GB2186282A

GB2186282A - Asymmetric 1:2-chromium complex dyes

Info

Publication number: GB2186282A
Application number: GB08702706A
Authority: GB
Inventors: Fabio Beffa
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1986-02-07
Filing date: 1987-02-06
Publication date: 1987-08-12
Anticipated expiration: 2007-02-06
Also published as: FR2594128B1; DE3703361A1; GB8702706D0; FR2594128A1; CH672136A5; GB2186282B

Abstract

The novel dyes of the formula (1) are suitable for dyeing wool, polyamide and, in particular, leather and furs <IMAGE> wherein Z is nitrogen or a CH group, A is a radical of the benzene or naphthalene series, which radical carries a hydroxyl or carboxyl group in the o-position to the azo or azomethine group, B is the radical of a coupling component if Z is nitrogen, which coupling component carries the group X in the o or ???-position to the azo group, or is the radical of an o-hydroxyaldehyde if Z is the CH group, X is oxygen or, if Z is nitrogen, is also a group of the formula -NR-, in which R is hydrogen or a C1-C4 alkyl group, Y<1> is sulfo, chlorine C1-C4alkyl SO2-R<2>, in which R<2> is C1-C4alkyl, or Y<1> is -SO2-NRR<3>, in which R and R<3> are each independently of the other hydrogen or C1-C4alkyl, Y<2> is hydrogen, sulfo, chlorine or C1-C4alkyl, R<1> is hydrogen or a group of the formula -SO2-Q or -CO-(O)n-Q, in which n is 0 or 1 and Q is C1-C5alkyl or phenyl, which phenyl group may be substituted by nitro, halogen, C1-C5alkyl or C1-C5alkoxy, P is 0 or 1 and Ka(+) is a cation.r

Description

SPECIFICATION Asymmetric 1:2-chromium complex dyes The present invention relates to asymmetric 1:2-chromium complex dyes of the formula

wherein Z is nitrogen or a CH group, A is a radical of the benzene or naphthalene series, which radical carries a hydroxyl or carboxyl group in the o-position to the azo or azomethine group, B is the radical of a coupling component if Z is nitrogen, which coupling component carries the group X in the o- or a-position to the azo group, or is the radical of an o-hydroxyal dehyde if Z is the CH group, X is oxygen or, if Z is nitrogen, is also a group of the formula -NR-, in which R is hydrogen or a C1-C4 alkyl group, Y2 iS sulfo, chlorine, C1-C4 alkyl, SO2-R2, in which R2 is C1-C4-alkyl, or Y is -SO2-NRR3, in which R and R3 are each independently of the other hydrogen or C1-C4 alkyl, Y2 iS hydrogen, sulfo, chlorine or C1-C4 alkyl, R1 is hydrogen or a group of the formula -S02-Q or -CO-(O)n-QE in which n is O or I and Q is C1-C5 alkyl or phenyl, which phenyl group may be substituted by nitro, halogen, C1-C5 alkyl or C1-C5 alkoxy, p is 0 or 1 and Ka is a cation.

The dyes of the present invention are asymmetric 1:2-chromium complexes. If X is oxygen, Z is nitrogen and p is 0, then the diazo component A may not be identical with the diazo component of the other azo dye if the coupling component B is identical with the coupling component of said other azo dye.

In the chromium complex dyes of the above formula (1), the radical A may additionally carry one or more further substituents, for example low molecular alkyl or alkoxy, halogen, e.g.

chlorine or bromine, nitro, cyano, sulfo, carboxy, phosphono, alkylsulfonyl, e.g. methylsulfonyl, sulfamides, e.g. sulfamide or N-methylsulfamide, acylamino, phenylazo, sulfophenylazo or methoxyphenylazo. Throughout this specification, low molecular alkyl or alkoxy groups shall generally be understood as meaning those groups which contain 1 to 6, preferably 1 or 2, carbons atoms; and the term "acylamino" denotes low molecular alkanyolamino, alkysulfonylamino and alkoxycarbonylamino radicals as well as aroylamino, aryloxycarbonylamino and arylsulfonylamino radicals.

