DE2522612A1 - NEW ANTHRAQUINONE COMPOUNDS AND METHODS FOR MAKING THEM - Google Patents

Description

New Anthraquinone Compounds and Processes for Their

Manufacturing

The invention relates to anthraquinone compounds and their preparation.

The invention relates to new anthraquinone compounds which are characterized by the following general formula:

(D

wherein the nitro group is at the 6- and 7-positions on the anthraquinone ring sits, X is a chlorine or bromine atom and Υ is a chlorine or bromine atom or the group -NHR, in R, (A) is an unsubstituted or one with one or more chlorine atoms, methyl, ethyl, methoxy, ethoxy and / or phenoxy groups substituted phenyl group, (B) a hydrogen

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atom or (C) denotes the group -SO ₂ R ₃ , in which R, denotes an unsubstituted or a phenyl group substituted by one or more chlorine atoms or methyl radicals. Isomeric compounds can exist as mixtures. The term "mixtures" is used in the present description for a mixture of two isomeric compounds which differ with regard to the position of the nitro group, which is located on the anthraquinone ring on the one hand in the 6-position and on the other in the 7-position.

The compounds or mixtures according to the invention are in water insoluble. They have a high affinity for hydrophobic fibers, in particular for fibers made of polyethylene terephthalate, cellulose triacetate and the like, and the staining strength on the dyed Fiber is excellent.

The compounds according to the invention or mixtures of the general Formula (D can be obtained from 1,6- or 1,7-dinitroanthraquinone. Or mixtures thereof. These compounds are has never been used as precursors or intermediates for dye production.

The oC, <* I-disubstituted anthraquinones that prove to be excellent Offer starting components for the production of dyes, one has so far mostly from oC, oO-an thromachinondisulfonic acid on an industrial scale manufactured. The disulfonic acid compound

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obtained by disulfonation of anthraquinone in the presence of mercury as a catalyst. In view of the strong concerns that have arisen in recent years about the by Environmental pollution caused by mercury can be expected that this method method in the future, very strong will be restricted. Instead, as an effective measure, a way of working has gained increasing interest in as the starting component dinitroanthraquinone, which by di-. nitration of anthraquinone is obtained, is used.

It is known that in the dinitration of anthraquinone in addition to the desired main product, 1,5- or 1,8-dinitroanthraquinone 1,6- or 1,7-dinitroanthraquinone is obtained as a by-product in an amount of 20 to 30%.

From an industrial point of view, it is a significant technical advance if one succeeds in removing this by-product 1,6- or to utilize 1,7-dinitroanthraquinone and the mixture thereof.

The compounds of the formula (1) according to the invention in which X and Y each represent a chlorine or bromine atom, in particular the Mixtures and compounds of the formula

NH ₀

s, - X

(3)

ö χ
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wherein the nitro group is in the 6- or 7-position on the anthraquinone ring attached can be produced according to the invention by halogenation of compounds or mixtures of the formula

(2)

wherein the nitro substituent is in the position indicated above is available.

The compounds of the formula (1) according to the invention in which X is a chlorine or bromine atom and Y is a -NHR ₁ group, in particular the compounds or mixtures of the formula

(5)

wherein X and R, have the meaning given above and the nitro substituent is present in the positions given above can be obtained according to the invention by reaction of the compounds of the formula (3) with an amine of the general formula

H ₂ NR ₁ , (4)

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in R. (A) a phenyl group which is unsubstituted or substituted by one or more chlorine atoms, methyl, ethyl, methoxy, ethoxy and / or phenoxy groups, or (B) a
Group -SO ₃ R ₂ , in which R _{3 represents} an unsubstituted or a
with one or more chlorine atoms or methyl radicals substituted phenyl group is.

The compounds of the formula (1) according to the invention in which X
represents a chlorine or bromine atom and Y represents an HN group, in particular the compounds or mixtures of the formula

(7)

in which X has the meaning given above and the nitro substituent is in the positions given above on the anthraquinone ring can be prepared according to the invention by
Hydrolysis of the compounds of formula (5) wherein X is a
Chlorine or bromine atom and R 1 is the group -SO ₃ R ₃ , where R _{3 has} the meaning given above, in particular the compounds and mixtures of the formula

0 NIL

(6)

NHO ₂ SR ₂

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wherein X and R »have the meaning given above and the Nitro substituent present in the positions indicated above is.

