FR2576312A1 - DYES WITH A CHROMIUM COMPLEX 1: 2 ASYMMETRIC - Google Patents

Abstract

THE NEW DYES CORRESPONDING TO FORMULA 1 DEFINED IN CLAIM 1 ARE SUITABLE FOR DYING WOOL, POLYAMIDE AND ESPECIALLY LEATHER.

Description

-1- Chromium complex dyes 1: 2 asymmetric The invention relates to

  asymmetric 1: 2 chromium complex dyes of formula (1) -20

A-N = Z-B

A - N = Z -B -2

(Co1 / 2 KaRa (CO) p

DN = N- -1

  Wherein Z represents a nitrogen atom or a CH group; A and D are each, independently of each other, a residue of the benzene or naphthalene series, which has a hydroxyl or carboxyl group ortho to the azo or azomethine moiety; B represents, when Z is a nitrogen atom, the remainder of a coupling component, the coupling component containing the X group at the ortho or alpha position with respect to the azo group, or when Z represents the CH group, the remainder an o-hydroxy-aldehyde; X represents an oxygen atom or, when Z is a nitrogen atom, a group of formula -NR-, where R represents a hydrogen atom or a C14 alkyl radical; 1-4; Y represents a hydrogen atom or a group of formula -SO 2 -Q or -CO- (O) nQ, it is equal to 0 or 1 and Q is a C 1 -C 5 alkyl or phenyl radical, the phenyl radical may be substituted by a nitro, halo, C1-5 alkyl or C1-5 alkoxy group;

9- - -2-

  p and q are each, independently of one another, 0 or 1 and

Ka) represents a cation.

  In the case of the dyes according to the invention, these are asymmetric chromium 1: 2 complexes. In the case where A and D and p and q are identical, the coupling component B in an azo dye must not be identical to the copulation component of the other

azo dye.

  In the chromium complex dyes according to the invention, of formula (1) above, the radicals A and D may also carry one or more other substituents, for example, lower alkyl or lower alkoxy, halogen, as per chloro or bromo, nitro, cyano, sulpho, carboxyl, phosphono, alkylsulphonyl; as for example methylsulfonyl, sulfamido groups such as for example

  sulfamido or N-methylsulfamido, acylamino, phenylazo, sulfo

  phenylazo or methoxyphenylazo. By "lower alkyl or lower alkoxy" is meant in general in the context of this application those having 1 to 6, preferably 1 or 2 carbon atoms, and "acylamino" means alkanoylamino, alkylsulfonyl-mino and lower alkoxycarbonylamino as well as aroylamino groups,

  aryloxycarbonylamino and arylsulfonylamino.

  The radicals A and D are derived, for example, from the following amines: anthranilic acid, 4- or 5-chloro-anthranilic acid, 4- or -sulfoanthranilic acid, 2-amino-3-naphthoic acid, 2-amino-1-hydroxybenzene,

  4-chloro 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-hydroxy-

  benzene, 4-cyano-2-amino-1-hydroxybenzene, 4-sulfonamido-2-amino-1-

  hydroxybenzene, 1-hydroxy-2-aminobenzene-4-sulfo-anthranilide, 4-methoxy-

  2-amino-1-hydroxybenzene, 4-methoxy-5-chloro-2-amino-1-hydroxybenzene,

  4-methyl-2-amino-1-hydroxybenzene, 4-chloro- and 4-methyl-5-nitro-2-amino-

  t-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-hydroxybenzene-4- or -5-sulfonic acid, 4-nitro-2-acid

  amino-1-hydroxybenzene-6-sulfonic acid, 6-nitro-2-amino-1-hydroxy-acid

  benzene-4-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid, -3-

  1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-acid

  6-nitronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-chloroacetate

  naphthalene-4-sulfonic acid, 1-amino-2-hydroxynaphthalene-4,6-

  disulfonic acid, 2-amino-1-hydroxybenzene-4,6-disulfonic acid. -

  In place of the amines containing hydroxyl groups mentioned above, the corresponding methoxy compounds or the corresponding compounds whose radical is also taken into account for A and D are also taken into consideration.

  hydroxyl has been tosylated, such as anisidine, 4- or 5-chloro

  anisidine, 4- or 5-nitroanisidine, anisidine-4- or -sulfonic acid, or tosylated 1-hydroxy-2-aminobenzene, the methoxy or O-tosyl radical being converted to OH before metallation or during this one. Most of the compounds containing these radicals are used when

  the corresponding 1-hydroxy-2-amino compounds poorly copulate.

  In the preferred dyes of formula (1), A and D each represent the residue of a 1-hydroxy-2-aminobenzene which is optionally substituted by halo, nitro, sulfo or lower alkyl or lower alkoxy, or the remainder a 1-amino-2-hydroxy-4-sulfonaphthalene which is optionally substituted in the 6-position by a halo group

  such as bromo, or in particular chloro, a nitro or sulfo group.

  Particularly preferred are the dyes of formula (1) in which A and D each represent, independently of one another, the residue of a 1-hydroxy-2-aminophenol which is substituted by a group

  nitro, as well as possibly by a sulfo group.

  Among the dyes of formula (1), those in which

Z is a nitrogen atom. -

  The remainder B preferably derives from groups of

  following copula: phenols copulating in the ortho position, possibly

  substituted by alkyl or lower alkoxy groups, dialkyl-

  amino or acylamino, "acylamino" -signifying C1-4alkanoylamino, C1-4alkylsulfonylamino, C1-4alkoxycarbonylamino, aroylamino or arylsulfonylamino radicals; naphthols which are optionally substituted by C14 alkyl or C14 alkoxy, chloro, amino, acylamino groups;

  or sulpho, "acylamino" having the same meaning as given below.

  above; 5-pyrazolones or 5-aminopyrazoles, preferably those having in the 1-position a phenyl or naphthyl radical optionally substituted by chloro, nitro, C 1-4 alkyl or C 1-4 alkoxy or sulpho groups, and present in the 3-position a C1-C4 alkyl or carboxyl radical, in particular a methyl group; naphthylamines which are optionally substituted with sulpho, sulphonamido or sulphonyl groups; acetylacetamides, primarily acetylacetanilide, and benzoylacetanilides, which may be optionally substituted in the anilide ring with chlorine, bromine, nitro, C1-4alkyl or C1-4alkoxy, or with sulfo groups; 6-hydroxy-3-cyano- or 6-hydroxy-3-carbamyl-4-alkyl-2-pyridones

  which are substituted in position 1 by a C14 alkyl group

  substituted, for example, methyl, isopropyl, f-hydroxy-

  ethyl, P-aminoethyl or Y-isopropoxypropyl, or with a phenyl group,

  and which can carry a C 1-4 alkyl group in position 4, in particular

  a methyl group; or hydroxyquinolines.

