Reactive dyes, process for their preparation and their use

The present invention relates to novel reactive dyes, to processes for their preparation and to their use for dyeing or printing fibre materials.

The practice of dyeing with reactive dyes has given rise in recent times to more stringent demands being made on the quality of the dyeings and on the economy of the dyeing process. For this reason, there is still a need for novel reactive dyes with improved properties, especially application properties.

Dyeing today calls for reactive dyes which have sufficient substantivity and which at the same time have good washing off properties with respect to unfixed dye. In addition, the dyes shall have a good tinctorial yield and high reactivity, and they shall also give, in particular, dyeings with high degrees of fixation. The dyes of the prior art do not meet these requirements in all respects.

This invention therefore has for its object to provide novel improved reactive dyes for dyeing and printing fibre materials and which have the above specified qualities to a high degree. The novel dyes shall be distinguished in particular by excellent fixation yields and superior fibre-dye bond stability, and further they shall have the property of being easily washed off to remove unfixed dye. They shall also produce dyeings with good allround fastness properties, for example lightfastness and wetfastness.

It has been found that this object is substantially achieved with the novel reactive dyes defined below.

This invention thus relates to reactive dyes of formula (1)

wherein

A is phenyl or naphthyl, each of which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or a fibre-reactive group of formula (2a), (2b), (2c), (2d) or (2e)

—SO 2 —Y  (2a),

—NH—CO—(CH 2 ) 1 —SO 2 —Y  (2b),

—CONH—(CH 2 ) m —SO 2 —Y  (2c),

—NH—CO—CH(Hal)—CH 2 Hal  (2d)

or

—NH—CO—C(Hal)═CH 2   (2e),

B is an aliphatic linking group,

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

R 1 is hydrogen or unsubstituted or substituted C 1 -C 4 alkyl,

R 2 is hydrogen, cyano, carbamoyl or sulfomethyl,

R 3 is hydrogen or C 1 -C 4 alkyl,

R is hydrogen or unsubstituted or substituted C 1 -C 4 alkyl or corresponds to a radical of formula (3)

wherein B, D, R 2 and R 3 have the meanings cited above,

X 1 is halogen, hydroxy, C 1 -C 4 alkoxy, unsubstituted or substituted C 1 -C 4 alkylthio or amino, or a N-heterocycle which may contain additional heteroatoms,

Hal is chloro or bromo,

Y is vinyl or a —CH 2 —CH 2 —U radical, U is a group a which is removable with alkali, and l and m are each independently of the other the number 2, 3 or 4,

with the proviso that A and D are not simultaneously a phenyl radical which is substituted by the radical of formula (2a) if R is β-hydroxyethyl or β-sulfatoethyl and R 1 is C 1 -C 4 alkyl.

The novel dyes of formula (1) are fibre-reactive. Fibre-reactive compounds are to be understood as meaning compounds which are capable of reacting with the hydroxyl groups of the cellulose, amino, carboxy, hydroxy or thiol groups in wool and silk, or with the amino and, optionally, with the carboxy groups of synthetic polyamides with formation of covalent chemical bonds.

In the novel reactive dyes of formula (1) at least one of the radicals A and D contains a fibre-reactive group, or X 1 is halogen.

The dyes of formula (1) contain at least one, preferably 2 to 6 and, more preferably, 2 to 4, sulfo groups, which are either in the form of their free acid or, preferably, in the form of their salts. Suitable salts are, for example, the alkali metal salts, alkaline earth metal salts or ammonium salts, the salts of an organic amine, or mixtures thereof. Examples to be mentioned are the sodium, lithium, potassium or ammonium salts, the salt of mono-, di- or tri-ethanolamine, or Na/Li— or Na/Li/NH 4 mixed salts.

R and R 1 defined as unsubstituted or substituted C 1 -C 4 alkyl may be methyl, ethyl, n- or isopropyl or n-, sec-, tert- or isobutyl which is unsubstituted or substituted e.g. by hydroxy, sulfo, sulfato, carboxy, cyano, halogen, C 1 -C 4 alkoxycarbonyl or carbamoyl, preferably by hydroxy, sulfo, sulfato or carboxy.

