GB1559752A - Triphendioxazine dyestuffs - Google Patents

Description

(54) TRIPHENDIOXAZINE DYESTUFFS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Milibank, London SW1P 3JF, a British Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to triphendioxazine dyestuffs in particular to triphen dioxazine dyestuffs having cellulose reactive substituents.

It is known to prepare cellulose reactive dyestuffs containing a 6,13-dichloro- triphendioxazine nucleus and such dyes, usually blue in colour, are associated with good properties. However these known dyes can show less than desirable stability to alkaline agents. The present invention relates to triphendioxazine reactive dyes, other than 6,13-dichlorotriphendioxazines, which in many instances show good levels of stability to alkali.

According to the present invention there are provided cellulose-reactive dyestuffs containing a triphendioxazine nucleus having an atom or group other than chlorine on one or both of the 6- and 13-positions of said nucleus.

A preferred class of such triphendioxazine dyestuffs are those in which there is attached to one of the 6- and 13-positions of the triphendioxazine nucleus a hydrogen atom or an alkyl, aralkyl, aryl, alkoxy, aryloxy or aralkoxy group, all of which groups may optionally be substituted or cycloalkyl and in which the other of the 6- and 13-positions has attached one of the aforementioned groups or a hydrogen or halogen atom.

A further preferred class of dyes of the present invention may be represented as TPD(NR'Q)" (1) where TPD represents a n-valent triphendioxazine residue of the type defined above.

R' is H or an optionally substituted hydrocarbyl group.

n ss 1 or 2, and Q is cellulose reactive group.

The N atom linking TPD and Q 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, optionally substituted arylene or optionally substituted, aralkylene group which is itself attached to the triphendioxazine nucleus by O or especially NH.

As examples of optionally substituted hydrocarbyl groups represented by R' there may be mentioned lower ie. C1 alkyl optionally substituted by OH, OSO,H, CN or SO3H such as H, CH,, CHsCH2, CH3CH2CHCH2CH2CH20H, CH2CH2CN, CH2CH2OSO3H and CH2SO3H; phenyl optionally substituted by SO3H, C1-4 alkyl or C1-4 alkoxy such as m- or p-sulphophenyl o-, m- or p-methylphenyl, o-, m- or p-methoxyphenyl, 3,5-disulphophenyl or 3-sulpho-5-methoxyphenyl.

It is usually preferred that R' is CH3, CH3CH2 or especially H.

The cellulose reactive group Q is any group capable of forming a covalent bond with a cellulose substrate under alkaline conditions. The group Q may be any conventional cellulose reactive group of this type such as those disclosed in the patent specifications and other literature on reactive dyes, e.g. U.K Patent Specification No.

1,440,948.

As examples of cellulose-reactive groups, there may be mentioned aliphatic sulphone groups which contain a sulphate ester group in ,B-position to the sulphur atom, e.g. ss-sulphatoethylsulphonyl; unsaturated acyl radicals of aliphatic carboxylic adds, for example acrylic acid, erchloroacrylic acid, ebromoacrylic add, propiolic add, 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 add such as chloroacetic acid,ss- chloro- and ss-bromopropionic acids, and α,ss-dichloro- and dibromopropionic acids or radicals of vinylsulphonyl- or ss-chloroethyl sulphonyl or ss-sulphatoethylsulphonyl- endo-methylene cyclohexane carboxylic acids.Other examples of cellulose-reactive groups are tetrafluorocyclobutyl carbonyl, trifluorocyclobutenyl carbonyl, tetrafluoro- cyclobutylethenyl carbonyl, trifluorocyclobutenylethenyl carbonyl, and heterocyclic radicals which preferably contain 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 specifications As examples of such heterocyclic radicals there may be mentioned for example: - 2: 3-dichloroquinoxaline-5- or -6-sulphonyl, 2: 3-dichloroquinoxaline-5 or Scarbonyl, 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-1-yl)benzoyl, 2-chiorobenzth$zole-6-cartonyl, 3,6-dichloropyrazin-4-carbonyl, 4-(4': 5'-dichloropyridaz-6'-on-1'-yl)phenylsulphonyl, and more particularly triazinyl 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 (N 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-chloro-2-methylsulphonyl-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-difluoro-5-cyanopyrimidin-4-yl, 4,6-difluoro-5-cyanopyrimidin-2-yl.

Examples of particular triazinyl groups are triazin-2-yl groups having cellulosereactive 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)8N- 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 alkylthio or arylthio groups, alkoxy groups and optionally substituted amino groups.

Preferred forms of these groups include lower, (i.e. C1) alkoxy, e.g. methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy and lower alkoxy, e.g. ss-methoxyethoxy, ss-ethoxyethoxy; phenoxy and sulphophenoxy; 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 or SO3H, e.g. ss-hydroxyethylamino di(ss-hydroxyethyl)amino, ss-cyanoethylamino, di(ss-cyanoethyl)amino, sssulphoethylamino, ss-hydroxypropylamino, (ss-hydroxybutyl)ethylamino and (ss-hydroxyethyl)methylamino; cycloalkylamino, e.g. cyclohexylamino; cyclic amino, e.g. morpholino or piperazino; naphthylamino substituted by 1, 2 or 3 SO3H groups and optionally substituted phenylamino groups.

As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups of the formula:

where G is H, methyl, ethyl, #-sulphomethyl, ss-carboxyethyl,ss-hydroxyethyl or sscyanoethyl and Z and X are each independently selected from H, COOH, SO3HCH3 C2H5, OCH3, OC2H6, Cl, Br, CN, NO2, MHCOCH,, NH3, phenylamino and methylamino.

As specific examples of such groups there may be mentioned anilino, o-, m- and psulphoanilino, o-, m- and 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, 4and 5-sulpho-2-methoxyanilino, n-methyl-o-, m- and p-sulphoanilino, N-#-sulpho- methylanilino, N-(ss-hydroxyethyl)-3-sulphoanilino.

If desired, the cellulose-reactive group Q may take the form: -Ht-Dm-Q' 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 Q' to a cellulose-reactive group having the meaning stated above for Q.

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

When symbol Q represents a s-triazine ring containing a halogen atom and a nonreactive substituent, the latter can be the residue of a coloured amine, e.g. of the azo, anthraquinone, nitro or phthaloyyanine series, but more especially a residue of formula (1) less the group Q so that the dyestuff as a whole contains 2 residues of formula (1) less the group Q linked by a halo-s-triazine radical or 2 such residues linked through two halo-s-triazine groups and a diamine radical Dm as given above.

In these dyestuffs the halogen may be F or Br but it is usually preferred that it is Cl.

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 sulphatoalkylene diamines especially those having 2 ó carbon atoms, e.g. ethylene diamine 1,2 and 1,3-propylene diamines 1,6-diaminohexane ss-hydroxyethylaminoethylamine 2-hydroxy-1,3-diaminopropane 2-sulphato-1,3-diaminopropane other α,#-diamino aliphatic compounds e.g.

triethylene tetramine di(ss-aminoethyl)ether naphthylenediamine sulphonic acids, e.g.

2,6-diaminonaphthalene-1,5- and 4,8-disulphonic acids 1,5-diaminonophthalene-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-phenylenediamines 1,3-phenylenediamine-S-sulphonic and 4,6-lisulphonic 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, al,, C,H,, NH, NHCONH, e.g.

4,4'-diaminostilbene-2,2'-disulphonic acid benzene-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'-disulphonic acid 4,4'-diaminodiphenylmethane 4,4'-diaminodiphenylmethane-2,2'-disulphonic acid 4,4'-diaminodiphenylsulphone and the N-lower alkyl and N,N'-di(lower alkyl)derivatives of the above dianiines, e.g.