The preparation of the compounds of the formula (2) has now become technically possible after it has surprisingly been found that in the implementation of 1,6- and 1,7-dinitroanthraquinone and their mixtures with ammonia, preferably in the presence of a solvent, those present therein in the 1-position Nitro group can be selectively converted into the amino group,

Particularly advantageous compounds according to the invention are those of (1) in which X is a chlorine or bromine atom and Y is a chlorine or bromine atom or for the group -NHR. stands in which R is a phenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, xthylphenyl, diethylphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl group, a hydrogen atom or a group -SO ₂ R _? means where R _{2 is} a phenyl, methylphenyl or chlorophenyl group.

In the mixture of 1,6-dinitro-anthraquinone and 1,7-dinitro-anthraquinone these two isomers can be present in any ratio to one another. A mixture is preferably used, in which the ratio of 1,6- to 1,7-dinitroanthraquinone of 40; 60 to 60:40.

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The compounds or mixtures of the formula (3) can be prepared in such a way that in the presence of sulfur. acidic, water or an organic solvent such as Benzene, nitrobenzene, o-dichlorobenzene, trichlorobenzene, toluene, Xylene, monochlorobenzene, dimethyl sulfoxide, dimethylformamide, Methanol, ethanol, isopropanol, 2-ethoxyethanol or ethylene glycol a halogenation agent such as chlorine or bromine with compounds or at a temperature in the range from 0 to 50 ° C Brings mixtures of formula (2) to the reaction.

Compounds or mixtures of the formula (5) can be used according to the invention win in such a way that one compounds or mixtures of formula (3) either in an organic solvent or in the presence of a large excess of the amine with an amine of the formula (4).

Examples of those which can be expediently used in this conversion reaction organic solvents are isopropanol, 2-methoxyethanol, 2-ethoxyethanol, n-amyl alcohol, ethylene glycol, benzyl alcohol, Diethylene glycol, Whore thy is ulfoxide, N, N-dimethylformamide, Nitrobenzene, chlorobenzene, toluene and xylene.

The reaction can be accelerated if, in the presence of an acid-binding agent, for example an alkali metal carbonate, -bicarbonates or -acetates heated.

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The reaction is effectively catalyzed with a copper catalyst such as copper dust, copper chloride, copper sulfate or copper acetate. At temperatures ranging from 50 to 150 ⁰ C, the relaying is ungs reaction after 30 minutes to 5 hours to completion.

After the reaction has ended, the reaction product can be obtained by cooling the reaction mixture to 20.degree. To 30.degree
and separating, for example filtering off, the product from the cooled mixture. Alternatively, the reaction mixture can be diluted with water, methanol or ethanol and the product can be separated off from the diluted mixture, for example by filtration. Alternatively, you can use the reaction product
also thereby gain from the reaction mixture that one from
This removed the solvent and the excess amine by steam distillation.

The compounds or mixtures of the formula (7) can be prepared according to the invention in such a way that compounds
or mixtures of the formula (6) in concentrated sulfuric acid
enters the resulting mixture from 30 minutes to 2 hours
stirred for a long time at 30 to 60 ° C, the reaction mixture poured into a lot of ice water, the separated crystals filtered off, washed with water and then dried.

The compounds or mixtures of the formula (1) according to the invention can be used to dye hydrophobic fibers such as polyethylene

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terphthalate. Appropriate dyeing methods for this are for example dyeing at high temperatures and / or using dye accelerators, printing, e.g. by the blind printing or rotary film printing process, or solvent dyeing.

If one or more compounds according to the invention of the formula (1) wants to dye a hydrophobic fiber, the compound is suitably mixed with a dispersant such as a naphthalenesulphonic acid-formalin condensate or a sodium salt of ligninsulphonic acid, kneaded well, then finely ground and dispersed and used as a dispersion dye used for dyeing.

The compounds according to the invention are excellent lightfast, they sublime well and are washable, they show excellent pH behavior and are alkali-resistant. You can therefore use together with reactive dyes when dyeing mixed fibers made of cotton and polyester. The invention Compounds of the formula (3) are very useful precursors for the manufacture of various dyes. The reactivity of the chlorine or bromine atom attached to the anthraquinone ring can be used.

In the examples below, in which advantageous embodiments the invention are illustrated in more detail, loading

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the specified parts and percentages mean parts and percentages by weight.

