DE4402209A1 - New reactive dyestuff - Google Patents

Abstract

New dyestuffs with 2-mono- or 2,4-di-(vinylsulphonylalkyl) -amino-1,3,5-triazin-6-yl-amino or precursor substit(s). are of formula F-Zn (I). In (I), F = the radical of a sulphonated mono-, dis- or polyazo dyestuff or its metal complex or an anthraquinone, azomethine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthene, nitroaryl, naphthoquinone, pyrenequinone, perylenetetracarbimide, formazan, Cu formazan, phthalocyanine, Cu, Ni or Co phthalocyanine or triphenodioxazine dyestuff; Z = a substd. triazinylamino gp. of formula (II) (where R<1> = H or 1-4C alkyl (opt. substd. by halogen, OH, CN, 1-4C alkoxy, 2-5C alkoxycarbonyl, COOH, sulphamoyl, SO3H, OSO3H or phosphato); X = halogen, cyanoamino, (m)ethylsulphonylamino, carboxypyridyl, aminocarbonylpyridyl or -N(R)-S-(SO2-Y)z; R = 1-6C alkyl (opt. substd. by halogen, OH, CN, 1-4C alkoxy, 2-5C alkoxycarbonyl, COOH, sulphamoyl, SO3H, OSO3H, phosphato, phenyl or sulphophenyl); or phenyl (opt. mono-, di- or tri-substd. by halogen, 1-4C alkyl, 1-4C alkoxy, SO3H and COOH); W = 3-8C alkylene (which may be mono- or di-substd. by 1-6C alkoxy, halogen, 2-5C alkoxycarbonyl, COOH, SO3H and OSO3H or mono-substd. by phenyl, which is opt. mono- or di-substd. by SO3H, COOH, OMe, OEt and Me, and opt. also mono-substd. by SO3H, OSO3H or COOM or mono-substd. by a heterocyclic gp.); Y = vinyl or -CH2-CH2-Q; Q = OSO3H, thiosulphato, phosphato, 2-5C alkanoyloxy, benzoyloxy, sulphobenzoyloxy, p-toluenesulphonyloxy or halogen; z, n = 1 or 2). Also claimed are new psi -vinylsulphonyl- n-propyl-amine and precursor cpds. of formula R<0>NHWSO2Y<1>(III) (where W = -(CH2)3-; Y<1> = vinyl or -CH2-CH2-Q<1>; Q<1> = Q, 1C alkanoyloxy or OH; R<0> = phenyl (opt. mono-, di- or tri-substd. by halogen, 1-4C alkyl, 1-4C alkoxy, SO3H and COOH)).

Description

The invention is in the technical field of fiber-reactive dyes. The present invention relates to fiber-reactive triphendioxazine dyes general formula (1)

in which mean:

Z is a group of the general formula (2)

in which
R ^{A is} hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, by halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, alkoxycarbonyl of 2 to 5 C atoms, such as carbethoxy and carbomethoxy, carboxy, sulfamoyl, sulfo, sulfato or phosphato, can be substituted, and is preferably methyl or ethyl and particularly preferably hydrogen,
R is alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as in particular methyl or ethyl, which by halogen, such as chlorine and bromine, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, such as Methoxy and ethoxy, alkoxycarbonyl of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carboxy, sulfamoyl, sulfo, sulfato, phosphato, phenyl or sulfophenyl, or phenyl which can be substituted by 1, 2 or 3, preferably 1 or 2, substituents from the group halogen, such as chlorine and bromine, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, sulfo and carboxy, preferably by methyl, methoxy or sulfo , can be substituted,
X halogen, such as fluorine and chlorine, cyanoamino, methylsulfonylamino, ethylsulfonylamino, carboxypyridinyl, aminocarbonylpyridinyl or a radical of the formula -N (R) -W- (SO₂-Y) _z with R, W, Y and z one of the meanings given below,
W is alkylene of 3 to 8 carbon atoms, preferably of 3 to 6 carbon atoms, is particularly preferably n-propylene which has 1 or 2 substituents, preferably 1 substituent, from the group alkoxy of 1 to 6 carbon atoms , preferably 1 to 4 carbon atoms, halogen, such as chlorine and bromine, alkoxycarbonyl of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carboxy, sulfo and sulfato, can be substituted,
Y is vinyl or β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β- (C₂-C₅-alkanoyloxy) -ethyl, such as β-acetyloxyethyl, β-benzoyloxyethyl, β- (sulfobenzoyloxy) -ethyl, β- (p- Toluenesulfonyloxy) ethyl or β-haloethyl, such as β-bromoethyl or β-chloroethyl, and preferably vinyl and particularly preferably β-chloroethyl or β-sulfatoethyl and
z is the number 1 or 2, preferably 1;
M is hydrogen or an alkali metal, such as sodium, potassium or lithium, or the molar equivalent of an alkaline earth metal, such as calcium, and preferably hydrogen or an alkali metal;
B ° is the oxy group -O- or the amino group -NH-;
A ° is alkylene of 2 to 6 carbon atoms which is interrupted by 1 or 2 hetero groups, such as groups of the formulas -O-, -NH-, -NH-CO- and / or -CO-NH- and / or that may be substituted, for example by hydroxy, sulfo, sulfato or carboxy, or is cyclohexylene;
or the grouping -A ° -B ° - or -B ° -A ° - means in each case a direct bond;
the two sulfo groups -SO₃M are preferably bound to the benzene nucleus in the ortho position to the oxygen atom of the heterocyclic ring.

