1:2 metal complexes of polyazo dyes having a sulpho substituted 1-hydroxy-2-naphthyl group as the coupling component and their use as dyestuffs

• US 5,602,237 A
• Filed: 03/29/1995
• Issued: 02/11/1997
• Est. Priority Date: 03/30/1994
• Status: Expired due to Fees

• Current Assignee: Clariant Finance (Bvi) Limited
• Original Assignee: Sandoz Inc. (Novartis Ag)
• Inventors: Sorolla, Jose R., Barra, Jordi B.
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US08/412,670
• Time in Patent Office: 685 Days
• Field of Search: 534/718, 534/700, 534/701, 534/704, 534/705, 534/706, 534/707, 534/709
• US Class Current: 534/718
• CPC Class Codes: C09B 45/24 Disazo or polyazo compounds

Abstract

The invention provides a 1:2 metal complex in which at least one of the complexants is a polyazo compound of formula ##STR1## wherein --A₁ --(CO)_p --OH signifies the radical of a diazo component of formula H₂ N--A--(CO)_p --OH, in which the substituent --(CO)_p --OH is in ortho-position to the diazotizable amino group --NH₂, --A-- is the ortho-bivalent radical and p signifies 0 or 1, or a modified derivative thereof,

--X-- signifies an aromatic bivalent radical,

--B₁ signifies the radical of a coupling component HB, or a modified derivative thereof,

m signifies 0 or 1,

n signifies 0, 1 or 2

and M signifies hydrogen or a cation, with the proviso that m+n=1 or 2,

or a mixture of such complexes and to the use thereof as dyestuffs, in particular for the dyeing of a substrate dyeable with anionic dyes, especially of leather or pelts.

Claims

1. A 1:

2 metal complex of (i) a polyazo compound of formula ##STR50## wherein --A₁ --(CO)_p --OH signifies the radical of a diazo component of formula H₂ N--A--(CO)_p --OH,

in which the substituent --(CO)_p --OH is in ortho-position to the diazotizable amino group, NH₂,

--A-- is a bivalent aromatic radical, and p signifies 0 or 1,

--X-- signifies a bivalent aromatic radical,

--B₁ signifies the radical of a coupling component, HB,

m signifies 0 or 1,

n signifies 0,1 or 2,

and M signifies hydrogen or a cation, with the proviso that m+n=1 or 2;

(ii) two different polyazo compounds of said formula (I);

(iii) a polyazo compound of formula (I) and one or more chromophoric or a non-chromophoric complex-forming ligands provided that said chromophoric or a non-chromophoric complex-forming ligands are not polyazo compounds of formula (I);

or a mixture of such complexes.

2. A 1:

2 metal complex or 1;

2 metal complex mixture according to claim 1, wherein the compounds of formula (I) correspond to formula ##STR51## wherein R signifies hydrogen or methyl.

3. A 1:

2 metal complex or mixture according to claim 1, wherein --A₁ --(CO)_p --OH is the radical of a benzene or naphthalene diazo component,

--B₁ is the radical of a benzene, naphthalene, heterocyclic or open-chain methylene-active coupling component,

and the complex-forming metal is iron, chromium or cobalt.

4. A 1:

2 metal complex according to (i), (ii) or (iii) of claim 1 having the formula ##STR52## wherein Me signifies a 1;

2 complex-forming metal;

Lg signifies one or more chromophoric or non-chromophoric complex-forming ligands;

t is the number of negative charges of the 1;

2 metal complex; and

(Kat)⁺ signifies a cation, or a mixture of such complexes.

5. A metal complex according to claim 4 of the formula ##STR53## wherein Me₁ signifies iron, cobalt or chromium and t'"'"' signifies 0 or 1, or a mixture of such complexes.

6. A metal complex according to claim 5 of the formula ##STR54## wherein R signifies hydrogen or methyl, or a mixture of such complexes.

