GB2059985A - Triphendioxazine dyes - Google Patents

Abstract

Dyes in the free acid form are of the formula: <IMAGE> wherein TPD represents a (x+n) valent radical of a triphenodioxazine compound having bromo substituents in the 6,13-positions of the triphenodioxazine nucleus x is at least 1 n is q or 2 R<7> is H or an optionally substituted hydrocarbyl group, and Q is H, an optionally substituted hydrocarbyl group or a cellulose reactive group. Dyes are valuable acid or reactive dyes depending on the nature of Q. They are usually blue shades and have good tinctorial power and build up with good fastness properties.

Description

SPECIFICATION Triphendioxazine dyes This invention relates to triphendioxazine dyes particularly 6,1 3-dibromotriphenodioxazine dyes bearing sulphonic acid groups and amino groups which may optionally have a cellulose reactive group as substituent.

Dyestuffs of the triphendioxazine class are well known including reactive dystuffs. Many of these dyes have chloro substituents in the 6,13-positions of the triphenodioxazine nucleus but alternative substituents for these positions are known, e.g. see Offenlegungsschrifts 2823828 and 2355694.

We have now found a novel class of 6,1 3-dibromotriphenodioxazine dyes which often show desirable properties.

According to the present invention there are provided dyes which in the free acid form are of the formula

wherein TPD represents a (x+n) valent radical of a triphenodioxazine compound having bromo substituents in the 6,13-positions of the triphenodioxazine nucleus x is at least 1 n is 1 or 2 R7 is H or an optionally substituted hydrocarbyl group and Q is H, an optionally substituted hydrocarbyl group or a cellulose reactive group. When n is 2 the two groups R7 and 0 may be different but it is usually preferred they are the same.

The N atom linking TPD and 0 is preferably attached to a carbon atom in TPD, though it may be joined via other groups such as SO2.

The NR7Q group may be linked directly to a carbon atom in the triphendioxazine nucleus but it is preferred that it is attached to an optionally substituted alkylene, arylene or aralkylene group which is itself attached to the triphendioxazine nucleus by an O or especially an NH group.

As examples of optionally substituted hydrocarbyl groups represented by R7 or 0 there may be mentioned lower, i.e. C,.4alkyl optionally substituted by OH, OS03H, CN or S03H such as CH3, CH3CH2, CH3CH2CH2CH2, CH2CH2OH, CH2CH2CN, CH2CH20SO3H and CH2SO3H; phenyl optionally substituted by SO3H, C1.4alkyl or C1.4alkoxy such as phenyl, m orp-sulphophenyl, o-, m- orp-methylphenyl, o, m- orp-methoxyphenyl, 3,5-disulphophenyl or3-sulpho-5-methoxyphenyl.

It is usually preferred that R7 and 0, when not a cellulose reactive group, is CH3, CH3CH2 or especially H.

The sulphonic acid groups are usually present in sufficient numbers to give significant water-solubility to the dyes, e.g. more than 5g./litre at 25on. The value of x will usually range from 1 to 8 especially 2 to 6. It will be appreciated that additional sulphonic acid groups may be present as substituent or R7 or 0.

The cellulose reactive group represented by Q may be any group capable of forming a covalent bond with a cellulose substrate. They may be any convential cellulose reactive groups of this type such as those disclosed in patent specifications and other literature on reactive dyes, e.g. UK Patent Specification No.1440948.

As examples of cellulose reactive groups there may be mentioned aliphatic sulphonyl groups which contain sulphate ester group in B-position to the sulphur atom, e.g. B-sulphatoethylsulphonyl groups, a,ss-unsaturated acyl radicals of aliphatic, carboxylic acids, for example acrylic acid, a-chloroacrylic acid, a-bromoacrylic acid, propiolic acid, maleic acid and mono- and dichloro maleic acids; also the acyl radicals of acids which contain a substituent which reacts with cellulose in the presence of an alkali, e.g. the radical of a halogenated aliphatic acid such as chloroacetic acid, dichloro and ss-bromopropionic acids and a,l3-dichloro- and dibromopropionic acids or radicals of vinylsulphonyl- or ss-chloroethylsulphonyl- or (S-sulphatoethylsu Iphonyl-endo-methylene cyclohexane carboxylic acids.Other examples of cellulose reactive groups are tetrafluorocyciobutyl carbonyl, trifluorocyciobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl, trifluorocyclobutenylethenyl carbonyl; activated halogenated 1,3-dicyanobenzene radicals such as 2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6-nitrophenyl, 2,4dicyano-3,5,6-trifluorophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5-difluorophenyl, 2,4,6tricyano-3,5-dichlorophenyl and heterocyclic radicals which contain 1,2 or 3 nitrogen atoms in the heterocyclic ring and at least one cellulose reactive substituent on a carbon atom of the ring.