In the general formulas (1) and (2) and in the following general ones Formulas can be the individual formula elements, both different and same name within a general formula, in the context of their Meaning mutually identical or different meanings to have.

The groups "Sulfo", "Carboxy", "Phosphato" and "Sulfato" both include their acid form as well as their salt form. Accordingly mean Sulfo groups according to the general formula -SO₃M Thiosulfato groups according to the general formula -S-SO₃M Carboxy groups according to the general formula -COOM, Phosphato groups according to the general formula -OPO₃M₂ and sulfato groups according to the general formula -OSO₃M in which M has the meaning given above.

The present invention further relates to methods for producing the Dyes of the general formula (1) according to the invention. You get in on and known for themselves in a conventional manner, for each Produce dye class specific synthetic routes by a Halogenotriazine compound of the general formula (21)

in which X has one of the above-mentioned, particularly preferred meanings and Hal represents halogen, such as chlorine or fluorine, such as 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) or 2,4,6-trichloro-1,3,5-triazine (Cyanuric chloride), in any order with an amino group Compound of the general formula (20)

in which R ^{A has} the meaning given above and F is a radical of the formula (21A)

with M, A ° and B ° has the meaning given above, and with an amino compound of the general formula (22)

with R, W, Y and z of the abovementioned meanings in a double molar amount.

Process variants of this invention according to the invention Procedures are characterized, for example, that one Compound of the general formula (23)

in which F, R ^A , X and Hal have the abovementioned meanings, with an amino compound of the general formula (22), or in that a compound of the general formula (24)

in which Hal, X, R, W, Y and z have the meanings given above, with a compound of the general formula (20) of the abovementioned meaning implements.

In the condensation reactions, care must be taken that the fiber-reactive Groups in the alkaline range must not be damaged.

The reactions of the starting compounds are carried out in aqueous or aqueous organic medium in suspension or solution. Do the implementations in through an aqueous-organic medium, so is the organic medium for example acetone, dimethylformamide, dimethyl sulfoxide or N-methyl pyrrolidone. The one released during the condensation is advantageous Hydrogen halide continuously by adding aqueous alkali or Alkaline earth metal hydroxides, carbonates or bicarbonates neutralized. The first Condensation reaction of the halogen-s-triazine of the general formula (21) usually takes place at a temperature between -5 ° C and + 20 ° C, in the case Hal is fluorine, preferably at a temperature between -5 ° C and + 5 ° C,  and at a pH between 2 and 10, preferably between 4 and 6. Die subsequent condensation reaction with the second amino compound takes place in usually at a temperature between 0 and 60 ° C and a pH value between 3 and 10, in the case of Hal equal to fluorine, preferably at one temperature between 0 and 20 ° C and a pH between 6 and 10 and in the case of Hal is preferably chlorine at a temperature between 40 and 60 ° C and pH between 4 and 5.