R is preferably hydrogen, unsubstituted or hydroxy-substituted C 1 -C 4 alkyl or a radical of formula (3), particularly preferably hydrogen, methyl, ethyl or β-hydroxyethyl or a radical (3) and, very particularly preferably, hydrogen or a radical (3), wherein B, D, R 2 and R 3 have the meanings cited above. In a very particularly preferred embodiment of this invention, R is a radical of formula (3).

R 1 is preferably hydrogen or C 1 -C 4 alkyl, particularly preferably hydrogen, methyl or ethyl and, very particularly preferably, hydrogen.

R 2 is preferably carbamoyl or sulfomethyl, more preferably carbamoyl.

R 3 defined as C 1 -C 4 alkyl is, for example, methyl, ethyl, n- or isopropyl or n-, sec-, tert- or isobutyl, preferably methyl or ethyl.

R 3 is preferably methyl or ethyl, more preferably methyl.

R 2 is preferably carbamoyl or sulfomethyl, more preferably carbamoyl, and R 3 is C 1 -C 4 alkyl, more preferably methyl.

The aliphatic linking group B is, for example, straight-chain or branched C 2 -C 12 alkylene which is unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy, sulfato or sulfo and/or interrupted once or several times by —O— or —NR 4 —, wherein R 4 is hydrogen or C 1 -C 4 alkyl, preferably hydrogen, methyl or ethyl, particularly preferably hydrogen. B is preferably straight-chain or branched C 2 -C 6 alkylene which is unsubstituted or substituted by hydroxy, sulfo or sulfato and, particularly preferably, unsubstituted straight-chain or branched C 2 -C6alkylene. Examples of particularly preferred linking groups B are 1,2-ethylene, 1,3-propylene, 2-hydroxy-1,3-propylene, 1,4-butylene, 2-methyl-1,5-pentylene, 1,6-hexylene, particularly preferably 1,2-propylene and 1,2-ethylene and, very particularly preferably, 1,2-ethylene.

X 1 defined as halogen is e.g. fluoro, chloro or bromo.

X 1 defined as C 1 -C 4 alkoxy is suitably, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or isobutoxy, preferably methoxy or ethoxy and, particularly preferably, methoxy.

X 1 defined as C 1 -C 4 alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio or n-butylthio, preferably ethylthio or n-propylthio. The cited radicals are unsubstituted or substituted in the alkyl moiety by hydroxy, carboxy or sulfo. The substituted radicals are preferred.

X 1 defined as unsubstituted or substituted amino is amino which is unsubstituted or substituted at the N-atom, for example the following radicals:

N-mono- or N,N-di-C 1 -C 4 alkylamino, which encompasses both the unsubstituted radicals and the radicals which are substituted in the alkyl moiety, for example by C 1 -C 4 alkoxy, hydroxy, carboxy, sulfo or sulfato; the radicals substituted in the alkyl moiety being preferred;

C 5 -C 7 cycloalkylamino, which encompasses both the unsubstituted radicals and the radicals which are substituted in the cycloalkyl ring, for example by C 1 -C 4 alkyl, preferably methyl; of such radicals the corresponding cyclohexyl radicals are preferred;

phenylamino or N—C 1 -C 4 alkyl-N-phenylamino, which encompasses both the unsubstituted radicals and the radicals which are substituted in the phenyl ring, for example by C 1 -C 4 alkyl,

C 1 -C 4 alkoxy, halogen, carboxy or sulfo; these radicals are preferably unsubstituted or sulfo-substituted in the phenyl ring.

X 1 defined as a N-heterocycle which may contain further heteroatoms is suitably, for example, morpholino or piperidin-1-yl.

X 1 is preferably fluoro or chloro.

The group U which may be removed with alkali is suitably, for example, —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 . U is preferably a group of formula —Cl, —OSO 3 H, —SSO 3 H, —OCO—CH 3 , —OCO—C 6 H 5 or —OPO 3 H 2 , more preferably —Cl or —OSO 3 H and, particularly preferably —OSO 3 H.

