Reactive dyes, a process for their preparation and their use

The present invention relates to novel asymmetric dioxazine dyes which are fibre-reactive, to a process for their preparation and to their use in the dyeing or printing of fibre materials.

The practice of dyeing using reactive dyes has recently led to higher demands being made on the quality of the dyeings and the efficiency of the dyeing process. As a result, there continues to be a need for novel reactive dyes having improved properties, especially in respect of their application.

Dyeing nowadays requires reactive dyes that exhibit high levels of exhaustion and fixing, it being possible, in particular, to dispense with an alkaline after-treatment for removing unfixed dye. They should also have a good colour yield and high reactivity. EP-A-O 356 014 and US-A-4 841 049 disclose asymmetric, fibre-reactive dioxazine dyes. The known dyes do not, however, satisfy those requirements in all properties.

The problem underlying the present invention is accordingly to find, for the dyeing and printing of fibre materials, novel, improved fibre-reactive dioxazine dyes having the qualities characterised above to a high degree. The novel dyes should especially be distinguished by high levels of exhaustion, high fixing yields and high fibre-dye bond stabilities. The dyes should also yield dyeings having good allround fastness properties, for example fastness to light and to wetting.

It has been found that the problem posed is largely solved by the reactive dyes defined hereinbelow.

The present invention accordingly relates to reactive dyes of formula

wherein

Ri is halogen,

R ₂ , R3 and R ₄ are each independently of the others hydrogen or unsubstituted or substituted

CrC ₄ alkyl,

(R ₅ )o- ₂ and (Re)o- ₂ each independently of the other denote from 0 to 2 identical or different substituents from the group CrC ₄ alkyl, Ci-C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, carboxy, sulfo, carbamoyl, N-Ci-C ₄ alkylcarbamoyl, N,N-di-Ci-C ₄ alkylcarbamoyl, CrC ₄ alkylsulfonyl, sulfamoyl, N-Ci-C ₄ alkylsulfamoyl and N,N-di-Ci-C ₄ alkylsulfamoyl,

B ₁ is an aliphatic or aromatic bridging member,

D ₁ is a radical of the aliphatic, aromatic or heterocyclic series substituted by at least one fibre-reactive group,

V ₁ and V ₂ are each independently of the other hydrogen, halogen, Ci-C ₄ alkyl, C-ι-C ₄ alkoxy, or unsubstituted or substituted phenyl, unsubstituted or substituted phenoxy, unsubstituted or substituted C ₂ -C6alkanoylamino or unsubstituted or substituted benzoylamino, and

X ₁ is halogen, hydroxy, CrC ₄ alkoxy, CrC ₄ alkylthio, unsubstituted or substituted amino or an

N-heterocycle which may contain further hetero atom(s).

R ₁ is, for example, fluorine, chlorine or bromine, preferably chlorine or fluorine and especially fluorine.

The radicals R ₂ , R3 and R ₄ as alkyl radicals are straight-chain or branched. The alkyl radicals may themselves be substituted, for example by hydroxy, sulfo, sulfato, cyano or by carboxy. The following radicals may be mentioned as examples: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl as well as the corresponding radicals substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Preferred as substituents are hydroxy, sulfo, sulfato and carboxy, especially hydroxy and sulfato. For the radical R ₄ , a radical of formula -(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -CI also comes into consideration.

As CrC ₄ alkyl there come into consideration for (R ₅ )o _-2 , (RβW, V ₁ and V ₂ each independently of the others e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and ethyl and especially methyl, the definitions and preferred meanings indicated also applying to the C-ι-C ₄ alkyl radicals hereinbelow.

As Ci-C4alkoxy there come into consideration for (R5)o-2, (Re)o-2, V ₁ , V ₂ and Xi each independently of the others e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy and especially methoxy, the definitions and preferred meanings indicated also applying to the CrC ₄ alkoxy radicals hereinbelow.

As C ₂ -C ₄ alkanoylamino there come into consideration for (Rs) _0-2 and (Re) _0-2 each independently of the other e.g. acetylamino and propionylamino, especially acetylamino, the definitions and preferred meanings indicated also applying to the C ₂ -C ₄ alkanoylamino radicals hereinbelow.

As N-Ci-C ₄ alkylcarbamoyl there come into consideration for (Rs) _0-2 and (Re) _0-2 each independently of the other e.g. N-methyl-, N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-sec- butyl-, N-tert-butyl- and N-isobutyl-carbamoyl, preferably N-methyl- and N-ethyl-carbamoyl and especially N-methyl-carbamoyl.

As N,N-di-Ci-C ₄ alkylcarbamoyl there come into consideration for (R ₅ ) _o-2 and (Re) _0-2 each independently of the other e.g. N,N-di-methyl-, N,N-di-ethyl-, N,N-di-propyl-, N,N-di- isopropyl-, N,N-di-butyl-, N,N-di-sec-butyl- and N,N-di-isobutyl-carbamoyl, preferably N,N-di- methyl- and N,N-di-ethyl-carbamoyl and especially N,N-di-methyl-carbamoyl.

As Ci-C ₄ alkylsulfonyl there come into consideration for (Rs) _0-2 and (Re) _0-2 each independently of the other e.g. methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert- butyl- and isobutyl-sulfonyl, preferably methyl- and ethyl-sulfonyl and especially methyl- sulfonyl.

As N-Ci-C ₄ alkylsulfamoyl there come into consideration for (R ₅ ) _o-2 and (Re) _0-2 each independently of the other e.g. N-methyl-, N-ethyl-, N-propyl-, N-isopropyl-, N-butyl-, N-sec- butyl-, N-tert-butyl- and N-isobutyl-sulfamoyl, preferably N-methyl- and N-ethyl-sulfamoyl and especially N-methyl-sulfamoyl.

As N,N-di-Ci-C ₄ alkylsulfamoyl there come into consideration for (Rs) _0-2 and (Re) _0-2 each independently of the other e.g. N,N-di-methyl-, N,N-di-ethyl-, N,N-di-propyl-, N,N-di- isopropyl-, N,N-di-butyl-, N,N-di-sec-butyl- and N,N-di-isobutyl-sulfamoyl, preferably N,N-di- methyl- and N,N-di-ethyl-sulfamoyl and especially N,N-di-methyl-sulfamoyl.

- A -

As an aliphatic bridging member, B ₁ is, for example, a C ₂ -Ci ₂ alkylene radical, especially a C ₂ -C6alkylene radical, which may be interrupted by 1 , 2 or 3 members from the group -NH-, -N(CH ₃ )- and, especially, -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy. Preferred as substituents of the alkylene radicals mentioned for B ₁ are hydroxy, sulfo and sulfato, especially hydroxy and sulfato.

As aliphatic bridging members there also come into consideration for B ₁ e.g. C ₅ -C ₉ cyclo- alkylene radicals, especially cyclohexylene radicals. The said cycloalkylene radicals may be unsubstituted or substituted by Ci-C ₄ alkyl, CrC ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or by carboxy, especially by Ci-C ₄ alkyl. There may also be mentioned as aliphatic bridging members for B ₁ methylenecyclohexylene, ethylenecyclohexylene and methylenecyclo- hexylenemethylene radicals, each unsubstituted or substituted in the cyclohexylene ring by Ci-C ₄ alkyl, especially by methyl.

