CH680071A5 - - Google Patents

Description

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CH 680 071 A5

description

The invention relates to new metal complex compounds in the form of the free acid of the formula

©

H ©

(1),

and mixed metal complex compounds containing them, in which Di and D2 independently of one another each represent the residue of an optionally further substituted diazo component of the benzene or naphthalene series which bears a hydroxyl or carboxy group in the ortho position to the azo group,

Z is nitrogen or a CH group,

X represents oxygen or a group -NR1-, in which Ri is hydrogen or Ci-C4-alkyl,

K represents the residue of an optionally further substituted o-hydroxybenzaldehyde or o-hydroxy-naphthaldehyde if Z is the CH group, or the residue of an optionally further substituted coupling component of the benzene or naphthalene series or the heterocyclic series which are in 0 or A position to the azo group which contains group X means, if Z is nitrogen, with the proviso that -KX- is not a radical of the formula

R

is

R represents an alkyl, aryl, cycloalkyl or aralkyl radical,

Me stands for chromium, cobalt or iron and p and q independently of one another represent the number 0 or 1.

If Z is nitrogen, the coupling component -KX- is not dihydroxybenzophenone, since the subject of the invention is only asymmetrical 1: 2 complexes.

The diazo residues Di and D2 derive e.g. from a 1- or 2-naphthylamine or aminobenzene, where the aromatic amines mentioned each have a hydroxyl or carboxy group in the ortho position to the amino group and may also be further substituted by one or more identical or different radicals.

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CH 680 071 A5

Suitable substituents on the phenyl or naphthyl radical Di and D2 are, for example: Ci-C4-alkyl, which here and in general methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl includes; Ci-C-t-alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy; Halogen, which generally e.g. Fluorine, bromine and especially chlorine is meant; Trifluoromethyl; Ci-C4-alkylsulfonyl, especially methyl- or ethylsulfonyl; Sulfamoyl; N-mono- or N, N-di-Ci-C4-alkylsuifamoyl; Carbamoyl; N-mono- or N, N-di-Ci-C4-alkylcarbamoyl, sulfo; Nitro; Cyano; Carboxy; Phenoxy; Ci-C4-alkanoylamino, especially acetylamino, propionylamino; Ben-zoylamino; Ci-C4-alkoxycarbonyl, e.g. Methoxy or ethoxycarbonyl; phenylazo which is unsubstituted or substituted in the phenyl part by sulfo, nitro, chlorine, methyl or methoxy.

The residues Di and D2 are derived, for example, from the following amines: anthranilic acid, 4- or 5-chloroanthranilic acid, 4- or 5-sulfoanthranilic acid, 2-amino-3-naphthoic acid-2-amino-1-hydroxy-benzene, 4-chlorine - And 4,6-dichloro-2-amino-1-hydroxybenzene, 4- or 5-nitro-2-amino-1-hydroxybenzene, 4-chloro, 4-methyl and 4-acetylamino-6-nitro-2 -amino-1-hydroxybenzene, 6-acetylamino and 6-chloro-4-nitro-2-amino-1-hydroxybenzene, 4-cyan-2-amino-1-hydroxybenzene, 4-sulfonamido-2-amino-1 - hydroxybenzene, 1-hydroxy-2-aminobenzene-4-suIfoanthranilide, 4-methoxy-2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-1-hydroxybenzene, 4-methyl-2- amino-1-hydroxybenzene, 4-chloro-5-nitro-2-amino-1-hydroxybenzene, 3,4,6-trichloro-2-amino-1-hydroxybenzene, 6-acetylamino-4-chloro-2-amino -1-hydroxybenzene, 4,6-dinitro-2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzoI-4- or -5-sulfonic acid, 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid , 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-1-hydrox ybenzoI-6-sulfonic acid, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-chloronaphthaiine-4-sulfonic acid, 1-amino-2-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-1-hydroxybenzene-4,6-disulfonic acid, 4-phenylazo-2-aminophenol.