Examples of suitable radicals Y are correspondingly vinyl, β-bromo- or β-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl, β-chloroethyl or β-sulfatoethyl and, more preferably vinyl or β-sulfatoethyl.

Hal is preferably bromo.

l and m are each independently of the other preferably the number 2 or 3.

Particularly preferably, l is the number 3 and m is the number 2.

Substituents which are customary in dyes are suitable for D. The following examples may be mentioned: C 1 -C 4 alkyl, meaning methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl; C 1 -C 4 alkoxy, meaning methoxy, ethoxy, n- or isopropoxy or n-, iso-, sec- or tert-butoxy; hydroxy-C 1 -C 4 alkoxy; phenoxy; C 2 -C 6 alkanoylamino which is unsubstituted or substituted in the alkyl moiety by hydroxy or C 1 -C 4 alkoxy, for example acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino; benzoylamino which is unsubstituted or substituted in the phenyl moiety by hydroxy, sulfo, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; C 1 -C 6 alkoxycarbonylamino which is unsubstituted or substituted in the alkyl moiety by hydroxy, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; phenoxycarbonylamino which is unsubstituted or substituted in the phenyl moiety by hydroxy, C 1 -C 4 alkyl or C 1 -C 4 alkoxy; amino; N—C 1 -C 4 alkyl- or N,N-di-C 1 -C 4 alkylamino which unsubstituted or substituted in the alkyl moiety by hydroxy, C 1 -C 4 alkoxy, carboxy, cyano, halogen, sulfo, sulfato, phenyl or sulfophenyl, for example methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino, β-sulfatoethylamino, N-(3-sulfobenzyl)amino, N-ethyl-N-(3-sulfobenzyl)amino, N-(β-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or N-C 1 -C 4 alkyl-N-phenylamino which is unsubstituted or substituted in the phenyl moiety by nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, halogen or sulfo; C 1 -C 4 alkoxycarbonyl, e.g. methoxy- or ethoxycarbonyl; trifluoromethyl; nitro; cyano; halogen, generally meaning e.g. fluoro, bromo or, preferably, chloro; ureido; hydroxy; carboxy; sulfo; sulfomethyl; carbamoyl; N—C 1 -C 4 alkylcarbamoyl, such as N-methylcarbamoyl or N-ethylcarbamoyl; carbamido; sulfamoyl; N—C 1 -C 4 alkylsulfamoyl, such as N-methylsulfamoyl or N-ethylsulfamoyl; N-phenylsulfamoyl or N—C 1 -C 4 alkyl-N-phenylsulfamoyl which is unsubstituted or substituted in the phenyl moiety by sulfo or carboxy; C 1 -C 4 alkylsulfonyl, such as methyl- or ethylsulfonyl.

Suitable substituents for D are also fibre-reactive radicals.

Fibre-reactive radicals for D are, for example, the radicals of formula (2a), (2b), (2c), (2d) or (2e), wherein Y, Hal, l and m have the meanings and preferred meanings cited above, or (2f) or (2g)

wherein

X 2 is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl;

T 1 has each independently of one another the meaning of X 2 , a substituent which is not fibre-reactive or a fibre-reactive radical of formula (4a), (4b), (4c), (4d) or (4e)

—NH—(CH 2 ) 2-3 —SO 2 Y  (4a),

—NH—(CH 2 ) 2-3 —O—(CH 2 ) 2-3 —SO 2 Y  (4b),

—NH-arylene-SO 2 —Y  (4c),

—NH-arylene-CO—NH—(CH 2 ) 2-3 —SO 2 —Y  (4d)

or

—NH-arylene-NH—CO—Y 1   (4e),

wherein

R 5 is hydrogen or C 1 -C 4 alkyl,

arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxy, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen,

T 2 is hydrogen, cyano or halogen,

X 3 is halogen or C 1 -C 4 alkylsulfonyl,

X 4 is halogen or C 1 -C 4 alkyl,

Y has the meanings and preferred meanings cited above,

Y 1 is a group —CH(Hal)—CH 2 Hal or —C(Hal)═CH 2 , and Hal has the meanings and preferred meanings cited above.

