Azo dyes for dyeing and printing hydrophobic materials

1. A dye of the general formula (I)

where

D is the residue of a diazo component;

R 1 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C 1 -C 6 )-alkyl, —NHCOaryl, —NHSO 2 (C 1 -C 6 )-alkyl or —NHSO 2 aryl;

R 2 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, phenoxy or halogen;

R 3 is hydrogen, (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, (C 3 -C 4 )-alkenyl or substituted (C 3 -C 4 )-alkenyl;

or R 2 and R 3 combine to form the radical —C*H(CH 3 )CH 2 C(CH 3 ) 2 —, where the carbon atom marked * is attached to the phenyl nucleus;

R 4 is hydrogen, (C 1 -C 6 )-alkyl or phenyl;

R 5 is vinyl or a group of the formula —CHR 6 COR 7 , where R 6 is hydrogen, (C 1 -C 6 )-alkyl or phenyl; R 7 is (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, phenyl or substituted phenyl; and

X is (C 1 -C 5 )-alkylene.

2. The dye as claimed in claim 1 , wherein D represents a group of the formula (IIa)

where

T 1 and T 2 are independently hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, —SO 2 (C 1 -C 6 )-alkyl, —SO 2 aryl, cyano, halogen or nitro; and

T 4 and T 3 are independently hydrogen, halogen, trifluoromethyl, cyano, —SCN, —SO 2 CH 3 or nitro;

with the proviso that at least one of T 1 , T 2 , T 3 and T 4 is not hydrogen;

or represents a group of the formula (IIb)

where

T 5 and T 5′ are independently hydrogen or halogen; and

T 6 is hydrogen, —SO 2 CH 3 , —SCN, (C 1 -C 4 )-alkoxy, halogen or nitro;

with the proviso that at least one of T 5 , T 5′ and T 6 is not hydrogen;

or represents a group of the formula (IIc)

where

T 12 is hydrogen or halogen;

or represents a group of the formula (IId)

where

T 7 is nitro, —CHO, cyano, —COCH 3 or a group of the formula

where T 10 is hydrogen, halogen, nitro or cyano;

T 8 is hydrogen, (C 1 -C 6 )-alkyl or halogen; and

T 9 is nitro, cyano, —COCH 3 or —COOT 11 ; where T 11 is (C 1 -C 4 )-alkyl;

or represents a group of the formula (IIe)

where T 7 and T 8 are each as defined above;

or represents a group of the formula (IIf)

where T 13 is phenyl or S—(C 1 -C 4 )-alkyl;

or represents a group of the formula (IIg)

where T 14 is cyano or —COCH 3 or —COOT″, where T 11 is (C 1 -C 4 )-alkyl; and

T 15 is phenyl or (C 1 -C 4 )-alkyl;

or represents a group of the formula (IIh)

where T 14 is as defined above and T 16 is (C 1 -C 4 )-alkyl;

or represents a group of the formula (IIi)

where T 17 is cyanomethyl, benzyl or allyl;

or represents a group of the formula (IIj)

3. The dye as claimed in claim 1 , wherein

R 1 is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino;

R 2 is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;

R 3 is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C 2 H 4 OCOCH 3 , —C 2 H 4 OCOC 2 H 5 , —C 2 H 4 COOCH 3 , —C 2 H 4 COOC 2 H 5 or allyl;

R 4 is hydrogen, methyl or phenyl;

R 6 is hydrogen, methyl or phenyl;

R 7 is methyl, ethyl or phenyl; and

X is —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, —CH(CH 3 )CH 2 — or —CH 2 CH(CH 3 )—.

4. The dye as claimed in claim 2 , wherein

R 1 is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino or phenylsulfonylamino;

R 2 is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy or phenoxy;

R 3 is hydrogen, methyl, ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C 2 H 4 OCOCH 3 , —C 2 H 4 OCOC 2 H 5 , —C 2 H 4 COOCH 3 , —C 2 H 4 COOC 2 H 5 or allyl;

R 4 is hydrogen, methyl or phenyl;

R 6 is hydrogen, methyl or phenyl;

R 7 is methyl, ethyl or phenyl; and

X is —CH 2 —, —C 2 H 4 —, —C 3 H 6 —, —CH(CH 3 )CH 2 — or —CH 2 CH(CH 3 )—.

5. The dye as claimed in claim 1 , conforming to the general formula (Ia)

where T 1 to T 4 , R 1 to R 5 and X are each as defined in claim 1 .

6. The dye as claimed in claim 5 , conforming to the general formula (Iaa)

where

T 1 is hydrogen, nitro, halogen or methyl;

T 2 is hydrogen, nitro or chlorine;

T 3 is hydrogen, cyano, chlorine or bromine;

T 4 is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;

R 1 is hydrogen, hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino, phenylsulfonylamino or methylsulfonylamino;

R 2 is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;

R 3 is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl or allyl;

R 4 is hydrogen, methyl or phenyl;

R 6 is hydrogen, methyl or phenyl; and

R 7 is methyl, ethyl or phenyl.