— N-B ₁ -N —

For the radical of formula I I there also comes into consideration e.g. a

R ₂ R ₃

radical of formula — N N — or — N N - alk — NH ₂ , wherein alk is

CrC ₄ alkylene, for example ethylene.

As an aromatic bridging member, B ₁ is, for example, CrC ₆ alkylenephenylene, for example methylenephenylene, CrC ₄ alkylenephenylene-C"i-C ₄ alkylene, for example methylene- phenylenemethylene, or phenylene, each unsubstituted or substituted by Ci-C ₄ alkyl, C-ι-C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or by carboxy; or a radical of formula

wherein the benzene rings I and Il are unsubstituted or substituted by Ci-C ₄ alkyl, C ₁ -C ₄ - alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or by carboxy and L is a direct bond or a C ₂ -C ₁ O- alkylene radical which may be interrupted by 1 , 2 or 3 oxygen atoms, or L is a bridging

member of the formula -CH=CH-, -N=N-, -NH-, -CO-, -NH-CO-, -NH-SO ₂ -, -NH-CO-NH-, -O-, -S- Or -SO ₂ -. As an aromatic bridging member, B ₁ is preferably phenylene which may be substituted as indicated above. Preferably, the aromatic bridging members mentioned for B ₁ are unsubstituted or substituted by sulfo.

Preferably, B ₁ is a C ₂ -C ₁₂ alkylene radical which may be interrupted by 1 , 2 or 3 members from the group -NH-, -N(CH ₃ )- and -O- and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy; a C ₅ -Cgcycloalkylene radical, CrCβalkylenephenylene radical or phenylene radical, each unsubstituted or substituted by Ci-C ₄ alkyl, CrC ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or by carboxy; or the radical of formula

— N-B ₁ -N — / — \ I I is a radical of formula — N N — R ₂ ^R 3 \ /

More especially, B ₁ is a C ₂ -C ₁₂ alkylene radical which may be interrupted by 1 , 2 or 3 -O- members and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy, or a phenylene radical unsubstituted or substituted by Ci-C ₄ alkyl, C-ι-C ₄ alkoxy, C ₂ -C ₄ alkanoyl- amino, sulfo, halogen or by carboxy.

Very especially, B ₁ is a C ₂ -C ₁₂ alkylene radical, especially a C ₂ -C ₆ alkylene radical, for example 1 ,2-ethylene, 1 ,3-propylene, 1 ,2-propylene, 1 ,4-butylene, 1 ,3-butylene, 1 ,5- pentylene, 3,5-pentylene, 1 ,6-hexylene, 2,5-hexylene, 4,6-hexylene or a radical of formula

CH ₂ , which may be interrupted by 1 , - CH ₉ 2 -CH ₉₂ - CH ₉₂ -

2 or 3 -O- members and is unsubstituted or substituted by hydroxy or by sulfato, but is preferably not interrupted by -0-.

Especially important as bridging member B ₁ is the group of formula -CH ₂ -CH(R ₇ )- or -(R ₇ )CH-CH ₂ - wherein R ₇ is Ci-C ₄ alkyl, especially methyl.

Fibre-reactive radicals present in the radical D ₁ are to be understood as being radicals which are capable of reacting with the hydroxy groups of cellulose, with the amino, carboxy, hydroxy and thiol groups in wool and silk or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds. The fibre-reactive radicals are generally bonded to the dye radical directly or via a bridging member. Suitable fibre-reactive radicals are, for example, those having at least one removable substituent on an aliphatic, aromatic or heterocyclic radical or those wherein the mentioned radicals contain a radical suitable for reaction with the fibre material, for example a vinyl radical.

As fibre-reactive radicals for D ₁ , preferably the radicals of the following formulae come into consideration:

-SO ₂ -Y (2a),

-NH-CO-(CH ₂ )I-SO ₂ -Y (2b),

-CONR ₈ -(CH ₂ ) _m -SO ₂ -Y (2c),

-NH-CO-CH(HaI)-CH ₂ -HaI (2d),

-NH-CO-C(HaI)=CH ₂ (2e),

wherein

Hal is chlorine or bromine;

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

T ₁ has independently the same definitions as X ₂ or is a non-fibre-reactive substituent or a fibre-reactive radical of formula

wherein

Re and Rio are each independently of the other hydrogen, Ci-C ₄ alkyl unsubstituted or

R ₁₁ substituted by hydroxy, sulfo, sulfato, carboxy or by cyano, or a radical I alk SO ₂ Y

Rg and Ri ₂ are each independently of the other hydrogen or d-C ₄ alkyl,

Rn is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen, CrC ₄ alkoxycarbonyl,

CrC ₄ alkanoyloxy, carbamoyl or the group -SO ₂ -Y, alk and alk-i are each independently of the other linear or branched C-i-Cealkylene, arylene is a phenylene or naphthylene radical unsubstituted or substituted by sulfo, carboxy, CrC ₄ alkyl, CrC ₄ alkoxy or by halogen,

Q is a radical -O- or -NR ₁₂ - wherein R ₁₂ is as defined above,

W is a group -SO ₂ -NR ₈ -, -CONR ₈ - or -NR ₈ CO- wherein R ₈ is as defined above,

Y is vinyl or a radical -CH ₂ -CH ₂ -U and U is a group removable under alkaline conditions,

Y ₁ is a group -CH(HaI)-CH ₂ -HaI or -C(HaI)=CH ₂ and Hal is chlorine or bromine, and

I and m are each independently of the other an integer from 1 to 6 and n is the number 0 or 1 , and

X ₃ is halogen or CrC ₄ alkylsulfonyl,

X ₄ is halogen or d-C ₄ alkyl and

T ₂ is hydrogen, cyano or halogen.

As a group U removable under alkaline conditions there come into consideration, 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 _r C ₄ alkyl and -OSO ₂ -N(C _r 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 , especially -Cl or -OSO ₃ H and more especially -OSO ₃ H.

Examples of suitable radicals Y are accordingly vinyl, β-bromo- or β-chloro-ethyl, β-acetoxy- ethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thiosulfatoethyl. Y is preferably vinyl, β-chloroethyl or β-sulfatoethyl and especially vinyl or β-sulfatoethyl.

Re and R ₁ 0 are each independently of the other preferably hydrogen or CrC ₄ alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl and more especially hydrogen, methyl or ethyl. More especially, Re and R ₁ 0 are hydrogen.

Rg and Ri ₂ are each independently of the other preferably hydrogen, methyl or ethyl and more especially hydrogen.

R ₁₁ is preferably hydrogen.

I and m are each independently of the other preferably the number 2, 3 or 4 and more especially the number 2 or 3.

More especially, I is the number 3 and m is the number 2.

