show practically no phototropy.

The following examples serve to explain the invention. The temperatures are given in degrees Celsius, parts are parts by weight that refer to percentages percentages by weight, unless otherwise noted. Parts by weight are due Parts by volume in the ratio of kilograms to liters.

example 1

The hydrochloric acid diazotized solution of 27.0 parts of 2- (4'-amino-phenylsulfonyl) ethyl hydrogen sulfate becomes a solution of at 0 to 10 ° C and pH = 6 to 7 43.4 parts of 4,6-bis (2'-sulfatoethylamino) -2-methylpyrimidine added and coupled. The yellow monoazo dyes are isolated, they correspond to the formula

and dyes cellulose fibers in golden yellow shades.

Example 2

The dye mentioned in Example 1 is at room temperature and pH 10 Vinylized for 30 minutes. The pH is reset to 6.0 with hydrochloric acid. The Monoazo dye is isolated, it corresponds to the formula

Example 3

33.6 g of the primary condensation product from 1 mol of cyanuric chloride and 1 mol of 1,3-diaminobenzene-4-sulfonic acid in 300 ml of water, 300 g of ice and 30 ml Stirred 30% hydrochloric acid and diazotized at 0 to 5 ° C with 6.9 g of sodium nitrite. The Congo-acid diazonium suspension obtained is mixed with sodium carbonate solution  pH 6.5 and then to a solution of 42 g of 4,6-bis (2-sulfatoethylamino) -2-methylpyrimidine placed in 900 ml of water and 20 g of sodium carbonate. To when the coupling is complete, the dye is separated off by adding sodium chloride, filtered, washed with sodium chloride solution and dried at 40 ° C in a vacuum. The monoazo dye of the formula thus obtained

dyes cellulose fibers in yellow shades.

Example 4

33.6 g of the primary condensation product from 1 mol of cyanuric chloride and 1 mol of 1,3-diaminobenzene-4-sulfonic acid in 300 ml of water, 300 g of ice and 30 ml Stirred 30% hydrochloric acid and diazotized at 0 to 5 ° C with 6.9 g of sodium nitrite. The Congo-acid diazonium suspension obtained is mixed with sodium carbonate solution Set pH of 6.5 and then to a solution of 42.2 g of 4,6-bis (2'-sulfatoethylamino) -2-ethylpyrimidine placed in 900 ml of water and 20 g of sodium carbonate. To when coupling is complete, 22.4 g of β- (β'-chloroethylsulfonyl) ethylamine hydrochloride are added and leaves the reaction solution for 3 hours at room temperature and pH 7.0-7.5 condense.

By adding sodium chloride, the dye is separated, filtered, with Washed sodium chloride solution and dried at 40 ° C in a vacuum. The so obtained Monoazo dye of the formula

dyes cellulose fibers in yellow shades with very good fastness properties.

Example 5

23 g of 1-acetylamino-3-aminobenzene-4-sulfonic acid are dissolved in 200 ml of water dissolved neutral and with 6.9 g of sodium nitrite and 30 ml of 30% hydrochloric acid at 0 to 5 ° C diazotized. The congo acid diazo suspension obtained is mixed with sodium carbonate solution adjusted to a pH of 4.5 and then to a solution of 33 g of 4-amino-6- (3'-sulfophenylamino) -2-methylpyrimidine in 800 ml of water and 15 g of sodium bicarbonate given. After the coupling has ended, the dye solution is mixed with sodium hydroxide, so that a 5% sodium hydroxide solution is formed and heated to 70 to 80 ° C until the saponification of the acetylamino group is complete. You cool it down Reaction solution, neutralized with concentrated hydrochloric acid and separates the dye completely by adding sodium chloride. after filtering and washing with dilute sodium chloride solution, the aminomonoazo dye thus obtained is dissolved in 400 ml of water. A solution of 21 g is added dropwise to this dye solution at 70.degree 2,4,5,6-tetrachloropyrimidine in 50 ml acetone and maintains the pH by simultaneous Add sodium carbonate solution at 6 to 7. After the condensation has ended, the Dye precipitated by adding sodium chloride, filtered and with sodium chloride solution washed. After drying in vacuo, the monoazo dye is obtained formula

which dyes cellulose fibers in yellow shades.