The radical A is derived for example from the following amines: anthranilic acid, 4- or 5chloroanthranilic acid, 4- or 5-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 -hydroxybenenzene, 4-cyano-2-amino- 1 -hydroxyben- zone;; 4-sulfonamido-2-amino-1-hydroxybenzene, 1-hydroxy-2-aminobenzene-4-sulfoanthranilide, 4 methoxy-2-amino- 1 -hydroxybenzene, 4-methoxy-5-chloro-2-amino- 1 -hydroxybenzene, 4-methyl-2amino-1-hydroxybenzene, 4-chloro- and 4-methyl-5-nitro-2-amino-hydroxybenzene, 3,4,6-trichloro2-amino- 1 -hydroxybenzene, 6-acetylamino-4-chloro-2-amino- 1 -hydroxybenzene, 4,6-dinitro-2-am ino- 1 -hydroxybenzene, 2-amino- 1 -hydroxybenzene-4- or -5-sulfonic acid, 4-nitro-2-amino- 1 -hy- droxybenzene-6-sulfonic acid, 6-nitro-2-amino- 1 -hydroxybenzene-4-sulfonic acid, 4-chloro-2-am ino- 1 -hydroxybenzene-6-sulfonic acid, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2- hydroxy-6-nitronaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-chloronaphthalene-4-sulfonic acid, 1 -amino-2-hydroxynaphthalene-4,6-disulfonic acid, 2-amino- 1 -hydroxybenzene-4,6-disulfonic acid.

Instead of the above hydroxylated amines, suitable contenders for A are also corresponding methoxy compounds or corresponding compounds whose hydroxyl group has been tosylated, for example anisidine, 4- or 5-chloroanisidine, 4- or 5-nitroanisidine, anisidine-4- or 5-sulfonic acid, or tosylated 1-hydroxy-2-aminobenzene, the methoxy or O-tosyl group of which is converted into an -OH group before or during metallising. Compounds containing these groups are used in particular whenever the corresponding 1-hydroxy-2-amino compounds couple reluctantly.

In preferred dyes of formula (1), A is the radical of a 1-hydroxy-2-aminobenzene which is unsubstituted or substituted by halogen, nitro, sulfo or low molecular alkyl or alkoxy, or is the radical of a 1-amino-2-hydroxy-4-sulfonaphthalene which is unsubstituted or substituted in the 6position by halogen, e.g. bromine or, preferably, chlorine, nitro or sulfo.

In particularly preferred dyes of formula (1), A is the radical of a 1-hydroxy-2-aminobenzene which is substituted by nitro and may be further substituted by a sulfo group.

The radical B is derived preferably from the following groups of coupling components: phenols which couple in the ortho-position and which are unsubstituted or substituted by low molecular alkyl or alkoxy, dialkylamino or acylamino, where acylamino denotes C1-C4-alkanoylamino, C1-C4 alkylsulfonylamino, C1-C4 alkoxycarbonylamino, aroylamino or arylsulfonylamino radicals; naphthols which are unsubstituted or substituted by C1-C4 alkyl or C1-C4 alkoxy, chlorine, amino, acylamino or sulfo, where acylamino is as defined above; 5-pyrazolones or 5-aminopyrazoles, preferably those which carry in the 1-position a phenyl or naphthyl radical, each unsubstituted or substituted by chlorine, nitro, C1-C4 alkyl or C1-C4 alkoxy groups or sulfo groups, and in the 3position carry a C1-C4 alkyl group or a carboxyl group, preferably a methyl group; naphthylamines which are unsubstituted or substituted by sulfo, sulfonamido or sulfone groups; acetoacetamides, preferably acetoacetanilides, and benzoylacetanilides which may be substituted in the anilide nucleus by chlorine, bromine, nitro, C1-C4 alkyl or C1-C4 alkoxy groups or sulfo groups; 6-hydroxy-3-cyano or 6-hydroxy-3-carbamoyl-4-alkyl-2-pyridones which are substituted in the 1position by unsubstituted or substituted C1-C4 alkyl, for example methyl, isopropyl, fi-hydroxye- thyl, fi-aminoethyl or ;I-isopropoxypropyl or by phenyl, and in the 4-position can carry a C1-C4 alkyl group, preferably methyl; or hydroxyquinolines.