R 5 defined as C 1 -C 4 alkyl is, for example, methyl, ethyl, n- or isopropyl, n-, iso- or tert-butyl.

R 5 is preferably hydrogen, methyl or ethyl and, particularly preferably, hydrogen.

T 1 defined as a non-reactive substituent may be, for example, hydroxy; C 1 -C 4 alkoxy; C 1 -C 4 -alkylthio which is unsubstituted or substituted by hydroxy, carboxy or sulfo; amino; amino which is mono- or disubstituted by C 1 -C,alkyl, wherein the alkyl may be further substituted e.g. by sulfo, sulfato, hydroxy, carboxy or phenyl, preferably by sulfo or hydroxy and may be interrupted by an —O— radical; cyclohexylamino; morpholino; N—C 1 -C 4 alkyl-N-phenylamino or phenylamino or naphthylamino, wherein phenyl or naphthyl is unsubstituted or substituted by e.g. C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy, sulfo or halogen.

Examples of suitable non-reactive substituents T 1 are amino, methylamino, ethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino, 2-, 3- or 4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n- or isopropoxy and hydroxy.

As a radical which is not fibre-reactive, T 1 is preferably C 1 -C 4 alkoxy; C 1 -C 4 alkylthio which is unsubstituted or substituted by hydroxy, carboxy or sulfo; hydroxy, amino; N-mono- or N,N-di-C 1 -C 4 alkylamino which is unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or sulfo; morpholino; phenylamino or N—C 1 -C 4 alkyl-N-phenylamino which is unsubstituted or substituted in the phenyl ring by sulfo, carboxy, acetylamino, chloro, methyl or methoxy, wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or sulfato, or naphthylamino which is unsubstituted or substituted by 1 to 3 sulfo groups.

Particularly preferred radicals T 1 which are not fibre-reactive are amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or N—C 1 -C 4 alkyl-N-phenylamino.

X 2 defined as halogen is, for example, fluoro, chloro or bromo and, preferably, chloro or fluoro.

Arylene is preferably a phenylene radical, particularly preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted e.g. by sulfo, methyl or methoxy.

T 2 , X 3 and X 4 defined as halogen are, for example, fluoro, chloro or bromo, preferably chloro or fluoro.

X 3 defined as C 1 -C 4 alkylsulfonyl is, for example, ethylsulfonyl or methylsulfonyl, preferably methylsulfonyl.

X 4 defined as C 1 -C 4 alkyl is, for example, methyl , ethyl, n- or isopropyl, n-, iso- or tert-butyl, preferably methyl.

X 3 and X 4 are preferably each independently of the other chloro or fluoro.

T 2 is preferably cyano or chloro.

In the case of the radicals of formulae (4a) and (4b), Y is preferably β-chloroethyl. In the case of the radicals of formulae (4c) and (4d), Y is preferably vinyl or β-sulfatoethyl.

Suitable fibre-reactive radicals D are preferably radicals of formula (2a), (2b), (2c), (2d), (2e), (2f) or (2g), wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromo, l and m are each independently of the other the number 2 or 3, R 5 is hydrogen, and X 2 , X 3 and X 4 are each independently of one another chloro or fluoro, T 1 is a fibre-reactive radical of formula (4c′) or (4d′),

preferably (4c′), wherein Y is vinyl or β-sulfatoethyl, and T 2 is cyano or chloro.

Those novel reactive dyes are preferred, wherein at least one of the radicals A and D contains a fibre-reactive group.

D is preferably a phenyl or naphthyl radical which may be further substituted by substituents customarily used for dyes, preferably by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, sulfo, nitro, carboxy or a fibre-reactive radical of formula (2a), (2b), (2c), (2d), (2e), (2f) or (2g), the above meanings and preferred meanings applying to the cited fibre-reactive radicals.

