DE2531557A1 - Anthraquinone dispersion dye mixts. - contg. halogenated aryl gps. in alkoxy side chain - Google Patents

Abstract

Antraquinone dispersion dye mixts. are of formula (I):- In (I) A and B are NH2 or OH; R is an opt. substd. O interrupted alkylene gp.; X is a direct bond, O, S, NH or N-alkyl, Ar is opt. substd. aryl; D1 and D2 are each H or halogen; Hal is Cl or Br; n is an average value of 0.1-2.5. Used for dyeing or printing of synthetic fibres from aq. dispersions or in some cases, from organic solvents, in orange, red or violet shades. (I) give strong colours with good fastness, esp. to light and sublimation. In an example, 111 g. brominated phenoxyethanol is heated with 8 g. KOH for 1.5 hr. at 150 degrees C. After adding 32 g. 1-amino 2-phenoxy 4-hydroxy anthraquinone, the mixt. is heated for 10 hr. at 150 degrees C., cooled and the dye contng. 9.0% Br is pptd. with methanol.

Description

Anthraquinone dyes The present invention relates to mixtures of water-insoluble anthraquinone dyes of the formula in which A and B for an amino or hydroxyl group, R for an optionally substituted and / or oxygen-interrupted alkylene radical, X for a direct bond, oxygen, sulfur or an imino group optionally substituted by alkyl groups, Ar for an optionally substituted aryl radical, D1 and D2 for hydrogen or. Halogen, Hal stands for chlorine or bromine and n stands on average for a number from 0.1 to 2.5, as well as their production and use for dyeing and / or printing synthetic fiber materials.

Suitable alkylene radicals are optionally by C1 -C3 -alkyl, Hydroxy, Tolyloxy or phenoxy-substituted C2-C10-alkylene radicals interrupted by 0 could be. The alkylene radical can preferably contain 1 or 2 such substituents be.

Suitable alkylimino groups are those with 1 to 4 carbon atoms in the alkyl radical.

Suitable halogen atoms D1 and D2 are chlorine and fluorine, which are preferred are in the 6 and / or 7 position.

Suitable radicals Ar are phenyl groups, which are replaced 1 to 2 times by chlorine, C1-C8-alkyl, C1-C4-alkoxy C1-C4-alkyl mercapto residues through hydroxyl, hydroxyalkyl, Dihydrokypropyl, hydroxyalkoxy, trifluoromethyl, phenyl, phenoxy, benzyl or Benzyloxy groups can be substituted, also * - or ß-naphthyl, tetrahydronaphthyl, 2- or 3-diphenyleneoxidyl, dioxymethylene phenyl or dimethylcoumaranyl radicals. Phenyl radicals which are optionally monosubstituted are preferred.

Examples include: phenyl, tolyl, ethylphenyl, n- and i-propylphenyl, n- and t-butylphenyl, n-pentylphenyl, n-octylphenyl, chlorophenyl, fluorophenyl, trifluoromethylphenyl, cresyl, chloromethylphenyl, anisyl, isopropoxyphenyl and The dyes prepared according to the invention are preferably mixtures of compounds of the formula 1 with n = Ol 1 and 2, the other radicals being identical. The most favorable coloristic properties are achieved with dyes in which the aryl nucleus Ar contains 0.1 to 1.5, preferably 0.2 to 0.6 bromine atoms or

0.1 to 1.5, preferably 0.2-0.8 chlorine atoms per dye molecule are included.

The dye mixtures I stand out from the non-halogenated ones Connections through better drawability or better sublimation fastness and opposite the defined halogen-containing anthraquinone dyes, such as aie for example in the Japanese Auslegeschriften 64 05 967, 65 53 950, 63 08 498 or in the U.S. Patent 3,787,177 can be described by improved design capabilities and greater color strength. In addition, have the manufactured according to the invention Anthraquinone dyes I have the advantage over the more economical preparation corresponding defined halogen-containing compounds, as they are generally composed of cheaper raw materials are available.

Preferred compounds of the formula I given are those in which 1 is an imino group, B is an amino or hydroxyl group and D1 and D2 are hydrogen and of these, in turn, those in which X is oxygen or a direct bond stands.

Particularly preferred dye mixtures I are also those in which A is an amino group, B is a hydroxyl group, D1 and D2 are hydrogen and Br is optionally Phenyl radical substituted 1 - 2 times by C1 - C8 alkyl radicals mean, of which, in turn, those compounds are of particular interest in which X oxygen. or a direct bond and R a straight-chain or branched one C2 - C8 alkylene radical.

Anthraquinone dye mixtures of the formula in are of very particular interest R1 for a straight-chain C2 - c6-AlkYlenresfi, preferably C2H4 I x for a direct bond or preferably oxygen1 Ar1 for a phenyl radical, which is optionally 1 to 2 times substituted by a C1-C4 (preferably C1-C2) -alkyl radical, Hal for Bromine and m stand for 0.2 to Ot8.

If the above-mentioned alkyl radicals are branched, are these are preferably in the p-position of the phenyl radical.

The dye mixtures according to the invention are prepared in a manner known per se, for example by adding compounds of the formula in which A, B, D1 and D2 have the meaning given above and E represents an exchangeable substituent, with compounds of the formula EO-RX-ir- (Hal) n IV in which R, X, Ar, Hal and n have the meaning given above, in the presence of basic compounds and optionally in the presence of an organic solvent at elevated temperatures. Such reactions are described, for example, in British patent specification 974 404 or in US patents 3,124,601 and 2,992,240, respectively.

Suitable exchangeable substituents are halo, such as chlorine and Bromine, lower alkoxy groups, especially the methoxy group, optionally substituted Aryloxy groups, preferably phenoxy groups, or sulfonic acid groups.

Suitable organic solvents are, for example, dimethylformamide, Dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone-caprolactam, tetramethylene sulfone or pyridine.

Suitable basic compounds are sodium or potassium hydroxide, Sodium or potassium carbonate or organic bases such as trimethylamine, triethylamine or benzyl trimethyl ammonium hydroxide.

As suitable anthraquinone compounds with exchangeable substituents are particularly mentioned l-amino-4-hydroxy-2-phenoxy-anthraquinone, 1-amino-4-hydroxy-2- (p-chlorophenoxy) -anthraquinone, l-amino-4-hydroxy-anthraquinone-2-sulfonic acid, l-amino-4-hydroxy-2-bromo-anthraquinone l-Amino-4-hydroxy-5- (6-, 7- or 8-) chl3r-2-phenoxy-anthraquinone, 1-amino-4-hydroxy-6- (or 7-) fluoro-2-phenoxyanthraquinone, 1,4-diamino-2-phenoxy-anthraquinone and 1,4-dihydroxy-2-phenoxy-anthraquinone.

The hydroxy compounds IV are by bromination or chlorination, possibly in the presence of inert organic solvents, for example according to the Information in C.r. 196 (1933) 622 or A.ch. (11) 1 (1934) 418 accessible.

Examples of suitable compounds are: in each case brominated or chlorinated 8 phenoxyethanol, cresoxyethanol, dimethylphenoxyethanol, phenoxypropanol, Phenoxybutanol, hydroxyethylaniline, glycerin monophenyl ether, glycerol diphenyl ether, Phenylethanol, phenylpropanol and phenoxyhexanol.