4-methylamino and 4-ethyluinoaniline-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 groups R6 where each R6 is independently halogen, C1-4 alkyl C1-4 alkoxy or COOH, m is 0 to 3 a+b is 1 to 4 X is a direct link ora linking atom or group Y is an optionally substituted linking group of the aromatic, araliphatic, or aliphatic series, or X and Y together are a direct link X, is H, cycloalkyl or AR8 where A is 0, or a direct link and R8 is alkyl, aryl aralkyl all of which may be optionally substituted, X2 is an atom or group of the type defined for X, or halogen and one of Z and Z1 is a cellulose reactive group Q as hereinbefore defined and the other is H or a second cellulose reactive group of the type defined by Q and R? 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=l, 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, X1, 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, CH, CO, CH=CH, NHCONH, NHCH2CH2NH, OCH2CH20, N=N

and, preferably, NH.

Preferred types within the general classes defined by formula (4) and (5) are (a) those in which X and Y together 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 ethylenc, 1,2- and 1,3-propylene, 2-(4'-sulphopenyl)-1,3-propylene, 1,4, 2,3- and 2,4-butylene, 2-methyl-1,3-propylene, 2-methyl-2,4-pentylene, 2,2-dimethyl-1,3propylene, l-phenylethylene, 1-chloro-2,3-propylene, 1,6- and 2,5-hexylene, 2,3-diphenyl-1,4-butylene, 1-methoxycarbonyl-1,5-pentylene, 1-carboxy-1,5-pentylene, 2,7heptylene, 3-methyl-1,6-hexylene, -CH2CH2OCH2CH2-, -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 alkylene group which may be optionally substituted by OH or OSO,H.

In those type (C) cases where X is a substituted amino the group linked to the nitrogen of X may, in addition to the group Y, be linked to both nitrogen atoms in the structure -X-Y-NR'-. As a preferred example of such a group there may 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.

In the dyestuffs of formula (4) and (5) above it is usually preferred that X1 and X,, which may be the same or different, are H cyclohexyl, cyclopentyl or groups of the formula AR8 wherein A has the meaning given before in which R8 is alkyl, especially C1-4 alkyl which may optionally be substituted by OH, halogen especially chlorine, alkoxyl especially C1-4 alkoxyl and aryloxy especially phenoxy; or aryl especially naphthyl and more especially phenyl both of which may optionally be substituted by halogen especially chlorine, nitro, alkyl especially C1-4 alkyl, alkoxy especially C1-4 alkoxy, acyl especially C1-@ acyl and alkoxy carbonyl especially C1-@ alkoxycarbonyl; or aralkyl especially benzyl or phenylethyl in which the aromatic nucleus may optionally be substituted as given for naphthyl and phenyl above.

It is particularly preferred that AR8 is alkyl especially C1-4, alkoxy especially C1-4; or phenoxy or phenyl in each of which the nucleus may be optionally substituted by Cl, NO2 or C1-4 alkyl.

When one of X1 and X2 are halogen it is usually preferred that this is chlorine or bromine. As specific examples of groups X1 and X2 there may be mentioned: hydrogen; alkyl such as methyl, ethyl, n-propyl, isopropyl; substituted alkyl such as 2-ethoxyethyl, ethoxymethyl, l-ethoxypropyl, methoxymethyl, phenoxymethyl, 2hydroxyethyl; cycloalkyl such as cyclohexyl, cyclopentyl; aralkyl such as benzyl; substituted aralkyl such as 4'-methoxybenzyl and 2',5'-dimethylbenzyl; aryl such as phenyl; substituted aryl such as 4'-methylphenyl, 4'-methoxyphenyl, 4'-chlorophenyl, 2'chlorophenyl, 3'-chlorophenyl, 2'-chloro-4'-methylphenyl, 4'-nitrophenyl, 4'-acetylphenyl, 4'-ethoxycarbonylphenyl, 3 ',4'-dimethylphenyl, 2',5 '-dimethylphenyl; alkoxy such as methoxy, ethoxy-n-amyloxy, n-propyloxy; aryloxy such as phenoxy; substituted aryloxy such as 4'-methylphenoxy, 4'-bromophenoxy, 4 '-methoxyphenoxy, 4'-chlorophenoxy, 4'-methylsulphonylphenoxy, 3',4'dkhlorophenoxy; aralkyloxy such as benzyloxy and 2'-phenylethoxy.

Especially preferred dyes are those in which X1 and X2 are both C1 < alkyl groups.

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

wherein X1, X2, 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, X1, X.2, Y, R8, R7 and Q of the general classes given above.

The present invention also provides a process for the manufacture of dyes of formula (1) except where Q represents ss-sulphatoethylsulphonyl which comprises reacting an aminotriphendioxazine of the formula: TPD(NR?H)n where TPD, R7 and n have the meaning given herein before with n moles of a compound of the formula Qhal where Q is a cellulose-reactive group as hereinbefore defined other than ,ss-sulphatoethylsulphonyl and hal represent halogen.

In the above process when n is 1 it is possible that the aminotriphendioxazine TPDNR'H may contain more than one NR7H group, i.e. TPD is a triphendioxazine radical bearing one or more additionat NR7H groups which are not utilised in the reaction with Qhal.

Thus, in manufacturing the preferred general class of dyestuffs of formula (4) the aminotripherdioxazine TPD(NR'H)n used in the process of the present invention will be a compound of formula (4) in which both Z and Z' are H. This can be reacted with mole of compound Qhal to give a dye of formula (4) in which one of Z and Z' is Q and the other is H, i.e. a dye of formula (1) in which n= 1 and the group TPD includes a NR7H group. Alternatively reaction with 2 moles of Qhal gives a dye of formula (4) in which bothZ and Z' are Q, i.e. a dye of formula (1) in which n=2.

In the instances where the group(s) NR'H are directly linked to the triphendioxazine nucleus it is usually found that R7 must be H to ensure an adequate rate of reaction with Qhal to result in good yields of reactive dyestuff.

The above process may be conveniently carried out in an aqueous medium desirably in the presence of an acid-binding material, e.g. sodium carbonate, bicarbonate or hydroxide and at a temperature appropriate to the reactivity of the compound Qhal usually in the range e-1000C.

In the case where Q is ss-sulphatoethylsulphonyl the dyestuffs may be manufactured using the above process using carbyl sulphate in place of the compound QhaL Specific examples of compounds Qhal will be apparent from the specific examples of Q given above. It is normally preferred that hal is chlorine, e.g. Qhal is ss-chloro- propionyl chloride, cyanuric chloride, methoxy dichloro-s-triazine, 2,4,5,6-tetrachloro- pyrimidine etc., but in some instances hal may be more conveniently another halogen, e.g. fluorine when this is the cellulose-reactive substituenr present in Q, for example Qhal may be 2,4,6-trifluoro-5-chloropyrimidine to introduce the difluoro-5-chloro- pyrimidinyl group. When the reactive group Q is to have the formula -Ht-Dm-Q', as defined above, the reactanr Qhal used in the above processes has the formula: hal-Ht-Dm-Q' This compound may be obtained by reacting 1 mole of a diamine DmH, with 1 mole of carbyl sulphate or Qhal as defined above in connection with the first 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 Q is a striazine 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 of from 30-6OOC, and preferably maintaining the pH at from 5-8 by adding an acid-binding agent to neutralise the hydrogen halide formed during the reaction. Suitable acid-binding agents are alkali metal hydroxides, carbonates and bicarbonates, or an excess or ammonia or aliphatic amine where this is one of the reactants.

Also, by use of a diamine in the proportion of 1 mole of dmmine to 2 moles of the dichloro-, dibromo- or difluoro-s-rriazinyl dye, the product obtained is of the kind mentioned above where the dyestuff as a whole contains 2 groups of formula (1) less Q, linked through two chloro-, bromo- or fluoro-s-triazine groups and a diamine radical. In the above process, there may be used any of the diamines DmH2 mentioned above.

