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US 8,080,101 B2Granted
Azo reactive dyes and mixtures of fiber-reactive azo dyes, their preparation and their use
AssigneeDyStar Colours Deutschland GmbH
InventorsJoachim Eichhorn, Stefan Meier, Werner Hubert Russ
Life of this patent
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Abstract
The present invention relates to dye mixtures which comprise at least one dye of the formula (I), at least one dye of the formula (II) and optionally at least one dye of the formula (III) and/or optionally at least one dye of the formula (IV) in which D1 to D7, R201 to R203, R0, R* and R**, T, M, v and f are as defined in claim 1, to dyes of the formula (II), to processes for their preparation, and to their use for dyeing and printing hydroxyl- and carboxamido-containing materials.
Claims20
A dye mixture which comprises at least one dye of the formula (I),
- at least one dye of the formula (II-a), (II-b) or (II-c)
- and optionally at least one dye of the formula (III)
- and optionally at least one dye of the formula (IV)
- in which:
- D1, D2, D3, D4, and D5 are independently of one another a group of the formula (1)
- in which
- R1 and R2 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- X1 is hydrogen or a group of the formula —SO2—Z, where
- Z is —CH═CH2, —CH2CH2Z1 or hydroxyl, in which
- Z1 is hydroxyl or a group which can be eliminated under the action of alkali;
- or
- D1, D2, D3, D4 and D5 are independently of one another a naphthyl group of the formula (2)
- in which
- R3 and R4 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- X2 has one of the definitions of X1;
- or
- D1, D2, D3, D4, and D5 are independently of one another a group of the formula (3)
- in which
- R5 and R6 independently of one another have one of the definitions of R1 and R2;
- R7 is hydrogen, (C1-C4)-alkyl, or phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen or carboxyl;
- and
- Z2 is a group of the formula (4) or (5) or (6)
- in which
- V is fluorine or chlorine;
- U1 and U2 independently of one another are fluorine, chlorine or hydrogen;
- and
- Q1 and Q2 independently of one another are chlorine, fluorine, cyanamido, hydroxyl, (C1-C6)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C1-C6)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (7) or (8)
- in which
- R8 is hydrogen or (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl or phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;
- R9 and R10 have independently of one another one of the definitions of R8, or form a cyclic ring system of the formula —(CH2)j— where j is 4 or 5, or alternatively —(CH2)2-E-(CH2)2—, where E is oxygen, sulfur, sulfonyl or —NR11 with R11═(C1-C6)-alkyl;
- W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, wherein said substituents (C1-C4)-alkoxy, carboxyl, sulfo, chlorine or bromine, or is (C1-C4)-alkylene-arylene or (C2-C6)-alkylene which is interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carboxamido, or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups;
- and
- Z is as defined above;
- or
- D1, D2, D3, D4, and D5 are independently of one another a group of the formula (9)
- in which
- R12 is hydrogen, (C1-C4)-alkyl, aryl or a substituted aryl radical;
- R13 and R14 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- A is a phenylene group of the formula (10)
- in which
- R15 and R16 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a naphthylene group of the formula (11)
- in which
- R17 and R18 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a polymethylene group of the formula (12)
- —(CR19R20)k- (12)
- in which
- k is an integer greater than 1;
- and
- R19 and R20 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, cyano, amido, halogen or aryl;
- and
- X3 has one of the definitions of X1;
- and
- R0 is a group of the formula (4) or (5) or is a group of the formula (13)
- in which
- R21 is (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, carboxy-(C1-C6)-alkyl or phenyl which is unsubstituted or substituted (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;
- G is C—R200 or N, in which
- R200 is hydrogen, C1-C6-alkyl, which is unsubstituted or substituted by amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is sulfo, carboxyl, cyano or halogen, or is a group of the formula (100);
- —N═N-D8 (100)
- in which D8 possesses one of the definitions of D1 or is a group of the formula (101)
- in which D01 possesses one of the definitions of D1;
- R01 and R02 independently of one another are hydrogen, C1-C6-alkyl, amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, acetamido, ureido, sulfo or carboxyl;
- x is 0 or 1;
- R201 and R202 independently of one another are amino, hydroxyl, (C1-C4)-alkylamino, (C1-C4)-alkoxy or mercapto;
- or one of the radicals R201 and R202 is hydrogen and the other has one of the aforementioned definitions;
- R203 is hydrogen, C1-C6-alkyl, which is unsubstituted or substituted by amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, carboxyl, cyano, halogen, nitro, amido or ureido;
- b, f and v independently of one another are 0 or 1;
- R* and R** independently of one another are hydrogen, (C1-C4)-alkyl or a group of the formula (14)
- —CH2—SO3M (14);
- R105 to R110 independently of one another are hydrogen, C1-C4-alkyl, C1-C4-alkoxy, sulfo, carboxyl or halogen;
- R300 and R301 independently of one another are hydrogen, (C1-C4)-alkyl, hydroxyl-, alkoxy-, amino-, alkylamino-, sulfo-, sulfato- or carboxyl-substituted (C1-C4)-alkyl or aryl;
- Z is vinyl, β-sulfatoethyl or hydroxyl;
- T is hydroxyl or —NH2, and if T is NH2 and v is 0;
- and
- M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.
