GB2259710A

GB2259710A - Reactive dyes, their preparation and use

Info

Publication number: GB2259710A
Application number: GB9219711A
Authority: GB
Inventors: Athanassios Tzikas; Herbert Klier
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1991-09-23
Filing date: 1992-09-17
Publication date: 1993-03-24
Also published as: DE4231537A1; GB9219711D0; JPH05222308A; FR2681605A1

Abstract

The invention relates to reactive dyes of the formula <IMAGE> in which D is the radical of a diazo component, Q is hydrogen or a substituted or unsubstituted alkyl, alkoxy, alkylthio or amino radical and A1 and A2 independently of one another are a radical of the formula <IMAGE> in which R1 and R2 independently of one another are hydrogen, substituted or unsubstituted C1-C6alkyl or substituted or unsubstituted aryl, or R1 and R2, together with the N atom, form a heterocyclic 5-membered or 6-membered ring, which may or may not be further substituted, with the proviso that at least one of the radicals A1, A2 and D contains a fibre-reactive group. Coupling components are also referred to.

Description

? r c 0,1 4 1 1 Reactive dyes, their preparation and use For a long time,

reactive dyes have been employed on a large scale for the dyeing and printing of textiles composed of fibre materials, and today there are a large number of utilisable reactive dyes available with different properties and for various application areas. In view of the higher and higher demands on reactive dyes in relation to economicalness, application and level of fastness, the technological level achieved, however, is frequently not completely satisfactory.

Thus, for example, it is frequently to be found that the degree of fixing is too low, and the difference between degree of exhaustion and degree of fixing is too great (high soap loss), so that a considerable part of the reactive dye for the dyeing operation is wasted. In addition, the buildup power in many cases leaves something to be desired.

The present invention is based on the object of finding novel improved reactive dyes which have a high reactivity and a good build-up power, which can be dyed with high fixing yield, which are primarily suitable for the exhaust dyeing process, and which give wet- and light-fast dyeings on cellulose-containing fibre material.

It has been shown that the novel reactive dyes defined below meet these demands.

The invention relates to reactive dyes of the formula N Q--/ N=N-D N:

(1), A2 in which D is the radical of a diazo component, Q is hydrogen or a substituted or unsubstituted alkyl, alkoxy, alkylthio or amino radical and A, and A2 independently of one another are a radical of the formula R, 1 -N \ R2 (1a), in which R, and R2 independently of one another are hydrogen, substituted or unsubstituted Cl-C6alkyl or substituted or unsubstituted aryl, or R, and R2, together with the N atom, form a heterocyclic 5-membered or 6- membered ring, which may or may not be further substituted, with the proviso that at least one of the radicals A,, A2 or D contains a fibre- reactive group.

D is, for example, the radical of an aminobenzene, aminonaphthalene, phenylazoaminobenzene, naphthylazoaminobenzene, phthalocyanineaminobenzene, phenylazoaminonaphthalene or naphthylazoaminonaphthalene, which can in each case be unsubstituted or, preferably, substituted as outlined below. D is preferably a substituted or unsubstituted radical of an aminobenzene or aminonaphthalene.

Suitable substituents on the radical D are, for example: Cl-C4alkyl, which generally includes methyl, ethyl, n- or isopropyl or n-, sec- or tert-butyl; Cl-C4alkoxy, which is generally to be understood as meaning methoxy, ethoxy, n- or isopropoxy or n-, sec- or tert-butoxy; amino; Nmono: or N,N-di-Cl-C4alkylamino, where the alkyl may or may not be further substituted, for example by -OH, -OCOCH3, -OSO3H, -CN or halogen, for example methylamino, ethylamino, n- or isopropylamino or n-, see- or tert-butylamino, N,N-dimethyl- or -diethylamino, B-chloroethylamino, 8cyanoethylamino, 8-acetoxyethylamino, N-(B-hydroxyethyl),N-ethylamino," 8sulfatoethylamino, N,N-di-(B-hydroxyethyl)amino, N,N-di-(Bsulfatoethyl)amino or hydroxypropylamino; phenylamino; Cl-C4alkanoylamino, particularly acetamido, propionamido; benzarnido; Cl-C4alkoxycarbonyl, for example methoxycarbonyl or ethoxycarbonyl; nitro; cyano; trifluoromethyl; halogen, which is generally to be understood as meaning fluorine, chlorine and bromine; hydroxyl; carboxyl; sulfb; sulfomethyl; sulfamoyl; N-mono- or N,N-di-Cl-C4alkylsulfamoyl; N-phenyIsulfamoyl; carbamoyl; N-mono- or N,N-di-Cl-C4alkylcarbamoyl; ureido; Cl- C4alkylsultonyl, for example methylsulfonyl or ethylsulfonyl.

D may also contain a reactive radical, for example a C2-C4alkanoyl or C2COlkylsulfonyl radical substituted by a group which can be eliminated or an atom which can be t.1 t t.' eliminated, a C2-C4alkenoyl or C2-COlkenesulfonyl radical which is unsubstituted or substituted by an atom which can be eliminated or a group which can be eliminated andlor a radical containing a carbocyclic or heterocyclic 5- or 6-membered ring substituted by an atom which can be eliminated or a group which can be eliminated, it being possible for the said radicals to be bonded to the chromophore directly or via a bridge member. The bridge member can in this case consist, for example, of a functional group, for example an amino, carbonyl, carbonylamino, aminocarbonyl, sufonyl, sulfonylamino or aminosulfonyl group or of an aliphatic, cycloaliphatic, aliphatic-heterocyclic, aromatic or mixed aliphatic-aromatic group which carries one of the said functional groups.

A group of suitable reactive dyes according to the invention includes compounds of the aforementioned formula (1), in which D contains a reactive radical of the formula -SO2-Z (2), - W- alk - S02 - Z 1 R (2a) -W-alk-E-alW-SO2-Z (2b), - alk - W - alk'- S02 - Z (2c), 1 R (2d) or - W -arylene - N - alk - S02 1 1 R3 R (2e) in which W is a functional group, for example -SO2NR3-, -CONRY or -NR3C0-, R3 is hydrogen, Cl-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfb, sulfato, carboxyl or cyano, or a radical - alk - S02 - Z, R is hydrogen, hydroxyl, sulfb, sulfatd, k carboxyl, cyano, halogen, Cl-C4alkoxycarbonyl, Cl-COlkanoyloxy, carbamoyl or the group -S02-4 Z is -CH=CH2 or -CH2-CH2-Y and Y is a leaving group, E is -0- or -NR4-, R4 is hydrogen or Cl-C4alkyl, alk and alk' independently of one another are a Cl-C6alkylene radical and arylene, for example, is a phenylene or naphthalene radical which is unsubstituted or substituted, for example, by sulfb, carboxyl, Cl-C4alkyl, Cl-C4alkoxy andlor halogen.

Suitable leaving groups Y are, for example, -Cl, -Br, -F, -0503H, -SS03H, -OCO-CH3, -OCO-CA, -0p03H2, -OCO-CC13, -OCO-CHC12, -OCO-CH2C1, OS02-R, in which R is Cl-C4alkyl or phenyl which is unsubstituted or substituted by Cl-C4alkyl, or -OS02-N(C1-COlkyl)2.

Y is preferably a group -Cl, -OSO3H, -SS03H, -OCOCH3, -OCO-C6H5 or OPO3H2.

alk and alk' independently of one another are, for example, a methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radical or their branched isomers.

alk and alk' independently of one another are preferably a Cl-C4alkylene radical and in particular are preferably an ethylene radical.

R is preferably hydrogen or the group -S02-4 in which Z is as defined above. R is particularly preferably hydrogen.

R3 is preferably hydrogen, Cl-C4alkyl or a group -alk-S02-Z in which alk and Z each have the aforementioned meaning.

arylene is preferably a 1,3- or 1,4-phenylene radical which is unsubstituted or substituted, for example, by sulfb, methyl, methoxy or carboxyl.

E is preferably -NH- and in particular is preferably -0-.

W is preferably a funcdonal group -CONH- or -NHCO, D preferably contains a reactive radical of the aforementioned formula (2) or (2a), in which W is -CO-NH- or -NH-CO-, Z in each case is as defined above and alk is a Cl-C4alkylene radical.

In a further group of suitable reactive dyes of the formula (1) according to the invention, D contains a reactive radical of the formula -N T 1 -ri 1_ P15 N N X (3), in which RS is hydrogen or Cl-C4alkyl which is unsubstituted or substituted by carboxyl, cyano, hydroxyl, sulfo or sulfato, X is a group which can be eliminated as an anion and T either independently is X or is a group containing a further reactive radical or is a non-reactive substituent.

In this case, R5 is preferably a Cl-C4alkyl radical and in particular is preferably hydrogen.

X is, for example, fluorine, chlorine, bromine, sulfb, Cl-C4alkylsulfonyl or phenylsulfonyl and is preferably fluorine or chlorine.

A non-reactive substituent T can be, for example, a hydroxyl, Cl-C4alkoxy, Cl-C4alkylthio, amino, N-Cl-C4alkylamino or N,N-di-Cl-C4alkylamino radical, where the alkyl is unsubstituted or substituted, for example, by sulfb, sulfato, hydroxyl, carboxyl or phenyl, cyclohexylamino, morpholino, phenylamino, N-Cl-C4alkyl,N-phenylamino, or naphthylamino radical, where the phenyl or naphthyl is unsubstituted or substituted, for example, by Cl-C4alkyl, Cl-C4alkoxy, carboxyl, sulfo andlor halogen.