In particular, the conversion takes place between a compound of the general Formula (23) and a compound of general formula (22) in one Temperature between 0 and 50 ° C, preferably between 10 and 30 ° C, and at a pH value between 3 and 10, preferably between 6 and 8, If Hal is a fluorine atom in the compound for formula (23), preferably the Reaction carried out at a temperature between 0 and 20 ° C.

The starting compounds of the general formula (23) can be started of the compounds (20), in a manner known per se Implementation of halogen-substituted triazines with amino groups Make connections like this for example above Procedures according to the invention is described, so also in aqueous or aqueous-organic medium usually at a temperature between -5 ° C and + 40 ° C, preferably between 0 and 30 ° C, and at a pH between 2 and 10, preferably between 3 and 6, where in the case of a Starting compound of formula (21) with Hal equal to fluorine preferably one Select reaction temperature between -5 ° C and + 5 ° C. In the same way and under the same process conditions Starting compounds of the general formula (24) by reacting a Compound of general formula (21) with a compound of general Prepare formula (22).

If you go to the preparation of the dyes of the general Formula (1) from starting compounds of the general formula (23), in  which X is a radical of the general formula -N (R) -W-SO₂-Y of the above What is important is the reaction with the amino compound general formula (22) at a temperature between 60 and 95 ° C, preferably between 80 and 90 ° C, and at a pH between 6 and 10, preferably between 8 and 9.5, provided that Hal is chlorine and Y both in Amino radical X and also in the starting compound of the formula (22) hydroxy means; the dye compound thus obtained with β-hydroxyethylsulfonyl Groups can then be esterified into an inventive Dye are converted, for example into the β-sulfatoethylsulfonyl Colorants containing sulfuric acid or sulfur trioxide Sulfuric acid, preferably at a temperature between 20 and 40 ° C. Is in the starting compounds of formula (23) with X equal to one Rest of the formula -N (R) -W-SO₂-CH₂-CH₂-OH with R and W of the above If Hal is fluorine, the reaction takes place with the Amino compound of general formula (22) at a temperature between 25 and 70 ° C, preferably between 40 and 60 ° C, and at a pH between 3 and 8, preferably between 4 and 7.

The starting compounds of the general formula (21) and the general Formula (20) and its precursors are generally known and in the literature described in numerous. Are compounds of general formula (21) for example cyanuric chloride and cyanuric fluoride. They are also Starting compounds of the general formula (22) are known in some cases, so from British Patent No. 1,576,237. Not described expressly verbis are, on the other hand, compounds of the general formula (22) in which W is the is n-propylene group and z stands for the number 1, such as compounds according to the general formula (22A)

in which Y¹ is one of the particularly preferred ones specified for Y,  Has meanings or is the β-hydroxyethyl group and R ° for phenyl stands by 1, 2 or 3, preferably 1 or 2, substituents from the group Halogen, such as chlorine and bromine, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy from 1 to 4 carbon atoms, such as methoxy and ethoxy, sulfo and carboxy, are preferred Methyl, methoxy and sulfo, may be substituted.

The amino compounds of the general formula (22A) can be, for example in such a way that N-allyl-N-acetyl-aniline (see J. Org. Chem. 14, 1099 (1949)) analogous to that in German Offenlegungsschrift No. 41 06 106 described procedure with 2-mercapto-ethanol in the presence of a Radical initiator, the resulting N- [γ- (β'-hydroxyethylthio) propyl] -N- Acetyl-aniline compound oxidized to the sulfonyl compound, for example by means of Hydrogen peroxide in the presence of a catalytic amount of one Transition metal compound, such as tungsten oxide. From that The sulfonyl compound obtained is the acetyl group in alkaline or acidic Range, preferably in hydrochloric acid aqueous solution, such as in 5 to 30% aqueous hydrochloric acid, at a temperature between 80 and 100 ° C split off hydrolytically.

The N-phenyl-N- [γ- (β'-hydroxyethylsulfonyl) propyl] amine thus obtained can be from the neutral aqueous synthesis solution from the aqueous phase be separated. Its β-hydroxyethylsulfonyl group can be removed esterify usual methods, for example by means of concentrated Sulfuric acid at a temperature between 10 and 30 ° C in the β-sulfatoethylsulfonyl compound or with thionyl chloride or gaseous Transfer hydrogen chloride to the β-chloroethylsulfonyl compound.

