Fiber-reactive copper complex disazo dyes

1. A dye of the formula (I)

in which

R 1 and R 2 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, or ureido or are a group of the formula —SO 2 —Z 1 , where

Z 1 is —CH═CH 2 , —CH 2 CH 2 G or hydroxyl, and

G is hydroxyl or an alkali-detachable group;

R 3 is (C 1 -C 4 )-alkyl; (C 1 -C 4 )-alkyl substituted by sulfo, carboxyl, halogen, hydroxyl, amino or acetamido; phenyl; or phenyl substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;

R 4 is hydrogen or has one of the definitions of R 3 ;

f is 0 or 1;

D 1 is a group of the formula (1)

in which

R 5 and R 6 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and

X 1 is hydrogen or a group of the formula —SO 2 —Z 2 , where Z 2 has one of the definitions of Z 1 ;

D 1 is a group of the formula (2)

in which

R 7 and R 8 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and

X 2 has one of the definitions of X 1 ; or

D 1 is a group of the formula (3)

in which

R 9 and R 10 independently of one another have one of the definitions of R 5 and R 6 ;

R 11 is hydrogen, (C 1 -C 4 )-alkyl, or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen or carboxyl; and

Z 3 is a group of the formula (4) or (5) or (6)

in which

V is fluorine or chlorine;

U 1 and U 2 independently of one another are fluorine, chlorine or hydrogen; and

Q 1 and Q 2 independently of one another are chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 4 )-alkylmercapto, pyridino, carboxypyridino or carbamoylpyridino, or are a group of the formula (7) or (8)

in which

R 12 is hydrogen, (C 1 -C 4 )-alkyl, sulfo-(C 1 -C 4 )-alkyl, unsubstituted phenyl or phenyl which is substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;

R 13 and R 14 independently of one another have one of the definitions of R 12 or together form a group of the formula —(CH 2 ) j — where j is 4 or 5, or a group of the formula —(CH 2 ) 2 -E-(CH 2 ) 2 —, in which E is oxygen, sulfur, sulfonyl or —N((C 1 -C 4 )-alkyl)-;

W is unsubstituted phenylene; phenylene substituted by 1 or 2 substituents selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, and bromine; unsubstituted naphthylene; naphthylene substituted by 1 or 2 sulfo groups; (C 1 -C 4 )-alkylene-arylene; (C 1 -C 4 )-alkylene-arylene which is interrupted by oxygen, sulfur, sulfonyl, —NH—, carbonyl, —CONH— or —CON(CH 3 )—; (C 2 -C 6 )-alkylene; (C 2 -C 6 )-alkylene which is interrupted by oxygen, sulfur, sulfonyl, —NH—, carbonyl, —CONH— or —CON(CH 3 )—; phenylene-CONH-phenylene; or phenylene-CONH-phenylene, where one or both phenylene groups are substituted each by 1 or 2 substituents selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido, and halogen; and

Z 4 has one of the definitions of Z 1 ; or

D 1 is a group of the formula (9)

in which

R 15 is hydrogen, (C 1 -C 4 )-alkyl, aryl or an aryl substituted by one, two or three mutually independent groups from the selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, and halogen;

R 16 and R 17 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;

A is a group of the formula (10)

in which

R 18 and R 19 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or

A is a group of the general formula (11)

in which

R 20 and R 21 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or

A is a group of the formula (12)

—(CR 22 R 23 ) k —  (12)

in which

k is an integer greater than 1 and

R 22 and R 23 independently of one another are hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and

X 3 has one of the definitions of X 1 ; and

M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;

and the dye of the formula (I) comprises at least one fiber-reactive group selected from the group consisting of —SO 2 —Z 1 , —SO 2 —Z 2 and Z 3 .

2. The dye as claimed in claim 1 , wherein R 1 and R 2 independently of one another are hydrogen, methyl, methoxy, sulfo or a group of the formula —SO 2 —Z 1 .

3. The dye as claimed in claim 1 , wherein R 3 is methyl or sulfomethyl and R 4 is hydrogen or methyl.

4. The dye as claimed in claim 1 , wherein Z 1 , Z 2 and Z 4 are vinyl, β-chloroethyl or β-sulfatoethyl.

5. The dye as claimed in claim 2 , wherein R 3 is methyl or sulfomethyl and R 4 is hydrogen or methyl and

Z 1 , Z 2 and Z 4 are vinyl, β-chloroethyl or β-sulfatoethyl.

6. The dye as claimed in claim 1 , wherein D 1 is a group of the formula (1), (3) or (9).

7. The dye as claimed in claim 5 , wherein D 1 is a group of the formula (1), (3) or (9).

8. The dye as claimed in claim 1 , which conforms to the formula (Ib)

or the formula (Ic)

in which R 1 , R 2 , R 3 , R 5 , R 6 , X 1 , Z 1 , Z 2 , M, and f are defined as indicated in claim 1 .

9. The dye as claimed in claim 1 , which conforms to the formula (Ib)

or the formula (Ic)

wherein R 1 and R 2 independently of one another are hydrogen, methyl, methoxy, sulfo or a group of the formula —SO 2 —Z 1 ,

R 3 is methyl or sulfomethyl

Z 1 and Z 2 are identical or different and are vinyl, β-chloroethyl or β-sulfatoethyl and

R 5 , R 6 , X 1 , M, and f are defined as indicated in claim 1 .

10. A process for preparing the dye of the formula (I) as claimed in claim 1 , which comprises reacting a compound of the formula (13)

in which R 24 is hydrogen, hydroxyl or methoxy and R 1 to R 4 , D 1 , f, and M are defined as indicated in claim 1 with a copper(II) salt.

11. A process for preparing the dye of the formula (I) as claimed in claim 1 , which comprises reacting a compound of the formula (18)

in which R 1 to R 4 , f, and M are defined as indicated in claim 1 with the diazotized compound of an amine of the formula (14)

D 1 -NH 2   (14),

in which D 1 is defined as indicated in claim 1 .

12. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, which comprises contacting the dye of the formula (I) as claimed in claim 1 with the material.

13. An ink for digital textile printing by the inkjet process, which comprises the dye of the formula (I) as claimed in claim 1 .

14. A dye of the formula (I-1) through (I-67)