Examples of suitable non-reactive substituents T are amino, methylamino, ethylamino, B-hydroxyethylamino, N,N-di-B-hydroxyethylamino, Bsulfoethylamino, cyclohexylamino, morpholino, o-, m- or pmethylphenylamino, o-, m- or p-methoxyphenylamino, o-, m- or pchlorophenylamino, o-, m- or p-sulfophenylamino, disulfbphenylainino, ocarboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylwnino, 4,8disulfo-2-naphthylamino, N-ethyl,N-phenylamino, N-methyl,N-phenylamino, methoxy, ethoxy, n- or isopropoxy, hydroxyl.

The non-reactive substituent T preferably is amino, N-Cl-COlkylamino in which the alkyl is unsubstituted or substituted by hydroxyl, sulfato or sulfb, morpholino, phenylamino or N-Cl-C4alkyl,N-phenylamino in which the phenyl is in each case unsubstituted or substituted by sulfb, carboxyl, methyl or methoxy.

T which independently has the meaning of X is preferably chlorine or fluorine.

T which is a group which contains another reactive radical can have, for example, the formula R 1 -N- alk- S02- Z 1 R3 -N - alk - E - alk- S02 - Z 1 RS - N - arylene - S02 - Z 1 R5 - N - arylene (alk - W aW- S02 - Z 1 RS - N /--\ N - alk-SO2-Z (4), (4a), (4b), (4c) or (4d), in which the above definitions and preferences apply to R, R3, RS, E, W, Z, alk, alk' and arylene and p is 0 or 1.

As a group which contains a further reactive radical, T preferably corresponds to one of the formulae given below R# 1 - N - alk - S02 - Z 1 R -N - alk - F- alk' S02 - Z 1 R (4), (4a), R6 N-N - S02-Z 1 R5 (4b), R6 -N-N W-alk-S02-Z 1 1/- - M5 (40 or - N /--\ N - alk-S02-Z (4d), in which Wis -CONR5'- or -NRSW-, Wis hydrogen or the group -S02-Z, R3'iS hydrogen, Cl-C4alkyl or the group -alk-SO2-Z, RS'is hydrogen or Cl-COlkyl, Wis -0or -NH- and R6 is hydrogen, sulfb, carboxyl, chlorine, methoxy or methyl, alk and alk' independently of one another are a Cl-C4alkylene radical, and the aforementioned meanings and preferences apply to Z.

D which contains a reactive radical can in this case also be,.for example, a pyrimidine or quinoxaline radical which in each case has at least one group which can be eliminated as an anion. Examples are the 2,3dichloroquinoxaline-6-carbonylarnino radical, 2,4-dichloropyrimidine-5carbonylamino radical or a radical of the formula X2 X, -N 6 4 R5 N N 3 2 X, (5) in which one of the radicals Xp preferably that in the 2-position, is a group which can be eliminated as an anion and the other radical X, is defined as given for T in the formula (3), X2 is a negative substituent and R5 independently is defined as given in formula (3).

In this case, the aforementioned meanings and preferences apply to RS and T; the radical X, which can be eliminated as an anion is preferably fluorine or chlorine. Examples of suitable radicals X2 are nitro, cyano, Cl-C4alkylsulfonyl, carboxyl, chlorine, hydroxyl, Cl-C4alkoxysulfonyl, Cl-C4alkylsulfinyl, Cl- C4alkoxycarbonyl or Cl-C4alkanoyl, where the meanings chlorine, cyano, formy], and methylsulfonyl for X2 are preferred.

Examples of preferred reactive radicals of the formula (5) on the radical D are 2,4,5-trichloropyrimidine-6-amino, 2,4-difluoro-5-chloropyrimidine6-amino, 2,4-dichloro-5-methylsulfonylpyrimidine-6-amino or a radical of the formula X2 N N - alk-(E'-alk') -SO2-Z HS N N R5 (6) or CL, F X2 R6 N N W-alk-S02-Z 1 1 1 - H5 N N R5 CL, F (7) in which Rs', S, W, R6 and Z are as defined above, X2 is chlorine, cyano or methylsulfonyl, p is the number 0 or 1 and alk and alk' independently of one another are a Cl-C4alkylene radical.

In the radical D which contains no fibre-reactive group, D is preferably the radical of an aminobenzene or aminonaphthalene which is unsubstituted or substituted by sulfb, carboxyl, Cl-C4alkoxy, Cl-C4alkyl, ClC4alkanoylamino andlor halogen.

D which contains a fibre-reactive group is preferably the radical of-an aminobenzene or aminonaphthalene which is unsubstituted or substituted by sulfb, acetamido, methyl, methoxy, chlorine or bromine and moreover carries a reactive radical of the aforementioned formula (2), (2a) or (3).

1 R, andlor R2 in formula (Ia) which are a substituted or unsubstituted Cl- C6alkyl radical are, for example, a methyl, ethyl, n- or isopropyl, n-, see- or tert-butyl or a straight-chain or branched pentyl or hexyl radical, where these radicals can be substituted, for example, by hydroxyl, sulfb, sulfato, carboxyl, cyano, halogen, Cl-C4alkoxycarbonyl, Cl-C4alkanoyloxy, carbarnoyl andlor a reactive radical and, with the exception of methyl, the alkyl radical additionally may or may not be interrupted, for example, by a group -0or - NR4-; in this case R4 is as defined above.

The alkyl radical R, andlor R2 which is substituted by a reactive radical can in this case be, for example, a radical -S02-Z in which Z is as defined above.

In a preferred embodiment of the reactive dyes according to the invention, R, and R2 independently of one another are hydrogen or a Cl-C4alkyl radical which is unsubstituted or substituted by hydroxyl, sulfb, sulfato, carboxyl, cyano or the group -S02-Z andlor interrupted by -0-; preferably in this case one of the radicals R, or R2 is hydrogen.

Examples of particularly preferred non-reactive alkylamino radicals A, and A2 are: -NH-CH3, -NH-CH2-SO311, -NI1-CH2-COOH, -NH-C2H5, -NH-CH2-CH2- 0H, -NH-CH2-CH2-SO3H, -NH-CH2-CH2-OSO3H, -NH-CH2-CH2-W, -NH-CH2-CH2-COOH, -NH-CH2-CH2-CH2-OSO3H, -NH-CH2-CH2-CH2-0H, -NH-CH2- '-CH2-CH3, -NH-CH2CH2-0-CH2-CH2-0H, -NH-CH2-CH2-0-CH2-CH2-OSO3H.

Examples of preferred reactive alkylamino radicals A, and A2 are the aforementioned radicals of the formulae (4) or (4a) and in particular the radicals of the formulae (4) or (4a').

A heterocyclic radical formed by R, and R2, together with the nitrogen atom to which the two are bonded, can be, for example, a piperidinyl, piperazinyl or pyrrolidinyl radical which is in each case unsubstituted or substituted, for example, by a reactive radical of the formula (alkYS02-Z, in which alk, p and Z in each case are as defined above. The non-reactive radical preferred in this case is the piperidinyl radical and the reactive radical preferred is a radical of the aforementioned formula (4d).

R, or R2 which is an aryl radical can be, for example, a phenyl or naphthyl radical which is unsubstituted or substituted, for example, by sulfb, carboxyl, Cl-COlkyl, Cl-C4alkoxy, halogen, a reactive radical andlor a group -N=N-K, in which K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series.

Z In this case, K is preferably the radical of a benzene, naphthalene, pyrazolone, 1-phenyl-5-pyrazolone or pyridone which is substituted, for example, by one or more identical or different substituents of those mentioned above for D.

Se K particularly preferably has one of the formulae shown in the following:

(S03H)C-2 HO -- N---0 1 -N (8), CH3, COOH CH3 CN, CONH2, CH2SO3H 1 HO N 0 1 (-;2t15hU (8a), OH NH-COCH3, COC6H5 :C03H H03S (8b).

R, or R2 as aryl which contains a reactive radical can in this case be, for example, a radical of the aforementioned formula (2), (2a), (3) or (5) or the 2,3-dichloroquinoxaline-6-carbonylamino or 2,4-dichloropyrimidine-s- carbonylamino radical.

A, and/or A2 which is a non-reactive aryl radical has, for example, the formula R6 -NH __OR6' (9), in which R6 is hydrogen, sulfb, chlorine, methoxy or carboxyl and R6' independently has the meaning of R6 or is a group of the aforementioned formula (8).

Preferred reactive aryl radicals A, and A2 are the groups of the aforementioned formula (4b) or (4c) or a group of the formula R6 -N N T H RS N k, N (3a), X in which RS, R6, X and T in each case are as defined above and B is -, -= or 1 02CH3 - N and in particular -N=.

A preferred group of reactive dyes according to the invention includes compounds of the formula (1) in which A, and A2 independently of one another are amino, N-Cl-C4alkylarnino in which the alkyl is unsubstituted or substituted by hydroxyl, sulfato or sulfb, or phenylamino in which the phenyl is unsubstituted or substituted by sulfb, carboxyl, methyl, methoxy, chlorine andlor by a radical of the formula H3, COOH N -N=N 1 N (S03%-2 OH (8).