Another process for the preparation of the dyes according to the invention consists in the reaction of anthranhinone compounds of the formula in which A, B, R, D1 and D2 have the meaning given and T stands for chlorine, bromine or an arylsulphonyl or alkanesulphonyloxy group, preferably a methanesulphonyloxy group} 7 with compounds of the formula HXl-Ar- (Hal) n VI in which Ar, Hal and n have the meaning mentioned and X1 stands for oxygen, sulfur or an amino group optionally substituted by alkyl groups, in the presence of basic compounds and optionally in the presence of an organic solvent at elevated temperatures, for example in accordance with the information in English patent specification 835 819.

Suitable arylsulfonyloxy or alkanesulfonyloxy groups are: aie benzenesulfonyloxy, Toluolsulfonyloxy-, Methanesulfonyloxy-, Xthanesulfonyloxy-, PropansulKonyloxy- and the butanesulfonyloxy group.

The anthraquinone compounds required for such reactions V is in turn obtained according to the information in Q 870 948 or 1 195 151.

Suitable basic compounds are: alkali hydroxides, such as sodium or potassium hydroxide, alkali carbonates, such as sodium or potassium carbonate alkali acetates, such as sodium or potassium acetate, and organic bases such as trimethylamine or triethylamine or benzyl trimethyl ammonium hydroxide.

Suitable solvents are formamide or dimethylformamide, dimethylacetamide, N-methylpyrrolidone, # - caprolactam, dimethyl sulfoxide, tetramethylene sulfone or pyridine.

Dye mixtures of the formula I can also be obtained by using inthraquinone compounds of the formula in which A, 3, D1 and D2 have the abovementioned meaning, with compounds of the formula URX-Ar- (Hal) n VIII in which R, X, Ar, Hal and n have the meaning given above and U for chlorine, bromine , the phenyl or p-ethylphenylsulfonyloxy radical is present in the presence of basic compounds and an organic solvent at elevated temperatures, for example in accordance with the information in Japanese Auslegeschrift 65 53 950 or the DAS 2 316 291 implements.

The manufacturing process mentioned for the inventive substance mixtures What I have in common is that it was not to be expected from the outset that halogen-containing compounds of formula IV, VI or VIII after the reaction with the respective anthraquinone compounds III, V or VII to halogen-containing dyes I with a corresponding halogen content lead, as individual components are preferred from the mixtures used could react.

The preferred variant for the preparation of anthraquinone dyes of the formula I in which Hal stands for bromine is characterized in that anthraquinone compounds of the formula in which A and B for an amino or hydroxyl group, R for an optionally substituted and / or oxygen-interrupted alkylene radical, X for a direct bond, oxygen, sulfur or an imino group optionally substituted by alkyl groups, Ar for an optionally substituted aryl radical and D1 andD2 is hydrogen or halogen, Ar is brominated on the aryl radical.

The bromination of the aryl radicals in compounds of the formula IX takes place by methods known per se (see e.g. British patent specification 979 567).

The implementation of the method according to the invention can, for example, in the Wise done that one the anthraquinone compound of formula IX in War, diluted Sulfuric acid, dilute or concentrated hydrohalic acid, preferably in concentrated hydrochloric acid or in organic solvents, e.g.

Introduces chloro- or nitrobenzenes, glacial acetic acid or chlorinated hydrocarbons and then preferably bromine or a brominating compound, such as, for example Sn Houben-Weyl, Methods of Organic Chemistry, Volume 5/4, pages 13-37 are, adds.

The bromination is carried out at temperatures between 0 and 100 ° C., preferably at room temperature to 900C by, if necessary, the reaction mixture Boric acid or the catalysts commonly used in bromination, such as Iodine, can add.

The bromination products prepared by the process according to the invention are preferably mixtures of unbrominated starting material and mono- and dibrominated reaction products, such dyes being the most favorable coloristic Have properties in which 0.2 to 0.6 bromine atoms per dye molecule IX have been recorded. Such mixtures can of course also be used by mechanical mixing of unbrominated and defined bromine compounds.

Preferred compounds of the formula IX given, according to the invention are brominated are those in which A is an amino group, B is an amino or hydroxyl group and D1 and D2 denote hydrogen and of these in turn particularly those at where X is oxygen or a direct bond.

Particularly preferred starting compounds IX for the inventive Processes are also those in which A is an amino group, B is a hydroxyl group, D1 and D2 mean hydrogen and of these in turn especially those where X stands for oxygen or a direct bond.

Particularly preferred starting compounds IX for the inventive Processes are also those in which A is an amino group, B one Hydroxyl group, Di and D2 are hydrogen and Ar is optionally 1 to 2 times through C1-C8-alkyl radicals substituted phenyl radical, of which in turn those compounds are special Are of interest in which X is oxygen or a direct bond and R is an optionally substituted C2-C8-alkylene radical.

Compounds of the formula are of very particular interest as starting materials (IX) to be used according to the invention in which R1 stands for a straight-chain C2-C6 (preferably C2-Cs) 'alkylene radical, X for oxygen or a direct bond and Ar1 for a phenyl radical, which is optionally substituted 1 to 2 times by a C1-C4-alkyl radical, preferably C1- C2-alkyl radical is substituted, where the statements made above apply to branched alkyl radicals.

The starting compounds required for the preparation of the dyes according to the invention the formula IX is obtained by processes known per se, for example by Implementation of 1-amino-4-hydroxy- or 1,4-dihydroxyanthraquinones, which are in the 2-position carry an exchangeable aryloxy or sulfonic acid group with alcohols of the formula HO - R - X - Ar (XI) in which R, X and Ar have the meanings given above, in the presence alkaline condensing agent and optionally in the presence of solvents.

Suitable alcohols XI are, for example: phenylethanol, phenylpropanol, Phenoxyethanol, cresoxyethanol, dimethylphenoxyethanol, phenoxypropanol, phenoxybutanol, Hydroxyethylaniline, glycerol monophenyl ether and glycerol diphenyl ether.

The colorants produced by the process according to the invention are, as mentioned above, dye mixtures in most cases.

But you can also through specific reaction conditions and / or specific Establish defined mono- and dibromine compounds in cleaning operations. While the last ones not yet generally described are in the case of monobromine compounds Such dyes of formula I are still new, in which A and B have the same meaning. If in formula I A is an amino group and B is a hydroxyl group, are those redefined monobromo dyes in which R is a straight-chain or branched C3-C10-alkylene radical, X for oxygen, a direct bond or a amino group optionally substituted by C1 -C4 alkyl groups and Ar for optionally phenyl substituted by 1 to 3 C1-C4-alkyl groups.

These new compounds are also the subject of the present invention Invention.

In the case of the synthetic fiber materials that are produced with the inventive produced dyes are colored, it is mainly those on based on polyesters such as polyethylene terephthalate, polycyclohexanedimethylene terephthalate, heterogeneous polyesters made from terephthalic acid, sulfoisophthalic acid and ethylene glycol or copolyether esters of 4-hydroxy-benzoic acid and ethylene glycol, cellulose triacetate or cellulose 2 1/2 acetate, synthetic polyamides, such as hexamethylene diamine adipate, Poly-t-caprolactam or (aaminoundecanoic acid, polyurethanes, polyacrylonitrile, polyolefins or Polycarb "'n, e.g. from 2,2-bis (hydroxyphenyl) propane.