It may be noted that many reactive groups may be defined as both heterocyclic or acyl groups since they consist of an acyl group carrying a heterocyclic substituent. For convenience in such cases where the heterocyclic ring carries the cellulose substituent these are usually referred to as heterocyclic reactive groups in this specification.

As examples of such heterocyclic radicals there may be mentioned for example: 2:3-dichloroquinoxaline-5- or -6-sulphonyl, 2:3-dichloroquinoxaline-5- or-6-carbonyl, 2:4-dichloroquinazolin-6- or-7-sulphonyl, 2:4:6-trichloroquinazolin-7- or -8-sulphonyl, 2:4:7- or 2:4:8-trichloroquinazolin-6-sulphonyl, 2:4-dichloroquinazolin-6-carbonyl, 1 :4-dichlorophthalazine-6-carbonyl, 4:5-dichloropyridazon-1 -yl-ethylcarbonyl, 2:4-dichloropyrimidine-5-carbonyl, 4-(4':5'-dichloropyridaz-6'-on-l-yl)benz 2-chlorobenzthiazole-6-carbonyl, 3,6-dichloropyrazin-4-carbonyl, 4-(4' :5'-dichlornpyridaz-6'-on-1 '-yl)phenylsulphonyl; activated 4,6-dihalopyridin-2-yl and 2,6-dihalopyridin-4-yl groups such as 3,4,5,6-tetrafluoropyridin-2-yi, 2,3,5,6-tetrafluoropyridin-4-yl, 2,5,64rifl uoro-3-cyanopyridin-4-yl, 2,5, 6-trichloro-3-cyanopyridin-4-yl, 2,6-difluoro-3-cyano-5-chloropyridin-4-yl, 2,6-difluoro-3,5-dichloropyridin-4-yl and more particularlytriazinyl or pyrimidinyl groups.

Examples of particular pyrimidinyl groups are pyrimidin-2-yl or -4-yl groups having a cellulose reactive atom or group especially Cl, Br or F in at least one of the remaining 2-, 4- and 6-positions. The 5-position may carry various substituents such as Cl or CN which are not normally cellulose reactive in themselves but may enhance the reactivity of substituents in other positions of the pyrimidine ring.As specific examples of such pyrimidinyl groups there may be mentioned;2,6-dichloropyrimidin-4-yl, 4,6-dichloropyrimidin-2-yl, 2,5,6-trichloropyrimidin-4-yl, 4,5,6-trichloropyrimidin-2-yl, 5-ch loro-2-methylsu I phonyl-6-methyl pyrimidin-4-yl, 2,6-dichloro-5-cyanopyrimidin-4-yl, 4,6-dichloro-5-cyanopyrimidin-2-yl, 2,6-difluoro-5-chloropyrimidin-4-yl, 4,6-difluoro-5-chloropyrimidin-2-yl, 2,6-dif luoro-5-cyanopyrimidin-4-yl, 4,6-difluoro-5-cyanopyrimidin-2-yl.

Examples of particular triazinyl groups are triazin-2-yl groups having cellulose reactive atoms or groups on one or both of the 4- and 6-positions. In this instance a wide range of cellulose reactive atoms or groups are available such as activated aryloxy or various groups linked through a sulphur atom but the preferred reactive atoms or groups are F, Br or especially Cl; quaternary ammonium groups such as tri-lower alkyl ammonium, e.g. (CH3)3N- and pyridinium groups especially those derived from pyridine carboxylic acids in particular from nicotinic acid.

The triazinyl groups having only one reactive atom or group on the nucleus in the 4-or 6-position may have a substituent not reactive to cellulose in the remaining 4-or 6-position.

As examples of such non-reactive substituents there may be mentioned alkyl or aryl thio groups, alkoxy or aryloxy groups and optionally substituted amino groups.