A further group of preferred reactive dyes according to the invention includes compounds of the formula (1) in which A, is a radical of the aforementioned formula (1 a), (4) or (4a) in which R, is hydrogen and R2 is hydrogen or Cl-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato, R', R3'and RS'are each hydrogen, Wis -0-, and alk, alk' and Z each are as defined above, and A2 independently has the meaning of A, or is phenylamino which is unsubstituted or substituted by sulfb, chlorine, methoxy, carboxyl or a radical of the aforementioned formula (2), (2a) or (3).

- 12 Q defined as an alkyl radical can be Cl-C6alkyl which is unsubstituted or substituted, for example, by Cl-C4alkyl, Cl-C4alkoxy, halogen, nitro, cyano, Cl-C4alkoxycarbonyl, Cl-C4alkylstilfonyl, sulfo or trihalomethyl. In this case, the alkyl radical is preferably unsubstituted.

Q defined as an alkoxy radical can be Cl-C6alkoxy which is unsubstituted or substituted, for example, by Cl-C4alkyl, Cl-C4alkoxy, halogen, nitro, cyano, Cl-C4alkoxycarbonyl, Cl-C4alkylstilfonyl, sulfo or trihalomethyl. In this case, the alkoxy radical is preferably unsubstituted.

Q defined as an alkylthio radical can be Cl-C6alkylthio which is unsubstituted or substituted, for example, by Cl-C4alkyl, Cl-C4alkoxy, halogen, nitro, cyano, Cl-C4alkoxycarbonyl, Cl-C4alkylsulfonyl, sulfo or trihalomethyl. In this case, the alkylthio radical is preferably unsubstituted.

Q defined as an amino radical can be the radical -NH2 or a ClC6alkylamine which is unsubstituted or substituted, for example, by ClC4alkyl, Cl-C4alkoxy, halogen, nitro, cyano, Cl-COLkoxycarbonyl, ClC4alkylsulfonyl, sulfo or tdhalomethyl. In this case, the alkylamino radical is preferably unsubstituted.

Q is preferably a methyl, methoxy or methylthio radical.

A particularly preferred embodiment of the dyes according to the invention relates to compounds of the formula (1) in which Q is a methyl radical.

The compounds of the formula (1) can be prepared in a manner known per se, for example by reacting a diazo component of the formula D-NH2 (10) or its precursor with a compound of the formula N 0-/ 1 N- A, (11) A2 or its precursor by diazotisation and coupling to give reactive dyes of the formula (1), or converting the intermediates obtained into the desired final dyes, and if desired a further conversion reaction is added; in this case the definitions and preferences above apply to D, Ap A2 and Q.

The diazotisation of the compounds of the formula (10) and the coupling with the compounds of the formula (11) are in this case each carried out by the customary methods.

The compounds of the formula (10) which have no reactive radical are known or can be prepared by methods known per se. Compounds of the formula (10) which contain areactive radical are known, for example, from European Patent Applications No. 144 766, 174 909, 208 655 or 214 093 or can be prepared analogously thereto.

The compounds of the formula (11) are new in some cases; they can be prepared, for example, by reacting a compound of the formula N C)--, N Hal (12) Hal with an amine of the formula R, \ NH (1 a) R2 to give the compound of the formula A 1 N Q--/ N- Hal (13) and subsequently reacting this with a further amine of the formula (1 a) to give the compound of the formula (11). In the formulae (12), (1 a) and (13), Q, R,, R2 and A l each are as defined above and Hal is halogen, for example bromine and in particular chlorine.

The reaction of the compounds (12) and (1a) is preferably carried out in a polar solvent, those suitable being, for example, Cl-C4alkanols, for example methanol or ethanol, glycols and glycol ethers such as ethylene glycol or ethylene glycol monomethyl ether or dimethyl ether, formamides such as N,N-dimethylformamide and in particular water, mixtures of several solvents are also suitable. The reaction temperature is about 50 to 15TC and preferably 60 to 100'C.

The components of the formulae (12) and (1a) can be employed in a stoichiometric ratio, but an excess of the component (1a) often proves more favourable.

The reaction of the compounds of the formula (13) with a further amine of the formula (1a) is preferably carried out in one of the abovementioned solvents at a temperature above 100'C. The temperature is normally between 120 and 2SO'C and preferably between 140 and 20WC. The reaction step can be carried out in an open vessel under normal pressure or, preferably, in a closed vessel (autoclave) under autogenous pressure. The components (13) and (1a) can be employed in stoichiometric amounts; but the amine of the formula (1 a) is preferably present in an excess of up to 5-fold, based on the compound of the formula (13).

The amines of the forTnula (1a) on which the radicals A, and A2 in formula (11) are based can be identical or different.

Where A, and A2 are radicals of different amines, the two-step route for the synthesis of the compounds of the formula (11) described above is preferably chosen and in this case the components are employed in approximately stoichiometric amounts; however, an excess of amine of the formula (1a) often proves more favourable.

Where A, and A2 are each the radical of an identical amine, the compounds of the formula (11) can advantageously be prepared in one step by reacting the compound of the formula (10) with an appropriate excess of amine of the formula (1a).

The compounds of the formula (12) are known, for example, from EP-A 55 693 or can be prepared analogously thereto.

Compounds of the formula (1 a) which have no reactive radical are likewise known or can be prepared in a manner known per se. Amines of the formula (1a) which have a reactive radical are known, for example, from the aforementioned EP-A- 144 766, 174 909, 208 655 or 214 093 or can be prepared analogously thereto.

If desired, appropriate precursors are used instead of the diazo component of the formula (10) and/or the coupling component of the formula (11) in the preparation of the compounds of the formula (1) and the final dye is finished by a further diazotisation and/or coupling or other conversion reactions with the intermediate.

A modified embodiment of the process consists in first preparing a dye which contains a precursor of the reactive radical and subsequently converting this into the final stage, for example by esterification or an addition reaction. For example, a dye in which Z is a radical HO-CH2-CH2can be prepared and the intermediate can be reacted with sulfuric acid before or after acylation so that the hydroxyl group is converted to the sulfato group; or an analogous dye is used in which Z is the group H2C=CH, and thiosulfuric acid is added to the intermediate, a radical H03SSCH2CH2- resulting. The sulfation of the hydroxyl group in a dye of the formula (1) or a suitable precursor is carried out, for example, by reaction with concentrated sulfuric acid at O'C to moderately elevated temperature. The sulfation can also be carried out by reaction of the hydroxy compound with two equivalents of chlorosulfonic acid per hydroxyl group in a polar organic solvent, for example N-methylpyrrolidone, at 10 to 80T. The sulfation is preferably carried out by introducing the compound in question in sulfuric acid monohydrate at temperatures between 5 and 15T. The introduction of similar groups, for example a thiosulfato or phosphato group, is carried out in a manner known per se.

Elimination reactions can additionally be added to the synthesis. For example, reactive dyes of the formula (1) which contain sulfatoethylsulfonyl radicals can be treated with hydrogen halide-cleaving agents, such as sodium hydroxide, the sulfatoethylsulfonyl radicals being converted to vinylsulfonyl radicals.

A further subject of the invention relates to compounds of the aforementioned formula (11) in which Q, A, and A2 each are as defined above, with the proviso that A, andlor A2 contains a reactive radical. Suitable reactive radicals are, for example, evident from the explanations made previously.

The dyes of the formula (1) according to the invention are fibre-reactive. Fibre-reactive dyes are understood as meaning those which are able to react with the hydroxyl groups of the cellulose or with the reactive centres of natural or synthetic polyamides with the formation of covalent chemical bonds.

The reactive dyes of the formula (1) are suitable for dyeing and printing all types of materials, such as silk, leather, wool, polyamide fibres and particularly cellulose-containing fibre materials of any type. Examples of such fibre materials are the natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The reactive dyes according to the invention are also suitable for dyeing or printing fibres containing hydroxyl groups, which are present in blended fabrics, for-example blends of cotton with polyester fibres or polyamide fibres.

The dyes according to the invention can be applied to the fibre material and fixed to the fibre in various ways, in particular 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, according to which the material is impregnated with aqueous dye solutions which may contain salts, and the dyes are fixed after an alkali treatment or in the presence of alkali, if desired with the action of heat. They are particularly suitable for the so-called cold pad-batch process, according to which the dye is applied to the pad together with the alkali and then fixed by storing at room temperature for several hours. After fixing, the dyeings or prints are rinsed thoroughly with cold and hot water, if desired with the addition of an agent having a dispersing action and promoting the diffusion of the unfixed portions.

The reactive dyes according to the invention are distinguished by high reactivity, good fixing power and a good build-up power. They can therefore be employed by the exhaust dyeing process at low dyeing temperatures and only require short steaming times in the pad-stearn process. The degrees of fixing are high, and the unfixed portions can easily be washed out, the difference between degree of exhaustion and degree of fixing being remarkably small, i.e. the soap loss being very low. The reactive dyes according to the invention are also particularly suitable for printing, especially on cotton, but likewise also for printing nitrogen-containing fibres, for example wool or silk or blend fabrics which contain wool or silk.

The dyeings and prints on cellulose fibre materials produced using the dyes according to the invention have a high colour strength and a high fibre-dye bond stability, both in the acidic and in the alkaline range, and furthermore have a good light fastness and very good wet fastness properties, such as fastnesses to washing, water, sea water, overdyeing and perspiration, and also a good fastness to pleating, fastness to ironing and fastness to rubbing. The very good chlorine fastness of the reactive dyes according to the invention is to be emphasised in particular; the compounds of the formula (1) moreover show virtually no phototropy at all.

