DE2902485A1 - 6/7 HALOGEN-ANTHRACHINONE COMPOUNDS, THEIR PRODUCTION AND USE - Google Patents

Description

DR. BERG DIPL.-ING. STAPF
DIPL.-ING. SCHWABE DR. DR. SANDMAIR

P.O. Box 86024580 »Munich 86

Attorney's File: 29 808 23 » January 1979

CIBA-GEIGY AG
Basel, Switzerland

6 / T-halogen-anthraquinone compounds, their preparation and
use

Case 1-11555 / *

• (089) 988272 telegrams: Bank accounts: Hypo-Bank Munich 4410122850

988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

988274 TELEX: Bayer Vereinsbank Manchen 453100 (bank code 70020270) 983310 0524560BERGd 909830/0826 Postscheck München 65343-808 (bank code 70010080)

CIBA-GEIGY AG. CH-4002 Basel

CIBAr

• GEIGY

1-11555 )

6/7 halo-anthraquinone compounds / their preparation and use

The invention relates to new 6/7 halogen anthraquinone compounds, Process for their production, their use for dyeing and printing textile materials and the textile materials dyed and printed by means of these compounds.

The new 6/7 halogen anthraquinone compounds correspond of formula I.

(D

where mean:

X is a halogen atom in the 6- or 7-position of the

Anthraquinone is located
R.

or -NH-Cycloalkyl-vB ^ group, where the phenyl radical A

die -OH, -NH ₂ , -NH-alkyl, -NH- ^ B ^), -NH-Alky1- ^ ^B /

is further substituted at least in the X "position and / or B can be further substituted one or more times and independently of A, and at least one X _{1 is} a halogen atom and the other is hydrogen or

Halogen atom.

Preferred anthraquinone compounds consist of a mixture of a 6-halo-anthraquinone compound and one 7-halo-anthraquinone compound.

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~ ^ 3 2902435

X in the meaning of a halogen atom represents, for example, a fluorine, chlorine or bromine atom. Preference is given it is the chlorine atom.

At least one X also means one per molecule Halogen atom such as fluorine, chlorine or bromine; it is preferably the bromine atom and the other X- is hydrogen or another substituent. However, compounds in which both X, per molecule are bromine are also valuable.

If R is the -NH-alkyl group, then the alkyl group preferably 1 to 9 carbon atoms; These are for example straight and branched alkyl groups and cycloalkyl groups. The methyl, ethyl, n- and iso-propyl, n-, sea- and tert-butyl groups, the straight or branched pentyl group and the cyclohexyl and trimethylcyclohexyl group. R denotes the phenylamino group in which the phenyl radical is further substituted one or more times can, the main possible substituents are:

Halogen, such as fluorine, chlorine or bromine; Alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, n- and iso-propyl, straight and branched butyl and pentyl; Cycloalkyl with 5 to 8 carbon atoms, especially cyclohexyl; Alkoxy having 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy; Acylamino groups such as acetylamino and benzoylamino; Alky! Amino groups, such as mono- and dialkylamino groups with 1 to 5 carbon atoms in the alkyl radical; the phenoxy group; a heterocyclic radical, such as, in particular, a benzothiazole radical; water-solubilizing groups, especially the SOoM group, in which M denotes the hydrogen atom or a cation, or a group of the formula -CH ₂ -NH-CO-Y, in which Y is an alkyl or alkylene radical which is optionally mono- or disubstituted by halogen with 1 to 4 carbon atoms, an unsubstituted phenyl radical or a phenyl radical which is further substituted by halogen or alkyl. If R is a phenyl-alkyl-amino group or phenylcycloalkyl-amino group, the phenyl radical can also be further substituted here as indicated above. In the phenyl-alkylamine group, the alkyl radical has 1 to 5 carbon atoms

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and the phenyl-cycloalkyl-amino group is Cycioalkyl radical around one which has 5 to 8 carbon atoms; above all it is about the cyclohexyl group. The substituents mentioned in connection with the radical B can be one or more times, identical or different to be available. In preferred compounds, R denotes the phenylamino group in which the phenyl radical is unsubstituted or is substituted by halogen, alkyl, cycloalkyl, alkoxy, acylamino, alkylamino, phenoxy, by a heterocyclic one Remainder, SOoM, where M is the hydrogen atom or a cation means, or by a group of the formula -C ^ -NH-CO-Y, in which Y is optionally mono- or by halogen disubstituted alkyl radical, an unsubstituted phenyl radical or denotes a phenyl radical which is further substituted by halogen or alkyl. Of importance in context with the symbol R is also the phenyl-alkyl-amino group, whose phenyl radical can be further substituted as indicated.