Instead of the abovementioned amines with hydroxyl groups, corresponding methoxy compounds or corresponding compounds whose hydroxyl group has been tosylated, such as anisidine, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine, anisidine-4- or - 5-sul-foic acid or tosylated 1-hydroxy-2-aminobenzene, the methoxy or o-tosyl group being converted into an OH group before or during the metallization. Compounds with these groups are used especially when the corresponding 1-hydroxy-2-amino compounds couple poorly.

In preferred dyes of the formula (1), Di and D2 independently of one another each represent the residue of a 1-hydroxy-2-aminobenzene which is optionally further substituted by chlorine, nitro, sulfo, methyl, methoxy, methylsulfonyl, carbamoyl, sulfamoyl and / or phenylazo , the remainder of a 2-hydroxy-1-aminonaphthalene which is unsubstituted or substituted by sulfo and / or nitro, or the remainder of anthranilic acid.

Particularly preferred diazo components Di and D2 are: 4-nitro-2-amino-1-hydroxybenzene-6-sulphonic acid, 6-nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4- or 5-nitro-2 -aminophenol, 4-chloro-2-aminophenol, 4-sulfamoyl-2-aminophenol, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hy-hydroxy-6-nitronaphthalene-4-sulfonic acid.

q and p each independently represent the number 0.

If Z stands for the CH group, K means the residue of an o-hydroxynaphthaldehyde or preferably o-hydroxybenzaldehyde, the aromatic aldehydes mentioned in each case being unsubstituted or e.g. may be further substituted by Ci-C4-alkyl, halogen, sulfo or unsubstituted or in the phenyl part by sulfo, nitro, chlorine, methyl, carboxy and / or methoxy substituted phenylazo.

Here, K preferably means the residue of an o-hydroxybenzaldehyde which is unsubstituted or substituted by phenylazo, sulfophenylazo or disulfophenylazo.

Examples of particularly preferred o-hydroxybenzaldehydes on which the radical K is based are: 2-hydroxybenzaldehyde, 5-phenylazo-2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-sulfophenylazo) -2-hydroxy-benzaldehyde, 5 - (2 ', 5'-Disulfophenylazo) -2-hydroxybenzaldehyde.

If Z is nitrogen, which is preferred, the coupling component on which the rest K is based is e.g. an unsubstituted or e.g. phenol substituted by Ci-Cs-alkyl, Ci-C4-alkoxy, N, N-di-Ci-C4-A! kylamino, Ci-C4-alkoxycarbonylamino or Ci-C4-alkanoylamino; an unsubstituted or e.g. 1- or 2-naphthol substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, amino, Ci-C4-alkanoylamino, benzoylamino and / or sulfo; a 5-pyrazolone which in the 1-position represents an unsubstituted or e.g. phenyl or naphthyl radical substituted by chlorine, nitro, sulfo, Ci-C4-alkyl and / or Ci-C4-alkoxy; a 6-hydroxy-3-cyano- or 6-hydroxy-3-carbamoyl-2-pyridone which is substituted in the 1-position by optionally substituted Ci-C4-alkyl, e.g. Methyl, isopropyl, ß-hydroxyethyl, ß-aminoethyl or ylsopropoxypropyl or substituted by phenyl and in the 4-position can carry a C 1 -C 4 -alkyl group, in particular methyl; an acetoacetic acid amide, in particular an acetoacetic acid anilide or benzoylacetic acid anilide, which can be substituted in the anilide core by chlorine, nitro, Ci-C4-alkyl, Ci-C4-alkoxy or sulfo; or a 1- or 2-naphthylamine which is optionally substituted by sulfo, sulfamoyl or N-mono- or N, N-di-Ci-C4-alkylsulfamoyl.

The radical K is preferably derived from an unsubstituted or sulfo and / or amino-substituted 1- or 2-naphthol or a 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide,

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CH 680 071 A5

ren phenyl radical in each case unsubstituted or e.g. is substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, nitro and / or sulfo, from; accordingly, X is preferably oxygen.