The following examples serve to illustrate the invention. The temperatures are given in degrees Celsius, parts are parts by weight, the percentages relate to percentages by weight, if not stated otherwise. Parts by weight are to parts by volume in the ratio of the kilogram to the litre.

Example 1: The hydrochloric acid-diazotised solution of 27.0 parts of 2(4'-aminophenylsulfonyl)ethyl hydrogen sulfate is added and coupled at 0 to 10T and pH = 6 to 7 to a solution of 43.4 parts of 4,6-bis(2'sulfatoethylamino)-2-methylpyrimidine. The yellow monoazo dye is isolated; it has the formula W-(CH2)2-OSO3H N H3C -/ N=N S02-CH2CH2-OSO3H (201) N --0- NW(CH2)2-OSO3H and dyes cellulose fibres in golden yellow shades.

Example 2: The dye mentioned in Example 1 is vinylated for 30 minutes at room temperature and pH 10. The pH is returned to 6.0 with hydrochloric acid. The monoazo dye is isolated; it has the formula NW(CH2)2-OSO3H N H3C N=N--- S02-CH=CH2 (202) N- NW(CH2)2-OSO3H Example 3: 33.6 g of the primary condensation product of 1 mol of cyanuric chloride and 1 mol of 1,3-diaminobenzene-4sulfonic acid are stirred in 300 mI of water, 300 g of ice and 30 mI of 30 % hydrochloric acid and diazotised at 0 to ST using 6.9 g of sodium nitrite. The congo- acid diazonium suspension obtained is adjusted to a pH of 6.5 with sodium carbonate solution and then added to a solution of 42 g of 4,6-bis(2- sulfatoethylamino)-2rnethylpyrimidine in 900 mI of water and 20 g of sodium carbonate. After coupling has ended, the dye is precipitated by addition of sodium chloride, filtered, washed with sodium chloride solution and dried at 40T in vacuo. The monoazo dye thus obtained of the formula cl / NH S03H N 1 N cl W-(CH2)2-OSO3H (203) N=N N H03SO-(HA2-NH N CH3 dyes cellulose fibres in yellow shades.

Example 4 33.6 g of the primary condensation product of 1 mol of cyanuric chloride and 1 mol of 1,3-diaminobenzene-4-sulfonic acid are stirred in 300 mI of water, 300 g of ice and 30 mI of 30 % hydrochloride acid and diazotised at 0 to 5'C using 6.9 g of sodium nitrite. The congo-acid diazonium suspension obtained is adjusted to a pH of 6.5 with sodium carbonate solution and thereafter added to a solution of 42.2 g of 4,6bis(2'-sulfatoethylamino)-2-ethylpyrimidine in 900 mI of water and 20 g of sodium carbonate. After coupling has ended, 22.4 g of 8-(B'chloroethylsulfonyl)ethylamine hydrochloride are added and the reaction solution is allowed to condense at room temperature and pH 7.0-7.5 for 3 hours.

t The dye is precipitated by addition of sodium chloride, filtered, washed with sodium chloride solution and dried at 4WC in vacuo. The monoazo dye thus obtained of the formula cl N)"' N Cl-(HP2-02S-(HP2-NH N jL- NH-1 SO3H NW(CH2)2-OSO3H (204) - N N=N C2H5 N NW(CH2)2-OSO3H dyes cellulose fibres in yellow shades having very good fastness properties.

Example 5: 23 g of 1-acetamido-3-aminobenzene-4-sulfonic acid are dissolved in 200 mI of water under neutral conditions and diazotised with 6.9 g of sodium nitrite and 30 ml of 30 % hydrochloric acid at 0 to YC. The congo-acid diazo suspension obtained is adjusted to a pH of 4.5 with sodium carbonate solution and then added to a solution of 33 g of 4-amino6-(3'-sulfophenylamino)-2-methylpyrimidine in 800 nil of water and 15 g of sodium bicarbonate. After coupling has ended, the dye solution is treated with sodium hydroxide so that a 5 % sodium hydroxide solution results, and warmed to 70 to WC until the acetamido group is completely hydrolysed. The reaction solution is then cooled and neutralised with concentrated hydrochloric acid, and the dye is precipitated completely by addition of sodium chloride. After filtering and washing with dilute sodium chloride solution, the aminomonoazo dye thus obtained is dissolved in 400 nil of water. A solution of 21 g of 2,4,5,6-tetrachloropyrimidine in 50 nil of acetone is added dropwise at 7WC to this dye solution and the pH is maintained at 6 to 7 by simultaneous addition of sodium carbonate solution. After condensation has ended, the dye is precipitated by addition of sodium chloride, filtered and washed with sodium chloride solution. After drying in vacuo the moneazo dye of the formula N NH S03H NH (205) cl cl N=N N SO3H NH2 N CH3 cl is obtained which dyes cellulose fibres in yellow shades.

Example 6 33 g of 4-ainino-6-(3-amino-4'-sulfophenylarnino)-2methylpyrimidine are dissolved in 1000 mI of water at a pH of 8, after which the solution is cooled to 0 to 5'C. A solution of 24 g of 2,4dichloropyrimidine-5-carbonyI chloride in 100 mI of acetone is added dropwise at this temperature in the course of 30 minutes and the pH of the reaction mixture is maintained at 7 to 8 by addition of sodium carbonte solution. As soon as unchanged amino compound can no longer be detected, the reaction mixture is treated with 30 g of sodium bicarbonate and a solution of 17.3 g of diazotised 1-aminobenzene2-sulfonic acid is then allowed to flow in. After coupling has ended, the reaction mixture is clarified, the reaction solution is then treated with sodium chloride, and the precipitated dye is filtered off and washed with sodium chloride solution. After drying in vacuo at 4TC, the monoazo dye of the formula SO3H NH-Q- SO3H e-N=N- N NH2 N CH3 In NHCO- \- Cl (206) - N cl is obtained which dyes cellulose fibres in yellow shades.

Example 7: 54.1 g of the dye of the formula NH N=N N NH2 NH2 N OCH3 SO H SO3H (207a) (obtained by coupling diazotised 1-aminobenzene-2-sulfonic acid with 4- amino6-(3'-amino-6'-sulfophenylamino)-2-methoxypyrimidine) are dissolved in 1000 nil of water under neutral conditions. A solution of 23 g of 2,4- dichloropyrimidine-5-carbonyl chloride in 50 nil of acetone is added dropwise at 0 to 10T to this dye solution and the pH is kept at 6 by simultaneous addition of sodium carbonate solution. The reaction mixture is stirred until diazotisable arnino groups are no longer detectable, 12. 6 g of sodium sulfilte are added at room temperature and the mixture is stirred until the pH no longer changes. The newly formed dye is salted out with sodium chloride, filtered off, washed with sodium chloride solution and dried in vacuo at 40 to SO'C.

The monoazo dye of the formula S03H SO3H NH cl =N N N NHCO cl W2 N OCH3 (207b) is obtained which dyes cotton in wet-fast yellow shades by the processes customary for reactive dyes.

Example 8: 67.1 g of the aminoazo dye of the formula S03H NH N=N N NH2 NH2 N CH3 S03H SO3H (208a) (obtained by coupling diazotised 2-naphthylamine-1,5-disulfonic acid with 4-amino6-(3'-amino-6'-sulfophenylamino)-2-methylpyrimidine) are dissolved under neutral conditions as the sodium salt in 1000 mI of water. A solution of 29 g of 2,3-dichloroquinoxaline-6-carbonyl chloride in 50 mI of acetone is added dropwise at 4TC to this dye solution and the pH is kept at 7 by simultaneous addition of sodium carbonate solution. After condensation has ended, the dye is precipitated by addition of sodium chloride, filtered and washed with sodium chloride solution. After drying in vacuo at 4TC, the monoazo dye of the formula S03H S03H NH N N=N_ NHCOcl WCN." CH 2 3 cl 03H is obtained which dyes cellulose fibres in golden yellow shades.

(208b), Example 9: 38.3 g of 2-naphthylwnine-1,5,7-trisulfonic acid are dissolved in 300 mI of water under neutral conditions and diazotised at 0 to 5 T with 25 mI of 30 % hydrochloric acid and 6.9 g of sodium nitrite. The diazonium solution neutralised to a pH of 4.5 with sodium carbonate is then allowed to flow into a suspension of 39 g of 4-cyclohexylamino-6-(3'nitrophenylarnino)-2-methylpyrimidine in 900 mI of water and 20 g of sodium bicarbonate. After coupling has ended, the pH of the dye solution is increased to 9 and a solution of 14 g of sodium sulfide in 100 nil of water is then allowed to drip in slowly at 70 to SOT. The mixture is reduced at this temperature until nitro compound is no longer detectable, and the cooled dye solution is treated with 40 g of sodium bicarbonate and freed from precipitated sulfur. The dye is completely precipitated by addition of sodium chloride, filtered, washed with sodium chloride solution and then dissolved in 700 mI of water again. After addition of 20 g of 2,4,5,6- tetrachloropyrimidine, the solution is heated to 80 to 90C and condensed at this temperature until free amino groups are no longer detectable. After cooling, the novel dye is completely precipitated by addition of sodium chloride, filtered, washed with sodium chloride solution and dried at 60 to 7WC in vacuo. The monoazo dye of the formula SO3H NH- ,P N-' H03S N=N N NH---( \\\\IN (209), N N CH3 SO3H H3 cl cl is obtained which dyes cellulose fibres in golden yellow shades.