The fiber materials can be in various processing stages exist, e.g. as thread, flake, sliver, as piece goods, such as woven or knitted fabrics or as packaged goods.

The coloring or printing can be done for the coloring aqueous liquor known methods take place. It is advantageous to use the dyes or the dye mixtures before use by the customary methods to bring into a state of fine distribution.

When dyeing fibers made from aromatic polyesters, for example Polyethylene glycol terephthalate, one can add the uSL L en carrier to the aqueous dye bath or carry out the staining without the addition of a carrier at 120-145 ° C. under pressure. When dyeing according to the thermosol process, the printed or padded fiber materials, if necessary after intermediate drying, briefly to temperatures of 180-2400C heated.

The heating is generally carried out for periods of 30 seconds up to 2 minutes.

Cellulose triacetate, cellulose 2 1/2 acetate and polyamide fibers can you dye at about 1000C from aqueous liquors, optionally in the presence of the usual tools. The dyeing of blended fabrics made of polyester fibers and cellulose fibers, like cotton, after the mentioned thermosol process also leads to excellent Results. The padding liquor is used in addition to those produced according to the invention Dyes or dyes suitable for dyeing cotton, such as vat dyes or reactive dyes added.

Some types of the dyes made according to the invention, in particular those that have a minimum solubility in tetrachlorethylene due to longer alkyl chains of 5 g / l (preferably 10 g / l) are also suitable for dyeing synthetic materials Fiber materials made from organic solvents using the so-called continuous process.

The dyeing conditions suitable for this are known and are for example has been described in more detail in Belgian patent 753 315.

According to the above-mentioned process, with the according to the invention produced dyes on the fibers mentioned have strong orange, red or purple colors Dyeings or prints with good fastness properties, in particular good lightfastness and sublimation fastness.

example 1 a) 111 g of brominated phenoxyethanol (obtained by bromination of 100 g of 2-phenoxyethanol-1 with 22 g of bromine in 100 ml of concentrated hydrochloric acid) are heated to 15,000 for 1 1/2 hours with 8 g of anhydrous potash.

After entering 32 g of l-bmino-2-phenoxy-4-hydroxy-anthraquinone the mixture is stirred for 10 hours at 1500C, cooled to 700C, diluted with 100 ml of methanol, sucks after receiving and washes with * 1 methanol and hot water. You get after drying, 33.5 g of a dye mixture with a bromine content of 9.0%.

b) If the same reaction is carried out with a brominated phenoxyethanol by which you can easily by the action of 19 g of bromine on 50 g of phenoxyethanol Wins diluent, a dye with 8.1 X bromine is obtained.

c) With 1 g of the dye mixture prepared according to Example la, that has previously been finely divided in the presence of dispersants, 100 g of polyethylene terephthalate fibers in 4 1 of H20 in the presence of 15 g of methyl o-cresotinate dyed as a carrier for 2 hours at 100 ° C. and pH 4.5. You win a brilliant yellow color Pink color, which is due to the very good structure, high wasoh, heat-setting, rubbing and Lightfastness is excellent. Tine-like coloring is obtained when one as polyester fibers those made from 1,4-bio (hydroxymethyl) -oyolohexane and terephthalic acid used.

d) With 1 g of that mentioned in example la), previously with the usual auxiliaries 100 g of polyester fibers (polyethylene terephthalate) are used to finely distribute the dye mixture dyed in 3 l of water for one hour at 125-130 ° C under pressure. lan receives a clear, strong red coloration with good fastness properties.

e) With 1 g of the dye mixture mentioned in Example la), which one has been finely divided by the usual methods, 100 g Polyamide fabric dyed in 4 liters of water for 1 hour at 100.degree.

The fabric is then rinsed warm and cold and dried. A clear pink coloration of very good: fastness to washing and lightness is obtained.

Instead of polyamide fibers, polyurethane fibers can be used with equal success use.

f) With 1 g of the dye mixture prepared according to Example la), this beforehand in fine distribution using the auxiliaries customary for this purpose was brought, 6 g of fatty alcohol sulfonate and 3 l of water, a dye bath is prepared, in which 100 g of cellulose triacetate fibers are dyed at 100 ° C. for 1 hour. You get a yellowish red coloration of very good quality, fastness to heat, rubbing and light.

g) 20 g of cellulose 2 1/2 acetate fibers are in a liquor of 600 ml of water, 1 g of Marseille soap and 02 g of the one mentioned in example la) in fine Distribution brought dye mixture dyed at 750 for 1 hour. You get one brilliant pink color lit good rubbing, light and water fastnesses.

EXAMPLE 2 a) 160 g of chlorinated phenoxyethanol (produced by introducing chlorine into phenoxyethanol at 250C), 12 g of anhydrous Pottasohe and 40 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone are heated to 150-160 ° C for 10 hours. After 200 ml of methanol and 10 μl of glacial acetic acid have been added, the paraffin mixture is filtered off with suction, washed with 100 ml of methanol and warm water and dried. 41.4 g of a dye with 6-3 P chlorine content are obtained.

b) 1 g of this dye mixture prepared in this way, finely divided is placed in a dye bath, 100 g of polyester fibers (polyethylene terephthalate) in 3 l of water contains. The dyeing is carried out for one hour at 125 ° -130 ° C. under pressure and one obtains a clear, strong yellow-tinged red dyeing with very good fastness properties.

Example 3 a) 8.4 g of 1-amino-4-hydroxy-2 - (# - bromohexoxy) anthraquinone (prepared from the <J-hydroxyhexoxy compound with boiling 4 above hydrobromic acid) are dissolved in 60 ml of N-methylpyrrolidone with a mixture of 1, 17 g of phenol, 0.8 g of o-chlorophenol, 0.8 g of p-chlorophenol and 1 g of powdered sodium hydroxide were heated to 70-80 ° C. for 2Q hours. After adding 80 ml of methanol and a little glacial acetic acid, the dye mixture is filtered off with suction, washed with methanol and water and dried. 5.6 g of dye with a chlorine content of 4.7% are obtained.

b) the 8.4 g of 1-amino-4-hydroxy-2 - (# - bromohexoxy) anthraquinone are replaced with 8.7 g of 1-amino-4-hydroxy-2 - (# - mesyloxyhexoxy) anthraquinone, ao is obtained analogously a dye mixture of the formula given.

c) A pre-cleaned and heat-set fabric made of polyethylene tere phthalate is printed with a paste consisting of the following components: 20 g of the dye prepared according to Example 3a) in finely divided form, 520 g of water 450 g crystal rubber 1s2 and 10 g methyl cresotinate.

An alginate thickening can also be used instead of crystal rubber Find. The printed and dried goods are used for dye fixation at 2000C Treated with hot air or at 190 - 20000 over a high-performance stenter frame or driven through a condenser. The exposure time is 30 - 60 seconds. The fixed pressure obtained is then rinsed with cold water 1-2 g / l anion-active detergent Soaped at 70 - 80 ° C for approx. 10 minutes, first hot, then rinsed cold and dried. A clear red print is obtained very good fastness to light and sublimation.

Similarly, if you get a brilliant pink print you will win instead of polyethylene terephthalate fibers, cellulose triacetate, polyamide or polyurethane fibers begins.