When T ₁ is a non-fibre-reactive substituent, that substituent may be, for example, hydroxy; CrC ₄ alkoxy; CrC ₄ alkylthio unsubstituted or substituted e.g. by hydroxy, carboxy or by sulfo; amino; amino mono- or di-substituted by C-i-Cealkyl, wherein the alkyl is unsubstituted or is itself substituted e.g. by sulfo, sulfato, hydroxy, carboxy or by phenyl, especially by sulfo or

by hydroxy, and may be interrupted one or more times by the radical -O-; cyclohexylamino; morpholino; N-Ci-C ₄ alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the phenyl or naphthyl are unsubstituted or substituted e.g. by CrC ₄ alkyl, Ci-C ₄ alkoxy, C ₁ -C ₄ - alkanoylamino, carboxy, sulfo or by halogen and the alkyl is unsubstituted or substituted e.g. by hydroxy, sulfo or by sulfate

Examples of suitable non-reactive substituents T ₁ are amino, methylamino, ethylamino, β- hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholino, o-, m- or p-chlorophenylamino, o-, m- or p-methylphenylamino, o-, m- or p- methoxyphenylamino, o-, m- or p-sulfophenylamino, disulfophenylamino, o-carboxyphenyl- amino, 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 iso-propoxy and hydroxy.

As a non-fibre-reactive radical, T ₁ is preferably CrC ₄ alkoxy; CrC ₄ alkylthio unsubstituted or substituted by hydroxy, carboxy or by sulfo; hydroxy; amino; N-mono- or N,N-di-CrC ₄ - alkylamino unsubstituted or substituted in the alkyl moiety by hydroxy, sulfato or by sulfo; morpholino; phenylamino or N-CrC ₄ alkyl-N-phenylamino, each unsubstituted or substituted on the phenyl ring by sulfo, carboxy, chlorine, acetylamino, methyl or by methoxy, wherein the alkyl is unsubstituted or substituted by hydroxy, sulfo or by sulfato; or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups.

Especially preferred non-fibre-reactive radicals T ₁ are amino, N-methylamino, N-ethylamino, morpholino, phenylamino, 2-, 3- or 4-sulfophenylamino and N-CrC ₄ alkyl-N-phenylamino.

X ₂ as halogen is, for example, fluorine, chlorine or bromine and especially chlorine or fluorine.

T ₂ , X3 and X ₄ as halogen are, for example, fluorine, chlorine or bromine, especially chlorine or fluorine.

X ₃ as CrC ₄ alkylsulfonyl is, for example, ethylsulfonyl or methylsulfonyl and especially methylsulfonyl.

X ₄ as Ci-C ₄ alkyl is, for example, methyl , ethyl, n- or iso-propyl, n-, iso- or tert-butyl and especially methyl.

X ₃ and X ₄ are preferably each independently of the other chlorine or fluorine.

T ₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and all^ are each independently of the other e.g. a methylene, ethylene, 1 ,3-propylene, 1 ,4-butylene, 1 ,5-pentylene or 1 ,6-hexylene radical or a branched isomer thereof.

Preferably, alk and alk-i are each independently of the other a CrC ₄ alkylene radical and more especially an ethylene radical or propylene radical.

arylene is preferably a 1 ,3- or 1 ,4-phenylene radical unsubstituted or substituted e.g. by sulfo, methyl, methoxy or by carboxy, and more especially an unsubstituted 1 ,3- or 1 ,4- phenylene radical.

Q is preferably -NH- or -O- and more especially -O-.

W is preferably a group of formula -CONH- or -NHCO-, especially a group of formula -CONH-.

n is preferably the number O.

The reactive radicals of formulae (3a) to (3f) are preferably those wherein W is a group of formula -CONH-, R ₁₀ and Rn are each hydrogen, R ₁₂ is hydrogen, methyl or ethyl, Q is the radical -O- or -NH-, alk and alk-i are each independently of the other ethylene or propylene, arylene is phenylene unsubstituted or substituted by methyl, methoxy, carboxy or by sulfo, Y is vinyl, β-chloroethyl or β-sulfatoethyl, Y ₁ is -CHBr-CH ₂ Br or -CBr=CH ₂ and n is the number O.

As fibre-reactive radicals for D ₁ there come into consideration more especially radicals of formulae (2a), (2c), (2d), (2e) and (2f) wherein Y is vinyl, β-chloroethyl or β-sulfatoethyl, Hal is bromine, R ₈ and R ₉ are hydrogen, m is the number 2 or 3, X ₂ is chlorine or fluorine, T ₁ is C-ι-C ₄ alkoxy; CrC ₄ alkylthio unsubstituted or substituted by hydroxy, carboxy or by sulfo; hydroxy; amino; N-mono- or N,N-di-CrC ₄ alkylamino unsubstituted or substituted in the alkyl moiety or moieties 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, chlorine, acetylamino, methyl or by methoxy; or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, or is a fibre-reactive radical of formula

-NH-(CH ₂ )2-3-SO ₂ Y (3a ¹ ),

-NH-(CH ₂ )2-3-O-(CH2)2-3-SO ₂ Y (3b ¹ ),

especially (3c ¹ ) or (3d ¹ ), wherein

Y is as defined above, and

Y ₁ is a group -CH(Br)-CH ₂ -Br or -C(Br)=CH ₂ .

In the radical of formula (3c ¹ ), Me denotes the methyl radical and Et the ethyl radical. The said radicals come into consideration, in addition to hydrogen, as substituents at the nitrogen atom.

In the case of the radicals of formulae (3a ¹ ) and (3b ¹ ), Y is preferably β-chloroethyl. In the case of the radicals of formulae (3c ¹ ) and (3d ¹ ), Y is preferably vinyl or β-sulfatoethyl.

D ₁ as a radical of the aliphatic series is, for example, a radical of formula

-(CH ₂ ) ₂ -Sθ ₂ -(CH ₂ ) ₂ -CI or -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -Sθ ₂ -(CH ₂ ) ₂ -CI.

As a radical D ₁ of the aromatic series there come into consideration e.g. radicals of the benzene or naphthalene series.