Example 10: 65.0 g of the aminomonoazo dye of the formula cl N NH S03H N NH2 NH SO3H N=N_ N NH2 NH2 N CH3 (obtained by coupling diazotised 1-amino-3-[2'-chloro4'-aminotriazinyl- (6')-aminolbenzene-6-sulfonic acid with 4-amino-6-(3'-amino-4'- sulfophenylamino)-2-methylpyrimidine) are suspended in 1000 nil of water and the suspension is diazotised at 0 to IOT with 30 nil of 30 % hydrochloric acid and 6.9 g of sodium nitrite. The diazonium suspension obtained is then allowed to flow into a solution of the sodium salt of 25. 4 g of P(4'-sulfophenyl)- cl (210a) 3-methyl-5-pyrazolone in 200 mI of water and 30 g of sodium bicarbonate. After coupling has ended, the dye is precipitated by addition of sodium chloride, filtered off and washed with dilute sodium chloride solution.

After drying in vactio at 4TC, the bisazo dye of the formula 4 cl / - N N \-NH 503H NH SO3H N=N 11.IN NH2 N=N-C-C-CH (210b), 1 11 W2" N -51, CH3 HOC N 11 N 01 S03H is obtained which dyes cellulose fibres in yellow shades.

Examples 11-143: Analogously to Examples 1-10, the dyes listed in the following tables 1-10 are obtained, which dye cotton in the shade indicated.

Table

Ex ample Shade No.

M-(CH2)2-OSO3H S 11 C2H5 -/X/ N \ N=N: S02-CH=CH2 Yellow N M-(CH2)2-OSO3H M-(CH2)2-OSO3H 12 C3H7 / N N=W-PS02-CH 2CH2C1 Yellow N NHCH3S03H NW(CH2)2-OSO3H _\,N 13 H N=N S02-CH=CH2 Yellow N- -0NW(CH2)2-OSO3H H03S NH2 N 14 C4H9 --/ N=N- YNH - C-(CH2)3-SO2CH=CH2 Yellow N- 11 0 NW(CH2)2-OSO3H NW(CH2)2-OSO3H N 0 II CH30 N=NC-NW(CH2)2-SO2-(CH2)2-ClYellow N - -Q, H03S W-(CH2)2-OSO3H NW(CH2)2-OSO3H N 16 CH3S --/ N=N Yellow Nc-NH-(CH2)2-SO2-(C'H2)2-OSO3H 11 0 NW(CH2)2-OSO3H Table 1: (Continuation) Example No.

17 18 19 21 Shade NW(CH2)2-0-(CH2)2-0H SO3H N H2N --/ N=N S03H Yellow N 1 t NH- C-(CH2)3-SO2-CH=CH2 AI 0 W-(CH2)2-0-(CH2)2-0H NH2 SO3H N C2H50 --/ N=N-0^-- SO3H Yellow N NH- C-(CH2)3-SO2-CH=CH2 NH-CM 98 0 NW(CH2)2-0H S03H N C2H5S N=N SO,H NW(CH2),-SO2-CH=CH2 Yellow NH- C M-(CH2)2-0H 0 M-(CH2)2-OSO3H S03H N H --/ N=N0_ Yellow N NH- C-(CH2)3-SO2-CH=CH2 AI 0 NW(CH2)2-OSO3H M-(CH2)2-OSO3H SO3H N Yellow C3H70 N=N NH C-(CH2)3-SO2-(CH2)2-Cl N 0 NW(CH2)2-OSO3H Table 1: (Continuation) Ex ample Shade No.

NW(CH2)3-OS03H N 7 \ Golden 22 H3C N=N-, C-NW(CH2)2-SO2-CH=CH2 yellow N 3-11 0 NH-(CH2)3-OSO3H NW(CH2)2-OS03H N SO3H Golden 23 CH3HN N=N yellow N NH-CA S02-(CH2)2-OSO3H NW(CH2)3-OS03H SO3H N N=N Golden 24 C2H5HN / yellow N - 1 NH2 S02-CH=CH2 NW(CH2)2-OS03H H5C N OCH3 Orange CH/ N=WO N- H3C/ S02-CH=CH2 W-(CH2)2-OS0:3H NW(CH2)2-OS03H N OCH3 26 H3C --/ N=N-Q- S02-CH=CH2 Orange N CH3 W-(CH2)2-OS03H W-(CH2)2-OS03H OCH3 N 27 H5C2 N=N C-NH-(CH2)2-SO2-CH=CH2 -01 Orange N 0 W-(CH2)2-OS03H Table_1. (Continuation) Ex amplc: Shade No.

NW(CH2)2-OS03H N Golden 28 H3CS --/ N=N C-NW(CH2)2-SO2-CH=CH2 yellow N -0-11 C] 0 W-(CH2)2-OS03H NW(CH2)2-OS03H Br N 29 H5C2S N=N S02-(CH2)2-OSO3H Yellow N NW(CH2)2-OS03H W-(CH2)2-OS03H H3C, N S02-CH=CH2 CHHN-/ N=N Orange H,C' N S03H W(CH2)2-OS03H NW(CH2)2-OS03H S02-(CH2)2-OSO3H N 31 H3C -/ N=N Orange N 1 NW(CH2)2-OS03H N NW(CH2)2-OS03H 0 (CH2)2-SO2CH=CH2 Golden N=N- 0 - CH l& NI 32 H3C --/ 2'C yellow N (CH2)2-SO2CH=CH2 NW(CH2)2-OS03H NW(CH2)2-OS03H N SO3H 33 H3C --/ N=N cl Golden N Q F yellow NH- Y1 N, N NH-(CH2)2-OS03y F Table 1: Continuation) Ex ample Shade No.

W-(CH2)2-OS03H N SO3H Golden 34 H -/ N=N yellow N N O-CH3 Y, NW(CH2)2-OS03H Nz,, N y cl NW(CH2)2-OS03H N S03H H5C2-/ N=N-NH NH--0 Golden N- N N yellow NW(CH2)2-OS03H cl N NH2 S 3H N 0 -CH / CH3 36 H3C N=N-Q NH--1 Y1 Orange N- N, N CH3 NH2 S03H Y cl NH-CM S03H N N=N 2 - NHC-(CH2)2-SO2-CH=CH2 Orange 37 H3C -/ -0 11 N 0 S03H NH-CA Table 1: (Continuation) Ex ample Shade No.

S02CH3 NH-CH2CH2-OSO3H cl NH Yellow 38 H5C2 N=N Y N cl H03S NH-CH2CH2-OSO3H W-(CH2)2-OS03H S02CH3 N yHN-Q 39 H3C N=N Orange N N N C=0 H03S 1 cl NH NH-(CH2)2-OSO3H 1 kk 1;yV2 S02 1 kk;t12)2-US03H NW(CH2)2-OS03H N SO3H H,9C N=N-N=bN-. S02-CH=CH2 Brown NH NW(CH2)2-OS03H =0 CH3 NW(CH2)2-OS03H NH-CO-(CH2)3-SO2-CH=CH2 N 41 H3C --/ N=N--0- -N=N-OS02-CH=CH2 Brown N H03S NW(CH2)2-OS03H Table 1: (Continuation) Ex ample Shade No.

NW(CH2)2-SO2-(CH2)2-OS03H cl 42 N H03S N)"'N Orange H3C0 --/ N=N N H N N NWC2H4-OS03H NW(CH2)2-SO2-CH=CH2 NH-(CH2)2-SO2-(CH2)2-OSO.9H H03S N F 43 H -/ N=N Golden N- N:k N yellow NH-CH3 NH--1z:N 'J1,' N H-Q S03H NW(CH2)2-SO2-(CH2)2-OS03H N 44 H3C --/ N=N Yellow N S03H NW(CH2)2-OS03H NW(CH2)2-SO2-(CH2)2-OS03H H03S N HAS N=N Golden N yellow NH2 SO3H Table 1,.. _(Continuation) Ev- ample No.

W-(CH2)2-SO2-(CH2)2-OSO3H N CH3HN N=N SO3H 46 N H03S W-(CH2)2-SO2-(CH2)2-OSO3H NH-O- S02-CH2-CH2-OSO3H H03S N 47 H N=N N SO3H NH-(CH2)2-0-(CH2)2-S02-CH2-CH2-OSO3H NW(CH2)2-SO2-CH=CH2 N S03H 48 H3C / N=N N 1 H03S SO3H W-(CH2)2-SO2-CH=CH2 CH2=CH2-SO2-(CH2)2-HN H03S N 48a H3C / - N=N N - 1 CH2=CH2-SO2-(CH2)2-M SO3H CH2=CH2-SO2-(CH2)2-M SO3H N 48b H3C - N=N N CH2=CH2-SO2-(CH2)2-M SO3H Shade Yellow Golden yellow Golden yellow Yellow Yellow - 33 Table 2:

Ex- M-CH2-CH2-OSO3H ample SO3H No. N cl H3C --/ N:- N -0 N WkN N A NH-CH2-CH2-OSO3H A Shade 49 -NH-(CH2)2-SO2-CH=CH2 Golden yellow -NW(CH2)3-SO2-CH=CH2 Golden yellow 51 -NH-(CH2)2-0-(CH2)2-SO2-CH=CH2 Golden yellow 52 -N /CH2-CH2-SO2-CH=CH2 Golden yellow CH2-CH2-SO2-CH=CH2 53 - N \--/ W(CH2)3-SO2-(CH2)2-Cl Golden yellow 54 -NH-- S02-(CH2)2-OSO3H Golden yellow NH-Q Golden yellow 02 2 -CH=CH 56 NH-O- C NW(CH2)2-SO2-CH=CH2 Golden yellow NH-Q Golden yellow 57 C-NW(CH2)2-SO2-(CH2)2-OSOP 11 0 58 NH-Q Golden yellow S02-CH2-CH2-OSOP Table 1._(Continuation) Ex- NH-CH ample 2-CH2-OSO3H No. S 3H N cl H3C -/ N:N N -- -o N:kN N W----1,, N LA NH-CH2-CH2-OSO3H A Shade -NH-CH2W(CH2)3-SO2-CH=CH2 Golden yellow 102-CH=CH2 59 -NH-(CH2)2-NH-(CH2)2-S02-CH=CH2 Golden yellow CH3 61 1 Golden yellow _W(CH2)2-SO2-CH=CH2 62 -NH-(CH2)5-SO2-CH=CH2 Golden yellow 63 _<CH2)3-SO2-CH=CH2 Golden yellow CH2)3-SO2-CH=CH2 64 -N \-i 0 Golden yellow Table 3:

Ex- NW(CH ample 2)2-OSO3H No. SO3H N F H3C -/ N:- N -0 N N N NH------, N A NW(CH2)2-OSO3H A Shade -NW(CH2)2-CO2-CH=CH2 Golden yellow 66 -NH-(CH2)2-0-(CH2)-SO2-CH=CH2 Golden yellow CH3 67 1 Golden yellow W(CH24-SO2-CH=CH2 68 CH2) 2-SO 2-CHCH2 Golden yellow (CH 2) 2 _SO2 _CH=CH2 69 _NH-CH2- W(CH2)3-SO2-CH=CH2 Golden yellow S02-CH=CH2 -NH-(CH2)5-SO2-CH=CH2 Golden yellow 71 -NH-(CH2)2-NH-(CH2)2-SO2-CH=CH2 Golden yellow 72 N \-i N - (CH2)2-SO2-CH=CH2 Golden yellow 73 -NH -Q Golden yellow S02-CH=CH2 C2 74 1 -N S02-CH=CH2 Golden yellow Table 3: (Continuation) Ex- NW(CH H ample 2)2-OS03 No. SO3H H3C N:N -o N:kN NW-L,, N L A NW(CH2)2-OSO3H A Shade -NH Golden yellow NHC-(CH2)3-SO2-CH=CH2 11 0 -NH 76 -Q Golden yellow C - NW(CH2)2-S02-CH=CH2.

11 0 0 77 11 Golden yellow -NH -C- CH2- C-NW(CH2)2-SO2-CH=CH2 H03S 78 -NH Golden yellow S02-CH=CH2 C2 Golden yellow 1 79 -N Table 4:

Ex ample H03S No. cl S03H NH N J''N N=N N A N H2NN CH3 SO3H A Shade -NH-CH2-CH2-SO2-CH2-CH2-Cl Golden yellow 81 -0-CH 'AH3 Golden yellow \CH3 82 -NH- S02-CH=CH2 Golden yellow 83 -N I CH2-CH2-SO2-CH=CH2 Golden yellow "-,CH2-CH2-SO2-CH=CH2 84 -NH -Q C-NH-CH2-CH2-SO2-CH=CH2 Golden yellow 11 0 Table 5:

Ex- S03H ample NH S03H No.

N=N N N -%rk NH-r:,-, N '[I- A H2N CH3 N N cl A Shade -NH Yellow S03H 86 -NH-CH2-CH2-0-CH2-CH2-SO2-CH=CH2 Yellow 87 -NH-CH2 H-CH2-CH2-CH2-SO2-CH=CH2 Yellow 102-CH=CH2 -NH 88 -Q Yellow S02-CH2-CH2-OSO3H C2H5 1 89 -N Q- Yellow S02-CH=CH2 0 11 -NH -0C-NH-CH2-CH2-SO2-CH=CH2 Yellow Table 6:

Ex- SO3H ample No. F S03H NH N=N_ N A 1 NH N CH3 1 SO3H t12 CH3 A Shade C2H5 91 -N Golden yellow 92 -NW(CH2)2-SO2-CH=CH2 Golden yellow 93 -NW(CH2)5-SO2-CH=CH2 Golden yellow 94 -NH-(CH2)2-0-(CH2)2-SO2-CH=CH2 Golden yellow - N 0 Golden yellow 96 -HN SO3H Golden yellow 97 -NH S02-CH2CH2C1 Golden yellow 0 11 98 -HN C-NW(CH2)2-SO2-CH=CH2 Golden yellow 99 -HN -Q C-NW(CH2)2-SO2-CH=CH2 Golden yellow Table. (Continuation) Exampl No.

101 102 103 104 SO3H SO3H NH _ N=N-".f t, N F N':kN NH 1 N-;k CH H --- tz, N L- A 1 SO3H UN2 H, Shade -NH -Q N H- C-(CH2)3-S02-CH=CH2 11 0 Golden yellow 0 11 -HN --..IH2 - C-NH-(CH2)2-SO2-CH=CH2 Golden yellow -NH -Q S02-CH=CH2 Golden yellow C2H5 1 -N S02-CH=CH2 Golden yellow -NH-(CH2) -0S02-CH2=CH2 Golden yellow Table 7:

Ex ample S03H NH- No. H03S N=N_ NQNWA NH N':'kCH3 1 S03H t'2 CH3 A Shade F N N Orange N - NH-CH2-CH2-OH cl 106 N ';:k N Orange N NW(CH2)2-SO2-CH=CH2 cl 107 y, N z, N Orange y F S02CH3 108 y, cl Orange N z, N "Y cl y, SCH3 109 N zt, N Orange T cl Table 7: Continuation) Ex ample SO3H NH No. H03S N=NI NQW-A N ' H NI:.kCH3 1 S03M CH2 H3 A Shade N NH-0 Orange N, N y cl 111 N v, NH-0- S02-CH=CH2 Orange N N v F N cl 112 N_ N Orange y cl Table 8:

Ex- A-NH S03H ample NH No.

P N=N N S03H H2N N OCH3 A Shade H2C=HC-02S-(H2C)2-0-(H2C)2-HN y N 113 N N Yellow F H2C=HC-02S HNyN, 114, 1 _ Yellow N N F cl F,,_ 1 Yellow N v N F H2C=HC-OP-(HP2, -- yN,, 116 H2C=HC-02S-(HP2 ", 1 Yellow N ly N F H N N,' 117 1 Yellow H2C=HC-02S N ly N cl H3 N YN,_1 118 Yellow N N F H03S-(HP2-M y N Yellow 119 N N y F Table 9:

Ex- A-HN SO3H NH H ample S03 No. -Q COOH WN-: N J1 / 1 N=N-C-C H2N N SCH3 HO' C, N' N S03H A Shade HO-(H2C)2-M y N 'I, N N Yellow Cl H2c=HC-OP-(HP2 N 121 H2C=HC-OP-(HP2 Yellow N N cl H2C=HC-02S-(H2C)2-HN N 122 N:t, N y Yellow F 123 H2C=HC-02S -O-HN "Y N N N Yellow F cl F,1.

124 1 Yellow N I N F CH3 H6HC N 1 Y II Yellow CH3 N K N cl 126 H2C=HC-02S-(H2C)2- Yellow Table 10:

Ex ample Shade No.

NW(CH2)2-OSOP 127 C2H50 N N=N S02-(CH2)2-OSO3H Golden yellow N NW(CH2)2-OSO3H NW(CH2)2-CH3 128 H N NN-QS 5C2 -/ _ Golden yellow N O-CH=CH2 NW(CH2)2-OSO3H W-(CH2)2-OSO3H S03H N Golden yellow 129 H3C --/ N=N-O N NH- C-(CH2)3-SO2-CH=CH2 11 NW(CH2)2-OSO3H 0 NW(CH2)2-OSOP N 0 H5C2 --/ - N=N-0- C$$-NW(CH2)2-SO2-CH=CH2 Golden yellow N NH S03H NW(CH2)2-OSO3H 131 H3 0 N S03H \CH-/ N=N S02-CH=CH2 Golden yellow H3C N W-(CH2)2-OSO3H NW(CH2)2-OSO3H N 0 11 132 H N=N C-NW(CH2)2-SO2-CH=CH2 Golden yellow N - -Q- S03H H-CH3 Table 10: (Continuation) Ex ample Shade No.

W-(CH2)2-OSO3H N HP N=N- S02-CH=CH2 N 133 NH SO3H Golden yellow &SO3H NH-(CH2)3-SO2-(CH2)2-OSO3H H 03S N N= 134 H3C NH NH2 Yellow N N NHCH2CH20H cl NH-(CH2)2-0-(CH2)2-SO2-(CH2)2-OSO3H H 03S N __fl:r N -NHP Yellow H --/ N=N-NH N N N NHCH2CH20H S03H cl NW(CH2)3-S02-(CH2)2-OSOP 136 H N=N NH _fN NHCH2CH2SO3H 3C --/ ' i- Yellow N N N H03S WCH2CHZ0H c NH-(CH2)2-0-(CH2)2-SO2-(CH2)2-OSO3H N H03S 137 H3C0 N=N-NH -I,- N H Yellow H03S N N T SO3H cl NHCH2CH2OCH2CH20H Table 10: Continuation) Ex ample Shade No.