Example 6

33 g of 4-amino-6- (3'-amino-4'-sulfophenylamino) -2-methylpyrimidine dissolved in 1000 ml of water at a pH of 8, whereupon the solution at 0 to 5 ° C. cools down. At this temperature, a solution of 24 g is added dropwise within 30 minutes 2,4-dichloropyrimidine-5-carboxylic acid chloride in 100 ml of acetone and maintains the pH of the Reaction mixture by adding sodium carbonate solution at 7 to 8. As soon as none  unchanged amino compound can be determined, the reaction mixture is added with 30 g of sodium bicarbonate and then leaves a solution of 17.3 g inflow diazotized 1-aminobenzene-2-sulfonic acid. After the clutch has been completed Clarified reaction mixture, the reaction solution was then mixed with sodium chloride, the the precipitated dye is filtered off and washed with sodium chloride solution. After this Drying in vacuo at 40 ° C. gives the monoazo dye of the formula

which dyes cellulose fibers in yellow shades.

Example 7

54.1 g of the dye of the formula

(obtained by coupling diazotized 1-aminobenzene-2-sulfonic acid with 4-amino-6- (3'-amino-6'-sulfophenylamino) -2-methoxypyrimidine) are neutral in 1000 ml of water solved. A solution of 23 g is added dropwise to this dye solution at 0 to 10 ° C 2,4-dichloropyrimidine-5-carboxylic acid chloride in 50 ml acetone and maintains the pH simultaneous addition of sodium carbonate solution at 6. The reaction mixture is stirred, until no more diazotizable amino groups are detectable, there is at room temperature Add 12.6 g sodium sulfite and stir until the pH no longer changes. The new one formed dye is salted out with sodium chloride, filtered off, with sodium chloride solution washed and dried at 40 to 50 ° C in a vacuum.  

The monoazo dye of the formula is obtained

which cotton is wet-fast according to the processes customary for reactive dyes colors yellow tones.

Example 8

67.1 g of the aminoazo dye of the formula

(obtained by coupling diazotized 2-naphthylamine-1,5-disulphonic acid with 4-Amino-6- (3'amino-6'-sulfophenylamino) -2-methylpyrimidine) are used as the sodium salt dissolved neutral in 1000 ml of water. One drips into this dye solution at 40 ° C Solution of 29 g of 2,3-dichloro-quinoxaline-6-carboxylic acid chloride in 50 ml of acetone and holds the pH value by simultaneous addition of sodium carbonate solution at 7. After after the condensation has ended, the dye is precipitated by adding sodium chloride, filtered and washed with sodium chloride solution. After drying in a vacuum The monoazo dye of the formula is obtained at 40 ° C

which dyes cellulose fibers in golden yellow shades.

Example 9

38.3 g of 2-naphthylamine-1,5,7-trisulfonic acid become neutral in 300 ml of water dissolved and diazotized at 0 to 5 ° C with 25 ml of 30% hydrochloric acid and 6.9 g of sodium nitrite. The diazonium solution blunted with sodium carbonate to a pH of 4.5 then to a suspension of 39 g of 4-cyclohexylamino-6- (3'-nitrophenylamino) - Flow 2-methylpyrimidine in 900 ml water and 20 g sodium bicarbonate. To When the coupling is complete, the pH of the dye solution is increased to 9 and then left slowly add a solution of 14 g sodium sulfide in 100 ml water at 70 to 80 ° C. The mixture is reduced at this temperature until no more nitro compound can be detected adds 40 g of sodium bicarbonate to the cooled dye solution and frees it from fancy sulfur. The dye is completed by adding sodium chloride precipitated, filtered, washed with sodium chloride solution and then in 700 ml of water solved again. After adding 20 g of 2,4,5,6-tetrachloropyrimidine, the mixture is heated to 80 to 90 ° C and condenses at this temperature until no free amino groups are more detectable. After cooling, the new dye is added by adding Sodium chloride completely precipitated, filtered, washed with sodium chloride solution and dried in vacuo at 60 to 70 ° C. The monoazo dye of the formula is obtained

which dyes cellulose fibers in golden yellow shades.  