Radicals of the benzene or naphthalene series D ₁ are, for example, phenyl or naphthyl which are unsubstituted or are themselves substituted by non-fibre-reactive substituents. The following examples of non-fibre-reactive substituents come into consideration: Ci-C ₄ alkyl, which is to be understood as being methyl, ethyl, n- or iso-propyl, and n-, iso-, sec- or tert-butyl; CrC ₄ alkoxy, which is to be understood as being methoxy, ethoxy, n- or iso-propoxy and n-, iso-, sec- or tert-butoxy; hydroxy-CrC ₄ alkoxy; phenoxy; C ₂ -C ₆ alkanoyl- amino unsubstituted or substituted in the alkyl moiety by hydroxy or by CrC ₄ alkoxy, e.g. acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino; benzoylamino unsubstituted or substituted in the phenyl moiety by hydroxy, sulfo, halogen, CrC ₄ alkyl or by CrC ₄ alkoxy; CrC ₆ alkoxycarbonylamino unsubstituted or substituted in the alkyl moiety by hydroxy, CrC ₄ alkyl or by CrC ₄ alkoxy; phenoxycarbonylamino unsubstituted or substituted in the phenyl moiety by hydroxy, CrC ₄ alkyl or by CrC ₄ alkoxy; amino; N-CrC ₄ alkyl- or N,N-di-C-ι-C ₄ alkyl-amino unsubstituted or substituted in the alkyl moiety or moieties by hydroxy, CrC ₄ alkoxy, carboxy, cyano, halogen, sulfo, sulfato, phenyl or by sulfophenyl, e.g. 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-ethyl-N-(3-sulfobenzyl)-amino, N-(β-sulfoethyl)-N-benzylamino; cyclohexylamino; N-phenylamino or N-CrC ₄ alkyl-N-phenylamino each unsubstituted or substituted in the phenyl moiety by nitro, Ci-C ₄ alkyl, CrC ₄ alkoxy, carboxy, halogen or by sulfo; CrC ₄ alkoxycarbonyl, e.g. methoxy- or ethoxy-carbonyl; trifluoromethyl; nitro; cyano; halogen, which is to be understood generally as being, for example, fluorine, bromine or especially chlorine; ureido; hydroxy; carboxy; sulfo; sulfomethyl; carbamoyl; carbamido; sulfamoyl; N-phenylsulfamoyl or N-CrC ₄ alkyl-N-phenylsulfamoyl each unsubstituted or

substituted in the phenyl moiety by sulfo or by carboxy; CrC ₄ alkylsulfonyl, e.g. methyl- or ethyl-sulfonyl.

D ₁ as radicals of the benzene, naphthalene or heterocyclic series are also, for example, monoazo or bisazo radicals of formula (4) or (5)

D ^* -N=N-(M-N=N) _U -K- (4) or

-D ^* -N=N-(M-N=N) _U -K (5),

wherein

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

M is the radical of a central component, of the benzene or naphthalene series,

K is the radical of a coupling component, of the benzene, naphthalene, pyrazolone, 6- hydroxypyrid-2-one or acetoacetic acid arylamide series, and u is the number 0 or 1 , preferably 0, it also being possible for D ^* , M and K to carry substituents customary for azo dyes, for example the non-fibre-reactive substituents mentioned above for D ₁ as phenyl or naphthyl and preferably CrC ₄ alkyl or CrC ₄ alkoxy unsubstituted or substituted by hydroxy, sulfo or by sulfato; halogen; carboxy; sulfo; nitro; cyano; trifluoromethyl; sulfamoyl; carbamoyl; amino; ureido; hydroxy; sulfomethyl; C ₂ -C ₄ - alkanoylamino; CrC ₄ alkylsulfonylamino; benzoylamino unsubstituted or substituted in the phenyl ring by Ci-C ₄ alkyl, CrC ₄ alkoxy, halogen or by sulfo; or phenyl unsubstituted or substituted by Ci-C ₄ alkyl, CrC ₄ alkoxy, halogen, carboxy or by sulfo.

Preferred monoazo or bisazo radicals D ₁ of formula (4) or (5) are the radicals of formulae (6a), (6b), (6c), (6d), (6e), (6f), (6g), (6h), (6i), (6j), (6k), (6I), (6m), (6n) and (60)

wherein (^ ₃ ) ₀ - ₂ denotes from 0 to 2 identical or different substituents from the group C-ι-C ₄ alkyl, CrC ₄ alkoxy, halogen, carboxy and sulfo and Z ₁ is a radical of formula (2a), (2b),

(2c), (2d), (2e), (2f) or (2g), the radicals of formulae (2a), (2b), (2c), (2d), (2e), (2f) and (2g) having the definitions and preferred meanings given above,

wherein (Ri3)o-2 is as defined above,

wherein (Ri ₄ )o _-4 denotes from O to 4 identical or different substituents from the group halogen; nitro; cyano; trifluoromethyl; sulfamoyl; carbamoyl; CrC ₄ alkyl; Ci-C ₄ alkoxy unsubstituted or substituted by hydroxy or by Ci-C ₄ alkoxy; amino; C ₂ -C ₄ alkanoylamino; ureido; hydroxy; carboxy; sulfomethyl; Ci-C ₄ alkylsulfonylamino and sulfo, and Z ₁ is as defined above,

wherein Z ₁ is as defined above and Z ₂ corresponds to a radical of formula (2b), (2d), (2e), (2f) or (2g), the radicals of formulae (2b), (2d), (2e), (2f) and (2g) having the definitions and preferred meanings given above,

wherein Z ₂ is as defined above,

CH,, COOH

wherein (Ri3)o _-2 is as defined above, (Ri ₅ )o-3 denotes from O to 3 identical or different substituents from the group Ci-C ₄ alkyl, CrC ₄ alkoxy, halogen, carboxy and sulfo, and Z ₁ is as defined above,

B ₂ -Z ₂

wherein B ₂ is unsubstituted or substituted C ₂ -C6alkylene, Ri6 is hydrogen, Ci-C ₄ alkyl or phenyl, and Ri ₇ is hydrogen, cyano, carbamoyl or sulfomethyl, and Z ₂ is as defined above,

wherein

(Ri3)o-2, (Ri ₄ )o-3 _> (Ri5)o-3 and Z ₁ are each as defined above and (R13V3 denotes from O to 3 identical or different substituents from the group CrC ₄ alkyl, Ci-C ₄ alkoxy, halogen, carboxy and sulfo.

The numbers on the naphthyl rings of the radicals of formulae (6a), (6b), (6c), (6d), (6f), (6g) and (6h) indicate the possible bonding positions of the substituent in question.

As Ci-C ₄ alkylsulfonylamino there come into consideration for R ₁₄ e.g. methyl-, ethyl-, n- propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- and isobutyl-sulfonylamino, preferably methyl- and ethyl-sulfonylamino and especially methylsulfonylamino.

As C ₂ -C ₆ alkylene there come into consideration for B ₂ straight-chain or branched alkylene groups, e.g. 1 ,2-ethylene, 1 ,3-propylene, 1 ,2-propylene, 1 ,4-butylene, 1 ,3-butylene, 1 ,5- pentylene, 3,5-pentylene, 1 ,6-hexylene, 2,5-hexylene, 4,6-hexylene or the radical of formula

CH,

CH ₂ -C- CH ₂ - or . The said radicals B ₂ are

- CH ₂ -CH- CH ₂ -CH ₂ - CH ₂ - CH _Q

unsubstituted or substituted e.g. by hydroxy, sulfo, carboxy or by sulfato, preferably by hydroxy or by sulfato and especially by sulfato, but are preferably unsubstituted.

Preferably, B ₂ is C ₂ -C ₄ alkylene and especially 1 ,2-ethylene.

Especially preferred as monoazo or bisazo radical D ₁ is the radical of formula (6j) wherein B ₂ , R^, Ru and Z ₂ have the definitions and preferred meanings given above.