Examples of particularly preferred coupling components which can form the basis of the radical K are: 1-naphthol, 2-naphthol, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-phenyl-3-methylpyrazole-5- on, 1- (2'-, 3'- or 4'-sulfophenyl) -3-methylpyrazol-5-one, acetoacetic anilide.

Me preferably means chromium.

If R stands for an alkyl radical, it is e.g. an unsubstituted or e.g. C 1 -C 4 -alkyl radical substituted by hydroxy, C 1 -C 4 -alkoxy or phenoxy.

R preferably represents the ethyl, n- or iso-propyl and particularly preferably the methyl radical as the alkyl radical.

If R is an aryl radical, this is e.g. an unsubstituted or substituted by halogen, Ci-C4-Aikyl, Ci-C4-alkoxy and / or nitro or a 1- or 2-naphthyl radical.

R as the aryl radical is preferably an unsubstituted or chlorine, methyl and / or methoxy-substituted phenyl radical and particularly preferably the phenyl radical.

The cycloalkyl radical for R is e.g. the cyclopentyl, cycloheptyl and especially the cyclohexyl radical in question.

If R represents an aralkyl radical, this is e.g. a C7-Ci2-araiki radical and preferably the benzyl or phenylethyl radical.

R is preferably a C 1 -C 4 -alkyl radical or an unsubstituted or substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and / or nitro phenyl radical.

For R the meanings are particularly preferably methyl, ethyl, n- or isopropyl, phenyl, 3- or 4-chlorophenyl, 3- or 4-methylphenyl, 3- or 4-methoxyphenyl and 2,4-dichlorophenyl.

A particularly preferred embodiment of the present invention relates to compounds of the formula (1) in which R is phenyl or in particular methyl.

The metal complex compounds of formula (1) carry e.g. 0 to 4, preferably 1 to 3 and particularly preferably 1 or 2 sulfo groups, the meaning sulfo comprising both the free acid form (-SO3H) and the salt form.

The metal complex compounds of the formula (1) according to the invention are advantageously isolated in the form of their salts, in particular alkali metal salts, such as lithium, potassium and above all sodium salts or also ammonium salts.

Of particular importance because of their good coloring properties are the asymmetrical 1: 2 metal complex dyes which correspond in the form of the free acid to the formula and contain 1 or 2 sulfo groups, in which

D'i and D'2 each independently represent the residue of a 1-hydroxy-2-aminobenzene which is unsubstituted or e.g. is further substituted by chlorine, nitro, sulfo, methyl, methoxy, methylsulfonyl, carbamoyl, sulfamoyl and / or phenylazo, or the residue of a 2-hydroxy-1-aminonaphthalene which is unsubstituted or e.g. is further substituted by sulfo and / or nitro,

K 'the residue of an unsubstituted or sulfo and / or amino-substituted 1- or 2-naphthol or the residue of a 1-phenyl-3-methyl-5-pyrazolone or acetoacetic anilide, the phenyl residue of which is in each case unsubstituted or e.g. substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, nitro and / or sulfo

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CH 680 071 A5

is, represents and R 'represents a Ci-C4-alkyl radical or an unsubstituted or substituted by halogen, C1-C4-alkyl, Ci-C4-alkoxy and / or nitro phenyl radical.

A particularly preferred embodiment of the present invention relates to compounds of the formula (1 a) given above, in which D'i and D'2 independently of one another are the residue of 4-nitro-2-ami-no-1-hydroxybenzene-6-sulfonic acid, 6 -Nitro-2-amino-1-hydroxybenzene-4-sulfonic acid, 4- or 5-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-suifamoyl-2-aminophenol, 1-amino-2-hydroxynaphthalene 4-sulfonic acid or 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, K 'is the remainder of 1-naphthol, 2-naphthol, 1-naphthol-3-, -4- or-5-sulfonic acid, 1-Phenyl-3-methylpyrazoI-5-one, 1- (2'-, 3'- or 4'-sulfophenyl) -3-methylpyrazol-5-one or acetoacetic anilide and R 'is methyl or phenyl.