The deposition of the general dyes produced according to the invention Formula (1) from the synthesis approaches is carried out according to generally known Methods either by means of precipitation from the reaction medium Electrolytes, such as sodium chloride or potassium chloride, or by Evaporation of the reaction solution, for example by spray drying, where a buffer substance can be added to this reaction solution.  

The dyes of the general formula (1) - hereinafter dyes (1) called - are suitable for dyeing and printing the most diverse Materials such as silk, leather, wool, polyamide fibers and polyurethanes, and in particular cellulose-containing fiber materials of all kinds. Such fiber materials are, for example, the natural cellulose fibers such as cotton, linen and Hemp, as well as cellulose and regenerated cellulose. The dyes (1) are too suitable for dyeing or printing fibers containing hydroxy groups, which in Blended fabrics are included, e.g. B. of mixtures of cotton with Polyester fibers or polyamide fibers.

The dyes (1) can be applied to the fiber material in different ways apply and fix on the fiber, especially in the form of aqueous Dye solutions and printing pastes. They are suitable for both Exhaust process as well as for dyeing according to the foulard dyeing process, after which the goods with aqueous, optionally saline dye solutions impregnated and the dye after an alkali treatment or in the presence of alkali, optionally under the action of heat. After this The dyeings or prints are fixed with cold and hot water, optionally with the addition of a dispersing and the Diffusion of the non-fixed portions of the conveying agent, rinsed thoroughly. These Dyeing and printing processes are numerous in the general specialist literature such as also in the patent literature, such as those mentioned at the beginning Publications.

The present invention therefore also relates to the use of Dyes (1) for dyeing (including printing) these materials or Process for dyeing (and printing) such materials in and of itself usual procedure in which a dye (1) is used as the colorant is by placing the dye (1) in an aqueous medium on the material applied and using heat or an alkaline Connection or by means of both fixed on the material.

The dyes (1) are notable for high reactivity and good fixing properties and a very good build-up ability. The degrees of fixation are high, and the  unfixed 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 dyes (1) are also particularly suitable for printing all on cotton, but also for printing nitrogenous ones Fibers, e.g. B. of wool or silk or of mixed fabrics, the wool or silk contain.

The dyeings and prints produced with the dyes (1) have especially on cellulose fiber materials, a high color strength and a high Fiber-dye binding stability in both acidic and alkaline Area, continue to have good lightfastness and very good Wet fastness properties, such as washing, water, seawater, over-dyeing and Sweat fastness, as well as good pleating fastness, ironing fastness and Fastness to rubbing.

The following examples serve to explain the invention. The parts are Parts by weight, the percentages are percentages by weight, if not noted otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

The compounds described by formula in the examples are in the form of specified free acid; generally they are in the form of their Alkali metal salts, such as lithium, sodium or potassium salts, prepared and isolated and used in the form of their salts for coloring. Likewise, in the following examples, especially table examples, in the form of the free Starting compounds and components mentioned as such or in acid Form of their salts, preferably alkali metal salts, used in the synthesis become.

The absorption maxima (λ _max ) in the visible range specified for the dyes according to the invention were determined on the basis of their alkali metal salts in aqueous solution. In the table examples, the λ _max values are given in brackets when specifying the color; the wavelength specification refers to nm.

example 1

58.9 parts of 2,9-diamino-6,13-dichloro-1,8-disulfo-triphendioxazin are in 1500 Parts of water mixed and with an aqueous lithium hydroxide solution set a pH of 7. 60 parts are added at 20 to 25 ° C Add cyanuric chloride, the pH being adjusted using an aqueous Lithium hydroxide solution holds between 4 and 5. One touches the approach one more time Keep going until the implementation is complete. Then you give 66 parts N- Phenyl-N- (γ-sulfatoethylsulfonyl) propylamine, dissolved in 200 parts of water, increases the temperature to 60 ° C and stirs while maintaining a pH value between 4 and 5 until complete implementation.