Preferred forms of these groups include lower, i.e. C1.4alkoxy, e.g. methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy and lower alkoxy lower alkoxy, e.g. B-methoxy-ethoxy, (3-ethoxyethoxy, phenoxy and suiphophenoxy; amino; lower alkylamino, e.g. methylamino, ethylamino, butylamino, di(lower alkyl)amino, e.g. dimethylamino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types in which the alkyl groups are substituted, in particular by OH, CN orSO3H,e.g. ss-hydroxyethylamino, di(ss-hydroxyethyl)amino, frcyanoethylamino, di(P-cyanoethyl lamino, ss-sulphoethy]amino, (3- hydroxypropylamino, (13-hydroxybutyl)ethylamino and (ss-hydroxyethylmethylamino; cycloalkylamino, e.g.

cyclohexylamino; cyclic amino, e.g, morpholino or piperazino; naphthylamino substituted by 1,2 or 3 SO3H groups and optionally substituted phenyl amino groups.

As a particularly preferred form of the optionally substituted pbenylamino grnupsthere may be mentioned groups of the formula:

where G = H, methyl, ethyl, to-sulphomethyl, (3-carboxy-, ss-hydroxy or -cyanoethyl and Z and X are each independently selected from H, COOH, SO3H, CH3, C2H5, OCH3, OC2H5, Cl, Br, CN, NO2, NHCOCH3 and (3-sulphatoethylsulphonyl.

As specific examples of such groups there may be mentioned anilino, o-, m- and p-sulphoanilino, o-, mand p- carboxyanilino, 4- and 5-sulpho-2-carboxyanilino, 4- and 5-sulpho-o-tolylamino, 2,4-, 2,5- and 3,5-disulphoanilino, 2,4-dicarboxyanilino, 4- and 5-sulpho-2-methoxyanilino, N-methyl-o-, m- and psulphoanilino, N-(o-sulphomethylanilino, N-(P-hydroxyethyl)-3-sulphoanilino.

If desired, the cellulose reactive group 0 may take the form: - Ht - Dm - 0" where Ht is a s-triazine nucleus which contains a cellulose reactive atom or group, Dm represents a diamine residue linking Ht and Q' by the 2 amino groups and 0' to a cellulose reactive group having the meaning stated above for 0.

In particular it is usually preferred that the cellulose reactive atom or group on Ht is F, Br or especially Cl and that 0' is a s-triazine residue as defined above for 0.

As examples of the diamines DmH2 which may provide the residue Dm there may be mentioned:heterocyclic diamines, e.g. piperazine, aliphatic diamines, e.g. alkylene-, hydroxyalkylene- or sulphato alkylene diamines especially those having 2-6 carbon atoms, e.g. ethylene diamine 1,2 and 1,3-propylene diamines 1,6-diaminohexane (3-hydroxyethylaminoethylamine 2-hydroxy-1 ,3-diaminopropane 2-sulphato-1 ,3-diaminopropane other a-, w-diamino aliphatic compounds, e.g.

triethylene tetramine di-(B-aminoethyl)ether naphthylene diamine sulphonic acids, e.g.

2,6-diaminonaphthalene-1 ,5- and 4,8-disulphonic acids 1 ,5-diaminonaphthalene-3,7-disulphonic acid and diamine derivatives of mono- and di-cyclic compounds of the benzene series, e.g. phenylene diamines and their mono- and disulphonic acids, e.g. m- and p-phenylene diamines 1,3-phenylenediamine-5-sulphonic and 4,6-disulphonic acids 1 ,4-phenylenediamine-2-sulphonic and 2,5-disulphonic acids diamines of the formula:

where p and q are each 0 or 1 and E is a direct link or a group selected from SO2, O,CH2, C2H2, C2H4, NH, NHCONH, e.g.

4,4'-diaminostilbene-2,2'-disulphonic acid benzidine-2-sulphonic and 2,2'-disulphonic acids 3,3'- and 4,4'-diaminodiphenylureas 4,4'-diaminodiphenylurea-2,2'- and 3,3'-disulphonic acids 4,4'-diaminodiphenylamine-2,2'-disulohonic acid 4,4'-diaminodiphenylmethane 4,4'-diaminodiphenylmethane-2,2'-disulphonic acid 4,4'-diaminodiphenylether 4,4'-diaminodiphenylsulphone 4,4'-diaminodiphenylethane-2,2'-disulphonic acid and the N-lower alkyl and N,N'-di(lower alkyl) derivatives of the above diamines, e.g.

4-methylamino and 4-ethylaminoaniline-2-sulphonic acids N,N'-dimethyl-4,4'-diaminodiphenylamino-2,2'- disulphonic acid.