Example 1 :

29.8 parts of a mixture of 1,6- and 1,7-dinitroanthraquinone (80.2% purity, wherein 13.6% 1,8- and 1,5-dinitroanthraquinones were included) were added to 100 parts of nitrobenzene. The resulting solution was kept at 130 to 140 ° C, and gaseous ammonia was passed through for 20 hours pearled. The solution was then cooled. 100 parts of methanol were added. The resulting precipitate was filtered off. In this way there were 21.1 parts of a mixture of 1-amino-6-nitroanthraquinone and 1-amino-7-nitroanthraquinone obtain.

The mixture of 1,6- and 1,7-dinitroanthraquinone used in this example was obtained as described below: 51 parts of anthraquinone in 220 parts were added with stirring 20 oelum dissolved. In this solution were added dropwise within 103 parts of a mixed acid with 34% nitric acid were introduced over a period of three hours. The mixed solution obtained in this way was heated to 90 ° C for two hours and then kept at this temperature until the anthraquinone and the mononitro compound of the anthraquinone had completely disappeared. The mixed solution was cooled while stirring. It took place Precipitation of 1,5- and 1,8-dinitroanthraquinone, which is filtered off

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- li -

iond was washed with 190 parts of concentrated sulfuric acid. The filtrate was cooled to 70 ° C. with stirring. Then 40 parts were added dropwise over a period of one hour Water was added and the temperature rose to 80-84 ° C. After 30 minutes the product was filtered off at 75 to 80 ° C. It was washed with 100 parts of about 90% strength sulfuric acid. The product was then added to 1000 parts of water. It was stirred for an hour. It was then filtered off. The filter residue was washed with water until neutral and then dried. There were thus 17 parts of the product of the following composition won:

1,6-dinitroanthraquinone 41.2%

1,7-dinitroanthraquinone 39.0%

1,8- and 1,5-dinitroanthraquinone 13.6%

Other types of by-products 6.2%.

From the isomer η mixture of 1,6- and 1,7-dinitroanthraquinone 1,6-dinitroanthraquinone and 1,7-dinitroanthraquinone were based on their different solubility in different organic Solvents separated from each other.

Example 2;

14 parts of potassium acetate, 40 parts of m-chloroaniline and a catalytic Amount of copper acetate were mixed with 42.6 parts of a mixture of 1-amino-2,4-dibromo-6-nitroanthraquinone and 1-amino-2,4-di.bromo-7-nitroanthraquinone mixed. The resulting

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The mixture was stirred at 120 ° C. for five hours. After the starting substances, such as by means of thin layer chromatography was checked, were fully implemented, the reaction system was cooled to 20 ° C. and 200 parts of methanol were added. The crystals that then separated were filtered off, washed first with a small amount of methanol and then extensively with water.

The filter cake thus obtained was suspended in 500 parts of hot water containing 20 parts of concentrated hydrochloric acid. It was stirred for one hour. Then yet filtered hot and washed well with 70 ⁰ C water. In this way, a mixture of 1-amino ^ -bromo-'lm-chloroaniline-6-nitroanthraquinone and 1-amino ^ -bromo- ^ m-chloroaniline-T-nitroanthraquinone was obtained.

With this mixture, polyethylene terephthalate fibers were made color greenish blue. The dyed fibers showed excellent lightfastness, resistance to sublimation and washing.

The mixture of l-amino-2,4-dibromo-6-nitroanthraquinone used in this example and l-amino-2,4-dibromo-7-nitroanthraquinone was synthesized as follows: 26.8 parts of the mixture obtained as described in Example 1 from l-amino-6-nitroanthraquinone and 1-amino-7-nitroanthraquinone were dissolved in 46 parts of concentrated sulfuric acid. This solution was added to 400 parts of ice water.

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Then 38.5 parts of bromine were added dropwise at 25 ° C. with stirring. After stirring for two to three hours, an aqueous solution of acidic sodium sulfite was added, thereby rendering the excess bromine ineffective. The solid was then filtered off, washed with water and dried. In this way, 42 parts of a mixture of 1-amino-2 ^ -dibromo-G-nitroanthraquinone and 1-amino-2 _/ 4-dibromo-7-nitroanthraquinone were obtained.

The elemental analysis showed a bromine content of the mixture of 37.7%.