Substituents in the phenyl radical A are preferably Question: Halogen, how

Fluorine, chlorine or bromine; Alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, n- and iso-propyl, straight and branched butyl and pentyl; Cycloalkyl with 5 to 8 carbon atoms, especially cyclohexyl; Alkoxy having 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy; Acylamino groups such as acetylamino and benzoylamino; Alky! Amino groups, such as mono- and dialkylamino groups with 1 to 5 carbon atoms in the alkyl radical; Water-solubilizing groups, especially the SOoM group, in which M is the hydrogen atom or a cation, or a group of the formula -CH ₂ -NH-CO-Y, in which Y is an alkyl or alkylene radical optionally mono- or disubstituted by halogen with 1 up to 4 carbon atoms, an unsubstituted phenyl radical or a phenyl radical which is further substituted by halogen or alkyl. The substituents mentioned in connection with the radical A can

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be present once or more times, identically or differently.

In preferred anthraquinone compounds, A denotes a phenyl ring which is substituted by: halogen, in particular bromine, alkyl, cycloalkyl, alkoxy, acylamino, alkylamino, SO ₃ M, in which M denotes the hydrogen atom or a cation, or by a group of the formula -CH ₂ -NH-CO-Y, in which Y denotes an alkyl or alkylene radical with 1 to 4 carbon atoms optionally mono- or disubstituted by halogen, an unsubstituted phenyl radical or a phenyl radical which is further substituted by halogen or alkyl

Preferred anthraquinone compounds of the formula I contain

in the phenyl radicals A and / or B at least one water-solubilizing group, especially the SO ₃ H group, and correspond to the formula Ia

(Ia)

Where mean:

R ¹ denotes the radical -NH- (CH ₂ ) i_4 \ | L / » ^an unsubstituted or substituted phenylamino radical of the formula -ΝΗ — ΓΒ'λ, which in the phenyl nucleus B ^{1 is} substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 Carbon atoms, halogen, acylamino, phenoxy optionally substituted by lower alkyl, or by a benzothiazole radical substituted by lower alkyl,

A ^{1 is} a phenyl radical which is further substituted in the X ₂ position by lower-alkyl, acylamino or halogen and

X, 'hydrogen, -CH-, or bromine.

In preferred 6/7 halogen anthraquinone compound mixtures of the formula I, the two components are present in a ratio of about 1: 1.

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The O / T-halogen-anthraquinone compounds according to the invention are, provided they are water-soluble groups, especially the SO Η group contain water-soluble dyes that have good drawability on textile materials made of natural and synthetic polyamide and the dyeings obtained have good fastness properties, such as light fastness and Well, let's face it.

Contain the β / 7-halo-anthraquinone compounds according to the invention no water-solubilizing groups, it is disperse dyes, which are also a good one Have drawability on synthetic textile materials, and the dyeings obtained have good fastness properties, such as Light fastness and wet fastness.

The preparation of the 6/7 halogen anthraquinone compounds of the formula I is carried out in such a way that anthraquinone compounds of the formula II

X-,

(II)

Shark

where X, A and X _{2 are} as stated, Hal is halogen and at least one X _{1 is} the same halogen atom as Hai, by hydrolysis of the 4-position halogen atom or by condensation with a compound introducing the radical R, and the compounds obtained are optionally sulfated .

The hydrolysis of compounds of the formula II converts the 4-position halogen atom into an anthraquinone compound with R = OH. The hydrolysis itself is carried out for example in a mixture of oleum having about I07o free SO ^ and boric acid at a temperature of about 100 ⁰ C.