Example 4 5.1 g of 1-amino-2,4-dihydroxy-anthraquinone, 2.2 g of anhydrous soda, 6.5 g of brominated p-toluenesulfonic acid (β-phenoxyethyl ester) (Br - 16.3%, produced by bromination in carbon tetrachloride at room temperature ) and 40 ml of anhydrous nitrobenzene are heated to 150-160 ° C for 3 hours. It is allowed to cool, diluted with 50 ml of methanol and the dye mixture is filtered off with suction.

After washing and drying, 5.6 g of dye with a bromine content are obtained of 10.2% obtained, which dyes polyester materials in clear red tones.

b) Replace 5.1g of 1-amino-2,4-dihydroxy-anthraquinone with 5b1g l-Amino-3,4-dihydroxy-anthraohinone, eo is obtained analogously to 5.8 g of the isomeric dye mixture with 9 to 8% bromine, which colors polyester materials in real bluish red tones.

Example 5 9 g of 1-amino-2,4-dihydroxy-anthraquinone are dissolved in 50 ml of N-methylpyrrolidone. After adding 4 g of anhydrous potash and 12 g of brominated phenylethyl bromide (Brov4ehalt 45 O, the reaction mixture is heated to 13000 for 2½ hours. It is then diluted with 50 ml of methanol, the dyestuff mixture which has separated out is suctioned off and washed with methanol and water , 2 g of a dye mixture with 7.3% bromine content, which dyes polyester materials in real yellowish red tones.

Example 6 In a mixture of 60 ml of N-methylpyrrolidone, 2.15 g of brominated phenol with a bromine content of 33% (obtained according to the information in Organic Syntheses I, p. 122 by bromination in carbon tetrachloride), 1.17 g of phenol and 1 g of powdered sodium hydroxide are 8.4 g of 1-amino-4-hydroxy-2- (O-bromopentoxy) anthraquinone (obtained from the sulfoester of l-amino-4-hydroxy-2- (W-hydroxypentoxy) anthraquinone and hydrogen bromide acid) and heated to 70-80 ° C for 4 hours. After cooling, it is diluted with 80 ml of methanol and a little glacial acetic acid, the precipitated dye mixture is filtered off with suction and washed with methanol and water. This gives 78 g of a dye with a bromine content of 9.6%, which dyes polyester materials in real red shades.

EXAMPLES 7-45 Analogously to the information in Examples 1-6, the dye mixtures listed in Table 1 are obtained with the halogen contents indicated in column 6, which give the nuances indicated in column 7 on polyester materials.

Table 1 Example D1 D2 A 3 ORX-Ar- (Ha1) color on polyester 7 HH NH2 OH O (aO8ro, 6 yellowish red 8 HH NH2 OH OCaH401 yellowish red cH3 9 HH NH2 OH OCzH ~ O g BrO3 yellowish red 10 II II H2 OH OCH4058ro yellowish red 11 HH NH2 OH OC2HeO- to ßrO. yellowish red 12 HH NH2 OH OC2fl9Og yellowish red 13 H EI NH2 OH ° C294 Nd-CG a6 NY - IsS ct pink 14 HH H2 OH ° (3 H6 tinged red 15 II H NH2 OH o (cHa <o) 8roit yellowish red 16 HH H2 OH o (CFi-CW20) 343 BrO, 8 yellow, 3-tone red 17 HH äH2 OH Ocs 98 ° 4 ° ew yellowish red 18 HH bIH2 OH ocsHiooCL46 yellowish red 19 HH 2 OH OCHa -CHwCH3 pink O.8r03 20 HH OH NH2 OCH «CH ce2 0 atoæ4 pink OH 21 HH OH NH2 ob \ - tCH2 ~ ° e 8ru./ yellowish red 22 5-Cl H NH2 OH OC ~ O 4 orO6 bluish red 29 6-C1 H NH2 OH OC2 H-5 to ar 0.3 bluish red 24 7-C1 H NH2 OB OC, OH O - (/ lird, S bluish red 25 8-Cl H NE2 OH oceH4CQI8rost $ bluish red Example o, D2 AB Cj-RX-Ar- (Hal color on polyester n 26 6-F 7-F NH2 OH OC2 H4 oQ- OsS bluish red 27 6-C1 7-C1 NH2 OH OCa Hv o zu8r02 bluish red c 04 26 HH OH OH OCgHqcH3 orange 29 II H OH 1 OH, OC2H4 ° X BrO s orange 30 HH OH OH oC2840 [to -O3 ßrO6 orange 31 II H OH OH 0canOr4s orange 32 HH OH OH OC HrlioQoC3Hj orange 33 HH II NH2 MH2% ° tCt0t5 violet 34 HH NH2 NH2 HO - BF 6r purple , Or6'3, CH3 35 HH MH2 OH OCa d H4 C3 yellowish red 36 HH OCaO yellowish red CIS'CH CH3 37 H NS2 4 2 OH OC2880- S br ° .2 yellowish red 38 HH NE2 OH OCa CO SCHS yellowish red -T 39 EH NE2 OH 0C3OCL, o, sd, b CC o, S yellowish red 40 HH MH2 OH 4Ht ABro, yellowish red 41 HH NH2 OH OC5HsoO e .1 yellow tinged red 42 HH NH2 OH O (G 3% CH3ro3 yellowish red 43 HH NH2 OH O-CHi-CHg CHu yellowish red 44 HH NH2 OH O-CH2-CYICtb- o- B'6s yellow-tinged red Cas 45 HH MH2 OH OCW16 red Example 46 5.1 g of 1-amino-2,4-dihydroxy-anthraquinone are dissolved in 40 ml of N-methylpyrrolidone, 1 g of anhydrous potassium carbonate is added and, after the addition of 6.5 g of brominated phenoryethyl bromide (bromine content 48%, obtained by bromination), it is heated of phenoxyethyl bromide in carbon tetrachloride) for 1 hour to 80-90 ° C. After cooling, it is diluted with 80 ml of methanol, 20 ml of water and 1 ml of glacial acetic acid and the dyestuff which has separated out is filtered off with suction. 5.2 g of the specified compound with a bromine content of 7.7% are obtained, which gives true red colorations on polyester materials.

Example 47 1.6 g of brominated phenol (bromine content 33%), 1.6 g of a mixture of equal parts of o- and p-chlorophenol and 1 g of sodium hydroxide are stirred in 60 ml of N-methylpyrrolidone at 40 ° C. for one hour. 8.4 g of 1-amino-4-hydroxy-2- (W-bromohexoxy) anthraquinone are then introduced and the temperature is increased to 70-80.degree. The mixture is stirred for 3 1/4 hours at this temperature and, after cooling, diluted with 120 ml of methanol and a little glacial acetic acid.

The precipitated dye mixture is filtered off with suction, with methanol and Water washed and dried. 7.8 g of dye with 4.2% chlorine and 4.8 ffi bromine, which has a clear red color with good fastness properties on polyester fibers results.

Example 48 a) 6 g of 1-amino-4-hydroxy-2- (2-phenoxyethoxy) anthraquinone are suspended in 80 ml of concentrated aqueous hydrochloric acid.