  Examples of such copulation components are:

  2-Naphthol, 1-naphthol, 1-acetylamino-7-naphthol, 1-propionyl-

  amino-7-naphthol, 1-carboxymethoxy-amino-7-naphthol, 1-carbo-ethoxy-

  amino-7-naphthol, 1-carbopropoxy-amino-7-naphthol, 6-acetyl-2-naphthol, 2-naphthol-3-, -4-, -5-, -6-, -7 - or -8-sulphonic acid

  1-naphthol-3-, -4- or -5-sulfonic acid, 1-naphthol-3,6- or -4,8-

  disulfonic acid, 2-naphthol-6,8-disulfonic acid, 4-methyl-1-naphthol, 4-methoxy-11-naphthol, 4-acetyl-1-naphthol, 5,8-dichloro-1 naphthol,

  5-chloro-1-naphthol, 2-naphthylamine, 2-naphthylamine-1-acid

  sulphonic acid, 1-naphthylamine-4- or -5-sulphonic acid, 2-amino-

  naphthalene-6-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid,

  6-methylsulfonyl-2-aminonaphthalene, 1-phenyl-3-methyl-pyrazol

  -one, 1-phenyl-5-pyrazolone-3-carboxylic acid amide, 1- (2'-, 3'- or 4'-methylphenyl) -3-methylpyrazol-5-one, the - (2',

  3'- or 4'-sulfophenyl) -3-methylpyrazol-5-one, 1- (2'-chloro-5'-sulfo)

  phenyl) -3-methylpyrazol-5-one, 1- (2'- or 4'-methoxyphenyl) -3-methyl-

  pyrazol-5-one, 1- (2'-, 3'- or 4'-chlorophenyl) -3-methyl-pyrazol-5-one,

  1- (2'-, 3'- or 4'-nitrophenyl) -3-methylpyrazol-5-one, 1- (2 ', 5'-

  or 3 ', 4'-dichlorophenyl) -3-methylpyrazol-5-one, 1- (2', 5'-dichlorobenzene)

  4'-sulfophenyl) -3-methylpyrazol-5-one, 1- (2'-, 3'- or 4'-sulfophenyl) -

  3-methyl-5-aminopyrazole, 1-phenyl-3-methyl-5-aminopyrazole, -5-

  1- (2'-chloro-5'-sulfophenyl) -3-methyl-5-aminopyrazole, acetoacetate

  acetanilide, acetoacetanilide-4-sulfonic acid, acetoacetate

  aniside, acetoacetate-o-toluide, acetoacet-o-chloranilide,

  aceto-acetyl-xylide, tetralol, 4-methylphenol, 3-dialkyl-

  aminophenols, in particular 3-dimethylamino- and 3-diethylaminophenol, 4-butylphenol, preferably 4-tert.-butylphenol,

  4-amylphenol, in particular 4-tert.-amylphenol, 2-isopropyl-

  4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxy-

  carbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol and 3,4-dimethylphenol, 1-methyl-3-cyano-4-ethyl-6-hydroxypyridone,

  1-methyl-3-cyano-4-methyl-6-hydroxypyridone, 1-phenyl-3-carbamoyl

  4-methyl-6-hydroxypyridone, 1-ethyl-4-hydroxy-2-quinolone,

  2,4-dihydroxyquinoline or 3-methylpyrazol-5-one.

  The copulatory component B preferably represents a

  or 2-naphthol optionally substituted by an amino group and / or a sulfo group, a 1- or 2-naphthylamine optionally substituted with

  a sulfo group, a p-alkyl (C1 6) -phenol, a 1-phenyl-3-methyl-5-

  pyrazolone or acetylacetanilide, the phenyl radical in the last two compounds which may be substituted by an alkyl group

  C1-14, C1-4 alkoxy, chloro, nitro or sulfo.

  With regard to the coupling component B, it is particularly preferably a 1- or 2-naphthol, optionally substituted by an amino group and / or a sulfo group, and in particular

  2-amino-8-hydroxynaphthalene-6-sulfonic acid.

  When Z is CH, B represents the residue of an o-hydroxy-aldehyde, preferably an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, which may be substituted by lower alkyl, halo, sulpho, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo. Suitable aldehydes are, for example: 2-hydroxy-1-naphthaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxybenzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5-butyl-2-hydroxybenzaldehyde,

  5-chloro or 5-bromo-2-hydroxybenzaldehyde, 3-chloro

  2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo

  2-hydroxybenzaldehyde, 3-methyl-5-chloro-2-hydroxybenzaldehyde, -6-

  5- (phenylazo) -2-hydroxybenzaldehyde, 5- (2'-, 3'- or 4'-sulfophenyl)

  azo) -2-hydroxybenzaldehyde, 5- (6'-sulfonaphthyl-1H-azo) -2-hydroxy-

  benzaldehyde or 5- (4 "-sulfo-4'-phenylazo) -phenylazo-2-hydroxy-

  benzaldehyde. Ka represents a cation, for example an alkaline cation such as lithium, potassium or, preferably, sodium. K4 can in

  in addition to being an ammonium cation or the ammonium salt of an organic amine.