90983 0/0826

Compounds of the formula II are condensed with amines which, as the radical R, introduce the radical of the formulas -NH-alkyl, -NH- / Ö \ , -NH-alkyl - ^> or -NH-. The condensation reaction takes place in an organic medium (for example Cellosolve or butanol) at a temperature of about 100 to 150 ° C depending on the boiling point of the solvent used in a known manner and in the presence of a catalyst, such as. Copper powder or copper salt, and a base instead. It is also possible to use the amine itself as a solvent.

Possible amines which introduce the radical R are: ammonia; Alkylamines, such as methylamine, ethylamine and butylamine, phenylamines, such as phenylamine, 2-methylphenylamine, 4-methylphenylamine, 2,4-dimethylphenylamine, 3,4-dimethylphenylamine, 2,5-dimethylphenylamine, 2-methyl-5-methoxyphenylamine, 2 , 3-dimethylphenylamine, 2,6-dimethylphenylamine, 2,4,6-trimethylphenylamine, 4-ethylphenylamine, 2-ethylphenylamine, 4-tert-butylphenylamine, 2-methoxyphenylamine, 2-ethoxyphenylamine, 4-methoxyphenylamine, 4-butoxyphenylamine, 4 Chlorophenylamine, 4-acetylaminophenylamine, 4-phenoxyphenylamine, 4- (4'-methyl) -phenoxyphenylamine, 4- (6 ¹ -methyl) -benzthiazol-phenylamine and 2-methoxy-5-methylphenylamine; Phenylalkylamines such as benzylamine and phenylisobutylamine; Phenylcycloalkylamines, such as phenylcyclohexylamine.

Then the free of water-solubilizing groups the compounds can still be sulfonated, for example, with oleum containing 1 to L07 _o free Soo, at a temperature of O to 30 ° C. If it is desired that the end product of the formula I in core A and / or B has the substituent of the formula -C ^ -NH-CO-Y mentioned at the beginning, it is advantageous to introduce this substituent before the sulphonation. Such a group is introduced according to Tscherniak-Einhorn in such a way that the anthraquinone compound is reacted with an N-methylolamide which has the -COY group on the N atom in an acidic medium, preferably concentrated sulfuric acid.

909830/0826

The 6/7 halogen anthraquinone compounds are used of the formula I individually or preferably as mixtures which contain no water-solubilizing groups, as disperse dyes for dyeing and printing materials, especially textile materials, which can be dyed with disperse dyes are. Possible materials of this type are: mixed polymers made from dicyanoethylene and vinyl acetate, fibers made from polyurethanes and polypropylene fibers, as well as fibers made of cellulose tri- and -2 1/2-acetate and especially fibers made of aromatic polyesters, such as those made from terephthalic acid and ethylene glycol and copolymers made from terephthalic and isophthalic acid and ethylene glycol. These materials are dyed in a known manner, the dyeings obtained after an aftertreatment can be subjected, for example, by heating with an aqueous solution of an ion-free detergent. Man receives strong dyeings and prints with good fastness properties.

Strong colorations are also achieved when the dyes are applied from organic solvents, in which the dye is made up of a solvent in which it is dissolved or as a fine dispersion, towards the coloring textile material is applied. Petroleum fractions and, above all, come as organic solvents chlorinated hydrocarbons (e.g. perchlorethylene), used alone or as a dispersion together with water can be.

Contain the 6/7 halogen anthraquinone compounds of the formula I groups which make water soluble, especially the SOoH group, can be such water-soluble Compounds used as acidic dyes for dyeing and printing materials, especially textile materials, which can be dyed with acidic dyes. Such materials include, for example, natural and synthetic polyamide materials, such as wool, silk and nylon, in question. All these

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Materials can be shaped in the most varied of shapes available and dyed using conventional exhaust or padding processes.

Instead of impregnating both the disperse dyes as well as the acidic dyes can be applied by printing. For this purpose one uses e.g. a Printing ink that contains the dye in addition to the auxiliaries customary in printing, such as wetting agents and thickeners.