3 g of bromine are added to the reaction mixture at room temperature and stirred for 3 hours. It is then added to 200 ml of water and 20 ml of sodium bisulfite solution are added added, sucks off the precipitate and washes neutral. 6.8 g of a dye mixture are obtained which contains 15.8% bromine (calc .: for monobromine - 17.6 96).

b) With 1 g of the dye mixture prepared according to Example 1 a that has previously been finely divided in the presence of dispersants, 100 g of polyethylene terephthalate fibers in 4 l of water in the presence of 15 g of methyl o-cresotinate stained as a carrier for 2 hours at 1000C and pH 4.5. You win a brilliant yellowish tint Pink color, which is due to the very good structure, high washing, heat setting, rubbing and Lightfastness is excellent.

A similar coloration is obtained when using polyester fibers those from 1,4-bis (hydroxymethyl) cyclohexane and terephthalic acid are used.

c) With 1 g of the mentioned in Example 1 a), previously with the usual Auxiliaries in finely divided dye mixture are 100 g of polyester fibers (Polyethylene terephthalate) in 3 l of water for 1 hour at 125 ° -1300 ° C. under pressure colored. A clear, strong pink coloration with good fastness properties is obtained.

d) With 1 g of the dye mixture mentioned in Example 1 a), the one has previously brought into fine distribution according to the usual methods, become 100 g of polyamide fabric dyed in 4 l of water for 1 hour at 1000.degree. The tissue will then rinsed warm and cold and dried. A clear pink color is obtained very good wash and lightfastness.

Instead of polyamide fibers, polyurethane fibers can be used with equal success use.

e) With 1 g of the dye mixture prepared according to Example 1 a, this beforehand in fine distribution using the auxiliaries customary for this purpose was brought, 6 g of fatty alcohol sulfonate and 3 l of water, a dye bath is prepared, in which 100 g of cellulose triacetate fibers are dyed at 100 ° C. for 1 hour. You get a yellowish red dye with very good wash, heat-setting, rub and lightfastness.

f) 20 g of cellulose 2 1/2 acetate fibers are in a liquor of 600 ml of water, 1 g of Marseille soap and 0.2 g of that mentioned in Example 1 a), in fine Distribution of the dye mixture obtained was colored at 75 ° C. for 1 hour. You get a brilliant pink color with good rub, light and water fastness.

Example 49 a) 6 g of 1-amino-4-hydroxy-2- (2-phenoxyethoxy) anthraquinone are heated in 60 ml of glacial acetic acid together with 1.57 g of bromine to 90-100 ° C. for 10 minutes. then pour the reaction mixture into 200 ml of water to which 20 ml of sodium bisulfite solution has been previously added has added, sucks off the precipitate, washes neutral with water and dries. 6.5 g of a dye containing 9.8% bromine are obtained.

b) 1 g of this ßo prepared dye mixture in fine distribution is placed in a dye bath, 100 g of polyester fibers (polyethylene terephthalate) in 3 s of water contains. The dyeing is carried out for 1 hour at 125.degree.-130.degree. C. under pressure and an clear, strong yellow-tinted color with very good fastness properties1 c) A pre-cleaned and heat-set fabric made of polyethylene terephthalate is used with a paste consisting of the following components printed: 20 g of the example 2 a) produced dye in fine distribution, 520 g of water, 450 g of crystal gum 1: 2 and 10 g of methyl cresotinate.

An alginate thickening can also be used instead of crystal rubber Find. The printed and dried goods are used for dye fixation at 2000C treated with hot air or

at 190 - 2000C via a high-performance stenter frame or by a Condenser driven. The duration of the action is 30 - 60 seconds. The fixed print obtained is then rinsed with cold water with 1-2 g / l of anionic active substances Soaped detergent at 70 - 800C for approx. 10 minutes, rinsed first with hot and then with cold and dried. A clear print of very good lightfastness and sublimation fastness is obtained.

Similarly, one wins a brilliant pink print, though instead of polyethylene terephthalate fibers, cellulose triacetate, polyamide or Uses polyurethane fibers.

Example 50 a) 6 g of 1 1-amino-4-hydroxy-2- (2-phenoxyethoxy) anthraquinone o Suspended 60 ml of concentrated hydrochloric acid. After adding 6.3 g of bromine the reaction mixture was stirred for 12 hours at room temperature. Then you give in a mixture of 200 ml of water and 20 ml of sodium bisulfite solution, sucks off and washes neutral with water. 8 g of a dye mixture containing 25.3% bromine are obtained contains (calc .: for dibromine = 29.95%).

b) A fabric made of polyester fibers (polyethylene terephthalate) is on impregnated the padder with a liquor containing 20 g of dye per liter according to the example 3 a) contains, which is finely divided beforehand in the presence of dispersants brought. The tissue is squeezed off to a weight increase of 70% and dried in a floating nozzle dryer or drying cabinet at 80 - 1200C. Afterward the fabric is placed in a stenter or nozzle hotflue for approx. 45 seconds at 190 - 2200C treated with hot air, then rinsed, possibly reductive aftertreatment, washed, rinsed and dried. The reductive aftertreatment for removal of dye components adhering to the surface of the fibers can be done in this way that one with the fabric at 25 0C in a 3 - 5 cm3 / l sodium hydroxide solution of 380 Bé and 1 - 2 g / l liquor containing sodium dithionite (conc.) Is received within approx. Heated to 70 ° C. for 15 minutes and left at 0 ° 70 ° C. for a further 10 minutes. Afterward is rinsed hot, acidified with 2 - 3 cm3 / l 85 pointer formic acid at 500C, rinsed and dried. A brilliant pink color is obtained, which is distinguished by its high color Dye yield, very good structure and very good fastness properties, in particular good thermosetting, washing, rubbing and light fastness properties.

A similar coloration is obtained if instead of polyethylene terephthalate fibers Polyester fibers made from 1,4-bis (hydroxymethyl) cyclohexane and terephthalic acid are used.

Similarly, a brilliant pink color is obtained if you instead of polyethylene terephthalate fibers, cellulose triacetate fibers are used and the thermal insulation is carried out at 215 ° C or when using polyamide or polyurethane fibers is used and the thermal insulation is carried out at 190-2150C.

c) Dissolve 6 g of 1-amino-4-hydroxy-2- (2-phenoxyethoxy) anthraquinone at 10 - 150 ° C in 60 ml of 80 point sulfuric acid, the reaction mixture is mixed with some iodine and 9.4 g of bromine, then stirred for 8 hours at 200 ° C. and then added with 56 ml of sulfuric acid monohydrate is obtained after stirring for a further 10 hours at 200C and the usual work-up with ice and bisulfite solution, 9.8 g of dye mixture with a bromine content of 37.5 96 (calc .: for tribrom = 39.1 96), which according to the information in Example 3 b) thermosolated on polyethylene terephthalate fabric, also one provides a strong pink color with good fastness properties.