Examples of such coupling components are: 2-naphthol, 1-naphthol, 1-acetylamino-7-naphthol, 1-propionylamino-7-naphthol, 1-carboxymethoxyamino-7-naphthol, 1 -carboethoxyamino-7-na- phthol, 1-carbopropoxyamino-7-naphthol, 6-acetyl-2-naphthol, 2-napthol-3-, -4-, -5, -6-. -7- or -8sulfonic acid, 1-naphthol-3-, -4- or -5-sulfonic acid, 1-naphthol-3,6- or -4,8-disulfonic acid, 2naphthol-6,8-disulfonic acid, 4-methyl- 1 -naphthol, 4-methoxy-1-naphthol, 4-acetyl-1-naphthol, 5,8 dichloro- 1 -naphthol, 5-chloro- 1 -naphthol, 2-naphthylamine, 2-naphthylamine-1-sulfonic acid, 1-naphthylamine-4- or -5-sulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 2-aminonaphthalene-5-sulfonic acid, 6-methylsulfonyl-2-aminonaphthalene, 1 -phenyl-3-methylpyrazol-5-one, 1-phenyl-5-py- razolone-3-carboxamide, 1-(2'-, 3'- or 4'-methylphenyl)-3-methylpyrazol-5-one, 1-(2'-, 3'- or 4'sulfophenyl)-3-methylpyrazol-5-one, 1 -(2'-chloro-5'-sulfophenyl)-3-methylpyrazol-5-one, 1 -(2'- or 4'-methoxyphenyl)-3-methylpyrazol-5-one, 1-(2'-, 3'- or 4'-chlorophenyl)-3-methylpyrazol-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'-dichloro-4'-sulfophenyl)-3-methylpyrazol-5-one, 1-(2'-, 3'- or 4'-sulfophenyl)-3methyl-5-aminopyrazole, 1-phenyl-3-methyl-5-aminopyrazole, 1 -(2'-chloro-5'-sulfophenyl)-3-methyl5-aminopyrazole, acetoacetanilide, acetoacetanilide-4-sulfonic acid, acetoacet-o-anisidide, acetoacet-o-toluidide, acetoacet-o-chloroanilide, acetoacet-m-xylidide, tetralol, 4-methylphenol, 3-dialky laminophenols, preferably 3-dimethylamino- and 3-diethylaminophenol, 4-butylphenyl, preferably 4-tert-butylphenol, 4-amylphenol, most preferably 4-tert-amylphenol, 2-isopropyl-4-methylphenol, 2- or 3-acetylamino-4-methylphenol, 2-methoxycarbonylamino-4-methylphenol, 2-ethoxycarbonylamino-4-methylphenol and 3,4-dimethylphenol, 1 -methyl-3-cyano-4-ethyl-6-hydroxypyridone, 1methyl-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.

Preferably the coupling component B is a 1- or 2-naphthol which is unsubstituted or substituted by amino and/or sulfo; 1- or 2-naphthylamine, unsubstituted or substituted by sulfo; p C1-C6 alkylphenol, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone or acetoacetanilide, the phenyl moiety of which last two compounds may be substituted by C,-C4 alkyl, C1-C4 alkoxy, chlorine, nitro or sulfo.

If Z is the CH group, B is the radical of an o-hydroxyaldehyde, preferably of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, each of which may be substituted by low molecular alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo. Examples of suitable aldehydes are:: 2-hydroxy- 1 -naphthaldehyde, 1 -hydroxy-2-naphthaldehyde, 2-hydroxybenzaldehyde, 3- and 5-methyl-2-hydroxybenzaldehyde, 3,5-dimethyl-2-hydroxybenzaldehyde, 5-butyl2-hydroxybenzaldehyde, 5-chloro- or 5-bromo-2-hydroxybenzaldehyde, 3-chloro-2-hydroxybenzaldehyde, 3,5-dichloro-2-hydroxybenzaldehyde, 5-sulfo-2-hydroxybenzaldehyde, 3-methyl-5-chloro2-hydroxybenzaldehyde, 5-(phenylazo)-2-hydroxybenzaldehyde, 5-(2'-, 3'- or 4'-sulfophenylazo)-2hydroxybenzaldehyde, 5-(6'-sulfonaphthyl- 1 '-azo)-2-hydroxybenzaldehyde or 5-(4"-sulfo-4'-phenylazo)phenylazo-2-hydroxybenzaldehyde.

kas is a cation, e.g. an alkali metal cation such a lithium, potassium or, preferably, sodium. KaO may also be an ammonium cation or the ammonium salt of an organic amine.

Examples of suitable radicals R' in the dyes of formula (1) are: hydrogen, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, capronyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-pentoxycarbonyl, methylsulfonyl, ethlysulfonyl, butylsulfonyl, phenylsulfonyl, benzoyl or phenoxycarbonyl, the phenyl moiety of which last three compounds may be substituted for example by nitro, halogen, e.g. bromine or, preferably, chlorine, C,-C4 aklyl or C1-C4 alkoxy.

R' is preferably hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl, with hydrogen, methoxycarbonyl or acetyl being most preferred.

Preferred radicals Y' are sulfo, chlorine, methyl, sulfonamide, N-methylsulfonamide and methylsulfonyl, with sulfo being particularly preferred.

Preferred radicals y2 are hydrogen, sulfo, chlorine or methyl, with hydrogen being most preferred.