The invention also relates to new intermediates of formula II

(II)

Shark

X represents a halogen atom, the phenyl ring

A is further substituted at least in the X ₂ position, Hal represents halogen and at least one

X _I means the same halogen atom per molecule as Hai. The meaning of the symbols X, X ₁ and A is identical

with that given under the formula I. In preferred intermediates mixtures X is chlorine, the phenyl ring A is substituted in the X ₂ by alkyl, alkoxy, acylamino, cyclohexyl or halogen, and Hal and X ₁ represents bromine and the other X ₁ -bedeutet hydrogen or shark and both X, are each Bromine.

These intermediates of the formula II are obtained if a 1,6 / 1,7-dihalo-anthraquinone or a mixture of two compounds of the formula III

OX

(III)

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- sr-

SK ₀ 2902435

where X is the same halogen atom, preferably chlorine, by amination (cf. e.g. DT-OS 25 13 950) in Anthraquinone compounds of the formula IV

(IV)

transferred and this depending on how many halogen atoms to be introduced into the compound of formula IV with at least 2 equivalents of halogen, especially bromine, in stages or implemented all at once. The reaction with halogen takes place in the organic solvent at one temperature before about 40 to 60 ° C. If the compound of the formula IV is reacted with one equivalent of halogen, one arrives at Compounds which have the halogen atom in the 1-position phenyl nucleus in the o-position to the amino group. These connections are then reacted with a further equivalent of halogen, resulting in compounds which are then also in the 4-position of the anthraquinone nucleus have a halogen atom. But it is also possible that the compounds of the formula IV are the same with 2 equivalents of halogen, which leads to the same compounds which have a halogen atom in the 4-position of the anthraquinone nucleus and a halogen atom in the 1-position phenyl nucleus in the ortho-position to the amino group. If compounds of the formula II are desired which contain one halogen atom in the 4-position of the anthraquinone nucleus and two halogen atoms in the 1-position phenyl nucleus, namely each in the o-position to the amino group, it is possible to use compounds of the formula IV to implement with 3 equivalents of halogen. But it is also possible that the latter trihalogen compound from the Prepares dihalogen compound by reacting the latter with one equivalent of halogen.

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It is advantageous that the starting materials of the formula IV used are those which do not have any water-solubilizing properties Have group. If water-soluble intermediates of the formula IT are desired, they are introduced of especially the sulfo group following the halogenation.

These intermediate products are used for production of dyes.

The particular advantage of the invention is that as starting compounds for the production of the erfindungsgeiuässen Dyestuffs and intermediate products so far worthless waste products (e.g. bottom products from antrhachinone nitrations) can be used.

The inventive anthraquinone compounds of Formula I stand out over similar dyes which have no halogen in the 6- or 7-position better LIaasfastness, partly. purer nuances and better Structure of the water-soluble dyes on polyamide material. The latter advantage is also over similar ones Dyes with halogen in the 6- or 7-position but without halogen in the o-position of the arylamines in the 1-position. Draw the mixtures of G ^ V-halogenanthraquinone compounds are characterized by better solubility than the individual components.

The following examples explain the invention without limiting it thereto. Parts mean parts by weight and the temperatures are given in degrees Celsius.

Ü Π 9 83 0/0826 BAD ORIGINAL

Example 1 "'β

51 parts of 1- (2 ¹ -brom-4 ¹ -methylphenylamino) -4-bromo-6/7-chloroanthraquinone (obtained by brominating 1-p-toluidino-6/7-chloroanthraquinone), 22 parts of p-toluidine, 10 Parts of potassium acetate and 1 part of copper powder are heated for 4 hours with 500 parts of 1-pentanol with stirring to 130 °. The excreted reaction product of the formula

is suctioned off at 80 °, washed with methanol and dried under vacuum.

20 parts of the product mixture thus obtained is dissolved in 200 parts of 67 _o oleum and the solution rlihrt 3 hours at 25 °. The solution is then poured onto ice, the precipitate is filtered off and washed with 10% strength sodium chloride solution. It is then slurried in water, the slurry is neutralized with sodium hydroxide solution, and the whole is mixed with sodium chloride, the dye mixture of the formula

CH <

fails. It is filtered off and dried.