A preferred general class of dyestuffs of the present invention may be represented by the formula:

wherein (R6)m represents m substituent group R6 where each R6 is independently halogen, C1~4alkyl, Alkoxy or COOH, misOto3 a +bis 1 to4 Xis a direct link or a linking atom or group, Y is an optionally substituted linking group of the aromatic, araliphatic or aliphatic series, or X and Ytogether are a direct link, Z and Za are each independently groups as hereinbefore defined for Q and R7 has the meaning hereinbefore defined.

Where two cellulose reactive groups are present in the dyes of formula (4), i.e. both Z and Z1 are cellulose reactive groups they may be different though it is usually preferred that they are the same, Particularly preferred general classes of dyestuffs are compounds of formula (4) in which m = O, a = b = 1, or those in which each X is joined to a position para to a heterocyclic nitrogen and especially those having both such features, i.e. dyestuffs of the formula:

wherein X, Y, R7, Z and Z' have the meanings given above, As examples of atoms or groups represented by X, there may be mentioned 0, S, CH2, CO, CH=CH, NHCONH, NHCONHCH2NH, OCH2CH2O, N=N

and, preferably NH.

Preferred types within the general classes defined by formula (4) and (5) are: (a) those in which X and Ytogether are a direct link and in which R7 is H.

(b) those in which Y is a benzene or naphthalene linking group optionally substituted particularly by 1,2 or 3 SO3H groups, and especially when such groups are combined with an X representing NH, and (c) those in which Y is aliphatic or araliphatic linking group either of which may be optionally substituted.

As examples of such groups there may be mentioned ethylene, 1,2- and 1,3-propylene, 2-(4'-sulphophenyl)1,3-propylene, 1,4-, 2,3-and 2,4-butylene, 2-methyl-i 3-propylene, 2-methyl-2,4-pentylene, 2,2-dimethyl-1,3propylene, 1-phenylethylene, 1-chloro-2,3-propylene, 1,6- and 2,5-hexylene, 2,3-diphenyl-1,4-butylene, 1 -(m ethoxyca rbo nyl)-1,5-pentylene, 1 -carboxy-1 ,5-pentylene 2,7-heptylene, 3-methyl-1,6-h exyl ene, -CH2CH20CH2CH2, -CH2CH2SCH2CH2-, -CH2CH2SSCH2CH2-,

In this type also it is usually preferred that X is NH.

In particular it is preferred that Y when aliphatic or araliphatic it is

or C2~4alkylene groups which may be optionally substituted by OH or OSO3H.

In those type (C) cases where Xis a substituted amino the group linked to the nitrogen of X may be, in addition to the group Y, be linked to both nitrogen atoms in the structure -X-Y-NR7-. As a preferred example of such a nroup there mav be mentioned:

It is often further preferred that R7 in formula (5) is H.

Further structural features of preferred types of dyestuffs of the present invention will be apparent from compounds specifically referred to later to illustrate intermediates which may be employed in preparing the dyestuffs of the present invention.

A further preferred general class of dyes of the present invention are of the formula:

wherein Z and Z1 have the meanings given above.

It will be appreciated especially preferred sub-classes of dyes are those which combine two or more preferences for the integers X, Y, R6, R7 and 0 of the general classes given above.

Dyes of formula (1) in which 0 is not a cellulose reactive group and particularly dyes of the above general classes in which both Z and Z1 are not cellulose reactive groups are useful as acid dyes for nylon. When O in formula (1) or Z and/or Z1 in the above general classes are H they are useful intermediates for the manufacture of dyes containing cellulose reactive groups and form a preferred type of dye of the present invention. Cellulose reactive dyes of formulae (1), (4), (5) and (6) are a further preferred type of dye.

The present invention also provides a process for the manufacture of dyes of formula (4) in which Z and Z are both H or optionally substituted hydrocarbyl which comprises reacting tetrabrom-benzoquinone with 2 moles of a diamine of the formula:

wherein X, Y, R6, R7 and m have the meanings hereinbefore given and Z is H or optionally substituted hydrocarbyl and heating the resulting adduct, e.g. with oleum optionally also with ammonium persulphate to effect ring closure.

The reaction of tetrabrom-benzoquinone with the diamine of formula (7) is conveniently conducted in aqueous medium at 40-100"C especially 50-700C.