Example 51 a) 6 g of 1-amino-4-hydroxy-2- (2Lkresoxyethoxy) anthraquinone -Produced by the etherification of 1-amino-4-hydroxy-2-phenoxyanthraquinone with the Reaction product of ethylene oxide and the mixture of 70% m-cresol and 30% p-cresol - are suspended in 60 ml of water and mixed with 1.57 g of bromine. One stirs one Hour at room temperature, sucks the precipitate, washed with water and diluted Sodium bisulfite solution and dries. 6 g of a dye mixture with a bromine content of 6.196 are obtained.

b) 1 g of the dye mixture prepared according to Example 4 a), the has previously been finely divided in the presence of dispersants dispersed in 400 parts of water. 100 parts are dyed in the dyebath obtained Polyester fibers (polyethylene terephthalate) in the presence of 15 parts of methyl o-cresotinate as a carrier 120 minutes at boiling temperature. A clear yellow-tinged red is obtained Dyeing with good fastness properties, in particular good lightfastness and sublimation fastness.

Example 52 a) 30 g of 1-amino-4-hydroxy-2- (2'-phenoxyethoxy) anthraquinone are suspended in 300 ml of methylene chloride and at room temperature with 7.85 g of bromine offset. The mixture is then stirred for 2 hours at room temperature and the precipitated is filtered off Dye off and washed with water and sodium bisulfite solution. 28.5 are obtained g of a reaction product containing 7.5% bromine. Removed with otherwise the same If the methylene chloride is worked by distillation, 31.5 g of dye are obtained with a bromine content of 8.0%.

b) Is carried out in the same way as described in Example 5 a) the bromination in 300 ml of chloroform by, 31 g of dye are obtained with a Bromine content of 8.5%. Replace the 300 ml of methylene chloride with 300 ml of orthodichlorobenzene which is removed by steam distillation after the end of the bromination, so obtained using 6.3 g of bromine, 30.1 g of dye with 6.6 bromine content.

With the dyes prepared by the methods described above is achieved on polyester materials and the dyeing processes mentioned in Examples 1-4 strong, clear red dyeings with very good fastness properties.

Example 53 a) 6 g of 1-amino-4-hydroxy-2- (2'- 02 -isopropylphenoxyI-ethoxy) anthraquinone are in 60 ml of concentrated hydrochloric acid with 2.2 g of bromine for 1 1/2 hours at room temperature touched. After working up with water and dilute sodium bisulfite solution 6 g of dye mixture obtained containing 9.0 96 bromine.

b) With 1 g of this, finely dispersed beforehand with the usual tools applied dye are 100 g of polyester fibers (obtained by polycondensation of terephthalic acid with dimethylolcyclohexane) in 300 parts of water for 1 hour dyed under pressure at 125 - 1300C. A clear, yellowish-tinged red coloration is obtained of good fastness properties.

Example 54 4 g of 1-amino-4-hydroxy-2- (2'- "-dimethylphenoxy7-ethoxy) anthraquinone are suspended in 40 ml of 15 point hydrochloric acid and together with 1.57 g of bromine 1 1/2 Stirred for hours at room temperature. After the usual work-up, 4.3 g obtained a dye mixture containing 13.1, bromine and polyester fibers in strong, yellow-tinged red tones.

Example 55 Substitute for the starting material used in Example 7 by 5.5 g of 1-amino-4-hydroxy-2- (2 '- 1', 6 "-dimethylphenoxy3-ethoxy) -anthraquinone and carries out the bromination with 2.2 g of bromine in 80 ml of concentrated hydrochloric acid, this gives 6.1 g of a dye mixture with a bromine content of 10.5%, the polyester material colors in strong, yellow-tinged red, real tones.

Example 56 a) 4 g of 1-amino-4-hydroxy-2- (X-phenoxy-hexanoxy) -anthraquinone are in 60 ml of concentrated hydrochloric acid 1 1/2 hours at room temperature with 0.63 g bromine stirred. The dye worked up in the usual way, 4.1 g of which was obtained contains 7.296 bromine.

b) A fabric made of polyethylene terephthalate fibers is at room temperature impregnated with a clear, red solution containing 10 g of dye according to Example 9 a) and contains 7 g of nonylphenol heptoethylene glycol ether in 983 g of tetrachlorethylene. To the squeezing to a weight increase of 60%, the tissue is one minute 800C dried. The dye is then heated by heating the Tissue fixed to 190 - 220 ° C. Then by briefly rinsing with cold tetrachlorethylene the small, unfixed dye content washed out. Receives after drying you get a clear, yellowish red color, which is characterized by a good structure, as well characterized by their good fastness properties.

If tetrachlorethylene is replaced by the same amount of 1,1,2-trichloroethane, Pentachloroethane, 1,2-dichloropropane, 2-chlorobutane, 1,4-dichlorobutane, perfluoro-n-hexane, 1,2,2-trifluorodichloroethane, trifluoropentachloropropane, chlorobenzene, flurobenzene, Chlorotoluene or benzotrifluoride, equivalent red colorations are achieved.

Example 57 a) 10 g of 1 amino-4-hydroxy-2- (2'-phenylamino-ethoxy) -anthraquinone are dissolved at 15 - 200C in 80 ml 90 pointer sulfuric acid. After adding a little iodine and 4.4 g of bromine, the reaction mixture is stirred for 8 hours at room temperature. Then it is added to 500 g of ice containing 20 ml of sodium bisulfite solution, sucked the Precipitate and wash neutral with water. After drying, 10.2 g of dye mixture with 5.0, 'bromine obtained.

b) The same starting material is brominated instead of in sulfuric acid in concentrated hydrochloric acid with 5.55 g of bromine for 2 hours at room temperature 12 g of dye with 17.9% bromine were obtained.

c) With 1 g of dye according to Example 10 a) or 10 b) in fine distribution 100 g of polyamide fabric are passed in 4000 ml of water for 1 hour at 1000C. The fabric is then rinsed warm and cold and dried. You get one clear, red dyeing with good fastness properties.

Example 58 a) In a suspension of 6 g of 1-amino-4-hydroxy-2- (3'-phenylpropoxy) anthraquinone 6.28 g of bromine and a little iodine are added to 80 ml of concentrated hydrochloric acid and the mixture is stirred Reaction mixture for 12 hours at room temperature. Then with water and Sodium bisulfite solution worked up. 6.5 g of dye mixture are obtained with a Bromine content of 21.4.

b) If the bromination is carried out in 90 instead of concentrated hydrochloric acid ml of 80 point sulfuric acid, 6.8 g of dye are obtained from 6 g of starting material with 19.4, bromine.

c) 1 g of the previously in the presence of conventional dispersants in fine Distribution of the dye according to Example 11 a) or 11 b) is in 400 ml Water dispersed. 100 parts of polyester fibers are dyed in the dyebath obtained (Polyethylene terephthalate) in the presence of 15 parts of methyl o-cresotinate as a carrier 120 minutes at boiling temperature.

A clear yellow-tinged red dyeing with good fastness properties is obtained, especially good lightfastness and sublimation fastness.

Example 59 a) 12 g of 1-amino-4-hydroxy-2- (2'-phenylethoxy) anthraquinone are suspended in 120 ml of concentrated hydrochloric acid. After adding some iodine and 6.28 g of bromine are stirred for 65 hours at room temperature, working in the usual way and receives 12.8 g of dye with 13.5% bromine.

b) With 1 g of this previously with the usual tools in fine division Brought dye are 100 g of polyester fibers (polyethylene terephthalate) in 3000 ml of water passed under pressure for 1 hour at 125-1300C. You get a strong, yellow-tinged red dyeing with good fastness properties.