That obtained as described in Example 1 was obtained in the same way 1,7-Dinxtroanthraquinone selective to 1-Amino-7-nitroanthraquinone implemented and then brominated to l-amino-2, 4-dibromo-7-nitroanthraquinone. Eventually this became Bromo-substituted product reacted with m-chloroaniline and to l-amino ^ -bromo ^ -m-chloroaniline ^ -nitroanthraquinone implemented. With this product, polyethylene terephthalate fibers could be dyed greenish-blue. The colored fibers showed excellent lightfastness and were outstandingly resistant to sublimation and washing.

Example 3 :

A mixture of 42.6 parts of a mixture of l-amino-2,4-dibrora-6-nitroanthraquinone and l-amino-2, 4-dibromo-7-nitroanthraquinone, 35 parts of p-toluenesulfonamide, 20 parts of potassium

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acetate, 150 parts of nitrobenzene and a catalytic amount of copper acetate were stirred at 130 ° C. for two hours. After it was found by thin layer chromatography that the reaction of the starting substances was practically complete, the reaction system was cooled and stirred at a temperature below 30 ° C. for one hour together with 150 parts of methanol which had been added. Thereafter, the deposited crystals were filtered off and washed with 300 parts of methanol. The filter cake resulting after washing was introduced into 500 parts of water at 70 ^° C. containing 20 parts of concentrated hydrochloric acid. It was filtered while hot, the filter cake was washed extensively with water and then dried. In this way, a mixture of 1-amino-2-bromo-4- (p-toluenesulfonamide) -6-nitroanthraquinone and 1-amino-2-bromo-4- (p-toluenesulfonamide) -7-nitroanthraquinone was obtained. Polyethylene terephthalate fibers could be colored violet with this mixture. The amido compound was added to 500 parts of concentrated sulfuric acid. The resulting mixture was stirred at 40 ° C for 1 hour. The mixture was then poured into 5000 parts of ice water. The crystals separated out were filtered off and washed with a large amount of water. In this way, a mixture of 1,4-diamino-2-bromo-6-nitroanthraquinone and 1 ^ -Diamino ^ -hrGm - ^ - nitroanthraquinone was obtained. Polyethylene terephthalate fibers could be obtained with the mixture

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be colored blue. The fiber dyeings obtained with the product were extremely lightfast, resistant to sublimation and washable.

Example 4 :

A mixture of 33.7 parts of a mixture of l-amino-2,4-dichloro-6-nitroanthraquinone and l-amino-2 ^ -dichloro-T-nitroanthraquinone, 15 parts of potassium acetate, 35 parts of p-toluidine and a catalytic amount Copper acetate was ^{stirred at 130 °} C. for four hours. After the reaction of the starting substances had been checked by thin-layer chromatography, the reaction system was cooled ^{to 20 ° C.} Then 200 parts of methanol were added. The crystals which separated out were filtered off, washed first with a small amount of methanol and then extensively with water.

The filter cake present after washing was dissolved in 500 parts of 70 ° C. containing 20 parts of concentrated hydrochloric acid Suspended warnism water. It was stirred for one hour. It was then filtered while still hot and then washed extensively with warm water at 70.degree.

In this way there were 40.5 parts of a mixture of 1-amino-2-chloro-4-p-toluidine-6-nitroanthrachi.non and l-amino-2-chloro-4-p-toluidine-7-nitroanthraquinone won.

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With this mixture, polyethylene terephthalate fibers could be dyed greenish-blue. The fiber coloring was excellent lightfast, sublimation and washable.

The mixture of l-amino-2,4-dichloro-6-nitroanthraquinone and l-amino-2,4-dichloro-7-nitroanthraquinone used in this example was synthesized as follows: A mixture of 26.8 parts of a mixture of 1-Amino-6-nitroanthraquinone and 1-amino-7-nitroanthraquinone and 100 parts of dimethylformamide were kept at a temperature of 0 to 5 ° C., and 15.7 parts of chlorine were passed in over a period of five hours. ^{The mixture was then heated to 60 °} C. over a period of one hour and kept at this temperature for one hour. It was then cooled. The precipitate formed was filtered off and washed with water. In this way, a mixture of 1-amino-2,4-dichloro-6-nitroanthraquinone and 1-amino-2,4-dichloro-7-nitroanthraquinone was obtained. A value of 20.9% was determined for the chlorine content of the mixture.

Example 5 ;

14 parts of potassium acetate, 80 parts of aniline and a catalytic one Amount of copper acetate were mixed with 42.6 parts of l-amino-2,4-dibromo-7-nitroanthraquinone mixed. The mixture was stirred at 120 ° C. for six hours. After the implementation of the starting substances, as was checked by thin layer chromatography, When it was completed, the reaction system was cooled to 20 ° C. and 200 parts of methanol was added.