Example 10

65.0 g of the aminomonoazo dye of the formula

(obtained by coupling diazotized 1-amino-3- [2′Chlor-4′-aminotriazinyl- (6 ′) - amino] -benzene-6-sulfonic acid with 4-amino-6- (3′amino-4′-sulfophenylamino) - 2-methylpyrimidine) are suspended in 1000 ml of water and at 0 to 10 ° C with 30 ml 30% hydrochloric acid and 6.9 g sodium nitrite diazotized. The diazonium suspension obtained is then allowed to a solution of the sodium salt of 25.4 g of 1- (4'-sulfophenyl) -3- Flow methyl-5-pyrazolone in 200 ml water and 30 g sodium bicarbonate. To when the coupling is complete, the dye is precipitated by adding sodium chloride, filtered off and washed with dilute sodium chloride solution.

After drying in vacuo at 40 ° C., the bisazo dye of the formula is obtained

which dyes cellulose fibers in yellow shades.

Examples 11-145

Analogous to Examples 1-10 are those in the following tables 1-10 dyes obtained, the cotton in the specified color to dye.  

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Further examples are the following reactive dyes:

Claims (28)

1. Reactive dyes of the formula wherein D is the residue of a diazo component, Q is hydrogen or an optionally substituted alkyl, alkoxy, alkylthio or amino radical and A₁ and A₂ independently of one another a radical of the formula in which R₁ and R₂ independently represent hydrogen, optionally substituted C₁-C₆-alkyl or optionally substituted aryl, or R₁ and R₂ together with the N atom form an optionally further substituted heterocyclic 5- or 6-ring, with the proviso that that at least one of the radicals A₁, A₂ or D has a fiber-reactive group. 2. Reactive dyes according to claim 1, characterized in that Q is -NH₂ or a unsubstituted C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkylthio or C₁-C₆ alkylamino radical. 3. Reactive dyes according to claim 2, characterized in that Q is methyl. 4. Reactive dyes according to one of claims 1 to 3, characterized in that D the rest of an optionally substituted aminobenzene, aminonaphthalene, Phenylazo-aminobenzene, phthalocyanine-aminobenzene, naphthyl-azo-aminobenzene, Phenylazo-aminonaphthalene or naphthylazo-aminonaphthalene. 5. Reactive dyes according to claim 4, characterized in that D is unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, amino, N-mono- or N, N-di-C₁-C₄-alkylamino - The alkyl part is unsubstituted or by -OH, -OCOCH₃, -SO₃H, -OSO₃H, -CN or halogen is substituted -, phenylamino, C₁-C₄-alkanoylamino, benzoylamino,  C₁-C₄ alkoxycarbonyl, nitro, cyano, trifluoromethyl, halogen, hydroxy, carboxy, sulfo, Sulfomethyl, sulfamoyl, N-mono- or N, N-di-C₁-C₆-alkylsulfamoyl, N-phenylsulfamoyl, Carbamoyl, N-mono- or N, N-di-C₁-C₄-alkylcarbamoyl, ureido, C₁-C₄ alkylsulfonyl and / or a reactive radical is substituted. 6. reactive dyes according to any one of claims 1 to 5, characterized in that D by a reactive radical of the formula wherein W is a functional group, R₃ is hydrogen, unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy or cyano-substituted C₁-C₄-alkyl or a radical of the formula R is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkanoyloxy, carbamoyl or the group -SO₂-Z, Z -CH = CH₂ or -CH₂-CH₂-Y, Y a leaving group, EO- or -NR₄, R₄ hydrogen or C₁-C₄-alkyl, alk and alk 'independently of one another C₁-C₆-alkylene, arylene an unsubstituted or by sulfo, carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy or halogen-substituted phenylene or naphthylene radical, R₅ hydrogen or unsubstituted or substituted by carboxy, cyano, hydroxy, sulfo or sulfato-substituted C₁-C₄-alkyl and X is a group which can be split off as an anion, T independently has the meaning of X or a group containing one represents another reactive radical or represents a non-reactive substituent, one of the radicals X₁ independently has the meaning of X and the other radical X₁ has the meaning of T and X₂ is a negative substituent, or by a 2,3-dichloroquinoxaline-6-carbonylamino - or it is substituted by 2,4-dichloropyrimidine-5-carbonylamino. 