Particularly preferred dyes of the present invention are those of the formula

wherein R2 is hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl, Z is nitrogen or a CH group, A1 is the radical of a 1-hydroxy-2-aminobenzene which is unsubstituted or substituted by halogen, nitro, sulfo or low molecular alkyl or alkoxy, or is the radical of a 1-amino-2 hydroxy-4-sulfonaphthalene which is unsubstituted or substituted in the 6-position by halo gen, e.g. bromine or, preferably, chlorine, nitro or sulfo, B1 is the radical of one of the following coupling components if Z is nitrogen: a 1- or 2 naphthol which is unsubstituted or substituted by amino and/or sulfo; 1- or 2-naphthylam ine, unsubstituted or substituted by sulfo; or p-C1-C6 alkylphenol, 1-phenyl-3-methyl-5 pyrazolone or acetoacetanilide, the phenyl moiety of which last two compounds may be substituted by C1-C4 alkyl, C,-C4 alkoxy, chlorine, nitro or sulfo, or, if Z is the CH group, B' is the radical of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, each of which may be substituted by low molecular alkyl, halogen, sulfo, phenylazo, sulfophenylazo, na phthylazo or sulfonaphthylazo, and KaO is a cation.

Among these compounds, those are particularly preferred in which R2 is hydrogen, methoxy carbonyl or acetyl, A' is the radical of 4-nitro-2-amino-1-hydroxybenzene, 4-nitro-2-amino-1hydroxybenzene-6-sulfonic acid or 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene, and, if Z is nitrogen, B' is the radical of a 2-naphthol which is unsubstituted or substituted by amino or acetylamino, of acetoacetanilide or of 1-phenyl-3-methyl-5-pyrazolone, the phenyl moiety of which last two compounds may be substituted by chlorine or sulfo, or, if Z is the CH group, B' is the radical of o-hydroxybenzaldehyde which is unsubstituted or substituted in the p-position by phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and KaB is a cation.

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

and then reacting said complex with the dye of the formula

or with a mixture of the amine of the formula

and the aldehyde of the formula HO-B-CHO (6) to give the 1:2-chromium complex, or by preparing the 1:1-chromium complex of a dye of formula (4) and reacting said complex with the dye of formula (3).

A, B, Z, X, y1, y2, R1 and p in formulae (3), (4), (5) and (6) are as defined for formula (1).

The dyes of formula (3) and (4) are known or they are prepared in a manner which is in principle known.

The novel chromium complex dyes of formula (1) obtainable by the above process are isolated in the form of their salts, preferably alkali metal, most preferably sodium, potassium or lithium salts, or also ammonium salts or salts of organic amines containing a positively charged nitrogen atom, and are suitable for dyeing and printing a variety of materials, in the absence or presence of a levelling agent. They are suitable especially for dyeing or printing nitrogen-containing materials such as silk, wool, and also synthetic fibres made of polyamides or polyurethanes, and, in particular, leather.

Olive, brown, grey or black dyeings with good fastness properties, in particular to light and wetness, are obtained.

The preferred area of application of the dyes of the invention is the dyeing of wool, polyamide and, in particular, furs or leather, all types of leather being suitable, e.g. chrome leather, retanned leather or suede leather made of goatskin, cowhide, sheepskin or pigskin. The dyes of the invention are suitable especially for the dyeing of leather with dye mixtures, in which case the dyes of the invention are employed in particular in admixture with one or more suitable 1:2metal complex dyes.

The invention is illustrated by the following non-limitative Examples. Parts and percentages are by weight.

Example 1

The 1:1-chromium complex, which contains 43.9 parts of the dye obtained from diazotised 2 amino- 1 -hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid as well as 5.2 parts of chromium, is added to 500 parts of water. Then 15.4 parts of 4-nitro-2amino-1-hydroxybenzene and 30.6 parts of the monoazo dye obtained from diazotised 2-aminobenzenesulfonic acid and salicylaldehyde are added. The reaction mixture is subsequently heated to 80-85"C, and the pH is adjusted to 7-7.5 with sodium hydroxide. The reaction mixture is kept at this temperature and at constant pH until no more starting materials can be detected.

When the addition reaction is complete, the dye is isolated by concentrating the reaction mixture by evaporation. A dark powder is obtained which dissolves in water to give an olive-green solution and dyes leather in fast olive shades.