The triphendioxazine dye of the formula (in Form of free acid)

by salting out using sodium chloride as the alkali metal salt (sodium salt). The dye according to the invention shows very good fiber-reactive properties and delivers on the materials mentioned in the description, in particular Cellulose fiber materials, according to those used in fiber reactive dye technology usual application methods strong, brilliant bluish red colorations and prints with high fixation rates and good fastness properties.  

Examples 2 to 4

The following table examples show further examples according to the invention Triphendioxazine dyes according to the general formula

described with the help of the visible components. You let yourself in way according to the invention, for example analogously to Example 1 above, by Implementation of the general formula given from the formula residues Establish apparent output connections. You have very good ones fiber-reactive dye properties and deliver on the in the description mentioned fiber materials, such as especially cotton, according to the fiber-reactive dyes usual application and fixing processes strong color Colorings and prints, with the in the respective table example for Cotton specified shade.

Claims (8)

1. dye of the general formula (1) in which mean: Z is a group of the general formula (2) in which
R ^{A is} hydrogen or alkyl of 1 to 4 carbon atoms, which is substituted by halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo, sulfato or phosphato can be,
R is alkyl of 1 to 6 carbon atoms, that is halogen, hydroxy, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfamoyl, sulfo, sulfato, phosphato, phenyl or sulfophenyl may be substituted, or is phenyl, which may be substituted by 1, 2 or 3 substituents from the group halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo and carboxy,
X is halogen, cyanoamino, methylsulfonylamino, ethylsulfonylamino, carboxypyridinyl, aminocarbonylpyridinyl or a radical of the formula -N (R) -W- (SO₂-Y) _z with R, W, Y and z being one of the meanings given below,
W is straight-chain or branched alkylene of 3 to 8 carbon atoms, which is substituted by 1 or 2 substituents from the group alkoxy of 1 to 6 carbon atoms, halogen, alkoxycarbonyl of 2 to 5 carbon atoms, carboxy, sulfo and sulfato a phenyl radical or a phenyl radical substituted by 1 or 2 substituents from the group sulfo, carboxy, methoxy, ethoxy and methyl or by such an optionally substituted phenyl radical and a sulfo, sulfato or carboxy group or by a heterocyclic radical,
Y vinyl, β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β- (C₂-C₅-alkanoyloxy) -ethyl, β-benzoyloxyethyl, β- (sulfobenzoyloxy) -ethyl, β- (p-toluenesulfonyloxy) -ethyl or β -Halogenoethyl, and
z is the number 1 or 2;
M is hydrogen or an alkali metal or the molar equivalent of an alkaline earth metal;
B ° is the oxy group -O- or the amino group -NH-;
A ° is alkylene of 2 to 6 carbon atoms which can be interrupted by 1 or 2 hetero groups and / or which can be substituted, or is cyclohexylene;
or the grouping -A ° -B ° - or -B ° -A ° - each means a direct bond. 2. Dye according to claim 1, characterized in that Y is β-sulfatoethyl, β-chloroethyl or vinyl. 3. Dye according to claim 1 or 2 of the general formula in which M and Y have the meanings given in Claim 1 or 2. 4. Dye according to claim 3, characterized in that Y is each β- Is sulfatoethyl. 5. A process for the preparation of a dye corresponding to the general formula (1) of claim 1, characterized in that a halogen-triazine compound of the general formula (21) in which X has one of the meanings given in Claim 1 and Hal represents halogen, with a compound of the general formula (20) containing amino groups in which R ^{A has} the meaning given in Claim 1 and F is a radical of the formula (21A) with M, A ° and B ° has the meaning given above, and with an amino compound of the general formula (22) with R, W, Y and z of the meanings mentioned in claim 1. 6. Use of a dye of claim 1 or one of claim 5 dye prepared for dyeing (including printing) of material containing hydroxyl and / or carbonamide groups, in particular Fiber material. 7. Process for dyeing (including printing) of hydroxy and / or material containing carbonamide groups, in particular fiber material which one applies a dye to the material and the Dye on the material using heat or with the help of an alkaline fixed agent or by means of both measures, thereby characterized in that the dye is a dye of claim 1 or uses a dye prepared according to claim 5.