7. reactive dyes according to claim 6, characterized in that D by a fiber-reactive radical of formula (2) or (2a) is substituted, wherein W is a group -CONH- or -NHCO- means alk is a C₁-C₄ alkylene radical and Z is the Claim 6 has the meaning given. 8. reactive dyes according to claim 6 or 7, characterized in that Y is a Group is -Cl, -OSO₃H-, -SSO₃H, -OCO-CH₃, -OCO-C₆H₅ or -OPO₃H₂. 9. reactive dyes according to one of claims 6 or 8, characterized in that D is substituted by a fiber-reactive radical of the formula (3), and X is fluorine, chlorine, Bromine, sulfo, C₁-C₄ alkylsulfonyl or phenylsulfonyl. 10. Reactive dyes according to one of claims 6, 8 or 9, characterized in that T represents a group containing a reactive radical, that of the formula corresponds in which R, R₃, R₅, E, W, Z, alk, alk 'and arylene have the meaning given in claim 6 and p is 0 or 1. 11. A reactive dye according to claim 10, wherein T is a group of the formula is where W'-CONR₅ 'or -NR₅CO-, R' is hydrogen or the group -SO₂-Z, R₃ 'is hydrogen, C₁-C₄-alkyl or the group -alk-SO₂-Z, R₅' is hydrogen or C₁-C₄ -Alkyl, E'-O- or -NH- and R₆ is hydrogen, sulfo, carboxy, chlorine, methoxy or methyl, alk and alk 'independently of one another are a C₁-C₄ alkylene radical and Z has the meaning given in claim 6. 12. Reactive dyes according to one of claims 6, 8 or 9, characterized in  that T as a non-reactive substituent amino, N-C₁-C₄-alkylamino in the alkyl part is unsubstituted or substituted by hydroxy, sulfato or sulfo, morpholino, phenylamino or N-C₁-C₄-alkyl, N-phenylamino, wherein the phenyl is unsubstituted or is substituted by sulfo, carboxy, methyl and / or methoxy. 13. Reactive dyes according to claim 6, characterized in that D by one Reactive radical of the formula (5) given in claim 6, wherein X₁ is chlorine or fluorine and X₂ is chlorine, cyano, formyl or methylsulfonyl, is substituted. 14. Reactive dyes according to one of claims 1 to 6, characterized in that D the rest of an unsubstituted or by sulfo, acetylamino, methyl, methoxy, chlorine or bromine substituted aminobenzene or aminonaphthalene, which is replaced by a Reactive radical of the formula (2), (2a) or (3) indicated in claim 6 further substituted is. 15. Reactive dyes according to one of claims 1 to 5, characterized in that D the residue of an unsubstituted or by sulfo, carboxy, C₁-C₄-alkoxy, C₁-C₄-alkyl, C₁-C₄ alkanoylamino and / or halogen substituted aminobenzene or Is aminonaphthalene. 16. Reactive dyes according to one of claims 1 to 15, characterized in that R₁ and R₂ independently of one another hydrogen, an unsubstituted or by hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkanoyloxy, Carbamoyl and / or a reactive radical substituted C₁-C₆-alkyl radical, where the alkyl with the exception of methyl is optionally interrupted by -O- or -NR₄- and R₄ has the meaning given in claim 6, or an unsubstituted or sulfo, carboxy, C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, a reactive radical and / or a group -N = NK, where K is the rest of a coupling component of the benzene or naphthalene series or the heterocyclic series, substituted phenyl or naphthyl radical or R₁ and R₂ together with the N atom represent a piperidinyl, piperazinyl or pyrrolidyl radical which is unsubstituted or by a radical of the formula wherein alk, p and Z have the meaning given in claim 10, are substituted. 17. Reactive dyes according to claim 16, characterized in that it is in the Reactive radical on the phenyl or naphthyl radical R₁ or R₂ by a radical which in claim 6 given formula (2), (2a), (3) or (5) or the 2,3-dichloroquinoxaline-6- carbonylamino or 2,4-dichloropyrimidine-5-carbonylamino residue and the reactive residue  on the C₁-C₆ alkyl radical R₁ or R₂ is the group -SO₂-Z. 18. Reactive dyes according to one of claims 1 to 17, characterized in that A₁ and / or A₂ is a group of the formulas given in claim 11 (4b ') or (4c') or a group of the formula wherein R₅, X and T have the meaning given in claim 6, R₆ is hydrogen, sulfo, chlorine, methoxy or carboxy and B is a group or -N = ist. 19. Reactive dyes according to one of claims 1 to 17, characterized in that A₁ and / or A₂ represent a radical of the formula (1a) given in Claim 1, wherein R₁ and R₂ are independently hydrogen or an unsubstituted or substituted by hydroxy, sulfo, sulfato, carboxy, cyano or the group -SO₂-Z and / or mean a C₁-C₄ alkyl radical interrupted by -O-, where Z is the one in claim 6 has the meaning given. 