The compounds of formula (1) according to the invention can be prepared by methods known per se, e.g. by using an azo compound of the formula d1-n = z-k (2)

<? 0) q xh

1'

and an azo compound of the formula

(3),

wherein Di, D2, K, R, X, Z, p and q each have the meaning given above, with a chromium, cobalt or iron donating agent. The corresponding mixed metal complex dyes are formed, i.e. Dye mixtures which, in addition to the asymmetrical compound of the formula (1), have two symmetrical 1: 2 metal complex compounds containing either two molecules of the formula (2) or (3). These mixed metal complex dyes are a further subject of the present invention.

Suitable cobalt or chrome releasing agents are e.g. Cobalt or chromium salts or complexes such as cobalt sulfate, acetate or chloride, chromium sulfate, acetate, chloride, formate or salicylate etc.

The metal-donating agent is advantageously used in excess, based on the compounds of the formulas (2) and (3), e.g. 1 to 8, preferably 1 to 5 moles per mole of the sum of the compounds of the formulas (2) and (3) can be used. The molar ratio in which the compounds of formula (2) and (3) are used is e.g. 1: 0.5 to 1: 2.0 and preferably 1: 0.8 to 1: 1.2.

The metallization takes place e.g. in an aqueous medium at a temperature of 10 to 100 ° C, preferably 20 to 60 ° C, and pH 3 to 12 or in a polar aprotic medium, e.g. in formamide, at a temperature of e.g. 50 to 150 ° C instead.

The mixed metal complex compounds can optionally be separated using simple separation processes, e.g. column chromatographic methods, broken down into their components and in this way the compounds of formula (1) are presented purely.

The 1: 2 chromium complexes of the formula (1) can also be prepared by preparing the 1: 1 chromium complex of a compound of the formula (3) or preferably a compound of the formula (2) and then using a non-metallized compound of formula (2) or preferably of formula (3). In this way, uniform asymmetric 1: 2 chromium complex dyes are accessible.

The 1: 1 chromium complex is prepared by methods known per se by treating one azo compound, preferably in an acidic solution, with chromium III salts. The 1: 1 chromium complex of this azo compound obtained is then reacted with the second non-metallized azo compound in weakly acidic, neutral or weakly alkaline medium.

The compounds of the formulas (2) and (3) are known or can be obtained in a manner known per se.

The compounds of formula (1) and mixed metal complex compounds containing them are anionic dyes and are generally suitable for dyeing textile and non-textile substrates dyeable with anionic dyes, e.g. for dyeing fiber material from natural

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cher or regenerated cellulose, natural or synthetic polyamides, polyurethanes or basic modified polyolefins, also of anodized aluminum or of leather and furs.

The dyes according to the invention can advantageously e.g. for dyeing cellulose nonwovens, wood and paper. In particular, cotton and natural polyamides such as wool and silk come into consideration as fiber materials, while the focus in the synthetic fiber materials is made of polyamides (e.g. polyamide 6,6) and basic modified polypropylenes.

The dyes according to the invention are preferably suitable for dyeing furs and in particular leather, all types of leather, e.g. Chrome leather, retanned leather or suede from goat, sheep, beef and pork are suitable.

Dyes with good general fastness properties, such as diffusion, washing, light, acid and alkali fastness, are obtained. The dyes of the formula (1) have good drawability, good acid and alkali stability, good electrolyte resistance and good build-up on various types of leather such as pure chrome leather and retanned leather.

The compounds of the formula (1) according to the invention are also suitable as constituents of inks and in particular of recording liquids for the ink-jet process.

The following examples serve to illustrate the invention without restricting it. Parts mean parts by weight and percentages percent by weight.

