Fibre-reactive dyes, their preparation and their use

1. A reactive dye of formula (1)

wherein

Q 1 , Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 –C 4 alkyl,

A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore,

D is the radical of a diazo component, of the benzene or naphthalene series,

X is halogen, 3-carboxypyridin-1-yl, 3-Carbamoylpyridin-1-yl, hydroxy, C 1 –C 4 alkoxy unsubstituted or substituted in the alkyl moiety, phenoxy unsubstituted or substituted in the phenyl moiety,

C 1 –C 4 alkylthio unsubstituted or substituted in the alkyl moiety, unsubstituted or substituted amino, or an N-heterocycle which may or may not contain further hetero atoms, and

Y is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions selected from the group consisting of —Cl, —Br, —F, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OPO 3 H 2 , —OCO—C 6 H 5 , —OSO 2 —C 1 –C 4 alkyl or —OSO 2 —N(C 1 –C 4 alkyl) 2 .

2. A reactive dye according to claim 1 , wherein Q 1 , Q 2 , Q 3 and Q 4 are hydrogen.

3. A reactive dye according to claim 1 , wherein X is fluorine or chlorine.

4. A reactive dye according to claim 1 , wherein D corresponds to a radical of formula (9) or (10)

wherein

(R 4 ) 0-3 and (R 13 ) 0-3 each independently of the other denote from 0 to 3 identical or different substituents selected from the group halogen, C 1 –C 4 alkyl, C 1 –C 4 alkoxy, carboxy and sulfo, K 3 is the radical of a coupling component of formula (11a) or (11b)

and

Z and Z 1 are each independently of the other a radical of formula (2a), (2c), (2d), (2e) or (2f)

—SO 2 —Y  (2a),

—CONR 2 —(CH 2 ) m —SO 2 —Y  (2c),

—NH—CO—CH(Hal)—CH 2 —Hal  (2d),

—NH—CO—C(Hal)═CH 2   (2e) or

wherein

R 1a and R 2 are hydrogen,

Hal is bromine,

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

T 1 is C 1 –C 4 alkoxy, C 1 –C 4 alkylthio, hydroxy, amino; N-mono- or N,N-di-C 1 –C 4 alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo; morpholino;

or phenylamino or N—C 1 –C 4 alkyl-N-phenylamino, wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato, each unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chlorine, methyl or by methoxy;

or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, or is a fibre-reactive radical of formula (3c′) or (3d′)

and Y is as defined above,

X 1 is chlorine or fluorine,

m is a number 2 or 3,

R′ 5 is hydrogen, sulfo, or C 1 –C 4 alkoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato,

R′ 5a is hydrogen, C 1 –C 4 alkyl, C 1 –C 4 alkoxy, C 2 –C 4 alkanoylamino, ureido or a radical of formula (2f) wherein the radicals R 1a , T 1 and X 1 are as defined above.

5. A reactive dye according to claim 4 , wherein the radical D corresponds to a radical of formula (9a), (9b), (9c), (9d) or (10a)

wherein

R′ 5 is hydrogen, sulfo, or ethoxy unsubstituted or substituted in the alkyl moiety by hydroxy or by sulfato, R′ 5a is hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino or ureido,

(R 13 ) 0-2 denotes from 0 to 2 identical or different substituents selected from the group consisting of halogen, C 1 –C 4 alkyl, C 1 –C 4 alkoxy and sulfo,

Y 1 is a group —CH(Br)—CH 2 —Br or —C(Br)═CH 2 ,

Y is vinyl, β-chloroethyl or β-sulfatoethyl, and

m is a number 2 or 3.

6. A reactive dye according to claim 1 , wherein A is the radical of a mono- or dis-azo dye.

7. A reactive dye according to claim 1 , wherein A is a dye radical of formula (8a), (8b), (8c), (8d), (8e), (8f), (8g), (8h), (19d) or (19e),

wherein

(R 4 ) 0-3 denotes from 0 to 3 identical or different substituents selected from the group consisting of methyl, methoxy and sulfo,

(R 5 ) 0-3 denotes from 0 to 3 identical or different substituents selected from the group consisting of methyl, methoxy, β-hydroxyethoxy, β-sulfatoethoxy, sulfo, acetylamino and ureido, and Z 1 may optionally, be a fibre-reactive radical of formula (2a)

—SO 2 —Y  (2a)

wherein Y is vinyl or β-sulfatoethyl.

8. A reactive dye according to claim 1 , wherein A is a dye radical of formula (19a), (19b), (19l) or (19n)

wherein

(R 4 ) 0-3 denotes from 0 to 3 identical or different substituents selected from the group consisting of methyl, methoxy and sulfo,

(R 5 ) 0-3 denotes from 0 to 3 identical or different substituents selected from the group consisting of methyl, methoxy, β-hydroxyethoxy, β-sulfatoethoxy, sulfo, acetylamino and ureido, and Z 1 may, optionally, be a fibre-reactive radical of formula (2a)

—SO 2 —Y  (2a)

wherein Y is vinyl or β-sulfatoethyl.

9. A method of dyeing or printing hydroxyl-group-containing or nitrogen-containing fibre materials, which comprises contacting said materials with a tinctorially effective amount of a reactive dye according to claim 1 .

10. A method according to claim 9 , wherein cellulosic fibre materials, are dyed or printed.

11. A reactive dye of formula (21)

wherein

Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 –C 4 alkyl,

D is the radical of a diazo component, of the benzene or naphthalene series, and

Y is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions selected from the group consisting of —Cl, —Br, —F, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OPO 3 H 2 , —OCO—C 6 H 5 , —OSO 2 —C 1 –C 4 alkyl or —OSO 2 —N(C 1 –C 4 alkyl) 2 .

12. A reactive dye of formula (23)

wherein

Q 1 , Q 2 , Q 3 and Q 4 are each independently of the others hydrogen or unsubstituted or substituted C 1 –C 4 alkyl,

A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore,

X is halogen, 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl, hydroxy, C 1 –C 4 alkoxy unsubstituted or substituted in the alkyl moiety, phenoxy unsubstituted or substituted in the phenyl moiety,

C 1 –C 4 alkylthio unsubstituted or substituted in the alkyl moiety, unsubstituted or substituted amino, or an N-heterocycle which may or may not contain further hetero atoms, and

Y is vinyl or a radical —CH 2 —CH 2 —U and U is a group removable under alkaline conditions selected from the group consisting of —Cl, —Br, —F, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OPO 3 H 2 , —OCO—C 6 H 5 , —OSO 2 —C 1 –C 4 alkyl or —OSO 2 —N(C 1 –C 4 alkyl) 2 .

13. A process for the preparation of a reactive dye according to claim 1 , which comprises reacting one molar equivalent of 2,4,6-trichloro- or 2,4,6-trifluoro-s-triazine first with one molar equivalent of a compound of formula (20)

A-NHQ 1   (20),

and then with one molar equivalent of a compound of formula (22)

 to form a compound of formula (23)

and coupling the compound of formula (23) to one molar equivalent of a conventionally diazotised compound of formula (24)

H 2 N-D  (24)

C, Q 1 , Q 2 , Q 3 , Q 4 , A, D and Y in each case being as defined in claim 1 and X being chlorine or fluorine.