Example 2

48.9 parts of the complex chromium compound of the type 1 atom of chromium: 1 molecule of dye, which compound contains 5.2 parts of chromium and 43.9 parts of the monoazo dye obtained from diazotised 2-amino- 1 -hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene, are suspended in 500 parts of water. Then 15.4 parts of 4-nitro-2-amino-1-hydroxybenzene and 30.6 parts of the monoazo dye obtained from diazotised 3-aminobenzenesulfonic acid and salicyaldehyde are added. The reaction mixture is subsequently heated to 80-85"C, and the pH is adjusted to 7-7.5 with 5n sodium hydroxide solution. The reaction mixture is kept at this temperature and at constant pH until no more starting materials can be detected.When the addition reaction is complete, the dye is isolated by spray drying. A dark powder is obtained which dissolves in water to give an olive-green solution and dyes leather in fast olive shades.

Example 3

The 1:1-chromium complex, which contains 43.9 parts of the dye obtained from diazotised 2 amino-i -hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid as well as 5.2 parts of chromium, is added to 600 parts of water. Then 15.4 parts of 4-nitro-2amino-1-hydroxybenzene and 35.6 parts of the coupling product obtained from diazotised 1aminonaphthalene-6-sulfonic acid and salicylaldehyde are added. The reaction mixture is subsequently heated to 80-85"C, and the pH is adjusted to 7-7.5 with sodium hydroxide. The reaction mixture is kept at this temperature and at constant pH until no more starting materials can be detected. When the addition reaction is complete, the dye is isolated by concentrating the reaction mixture by evaporation.After drying, a dark powder is obtained which dissolves in water to give an olive-green solution and dyes leather in fast olive shades.

Example 4

The 1:1-chromium complex, which contains 43.9 parts of the dye obtained from diazotised 2 amino-i -hydroxybenzene-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-sulfonic acid as well as 5.2 parts of chromium, is added to 500 parts of water. Then 23.4 parts of 4-nitro-2 amino-1-hydroxybenzene-6-sulfonic acid and 35.6 parts of the monoazo dye obtained from diazotised 1-aminonaphthalene-6-sulfonic acid and salicylaldehyde are added. The reaction mixture is subsequently heated to 80-85"C, and the pH is adjusted to 6.5-7 with 5n sodium hydroxide. The reaction mixture is kept at this temperature and at constant pH until the starting materials have disappeared.When the addition reaction is complete, the resultant dye is isolated by concentrating the reaction mixture by evaporation. After drying, a dark powder is obtained which dissolves in water to give an olive-green solution and dyes leather in very fast olive shades.

Examples 5 to 42 By following the procedures described in Examples 1 to 4 but employing the 1:1-chromium complex of the azo dye indicated in column 2 of the following tabie and reacting said complex with the azo or azomethine dye indicated in column 3, or with the amine which forms said azo or azomethine dye and with aldehyde, then 1:2-chromium complexes are obtained which dye leather in the shades indicated in column 4 with good fastness properties.

Table

NO Azo dye Azo or azomethine dye Shade IOH 9H OIH IOH -N=N- bisOWfl II violet \// HO3S \\ / H03S .

~ H3 ihó2 \' 0 6 0H 9H 9H -N=CH- ?H olive 6 | N=N / / il ssjN=CHI olive II QHo 03H \Iv HOlS/ + \. +e/ cO 2 2 i=Nw PH PH (?H 7 911 \\ / ;N=N-! brown \/O\\/NH0 I t'! I.' I violet HO3S + H033 ./ i / \\/ tH 2 < \ v NO IOH Y 11035 H 911 8 &commat; 911 H2 11 1 1 11911 NH olive I I II HO 35/ \\ / \// \// So: 02 H-CH3 OH 9H PH H 9 //\ \/NH2 11O3S\/\\ /;;+ N=N-Cv 1 brown -N=N-' /\ -N=N-C \\/' brown HO 35/ \\ !i62

NO Azo dye Azo or azomethine dye Shade 10 1103S OH OH 1105 /9O\\11 //H I//\lI violet 10 4 HO S/ 3 < 3\, +±N=N-Cv i il brown I 1103S \\/ \// a \,// =H3 \\/ 02 11 Cl 911 9H OH 11 \./; rIiz \\2 3\ I \C :E;i 39 / brown II i--N=N-C II brown I HO3S II \// \// O311 No2 12 1103S OH OH CH \/N112 9H &commat; 12 OS\ / HOsS\ / / 2 il -N=N-Ci brown brown 4 HO3S % \1 CH3 S03H H3 No2 ~ OH OH OH OH &commat;; 13 H3C\ / / PHi--N=NN- 4 CH3 SÓ It brown I l I bsown 8\ // 11O3S \\/ \// \// 113 O3H O311 No2 911 911 / N=N-fPH 911 H 14 113C / < N il / +/COOCI 1I l \C~| +. violet I II ti .N=N;1:1!ooCH3 tI N=NC\ brown 'Hos/'a/'\' i 4a,H No2 15 Cl OH 911 11 violet 15 i'\'"""(tl brown Il I \\/ I \ev CH3 SO3H 11035 No2 0H , 1103S t 911 911 ; + }+ //\ /\\112 HO3S\/\\ tI -N= & -N=N-C l I tI tI 113 No2