Alternatively, by reacting the dichloro-, dibromo- or difluoro-s-triazine dye with a diamine DmH, in equimolar proportion, the resulting product contains a free amino group and can be reacted with carbyl sulphate or a compound of the formula Qhal as defined above in connection with the first process whereby the dyestuff obtained contains a cellulose-reactive group of formula -Ht-Dm-Q' as defined above wherein Ht is chloro-, bromo- or fluorotriazinyl.

Dyestuffs of this kind can alternatively be obtained by first reacting the diamine with one mole of Qhal and reacting the resulting monoamine with one mole of dichloro-, dibromo- or difluoro-s-triazinyl dye.

In the above reactions where one mole of diamine is reacted with 1 mole of Qhal or of a dyestuff with a dichloro-, 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 reactants.

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- or fluorotriazinyl dyestuff with the appropriate tertiary amine or pyridine compound. Such a reaction is normally carried out in aqueous media at 300C to 1000C.

The dyestuffs prepared by the above processes may be isolated by any conventional means, e.g. spray drying or precipitation and filtration.

The dyes are represented above in their free acid form and may be isolated as such. However, it is usually found more convenient to isolate the dyes in the form of salts particularly alkali metal salts especially sodium.

The aminotriphendioxazine compounds TPD(NR7H)n, some of which are novel, used in the manufacture of the dyestuffs of the present invention may be obtained by various conventional methods For example, compounds of formula (4) in which both Z and Z' are H and the X--YY-NR'H groups are para to the nuclear nitrogens may be obtained by reacting quinones of the formula:

with 2 moles of a diamine of the formula:

wherein X, X1, X2, Y, R4 R7 and m have the meanings hereinbefore given, and heating the resulting adduct, e.g. with oleum optionally also with ammonium persulphate to effect ring closure.

In conducting the reaction between the quinone (7) and the diamine (8) it is often preferred to use an excess of quinone (7) over that necessary to take part in the reaction, e.g. up to about 3 moles of quinone may be added to the reaction mixture.

This reaction is found particularly suited to products in which X1 and X2 are H or C1-4 alkyl optionally substituted by OH or C1-4 alkoxyl.

Further SO3H substituents may be introduced concurrently with the ring closure.

As examples of quinones of formula (7) there may be mentioned: 1,4-benzoquinone 2-methyl-1,4-benzoquinone 2-ethyl-1,4-benzoquinone 2-n-propyl- 1,4-benzoquinone 2-isopropyl-1,4-benzoquinone 2,2'-ethoxyethyl-1,4-benzoquinone 2-phenyl-1 ,4-benzoquinone 2-(4'-methylphenyl)-1 ,4-benzoquinone 2-(4'-methoxyphenyl)- 1,4-benzoquinone 2-(3'-chlorophenyl)-1,4-benzoquinone 2-(4'-nitrophenyl)-1,4-benzoquinone 2,Sdimethyl-1,4-benzoquinone 2-methyl-5-ethyl-1,4-benzoquinone 2-methyl-5-cyclohexyl- 1,4-benzoquinone 2-cyclohexyl- 1,4-benzoquinone 2,5-dibenzyl-1,4-benzoquinone 2,5-dicyclohexyl-1,4-benzoquinone 2-phenyl-5-methoxy-1,4-benzoquinone 2-benzyl-5-methoxy-1,4-benzoquinone.

As examples of dianuaes of formula (8) 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-disulphonic acid 4,4'-diamino-2-chlorodiphenylamine-2',5'-disulphonic acid 4,4'-diaminodiphenylamine-2,2',5'-trisulphonic acid 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid 4-(3'-amino-2'-hydroxypropyl)aminoaniline-3-sulphonic acid 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'-aminoptopyl)aminoaniline-3-sulphonic acid 4- [2'K3 "-sulphophenyl)-3 '-aminopropyl)aminoaniline-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.

Alternatively aminotriphendioxazine compounds for use in the process of the present invention may be prepared by reacting quinones of the formula:

wherein X, and X2 have the meanings given above, one of X3 and X4 is H, Cl or Br and the other is Cl or Br with a diamine of formula (8) and cyclising the intermediate thus formed in the manner described above.

As examples of quinones of formula (9) there may be mentioned: 2-methyl-3-chloro-1,4-benzoquinone 2-methyl-6-chloro-1,4-benzoquinone 2-methyl-3,5-dichloro-1,4-benzoquinone 2-methyl-3,5,6-tribromo-1,4-benzoquinone 2-(4'-methylphenoxy)-3,6-dibromo-1,4-benzoquinone 2-(3'-methylphenoxy)-3,6-dibromo-1,4-benzoquinone 2-methyl-3,5,6-trichloro-1,4-benzoquinone 2-methyl-3-chloro-5-bromo-1,4-benzoquinone 2-methyl-3,6-dichloro-1,4-benzoquinone 2-methyl-3,6-dichloro-1,4-benzoquinone 2-methyl-3,6-dichloro-5-bromo-1,4-benzoquinone 2-phenyl-3,6-dichloro-1,4-benzoquinone 2-(4'-rnethoxyphenyl}3,6-dichloro-1,4-benzoquinone 2-(4'-chlorophenyl)-3,6-dichloro-1,4-benzoquinone 2-(4'-nitrophenyl)-3,6-dichloro-1,4-benzoquinone 2-(4'-nitrophenyl)-3,5,6-trichloro-1,4-benzoquinone 2,5-dimethyl-3,6-dibromo-1,4-benzoquinone 2,5-dimethyl-3-chloro-1,4-benzoquinone 2-methyl-5-n-propyl-6-bromo-1,4-benzoquinone 2-methyl-5-isopropyl-3,chloro-1,4-benzoquinone 2-methyl-5-isopropyl-6-bromo-1,4-benzoquinone 2-(2'-chlorophenyl)-3,5,6-tribromo-1,4-benzoquinone.

The above method is especially useful for preparing aminotriphendioxazines in which X1isalkyl or aryl and X2 is halogen.

A further method of preparing aminotriphendioxazines for use in the process of the present invention comprises reacting a quinone of the formula:

wherein X1 and X2 have the meanings given above and one of X5 and X6 are H, halogen or OR8 and the other is OR8 where R8 has the meaning given above with a diamine of formula (8) and cyclising the resulting intermediate as previously described.

When both X and X8 are OR8 in the quinone of formula (10) they may be the same or different groups of the types represented by OR8.

As examples of quinones of formula (10) there may be mentioned: 2-ethyl-3,6-dimethoxy-1,4-benzoquinone 2-chloro-3,6-dimethoxy-1,4-benzoquinone 2,3,5-trimethoxy-1,4-benzoquinone 2,5-dimethyl-3,6-dimethoxy-1,4-benzoquinone 2,5-dimethyl-3,6 dimethoxy-1,4-benzoquinone 2-methyl-3 ,6-dimethoxy-1,4-benzoquinone 2-methyl-5,6-dimethoxy-1,4-benzoquinone 2-ethyl-3,6-dimethoxy-1,4-benzoquinone 2-chloro-3-n-propyl-5-methoxy-1,4-benzoquinone 2-chloro-3,5-dimethoxy-1,4-benzoquinone 2-methyl-3-methoxy-1,4-benzoquinone 2,3,5,6-teuamethoxy-1,4-benzoquinone 2,3,5,6-tetraphenoxy-1,4-benzoquinone 2,3,5,6-tetra(4'-methylphenoxy)-1,4-benzoquinone 2,3 ,5,6-tetra(4'-methoxyphenoxy)- 1,4-beuzoquinone 2,3,5,6-tetra(4'-chlorophenoxy)-1 ,4-benzoquinone 2,3,5,6-tetra(3 ',5'-dimethylphenoxy)-1,4-benzoquinone 2,3,5,6tetra(3 '-methyl-4'-chlorophenoxy)-1,4-benzoquinone 2,3,5,6-tetra(2 '-naphthoxy)- 1,4-benzoquinone.

The above method of preparing aminotriphendiorazines is especially useful with quinones of formula (10) in which X,, X,, X5 and XG are all groups selected from the various types represented by OR8 as defined above.