7. The dye as claimed in claim 5 conforming to the formula (Iab)

where

T 1 is hydrogen, nitro, halogen or methyl;

T 2 is hydrogen, nitro or chlorine;

T 3 is hydrogen, cyano, chlorine or bromine;

T 4 is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;

R 1 is hydrogen, hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino, phenylsulfonylamino or methylsulfonylamino;

R 2 is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;

R 3 is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl or allyl;

R 4 is hydrogen, methyl or phenyl.

8. The dye as claimed in claim 1 conforming to the general formula (Ib)

R 1 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C 1 -C 6 )-alkyl, —NHCOaryl, —NHSO 2 (C 1 -C 6 )-alkyl or —NHSO 2 aryl;

R 2 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, phenoxy or halogen;

R 3 is hydrogen, (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, (C 3 -C 4 )-alkenyl or substituted (C 3 -C 4 )-alkenyl;

or R 2 and R 3 combine to form the radical —C*H(CH 3 )CH 2 C(CH 3 ) 2 —, where the carbon atom marked * is attached to the phenyl nucleus;

R 4 is hydrogen, (C 1 -C 6 )-alkyl or phenyl;

R 5 is vinyl or a group of the formula —CHR 6 COR 7 , where R 6 is hydrogen, (C 1 -C 6 )-alkyl or phenyl; R 7 is (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, phenyl or substituted phenyl;

X is (C 1 -C 5 )-alkylene and

D′ represents a diazo component of the formula 3,5-dicyano-4-chloro-2-thienyl, 3,5-dicyano-2-thienyl, 3,5-dicyano-4-methyl-2-thienyl, 3-cyano-5-nitro-2-thienyl, 3-cyano-4-chloro-5-formyl-2-thienyl, 3,5-dinitro-2-thienyl, 3-acetyl-5-nitro-2-thienyl, 5-acetyl-3-nitro-2-thienyl, 3-((C 1 -C 4 )-alkoxycarbonyl)-5-nitro-2-thienyl, 5-phenylazo-3-cyano-2-thienyl, 5-(4-nitrophenylazo)-3-cyano-2-thienyl, 5-nitro-2-thiazolyl, 4-chloro-5-formyl-2-thiazolyl-, 5-nitro-3-benzisothiazolyl, 7-bromo-5-nitro-3-benzisothiazolyl, 7-chloro-5-nitro-3-benzisothiazolyl, 3-methyl-4-cyano-5-isothiazolyl, 3-phenyl-1,2,4-thiadiazol-2-yl, 5-((C 1 -C 2 )-alkylmercapto))-1,3,4-thiadiazol-2-yl, 1-cyanomethyl-4,5-dicyano-2-imidazolyl, 6-nitro-2-benzthiazolyl, 5-nitro-2-benzthiazolyl, 6-rhodano-2-benzthiazolyl, 6-chloro-2-benzthiazolyl, or (5),6,(7)-dichloro-2-benzthiazolyl.

9. A process for preparing the dye of the general formula (I) as claimed in claim 1 , which comprises diazotizing and coupling a compound of the general formula (III)

D-NH 2   (III)

where D is as defined in claim 1 , onto a compound of the general formula (IV)

where

R 1 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, halogen, —NHCHO, —NHCO(C 1 -C 6 )-alkyl, —NHCOaryl, —NHSO 2 (C 1 -C 6 )-alkyl or —NHSO 2 aryl;

R 2 is hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 4 )-alkoxy, phenoxy or halogen;

R 3 is hydrogen, (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, (C 3 -C 4 )-alkenyl or substituted (C 3 -C 4 )-alkenyl;

or R 2 and R 3 combine to form the radical —C*H(CH 3 )CH 2 C(CH 3 ) 2 —, where the carbon atom marked * is attached to the phenyl nucleus;

R 4 is hydrogen, (C 1 -C 6 )-alkyl or phenyl;

R 5 is vinyl or a group of the formula —CHR 6 COR 7 , where R 6 is hydrogen, (C 1 -C 6 )-alkyl or phenyl; R 7 is (C 1 -C 6 )-alkyl, substituted (C 1 -C 6 )-alkyl, phenyl or substituted phenyl; and

X is (C 1 -C 5 )-alkylene.

10. A process for dyeing and printing hydrophobic material which comprises contacting the dye of the general formula I as claimed in claim 1 with the material.

11. An ink for digital textile printing by the ink jet process comprising the dye of the general formula (I) as claimed in claim 1 .