In a special embodiment of the present invention, D ₁ as a radical of the benzene, naphthalene or heterocyclic series is a monoazo or bisazo radical of formula (4) or (5), the radicals of formula (4) or (5) having the definitions and preferred meanings given above.

In a preferred embodiment of the reactive dyes according to the invention D ₁ is a radical of formula (7) or (6j')

wherein

(R ₁₈ )o-3 denotes from 0 to 3 identical or different substituents selected from the group halogen, Ci-C ₄ alkyl, CrC ₄ alkoxy, carboxy, nitro and sulfo and

Z is a radical of formula (2a), (2c), (2d), (2e) or (2f) wherein

Re and Rg are hydrogen,

Hal is bromine,

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

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

N-CrC 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, chlorine, acetylamino, methyl or by methoxy; or naphthylamino unsubstituted or substituted by from 1 to 3 sulfo groups, or is a fibre-reactive radical of formula

and Y is as defined above,

X ₂ is chlorine or fluorine, and m is the number 2 or 3, especially 2; or

wherein

B ₂ is C ₂ -C ₆ alkylene unsubstituted or substituted by hydroxy, sulfo, carboxy or by sulfato, preferably by hydroxy or by sulfato,

D ₂ is a radical of formula (7) wherein (Riβ)o-3 is as defined above and Z is a radical of formula (2a), (2c), (2d) or (2e), especially (2a), wherein R ₈ , Hal, Y and m are as defined above,

R ₁₆ is hydrogen, Ci-C ₄ alkyl or phenyl,

Ri ₇ is hydrogen, cyano, carbamoyl or sulfomethyl,

R-ig is hydrogen, methyl or ethyl, especially hydrogen, and

Rg and X ₂ are as defined above.

In an especially preferred embodiment of the reactive dyes according to the invention, D ₁ is a radical of formula (7a), (7b), (7c), (7d) or (6j")

wherein

(R ₁₈ )o- ₂ denotes from 0 to 2 identical or different substituents selected from the group halogen, Ci-C ₄ alkyl, Ci-C ₄ alkoxy and sulfo, especially methyl, methoxy and sulfo,

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

Y ₁ is a group -CH(Br)-CH ₂ -Br or -C(Br)=CH ₂ and m is the number 2 or 3, especially 2; or

wherein

B ₂ is C ₂ -C ₄ alkylene, especially ethylene,

D ₂ is a radical of formula (7a), (7b), (7c) or (7d), especially (7a), wherein (Ris)o-2, Y, Yi and m have the definitions and preferred meanings given above,

Ri ₆ is methyl or ethyl, especially methyl,

R- _I7 is carbamoyl or sulfomethyl, especially carbamoyl, and

X ₂ is fluorine or chlorine.

In a very especially preferred embodiment of the reactive dyes according to the invention, D ₁ is a radical of formula (7a), (7b), (7c) or (6j"), especially (7a), (7b) or (6j"), wherein (R ₁₈ )o- ₂ , Y, m, B ₂ , D ₂ , R ₁₆ , Rn and X ₂ have the definitions and preferred meanings given above.

As halogen there come into consideration for V ₁ and V ₂ each independently of the other e.g. fluorine, chlorine and bromine, preferably chlorine and bromine and especially chlorine.

V ₁ and V ₂ each independently of the other as phenyl are unsubstituted or substituted, for example by Ci-C ₄ alkyl, for example methyl or ethyl; CrC ₄ alkoxy, for example methoxy or ethoxy; C ₂ -C ₄ alkanoylamino; for example acetylamino or propionylamino; carboxy; carbamoyl; sulfo or halogen, for example chlorine or bromine.

V ₁ and V ₂ each independently of the other as phenoxy are unsubstituted or substituted in the phenyl ring, for example by Ci-C ₄ alkyl, for example methyl or ethyl; CrC ₄ alkoxy, for example methoxy or ethoxy; C ₂ -C ₄ alkanoylamino; for example acetylamino or propionylamino; carboxy; carbamoyl; sulfo or halogen, for example chlorine or bromine.

V ₁ and V ₂ each independently of the other as C ₂ -C ₆ alkanoylamino, especially C ₂ -C ₄ alkanoyl- amino, are unsubstituted or substituted in the alkyl moiety, for example by sulfo, sulfato, carboxy, hydroxy or by CrC ₄ alkoxy, for example methoxy or ethoxy. Acetylamino, hydroxy- acetylamino, methoxyacetylamino and propionylamino, especially acetylamino, may be mentioned by way of example.

V ₁ and V ₂ each independently of the other as benzoylamino are unsubstituted or substituted in the phenyl moiety, for example by hydroxy; sulfo; carboxy; carbamoyl; halogen, for example chlorine or bromine; Ci-C ₄ alkyl, for example methyl or ethyl; or by CrC ₄ alkoxy, for example methoxy or ethoxy.

Preferably, V ₁ and V ₂ are chlorine, bromine, acetylamino or propionylamino and especially chlorine.

V ₁ and V ₂ are identical or non-identical but are preferably identical.

X ₁ as halogen is, for example, fluorine, chlorine or bromine and especially chlorine or fluorine.

X ₁ as CrC ₄ alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio or n- butylthio, especially ethylthio or n-propylthio. The said radicals are unsubstituted or

substituted in the alkyl moiety by hydroxy, carboxy or by sulfo. The substituted radicals are preferred.

Xi as unsubstituted or substituted amino is amino which is unsubstituted or substituted at the N atom, such as, for example, the following radicals:

N-mono- or N,N-di-Ci-C ₄ alkylamino, which includes both the unsubstituted radicals and the radicals substituted in the alkyl moiety e.g. by CrC ₄ alkoxy, hydroxy, sulfo or by sulfato; the radicals substituted in the alkyl moiety are preferred;

C ₅ -C ₇ cycloalkylamino, which includes both the unsubstituted radicals and the radicals substituted in the cycloalkyl ring e.g. by CrC ₄ alkyl, especially methyl; the corresponding cyclohexyl radicals are preferred as such radicals; phenylamino or N-Ci-C ₄ alkyl-N-phenylamino, which includes both the unsubstituted radicals and the radicals substituted in the phenyl ring e.g. by CrC ₄ alkyl, CrC ₄ alkoxy, halogen, carboxy or by sulfo; those radicals are preferably unsubstituted or substituted by sulfo in the phenyl ring.

As N-heterocycles which may contain further hetero atom(s) there come into consideration for X ₁ e.g. morpholino and piperidin-1-yl.

Preferably, Xi is fluorine or chlorine.

Preferably, R ₂ , R3 and R ₄ are each independently of the other hydrogen or d-C ₄ alkyl.

When D ₁ is a radical of formula (7a), R ₄ is preferably hydrogen, methyl or ethyl.

More especially, R ₂ , R3 and R ₄ are hydrogen.

R ₅ and R ₆ are preferably hydrogen.

The reactive dyes according to the invention preferably correspond to formula

wherein R ₁ , B ₁ , D ₁ and X ₁ have the definitions and preferred meanings given above.