The dye mixture dyes from weakly acidic to acidic bath wool and synthetic polyamide fibers in pure, green shades of good lightfastness.

0 9 8 3 0/0826

- JtZ "-

Used instead of the aforementioned 1- (2'-BrOm-V-methylphenylamino) -4-bromo-6/7-chloroanthraquinone equivalent amounts of one of the anthraquinone compounds mentioned in Table 1, Kolonne'Il and instead of p-toluidine equivalent amounts of one of the amines listed in column III, otherwise proceed as indicated in the example, in this way, water-soluble dyes with similar properties are obtained, the nuances of which on wool are given in column IV are.

Table 1

II

III

IV

E.g.

Anthraquinone compound

Br

Ami η

R ₂ NH ₂

Shade on wool

Il

Il

It

green

Il

It

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- 43- -

II III

IV

Br / V CH

Il

Il

Il

It

It

Il Il

Il

Il OCH.

CH
CH., CH-

CH
CH.

CH,

CH-

OCH ₃
0CoH ₍

OCH ₃

° ^C 4 ^H 9

NHCOCH

green

Il

green blue

Il

green

Il

Il

Il

Il

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II III

IV

Br

Br

-CiL

CH

It It

Br

- NHCOCH

It

Br

/ V-CH,

It

CIL

CH,

CH ₃

/ V CH,

NHCOCH.

OClL

OQL

-A V

CH.

-CH-CH., -

ι t-

CH ₀

green

greenish blue

ti

It

green

Il

blue

- YYY -

Example 31

A mixture of 58.5 parts of 1- (2 ¹ , 6'-dibromo-4'-methylphenylamino) -4-bromo-6/7-chloroanthraquinone, obtained by brominating 1p-toluidino-δ / y-chloroanthraquinone, 22 parts p-Toluidine, 10 parts of potassium acetate, 1 part of copper powder and 500 parts of 1-pentanol is stirred for 4 hours at a temperature of 130 °. After cooling, the precipitated product mixture of the formula Br is filtered

CH.

and crystallize it from 1-pentanol.

This product mixture is sulfated as described in Example 1. The dye mixture of the formula obtained in this way

CH,

CiL

dissolves in water with a pure bright blue color and dyes wool and synthetic polyamide fibers from acetic acid to sulfuric acid bath in pure greenish blue tones very lightfast.

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If, instead of the amount of p-toluidine used, equivalent amounts of one of the amines mentioned in Table 2, column III, and instead of 1- (2 ¹ , 6'-dibromo-4'-methylphenylamino) -4-bromo-6/7 are used -chloranthraquinone equivalent amounts of one of the anthraquinone compounds listed in Table 2, column II, then with otherwise the same procedure, water-soluble dyes with similar properties are obtained.

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Table 2

II

III

IV

E.g.

Anthra chi no connection

Br

Ami η

R ₂ -NH ₂

Nuance on PA

Br

fl

Il

Br

Br

Br

Cl

Br

CH ₃

CH

CH

CH ₃

-CHh ₃

ΓΗ

grlinstichxg blue

blue

Il

grUnstichi blue

909830/0826

. I. Br
\ Il II III IV Br 39 -CH ₃ -CH-CH ₂ -CH
CH ₃ blue 40 -CH ₂ - Il

Example 41

In 120 parts by volume of 1-pentanol there are 27.7 parts 1,6 / 1,7-dichloroanthraquinone, 21.4 parts p-toluidine, 10 parts Potassium acetate and 0.5 part copper powder with "stirring while." Heated to 130 ° for 4 hours. It is cooled and the reaction product of the formula which has separated out is filtered off

off, washes it with methanol and water and dries it at 90 to 100 ° in a vacuum.

8.7 parts of the product mixture obtained in this way are stirred in 75 parts of chlorobenzene at 35 ° and, after the addition of 8 parts of bromine (2 'equivalents) kept at 40 to 50 ° for 15 hours. It is diluted with 100 parts of methanol and filtered with suction the precipitated reaction product of the formula

909830/082 6

-Uo

Br

Br

O Br

away.