The dyestuffs of the present invention may be used for colouring a wide range of textile materials containing hydroxy 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 watersoluble 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 materials 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, for example, methods will vary depending on whether the fibre is loose or spun into thread which in tum may be in hanks or wound on bobbins or converted into cloth or garments by knitting or weaving.

Any of the usual methods of dyeing or printing may be employed to apply the dye to the textile material and other dyestuffs and/or pigments may also be applied simultaneously or sequentially with the dyestuffs of the present invention using such combinations of conditions as are dictated by the properties of the dyestuffs and/or pigments. Such mixed dyeings are particularly valuable if the textile containing OH or NH2 groups is blended with other textile fibres free from such groups e.g. polyesters.The dyeing may be carried out in a batch wise manner using, for example, exhaustion techniques in a beck, winch, jet, paddle or jig device, in particular for hanks, woven or knitted fabrics or garments; or it may be applied by a "package" dyeing technique to fibres wound in cakes or on cones, bobbins- or warp beams, especially when these supports are perforated, or to loose fibres in permeable containers such as cages, pressure and/or vacuum may be employed to facilitate penetration and circulation through the packages.Alternatively, continuous or semicontinuous dyeing methods may be employed, such as those employing padding techniques, e.g. by padding mangles whereby the textile material is impregnated with dye liquor and then passed through rollers to control the amount of liquor retained, followed by one or more of a variety of post treatments e.g. drying, jig or winch development, baking, steaming, repadding in further solutions such as acid binding agents as mentioned above, storage in a moist conditions at ambient or elevated temperatures, passing over heated rollers or passing through batchwise or continuous washing procedures. These post treatments may also incorporate finishing stages at which for example antistatic or crease resistance agents can be incorporated.Textiles in sheet form may also be coloured by textile printing methods such as printing with engraved or embossed rollers or through screens or by transfer techniques such as wet transfer printing. Details of these and other suitable printing methods are described in "The Principles and Practise of Textile Printing" by E.

Knecht, J. B. Fothergill and G. Hurst, 4th Edition 1952 published by Griffin or in "An Introduction to Textile Printing" by W. Clarke, 4th Edition 1974 published by Newnes Butterworth.

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 level of alkali stability superior to that normally found in 6,13-dichlorotriphendioxazine reactive dyes and surprisingly often -have better buiki-up -of- shade -than their 6,13-dichloro triphendioxazine analogues.

The invention is illustrated by the following Examples in which all parts and proportions in wtlvol are kgs/litre and temperatures are in OC.

Examples 1-18 A neutral solution of 19 parts of aniline-3,5-disulphonic acid in 25 parts of water is added over 30 minutes to a suspension of 1.5 parts of cyanuric.chloride in 10 parts of acetone and 50 parts of water, keeping the temperature belts 5 and the pH in the range 6.5-7.0. The reaction mixture is stirred at e-50 at pH 6.5 7.0 for 1 hour, and filtered in order to remove unreacted cyanuric chloride. This solution is added to a solution of 1.48 parts of a triphendioxazine dyebase of formula:

in 250 parts of water. The resulting mixture is stirred for 4 hours at 50-55 , maintaining the pH at 9 with 2N aqueous sodium hydroxide.The mixture is adjusted to pH 7 with the addition of hydrochloric acid, and added to 2000 parts of acetone. The precipitated product is collected, washed with acetone and dried.

The product obtained dyes cellulose textile materials in bright reddish-blue shades with very good fastness properties.

The triphendioxazine dyebase used above is prepared as follows:- 20.4 parts of 2,5-dimethyl-1,4-benzoquinone are added at 600 over 45 minutes to a solution of 36.4 parts of 4-(2'-aminoethylaminoaniline-3-sulphonic acid of apparent molecular weight 364.0 in 400 parts of water. The mixture is stirred for 2 hours at 600 maintaining the pH at 6.5 throughout with 2N aqueous sodium hydroxide. The mixture is cooled to 200 and the product, 2,5-bis[4'-(2"-aminoethylamino)3'- sulphophenylamine]-3,6-dimethyl-1,4-benzoquinone, is filtered off, washed with a little cold water, slurried in acetone, re-filtered and dried.

9 Parts of the foregoing product are added to 180 parts of 23 O/ oleum, keeping the temperature below 10 . The mixture is warmed to 200, heated at 700 for 5 minutes and cooled to 2025 over 1 hour. The mixture is added to 500 parts of ice/water, and the product filtered off. The product is purified by slurrying into 300 parts of water at pH 9.0 filtering off and drying.

The product has the structure:

Following the above, similar dyestuffs are made using the following amines in place of aniline-3,5-disulphonic acid: Example amine 2 aniline-3-sulphonic acid 3 aniline-2,54isulphonic acid 4 2-carboxyaniline-4-sulphonic acid 5 2-carboxyaniline-4,5-disulphonic acid 6 2-rnethylaailine-5-sulphonic acid 7 N-sulphomethylamine 8 2-aminonaphthalene-6,8-disulphonic acid 9 l-aminonaphthalene-3,6,8-trisulphonic acid 10 aniline-2,4-disulphonic acid 11 2-aminonaphthalene-S,7-disulphonic acid 12 l-aminonaphthalene-3,8-disulphonic acid 13 sulphanilic acid 14 orthanilic acid 15 3aminoaniline-4-sulphonic acid 16 4-aminoamine-3-sulphonic acid 17 4-methoxyaniline-3-sulphonic acid 18 4-chloroaniline-3-sulphonic acid.

Examples 19-35 Following the- procedure of Examples 1, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 1-18 are replaced by equivalent amounts of- the following acylating agents: Example. acylatirg agent 19 cyanuric chloride 20 2,4-dichloro-6-ss-hydroxyethylamino-s-triazine 21 2,4-dichloro-6-ss-hydroxypropylamino-s-triazine 22 2,4-dichloro-6-methoxy-s-triazine Example acylating agent 23 2,4-dichloro-6-amino-s-uiazine 24 2,4-dichloro-6-methylamino-s-triazine 25 2,3-dichloroquinoxaline-6-sulphonyl chloride 26 2,4,5,6-tetrachloropyrirnidine 27 2,4-dichloro-6-dimethylamin-s-triazine 28 2,4,6-trichloropyrimidine 29 1,4-dichlorophthalazine-6-carbonyl chloride 30 2,4,6-trichloro-5-cyanopyrimidine 31 2,4-dichloro-6-p-sulphophenoxy-s-triazine 32 2,4,6-trifluoro-5-chloropyrimidine 33 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone 34 2,4,6-tribromopyrimidine 35 2,4-dichloro-6-ss-sulphatoethylamino-s-triazine 36 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",5"-disulphoanilino) 5-triazinylamino] benzene sulphonic acid 37 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-methoxy-s-triazinyl amino)benzene-1,5-disulphonic acid 38 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene-1,5-disulphonic acid 39 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-amino-s-triazinylamino) berzene-1,5-disulphonic add 40 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 41 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-methoxy-s-triazinyl amino)benzene-1,4-disulphonic acid 42 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino-s-triazinylamino) benzene-1,4-disulphonic acid 43 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(m-sulphoanilino)-s triazinylamino]benzene-1,4-disulphonic acid 44 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 45 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-5'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 46 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(4"-sulphoanilino)-s triazinylamino]benzene-1,4-disulphonic acid 47 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2"-methyl-5"-sulpho anilino)-s-triazinylamino]benzene-1,4-disulphonic acid 48 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(N"-sulphomethyl anilino)-s-triazinylamino]benzene-1,4-disulphonic acid 49 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",6",8"-trisulpho naphthyl-1"-amino)-s-triazinylamino]benzene-1,4-disulphonic acid 50 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(N"-methyl-3"-sulpho anilino)-s-triazinylamino]benzene-1,4-disulphonic acid 51 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2"-methyl-4",5" disulphoanilino]-s-triazinylamino]-benzene-1,4-disulphonic acid 52 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-sulphomethylamino-s triazinylamino]benzene-1,4-disulphonic acid 53 2-(2',4'-dichloro-s-triazinylamino)-6-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]naphthalene-4,8-disulphonic acid 54 1-(2',4'-dichloro-s-triazinylamino)-5[2'-chloro-4'-(3",6",8"-trisulpho naphthyl-1"-amino)-s-triazinylamino]naphthalene-3,7-disulphonic acid Example 55 The triphendioxazine dyebase used in Example 1 is reacted with one mole proportion of 2,4-bis(2',4'-dichloro-s-triazinylamino)-benzene-1,5-disulphonic acid at 40 C at pH 8.8-9.0 using essentially similar conditions to those used in Example 107 in U.K. Specification 1,450,746.