Special preference is given to the reactive dyes of formula (1 a) according to the invention wherein

R ₁ is fluorine or chlorine, especially fluorine;

B ₁ is a C ₂ -C ₁₂ alkylene radical, which may be interrupted by 1 , 2 or 3 -O- members and is unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano or by carboxy, or is phenylene unsubstituted or substituted by CrC ₄ alkyl, CrC ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or by carboxy, preferably a C ₂ -C-i ₂ alkylene radical, especially a C ₂ -C ₆ alkylene radical, which may be interrupted by 1 , 2 or 3 -O- members and is unsubstituted or substituted by hydroxy or by sulfato, and is more especially a radical of formula -CH ₂ -CH(R ₇ )- Or -(R ₇ )CH-CH ₂ -, wherein R ₇ is CrC ₄ alkyl;

X ₁ is fluorine or chlorine; and

D ₁ corresponds to a radical of formula (7) or (6j'), wherein Z, B ₂ , D ₂ , Rg, R ₁₆ , R ₁₇ , R ₁ 9 and X ₂ have the definitions and preferred meanings given above, especially of formula (7a),

(7b), (7c), (7d) or (6j"), wherein (R ₁₈ )o-2, Y, Yi, m, B ₂ , D ₂ , R ₁₆ , R ₁₇ and X ₂ have the definitions and preferred meanings given above.

Very special preference is given to the reactive dyes of formula (1a) according to the invention, wherein

R ₁ is fluorine or chlorine, especially fluorine,

B ₁ is a radical of formula -CH ₂ -CH(CH ₃ )- Or -(CH ₃ )CH-CH ₂ -,

X ₁ is fluorine or chlorine,

D ₁ corresponds to a radical of formula (7a), (7b), (7c) or (6j"), especially (7a), (7b) or (6j"), wherein (R-i8)o- ₂ , Y, rn, B ₂ , D ₂ , R ₁₆ , R ₁₇ and X ₂ have the definitions and preferred meanings given above.

The present invention relates also to a process for the preparation of the reactive dyes according to the invention, wherein a compound of formula

is reacted with a compound of formula

to form a compound of formula

the compound of formula (10) is reacted with a compound of formula

)

to form a compound of formula

the compound of formula (12) is cyclised to form a compound of formula

and the compound of formula (13) is condensed in any order with 2,4,6-trihalo-s-triazine and a compound of formula

to form a compound of formula

wherein R ₁ , R ₂ , R3, R ₄ , (Rs)o-2, (RβW, B ₁ , D ₁ , V ₁ and V ₂ have the definitions and preferred meanings given above, R' is Ci-C ₄ alkyl, V is chlorine or bromine, especially chlorine, and X is halogen and especially fluorine or chlorine.

The halogen atom X in the compound of formula (15) can be replaced by condensation of the compound of formula (15) with a compound of formula (16)

XrH (16),

wherein X ₁ has the meanings given above except for halogen.

Condensation reactions of amino-group-containing dyes with 2,4,6-trihalo-s-triazine are known and are described, for example, in EP-A-O 260 227 and US-A-4 841 049.

The compounds of formulae (8), (9), (11 ) and (14) are known or can be obtained in a manner known per se.

The end product can optionally also be subjected to a transformation reaction. Such a transformation reaction is, for example, the conversion of a vinylatable reactive group present in D ₁ 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 vinylsulfonyl radical. Such reactions are known per se.

The compounds of formula (1 ) according to the invention are suitable as dyes for the dyeing and printing of an extremely wide variety of materials, such as hydroxy-group-containing or nitrogen-containing fibre materials. Examples of nitrogen-containing fibre materials are silk, leather, wool, polyamide fibres and polyurethanes. The dyes according to the invention are suitable for the dyeing and printing of 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 dyes according to the invention are also suitable for the dyeing or printing of cellulosic blend fabrics, for example mixtures of cotton and polyamide fibres or, especially, of cotton/polyester fibre blends.

The dyes according to the invention can be applied to the fibre material and fixed thereto in a variety of ways, especially in the form of aqueous dye solutions or print pastes. They are suitable both for the exhaust method and for pad-dyeing, in which the goods are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat, or by

storage for several hours at room temperature. After fixing, the dyeings or prints are washed thoroughly with cold and hot water, optionally with addition of an agent that has a dispersant action and promotes diffusion of unfixed dye.

The dyes according to the invention are distinguished by high reactivity, good fixing capacity and very good build-up capacity. They can therefore be used in the exhaust dyeing method at low dyeing temperatures and require only short steaming times in the pad-steam method. The degrees of fixing are high and unfixed dye can be washed off readily, the difference between the degree of exhaustion and the degree of fixing being remarkably small, that is to say the soaping loss is very low. The dyes according to the invention are also suitable for printing, especially on cotton, and also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics that contain wool or silk.

The dyeings and prints produced using the dyes according to the invention exhibit high colour strength and high fibre-dye bond stability in both an acid and an alkaline medium, and also good light fastness and very good wet-fastness properties, such as fastness to washing, to water, to sea water, to cross-dyeing and to perspiration, as well as good fastness to pleating, to hot-pressing and to rubbing.

The reactive dyes according to the invention are also suitable as colorants for use in recording systems. Such recording systems are, for example, commercially available ink-jet printers for paper or textile printing, or writing implements, such as fountain pens or ballpoint pens, and especially ink-jet printers. For that purpose, the dye mixture according to the invention is first converted into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink comprising the reactive dyes according to the invention as colorant. The inks can be prepared in customary manner by mixing together the individual constituents customary in ink-jet printing in the desired amount of water.

Examples of substrates that come into consideration for ink-jet printing, in addition to paper or plastics films, include the above-mentioned hydroxy-group-containing or nitrogen- containing fibre materials, especially cellulosic fibre materials. The substrates are preferably textile fibre materials.

The following Examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

Example 1 : 24.2 parts of 2,3,5-trichloro-6-methoxy-1 ,4-benzoquinone are stirred under reflux for 3 hours together with 20.3 parts of 5-amino-2-fluorobenzenesulfonic acid and 9 parts of anhydrous sodium acetate in 2500 parts of methanol. 2500 parts of water are added to the reaction mixture, and the resulting precipitate is filtered off, washed with water and dried, yielding 22.5 parts of an orange-coloured powder which, in the form of the free acid, corresponds to formula

Example 2: 41.0 parts of the powder obtained according to Example 1 are stirred with 24.5 parts of 5-amino-2-(2-aminopropylamino)benzenesulfonic acid in 500 parts of water, a pH value of 8 being maintained during the reaction using aqueous sodium hydroxide solution. When the reaction is complete, the brown precipitate that has formed is filtered off, washed with water and dried in vacuo, yielding a compound which, in the form of the free acid, corresponds to formula

Example 3: 62.4 parts of the finely ground compound from Example 2 are introduced, in portions, into 300 parts of 25 % oleum. 55 parts of potassium peroxodisulfate are added to the reaction mixture at 0°C and the mixture is stirred for a further 3 hours at 0°C. When the reaction is complete, the reaction mass is poured into ice and partly neutralised with

concentrated sodium hydroxide solution. The blue precipitate that forms is filtered off, washed with water and dried in vacuo, yielding a compound which, in the form of the free acid, corresponds to formula