Used instead of the 8.7 parts of the condensation product from 1,6 / 1,7-dichloroanthraquinone with p-toluidine equivalent parts of the condensation products listed in Table 3 below, column 2, and equates these with 8 parts Bromine (2 equivalents), halogenated products of those in column 3 of the table are obtained with otherwise the same procedure 3 given "formula.

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Tabel

E.g,

Condensation product 0 NH-R ₁

Cl

Halogenated product

^l 2

O NH-R,

Cl

R,

'_y- OCHc Br

CH _C -ff

CH.

CH.

Br

NHCOCH. Br

COCH-

Br

46

/ ¹ Wh Br J / V

47 Br

303830/0826

Example 48

8.7 parts of the product mixture of the formula obtained in Example 41

Cl

are suspended in 7.5 parts of chlorobenzene at 35 °. To The addition of 12 parts of bromine (3 equivalents) is stirred for a further 15 hours at 40 to 50 °. The solvent is under vacuum distilled off, the reaction product of the formula

Cl

Br

separates and is isolated by filtration.

Used instead of the 8.7 parts of the condensation product from 1,6 / 1,7-dichloroanthraquinone with p-toluidine equivalent parts of the condensation products listed in Table 4 below, column 2, and sets them with 12 parts of bromine (3 equivalents) are obtained with the same procedure, halogenated products of those in column 3 of the table 4 given formula.

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Table 4

E.g.

Condensation product O NH-R-,

Cl

Halogenated product

O NH-R

Cl <

Br

iCOCH. Br

OCH-

Br

Br

—NHCO CH-

Br

Br

Br

Br

Cl

909830/0 826

όθ

Example 54

8.3 parts of l-anilino-o ^ -chloranthraquinone obtained by the process described in Example 41 are stirred in 75 parts of chlorobenzene at 35 °. Is added dropwise during \ hour at 35 to 45 ° 16 parts of bromine (4 equivalents) to the slurry, and then it is allowed for 15 hours at this temperature the mixture react.

The reaction product of the formula

Cl <

0 Br

can be separated out by adding methanol, it is filtered off, washed with methanol and dried.

Example 55

A dyebath is prepared from 4000 parts of water, 4 parts of ammonium acetate and 2 parts of the dye according to Example 1 and so much acetic acid that the pH of the bath is 6.0. You go into the dyebath obtained 100 parts of a synthetic polyamide tricot, heat it to a boil within half an hour and dye it 45 minutes at 100 °. A green dyeing is obtained which has good lightfastness.

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Claims (1)