The pH of the medium is usually maintained weakly acid, e.g. 5-6. A small excess of tetrabrombenzenequinone is often found desirable to ensure maximum yield.

The cyclisation is usually conducted at iSO to 1 000C and further SO3H groups may be introduced concurrently with the ring closure when oleum is used.

As examples of diamines of formula (7) there may be mentioned: 1,4-diaminobenzene-2-sulphonic acid 4,4'-diaminodiphenylamine-2,3'-disulphonic acid 3',4-diaminodiphenylamine-2,4'-disulphonic acid 3',4-diaminodiphenylamine-2',4',6'-trimethyl-2,5'-disulphonic acid 4,4'-diamino-2-methoxydiphenylamine-2',5-disulphonicacid 4,4'-diamino-2-chlorodiphenylamine-2',5'-disulphonicacid 4,4'-diaminodiphenylamine-2,2',5'-trisulphonicacid 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid 4-(3'-amino-2'-hydroxypropyl)aminoaniline-3-sulphonicacid 4-[2'-(3"-sulphophenyl)aminoethyl]aminoaniline-3-sulphonic acid 4-(2'-aminoethoxy)aniline 4-(3'-aminopropyl)aminoaniline-3-sulphonic acid 2,6-diaminonaphthalene-4,8-disulphonic acid 4-[2'-(4"-sulphophenyl)-3'-aminopropyl]aminoaniline-3-sulphonic acid 4-[2'-(3"-sulphophenyl)-3'-aminopropyljaminoaniline-3-sulphonic acid 4-(2'-phenyl-3'-aminopropyl)aminoaniline-3-sulphonic acid 4-(2'-phenylethyl)aminoaniline-3-sulphonic acid 4-[2'-(4"-sulphophenylamino)ethyl]aminoaniline-3-sulphonic acid 4-(2'-phenyl-2'-aminoethyl)aminoaniline-3-sulphonic acid The invention provides a further process for the manufacture of dyes of formula (1) bearing one or more cellulose reactive groups which comprises reacting dyes of formula (1 ) in which Q or at least one of Q represents H with carbyl sulphate or compound Q'hal where hal is halogen and Q' is a cellulose reactive group as defined above for Q except (3-sulphatoethylsulphone.

Carbyl sulphate reacts with amino groups to form a ss-sulphatoethylsulphonyl group.

By choice of the amount of carbyl sulphate or Q'hal all or only part of the NR7H groups in the compound of formula (1) in which Q or at least one of Q is H may be converted to cellulose reactive groups NR7Q.

The above process may be conveniently carried out in an aqueous medium desirably in the presence of an acid binding material, e.g. a sodium carbonate, bicarbonate or hydroxide and at a temperature appropriate to the reactivity of the compound Q hal usually in the range 0-1 00 C.

Compounds of formula (1 ) in which Q is H may be obtained, for example, by the process of the present invention described above using diamines of formula (7) in which Z is H.

Specific examples of compounds Q'hal will be apparent from the specific examples of Q given above. It is normally preferred that hal is chlorine, e.g. Q'hal is ss-chloropropionyl chloride, cyanuric chloride, methoxydichloro-s-triazine, 2,4,5,6-tetrachloropyrimidine etc, but in some instances hal may be more conveniently another halogen, e.g. fluorine, when this is the cellulose reactive substituent present in O, e.g.

Q'hal may be 2,4,6-trifluoro-5-chloropyrimidine to introduce the difluoro-5-chloropyrimidinyl group.

When the reactive group 0 is to have the formula - Ht - Dm - Q" as defined above, the reactant Q'hal used in the above process of the invention has the formula: hal - Ht - Dm - Q" This compound may be obtained by reacting a diamine DmH2 with a mole of carbylsulphate or Q'hal as defined above in connection with the further process and one mole of a s-triazine compound having the formula:

where Y is a cellulose reactive substituent. In a preferred instance where Ht is a chloro-s-triazinyl group Y is Cl, i.e. the above s-triazine compound is cyanuric chloride.

The reactive dyes of formula (1 ) wherein the cellulose reactive group 0 is a s-triazine nucleus substituted by a Cl, Br or F atom and an amino or substituted amino group can also be obtained by reacting a dye of formula (1) in which Q is a dichloro, dibromo or difluoro-s-triazine group with ammonia or an amine.