7. A 1:

2 metal complex according to claim 1 wherein the coupling component, HB, is selected from the group consisting of ##STR55## wherein R₁₀ signifies hydrogen, --OR₁₄ or --NHR₁₄ ;

R₁₁ signifies --OR₁₄ or --NHR₁₄ ;

R₁₂ signifies hydrogen, --SO₃ M, --SO₂ NR₃ R₄, --COOM or --CONR₃ R₄ ;

R₁₃ signifies hydrogen, --SO₃ M, --SO₂ NR₃ R₄, --COOM or --CONR₃ R₄ ;

R₃ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl;

R₄ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl, benzyl,

or a radical of the formula ##STR56## R₅ signifies nitrile, carbamoyl or --COOM;

R₆ signifies hydrogen, methyl, chlorine, nitro, --COOM or --SO₃ M;

R₁₄ signifies hydrogen, C_1-4 -alkyl, Ac'"'"' or a radical of formula ##STR57## Ac'"'"' signifies the acyl radical of an aliphatic carboxylic acid;

Q signifies --CO--, --SO₂ -- or a direct bond;

R₁₅ signifies hydrogen, methyl, --NH--Ac, --COOM, or --NO₂, or, if in formula (c₂) Q signifies --CO-- or --SO₂ --, then R₁₅ can also be --NH₂ ;

R₁₆ signifies --OH or --NH₂ ;

R₁₇ signifies hydrogen, C_1-4 -alkyl, C_1-4 -alkoxy, --OH, --NR'"'"'R" or --NH--Ac;

R₁₈ signifies hydrogen, C_1-4 -alkyl, C_1-4 -alkoxy;

R'"'"' and R" independently signify hydrogen, C_1-2 -alkyl or C_2-3 -hydroxyalkyl;

R₁₉ signifies hydrogen, sulphonaphthyl or a radical of formula ##STR58## W₁ signifies hydrogen, halogen, methyl, methoxy or --COOM;

W₂ signifies hydrogen, halogen, trifluoromethyl, nitrile, nitro, --COOM, --SO₃ M or --SO₂ NR₃ R₄ ;

R₂₀ signifies C_1-4 -alkyl, phenyl, --COOM, --CONR₃ R₄, --COOCH₃ or --COOC₂ H₅ ;

R₂₁ signifies ═

O or ═

NH;

R₂₂ signifies hydrogen, unsubstituted amino, phenylamino, sulphonaphthyl, open-chain C_1-8 -alkyl, C_6-9 -cycloalkyl, carboxy-(C_1-4 -alkyl), C_2-4 -alkylsubstituted with hydroxy, methoxy, ethoxy or a sulpho group in one of the positions β

to ω

, or a radical of formula (C₃);

R₂₃ signifies hydrogen, nitrilo, acetyl, --COOM, carbamoyl, --SO₃ M, pyridinio or 2-methylpyridinio, in which where R₂₃ stands for pyridinio or orthomethylpyridinio, any of the sulpho groups present may be in the form of the anion, --SO₃^- forming an inner salt counterion;

R₂₄ signifies hydrogen, hydroxy, methyl, carboxy, phenyl, sulphomethyl or carbamoyl;

R₂₅ signifies hydroxy, primary amino, nitrilamino, thiol or a radical of formula ##STR59## R₂₆ signifies hydroxy or primary amino;

R₂₇ signifies hydroxy or primary amino;

R₂₈ signifies hydrogen, methyl, chlorine, chloromethyl or chloroacetyl;

G signifies --O--, --NH--, or a direct bond;

R₂₉ signifies naphthyl, sulphonaphthyl or disulphonaphthyl or a radical of formula (C₃);

R₃₀ signifies C_1-4 -alkyl; and

Z signifies hydrogen, --NH₂, --OH, C_1-4 -alkoxy, a mono- or di-(C_1-4 -alkyl)amino group or an acylamino group.

8. A 1:

2 metal complex according to claim 1 wherein H₂ N--A--(CO)_p --OH is selected from the group consisting of ##STR60## wherein R₁ signifies hydrogen, nitro, --SO₃ M or --SO₂ NR₃ R₄ ;

R₂ signifies hydrogen, nitro, --SO₃ M or --SO₂ NR₃ R₄ ;

R₃ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl;

R₄ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl, benzyl,

or a radical of the formula ##STR61## R₅ signifies nitrile, carbamoyl or --COOM;

R₆ signifies hydrogen, methyl, chlorine, nitro, --COOM or --SO₃ M;

R₇ Signifies hydrogen, halogen, nitro, --SO₃ M, --SO₂ NR₃ R₄, methylsulphonyl, C_1-4 -alkyl or --NH--Ac;

R₈ signifies hydrogen, halogen, nitro, --SO₃ M, --SO₂ NR₃ R₄, methylsulphonyl, C_1-4 -alkyl or --NH--Ac;

R₉ signifies nitro, --SO₃ M or --SO₂ NR₃ R₄ ; and

Ac signifies an aliphatic acyl group.