Example 1 :

3 ©

c = 0

I.

ch3

3na

©

39 parts of the complex chromium compound of the 1 atom chromium type, which is produced in a manner known per se: 1 molecule of monoazo compound of the formula oh oh s03h is dissolved warm in water at pH 7. 40 parts of the azo compound of the formula are in this solution at 80 ° C and pH 7

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CH 680 071 A5

Oh oh

02n oh sogh c = 0

ch3

entered and the whole thing stirred at this temperature and constant pH until the starting products are no longer detectable.

After the addition reaction has ended, the dye is salted out with sodium chloride and isolated. A dark powder is obtained which dissolves in water with a blue color and dyes leather in navy blue tones with good general fastness properties.

Examples 2-19:

If the procedure is as described in Example 1, but in each case equivalent amounts of 1: 1-chromium complex of the azo dye 1 listed in the table are reacted with the azo dye 2, analogous 1: 2-chromium complex dyes are obtained which dye leather in the specified shade:

7

o> o ai

Ol a? O

• f * en

4 ^ o co

Ol co o w en ro o

Oil

Example No.

Azo dye 1

Azo dye 2

Nuance on leather

2nd

0H "V-.

n — E

^ ^ N = N ^ /

oh? h SOsH— / \ —N = N — fj-]

w y-0H

y y O ^ C ^ CH3

no2

brown

3rd

oh oh so3h-Q — N = N

\ _ / S03H

OH <j> H S03H - / \ - N = N— \ J

v / y-oh

^ y o * cxch3

no2

Gray

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OH OH

fVN = N "iT ^ X, ì

y

Ci

OH O "SOgH— $ \ —N = N— \ J

w y-oh

J V 0 "^ csch3

no2

Corinth

O) o

Ol o

• N ol

O

CO

o ro en

Example No.

Azo dye 1

Azo dye 2

Nuance on leather

5

OH OH

N02] i

S03H

OH ° H SOgH— / \ —N = N— \ 1

W y ^ OH

0 <tCvCH3

N02

Gray

6

COOH H0S / F ~ \ 1 Nc - n— <'V-SO3H

6- "~ u ch3

OH? H SOgH —— N = N— \ 1

W y ^ OH

yj O ^ C% CH3 no2

brown

7

a-ÇX-Z

2nd

II

2nd

OH ° H SO3H —Ì \ —N = N — 1

V = / ^ y ^^ OH O ^ CvCH3

no2

brown

O X

CD 00 O

>

en

Example No.

Azo dye 1

Azo dye 2

Nuance on leather

8th

oh ho sogh— / \ —n = n — i \

yj o n02

oh on sogh --J \ —n —n— (f 1

W y-OH

j V o * c ^ ch3 no2

Black-brown

9

oh oh n = n

no2 v y so3h oh cooh 1

-çl "

so2-nh2 ^ c

0 ^ nch3

Dark brown

10th

oh h °

no2 v V

Oh

OH j S02-NH2 o * ^ CHg

Yiolet brown

• I * r "

<J>

O

Oil

Oil

Ol o

Oil

• f * o

CO

o ro

Ol w o

Example No.

Azo dye 1

Azo dye 2

Nuance on leather

11

z o z

II z ryY5

oh oh I

^ rN = N-y.0H

s02-nh2 0 * ^ cha

Violet brown

12

Ohh O

SO3H— / \ —n = n — i \

o o no2

oh ° h s03h — ff \ —n = n— (f j

V = / ^^^ oh \ ff o ^ ° vch3

Gray

13

oh h °

sooh ^ \

3 —n = n— ^ y

\ / no2 '/

oh? h SO3H — ff \ —n = n — 1 |

W y-oh

J — ff o ^ Cvch3 no2

brown

Oil

Oil

Ol o

Oil

4 * o

CO Ol

CO

O

1 °

Oil

N> O

ü>

O

Oil

Oil

Ol o

4 ^

Ol o

CO

cn co o ro o

Example No.