If D carries one or more than one non-reactive substituent, then it is preferably sulfo, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen and, particularly preferably, sulfo, methyl or methoxy.

D defined as a radical of an unsubstituted or substituted diazo component of the benzene or naphthalene series also encompasses monoazo radicals, for example those of formula (5) or (6)

—D*—N═N—K*  (5)

or

D*—N═N—K**—  (6),

preferably of formula (6), wherein D* is the radical of a diazo component of the benzene or naphthalene series, K* is the radical of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone-(2) or acetoacetic acid arylamide series, and K** is the radical of a coupling component of the benzene or naphthalene series, it being possible for D*, K* and K** to carry substituents customarily used in dyes.

Suitable substituents for D*, K* and K** which are not fibre-reactive are preferably C 1 -C 4 alkyl or C 1 -C 4 alkoxy which may be further substituted by hydroxy, C 1 -C 4 alkoxy, sulfo or sulfato; halogen, carboxy, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxy, sulfomethyl, C 2 -C 4 alkanoylamino, C 1 -C 4 alkylsulfonylamino; benzoylamino which is unsubstituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or sulfo, or phenyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy or sulfo.

Suitable fibre-reactive substituents for D*, K* and K** are preferably the radicals of formula (2a), (2c), (2d), (2e) or (2f), preferably (2a), the above meanings and preferred meanings applying to the cited radicals.

The monoazo radicals of formula (5) or (6) preferably contain at least one sulfo group.

Preferred monoazo radicals D of formula (6) correspond to the radicals of formula (6a), (6b), (6c), (6d), (6e), (6f), (6g), (6h), (6i) or (6j)

wherein (R 6 ) 0-3 is 0 to 3 identical or different substituents from the C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxy and sulfo group, and Z 1 is a fibre-reactive radical of formula (2a), (2c), (2d), (2e) or (2f), preferably (2a), (2c), (2d) or (2e), particularly preferably (2a), the above meanings and preferred meanings applying to the cited fibre-reactive radicals,

wherein (R 6 ) 0-3 has the above meaning, (R 7 ) 0-3 is 0 to 3 identical or different substituents selected from the group consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy which is unsubstituted or substituted by hydroxy, sulfato or C 1 -C 4 alkoxy, amino, C 2 -C 4 alkanoylamino, ureido, hydroxy, carboxy, sulfomethyl, C 1 -C 4 alkylsulfonylamino and sulfo, and Z 1 has the meanings and preferred meanings given above.

The numbers at the naphthyl rings of the radicals of formulae (6a), (6b), (6e) and (6f) characterise the possible bonding positions.

Particularly preferred monoazo radicals D of formula (6) correspond to the radicals of formula (6a), (6b), (6c), (6d) or (6j), in particular (6j), the above meanings applying to (R 6 ) 0-3 , (R 7 ) 0-3 and Z 1 .

Very particularly preferred monoazo radicals D of formula (6) correspond to the radical of formula (6j′)

wherein

Z 1 may be a radical of formula (2a), wherein Y is vinyl or β-sulfatoethyl,

(R 6 ) 0-2 is 0 to 2 identical or different substituents from the C 1 -C 4 alkyl, C 1-C 4 alkoxy, halogen, carboxy and sulfo group, preferably methyl, methoxy or sulfo, R 7 is hydrogen, sulfo, or C 1 -C 4 alkoxy which is unsubstituted or substituted in the alkyl moiety by hydroxy or sulfato, and

R 7 ′ is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoylamino or ureido.

D preferably corresponds to a radical of formula (7)

wherein

(R 8 ) 0-3 is 0 to 3 identical or different substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxy and sulfo,

Z 2 may be a radical of formula (2a), (2b), (2c), (2d), (2e), (2f) or (2g), wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromo, l and m are each independently of the other the number 2 or 3, R 5 is hydrogen, and X 2 , X 3 and X 4 are each independently of one another chloro or fluoro, T 1 is a fibre-reactive radical of formula (4c′) or (4d′),

preferably (4c′), wherein Y is vinyl or β-sulfatoethyl, and T 2 is cyano or chloro; or a monoazo radical of formula (6j′), wherein (R 6 ) 0-2 , R 7 , R 7 ′ and Z 1 have the meanings and preferred meanings cited for formula (6j′).