Example 4: 28.1 parts of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate are added, in portions, to a slurry prepared from 19 parts of trichlorotriazine, 50 parts of an ice/water mixture and 5 parts of disodium hydrogen phosphate. The pH value is maintained at 4 with dilute aqueous sodium hydroxide solution until the end of the reaction, then increased to 6.5 and maintained at that value. To the resulting solution there is rapidly added dropwise a heated solution of 69.7 parts of the compound according to Example 3 and 2.5 parts of lithium hydroxide in 500 parts of water, the temperature being maintained at from 25 to 30°C and the pH value at from 9.5 to 10. Stirring is carried out for a further 1 hour under those conditions; the reaction mixture is neutralised with dilute hydrochloric acid, dialysed and concentrated by evaporation in vacuo, yielding a compound which, in the form of the free acid, corresponds to formula

λ _max = 592 nm

and dyes cotton a brilliant blue shade having good allround fastness properties.

Examples 5 to 28: If the procedure as described in Example 4 is carried out but instead of 28.1 parts of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate there is used an equimolar amount of an amine of formula D _x -NH ₂ wherein D _x has one of the meanings given in Table 1 , there is obtained a compound which, in the form of the free acid, corresponds to general formula

wherein D _x has one of the meanings given in Table 1. The dyes dye cotton in brilliant blue shades having good allround fastness properties.

Table 1 :

Example Amine D _x D _x -NH ₂

₂ -CH ₂ -OSO ₃ H

N H-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -OSO ₃ H

ONH-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -OSO ₃ H

CO-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -OSO ₃ H

Example 29: 13.3 parts of trifluorotriazine are added dropwise at 0°C to 28.1 parts of 2-(4- aminophenylsulfonyl)ethyl hydrogen sulfate in 300 parts of water, the pH value being maintained at 6 with dilute aqueous sodium hydroxide solution. To the resulting solution there is added a solution of 69.7 parts of the compound according to Example 3 and 2.5 parts of lithium hydroxide in 500 parts of water. The temperature is maintained at from 25 to 30°C and the pH value at from 9.5 to 10. Stirring is carried out for a further 1 hour under those conditions; the reaction mixture is neutralised with dilute hydrochloric acid, dialysed and concentrated by evaporation in vacuo, yielding a compound which, in the form of the free acid, corresponds to formula

λ _max = 594 nm

and dyes cotton a brilliant blue shade having good allround fastness properties.

Examples 30 to 53: If the procedure as described in Example 29 is carried out but instead of 28.1 parts of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate there is used an equimolar amount of an amine of formula D _x -NH ₂ wherein D _x has one of the meanings given in Table 1 , there is obtained a compound which, in the form of the free acid, corresponds to general formula

wherein D _x has one of the meanings given in Table 1. The dyes dye cotton in brilliant blue shades having good allround fastness properties.

Examples 54 to 71 : If the procedure as described in Examples 2, 3 and 4 is carried out but instead of 24.5 parts of 5-amino-2-(2-aminopropylamino)benzenesulfonic acid there is used

an equimolar amount of an amine of formula wherein the

radica has one of the meanings given in Table 2, column 2, there is obtained a compound which, in the form of the free acid, corresponds to general formula

wherein the radical has one of the meanings given in Table 2, column 3.

The dyes dye cotton in brilliant blue shades having good allround fastness properties.

Table 2

Example

54 (72) -NH-CH ₂ -CH ₂ -NH ₂ -N H-CH ₂ -CH ₂ -N H-

55 (73) -NH-CH ₂ -CH ₂ -CH ₂ -NH ₂ -NH-CH ₂ -CH ₂ -CH ₂ -NH-

56 (74) -NH-CH ₂ -CH ₂ -NH(CH ₃ ) -NH-CH ₂ -CH ₂ -N(CH ₃ )-

57 (75) -N(CHa)-CH ₂ -CH ₂ -NH(CH ₃ ) -N(CHa)-CH ₂ -CH ₂ -N(CH ₃ )-

58 (76) -NH-(CH ₂ ) ₃ -O-(CH ₂ ) ₄ -O-(CH ₂ ) ₃ -NH ₂ -NH-(CH ₂ ) ₃ -O-(CH ₂ ) ₄ -O-(CH ₂ ) ₃ -NH-

59 (77) -NH-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -NH ₂ -NH-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -NH-

60 (78) -NH-CH ₂ -CH ₂ -NH(CH ₂ CH ₃ ) -NH-CH ₂ -CH ₂ -N(CH ₂ CH ₃ )-

(79)

(80)

(81 )

(82)

(83)

(84)

(85)

(86)

(87)

(88)

71 (89) — N NH — N N—

Examples 72 to 89: If the procedure as described in Examples 2, 3 and 29 is carried out but instead of 24.5 parts of 5-amino-2-(2-aminopropylamino)benzenesulfonic acid there is used

an equimolar amount of an amine of formula wherein the

H-N-B- N— radical λ K ₃ i K ₂ has one of the meanings given in Table 2, column 2, there i is

obtained a compound which, in the form of the free acid, corresponds to general formula

— N-B _r N— wherein the radical λ K ₃ i K ₂ has one of the meanings given in Table 2, column 3.

The dyes dye cotton in brilliant blue shades having good allround fastness properties.

Example 90: If the procedure as described in Examples 1 to 4 is carried out but instead of 20.3 parts of 5-amino-2-fluorobenzenesulfonic acid there is used an equimolar amount of 5- amino-2-chlorobenzenesulfonic acid, there is obtained a compound which, in the form of the free acid, corresponds to formula

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 91 : If the procedure as described in Examples 1 , 2, 3 and 29 is carried out but instead of 20.3 parts of 5-amino-2-fluorobenzenesulfonic acid there is used an equimolar amount of 5-amino-2-chlorobenzenesulfonic acid, there is obtained a compound which, in the form of the free acid, corresponds to formula

)

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 92: If the procedure as described in Examples 1 to 4 is carried out but instead of 20.3 parts of 5-amino-2-fluorobenzenesulfonic acid there is used an equimolar amount of 5- amino-2-bromobenzenesulfonic acid, there is obtained a compound which, in the form of the free acid, corresponds to formula

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 93: If the procedure as described in Examples 1 , 2, 3 and 29 is carried out but instead of 20.3 parts of 5-amino-2-fluorobenzenesulfonic acid there is used an equimolar amount of 5-amino-2-bromobenzenesulfonic acid, there is obtained a compound which, in the form of the free acid, corresponds to formula

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 94: If the procedure as described in Examples 1 , 2, 3 and 4 is carried out but instead of 28.1 parts of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate there is used an

equimolar amount of an amine of formula , there is obtained a compound which, in the form of the free acid, corresponds to general formula

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 95: If the procedure as described in Examples 1 , 2, 3 and 4 is carried out but instead of 28.1 parts of 2-(4-aminophenylsulfonyl)ethyl hydrogen sulfate there is used an

equimolar amount of of an amine of formula , there is obtained a H ₂ J ₂ -SO ₂ (CH ₂ J ₂ OSO ₃ H compound which, in the form of the free acid, corresponds to general formula

and dyes cotton a brilliant blue shade having good allround fastness properties.