  The appropriate Y residues in the dyes of formula (1) are

for example:

  a hydrogen atom, an acetyl, propionyl, butyryl, isopropyl,

  butyryl, valeryl, isovaleryl, pivaloyl, capronyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-pentoxycarbonyl, methylsulfonyl,

  ethylsulfonyl, butylsulfonyl, phenylsulfonyl, benzoyl or phenoxy

  carbonyl, the phenyl radicals in the three compounds listed last which may be substituted, for example, with a nitro group, halo,

  such as bromo or above all chloro, C 14 alkyl or C 1-4 alkoxy.

  R preferably represents a hydrogen atom, a radical

  acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenyl

  sulfonyl, and in particular a hydrogen atom, a methoxy radical

carbonyl or acetyl.

  The dyes according to the invention which are particularly preferred correspond to formula (2)

A '- N = N - B' 20

  Cr 2Ka (2) wherein A 'and D' are each, independently of one another, the residue of a 1-hydroxy-2-aminobenzene which is optionally substituted with halo, nitro, sulpho, lower alkyl or lower alkoxy, or the residue of a 1-amino-2-hydroxy-4-sulphonaphthalene which is optionally substituted in position 6 with a nitro group or sulfo; B 'represents a 1 or 2-naphthol optionally substituted by an amino group and / or a sulfo group, a 1- or 2-naphthylamine optionally substituted by a sulfo group, a p-alkyl (Cl 6) -phenol, a 1-phenyl 10. 3-methyl-5-pyrazolone or acetylacetanilide, the phenyl radical in the two last-mentioned compounds which may be substituted by C1-4 alkyl, C1-4 alkoxy, chlora, nitro or sulfo; Y 'represents a hydrogen atom, a methoxycarbonyl or acetyl group and

Ka represents a cation.

  The dyes of formula (1) according to the invention can be prepared by methods known per se, for example by preparing the chromium complex 1: 1 of the azo dye of formula (3)

OH

(CO; OH

(co

I * 0

D - N = N - '\ -

I I, (3)

  ## STR1 ## and then reacting it with the dye of formula (4)

A - N = Z - B

I I (4).

(CO) q XIII 3q

O

  OH or with a mixture composed of the amine of formula (5)

A - NH2

(CO) (5)

  OH and aldehyde of formula (6)

HO-B-CHO (6)

  to result in the chromium 1: 2 complex, or by preparing the chromium 1: 1 complex of a dye of formula (4) and then reacting it with

with the dye of formula (3).

  A, B, D, Z, X, Y, p and q have the meanings given for the

Formula 1).

  The new metal complex dyes prepared by the above processes are advantageously isolated in the form of their salts, in particular alkali metal salts, such as lithium-potassium salts, but especially sodium salts, or also in the form of ammonium salts. They are suitable for the dyeing of materials containing nitrogenous groups, natural or synthetic, the most diverse, such as

  polyamides, polyurethanes, wool or especially leather.

  For the dyeing of wool or synthetic polyamide, dyes of formula (1) having 1-2 groups are especially suitable

  sulfo. The shades obtained are regular and have good

  such as fastness to light, washing, water, hot water, perspiration, rubbing, crushing, decapping

and carbonization.

  For dyeing leather, dyes having 2 to 5 sulfo groups are preferably used. These dyes give intense hues and cover well. They have good climbing power, exhibit good stability in the presence of acids and bases, and give hues with good fastness, such as diffusion, light, acid and alkali fastness. Particularly worth mentioning is the good calorific performance on various kinds of leather, both on leather tanned only with chromium salts and on leather retanned with vegetable or synthetic tannins. We get olive nuances,

  brown, blue or gray to black.

  The present invention is illustrated by the descriptive and nonlimiting examples hereinafter. In these examples, unless otherwise indicated

  contrary, the parts represent parts by weight and the percentages

  percentages by weight. Temperatures are given in

degrees Celsius.

-10-

Example 1

N02 40

  e / eRe O3S. '\ / 4 Na I2 I I e e e N H (7)

3 2

Cr

II I I II

NO2 ee / e N02

NH-COCH3

  The chromium complex 1: 1 is introduced into 600 parts of water.

  which contains 48.4 parts of the dye consisting of 4-nitro-

  Diazotized 2-amino-1-hydroxybenzene-6-sulfonic acid and 2-amino-8-acid

  hydroxynaphthalene-6-sulfonic acid, as well as 5.2 parts of chromium, and 44.6 parts of the mono-azo dye constituted from

  Diazotized 4-nitro-2-amino-1-hydroxybenzene and 2-acetylamino-6-

  hydroxynaphthalene-8-sulfonic acid. After which, the reaction mixture is heated

  At 80-85, the pH is adjusted to 7 with sodium hydroxide and maintained at this temperature and at constant pH until

  starting materials are no longer detectable. Once the reaction is complete

  The dye is isolated by evaporation. A dark powder is obtained which dissolves in the water giving a gray tint and dyes the

  leather in gray shades very solid in the light.

-11-

Example 2

NO 50

  N25 5.A'i 3s \. 'X. / 5 K II I I il I

3 I I 2

Cr / -

O / / \ O (8)

 3sx./L.-/l= N ,.

I t He I i3I

NO.

NH-COCH3

  The chromium complex 1: 1 is introduced into 600 parts of water.

  which contains 48.4 parts of the dye consisting of 4-nitro-

  Diazotized 2-amino-1-hydroxybenzene-6-sulfonic acid and 2-amino-8-acid

  hydroxynaphthalene-6-sulfonic acid, as well as 5.2 parts of chromium, and 52.6 parts of the mono-azo dye constituted from 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid diazotized with 2-acetylamino-6-hydroxynaphthalene-8-sulfonic acid. After that, the reaction mixture is heated to 80-85, the pH is adjusted to 7-7.5 with 5N sodium hydroxide, and the reaction mixture is maintained at this temperature and constant pH until starting dyes have disappeared. Once the reaction is complete, the dye is released by addition of potassium chloride, isolated by filtration and dried. After drying, it is in the form of a dark powder that dissolves in water giving a gray hue and dyes the

  leather in very solid gray shades.