NO Azo dye Azo or azomethine dye Shade PH PH PH PH 17 /rH2 olive 17 911 9H / 911 911 olive 11035 ' SO3H tOz 9H QH PH 18 911 IOH 18 /\\ .-N=N- f H2 / ssi-N=CH-tv 911 olive II I I II tI l I tI \&commat;;/ HO3S + \ 4 % / SO3H t 2 N t i1 I \ 19 911 911 IOH 19N=h'- /NH2 il +,i-N=CH-Tv -N=CH // HO3S + \// 0 # Oil AO,H il I NO2 N=N so3H 3 PH PH PH PH 20 911 9H 9H ?H brown o e -N=N- / / fNH2 ,/ *-N=CH-* ish '.1 I II I ii \.4 olive 03H t 2 4=N-t ' . '+,/' I ii 21 911 911 911 911 olive -N=N- N=N v /N 2 ./ sst-N=CH-* II I - I tI l tI I e II 03H 2 t=N-i il ~ &commat; C1

N" Azo dye Azo or azomethine dye Shade PH PH OH PH 22 9o11 911 9H 911 olive ./ O T T i, T t - N=CH - Tv i, olive I HO3S ol l # < \311}j03S/ oo SO3H ; 2 II tI.i f g v 1 SO3H ~ 911 911 NH 911 911 23wiz ,T ,+ ! i, T ,T ,, !SO3 olive \ // / ' 1103S I: \// \// \\/ 0311 SO3H t 2 I a SO3H OH PH PH PH violet 24 511-N=N-5" / T~N= i, T-N=N-Cv Vbirolnt tI I = /tI ti I l tI 1 0 0N= & \ \\ brown \// 1103S \\/ \// \/,,' 113 H ko OH 911 911 VH 25 / < < -N=N-Tv \/ CH2 T &commat; ssT - N - - N - to brown II I tI il I 0 0 tI violet + HO3S HOss/ violetHO3S \ violet 3 3 ii ; 2 O2 QH 911 911 26 + HO3S\/0\ ,,,,/\ brown ;/;;HO35 < Aoz D v! vlolet Ol I I l l I violet 011 02 tI

Azo dye Azo or azomethine dye Shade - //\ QH- gOH QH QH 27 911 v 11o H03S\ N3 il +!-N=N-Cv olive 0 .-N=N-. H03S/ 4-N=N 0 1103S 0 1 8\ CO!11 O311 Noz .ltl II IOH QH QH ,OH 98 / < 11o3S\/90\\11 N-N- \ N=N-C p olive .-N=N-. \. HO3SZ OCH3 ff HO 0 H03S 0 / 0\0 SO3H 2 T i, % , 911 911 VH ,OH 29 '0-N=N~~/\ /0 H03S\ 11O3S\/0\\ -N=N-C olive II I n--N=N-k I II 010 II I 0 1103S 0 \\/ 0 0 0 \/ 9 \- Ol I il \ 30 9H PH VH IOH 30 / %- - N=N - olive i} N=CH-Zv il 0 0-N=N- 0 12 tI I 3 \/y boil /\ P # 0311 tI / NO CH3 . .l 3 il PH 911 91111 31 ,i-N=N f c2H S ! 11o +!N=Ncv olive I/o 'i-N=N \0/ \\ \0/ 0\\/113 bc: 11035/I II IC2115 ti I Co11 \\/ \// \// 03H N02 / \0 It

NO Azo dye Azo or azomethine dye Shade QH /?11 QH QH QH greyish 32 /\\ /NH2 il i-N=N-f fi T tI t - I tI black 0 HO3S ss \// \// j \\/ 03H y PCH3 33 O/9O\\11.NN.//9O\11O/O\\O/NH2 /90\\H '-N=N-. QH QH sh PH gH PH PH 33 1 /NHZ /8.- greyish \// | &commat; \ # 0/ i/ O3H ;I-SOH 34 911 QH IOH QH 34 / /NHn / < -N CNH- brown N=N-; -N=N-Ci\C-NH- ish il I II I II i-il olive Ho r il 3i 1 \\0/NH /\\ brown -N=N- \\/ \// \// )=H3 \\/ ~ SO3H No 36 911 9H 911 11 violet 36 / % N N )3 \ / \\0AH2 /\\ N-%' 0 t 0 -N '01 brown g/B-,=,." . U\C=:6'a ~ SO3H SO2NH2 QH QH 0 QH QH 37 / ;-N=N- / . I olive ii HO3S I tl i it v\(O-NH ".:" \// S'./\.8 \// \// \/tl SO3H & 2NH2