77 more elements
A process for preparing a dye of the formula (II),
- which comprises diazotizing an amine of the formula (19)
- D7-NH2 (19),
- in which D7 and D6 are identical or different and are
- a group of the formula (9)
- in which
- R12 is hydrogen, (C1-C4)-alkyl, aryl or a substituted aryl radical;
- R13 and R14 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- A is a phenylene group of the formula (10)
- in which
- R15 and R16 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a naphthylene group of the formula (11)
- in which
- R17 and R18 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a polymethylene group of the formula (12)
- —(CR19R20)k- (12)
- in which
- k is an integer greater than 1;
- and
- R19 and R20 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, cyano, amido, halogen or aryl;
- and
- X3 has one of the definitions of X1;
- X1 is hydrogen or a group of the formula —SO2—Z, where
- Z is —CH═CH2, —CH2CH2Z1 or hydroxyl, in which
- Z1 is hydroxyl or a group which can be eliminated under the action of alkali;
- and coupling the resulting diazonium compound onto a compound of the formula (24)
- in which
- D6 is defined above,
- R201 and R202 independently of one another are amino or hydroxyl;
- R203 is hydrogen, C1-C6-alkyl, which is unsubstituted or substituted by amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, carboxyl, cyano, halogen, nitro, amido or ureido;
- G is C—R200 or N, in which
- R200 is hydrogen, C1-C6-alkyl, which is unsubstituted or substituted by amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is sulfo, carboxyl, cyano or halogen, or is a group of the formula (100);
- —N═N-D8 (100)
- in which D8 possesses one of the definitions of D1 or is a group of the formula (101)
- in which D01 possesses one of the definitions of D1;
- D1 is a naphthyl group of the formula (2)
- in which
- R3 and R4 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4) alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- X2 has one of the definitions of X1;
- or
- D1 is a group of the formula (3)
- in which
- R5 and R6 independently of one another have one of the definitions of R1 and R2;
- R1 and R2 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;
- R7 is hydrogen, (C1-C4)-alkyl, or phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen or carboxyl;
- and
- Z2 is a group of the formula (4) or (5) or (6)
- in which
- V is fluorine or chlorine;
- U1 and U2 independently of one another are fluorine, chlorine or hydrogen;
- and
- Q1 and Q2 independently of one another are chlorine, fluorine, cyanamido, hydroxyl, (C1-C6)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C1-C6) alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (7) or (8)
- in which
- R8 is hydrogen or (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl or phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;
- R9 and R10 have independently of one another one of the definitions of R8, or form a cyclic ring system of the formula —(CH2)j— where j is 4 or 5, or alternatively —(CH2)2-E-(CH2)2—, where E is oxygen, sulfur, sulfonyl or —NR11 with R11═(C1-C6)-alkyl;
- W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, wherein said substituents (C1-C4)-alkyl, (C1-C4)-alkoxy, carboxyl, sulfo, chlorine or bromine, or is (C1-C4)-alkylene-arylene or (C2-C6)-alkylene which is interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carboxamido, or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups;
- and
- Z is as defined above;
- or
- D1 is a group of the formula (9)
- in which
- R12 is hydrogen, (C1-C4)-alkyl, aryl or a substituted aryl radical;
- R13 and R14 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4) alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- and
- A is a phenylene group of the formula (10)
- in which
- R15 and R16 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a naphthylene group of the formula (11)
- in which
- R17 and R18 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4) alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
- or
- A is a polymethylene group of the formula (12)
- —(CR19R20)k- (12)
- in which
- k is an integer greater than 1;
- and
- R19 and R20 independently of one another are hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, cyano, amido, halogen or aryl;
- and
- X3 has one of the definitions of X1;
- and
- R01 and R02 independently of one another are hydrogen, C1-C6-alkyl, amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, acetamido, ureido, sulfo or carboxyl;
- x is 0 or 1.
84 more elements
A dye comprising the formula (II-b) or the formula (II-c)
- wherein
- R105 to R110 independently of one another are hydrogen, C1-C4-alkyl, C1-C4-alkoxy, sulfo, carboxyl or halogen;
- R201 and R202 independently of one another are amino or hydroxyl;
- R203 is hydrogen, C1-C6-alkyl, which is unsubstituted or substituted by amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is phenyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido, or is amino, (C1-C4)-alkylamino, hydroxyl, (C1-C4)-alkoxy, sulfo, carboxyl, cyano, halogen, nitro, amido or ureido;
- R300 and R301 independently of one another are hydrogen, (C1-C4)-alkyl, hydroxyl-, alkoxy-, amino-, alkylamino-, sulfo-, sulfato- or carboxyl-substituted (C1-C4)-alkyl or aryl;
- and
- Z is vinyl, β-sulfatoethyl or hydroxyl.
4 more elements
Dependencies are inferred from the claim text.