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The crystals which then separated out were filtered off. It was first with a small amount of methanol and afterwards washed extensively with water.

The filter cake resulting after washing was heated to 70 ° C. in 500 parts containing 20 parts of concentrated hydrochloric acid Suspended in water. The mixture was stirred for one hour, then filtered while hot and completely washed with hot water at 70.degree washed out. In this way became 1-amino ^ -bromo ^ -aniline-7-nitroanthrachinone obtain.

Polyethylene terephthalate fibers could be made with this product color greenish blue. The fiber dyeings were outstandingly lightfast, sublimation and washfast.

The 1-amino-2,4-dibromo-7-nitroanthraquinone used in this example was obtained by separating 1,7-dinitroanthraquinone (purity 94%) from a mixture of 1,6- and 1,7-dinitroanthraquinone, partial amination to 1-amino-7-nitroanthraquinone, as described in Example 1, and then bromination, as described in Example 2, obtained.

Example 6 :

70 parts of an alkylnaphthalenesulfonic acid-formalin condensate were used as a dispersant to 30 parts of a mixture of the compounds obtained as described in Example 2 the following format added:

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P NH,

Br

and

-η °

Cl

The mixture became a long time with a small amount Kneaded, dried and pulverized water. 2 parts of the dye preparation thus obtained were divided into 3,000 parts Water dispersed. 100 parts of a material to be dyed from polyethylene te re ph thai at fibers were one Treated immersed in the dispersion at 130 ° C for one hour. The material was then washed with hot water washed and dried. It was colored greenish-blue. The dyed material was extremely lightfast, sublimation- and washable, showed little ρH dependence and good alkali resistance.

Example 7:

In a sand mill, 30 parts of a mixture of the compounds of the following formulas obtained according to Example 3 were added

and

, -Br

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40 parts of naphthalenesulfonic acid-formalin condensate, 30 parts Sodium salt of lignin sulfonic acid and a small volume Wet-grind water to a finely divided powder. Then it was spray dried.

2 parts of the dye preparation thus produced were dispersed in 3000 parts of water. Then, 100 parts of a fabricated from Po Iy M thy len th Reph thai at- fiber material were immersed in this liquor, it was heated under pressure at 130 ⁰ C, and stained for one hour at the same temperature. The material obtained was colored blue.

The dyed material exhibited excellent light, sublimation, and lightness Washfastness, had little pH dependence and was good alkali resistance.

Example 8 ;

As described in Example 6, 30 parts of l-amino-2-bromo-4-aniline-7-nitroanthraquinone obtained according to the process described in Example 5 were obtained made a dye preparation.

In a high-performance stirrer, 100 parts of the dye preparation, 200 parts of nalka resin, 50 parts of naphthol diglycol ether and 700 parts of water work well together to form a printing paste prewipes. With this printing paste color, a polyethylene

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printed material made of lenterephthalate fibers. The printed material was then dried and ^{fixed at 200 °} C. for 60 seconds. It was then washed with hot water, and the material thus obtained was printed greenish-blue. The printed material was distinguished by various fastness properties.

Using the procedures in Examples 1 through 5, from suitable starting materials, those in the following were prepared Table listed dyes of the formula

I ^Δ

I-X

wherein X and Y have the meaning given above and the Nitro group seated as a substituent on the anthraquinone ring at the positions indicated above. With these dyes could polyethylene terephthalate fibers in the in color the shades given in the table.

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TABEL

Example position no. Of the NO ₂ group

hue

10

13 14

Br

6.7 Br

Cl

6.7 Br

Cl

6.7 Br -NH,

-Nile - CH.

H ₃ C

-nh;

H ₃ C blue

greenish blue

greenish blue

blue

6.7 green 1 i blue

6.7 Cl - ^NH0 2 ^S - CH.

violet

17th

6.7 Br

-NHO ₂ S

18th

6.7 Br -NH- </ y-OC ₂ H ₅

greenish blue

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TABLE (cont.)

Example position no. Of the N0 “group

hue

19 6.7

Cl -NH ■

^H 5 blue

2 ^H 5

greenish-

20 6.7

Cl -NH,

blue

21 6.7

22 6.7

Br> CH.