This process can conveniently be carried out by stirring the reactants in an aqueous medium, optionally in the presence of a water-soluble organic solvent, at a temperature offrom 30-60"C, and preferably maintaining the pH atfrom 5-8 by adding an acid binding agentto neutralisethe hydrogen halide formed during the reaction. Suitable acid binding agents are alkali metal hydroxides, carbonates and bicarbonates, or an excess of ammonia or aliphatic amine where this is one of the reactants.

By reacting the dichloro-, dibromo-or difluoro-s-triazine dye with a diamine DmH2 in equimolar proportion, the resulting product contains a free amino group and can be reacted with carbylsulphate or a compound of the formula 0'hay as defined above in connection with the first process whereby the dyestuff obtained contains a cellulose reactive group of formula -Ht- Dm - O" as defined above wherein Ht is chloro-, bromo- orfluorotriazinyl.

Dyestuffs of this kind can alternatively be obtained by first reacting the diamine with one mole of carbyl sulphate or Q 'hal and reacting the resulting monoamine with one mole of dichloro-, dibromo- or difluoro-s-triazine dye.

In the above reactions where one mole of diamine is reacted with 1 mole of carbyl sulphate or Q'hal or with a dyestuff with a dichioro-, dibromo- or difluoro-s-triazinyl group it is usually preferred that the diamine has amino groups of different reactivity to minimise the concomitant formation of unwanted reaction products from 1 mole of the diamine with two moles of the other reactant.

In the instances where Q is a triazinyl group having quaternary ammonium or pyridinium substituents as the cellulose reactive substituent these dyes may often be conveniently obtained by reacting the corresponding chloro-, bromo- orfluorotriazinyl dyestuffs with the appropriate tertiary amine or pyridine compound. Such a reaction is normally carried out in aqueous media at 30"C to 100"C.

The cellulose reactive dyestuffs of the present invention may be used for colouring a wide range of textile materials containing hydroxyl or amino groups, e.g. wool, silk, synthetic polyamides and natural or regenerated cellulose, for example cotton or viscous rayon materials, by conventional methods used for colouring such materials with water-soluble reactive dyes, e.g. in the case of cellulose they are preferably applied in conjunction with a treatment with an acid-binding agent, e.g. caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, which may be applied to the cellulose textile material before, during or after the application of the dyestuff.The method, technique and conditions used for applying the dyestuff to the textile material will be selected according to various factors, e.g. the nature of the fibre or fibres present and the physical form of the textile material.

The reactive dyes of the present invention form a valuable class of dyes, usually of blue shades, and textiles coloured with them show good resistance to light and washing treatments. The present dyes are usually associated with a high tinctorial power and build-up.

The invention is illustrated by the following Examples in which all parts are by weight and proportions in wt/vol are kgs/litre.

Example 1 (a) 55.3 Parts of 4-(ss-aminoethyl)-3-sulphoaniline (M.1.369) are dissolved in 100 parts of water at pH 6.5-7.0 and 38.1 parts of bromanil are added. The suspension is heated at 65-70DC, while maintaining the pH at 6.5-7.0, for 6 hours, then cooled, filtered, washed with water and dried to give the desired dianilide (45.5 parts).

(b) 25 Parts of the above dianilide are added to 400 parts of 20% oleum and the solution heated to 60"C for 1 hour. Drowing out into ice gives the desired dibromo-dyebase, which is filtered off, washed acid-free and dried to give 19.4 parts of the product.

(c) 25.7 Parts of aniline-2,5-disulphonic acid (M.1.285) are dissolved in 250 parts of water at pH 7.0 and 0.75 parts of pH 6.5 phosphate buffer added. The mixture is cooled to 0-5"C, 17.7 parts of cyanuric chloride in 160 parts of acetone are added dropwise keeping the pH at 6.0-7.0. After 5 hours the suspension is filtered and the filtrates are added to a solution of 25.7 parts of the dyebase from (b) in 1600 parts of water at pH 9.0.

The reaction is continued at 50-55"C and at pH 8.5-9.0 for a further 4 hours, then cooling to room temperature and salting to 30% with sodium chloride gives 42.4 parts of the desired reactive dyestuff (M.1.2491).

Claims (1)

1. Dyes which in the free acid form are of the formula:

wherein TPD represents a (x+n) valent radical of a triphenodioxazine compound having bromo substituents in the 6,13-positions of the triphenodioxazine nucleus x is at least 1 n is 1 or 2 R7 is H or an optionally substituted hydrocarbyl group, and Q is H, an optionally substituted hydrocarbyl group or a cellulose reactive group.