D is particularly preferably a radical of formula (7a), (7b), (7c), (7d) or (7e)

wherein

(R 8 ) 0-2 is 0 to 2 identical or different substituents selected from the halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy and sulfo group, preferably methyl, methoxy and sulfo,

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

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

m is the number 2 or 3, preferably 2.

The numbers in the radicals of formulae (7a), (7c), (7d) and (7e) characterise the possible bonding positions of the fibre-reactive radical.

D is preferably a radical of formula (7a), (7b) or (7e).

Suitable radicals A correspond, for example, to a radical of formula (7), wherein (R 8 ) 0-3 has the above meanings, and Z 2 is a radical of formula (2a), (2b), (2c), (2d) or (2e), the above meanings and preferred meanings applying to Y, Hal, l and m; preferably a radical of formula (7a), (7b), (7c) or (7d), in particular (7a) or (7b), wherein (R 8 ) 0-2 , Y, Y 1 and m have the meanings and preferred meanings given for formulae (7a), (7b), (7c) and (7d).

Suitable radicals A containing no fibre-reactive group are, for example, the following radicals: 2-,3- or 4-sulfophenyl, 2,4-di-sulfophenyl, 2,5-di-sulfophenyl, 1,5-di-sulfonaphth-2-yl or 1,6-di-sulfonaphth-2-yl and, preferably, 2,5-di-sulfophenyl.

A is preferably phenyl which is substituted by 1 to 2 identical or different substituents selected from the methyl, methoxy, sulfo and fibre-reactive group of formula (2a), wherein Y is vinyl or β-sulfatoethyl.

A is particularly preferably 2,5-di-sulfophenyl or 4-(β-sulfatoethylsulfonyl)phenyl.

In a preferred embodiment of this invention, the novel reactive dyes correspond to formula (1a)

wherein

A is phenyl which is substituted by 1 to 2 identical or different substituents selected from the group consisting of methyl, methoxy, sulfo and fibre-reactive group of formula —SO 2 —Y (2a), wherein Y is vinyl or β-sulfatoethyl,

B is straight-chain or branched C 2 -C 6 alkylene, preferably ethylene,

D corresponds to a radical of formula (7a), (7b), (7c), (7d) or (7e), preferably to (7a), (7b) or (7e), wherein (R 8 ) 0-2 , Y, Y 1 and m have the above meanings and preferred meanings,

R 2 is carbamoyl or sulfomethyl, preferably carbamoyl,

R is hydrogen or corresponds to a radical of formula (3a)

wherein B, D and R 2 have the meanings and preferred meanings cited above, and X 1 is chloro or fluoro.

This invention also relates to a process for the preparation of the novel reactive dyes, which comprises reacting about 1 molar equivalent each of an amine of formula (8)

of a compound of formula (9)

of a compound of formula (10)

in any sequence with each other, wherein A, B, D, R 1 , R 2 , R 3 and R have the above meanings and X is halogen, preferably fluoro or chloro.

The individual process steps described above can be carried out in different order, some of them, where appropriate, also simultaneously, so that different process variants are possible. The reaction is usually carried out in stepwise succession, the sequence of the single reactions between the individual reaction components advantageously being dependent on the particular conditions.

One process variant is that, wherein a compound of formula (8) is condensed with cyanuric chloride or cyanuric fluoride and the product obtained is reacted with a compound of formula (10).

The condensation reactions between the compounds of formulae (8), (9) and (10) are usually carried out in analogy to known processes, normally in aqueous solution at temperatures in the range from e.g. 0 to 35° C. and at a pH from e.g. 3 to 8.5. In the process in it also possible to replace the compound of formula (10) with the corresponding precursor of formula (11)

and to complete the azo chromophore only in the further course of the process by diazotisation of an amine of formula (12)

D—NH 2   (12)

and subsequent coupling reaction. B, D, R 2 , R 3 and R have the meanings given above.