S03H NW(CH2)2-SO2-(CH2)2-OS03H 138 H03S N=N N=N N CH3 Orange -CY -N NHCH2CH20H so 3 H OCH3 NW(CH2)3-SO2-(CH 2) 2-OSOH N 139 WN-0 N=N -OCH 3 Red 0 N HO 3s H3c NHCH2CH2OCH 2 CH20H SO3H OCH3 NW(CH2)3-SO2-(CH2)2-OS03H N N=N_ N=N \- H Red -N H03S S03H NHC2H4 NHCOCH3 Table 10: Continuation) ExampI No.

141 142 143 Shade OH H03S W-(CH2)2-SO2-(CH2)2-OSO3H N N=N N=N \- CH3 Violet N H03Si:: (5SO3H NHCH2CH20H CUPC---SOP - - S02NH2 -rsO2NH-1 S03H NW(CH2)2-SO2-(CH2)2-OSO3H Green N N=N CH3 NHCH2CH20H CUPC (S03% NW(CH2)2-SO2-(CH2)2-OSOP - N S02NH2 N=N- \- CH3 N Green -S02NH NW(CH2)2-SO2-(CH2)2-OSO3H H03S The following reactive dyes are further examples:

SO3H NW(CH2)3-SO2-(CH2)20SO3H N (144) H3C N=N CH3 N NH-(CH2)3-S02-(CH2)2C)S03H H03S Yellow (145) H03 S-CY N=N Yellow NW(CH24-SO2-(CH2)20SO3H N CH3 N W-(CH24-SO2-(CH2PS03H W-(CH2)5-SO2-(CH2)20SO3H N (146) H03S N=N \- CH3 N W-(CH2)5-SO2-(CH2)20SO3H Yellow W-(CH2)2-SO2-(CH2)2-OSO3H N (147) H3C0 N=N \- CH3 --Q- - - N SO3H W-(CH2)2-SO2-(CH2)2-OSO3H Yellow S03H (148) (149) NH(CH2)2S02(CH2)20SO3H N==N /- CH3 - \ N NH(CH2)2S02(CH2)20SO3H SO3H Yellow S03H NH(CH2)2S02(CH2)20SO3H N -N "C NN CH2CH3 H3C S N S03H Golden yellow NH(CH2)2S02(CH2)20SO3H -so- (150) (151) SO3H NH(CH2)2S02(CH2)20SO3H -N H03S -G N=N -d N=N CH2CH3 Orange NH(CH2)2S02(CH2)20SO3H S03H OCH3 NH(CH2)2S02(CH2)20SO3H - N NN NN //\-- CH3 p- --p- -- \ N S03H CH3 NH(CH2)2S02(CH2)20SO3H Scarlet 0e, NH(CH2)2S02(CH2)20SO3H _ ONH OH N (152) N=N -5- N=N - />-CH3 N H03S S03H NH(CH2)2S02(CH2)20SO3H Violet SO H NH2 OH NH(CH2)2S02(CH2)20SO3H -N (153) H03S -& NN NN N=N /- CH3 1 N H03S SO^H Navy blue NH(CH 2)2S02(CH 2)20SO3H H03S N N S02- NH S03H NH(CH2)2S02(CH2)20SO3H N - -C N - Cl u- N 1 N 1 N - N S03H S02NH2 (154) Green N N=N l- CH3 - \ N NH(CH2)2S02(CH2)20SO3H SO H NH(CH2)3S02(CH2)20SO3H N N=N CH2CH3 (155) _\ N SO3H (156) (157) (158) NH(CH2)3S02(CH2)20SO3H Yellow SO3H SO3H NH(CH2)3S02(CH2)20SO3H N N=N-?N=N /- CH3 N Red SO3H NH(CH2)3S02(CH2)20SO3H SO3H OCH3 -N N=N N=N /- CH3 1 -0-- \ N H NHCOCH3 H03S S03 Red SO3H NH(CH2)3S02(CH2)20SO3H NH(CH2)3S02(CH2)20SO3H NH(CH2)3S02(CH2)20SO3H - N N=N N=N - CH3 HO JZ-11 3S S03H N(CH2)3S02(CH2)20SO3H Violet 11 C, NH OH (159) N=N N=N -N CH /- 3 N H H03S SO3H NH(CHIS02(CH2)20S03 S 3H Violet NH(CH2)3S0AH2)20SO3H (160) S 3H H03S -0- N=N NH2 OH N=N H03S SO3H Navy blue (161) NH(CH2)3S02(CH2)20SO3H N N=N - -CH 3 N NH(CH2)3S02(CH2)20SO3H SO3H W-(CH2)2-SO2-(CH2)20SO3H N N=N -0- N=N - \-CH3 H03S -N SO3H Scarlet W-(CH2)2-SO2-(CH2)20SO3H S03H NW(CH2)3-SO2-(CH2)20SO3H N (162) N=N -0- N=N --)_ CH3 H03S -N 303H Scarlet - S03H (163) 3 CUPC- S02NH2 -S02-NH-P Green W-(CH2)3-SO2-(CH2)20SO3H W-(CH2)2-SO2-(CH2)20SO3H -N N === N - /- CH3 N NW(CH2)2-SO2-(CH2)20SO3H - - SO3H (164) (165) CUPC - - S02NH2 3 1 S02NH-P Green cupc - W-(CH2)3-SO2-(CH2)20SO3H N N=N - /- CH3 N NW(CH2)3-SO2-(CH2)20SO3H - S03H - S02NH2 S02-NH NW(CH24-SO2-(CH2)20SO3H -p -N NN - >- CH3 N NW(CH24-SO2-(CH2)20SOP Green

Claims

WHAT IS CLAIMED IS:

1. A reactive dye of the formula 1 N 0--- N=N-D N:

A (1), A2 in which D is the radical of a diazo component, Q is hydrogen or a substituted or unsubstituted alkyl, alkoxy, alkylthio or amino radical and A, and A2 independently of one another are a radical of the formula -N / R, R2 (1a), in which R, and R2 independently of one another are hydrogen, substituted or unsubstituted Cl-C6alkyl or substituted or unsubstituted aryl, or R, and R2, together with the N atom, form a heterocyclic 5-membered or 6- membered ring, which may or may not be further substituted, with the proviso that at least one of the radicals A,, A2 or D contains a fibre- reactive group

2. A reactive dye according to claim 1, wherein Q is -NH2 or an unsubstituted Cl-C6alkyl, Cl-C6alkoxy, Cl-C6alkylthio or Cl-C6alkylamino radical.

3. A reactive dye according to claim 2, wherein Q is methyl.

4. A reactive dye according to any one of claims 1 to 3, wherein D is the radical of a substituted or unsubstituted aminobenzene, aminonaphthalene, phenylazoarninobenzene, phthalocyanineaminobenzene, naphthylazoaminobenzene, phenylazbaminonaphthalene or naphthylazoaminonaphthalene.

5. A reactive dye according to claim 4, wherein D is unsubstituted or substituted by Cl-C4alkyl, Cl-C4alkoxy, amino, N-mono- or N,N-di-ClC4alkylarnino - where the alkyl moiety is unsubstituted or substituted by -011, -OCOCH3, -S03H, -OSO3H, -CN or halogen -, phenylamino, ClC4alkanoylarnino, benzamido, Cl-C4alkoxycarbonyl, nitro, cyano, trifluoromethyl, halogen, hydroxyl, carboxyl, sulfo, sulfomethyl, sulfamoyl, N-mono- or N,N-di-CI-C4alkylsulfamoyl, N-phenyIsulfamoyl, carbamoyl, N-mono- or -55N,N-di-Cl-C4alkylcarbarnoyl, ureido, Cl-C4alkylsulfonyl and/or a reactive radical.

6. A reactive dye according to any one of claims 1 to 5, wherein D is substituted by a reactive radical of the formula -SO2-Z (2), - W- alk S02 - Z 1 R (2a) -W-alk-E-aW-S02-Z (2b), - alk - W - alk'- S02 - Z (2c), (2d) - W -arylene - N - alk - S02 - Z 1 1 R3 R (2e), N -N T H5 N,:: N "If X X2 5YX, _r -N 1 H 5 N N 2 X, (3), (5) in which W is a functional group, R3 is hydrogen, Cl-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfb, sulfato, carboxyl or cyano, or a radical of the formula alk - S02 Z, R is hydrogen, hydroxyl, sulfb, sulfato, carboxyl, cyano, halogen, 1 R Cl-C4alkoxycarbonyl, Cl-C4alkanoyloxy, carbamoyl or the group -S02-4 Z'S CH=CH2 or -CH2-CH2-Y, Y is a leaving group, E is -0- or -NR4-, R4 is hydrogen or Cl-C4alkyl, alk and alk' independently of one another are ClC6alkylene, arylene, a phenylene or -56naphthalene radical which is unsubstituted or substituted by sulfb, carboxyl, Cl-C4alkyl, Cl-C4alkoxy or halogen, R5 is hydrogen or Cl- C4alkyl which is unsubstituted or substituted by carboxyl, cyano, hydroxyl, sulfo or sulfato and X is a group which can be eliminated as an anion, T independently has the meaning of X or is a group containing a further reactive radical or is a non-reactive substituent, one of the radicals X, independently has the meaning of X and the other radical X, has the meaning of T and X2 is a negative substituent, or is substituted by a 2,3-dichloroquinoxaline-6-carbonylamino or 2,4-dichloropyrimidine-5carbonylamino radical.