Example 96: 13.3 parts of trifluorotriazine are added dropwise at 0°C to 28.1 parts of 2-(4- aminophenylsulfonyl)ethyl hydrogen sulfate in 300 parts of water, the pH value being maintained at 6 with dilute aqueous sodium hydroxide solution. 21.1 parts of 1-(2-amino- ethyl)-6-hydroxy-4-methyl-2-oxo-1 ,2-dihydro-pyridine-3-carbonamide are added to the resulting reaction mixture. The pH value is increased to 8.5 with aqueous sodium hydroxide solution and maintained at that value until the end of condensation. The reaction mixture is heated at 30°C and the pH value is increased to 1 1 ; stirring is carried out for 15 minutes and the reaction mixture is neutralised with dilute hydrochloric acid. The reaction mixture contains the compound of formula

Example 97: 26.8 parts of 1 ,3-phenylenediamine-4,6-disulfonic acid are dissolved in 300 parts of water at pH 6 and cooled to 0°C, and 18.4 parts of trichlorotriazine and a small amount of wetting agent are added thereto. Stirring is carried out at 0°C and at pH 6 until the condensation reaction is largely complete, then 6.9 parts of sodium nitrite, 150 parts of ice and 29 parts of concentrated hydrochloric acid are added and stirring is continued for a further two hours. The excess nitrite is destroyed with a small amount of sulfamic acid and the reaction mixture obtained in accordance with Example 96 is added dropwise thereto in the course of 30 minutes. The pH value is then slowly raised to 6.5 and maintained at 6.5 for two hours. 100 parts of potassium chloride are added to the reaction mixture, and the

resulting precipitate is filtered off, washed with saturated potassium chloride solution and dried, yielding a compound which, in the form of the free acid, corresponds to formula

Example 98: 69.7 parts of the compound according to Example 3 are dissolved in 500 parts of water with 2.5 parts of lithium hydroxide at 60°C and added rapidly to a suspension of 91.7 parts of the compound prepared in accordance with Example 97 in 800 parts of water. The pH value is maintained at from 9 to 9.5 by addition of aqueous sodium hydroxide solution and the temperature is maintained at 30°C. When condensation is complete, the product is salted out with 260 parts of potassium chloride, filtered off, washed with saturated potassium chloride solution and dried, yielding a compound which, in the form of the free acid, corresponds to formula

and dyes cotton a brilliant green shade having good allround fastness properties.

In a manner analogous to that described in Examples 96, 97 and 98 it is possible to prepare the following compounds which, in the form of the free acid, correspond to the formulae given in Table 3. The dyes dye cotton in brilliant green shades having good allround fastness properties.

Table 3:

Dyeing procedure I: 2 parts of the dye obtained in accordance with Example 4 are dissolved in 400 parts of water; 1500 parts of a solution containing 53 g of sodium chloride per litre

are added thereto. 100 parts of cotton fabric are introduced into that dyebath at 40°C. After 45 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of calcined soda per litre are added. The temperature of the dyebath is maintained at 40°C for a further 45 minutes. The dyed goods are then rinsed, soaped at boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing procedure II: 2 parts of the reactive dye obtained in accordance with Example 4 are dissolved in 400 parts of water; 1500 parts of a solution containing 53 g of sodium chloride per litre are added thereto. 100 parts of cotton fabric are introduced into that dyebath at 35°C. After 20 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of calcined soda per litre are added. The temperature of the dyebath is maintained at 35°C for a further 15 minutes. The temperature is then increased to 60°C within a period of 20 minutes. The temperature is maintained at 60°C for a further 35 minutes. The goods are then rinsed, soaped at boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing procedure III: 8 parts of the reactive dye obtained in accordance with Example 4 are dissolved in 400 parts of water; 1400 parts of a solution containing 100 g of sodium sulfate per litre are added thereto. 100 parts of cotton fabric are introduced into that dyebath at 25°C. After 10 minutes, 200 parts of a solution containing 150 g of trisodium phosphate per litre are added. The temperature of the dyebath is then increased to 60°C within a period of 10 minutes. The temperature is maintained at 60°C for a further 90 minutes. The goods are then rinsed, soaped at boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing procedure IV: 4 parts of the reactive dye obtained in accordance with Example 4 are dissolved in 50 parts of water; 50 parts of a solution containing 5 g of sodium hydroxide and 20 g of calcined soda per litre are added thereto. The resulting solution is used for pad- dyeing cotton fabric so that its weight increases by 70 %, and the fabric is then wound onto a roll. The cotton fabric is stored on the roll for 3 hours at room temperature. The dyed goods are then rinsed, soaped at boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing procedure V: 6 parts of the reactive dye obtained in accordance with Example 4 are dissolved in 50 parts of water; 50 parts of a solution containing 16 g of sodium hydroxide and 0.04 litre of water glass (38 ⁰ Be) per litre are added thereto. The resulting solution is used for pad-dyeing cotton fabric so that its weight increases by 70 %, and the fabric is then wound onto a roll. The cotton fabric is stored on the roll for 10 hours at room temperature. The dyed goods are then rinsed, soaped at boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

Dyeing procedure Vl: 2 parts of the reactive dye obtained in accordance with Example 4 are dissolved in 100 parts of water with addition of 0.5 part of sodium m-nitrobenzene- sulfonate.The resulting solution is used for impregnating cotton fabric so that its weight increases by 75 %, and the fabric is then dried. The fabric is then impregnated with a solution at 20°C containing 4 g of sodium hydroxide and 300 g of sodium chloride per litre and squeezed off to a 75 % increase in weight; the dyeing is then steamed for 30 seconds at 100 to 102°C, soaped for a quarter of an hour in a boiling 0.3 % solution of a non-ionic detergent, rinsed and dried.

Printing procedure I: While stirring rapidly, 3 parts of the reactive dye obtained in accordance with Example 4 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5 % sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium hydrogen carbonate. The print paste so obtained is used to print a cotton fabric; drying is carried out and the resulting printed material is steamed in saturated steam at 102°C for 2 minutes. The printed fabric is then rinsed, if desired soaped at boiling and again rinsed, and then dried.

Printing procedure II: While stirring rapidly, 5 parts of the reactive dye obtained in accordance with Example 4 are sprinkled into 100 parts of a stock thickener containing 50 parts of 5 % sodium alginate thickener, 36.5 parts of water, 10 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 2.5 parts of sodium hydrogen carbonate. The resulting print paste, the stability of which conforms to the technical requirements, is used to print a cotton fabric; drying is carried out and the resulting printed material is steamed in saturated steam at 102°C for 8 minutes. The printed fabric is then rinsed, if desired soaped at boiling and again rinsed, and then dried.