-12- NO2 Exepl 33

"- / 3 KE

I I I II I

03S \ iA iX4s

/ II

o, Cr 'rr- / \ -'Y loI; CH3 \

NH-COCH

  48.9 parts of the chromium complex compound of the 1 chromium atom type are suspended in 600 parts of water: 1 molecule of dye, which contains 5.2 parts of chromium and 43.9 parts of the dye

  mono-azo compound formed from 6-nitro-1-amino-2-hydroxy-acid

  diazotized naphthalene-4-sulfonic acid and 2-hydroxynaphthalene, with 43.9

  parts of the mono-azo dye consisting of 6-nitro-4-methyl-

  Diazotized 2-amino-1-hydroxybenzene and 2-acetylamino-6-hydroxy-acid

  naphthalene-8-sulfonic acid. After that, the reaction mixture is heated to 80-85, the pH is adjusted to 7-7.5 with 5N sodium hydroxide, and the reaction mixture is maintained at this temperature and at constant pH until the starting materials have disappeared. Once the addition reaction is complete, the dye is released by addition.

  of potassium chloride, isolated by filtration and dried.

  After drying, it is in the form of a dark powder that dissolves in water giving a blue tint and dyes the leather

in very solid blue shades.

-13-

Example 4

NO N TO 40

12 1i

* -N = CH

  NO2; iv3 2 e Dancing 600 parts of water the chromium complex 1: 1

  which contains 48.4 parts of the dye consisting of 4-nitro-

  Diazotized 2-amino-1-hydroxybenzene-6-sulfonic acid and 2-amino-6- acid

  hydroxynaphthalene-8-sulfonic acid, as well as 5.2 parts of chromium, and 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts are added thereto.

  mono-azo dye consisting of 1-aminobenzene-2- acid

  diazotized suonic acid and salicylaldehyde.

  Nil2 The chromium complex 1: 1 is introduced into 600 parts of water after which the reaction mixture is extracted from 4-nitro

  2-amino-pH to 7 with -hydroxybenzene dne-6-sulfonic diazot in maint of temp2-amino-6--

  The addition of 5-hydroxy-8-naphthalenes until 5.25 parts of the total are added. 4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the dye by evaporation are 1-aminobenzedissin-2-out acid

  in water, using an olive diaz, and all of solid ensalicylaldhy leather.

  nuAprs what, one warms the racial mlancesge 80-85, one adjusteolive.

  the pH at 7 with sodium hydroxide, and this temperature is maintained at

  and at constant pH until the starting materials are no longer detectable. Once the addition reaction is complete, the dye is isolated by evaporation. We obtain a dark powder that dissolves in water giving an olive tint, and that dyes the leather into solids

olive shades.

- 14 -

Example 5

NHCOCH3

- NO2 3KO

_ _ _ NHCOH3 K_

A35- I 2 I 3

0 TO 0

3 3 '* 5 KO

  II II I IIIII 0 * t / -N = O - / 3s ',' ..2 /, /

AT.N = N40 K "

  No // '0 \ 03 Cr r 00 0 * e- N N -. N = -N I I II It NO2 NO2 one // '

NHCOCH3

  (11) NO2 * e-N = N-.4 K '3 I I II II II NO2N /

NHCOCH3

-15- -

  48.4 parts of the mono dye are stirred into 400 parts of water.

  azo compound consisting of 4-nitro-2-amino-1-hydroxybenzene-6-

  diazotized sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulphonic acid, as well as 44.6 parts of the mono-azo dye consisting of diazotized 4-nitro-2-amino-1-hydroxybenzene and 2-acetylamino acid -6-hydroxynaphthalene-8-sulfonic acid and, after addition of 300 parts by volume of a solution of sodium chromosalicylate (corresponding to 6.25 parts of chromium), is refluxed until the starting dyes are gone . Once the chromation is complete, the mixture of chromium-containing dyes is released by addition of potassium chloride, and is isolated by filtration. After drying, a dark powder is obtained which dissolves in the water giving a gray tint, and which

  dyes the leather in very solid gray shades.

  If the procedure is as in Examples 1-5, but using the azo or azomethine dyes listed in the table below, 1: 2 chromium complex dyes are obtained which have the grades indicated in the last column and that dye the leather in

giving very strong hues.

HOS HO IlI I H Os, / \ * *

\ / '** "N - \ /. N = N. \. N O

o. * N-, \ z

HO HO HO HO !: O0

HD-OD-HN '

O HOO

* * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

* 0 -N - = D "OH \

I I I

HO HO HO HO1

HD-OD-HN

ZO \ ONúHD

At - = - H-SOH-NNo.-

  III, III. III. III. III. III. III. III.

HO HO HO HO

waterin 'n' nt1PT '

MD HD-0D-HN

UON \ ú H

  ## STR1 ##

HOS IHOS / I / HO HO \

HD-0D-HN

UOI19ECHE HOOS {OSX, <, P,

  HtN-e / N-N = N-e- / e-N OH -N = N-

HO HO

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ HO HO

UHO-OD-HN

UOI.Iletu N 1) .HOS \, H s D

I II I I

/ N O * o, -N = N-a l / * N

HO HO HO HO

  ## EQU1 ## where: -. / ON OG * Itt

HO HO HO HO

8ouenN * ON No. Nuance

OH OH OH OH

  507 ee 02N-le * -N = N-_ * '/ -N = N -le-NH 1 I? I, - tS3I 3 II2gris-blue e SO Ha a' '' IIIIII I SOOH

CH3 NO2

NH-CO-CH3

OH OH OH qH

508 I I N

* .0 eIN-0

O N -lelle-N = N-o * a -N = N-CI e -

at 0I 'C-: N - / | brown * e

CH30 \ 'NO2 CH3

______ NH-CO-CH3

509 OH OH OH OH

I I. I I

  O2N-el * -N = N-e, \ N | 2 C113 |: II In tbleu pulling

CH S03H \ .SO

H3 '\.' 0

NH-CO-CH3L

,, No. Nuance

510 OH OH OH OH

  2N-10I N-HOS-10-1-N = N- -1b; blue I I So I I NH À e eN O2N-e / '* - N = ne *' HO3- / TN = -N Il311I I II blue x / * ': f' * SO3 'X ///: /

I {I {S03H 2

CH3 \ NO2

NH-CO-CH3

511 OH OH OH OH

I I I

  ## EQU1 ## N-to-N = N-N-N-N-N-O-N-O-N-1-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I-I II I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I 'V'SOH HO3S s 3 I.-il 1 3 3 lil SO H 20

CH 3

3rd,

I I

NH-CO-CH3 NO2

OH OH

512 1 I \ OH OH

512, I I

  ## EQU1 ## where ## EQU1 ## \ and * on the purple

CH *

CH3 \ * f NO tr 2 II

NH-CO-CH3 -.4

3, I ,, _, _ ^ I

No. Nuance

OH OH OH OH

513 I I I I

i i 1 / e / | joist

\ ** / \, / \ e '/ ee ,.