Azo dye 1

Azo dye 2

Nuance on leather

17th

oh hov n02 \ /

oh oh j

Vr "-" <JX.

so3h o ^ vch3

Corinth

18th

oh h °

H0's ^ _n_n_M

no2 \ ff oh oh so3h c — o

O

corinth

19th

oh oh h03s I 1 v ^ s — n == n

Y

no2 c = o ch3

Oh oh

Ò ~~ §

so3h light brown

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CH 680 071 A5

Example 20:

39 parts of the monoazo compound of the formula (4) mentioned in Example 1 and 40 parts of the monoazo compound of the formula (5) mentioned in Example 1 are heated together with 18 parts of chromium salicylic acid at pH 8 under reflux until the starting products are no longer detectable. A mixed metal complex dye is obtained which, in addition to the asymmetric 1 ^ chromium complex described in Example 1, a blue symmetrical 1: 2 chromium complex of the monoazo compound of the formula (4) and a red-brown symmetrical 1: 2 chromium complex of the compound of the formula (5) contains.

Example 21:

If the procedure is as described in Example 20 and 15 parts of C0SO4 • 7H2O are used instead of chromium salicylic acid, the analog cobalt mixed metal complex dye is obtained; the asymmetrical component has a reddish navy blue color, while the symmetrical 1: 2 complexes of the compounds of the formulas (4) and (5) have a violet or burgundy shade.

Dyeing instructions for wool

100 parts of wool knitting yarn are introduced at 50 ° C. into a dyebath containing 2 parts of dye of Example 2, 4 parts of ammonium sulfate and 2 parts of a leveling agent per 4000 parts of water. The liquor is brought to the boil over the course of 45 minutes and left at this temperature for a further 45 minutes. The brown-colored yarn is then removed, rinsed thoroughly with cold water and dried.

Dyeing instructions for leather

100 parts of suede clothing (dry weight) are rolled on at 50 ° C in a solution of 1000 parts of water and 2 parts of ammonia 24% for 2 hours and then at 60 ° C in a solution of 1000 parts of water, 2 parts of ammonia 24% and 6 parts of dye of Example 2 dyed for 1 hour. Then a solution of 40 parts of water and 4 parts of 85% formic acid is added and the dyeing is continued for a further 30 minutes. Then the leather is rinsed well and, if necessary, treated with 2 parts of a dicyandiamine formaldehyde condensation product for 30 minutes at 50.degree.

Other suede and glove leather can be dyed in the same way.

The brown dyeings obtained in this way are distinguished by good fastness properties and good hiding power.

Dyeing instructions for polyamide

100 parts of fabric made of textured polyamide (nylon-6,6) are placed at 40 to 50 ° C. in a dyebath containing 2 parts of the dye mentioned in Example 2 and 3 parts of ammonium sulfate per 4000 parts of water. The dyebath is heated to boiling within 45 minutes and left at this temperature for a further 60 minutes. The polyamide fabric removed after cooling to 80 ° C is dyed in a real brown after rinsing and drying.

Claims (19)