13. A 1:

2 metal complex according to (iii) of claim 1 comprising a polyazo compound and a non-chromophoric, complex-forming ligand.

14. A 1:

2 metal complex according to claim 13 wherein the non-chromophoric, complex-forming ligand is selected from coordinatively linkable aliphatic polyamines or hydroxycarboxylic acids.

15. A 1:

2 metal complex according to claim 13 wherein the non-chromophoric, complex-forming ligand additionally includes water or ammonia.

16. A 1:

2 metal complex according to claim 13 wherein the non-chromophoric, complex-forming ligand additionally includes water and ammonia.

17. A 1:

2 metal complex according to (iii) of claim 1 comprising a polyazo compound and chromophoric, complex-forming ligand.

18. A 1:

2 metal complex according to claim 17 wherein the chromophoric, complex-forming ligand is a metallizable azo compound.

22. A process for the dyeing of a substrate dyeable with anionic dyes, comprising applying a 1:

2 metal complex or a mixture thereof according to claim 1 to a substrate dyeable with anionic dyes.

23. A process according to claim 22 wherein said substrate is selected from the group consisting of leather and pelts.

9. A 1:

2 metal complex of

(i) a polyazo compound of formula ##STR62## wherein --A₁ --(CO)_p --OH signifies the radical of a diazo component of formula H₂ N--A--(CO)_p --OH,

in which the substituent --(CO)_p --OH is in ortho-position to the diazotizable amino group, NH₂,

--A-- is a bivalent aromatic radical

and p signifies 0 or 1,

--X-- signifies a bivalent aromatic radical,

--B₁ -- signifies the radical of a coupling component, HB,

m signifies 0 or 1,

n signifies 0, 1 or 2,

and M signifies hydrogen or a cation, with the proviso that m+n=1 or 2;

(ii) two different polyazo compounds of said formula (I);

or a mixture of such complexes.

10. A 1:

2 metal complex according to claim 9 corresponding to (i).

11. A 1:

2 metal complex according to claim 10 wherein the polyazo compound is of formula (I'"'"') ##STR63## wherein R signifies hydrogen or methyl.

12. A 1:

2 metal complex or mixture according to claim 10, wherein

--A₁ --(CO)_p --OH is the radical of a benzene or naphthalene diazo component,

--B₁ is the radical of a benzene, naphthalene, heterocyclic or open-chain methylene-active coupling component,

and the complex-forming metal of the 1;

2 metal complex is iron, chromium or cobalt.

19. A 1:

2 metal complex of a polyazo compound of formula ##STR64## wherein --A₁ --(CO)_p --OH signifies the radical of a diazo component of formula H₂ N--A--(CO)_p --OH;

H₂ N--A--(CO)_p --OH is selected from the group consisting of ##STR65## wherein R₁ signifies hydrogen, nitro, --SO₃ M or --SO₂ NR₃ R₄ ;

R₂ signifies hydrogen, nitro, --SO₃ M or --SO₂ NR₃ R₄ ;

R₃ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl;

R₄ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl, benzyl,

or a radical of the formula ##STR66## R₅ signifies nitrile, carbamoyl or --COOM;

R₆ signifies hydrogen, methyl, chlorine, nitro, --COOM or --SO₃ M;

R₇ Signifies hydrogen, halogen, nitro, --SO₃ M, --SO₂ NR₃ R₄, methylsulphonyl, C_1-4 -alkyl or --NH--Ac;

R₈ signifies hydrogen, halogen, nitro, --SO₃ M, --SO₂ NR₃ R₄, methylsulphonyl, C_1-4 -alkyl or --NH--Ac;

R₉ signifies nitro, --SO₃ M or --SO₂ NR₃ R₄ ; and

Ac signifies an aliphatic acyl group;

X signifies a phenylene or naphthalene radical;

B₁ signifies the radical of a coupling component, HB;