20. Reactive dyes according to claim 19, characterized in that one of the residues R₁ or R₂ is hydrogen. 21. reactive dyes according to any one of claims 1 to 20, characterized in that A₁ is a radical of the formula (1a), (4 ′) or (4a ′), wherein R₁ is hydrogen and R₂ is hydrogen or unsubstituted or by hydroxy, Sulfo or sulfato substituted C₁-C₄ alkyl, R ', R₃' and R₅ 'are each hydrogen mean E 'is -O-, and alk, alk' and Z 'each have the specified in claim 11 Have meaning is and A₂ independently has the meaning of A₁ or unsubstituted or by sulfo, chlorine, methoxy, carboxy or a radical of those in claim 6 specified formula (2), (2a) or (3) substituted phenylamino. 22. Reactive dyes of the formula (1) according to Claim 1, in which A₁ and A₂ are independently amino, N-C₁-C₄-alkylamino, in which the alkyl is unsubstituted or substituted by hydroxyl, sulfato or sulfo, or phenylamino, in which the phenyl is unsubstituted or by sulfo, carboxy, methyl, methoxy, chlorine and / or by a radical of the formula D is the radical of an aminobenzene or aminonaphthalene which is unsubstituted or substituted by sulfo, acetylamino, methyl, methoxy, chlorine or bromine and also a reactive radical of the formula (2), (2a) or ( 3) is, and Q is -NH₂ or an unsubstituted C₁-C₆ alkyl, C₁-C₆ alkoxy, C₁-C₆ alkylthio or C₁-C₆ alkylamino radical. 23. Reactive dyes of the formula (1) according to claim 1, characterized in that A₁ is a radical of the formula (1a), (4 ′) or (4a ′) given in claims 1 or 11, wherein R₁ is hydrogen and R₂ is hydrogen or unsubstituted or by hydroxy, sulfo or sulfato are substituted C₁-C₄-alkyl, R ′, R₃ ′ and R₅ ′ each represent hydrogen, E 'represents -O-, and alk, alk' and Z each have the meaning given in claim 11 have A₂ independently of the meaning of A₁ or unsubstituted or by sulfo, chlorine, methoxy, carboxy or a radical of the formula (2) given in claim 6, (2a) or (3) substituted phenylamino, Q is an unsubstituted or methyl group, Trifluoromethyl, methoxy, sulfo, nitro, chlorine or bromine substituted alkyl, and D the residue of an aminobenzene or aminonaphthalene which is unsubstituted or by sulfo, Carboxy, C₁-C₄-alkoxy, C₁-C₄-alkyl, C₁-C₄-alkanoylamino or halogen is substituted and optionally also a reactive radical of the formula (2) given in claim 6, (2a) or (3). 24. A process for the preparation of compounds of the formula (1), characterized in that a diazo component of the formula D-NH₂ (10) or its precursor with a compound of the formula or their preliminary product by diazotization and coupling to give reactive dyes of the formula (1), or converting the intermediate products obtained into the desired end dyes, and optionally a further conversion reaction, where D, A₁, A₂ and Q have the meaning given in claim 1. 25. Use of the reactive dyes according to claim 1 for dyeing and printing of cellulosic fiber materials. 26. Use according to claim 25 for dyeing and printing cotton. 27. Compounds of the formula wherein Q, A₁ and A₂ have the meaning given in claim 1, with the proviso that A₁ and / or A₂ contain a fiber-reactive radical. 28. A process for the preparation of compounds of the formula (11), characterized in that a compound of the formula with an amine of the formula to connect the formula implemented and then reacted with another amine of the formula (1a *) to give the compound of the formula (11), where Q, R₁, R₂ and A₁ each have the meaning given in claim 1 and Hal for halogen, for. B. for bromine and especially chlorine.