7. A reactive dye according to claim 6, wherein D is substituted by a fibre-reactive radical of the formula (2) or (2a), in which W is a group CONH- or -NHCO-, alk is a Cl-C4alkylene radical and Z has the meaning given in claim 6.

8. A fibre-reactive dye according to claim 6 or 7, wherein Y is a group Cl, -OSO3H, -SS03H, -OCO-CH3, -OCO-C6H5 or -OPO3H2.

9. A reactive dye according to either of claims 6 or 8, wherein D is substituted by a fibre-reactive radical of the formula (3), and X is fluorine, chlorine, bromine, sulfb, Cl-C4alkylsulfonyl or phenylsulfonyl.

10. A reactive dye according to any one of claims 6, 8 or 9, wherein T is a group containing a reactive radical which has the formula R 1 alk - S02 - Z R3 -N - alk - E - alk'- S02 - Z 1 RS (4), (4a), - N - arylene - S02 Z 1 (4b), RS - N - arylene - (alk),F W alk'- S02 - Z 1 (4c) or RS -N /-\ N - alk-S02-Z (4d), in which R, R3, RS, E, W, Z, alk, alk' and arylene have the meaning given in claim 6 and p is 0 or 1.

11. A reactive dye according to claim 10, in which T is a group of the formula 1 -N- alk- S02 - Z 1 R RI (4), - N - alk - E- alk'- S02 - z (4a), R R6 -N-N - S02-Z 1 H5 (4b), R6 -N-N W-alk-S02-Z (40 or M5 -N /--\ N alk-S02-Z (4d), in which Wis -CONRS'or -NRSW-, Wis hydrogen or the group -S02-Z, R3'iS hydrogen, Cl-C4alkyl or the group -alk-SO2-Z, RS'is hydrogen or Cl-COlkyl, Eis -0- or -NH- and R6 is hydrogen, sulfb, carboxyl, chlorine, methoxy or methyl, alk and alk' independently of one another are a Cl-C4alkylene radical and Z has the meaning given in claim 6.

12. A reactive dye according to any one of claims 6, 8 or 9, wherein T, as a non-reactive substituent, is amino, N-CI-C4alkylamino, which is unsubstituted in the alkyl moiety or substituted by hydroxyl, sulfato or sulfb, or is morpholino, phenylamino or -58N-Cl-C4alkyl,N-phenylamino, in which the phenyl is in each case unsubstituted or substituted by sulfb, carboxyl, methyl andlor methoxy.

13. A reactive dye according to claim 6, wherein D is substituted by a reactive radical of the formula (5) given in claim 6, in which X, is chlorine or fluorine and X2 is chlorine, cyano, forinyl or methylsulfonyl.

14. A reactive dye according to any one of claim s 1 to 6, wherein D, is the radical of an aminobenzene or aminonaphthalene which is unsubstituted or substituted by sulfb, acetamido, methyl, methoxy, chlorine or bromine, which is further substituted by a reactive radical of the formula (2), (2a) or (3) given in claim 6.

15. A reactive dye according to any one of claims 1 to 5, wherein D is the radical of an aminobenzene or aminonaphthalene which is unsubstituted or substituted by sulfb, carboxyl, Cl-C4alkoxy, Cl-C4alkyl, ClC4alkanoylamino andlor halogen.

16. A reactive dye according to any one of claims 1 to 15, wherein R, and R2 independently of one another are hydrogen, a Cl-C6alkyl radical which is unsubstituted or substituted by hydroxyl, sulfb, sulfato, carboxyl, cyano, halogen, Cl-C4alkoxycarbonyl, Cl-C4alkanoyloxy, carbamoyl and/or a reactive radical, where the alkyl, with the exception of methyl, may be interrupted by -0- or -NR4- and R4 has the meaning given in claim 6, or is a phenyl or naphthyl radical which is unsubstituted or substituted by sulfb, carboxyl, Cl-C4alkyl, Cl-C4alkoxy, halogen, a reactive radical andlor a group -N=N-K, in which K is the radical of a coupling component of the benzene or naphthalene series or of the heterocyclic series, or R, and R2, together with the N atom, form a piperidinyl, piperazinyl or pyrrolidinyl radical which is unsubstituted or substituted by a radical of the formula -(alk)p-S02-4 in which alk, p and Z have the meaning given in claim 10.

17. A reactive dye according to claim 16, wherein the reactive radical on the phenyl or naphthyl radical R, or R2 is a radical of the formula (2), (2a), (3) or (5) given in claim 6 or the 2,3-dichloroquinoxaline-6carbonylamino or 2,4-dichloropyrimidine-5-carbonylainino radical and the reactive radical on the Cl-C6alkyl radical R, or R2 is the group -S02-Z.

18. A reactive dye according to any one of claims 1 to 17, wherein A, andlor A2 is a group of the formula (4b') or (4e') given in claim 11 or a group of the formula -59R6 -N N B T 1 1 Ir H R5 N:, N 111, X (3a), in which RS, X and T have the meaning given in claim 6, R6 is hydrogen, sulfb, chlorine, methoxy or carboxyl and B is a group - ' _= l 02CH3 9 or is -N=. N

19. A reactive dye according to any one of claims 1 to 17, wherein A, andlor A2 is a radical of the formula (1 a) given in claim 1, in which R, and R2 independently of one another are hydrogen or a C,-C4alkyl radical which is unsubstituted or substituted by hydroxyl, sulfb, sulfato, carboxyl, cyano or the group -S02Z andlor interrupted by -0-, where Z has the meaning given in claim 6.

20. A reactive dye according to claim 19, wherein one of the radicals R, or R2 is hydrogen.

21. A reactive dye according to any one of claims 1 to 20, wherein A, is a radical of the formula (1 a), (4) or (4a) given in claims 1 or 11, in which R, is hydrogen and R2 is hydrogen or Cl-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato, R', R3'and R5'are each hydrogen, Fis -0-, and alk, aWand Z each have the meaning given in claim 11, and A2 independently has the meaning of A, or is phenylamino which is unsubstituted or substituted by sulfb, chlorine, methoxy, carboxyl or a radical of the formula (2), (2a) or (3) given in claim 6.

22. A reactive dye of the formula (1) according to claim 1, in which A, and A2 independently of one another are amino, N-Cl-C4alkylamino in which the alkyl is unsubstituted or substituted by hydroxyl, sulfato or sulfb, or phenylamino in which the phenyl is unsubstituted or substituted by sulfb, carboxyl, methyl, methoxy, chlorine andlor by a radical of the formula CH3, COOH -N -N=N - 1 N (S0A0-2 OH (8') -60D is the radical of an aminobenzene or aminonaphthalene, which is unsubstituted or substituted by sulfb, acetamido, methyl, methoxy, chlorine or bromine and moreover carries a reactive radical of the formula (2), (2a) or (3) given in claim 6, and Q is -NH2 or 0 an unsubstituted Cl-C6alkyl, Cl-C6alkoxy, Cl-C6alkylthio or Cl- C6alkylarnino radical.

23. A reactive dye of the formula (1) according to claim 1, wherein A, is a radical of the formula (1a), (4) or (4a') given in claims 1 or 11, in which R, is hydrogen and R2 is hydrogen or Cl-C4alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato, R', R3' and RS' are each hydrogen, E' is -0-, and alk, alk' and Z each have the meaning given in claim 11, A2 independently has the meaning of A, or is phenylamino which is unsubstituted or substituted by sulfb, chlorine, methoxy, carboxyl or a radical of the formula (2), (2a) or (3) given in claim 6, Q is an alkyl radical which is unsubstituted or substituted by methyl, trifluoromethyl, methoxy, sulfb, nitro, chlorine or bromine, and D is the radical of an arninobenzene or aminonaphthalene, which is unsubstituted or substituted by sulfb, carboxyl, Cl-C4alkoxy, Cl-C4alkyl, Cl-C4alkanoylamino or halogen and may also carry a reactive radical of the formula (2), (2a) or (3) given in claim 6.

24. A process for the preparation of compounds of the formula (1), wherein a diazo component of the formula D-NH2 or its precursor is reacted with a compound of the formula A, N 0-/ N- A2 (10) (11) or its precursor by diazotisation and coupling to give reactive dyes of the formula (1), or the intermediates obtained are converted into the desired final dyes, and if desired a further conversion reaction is added, where D, Ap A2 and Q have the meaning mentioned in claim 1.

25. The use of the reactive dyes according to claim 1 for dyeing and printing cellulose-containing fibre materials.

26. The use according to claim 25 for dyeing and printing cotton.

27. A compound of the formula N 0-/ N - (11) A2 in which Q, A, and A2 have the meaning given in claim 1, with the proviso that A, and/or A2 contains a fibre-reactive radical.

28. A process for the preparation of compounds of the formula (11), wherein a compound of the formula N 0--/ N Hal Hal (12) is reacted with an amine of the formula R, \ NH R2/ (1a) to give the compound of the formula AI N ()-/ 1 N H (13) al and this is then reacted with a further amine of the formula (1 a) to give the compound of the formula (11), where Q, R,, R2 and AI each have the meaning given in claim 1 and Hal is halogen, for exam le bromine, and in particular chlorine.

b p

29. A reactive dye according to claim 1, substantially as described in any of the Examples.