D R. B £ R ft "- · ^ t. -> - 'η« Attorney's file: 29 8θ8 ""'"'.-.'..- ■ - '''" ^: Claims 1. 6/7 halo-anthraquinone compounds or mixtures thereof of formula I. where mean: Ö R X is a halogen atom in the 6- or 7-position of the
Anthraquinone is located R die -OH, -NH ₃ , -NH-alkyl, -NH- or -NH-cycloalkyl-rBM group, where the phenyl radical A
is further substituted at least in the position X_
and / or B one or more times and independently of A
can be further substituted, and at least one X _{I is} a halogen atom and the other is hydrogen or
Halogen atom. 2. e / V-halogen-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that X is the chlorine atom. 3. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that one X .. per
Molecule is bromine and the other X _{1 is} hydrogen. 4. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that both X ₁ denote bromine per molecule. 5. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that R the Means group in which the phenyl radical B is optionally further substituted. 909830/0826
ORIGINAL INSPECTED 6. 6/7 halogen anthraquinone compounds or mixtures thereof according to claim 1, characterized in that R denotes the -NH-alkyl - <@ \ group. 7. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1 / characterized / that the phenyl radical A in X- is substituted by alkyl, acylamino or halogen. 8. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that they contain at least one SO, H group in the phenyl radicals A and / or B. 9. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 7, characterized in that the phenyl ring A is further substituted one or more times by halogen, in particular bromine, alkyl, cycloalkyl, alkoxy, acylamino, alkylamino, SO-, Μ, in which M is the hydrogen atom or a Cation means / or by a group of the formula -CH-NH-CO-Y, wherein Y is one optionally mono- or disubstituted by halogen Alkyl or alkylene radical with 1 to 4 carbon atoms, an unsubstituted phenyl radical or a phenyl radical means which is further substituted by halogen or alkyl. 10. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 5, characterized in that the phenyl ring B is further substituted one or more times by halogen, alkyl, cycloalkyl, alkoxy, acylamino, alkylamino, phenoxy, by a heterocyclic radical, SO -M, in which M is the hydrogen atom or a cation, or by a group of the formula -CH ₂ -NH-CO-Y, in which Y is an alkyl or alkylene radical with 1 to 4 carbon atoms, optionally mono- or disubstituted by halogen, an unsubstituted one Denotes phenyl radical or a phenyl radical which is further substituted by halogen or alkyl. 909830/0826 ORIGINAL INSPECTED _ "1 fi ' 11. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that this of the formula Ia Br (Ia) correspond, where mean: the rest -NH- an unsubstituted phenyl amino radical or a phenylamino radical, which is in the phenyl nucleus is substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, Halogen, acylamino, phenoxy optionally substituted by lower-alkyl or by one by lower-alkyl substituted benzothiazole radical, a phenyl radical further substituted in position X ₂ by lower-alkyl, acylamino or halogen and hydrogen, -CHo or bromine, with the proviso that these in the phenyl radical A 'and / or in the phenylamino radical R ^! ; at least one Have SO ^ H group. 12. 6/7 halo-anthraquinone compounds or mixtures thereof according to claim 1, characterized in that this is the formula Cl correspond. 909830/0826 13. Mixture of 6/7 halo-Änthraquinone compounds according to claim 1 of formula I, characterized in that the two components are present in a mixing ratio of approx. 1: 1. Process for the preparation of 6/7 halo-Änthraquinone compounds or mixtures thereof of the formula I according to claim X-, ti) in which, mean: X is a halogen atom in the 6- or 7-position of the Anthraquinone is located
R denotes -OH, "NH ₂ , -NH-alkyl, -NH- ^ Vy, -NH-alkyl- ^ Vy or -NH-cycloalkyl-vVy group, where the phenyl radical A is further substituted at least in the X- position and / or B one or more times and independently of A can be further substituted, and at least one X per molecule halogen and the other hydrogen or Halogen, characterized in that one anthraquinone compounds of the formula IT or mixtures thereof X ₁ (II) Shark X, A and X ₂ mean the above, Hal halogen and at least one X _{1 represents} the same halogen atom as Hai, is reacted by hydrolysis of the 4-position halogen atom or by condensation with a compound introducing the radical R, and the compounds obtained are optionally sulfated. 909830/0826 - _M - 2902435 15. Use of the 6/7 halogen anthraquinone compounds or mixtures thereof according to claim 1, which do not contain any water-solubilizing agents Groups, especially the SO, Η group, contain as disperse dyes for dyeing and printing polyester materials. 16. Use of the 6/7 halogen anthraquinone compounds or their mixtures according to claim 1, which contain water-solubilizing groups, especially the SO, Η group, as acidic dyes for dyeing and printing polyamide materials, especially wool. 17. The one with the 6/7 halogen anthraquinone compounds according to Claim 1 colored or printed material. 18. Intermediates of formula II (ID al wherein X is a halogen atom, the phenyl ring A is _{further substituted at least in the X 2} position, Hal is halogen and at least one X-. per molecule means the same halogen atom as Hai and the other means hydrogen or a halogen atom. 19. Intermediate products of the formula II according to claim 18, characterized in that X each denotes chlorine. 20. Intermediate products of the formula II according to claim 18, characterized in that the phenyl ring A in the X ₂ position is substituted by alkyl, alkoxy, acylamino, cyclohexyl or halogen. 909830/0826 21. Intermediate products of the formula II according to claim 18, characterized in that Hai and one X represents bromine and the other X represents hydrogen per molecule. 22. Intermediate products of the formula II according to claim 18, characterized in that shark and both X-, per molecule Mean bromine. 909830/0826