Claims 1. Metal complex compounds in the form of the free acid of the formula 14 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 680 071 A5 d1-n = z-k © oh h® (1): c = o r correspond to what Di and Dz independently of one another each represent the residue of an optionally further substituted diazo component of the benzene or naphthalene series which bears a hydroxyl or carboxy group in the ortho position to the azo group, Z is nitrogen or a CH group, X represents oxygen or a group -NRi-, in which Ri represents hydrogen or Ci-C4-alkyl, K represents the remainder of an optionally further substituted o-hydroxybenzaldehyde or o-hydroxy-naphthaldehyde if Z is the CH group, or the remainder of an optionally further substituted coupling component of the benzene or naphthalene series or the heterocyclic series which is in the o- or. a position to the azo group which contains group X means, if Z is nitrogen, with the proviso that -KX- is not a radical of the formula R represents an alkyl, aryl, cycloalkyl or aralkyl radical, Me stands for chromium, cobalt or iron and p and q independently of one another represent the number 0 or 1. 2. Metal complex compounds according to claim 1, which carry 1 to 3 and preferably 2 sulfo groups. 3. Metal complex compounds according to claim 1 or 2, characterized in that Di and D2 independently of one another each unsubstituted or by Ci-C4-alkyl, Ci-C4-alkoxy, halogen, trifluoromethyl, Ci-C4-alkylsulfonyl, sulfamoyl, N-mono - or N, N-di-Ci-C4-alkylsulfamoyl, carbamoyl, N-mono- or N, N-di-Ci-C4-alky! carbamoyl, sulfo, nitro, cyano, carboxy, phenoxy, C1-C4-alkanoylamino , Benzoylamino, C 1 -C 4 -alkoxycarbonyl and / or phenyl or 1-or 2-naphthyl radical which is unsubstituted or substituted in the phenyl part by sulfo, nitro, chlorine, methyl or methoxy-substituted phenylazo. 4. Metal complex compounds according to one of claims 1 to 3, characterized in that Di and D2 independently of one another each the residue of a 1-hydroxy-2-aminobenzene, which is unsubstituted oh c = 0 r 15 5 10th 15 20th 25th 30th 35 40 45 50 55 CH 680 071 A5 or is further substituted by chlorine, nitro, sulfo, methyl, methoxy, methylsulfonyl, carbamoyl, sulfamoyl and / or phenylazo, the remainder of a 2-hydroxy-1-aminonaphthalene which is unsubstituted or substituted by sulfo and / or nitro, or the remainder of anthranilic acid mean. 5. Metal complex compounds according to one of claims 1 to 4, characterized in that Di and D2 independently of one another each the rest of 4-nitro-2-amino-1-hydroxybenzoI-6-suIfonic acid, 6-nitro-2-amino-1- hydroxybenzene-4-sulfonic acid, 4- or 5-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-sulfamoyl-2-aminophenol, 1-amino-2-hydroxynaphthalene-4-sulfonic acid or 1-amino Mean -2-hydroxy-6-nitronaphthalene-4-sulfonic acid. 6. Metal complex compounds according to one of claims 1 to 5, characterized in that p and q each represent the number 0. 7. metal complex compounds according to any one of claims 1 to 6, characterized in that Z is the CH group and K is the rest of an unsubstituted or by Ci-C4-alkyl, Ci-C4-alkoxy, halogen, sulfo or unsubstituted or im Phenyl part represented by sulfo, nitro, chlorine, methyl, carboxy and / or methoxy substituted phenylazo substituted o-hydroxybenzaldehyde. 8. Metal complex compounds according to claim 7, characterized in that K is the residue of an unsubstituted or substituted by phenylazo, sulfophenylazo or disulfophenylazo o-hydroxybenzaldehyde. 9. Metallkompiexverbindungen according to any one of claims 1 to 6, characterized in that Z is nitrogen. 