EXAMPLES 60-171 If, as indicated in Examples 1-12, bromination is carried out in the same way with the dyes indicated in the table, dye mixtures with the indicated bromine contents are obtained which achieve the indicated nuances on polyester materials. At- D1 D2 AB ORX-Ar Br% nuances game polyethylene ~ terephthalate 60 HH NH2 OH OC2H4ffi '9.2 yellowish CH3 61 HH NH2 OH OC2H409 6.5 CH3 62 HH NH2 OH oC2H40iCH3 11.4 n 63 HH NH2 OH OC2H409 7.3 n C2H5 64 HH NH2 OH OG2H40XCH (CH3) 2 4.2 65 HH NH2 OH OC2H40oc4H9 8.4 66 HH NH2 OH OC2H40oC (CH3) 2 6.5 67 HH NH2 OH OC2H40 <) C8H1 68 HH NH2 OH OC2H40 5.8 69 HH NH2 OH OC2H40 8.7 n kL 70 HH NH2 OH ° C2H4 ° 9 7.9 ff CH3 CH3 At- DDAB ORX-Ar Br% nuances game 1 2 polyethylene terephthalate 71 HH NH2 OH to OC3H oC2H4043CH (CH3) 2 4.2 yellowish 3 72 HH NH2 OH OC2H40oF3 3.2 VI 73 HH NH2 OH OC2H409 4.8 n Cl Cl 74 HH NH2 OH OC2H40 <) 2.3 n CH3 75 HH NH2 OH OC2H409 8.9 n CH3O 76 H; H NH2 OH OC2H4OOCH3 8.2 77 HH NH2 OH OC2H4O 7.8 VI LTI 78 HH NH2 OH 2 4 (X 2 4 17.2 n 79 HH NH2 OH% 2H4 ° H 12.4 n 80 HH NH2 OH OC2H40tFSCH3 9.3 n 81 HH NH2 OH ° C2H4 ° oe 11 s 8 n 82 HH NH2 OH OC2H40 CH2t 10.5 II 83 HH NH2 OH oC2H4053 10 s 8 dd At- DDAB ORX-Ar Br 96 shades game 1 2 terephthalate 84 HH NH2 OH OC2H4O 6.9 yellowish Red CH, CH3 CH3 OCH 85 HH NH2 OH oC2H402 7.6 86 HH NH2 OH OC2H4O; 4.3 86 HH NH, OH 4.9 " 87 HH NH2 OH OC2H40¾) 3.1 n 88 HH NH2 OH oC2H40t3 5.9 89 HH NH2 OH oC2H40t, C3 4.8 90 HH NH2 OH OC2H40X13 r 7.2 a 91 HH NH2 OH OCH (CH3) -CH20 <) 111.3 n 92 HH NH2 OH OCH (CH3) -CH2 ° C 0.9 g 93 HH NH2 OH ° C «CH3) CH2 (<C (CH3? 3 & 1I 94 HH NH2 OH OCH (C2H5) -CH2O 6.8 n 95 HH NH2 OH OCH (C2H5) -CH2 ° 5s8 n 96 HH NH2 OH O (CH2CH2O) 2 7 s 3 n At- DD. AB ORX-Ar Br 9 «nuances game 1 2 PolyäthyX- terephthalate 97 HH NH2 OH o (CH2CH20) 3ß3 6.5 yellowish tint 98 HH NH2 OH ° (CH2) 3 ° 8.8 II 99 HH NH2 OH O (CH2CH2CH20) 2 <) 12.1 100 HH NH2 OH O (CH2) 40t) 10.6 n 101 HH NH2 OH O (CH2) 4-0CH3 4.9 102 HH NH2 OH O (CH2) 4-O 7.3 103 HH NH2 OH ° (CH2? 5 ° t 5.2 104 HH NH2 OH O (CH2) 5-0 4.1 105 HH NH2 OH O (CH,) 6'ot 7.1 n 106 HH NH2 OH O (CH2) 7-0bCH3 3.6 n 107 HH NH2 OH O (CH2) 8-O 2.1 108 HH NH OH O (CH2) 9-O 5.6 109 HH NH2 OH O (CH3) 8.4 n 110 HH NH? OH O (CH2) 4-0CH2 7.3 n 114 HH NH2 OH O (CH2) 4-OCH2oCH3 6.7 If 112 HH NH OH O (H2) 3-oCH2 8.9 " At- D D2 AB ORX-Ar Br 96 shades game 1 2 polyethylene terephthalate Red 113 HH NH2 OH OC2H4-S 10.1 red 114 HH NH2 OH OC 2H4S 5.3 red 115 HH NH2 OH -C2H4NHd 15.3 bluish tint- pink 116 HH NH2 OH -C2H4NHeCH3 12.1 tt 117 HH NH2 OH -C2H4NHt3 9.7 118 HH NH2 OH -C2H4N (CH3) t) 6.3 " 119 HH NH2 OH -C2H4N (CH) XCH3 5.8 120 HH NH2 OH -C2H4N (C2H5) e 6.2 121 HH NH2 OH -C2H4N (C2H40H) 43 3.8 If 122 HH NH2 OH -CH2CH (OH) -CH20t 5.1 red 123 HH NH2 OH -CH2-CH (C) @ <H2 <c; 10,210.2 o 124 HH NH2 OH CH2-CH (0H> (E2 (> a3 7.7 n 125 HH NH2 OH -ai2 (oH) -cs 6.3 n 126 HH NH2 OH H2H (0N) -C-NH "5.3 bluish tint - pink 127 HH NH2 OH CE2CH (Ot) "CH2oe 8.2 red 128 HH NH2 OH CH (f20CH3 1.1 red At- DDAB ORX-Ar Br% nuances aut game 1 2 polyethylene terephthalate 129 HH NH2 OH CH2CH (0 o Br) -CH20 14.3 red 130 HH NH2 OH CH2CH (O) -CH2OH 7.2 red 131 HH NH2 OH CH2CH (CH3) - (CH2) 3 6.6 yellowish 132 HH NH2 OH (CH2C (() 2-CH2 b ~ ° 4 3.8 ft 133 HH NH2 OH (CH2) 3-O-CH2CH2-O 4.9 134 Cl H NH2 OH OC 2H, e 7.9 pink 135 6 FH NH2 OH OC2H40 9.1 3 9 s 1 n 136 7 CH NH2 OH ° C2H4 8.3 137 7 FH NH2 OH OC3H6 4 10.2 138 5 C1 H NH2 OH OC2H40 5.1 139 5 CH NH2 OH OC3H60 e 9.6 140 8 C1 H NM OH ° C2H4 ° 4 7s5 n 141 6 C 7 XH OH OC2H4 4 11.2 142 6 F 7F NH2 OH OC2H40 at 8.1 143 HH NH2 OH e 3.8 yellowish ro 144 HH NH2 OH OCH2CH (O) - ° t 7.3 sBpie-l D1 D2 AB ORX-Ar Br% nuances terephthalate 145 HH NH2 OH OCH2CH (O) -OCH3 11.2 yellowish 146 HH NH2 NH2 OC2H40 4 9.7 purple 147 HH NH2 NH2 OC2H4OH3 7.3 n 148 HH NH2 NH2 OC2H40 9 6.8 cH (cH3) 2 149 HH NH2 NH2 ° C2H4 t 11.2 n 150 HH NH2 NH2 OC2H4CH3 5.3 n 151 HH NH2 NH2 ° C3% 4.8 ff 152 HH NH2 NH2 OC3H60 e 7.9 I1 153 HH NH2 NH2 ° (CH2) 4 ° e 10.5 If 154 HH NH2 NH2 O (CH2) 50 7.8 n 155 HH NH2 NH2 OCH (CH3) CH2 ° e 6.6 1I 156 HH NH2 NH2 O (CH2CH20) 2 e 5.9 n 157 HH NH2 NH2 OC2H40 at 11.1 n 158 HH OH OH OC2H40 4 12.8 orange 159 HH OH OH OC2H40 9. 24.3 C2H5 B D1 D2 AB ORX-Ar Br 96 shades game polyethylene terephthalate 160 HH OH OH OC2H. 40QCH3 14.6 orange 161 161 HH OH OH oC2H4045 7.5 CH3 <H3 162 HH OH OH O (CH2) 3043 21.6 n 163 HH OH OH ° (CH2) 4 ° 43 10.3 n 164 HH OH OH ° (CH2) 5 ° 93 6.7 165 HH OH OH O (CH2) 6O 7.3 n 166 HH OH OH OCH2-CH (OH) CH2043 9.1 167 HH OH OH oC2H443 5.8 n 168 HH OH OH 2,443 2 4 5.8 n fli9 HH OH OH OCOH 4.2 170 HH OH OH OC, H, NH 'oC3H64 6.1 171 HH OH OH OC2H4NE 16.3 n Example 172 6 g of 1-amino-4-hydroxy-2- (2-phenoxyethoxy) anthraquinone are introduced into a mixture of 40 ml of water and 20 ml of concentrated aqueous hydrochloric acid, and 1.89 g of bromine are added. The reaction mixture is stirred for 6- 1/2 hours at room temperature, then diluted with 100 ml of water, the precipitate is filtered off with suction and washed with water and dilute sodium bisulfite solution. After drying, 6.3 g of a dye mixture are obtained which contains 9.1 96 bromine and dyes polyester fibers in real red shades.