The product dyes cellulose textiles bright reddish-blue shades of good fastness to light and washing Example 56 The product described in Example 55 is reacted with ammonia at 25-300C for 12 hours, as described in Example 108 of U.K. Specification 1,450,746. There is obtained a dyestuff which dyes cellulose textiles bright reddish-blue shades with very good fastness to light and washing.

Examples 57 62 The product described in Example 55 is reacted with metanilic acid at 40-450C for 12 hours at pH 6.5-7.0, using essentially similar conditions to those described in Example 110 of U.K. Specification 1,450,746. There is obtained a dyestuff which dies cellulose textiles bright reddish-blue shades with very good fastness to light and washing.

Similar dyestuffs to those in Examples 56 and 57 are obtained if equivalent amounts of the following amines are used in place of metanilic acid in Example 57.

Example amine 58 aniline-3,5-sulphonic acid 59 1-aminonaphthalene-3,6,8-trisulphonic acid 60 sulphanilic acid 61 2-rnethyl-5-sulphonic acid 62 N-sulphornethylaniline.

Example 63 A similar dyestuff to that obtained in Example 55 is obtained if an equivalent amount of 2,5-bis(2',4'-dichloro-s-triazinylamino)benzene-1,4-disulphonic acid is used in place of 2,4-bis(2',4'-dichloro s-triazinylaminobenzene-1,5-disulphonic acid. The dyestuff shows similar dyeing properties to that described in Example 55.

Example 64 Reaction of the dyestuff of Example 63 with ammonia under similar conditions to that described in Example 56 gives a dyestuff which dyes cellulose textiles bright reddish-blue shades with very good fastness properties.

Examples 65-72 A similar dyestuff to that of Example 64 is obtained when the dyestuff of Example 63 is reacted with metanilic acid under similar conditions to those described in Example 57.

Similar dyestuffs to those in Example 65 are obtained if the metanilic acid is replaced with equivalent amounts of the following reactants: Example reactant 66 4-sulphophenol 67 sulphanilic acid 68 2-aminonaphthalene-4,6,8-rrisulphonic acid 69 N-methylaniline-5-sulphonic acid 70 sulphomethylamine 71 N-sulphomethylamine 72 aniline-3,5-disulphonic acid.

Example 73 The dyebase of Example 1 is reacted successively with 2,4-dichloro-6-(4'-Nmethylamino-3'-sulphophenylamine)-s-triazine and cyanuric chloride using reaction conditions essentially similar to those described in Example 73 of U.K. Specification 1,450,746.

The product obtained dyes cellulose textile materials in bright reddish-blue shades with good fastness to light and washing.

Examples 74-79 Reaction of the dyestuff of Example 73 prior to isolation by salting with 3,5disulphoaniline under essentially similar conditions to those outlined in Example 74 of U.K. Specification 1,450,746 yields a dye which dyes cellulose textiles in bright reddish-blue shades with very good fastness to light and washing.

Similar dyestuffs to those obtained in Example 74 when the 3,5-disulphoaniline is replaced by equivalent amounts of the following gamines: Example amine 75 3-sulphoaniline 76 4-sulphoaniline 77 N-sulphomethylaniline 78 N-sulphomethyl-3-sulphoaniline 79 2-methyl-5-sulphoaniline.

Example 80 The dyestuff of Example 15 is reacted with cyanuric chloride under essentially similar conditions to those described in Example 97 of U.K. Specification 1,450,746 giving a product which dyes cellulose textile materials in bright reddish-blue shades of good fastness to light and washing.

Examples 81-84 Reaction of the dyestuff of Example 80 with metanilic acid as described in Example 98 of U.K. Specification 1,450,746 gives a dyestuff which dyes cellulose textiles bright reddish-blue shades with good fastness to light and washing.

Dyestuffs with a similar shade are obtained if the following amines are used in place of metanilic acid in Example 81.

Example amine 82 3,5-disulphoaniline 83 sulphanilic acid 84 N-sulphomethylaniline.

Examples 83-103 A mixture of 2.55 parts of the reactive dye from Example 1 of apparent Mol.

wt. 1700.0, 0.41 parts of nicotinic acid and 50 parts of water at pH 7 is stirred and heated at 95-1000C for 24 hours. The mixture is cooled, added to 400 parts of acetone, and the product filtered off and dried.

The product dyes cellulose textile fibres in bright reddish-blue shades with very good fastness properties.

Similar reddish-blue dyestuffs are obtained following the above procedure with chlorotriazinyl dyestuffs and quaternising agents as detailed below: Example chlorotriazinyl dye quaternising agent 86 as Example 2 nicotinic acid 87 " " 3 " " 88 ,, " 3 trimethylamine 89 ,, ,, 3 pyridine 90 ,, " 3 rpicoline 91 ,, ,, 3 4-carboxypyndine 92 ,, ,, 3 pyridine-3-acetic acid 93 ,, " 3 pyridine-3-acrylic acid 94 ,, " 4 pyridine 95 ,, ,, 4 nicotinic acid 96 ,, " 5 trimethylamine 97 ,, ,, 7 nicotinic acid 98 ,, ,, 9 99 ,, ,, 10 100 ,, ,, 10 pyridinium 101 ,, ,, 11 nicotinic acid 102 " " 13 103 ,, ,, 15 Examples 104-113 Similar reddish-blue dyestuffs to that described in Example 1 are obtained following the procedure of that Example but using in the preparation of the triphendioxazine dyebase, equivalent quantities of the following diamines in place of 4(2'-aminoethyl)- aminoaniline-3-sulphonic acid, for the reaction with 2,5 dimethyl-1,4-benzoquinone.

Example Diamine Shade 104 1,4-diaminobenzene-2-sulphonic acid reddish blue 10S 4,4'-diaminodiphenylamine-2,3 '- disulphonic acid mid-blue 106 3,4'-diaminodiphenylamine-2,4' disulphonic acid 107 4-(3'-amino-2'-hydroxypropyl)amino aniline-3-sulphonic acid reddish blue 108 4,4'-diamino-2,2'-disulphodiphenylurea dull blue 109 2,6-diaminonaphthalene-4,8-disulphonic acid blue Example Diamine Shade 110 4-(2'-ss-hydroxyethylamine)ethylamino aniline-3-sulphonic acid reddish blue 111 4-(2'-aminopropyl)aminoaniline-3 sulphonic acid 112 4,4'-diamino-3-methyldiphenylamine 3',6-disulphonic acid blue 113 4,4'-diaminodiphenylamine-2,2',5' trisulphonic acid mid-blue Examples 114-118 A similar blue reactive dyestuff is obtained by following the procedure of Example 1 using in place of the triphendioxazine dyebase, an equivalent quanrity of the triphendioxazine base of formula:

The above dyebase is prepared as follows.

A hot solution of 10.8 parts of 1,4-benzoquinone in 200 parts of ethanol is added to a solution of 23.1 parts of 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid in 500 parts of water at pH 5.5-6.0. The mixture is stirred at 20-5 C for 30 minutes, filtered and the solid product washed with cold water, boiling ethanol and dried.