10. Metallkompiexverbindungen according to any one of claims 1 to 6 or 9, characterized in that K is the residue of an unsubstituted or by Ci-Cs-alkyl, Ci-C4-alkoxy, N, N-di-Ci-C4-A! amino, Ci-C4-Alkoxycarbonyiamino and / or Ci-C4-Alkanoylamino substituted phenol; an 1- or 2-naphthol which is unsubstituted or substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, amino, Ci-C4-alkanoylamino, benzoyl-amino and / or sulfo; a 5-pyrazolone, which in the 1-position carries an unsubstituted or substituted by chlorine, nitro, sulfo, C 1 -C 4 alkyl and / or C 1 -C 4 alkoxy phenyl or naphthyl radical; a 6-hydroxy-3-cyano- or 6-hydroxy-3-carb-amoyl-2-pyridone which carries an optionally substituted C 1 -C 4 -alkyl radical or a phenyl radical in the 1-position and optionally in the 4-position by Ci C4 alkyl is substituted; a benzoylacetic or acetoacetic acid which is unsubstituted in the anilide nucleus or substituted by chlorine, nitro, Ci-C4-alkyl, Ci-C4-alkoxy or sulfo, or the rest of an unsubstituted or by sulfo, sulfamoyl or N-mono- or N, N-Di-Ci-C4-alkylsulfamoyl substituted 1- or 2-naphthylamine. 11. Metallkompiexverbindungen according to any one of claims 1 to 6 or 9 to 10, characterized in that K is the residue of an unsubstituted or substituted by sulfo and / or amino 1-or 2-naphthol or a 1-phenyl-3-methyl-5- pyrazolones or acetoacetic acid, the phenyl radical of which is in each case unsubstituted or substituted by Ci-C4-alkyl, Ci-C4-alkoxy, chlorine, nitro and / or sulfo. 12. Metallkompiexverbindungen according to any one of claims 1 to 6 or 9 to 11, characterized in that K is the rest of 1-naphthol, 2-naphthol, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-phenyl -3-methylpyrazol-5-one, 1- (2'-, 3- or 4'-sulfophenyl) -3-methylpyrazol-5-one or acetoacetic anilide. 13. Metallkompiexverbindungen according to any one of claims 1 to 12, characterized in that R is a Ci-C4-alkyl radical or an unsubstituted or substituted by halogen, Ci-C4-alkyl, Ci-C4-alkoxy and / or nitro phenyl radical. 14. Metallkompiexverbindungen according to any one of claims 1 to 13, characterized in that R is methyl or phenyl. 15. Metallkompiexverbindungen according to claim 1, in the form of the free acid of the formula 16 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 CH 680 071 A5 © DY-N = N - K ' OH H® (la) C = 0 R ' correspond and contain 1 or 2 sulfo groups, wherein D'i and D'à each independently of one another the residue of a 1-hydroxy-2-aminobenzene which is unsubstituted or further substituted by chlorine, nitro, sulfo, methyl, methoxy, methylsulfonyl, carbamoyl, sulfamoyl and / or phenylazo, or the residue a 2-hydroxy-1-aminonaphthalene which is unsubstituted or further substituted by sulfo and / or nitro, K 'is the radical of an unsubstituted or sulfo and / or amino-substituted 1- or 2-naphthol or the radical of a 1-phenyl-3-methyl-5-pyrazolone or acetoacetic acid, the phenyl radical of which is in each case unsubstituted or by Cr-G4-alkyl, Ci-C4-alkoxy, chlorine, nitro and / or sulfo is substituted, and R 'represents a Ci-C4-alkyl radical or an unsubstituted or by halogen, C1-C4-alkyl, Ci-C4-alkoxy and / or nitro substituted phenyl radical. 16. Metallkompiexverbindungen according to claim 15 of formula (1a), wherein D'i and D'2 independently of one another the rest of 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid, 6-nitro-2-amino-1 -hy-hydroxybenzene-4-sulfonic acid, 4- or 5-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-sulfamoy! -2-aminophenol, 1-amino-2-hydroxynaphthalene-4-sulfonic acid or 1 -Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, K 'is the rest of 1-naphthol, 2-naphthol, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-phenyl -3-methylpyrazol-5-one, 1- (2'-, 3'- or 4'-sulfophenyl) -3-methylpyrazol-5-one or acetoacetic anilide and R 'is methyl or phenyl. 17. A process for the preparation of metal complex compounds of the formula (1) according to claim 1, characterized in that a compound of the formula D1-N = Z-K (2) and an azo compound of the formula XH 17th 5 10th 15 20th 25th 30th 35 40 45 50 55 CH 680 071 A5 ho d2 - n = n oh (3); oh c = 0 r in which Di, D2, K, R, X, Z, p and q each have the meaning given above, with a chromium, cobalt or iron donor. 18. A process for the preparation of metal complex compounds of the formula (1) according to claim 1, in which Me is chromium, characterized in that the 1: 1 chromium complex of a compound of the formula (2) or (3) given in claim 17 is prepared and this then reacted with a non-metallized compound of the formula (3) or (2) to give the 1: 2 complex. 19. Mixed metal complex dyes obtained by the process according to claim 17. 18th