NO Azo dye Azo dye Shade 9H 911 H QH 38 /NH2 N v /NH2 02N / +&commat;-N=N-CP | 7 I; violet 0 -N=N- /\ / \\,/ 0 \\ violet I I II I = II 0 HO HO3S ss .H CH3 H3 O3H 03H S 9 9H 9H QH violet 39 B o-N=N-o //\ N=N 0/0\\0/NH2 grey I I tI I tI I t' grey ~ b#; HO 3 S < \ v 7/ QH No2 9H 9H 911 911 0 NH 40 ? /0\\ -N=N-o /NH2 / %7-N=N - violet 0 /8.~N=N-i/\/h/H? o,E/ violet II I I grey . grey. . . . . . . . 03H QH QH QH QH 41 0 -N=N-. 0 0 \\ 0/NH2 II -N=N- violet II I I II I II I I II grey TH HO1S + \ \// v // 11N- \\ / How HO } \// I COUCH; ~ QH 9H QH QH violet 42 < ss - NH2 - 9H 911 /8 -N=N-. 0 0 -N=N-. 0 grey II I - 1 II I II I I II TO HOWS 0/0 \// + // H $0O O311 \{H023 0CH3

Dyeing Procedure for Leather 100 parts of garment suede leather (dry weight) are wet back at 50"C for 2 hours in a solution of 1000 parts by volume of water and 2 parts of 24% ammonia and subsequently dyed for 1 hour at 60"C in a solution of 1000 parts of volume of water, 2 parts of 24% ammonia and 6 parts of the dye of Example 1. A solution of 40 parts by volume of water and 4 parts of 85% formic acid is then added and dyeing is continued for a further 30 minutes. The leather is then thoroughly rinsed and, if desired, treated for 30 minutes at 50"C with 2 parts of a dicyandiamide/formaldehyde condensation product.

Other types of suede leather as well as glove leather may be dyed in the same manner.

The olive dyeings so obtained have good fastness properties and good covering power.

Dyeing Procedure for Polyamide 100 parts of polyamide knitting yarn are put at 50"C into a dye bath which contains 2 parts of the dye of Example 9, 4 parts of ammonium sulfate and 2 parts of a levelling agent in 4000 parts of water. The bath is brought to the boil over 45 minutes and kept at boiling temperature for a further 45 minutes. The goods are then removed from the bath, thoroughly rinsed with cold water and dried. A violet brown dyeing with good fastness properties is obtained on the polyamide.

Dyeing Procedure for Wool 100 parts of woollen knitting yarn are put at 50"C into a dye bath which contains 2 parts of the dye of Example 9, 4 parts of 80% acetic acid and 2 parts of a levelling agent in 4000 parts of water. The bath is brought to the boil over 45 minutes and kept at boiling temperature for a further 45 minutes. The goods are then removed from the bath, thoroughly rinsed with cold water and dried.

A violet brown dyeing with good fastness properties is obtained on the wool.

Claims

1. An asymmetric 1:2-chromium complex dye of the formula

wherein Z is nitrogen or a CH group, A is a radical of the benzene or naphthalene series, which radical carries a hydroxyl or carboxyl group in the o-position to the azo or azomethine group, B is the radical of a coupling component if Z is nitrogen, which coupling component carries the group X in the o- or a-position to the azo group, or is the radical of an o-hydroxyal dehyde if Z is the CH group, X is oxygen or, if Z is nitrogen, is also a group of the formula -NR-, in which R is hydrogen or a C,-C4 alkyl group, Y' is sulfo, chlorine, C1-C4 alkyl, S02-R2, in which R2 is C1-C4 alkyl, or Y' is -S02-NRR3, in which R and R3 are each independently of the other hydrogen or Ca-C4 alkyl, Y2 is hydrogen, sulfo, chlorine or C,-C4 alkyl, R' is hydrogen or a group of the formula -SO2-Q orCO-(Oìn-Q, in which n is O or 1 and Q is Ca-C5 alkyl or phenyl, which phenyl group may be substituted by nitro, halogen, C,-C5 alkyl or C,-C5 alkoxy, p is O or 1 and Kas is a cation.

2. A dye according to claim 1, wherein A is the radical of a 1-hydroxy-2-aminobenzene which is unsubstituted or substituted by halogen, nitro, sulfo or low molecular alkyl or alkoxy, or is the radical of a 1-amino-2-hydroxy-4-sulfonaphthalene which is unsubstituted or substituted in the 6-position by halogen, e.g. bromine or, preferably, chlorine, nitro or sulfo.