3 Parts of the foregoing addition product are added to 60 parts of 23% oleum over a period of 20 minutes keeping the temperature below 10 . The mixture is heated to 20-250 over 15 minutes and then at 70-750 for 1 hour. After drowning into 150 parts of ice/water and stirring for 30 minutes at 200, the product is filtered off, washed with ice-water and dried at 500.

Similar dyestuffs to that in Example 114 using the following amines in place of aniline-3,5-disulphonic acid are obtained.

Example amine 115 3-sulphoaniline 116 aniline-2,5-disulphonic acid 117 3,4-dicarboxyaniline 118 2-aminonaphthalene-6,8-disulphonic acid Examples 119-124 The dyestuff of Example 114 is reacted with nicotinic acid as described in Example 85. A product is obtained which dyes cellulosic textiles in blue shades with good fastness to light and washing.

Similar blue dyestuffs are obtained following the procedure of Example 119.

Example chlorotriazinyl dye quaternising agent 120 as Example 116 nicotinic acid 121 " " 116 pyridine 122 " " 116 trimethylamine 123 " " 115 nicotinic acid 124 ,, ,, 117 Example 125 A neutral solution of 4.2 parts of aniline-2,5-disulphonic acid in 50 parts of water is added over 30 minutes to a suspension of 3.1 parts of cyanuric chloride in 10 parts of acetone and 50 parts of water, keeping the temperature below 50 and the pH in the range 6.5-7.0. The reaction is stirred at 0-50C at pH 6.5-7.0 for 1 hour and filtered to remove unreacted cyanuric chloride. The filtrate is added to a solution of 4.6 parts of a triphendioxazine dyebase of formula:

in 400 parts of water. The mixture is stirred for 6 hours at 50-55 C, maintaining the pH at 9 with 2N aqueous sodium hydroxide.The mixture is adjusted to pH 7 with the addition of hydrochloric acid, and salted with 150 parts of sodium chloride.

The mixture is cooled, filtered and the product cake slurried into 250 parts of ethanol and water is added until the dyestuff just begins to dissolve. The purified dyestuff is filtered off at this stage, washed with ethanol and dried.

When applied to cellulosic textiles, the product gives a brilliant reddish-blue shade with very good fastness to light and washing and excellent build-up properties.

The above triphendioxazine dyebase is prepared as follows: 8.6 Parts of tetramethoxybenzo-1,4-quinone are added to a neutral solution of 16.8 parts of 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid containing a little Calsolene Oil. The mixture is stirred at 55-600C for 5 hours, cooled to room tem perature and filtered. The product is washed with ethanol and dried.

15.5 Parts of the foregoing product are added to 310 parts of sulphuric acid monohydrate, keeping the temperature below 150C The mixture is allowed to warm to room temperature. 17 Parts of ammonium persulphate are added, causing an exothermic temperature rise to 55-60 C. The mixture is cooled to 25 C over 30 minutes, added to 500 g. of ice-water mixture, stirred for 1 hour and added to 2000 parts of ethanol. The precipitated dyebase is collected, washed with alcohol and dried.

Following the above technique, similar dyestuffs are obtained using the following amines in place of aniline-2,5-disulphonic acid.

Example amine 126 aniline-3,5-disulphonic acid 127 as Example 2 128 " " 4 129 " " 5 130 " " 6 131 " " 7 132 " " 8 133 " " 9 134 " " 10 135 " " 11 136 " " 12 137 " " 13 138 " " 14 139 " " 15 140 " " 16 141 " " 17 142 " " 18 Following the procedure of Example 125, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 126-142 are replaced by the equivalent amounts of the following acylating agents:: Example acylating agent 143 as Example 19 144 " " 20 145 " " 21 146 " " 22 Example acylating agent 147 as Example 23 148 " " 24 149 " " 25 150 " " 26 151 " " 27 152 " " 28 153 " " 29 154 " " 30 155 " " 31 156 " " 32 157 " " 33 158 " " 34 159 " " 35.

Example 160 The triphendioxazine dyebase used in Example 125 is reacted with one mole of 2,4-bis(2',4'dichloro-s-triazinylamino)-benzene-1,5-disulphonic acid at 400C at pH 8.8-9.0 using essentially similar conditions to those used in Example 107 in U.K.

Specification 1,450,746.

The product dyes cellulose textiles bright reddish-blue shades of good fasmess to light and washing.

Example 161 The product described in Example 160 is reacted with ammonia at 25 ZOOC for 12 hours, as described in Example 108 of U.K. Specification 1,450,746. There is obtained a dyestuff which dyes cellulose textiles bright reddish-blue shades with very good fastness to light and washing.

Examples 162-167 The product described in Example 160 is reacted with metanilic acid at 40450C for 12 hours at pH 6.5-7.0, using essentially similar conditions to those described in Example 110 of U.K. Specification 1,450,746. There is obtained a dyestuff which dyes cellulose textiles bright reddish-blue shades with very good fastness to light and washing.

Similar dyestuffs to those obtained in Examples 161 and 162 are obtained if equivalent amounts of the following amines are used in place of metanilic acid in Example 162: Example amine 163 aniline-3,5-sulphonic acid 164 1-aminonaphalene-3,6,8-trisulphonic acid 165 sulphanilic acid 166 2-methyl-5-sulphonic acid 167 N-sulphomethylaniline Example 168 A similar dyestuff to that obtained in Example 160 if an equivalent amount of 2,5-Ms(2',4'-dichloro-s-triazinylamino)benzene-1,4-disulphonic acid is used in place of 2,4-bis(2',4'-dichloro-s-triazinylamino)benzene-1,5-disulphonic acid The dyestuff shows similar dyeing properties to that described in Example 160.

Example 169 Reaction of the dyestuff of Example 168 with ammonia under similar conditions to that described in Example 161 gives a dyestuff which dyes cellulose textiles bright reddish-blue shades with very good fastness properties.

Examples 170-177 A similar dyestuff to that of Example 169 is obtained when the dyestuff of Example 168 is reacted with metanilic acid under similar conditions to those described in Example 162.

Similar dyestuffs to those in Example 170 are obtained if the metanilic acid is replaced with equivalent amounts of the following reactants: Example reactant 171 4-sulphopbenol 172 sulphanilic acid 173 2-aminonaphthalene-4,6,8-trisulphonic acid 174 N-niethylaniline-5-sulphonic acid 175 sulphomethylamine 176 N-sulphomethylamine 177 anilene-3,5-disulphonic acid Examples 178-190 4.7 Parts of rhe dyestuff described in Example 125 having an apparent molecular weight 3105 are added to a solution of 0.41 parts of nicotinic acid in 43 parts of water at pH 7. The mixture is stirred and heated at 95100 for 24 hours, cooled and poured into 250 parts of acetone. The precipitated dyestuff is collected washed with acetone and dried.

When applied to cellulose textiles, it produces very bright reddish-blue shades with very good fastness to light and washing.

Similar reddish-blue dyestuffs are obtained following the above procedure with chlorotriazinyl dyestuffs and quaternising agents as detailed below: Example chlorotriazinyl dye quaternising agent 179 as Example 126 nicotinic acid 180 ,, ,, 126 pyridine 181 ,, ,, 126 4-carboxypyridine 182 " ,, 126 y-picoline 183 ,, ,, 126 trimethylamine 184 ,, ,, 127 nicotinic acid 185 ,, ,, 128 186 " 131 187 ,, ,, 131 pyridine 188 ,, ,, 133 nicotinic acid 189 " 134 190 " ,, 137 Examples 191-197 Similar reddish-blue dye stuffs to that described in Example 125 are obtained following the procedure of that Example but using in the preparation of the triphen dioxazine dyebase, equivalent quantities of the following diamines in place of 4(2'- aminoethyl)aminoaniline-3-sulphonic acid, for the reaction with tetrarnethoxybenzo- I ,4-quinone.