The compound of formula (10) is obtained by diazotising an amine of formula (12) and coupling the diazonium compound so obtained to a compound of formula (11).

The diazotisation of the compound of formula (12) and its coupling to the compound of formula (11), or to the condensate obtained according to the above procedure from the compound of formula (11), is carried out in customary manner, for example by diazotising the compound of formula (12) in mineral acidic solution, e.g. in hydrochloric solution, with a nitrite, e.g. sodium nitrite, at a low temperature, e.g. from 0 to 5° C., and then coupling the compound so obtained at a neutral to slightly acid pH, e.g. at a pH from 3 to 8.5, and at low temperatures, e.g. from 0 to 30° C., with the corresponding coupling component.

The compounds of formulae (8), (11) and (12) are known or can be prepared in analogy to known compounds.

The triazinyl compounds obtainable according to the process described above contain a halogen atom which, by reaction with a compound of formula X 1 —H and at an elevated temperature, preferably from 20 to 70° C., and at a neutral to slightly alkaline pH which, depending on the compound of formula X 1 —H used, may be e.g. from 7 to 9, can be converted into a X 1 group, wherein X 1 has the meanings given above except halogen. It is advantageous to use an excess of the compound of formula X 1 —H.

The end product may also be subjected to a conversion reaction. Such a conversion reaction is, for example, the conversion of a vinylatable reactive group present in A and/or D into its vinyl form by treatment with dilute sodium hydroxide solution, for example the conversion of the β-sulfatoethylsulfonyl or β-chloroethylsulfonyl group into the vinyl sulfonyl radical. Such reactions are known per se.

The novel compounds of formula (1) are suitable as dyes for dyeing or printing a very wide range of materials, such as hydroxyl group-containing or nitrogen-containing fibre materials. Typical examples of such materials are silk, leather, wool, polyamide fibres and polyurethanes. The novel reactive dyes are particularly suitable for dyeing and printing cellulosic fibre materials of all kinds. Such cellulosic fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose, preferably cotton. The novel reactive dyes are also suitable for dyeing or printing cellulose-containing blended fabrics, e.g. blends of cotton and polyamide fibres or, in particular, cotton/polyester fibre blends.

The novel reactive dyes may applied and fixed to the fibre material in different manners, preferably in the form of aqueous dye solutions and printing pastes. They are suitable both for the exhaust process and for dyeing by the pad-dyeing process, in which the goods are impregnated with aqueous dye solutions which may contain salts, and the dyes are fixed after treatment with alkali, or in the presence of alkali, with or without the application of heat or by being stored for several hours at room temperature. After fixation, the dyeings or prints are thoroughly rinsed with cold and hot water, where appropriate with addition of a dispersant promoting the diffusion of the unfixed dye.

The novel reactive dyes are distinguished by high reactivity, good fixation and excellent build-up. They can therefore be used by the exhaust dyeing process at low dyeing temperatures and require only short steaming times in the pad-steam process. The degrees of fixation are high, and unfixed dye can be readily washed off. The differences between degree of exhaustion and degree of fixation is remarkably small, i.e. the soap loss is very small. The dyes of this invention are also particularly suitable for printing, especially on cotton, and for printing nitrogen-containing fibres, e.g. wool or silk, or blends containing wool or silk.

The dyeings and prints obtained with the dyes of this invention have excellent tinctorial strength and excellent fibre-dye bond stability both in the acid and in the alkaline range, and they also have good lightfastness and excellent wetfastness properties such as fastness to washing, water, sea-water, cross-dyeing and perspiration, as well as good fastness to pleating, ironing and rubbing.

The following Examples illustrate the invention in more detail. Temperatures are given in degrees Celsius, and parts and percentages are by weight, unless otherwise stated. The ratio of parts by weight to parts by volume is the same as that of the kilogram to the liter.