NO2 \ e / NO2 NH2

514 OH OH OH

  It is NH2NH (II) -olive (II) II * e NO2, NO (N) = N-e. \

2 2II

goose I

NH {

2H

\ .././ \ S03H

OH OH -O

515 OH OH

  0-N = N7. e I IIIIIlA * e, O e -N = CH-e oi

NO III

NH2 NO

  .... S03H..DTD: _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ O 3 H OH_ _ _ _ _ _ _

No. Nuance No. "

516 OH OH OH OH

* / - N = N-e \ -NH-

I II III III

0r He And / SO Hi / olive I IlII I 3

NO2 \ / NO N = N- '

NO 2 I I / e / SO H OH OH

OH OH OH OH

  517 / N = ## EQU1 ## where ## STR2 ##

INO2 NO2 I

N = N-o e e NH2 SO H Nuance No.

518 OH OH OH OH

I I I I

  e // e / e 03He /. ## EQU1 ##

NO N-

2 I I

I 02N / e / e /

NH2 [/ II

SO 3H

OH OH OH OH

519 I I I I

HO S- / '-N = N -' *. -N = N - / "

  I3Iliil I IIl; tv / Ài /; o3H3. He. I + blue-gray sO3H e eI Cl x.// 'x. /

I I

NH2 NO2

-'i o'j r '> No. Nuance

520 OH OH OH OH

: .II I I1

H3O1, - = t i.; I-N = N-oIlIgris-blue

if (all \ SO3HHO S /% /. //.

3 3II

Cl '\ ./

I I

NH2 NO2

OH OH OH OH

521 I I I I

  ## EQU1 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## C1 ve e2 NH2

OH OH OH OH

522 I I '

  O2N-.? N-N = N-o e HO5 - N -'e2 Il IIl 311I i It has a a navy blue

\ //. "/.7.S0H * I II

  ## STR2 ## Nuance No. o.1.

OH OH OH? H

  523 I / - N-a HO S-N = N-e_ Il HOS / S - N = N-_C -a e 3, -Il It 31Imro a e e N / brown k.//? o3 { '/ \,

* * * SO3H

I III

C1 _ '\ / NO2 CH3

NH2 2 .....

ci OH

524 OH OH OH O

N 'N-

  HO S-, 9-N = N-N brown {* /, \\ ao \ 1 "I. '\' N 4r"! CN3 9, \ s 03H 1

I I 3 ISO H

Cl '//' NO2 CH3 3

NH2 OH

OH OH

9H OH

- e / 3 / N _ il 1

HO3 $ - = N-N = N-, AT *

\ e * eeC N * brown

*** /, \ SO0H C 3

I, J, 3. CHIS3H

Ci \ l NO2 3 NH2 2. Nuance No.

526 OH OH OH OH

I I I I

HO S> 'O

3rd-N = N-se At / - N = N-e

II III3 3I I I

* e HOSe \ e \ Ae /

Cl'x / '' \.

NH2 OH

OH OH OH

  527II HO3S \ / HO3S \ À / A / C-CH3 I le, -N = N- * II Il.1 - N = Nc / 3 IIII I1 III * olive \ S ../ "'o HCO-NH -_

I III3 II

Ci \ À * 0 NO2 NH

528 OHOH OH OH

  ## EQU1 ##

OH OH OH OH

529 ## EQU1 ## Iv 3Il. II IIlive NH2 e OH OH OH II

  II has 530HO | ## EQU1 ##

* 3

NO 2 I NO2

  2 | NO N = N-e NH2 SO3H% i -.a No. Nuance _o.

531 OH O OH OH OH

I I I I

  HO3S e IlI -m'- IIl I! III / liv | v / and; \ 50 efe e) e / | olive IIlI = NT / 'xi \ S.e

NO2 NO2N = N-O

2 22 I ^ I

NH 2Cl SQ H _ _3

OH OH OH OH

I I II

  HO3S, -N = N_ / ÀÀ / ÀXXÀ.N = CH.N .// oli \ To 311III1 IlIolive

NO NO N = N-0 *

2 2

I eI

NH2 \ OCH3

S03H /% No ... Nuance

533 OH OH OH OH

I I I {

HO3S ''

  ## STR2 ## ## STR1 ## where ## STR2 ## . *! SO H olive Xtv * s summeru'SoH 3 <

NO NO2 N = N- ,.

At e% e

NH2 2NO

  534 i3 s t -N = CH-N- o /.e xe e /. \ S eCOOH olive

NO2 NO N = N-} I

Ie e NH2 No. Nuance

OH OH OH OH

I I I I

535HOS 3 ci i

N NH203H O

OH OH OH

  e-N = N-e * N = aCH - '* I 36 H | OSI - il | I-N = N-Cl * ee e e eSOR olive

I1 II I I

02 N. 02

NH2 3 t) t in os

OH OH OH

I I

536 'I * C-N-eee

HO - = - OS-. '-NN "

  Brown NOC O2A \ f NO 2 H3 NHl2 -'- No. Nuance

OH OH OH OH

I I I I

537 HOS HOS

  ** - N = N-. H3 S3e -N = N- NO2 NO2 \ e NH2. _x. '.' o

OH OH OH OH

538 H3 /

  gray H 503 HO _S. I NO2

NH2 NO

LM M)! No. | Nuance

539 OH OH OH OH

I I I I

  HO3Se * 3'e / xl-N-N-eo \ Àe - = -. At 1: iii iIl 1 00 \ S0 HHO S / \ * / '00 \ * gray IIlI 3 3t I g i 3

NO2 \ * /

I I

NH2 NO2

... ,, ..