-ΝΗ- / Λ ^;

greenish blue

greenish blue

23

Br -NH,

blue

24 6.7

Br

-NH (/ \ CH ₃

V IMl /

greenish blue

25 6.7

Cl -NHO ₂ S

violet

26 6.7

Br -NH-

green 1 i blue

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Claims (1)

- 23 claims 1. Anthraquinone compounds or mixtures thereof, characterized by the general formula 0 Y wherein the nitro group is in the 6- or 7-position on the anthraquinone ring, X is a chlorine or bromine atom and Y is a chlorine or bromine atom or the group -NHR. in which R. (A) is a phenyl group which is unsubstituted or substituted by one or more chlorine atoms, methyl, ethyl, ethoxy, methoxy and / or phenoxy groups, (B) a hydrogen atom, or (C) a group -SO-R ₂ , in which R _{2 represents} an unsubstituted phenyl group or a phenyl group substituted by one or more chlorine atoms or methyl radicals. 2. Compounds or mixtures according to claim 1, characterized by the following formulas 0 NH, and or Br IH, Br 509850/0887 3. Compounds or mixtures according to claim 1, characterized by the following formulas 0 NH. or Cl 4. Compounds or mixtures according to claim 1, characterized by the following formulas 0 NH ₂ K ^ JLyK ^ or NH, 0 NH. 0 NH, 5. Compounds or mixtures according to claim !, characterized by the following formulas 0 NH, NH, or 0 NH-f V 6. Compounds or mixtures according to claim 1, characterized by the following formulas IT T 2 or 0 NH. 0 NH. 7. Compounds or mixtures according to claim 1, characterized by the following formulas 509850/0887 NH, - 25 - or •8th. Compounds or mixtures according to Claim 1, characterized by the following formulas Q, NH, or 0 9. Compounds or mixtures according to claim 1, characterized by the following formulas NHO ₂ S— ' 10. Compounds or mixtures according to claim 1, characterized by the following formulas [Γ T * 2 P Ψ2 ■ Br or i — Br 0 NHO ₂ S- 0 NHO ₂ S 11. Compounds or mixtures according to claim 1, characterized by the following formulas 509850/0887 12. Process for the preparation of compounds or mixtures the general formula O NH, (3) wherein X is a chlorine or bromine atom and the nitro group is in the 6- or 7-position on the anthraquinone ring, thereby characterized in that one 1,6- or 1,7-dinitroanthraquinone or mixtures thereof with ammonia reacts, selectively aminates the nitro group in the 1-position and compounds the formula 0 NH, (2) produces, wherein the Nitz-ogruppe the position indicated above takes, and then chlorinates or brominates these compounds. 509850/0887 13. Process for the preparation of compounds or mixtures of the general formula (5) wherein X is a chlorine or bromine atom and the nitro group is in the 6- or 7-position on the anthraquinone ring and R is an unsubstituted or with one or more chlorine atoms / methyl, ethyl, methoxy, ethoxy or phenoxy groups Substituted phenyl group or a group -SO-R ₂ in which R _{2 is} an unsubstituted phenyl group or a phenyl group substituted by one or more chlorine or methyl radicals, characterized in that a compound obtained according to the process according to claim 12 or a mixture thereof Compounds of the formula NH, (3) wherein X has the meaning given above and the nitro group is present in the position given above, with a Amine of the general formula I ₀ N - R, 2 1 (4) wherein R, has the meaning given above, converts, 509850/0887 14. Process for the preparation of compounds or mixtures of the general formula (7) NH, wherein X has the meaning given above and the nitro group is present in the position given above, characterized by that one obtained according to the process according to claim 13 compounds or mixtures of the general formula O NH, (6) wherein X and R "have the meaning given above and the Nitro group is present in the position indicated above, hydrolyzed. 15. A method for dyeing or printing hydrophobic fibers, characterized in that there are compounds or mixtures for this purpose the general formula used, (5) wherein the nitro group is at the 6- oar 7-position on the anthraquinone ring attached, X is a chlorine or broin atom, and 5098 5 0/0887 Y represents the group -NHR for a chlorine or bromine atom. in which R is a phenyl group which is unsubstituted or substituted by one or more chlorine atoms, methyl, ethyl, methoxy, ethoxy or phenoxy groups, a hydrogen atom or a group -SO ₂ R ₂ , in which R _{2 is} an unsubstituted or Pheny! group substituted by one or more chlorine atoms or methyl radicals. 509850/0887