HB is selected from the group consisting of ##STR67## wherein R₁₀ signifies hydrogen, --OR₁₄ or --NHR₁₄ ;

R₁₁ signifies --OR₁₄ or --NHR₁₄ ;

R₁₂ signifies hydrogen, --SO₃ M, --SO₂ NR₃ R₄, --COOM or --CONR₃ R₄ ;

R₁₃ signifies hydrogen, --SO₃ M, --SO₂ NR₃ R₄, --COOM or --CONR₃ R₄ ;

R₃ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl;

R₄ signifies hydrogen, C_1-4 -alkyl, C_1-3 -alkylene-R₅ or C_2-3 -hydroxyalkyl, benzyl,

or a radical of the formula ##STR68## R₅ signifies nitrile, carbamoyl or --COOM;

R₁₄ signifies hydrogen, C_1-4 -alkyl, Ac'"'"' or a radical of formula ##STR69## Ac'"'"' signifies the acyl radical of an aliphatic carboxylic acid;

Q signifies --CO--, --SO₂ -- or a direct bond;

R₁₅ signifies hydrogen, methyl, --NH--Ac, --COOM, or --NO₂, or, if in formula (c₂) Q signifies --CO-- or --SO₂ --, then R₁₅ can also be --NH₂ ;

R₁₆ signifies --OH or --NH₂ ;

R₁₇ signifies hydrogen, C_1-4 -alkyl, C_1-4 -alkoxy, --OH, --NR'"'"'R" or --NH--Ac;

R₁₈ signifies hydrogen, C_1-4 -alkyl, C_1-4 -alkoxy;

R'"'"' and R" independently signify hydrogen, C_1-2 -alkyl or C_2-3 -hydroxyalkyl;

R₁₉ signifies hydrogen, sulphonaphthyl or a radical of formula ##STR70## W₁ signifies hydrogen, halogen, methyl, methoxy or --COOM;

W₂ signifies hydrogen, halogen, trifluoromethyl, nitrile, nitro, --COOM, --SO₃ M or --SO₂ NR₃ R₄ ;

R₂₀ signifies C_1-4 -alkyl, phenyl, --COOM, --CONR₃ R₄, --COOCH₃ or --COOC₂ H₅ ;

R₂₁ signifies ═

O or ═

NH;

R₂₂ signifies hydrogen, unsubstituted amino, phenylamino, sulphonaphthyl, open-chain C_1-8 -alkyl, C_6-9 -cycloalkyl, carboxy-(C_1-4 -alkyl), C_2-4 -alkylsubstituted with hydroxy, methoxy, ethoxy or a sulpho group in one of the positions β

to ω

, or a radical of formula (C₃);

R₂₃ signifies hydrogen, nitrilo, acetyl, --COOM, carbamoyl, --SO₃ M, pyridinio or 2-methylpyridinio, in which where R₂₃ stands for pyridinio or orthomethylpyridinio, any of the sulpho groups present may be in the form of the anion, --SO₃^- forming an inner salt counterion;

R₂₄ signifies hydrogen, hydroxy, methyl, carboxy, phenyl, sulphomethyl or carbamoyl;

R₂₅ signifies hydroxy, primary amino, nitrilamino, thiol or a radical of formula ##STR71## R₂₆ signifies hydroxy or primary amino;

R₂₇ signifies hydroxy or primary amino;

R₂₈ signifies hydrogen, methyl, chlorine, chloromethyl or chloroacetyl;

G signifies --O--, --NH--, or a direct bond;

R₂₉ signifies naphthyl, sulphonaphthyl or disulphonaphthyl or a radical of formula (C₃);

R₃₀ signifies C_1-4 -alkyl; and

Z signifies hydrogen, --NH₂, --OH, C_1-4 -alkoxy, a mono- or di-(C_1-4 -alkyl)amino group or an acylamino group;

m signifies 0 or 1,

n signifies 0,1 or 2,

and M signifies hydrogen or a cation, with the proviso that m+n=1 or 2.

20. A 1:

2 metal complex according to claim 19 wherein X is a phenylene radical.

21. A 1:

2 metal complex according to claim 20 wherein said phenylene radical is substituted with one or more groups selected from the group consisting of C_1-4 -alkyl, C_1-4 -alkoxy and chlorine.