If the bromination is carried out in 60 ml of 10 instead of dilute hydrochloric acid If sulfuric acid shows through, 6.1 g of dye containing 8.3 bromine are obtained, the Real red colorations are also achieved on polyester materials.

Claims (20)

Claims 1. Water-insoluble anthraquinone dye mixtures of the formula in which A and B for an amino or hydroxyl group, R for an optionally substituted and / or oxygen-interrupted alkylene radical, X for a direct bond, oxygen, sulfur or an imino group optionally substituted by alkyl groups, Ar for an optionally substituted aryl radical, D1u. D2 represents hydrogen or halogen, Hal represents chlorine or bromine and n represents an average of 0.1 to 2.5. 2. Dyestuff mixtures according to claim 1, wherein A is an amino group, B an amino or hydroxyl group, D1 and D2 hydrogen and X oxygen or a direct one Mean bond, and R, Ar, Hal and n have the meanings given. 3. Dyestuff mixtures according to claim 1, wherein A is an amino group, B a hydroxy group, D 1u. D2 hydrogen and Ar one if necessary 1-2 times C1 -C8-alkyl radicals substituted phenyl radical, x oxygen or a direct bond and R is a straight-chain or branched C2 -C8 -alkylene radical and Hal and n have the meaning given. 4. Dyestuff mixtures according to claim 1, wherein A is an amino group B a hydroxyl group R a straight-chain C2-C6-alkylene radical x oxygen or a direct bond, Ar an optionally substituted 1-2 times by C1-C4-alkyl Phenyl radical, branched alkyl radicals being in the p-position. D1 and D2 hydrogen Hal bromine and n average a number of 0.2 to 0.8 mean. 5. Dyestuff mixtures according to Claim 1 of the formula 6. Dyestuff mixtures according to Claim 1 of the formula 7. Dye mixtures according to Claim 1 of the formula 8. Dyestuff mixtures according to Claim 1 of the formula 9. Process for the preparation of dye mixtures. characterized in that compounds of the formula wherein A, B, D1 and D2 have the meaning mentioned in claim 1 and E represents an exchangeable substituent, with compounds of the formula HO-RX-Ar- (Hal) wherein R, X, Ar, Hal and n are those mentioned in claim 1 Have meaning, in the presence of basic compounds and optionally in the presence of an organic solvent at elevated temperatures. 10. Process for the preparation of dye mixtures, characterized in that one anthraquinone compounds of the formula wherein A, B, R, D1 and D2 have the meaning given in claim 1 and T represents chlorine, bromine or an arylsulfonyloxy or alkanesulfonyloxy group, with compounds of the formula HX1-Ar- (Hal) wherein Ar, Hal and n are the have the meaning given in claim 1 and X1 is oxygen, sulfur or an amino group optionally substituted by alkyl groups, is reacted in the presence of basic compounds and optionally in the presence of an organic solvent at elevated temperatures. 11. A process for the preparation of dye mixtures, characterized in that one anthraquinone compounds of the formula in which A, B, D1 and D2 have the meaning given in claim 1, with compounds of the formula URX-Ar- (Hal) in which R, X, Ar, Hal and n have the meaning given in claim 1 and u is chlorine, bromine or an arylsulfonyloxy group is reacted in the presence of basic compounds and an organic solvent at elevated temperatures. 12. Process for the preparation of dye mixtures, characterized in that one anthraquinone compounds of the formula in which A, B, R, X, D1 and D2 have the meaning given in claim 1 and Ar represents an optionally substituted aryl radical on the aryl radical Ar is brominated. 13. The method according to claim 12, characterized in that one such Anthraquinone compounds of the formula given in claim 9, wherein A is a Amino group, B for an amino or hydroxyl group, D1 and D2 for hydrogen and X is oxygen or a direct bond and R and Ar are those in claim 1 have mentioned meaning, brominated. 14. The method according to claim 12, characterized in that such anthraquinone compounds are brominated which of the formula correspond in the R1 for a straight-chain C2-C6- (preferably C2-C4) -alkylene radical, X for oxygen or a direct bond and Ar1 for a phenyl radical, which is optionally substituted 1 to 2 times by a C1-C4-alkyl radical, preferably C1- C2-alkyl radical is substituted. 15.Verfahren according to claim 1, characterized in that the compound of formula is brominated. 16) Anthraquinone dyes of the formula wherein n stands for the number 2, and the other substituents have the meaning given in claim 1. 17) Anthraquinone dyes of the formula in which n stands for 1 or 2, A and B simultaneously stand for OH or at the same time for NH2 and the other substituents have the meaning given in claim 1. 18) Anthraquinone dyes of the formula where A is NH2, B is OH, R is C3 -C10-alkylene, X is 0, a direct bond or imino group optionally substituted by C1-C4-alkyl and Ar is phenyl optionally substituted by -1 to 3 C1-C4-alkyl groups. 19) processes for dyeing and / or printing synthetic fiber materials, characterized in that anthraquinone dye mixtures according to Claim 1 are used. 20) Mixtures of water-insoluble dyes consisting of the components of the formulas in which A, B, R, X, Ar, Hal, D1 and D2 are radicals of the same type as defined in claim 1.