OH OH OH OH

540HOS

  0 / e-N-N-e ^ O2N-e / -N = N-_ be. titSOH i * tgris

II 303H I I I

N / A N / A 2nd N3 NH2

541 OH OH OH OH

II. I '

  l3e e-N-e ilil <- N-J | gray pulling the, / N = N-a9 /, on the purple

III I

  ## EQU1 ## ## STR2 ## ## STR2 ##

542 OH OH OH OH

I I I

HO3S \ // \ '.. // * \

  I - N = N-1; 0; l gray pulling Y. fi / SO3 HOSH eS / Ni S0 3H H / N2 on the green

I I

NO2 NH2 tNO

2 2

543 OHOH OH OH

HO3S / H / / H2 gray-black

* -N = N-e "." - '-

I I 3 I. SO 3

NO NO2

2 2

  NH 03 \ i ./\.*/ HO 3S \ / \ N- a- \, the, el-N 'N-9,1 e

I: ', I:

* 544 OH OHO

  HO 3e / e-N = N- il -l / I gray drawing tH 02 lti iHO3S It \ (i / on the blue * ee s

NO2 VI \

NH2 -.

  _ 111,, i, 11i ..,. i ... N Nuance No. OH

545 OH OH OH

II-C-N-e / HO S e.-N = NC N I

3rd 1-N = N- * 1 r - = -

  | i / tIl \ l50'U | 1 C-N i | brown a \; \ C 3 AT e e e CN S 0 3

0 "'3 SO H

NO 50O CH3 3

NO2 2

NH2

OH OH OH OH

  I I it w 540O * t l i | r k - = - | black drawing "e-N = N-e" o-N = N-o '546 l NN - ,,, the 546i ilt 3); on the violet x. / / SO3Heeee / e

2O NO

NO2 2 e.

NH2

OH OH OH OH

  HO S t * e / To * _-N = N - = _ / To black pulling

547 N

  * eee ttIII II X ** ef e / X SH / 0 * on blue NO2 t e

NH2 -

No. Nuance

548 OH OH OH OH

  HoS * eHOS'.p-CH 3It \ N 3 \ Oi to 3_N = NC3 brown pulling 0 s-N = N-_ I I!

\ / $ 3H CO

NO NO2 I

2 rN2 NH-eI

22 I

NH2 '@ /

OH OH OH OH

  HOS * I brown i II I-N I IlIl 549 H 3S / t Il1 1-N v! H, brown * r-N = N - @ * il / _N = CH_7 it \\ e / r S03H N62 /

NO2 \

NH2

AT....._

OH OH OH OH

I *

550 HO3 '

  | ## STR2 ## ## STR0000 ## where ## STR2 ## N = N-_reIl NH2e U No. Nuance No.

OR OR OH OH

551 I I I

  II I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I I

........ DTD: OH OH OH OH

IO I I I

  * H3S e e 552 'e-, eN = N-e \ ,, / X-N = CH-_e it II, he

> SO H

\ / * '-.SO HNO * * I brown

IH I 3 2

NO2 N = N -_ /

III NH2 SO H No * Nuance

OH OH OH OH

553 I I I I

  HO3S 'N = *. + \ Olive 6-N = N-0t t * -N = CH-_I I Il II' 'SO H; DU + X NO2 \ e NO2

N H2 2_ /; _____

NH2

OH OH OH OH

I I. I I I

  HO 3S \ \ \ \ \ / \ o> 3 1e-N = N-e At * 0-N = CH- \ he olive pulling He I I Il He I \ He \ 's' s' s' o' o 'o' o on the chestnut

NO2 A / \ NO N = N- *

NO2 \ e 2 i Io e NH2

OH OH OH OH

_5,.,. . ,,,

  ## STR1 ## ## STR1 ## ## STR2 ## ## STR2 ##

I2 2

H2 No. Nuance No.

OH OH OH OH

556 I I I I

  ## EQU1 ##

2 * 2 I I

NH2t SO3H

OH OH OH OH

  it 3-N = N- \ I / \ -N = CH- olive t / n i / so3u l I NO NO N = N-e_ I N2 2 it I

NH2 SOH

$ 2 3H

OH OH OH OH-

I I I I <

Nuance No.

OH OH OH OH

558 I I I I

HOSe e has 3 * s' = N_ '' -N = CH-r

/, T /, \ S 03H

  ee503 oolive 3i I.lI 59No = _1NO N = N- * At 2 2Ie NH2 SQ H: i \ S03H gray

OH OH O OH

I I

559 -N-

  NN I \ l / ÀÀ_N = N_.e eeA IIIII1 HO Se0gris IIlI 3il I NO2 \ e / e To e

NH-CO-OCH3 NO

2N No. Nuance No.

OH OH OH OH

I I I I

  6-N = N- It is 3-N = N- * "\ // NH2 gray | H II I I

I I S03H

He There No2 NO2 \ v2,

NHCOOCH

OH OH OH OH

i. I I I,

561 HOS HO S / N

  e * -N = N-0e JN. T-N--? Y. / \ ". SO H gray I ilI 3 I SO3H NO '1 No

NH-COOCH3

OHO OH

OR OH

  HO3S Ie 562 -i = II II TO À, ÀÀÀ gray

At, / '?' '03

IIl \ O N / A

9 NO23

NO2 2e

NH-COOCH3 - '

Nuance No.

OH OH OH OH

  I. 563 HO3 \ HO. \ / 2 gray 3 H3S \? / NN- \ / \, jH2 * e eee gray

1 I I OI I

3 S03H

NO

2 NO2

NH-CO-T '

%, / oI

OH OH OH OH

I I I I

  564 03S \ / * o -N = N-0. ' 9 00 \ SO3H * \ ** \ 000 gray

2O '- NO2

NH-CO-r giN * eIlI NJ Nuance No.