3. A dye according to claim 2, wherein A is the radical of a 1-hydroxy-2-aminophenol which is substituted by a nitro group and may be further substituted by a sulfo group.

4. A dye according to any one of claims 1 to 3, wherein B is a 1- or 2-naphthol which is unsubstituted or substituted by amino and/or sulfo; 1- or 2-naphthylamine, unsubstituted or substituted by sulfo; p-C,-C6 alkylphenol, 1-phenyl-3-methyl-5-pyrazolone or acetoacetanilide, the phenyl moiety of which last two compounds may be substituted by C,-C4 alkyl, C,-C4 alkoxy, chlorine, nitro or sulfo, and wherein Z is nitrogen.

5. A dye according to any one of claims 1 to 3, wherein B is the radical of an ohydroxybenzaldehyde or o-hydroxynaphthaldehyde, each of which may be substituted by low molecular alkyl, halogen, sulfo, phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and wherein Z is the CH group.

6. A dye according to any one of claims 1 to 5, wherein R' is hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl.

7. A dye according to claim 6, wherein R' is hydrogen, methoxycarbonyl or acetyl.

8. A dye according to any one of claims 1 to 7, wherein Y is sulfo, chlorine, methyl, sulfonamide, N-methylsulfonamide or methylsulfonyl.

9. A dye according to claim 8, wherein Y is sulfo.

10. A dye according to any one of claims 1 to 9, wherein Y2 iS hydrogen, sulfo, chlorine or methyl.

11. A dye according to claim 10, wherein y2 iS hydrogen.

12. A dye according to claim 1 of the formula

wherein R2 is hydrogen, acetyl, methoxycarbonyl, benzoyl, phenylsulfonyl or methylphenylsulfonyl, Z is nitrogen or a CH group, A1 is the radical of a 1-hydroxy-2-aminobenzene which is unsubstituted or substituted by halogen, nitro, sulfo or low molecular alkyl or alkoxy, or is the radical of a 1-amino-2 hydroxy-4-sulfonaphthalene which is unsubstituted or substituted in the 6-position by halo gen, e.g. bromine or, preferably, chlorine, nitro or sulfo, B1 is the radical of one of the following coupling components if Z is nitrogen: a 1- or 2 naphthol which is unsubstituted or substituted by amino and/or sulfo; 1- or 2-naphthylam ine, unsubstituted or substituted by sulfo; or p-C,-C6 alkylphenol, 1-phenyl-3-methyl-5- pyrazolone or acetoacetanilide, the phenyl moiety of which last two compounds may be substituted by Ca-C4 alkyl, C,-C4 alkoxy, chlorine, nitro or sulfo, or, if Z is the CH group, B' is the radical of an o-hydroxybenzaldehyde or o-hydroxynaphthaldehyde, each of which may be substituted by low molecular alkyl, halogen, sulfo, phenylazo, sulfophenylazo, na phthylazo or sulfonaphthylazo, and KaO is a cation.

13. A dye according to claim 12, wherein R2 is hydrogen, methoxycarbonyl or acetyl, A' is the radical of 4-nitro-2-amino- 1 -hydroxybenzene, 4-nitro-2-amino- 1 -hydroxybenzene-6-sulfonic acid or 1-amino-2-hydroxy-4-sulfo-6-nitronaphthalene, and, if Z is nitrogen, B' is the radical of a 2-naphthol which is unsubstituted or substituted by amino or acetylamino, of acetoacetanilide or of 1-phenyl-3-methyl-5-pyrazolone, the phenyl moiety of which last two compounds may be substituted by chlorine or sulfo, or, if Z is the CH group, B' is the radical of o-hydroxybenzaldehyde which is unsubstituted or substituted in the p-position by phenylazo, sulfophenylazo, naphthylazo or sulfonaphthylazo, and KaO is a cation.

14. A process for the preparation of a dye of formula (1), which process comprises preparing the 1:1-chromium complex of the azo dye of the formula

and then reacting said complex with the dye of the formula

or with a mixture of the amine of the formula

and the aldehyde of the formula HO-B-CHO (6) to give the 1:2-chromium complex, or by preparing the 1:1-chromium complex of a dye of formula (4) and reacting said complex with the dye of formula (3), in which formulae (3), (4), (5) and (6) A, B, Z, X, Y1, y2, R1 and p are defined for formula (1).

15. Use of a dye of formula (1) for dyeing wool, polyamide and, in particular, leather and furs.