Example diamine shade 191 1,4-diaminobenzene-2-sulphonic acid reddish-blue 192 4-(3'-amino-2'-hydroxypropyl)amino aniline-3-sulphonic acid " " 193 4-(2'-aminopropyl)aminoaniline-3 sulphonic acid 194 4-(2'B-hydrxyerhylamino)ethylamino- aniline-3-sulphonic acid " 195 4,4'-diamino-2,2'-disulphodiphenylurea dull blue 196 2,6-diaminonaphthalene-4,8-disulphonic acid blue 197 N-(4'-amin2 '-sulphophenyl)piperazine Examples 198-222 Similar bright reddish-blue dyestuffs are obtained when the dyestuff of Example 192 is reacted with equivalent amounts of the following acylating agents in place of 2,4-dichloro-6-(2',5'-disulphoanilino)-s-triazine.

Example acylating agent 198 cyanuric chloride 199 2,4-dichloro-6-ss-hydroxyethylamino-s-triazine 200 2,4-dichloro-6-methoxy-s-triazine 201 2,4-dichloro-6-amino-s-triazine 202 2,4-dichloro-6-dimethylamin-s-triazine 203 2,4,6-trichloropyrimidine 204 1,4-dichlorophthalazine-6-carbonyl chloride 205 2,4,6-trichloro-5-cyanopyrimidine 206 2,4-dichloro-6-p-sulphophenoxy-s-triazine 207 2,4,6-trifluoro-5-chloropyrimidine 208 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone 209 2,4,6-tribromopyrimidine 210 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene sulphonic acid 211 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino-s-triazinylamino) benzene sulphonic acid 212 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-methoxy-s-triazinyl amino)benzene-1,5-disulphonic acid 213 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene-1,5-disulphonic acid 214 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-amino-s-triazinylamino) benzene-1,5-disulphonic acid Example acylating agent 215 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-methoxy-s-triazinyl amino)benzene- 1,4-disulphonic acid 216 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino-s-triazinylamino) benzene-1,4-disulphonic acid 217 2-(2',4'-dichloro-s-triazinylamino-5-[2'-chloro-4'-(m-sulphoanilino)-s triazinylamino]benzene-1,4-disulphonic acid 218 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 219 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 220 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(4"-sulphoanilino)-s triazinylamino] benzene-1,4-disulphonic acid 221 2,4-dichloro-6(3'-sulphoanilino)-s-triazine 222 2,4-dichloro-6-(3',4'-dicarboxyaniline)-s-triazine 223 2,4-dichloro-6-(3",5"-disulphoanilino)-s-triazine Examples 224-230 Similar bright reddish-blue dyestuffs are obtained if the 2,5-dimethylbenz1,4- quinone in Example 1 is substituted by equivalent amounts of the following quinones:: Example quinone 224 2-methyl-1,4-benzoquinone 225 2-ethyl-1,4-benzoquinone 226 2-phenyl-1,4-benzoquinone 227 2-(2'-chlorophenyl)-1,4-benzoquinone 228 2-methyl-5-ethyl-1,4-benzoquinone 229 2-methyl-5-cyclohexyl-1,4-benzoquinone 230 2,S-dibenzyl-1,4-benzoquinone Examples 231-234 Similar bright reddish-blue dyestuffs are obtained if the tetrarnethoxybenzo-1,4- quinone in Example 125 is substituted by equivalent amounts of the following quinones:: Example quinone 231 2-methyl-3,6-dimethoxy-1,4-benzoquinone 232 2-chloro-3,6-dimethoxy-1,4-benzoquinone 233 2,3,5,6-tetraethoxy-1,4-benzoquinone 234 2,5-dimethyl-3,6-dimethoxy-1,4-benzoquinone Example 235 A solution of 0.41 parts of cyanuric chloride in 12 parts of acetone is added to a solution of 1.45 parts of a sample having an apparent molecular weight 1451 of a triphendioxazine dyebase of formula:

in 50 parts of water, keeping the temperature below 5 C and the pH in the range 6.5 to 7.0. The mixture is stirred for 30 minutes at 0-SOC, filtered to remove unchanged cyanuric chloride and the filtrate salted to 25 % w/v with sodiurn chloride. The precipitated dyestuff is filtered off and vacuum-dried at room temperature.

When applied to cellulose textiles, the product yields bright blue shades with very good fastness to light The dyebase used in the above preparation is prepared by adding 8.55 parts of tetramethoxy-1,4-benzoquinone to a solution of 26.9 parts of 4,4'-diaminodiphenylamine-2,3'-disulphonic acid in 375 parts of water containing a little Calsolene Oil at pH 6, and stirring and heating the resultant mixture at 600C at pH 6 for 7i hours. The mixture is cooled to room temperature, salted to 10% and the product, the condensation product between the quinone and the diamine, filtered off, slurried in 750 parts of ethanol, refiltered and dried.

3 Parts of the foregoing condensation product is added to 100 parts of 22% oleum, keeping the temperature below 15OC, heated to 200C over 15 minutes, heated to 550C over 20 minutes, maintained at 550C for 5 minutes and then cooled to below 200C. The mixture is then added to 400 parts of ice-water, keeping the temperature below 100C, salted to 5% with potassium chloride and filtered. The product cake is slurried into 150 parts of water adjusted to pH 5.5 with 2N sodium carbonate, salted with about 70 parts of saturated aqueous potassium acetate. The precipitated purified product is filtered off, slurried in 100 parts of ethanol and filtered off and dried.

Example 236 The dyestuff described in Example 235 is reacted with ammonia using very similar conditions to those described in Example 56. The product dyes cellulose textiles bright blue shades with similar properties to those of the dyestuff of Example 235.

Examples 237-243 Similar bright blue dyestuffs are obtained when the dyestuff of example 235 is reacted with the following amines under similar conditions to those described in Example 57: Example amine 237 metanilic acid 238 3-aminobenzenesulphonamide 239 3-aniiaobenzoic acid 240 4-aminobenzoic acid 241 sulphanilic acid 242 3,5-disulphoaniline 243 N-sulphomethylaniline Examples 244-278 Similar bright blue dyestuffs are obtained if equivalent amounts of the following acylating agents are used in place of cyanuric chloride in Example 235:: Example acylating agent 244 2,4-dichloro-6-methoxy-s-triazine 245 2,4-dichloro-6-amino-s-triazine 246 2,4-dichloro-6-methylamine-s-triazine 247 2,3-dichloroquinoxaline-6-sulphonyl chloride 248 2,4,6-trichloro-5-cyanopyrimidine 249 2,4-dichloro-6-p-sulphophenoxy-s-triazine 250 2,4,6-trifluoro-5-chloropyrimidine 251 2,4-dichloro-6-methylamino-s-triazine 252 2,3-dichloroquinoxaline-6-sulphonyl chloride 253 2,4,5,6-tetrachloropyr dine 254 2,4-dichloro-6-n-butoxy-s-triazine 255 2,4-dichloro-6-dimethylamino-s-triazine 256 2,4,6-trichloropyrimidine 257 1,4-dichlorophthalazine-6-carbonyl chloride 258 2,4,6-trichloro-5-cyanopyrimidine 259 2,edichloro-6-p-sulphophenoxy-s-triazine 260 2,4,6-trifluoro-5-chloropyrimidine 261 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone 262 2,4,6-trirtomopyrirridine 263 2,4-dichloro-6-ss-sulphatoethylamino-s-triazine 264 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-m-sulphoanilino-s triar:lnylaono)benzene sulphonic acid 265 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino-s-triazinylamino) benzene suiphonic acid 266 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino)benzenesulphonic acid 267 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-methoxy-s-triazinyl arnino)benzene-1,5Zisulphonic acid 268 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene-1,5-disulphonic acid 269 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-amino-s-triazinylamino) benzene-1,5-disulphonic acid Example acylating agent 270 2-(2'4'-dichloro-s-trazinylamino)-4-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 271 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 272 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-methoxy-s-triazinyl amino)benzene-1,4-disulphonic acid 273 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino-s-triazinylamino) benzene-1,4-disulphonic acid 274 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(m-sulphoanilino)-s triazinylamino]benzene-1,4-disulphonic acid 275 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 276 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 277 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(4"-sulphoanilino)-s triazinylamino]benzene-1,4-disulphonic acid 278 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2",4"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid.