OH OH OH OH

565 I I \ v

HO S * OHO S À'H

  3-N = N -... N = N _... 2g t IIl I3 II gray

3I I I II H

* e 3

NO2 NO2

I NH-S02- 'II N 2 r il1

- / X \ CH!

he

3 4

OH

OH YH OH OH

HO I

  566IHO3S \ l A-N = N-_A \ H \ o-N = N-o / x / 'XoH /. \'. / Xe ee SOH / gray IIl * SO3H IS3H

NO2 NO2

I 2

  NH-S02-r / CH3 r uLn C'-L4 Nuance Nuance

OH OH OH OH

I I II

567 0 \ \

567 * / * -N = N-.) \ -I * -N = N- I

  ## EQU1 ##

NH-COCH3 NO2

OR OH OH OH

I I

  To this I / 568 * / e-N = N-_3 \ 3 \ / \ IlIIIl Ile l- = * ee to / e Is03H <* s ô \ so H t i gray-black * e I Il I

NO2 * \ N

1 2

NH-COCH3

- '. os No .. _Nuance OH

OH OH OH

* I HOS, - N_. \

N = N-a. / -N = N-C ,.

  569 I, I {C = N e * It e \ Ce \ 0 / \ SO H * I brown l 3 NO2 eXf NO 2 CH3

2 NO2

NH-COCH3

l. -_....... ', gs ir

OH OH OH OH

I Io3 I

-N = N-O NI1 11,.-.- = N-.

At // 03H gray-black

NO \ NO2 S03H

NH-COCH3

OH OH OH OH

TN e- = N_: x, i

H / t - "- N-f" navy blue.

2, SO 3H

NH-COCH3

No. | l Nuance

OH OH OH OH

I I I {

  572 | a \,. A +7 \ 0R | N-C a-N-N-oH Ae gi-ni 572 * t-N = N-e ". <- = - | lA i / ee0 2 - / - N a./- a

NO2 SO3H H \

NH-COCH3

OH OH OH OH

  Gray-black x. '/' SO3H H '- /' N- ",,, NO2 eXfe, / o eo, * e Ir o o I I

NH-COCH3NO

NO20 Nuance No.

OH OH OH OH

574 N-6 i /: \ / x 3 -

  At -N = N-o II Ie 575I; Dz IvI * e-N = N-C I OC ô | Brown

?. T XSO H 'C N

NO 3 CH 3

2 NO2 3

I

NH-COCH3

OH OH OH OH

I I '

  575 I = IiNx- / 3x / CH NO2e \ // e NO2 3

NH-COCH3

3U No. Nuance

OH OH OR

I I

  5776 a II / 3-N = N- "'" HOI 3 N | m I I II * * -N = N-. S II I I IIarron k // eT / eSO3H

* 3

NO

2 NO C4H9t

I 24 9

Nil-COCH3 o'o I

OH OH

OH OH I 1

  I HO0S / -N- a 577 HO S À 3 f, I 'Il 3./, _=_N__ x.0 577 H = NS \ / e \ i \' \ -l \ -N = N-C It is brown

I \ N

1 I ilI 3 N2CH

NO 3 // NO2 3

NH-COCH3

Ln -'I Cr% Nuance. _, I

O OH OH OH

578037 / s .: I I 'brown

NH-COCHx NN-.

[-N = N-e He. [=.

NO.,. _

2OOI CH SOQH

  579 ii t N N.% i _N = NC - NI \ T il T O1 X c = N% - /

NO2 NO 3

J N O 2

NH-COCH3

IF

OH OR OH O

  ## STR1 ## ## STR2 ## ## STR2 ## ## STR2 ##

I O NO2

NH-COCH3

-It 0% I "N HDOID-Hb I

ON ON

  /. ZoN /'.OHD-HN y erz 'y,>' / SOH I I I I I I / 'oT- / NNoOSH / * \ v \ / \ S \ OH \ OSHO

HO HO HO HO

e. l4nN OI

.z '.,,. ..-

  A lnen ONO I II II E: eC / SOH E: ._ IIl I sT25 I II {Il =. I - II - I - I - II

I I II OH O8

HOHO HO HO

uenlNI 'ON No. Nuance ...

OH OH OH OH

I II I

582H \.

e% t gray 583 / \ / S03H \ / $ g

NO NO

2 NO2

NH-COCH3

OH OH

OH OH

  583HO3Se aA e-N = Do not gray? -N = N-'eI --Negi

III III

* "e / e / eSOH I IH I I III 3rd

NO 5011 \ H

NO2 3 \ e

NH-COCH3

  3 'r'-ln lHODOD-HM 6H D ON e / \ ON

* \ / *** N = NI / \ I # 1NNo /.8

HO HO HO HO

  zON úHDOD-HN ON z H osHi S H OS / e $ S O / ee ek * \ o-eON = N - * / * S /

HO HO HO HO

a-uenN * ON No. jNuance No. ... .. _

OH OH

586 I I

_ .. // I

HO3s \. ' N /: "\ NT /"

a o-N = N-a 9 * -NN-

  * INI I I / I / S0 black I

NO2 "% /" N *. '/

3IN NO 0

NH2 N-

OH OH {

OH OH

587 HO3S L

It's V

I-N = N-I ,. // '\% - N N-T /' "

* e eI I 3 black 1-4

_I ....

No. Nuance

OH OH

  588H -N-Ii OH OH II NNH; he \ * v: | O d / brown I N NO 2 \ l / 2 NH

NH2 I |

  No. D03H-04-E-53- Dyeing method for leather leather parts velvet garment (dry weight) are streaked for 2 hours at 50 C in a solution of 1000 parts by volume of water and 2 parts of a 24% solution of ammonia, then dye for 1 hour at 60 ° C. in a solution of 1000 parts by volume of water, 2 parts of 24% ammonia solution and 1 part of ammonia solution. After this, a solution of 40 parts by volume of water and 4 parts of 85% formic acid is added, followed by dyeing for a further minute. The leather is then thoroughly rinsed and optionally further treated at 50 ° C. for 30 minutes with 2 parts of a condensation product.

of dicyandiamide-formaldehyde.

  Other velvet leathers, such as leather gloves, can be

to be dyed in the same way.

  The shades thus obtained are distinguished by good

  solidity and good covering powers.

  Dyeing method for wool 100 parts of yarn are introduced. knit wool in a 50 C dye bath which contains, for 4000 parts of water, 2 parts of the dye of Example 1, 3 parts of ammonium sulphate and 2 parts of a unison agent. The bath is boiled in the space of minutes and then maintained for 45 minutes at the boiling point. After that, the dyed item is removed, rinsed thoroughly with cold water, and then dried. We get a tinted wool

  in dark gray, having good solidity characteristics.

- 2576312

-54-

Claims (14)

  1. Chromium complex dyes 1: 2 asymmetric of formula (1) 20   Wherein Z represents a nitrogen atom or a CH group; A and D each represent, independently of one another, a remainder of the benzene or naphthalene series which carries a hydroxyl or carboxyl group ortho to the azo or azomethine moiety;   B represents, when Z is a nitrogen atom, the remainder of a copulatory component   the coupling component containing the X group at the ortho or alpha position relative to the azo group, or when Z represents the CH group, the residue of an o-hydroxy-aldehyde; X represents an oxygen atom or, when Z is an atom   nitrogen, a group of formula -NR-, where R represents a hydrogen atom   gene or a C14 alkyl radical; Y represents a hydrogen atom or a group of formula -SO 2 -Q or -CO- (O) nQ, it is equal to O or 1 and Q is a C 1 -C 5 alkyl or phenyl radical, the phenyl radical may be substituted by a nitro, halo, C15 alkyl or C1-5 alkoxy group; p and q are each, independently of one another, O or 1 and -55- Ka represents a cation.   2. Dyes according to claim 1, characterized in that in the formula (1) A and D each represent, independently of one another, the residue of a 1-hydroxy-2-aminobenzene, which is optionally substituted with halo, nitro, sulfo, lower alkyl or lower alkoxy, or the residue of a 1-amino-2-hydroxy-4-sulfonaphthalene which is optionally substituted in the 6-position by a nitro or sulfo group. 3. Dyes according to claim 1 or 2, characterized in that in the formula (1) A and D each represent, independently of one another, the residue of a 1-hydroxy-2-aminophenol which is substituted   by a nitro group and optionally by a sulfo group.   4. Dyes according to any one of claims 1 to 3,   characterized in that in the formula (1) Z is a nitrogen atom.   5. Dyes according to any one of claims 1 to 4,   characterized in that in the formula (1) Z is a nitrogen atom and B is a 1- or 2-naphthol optionally substituted with an amino group and / or a   sulfo group, a 1- or 2-naphthylamine optionally substituted with a -   sulfo group, a p-alkyl (C 16) -phenol, a 1-phenyl-3-methyl-5-pyrazolone or acetylacetanilide, the phenyl radical in the two compounds listed last may be substituted by a C14 alkyl group alkoxy C14, chloro, nitro or sulfo.   6. Dyes according to any one of claims 1 to 3,   characterized in that in the formula (1) Z represents a group CH and B represents the residue of a 6-hydroxybenzaldehyde which may be substituted   by a phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo group.   7. Dyes according to any one of claims 1 to 4,   characterized in that in formula (1) B is a 1- or 2-naphthol   optionally substituted with an amino group and / or a sulfo group.   8. Dyes according to claim 7, characterized by the   in the formula (1) B represents 2-amino-8-hydroxy-acid naphthalene-6-sulfonic acid.   9. Dyes according to any one of claims 1 to 8,   characterized in that in the formula (1) Y is a hydrogen atom, an acetyletethoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl group. 10. Dyes according to claim 9, characterized in that in formula (1) Y is a hydrogen atom or an acetyl group. 11. Dyes of formula (2) 2G A '-N - N - B'2 \ Cr 2KaeQ o // 0o (2) D '- N - \ (   I he e e to il 3 e \. Wherein A 'and D' are each, independently of one another, the residue of a 1-hydroxy-2-aminobenzene which is optionally substituted with halo, nitro, sulfo, lower alkyl or alkoxy - lower, or the residue of a 1-amino-2-hydroxy-4-sulfonaphthalene which is optionally substituted in the 6-position by a nitro or sulfo group; B 'represents a 1- or 2-naphthol optionally substituted by an amino group and / or a sulfo group, a 1- or 2-naphthylamine optionally substituted by a sulfo group, a p-alkyl (Cl 6) -phenol, a 1-phenyl 3-methyl-5-pyrazolone or acetylacetanilide, the phenyl radical in the two last-mentioned compounds which may be substituted by a C 1-4 alkyl, C 14 alkoxy, chloro, nitro or sulfo group; Y 'represents a hydrogen atom, a methoxycarbonyl or acetyl group and Kak represents a cation.   -57- 12. Process for the preparation of dyes of formula (1),   characterized by preparing the chromium 1: 1 chromium complex azo compound of formula (3) - OH 1 OH (co; D - N = N - 'e D-NN- * I II (3) * / SO   NI and then react with the dye of formula (4) A - N = Z - B A-N = Z-B I 1- (4)   (CO) q xH! Q OH or with a mixture composed of the amine of formula (5) A - NH I 2   (CO) q (5) OH and the aldehyde of formula (6) HO-B-CHO (6)   to result in the chromium 1: 2 complex, or that the chromium 1: 1 complex of a dye of formula (4) is prepared and then reacted with the dye of formula (3), A, B, D, Z, X, Y, p and q having   the meanings given for formula (1).   13. Dye mixtures, characterized by the fact that they contain   at least one dye of formula (1) according to claim 1.   14. Use of dyes of formula (1) for dyeing   wool, polyamide and in particular leather or hides.