Examples 279-281 Similar bright blue dyestuffs are obtained if equivalent amounts of the following diamines are used in place of 4,4'-diaminodiphenylamine-2,3'-disulphonic acid in Example 235.

Example diamine 279 3,4'-diaminodiphenylamine-2,4'-disulphonic acid 280 4,4'-diaminodiphenylamine-2,2',5 '-trisuiphonic add 281 4,4'-diamino-3-methyldiphenylamine-3',6-disulphonic acid Example 282 An equivalent amount of a triphendioxazine dyebase of formula:

is used in place of the triphendioxazine dyebase used in Example 1.A product is obtained which dyes cellulose textiles bright reddish-blue shades with very good fastness to washing and light The triphendioxazine dyebase used above is prepared as follows: 5.64 Parts of 2-methyl-3,5,ó-trichloro-1,4benzoquinone are added as a neutral solution of 9.1 parts of 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid in 200 parts of water containing a little Calsolene OiL The mixture is heated at 65-700C for 5f hours, keeping the pH at 6.5. The mixture is filtered hot, and the product cake is slurried into 400 parts of acetone, refiltered and dried.The product is purified by dissolving in 300 parts of water, neutralising with aqueous sodium hydroxide, adding decolorising carbon, filtering and acidying the liquors. The product is washed with a little cold water and dried.

1.5 Parts of the foregoing condensation product is added to 30 parts of 24% oleum, keeping the temperature below 15 cm. The mixture is stirred for 15 minutes whilst warming to 200 C, heated to 600C over 15 minutes, maintained at 600C for 10 minutes and cooled to 50C. The mixture is then added to 200 parts of ice-water.

The mixture is stirred for 15 minutes, filtered and the residue washed with cold water, dissolved in aqueous sodium carbonate and reprecipitated with the addition of 2N hydrochloric acid.

Examples 283-289 Similar bright reddish-blue dyestuffs are obtained if the following amines are used in place of aniline-3,5-disulphonic acid in Example 282: Example amines 283 as Example 2 284 " " 3 285 " " 5 286 " " 6 287 " " 7 288 " " 9 289 " " 11 Examples 290-301 Similar bright reddish-blue dyestuffs are obtained if the following acylating agents are used in place of 2,4-dichloro-6-(3',5'4isulphoanilinoks-triazine in Example 282:: Example acylating agent 290 2,4-dichloro-6-methoxy-s-triazine 291 2,4aichloro-6-IEbutoxy-s-triazine 292 2,3-dichloroquinoxaline-5-sulphonyl chloride 293 2-methylsulphonyl-4,5-dichloro-6-methylpyrimidine 294 2,4,6-trichloro-5-cyanopyrimidine 295 2,4,6-trifluoro-5-chloropyrimidine 296 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene-1,5-disulphonic acid 297 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 298 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 299 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(m-sulphoanilino)-s triazinylamino] benzene-1,4-disulphonic acid 300 2-(2',4'-dichloro-s-triazinylamino)-5-[2-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 301 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid Example 302 Reaction of the dyestuff of Example 282 with nicotinic acid using similar conditions to those outlined in Example 85 yields a similar bright reddish-blue dyestuff with very good fastness to light and washing when applied to cellulose.

Example chlorotriazinyl dye quaternising agent 303 as Example 289 nicotinic acid 304 " " 290 305 ,, ,, 292 306 ,, ,, 292 pyridinium 307 ,, ,, 289 308 ,, ,, 289 trimethylammonium Examples 309-312 Similar reddish-blue dyestuffs to that described in Example 282 are obtained following the procedure of that Example but using in the preparation of the triphendioxazine dyebase, equivalent quantities of the following diamines in place of 4-(2'aminoethyl)aminoaniline-3-sulphonic acid, for the reaction with tetramethoxybenzo-1,4quinone: : Example diamine shade 309 1,4-diaminobenzene-2-sulphonic acid reddish-blue 310 4-(3 '-amino-2 '-hydroxypropyl)amino- aniline-3-sulphonic acid " " 311 4,4'-diamino-2,2'-disulphodiphenylurea blue 312 4-(4'-ss-hydroxyethylamino)-aniline-3 sniphonic acid Examples 313-316 Similar bright reddish-blue dyes to those obtained in Example 282 are obtained if the 2-methvl-3,5,6-trichlorobenzo-1,4-quinone in Example 282 is replaced by equivalent amounts of the following quinones:: Example quinone 313 2-methyl-3,5-dichloro-1,4-benzoquinone 314 2-methyl-3,5,6-tribromo-1,4-benzoquinone 315 2-methyl-3,6-dichloro-1,4-benzoquinone 316 2-methyl-3,6-dichloro-5-bromo-1,4-benzoquinone Example 317 A solution of 0.31 parts of cyanuric chloride in 10 parts of acetone is added to a neutral solution of 1.05 parts of a sample having an apparent molecular weight 1410 of a uiphendioxazine dyebase of formula:

in 50 parts of water, keeping the temperature below 50C and the pH in the range 6.5-7.0. The mixture is stirred for 30 minutes at S5 C at pH 6.5-7.0, filtered to remove unchanged cyanuric chloride, and the filtrate salted to 15%. The product is filtered off.

The product, when applied to cellulose textiles, gives a bright mid-blue shade with excellent fastness to light The triphendioxazine dyebase used in the above Example is prepared as follows: 3.4 Parts of 2-methyl-3,5,6-trichlorobenzo-1,4-quinone are added to a neutral solution of 13.2 parts of 4,4'-diaminodiphenylamine-2,2',5-trisulphonic acid in 120 parts of water, and the mixture heated at 70 C for 16 hours, keeping the pH at 6.0.

Examples 318-323 Similar bright blue dyestuffs are obtained when the dyestuff of Example 322 is reacted with the following amines under similar conditions to those employed in Example Example amine 318 metanilic acid 319 4-aminobenzenesulphonamide 320 4-aminobenzoic acid 321 aniline-3,5-disulphonic acid 322 N-sulphomethylaniline 323 N-sulphomethyl-3-sulphoaniline Examples 324-336 Similar bright blue dyestuffs are obtained if equivalent amounts of the following acylating agents are used in place of the cyanuric chloride in Example 317:: Example acylating agent 324 2,4-dichloro-6-methoxy-s-triazine 325 2,4-dichloro-6-methylamino-s-triazine 326 2,3-dichloroquinoxaline-6-sulphonyl chloride 327 2,4,5,6-tetrachloropyrimidine 328 2,4,6-trichloro-5-cyanopyrimidine 329 2,4,6-trifluoro-5-chlorpyrimidine 330 2,4-dichloro-6-p-toluidino-s-triazine 331 2,4-dichloro-6-p-chloroanilino-s-triazine 332 2,4-dichloro-6-p-nitroanilino-s-triazine 333 2,4-dichloro-6-dimethylamino-s-triazine 334 2,4-dichloro-6-p-sulphophenoxy-s-triazine 335 2,4,5,6-tetrachloropyrimidine 336 1,4-dichlorophthalazine-6-carbonyl chloride Examples 337-338 Similar bright blue dyestuffs are obtained if equivalent amounts of the following diamines are used in place of 4,4' diaminodiphenylamine-2,2',5'-trisulphonic acid in Example 317:: Example diamine 337 4,4'diaminodiphenylamine-2,3 '-disulphonic acid 338 4,4'-diamin*3-methyldiphenylamine-3',6-disulphonic acid Example 339 By using an equivalent amount of the triphendioxazine dyebase of formula:

in place of the triphendioxazine dyebase used in Example 1, a bright reddish-blue reactive dye is obtained with good fastness properties.

The above dyebase is prepared by adding 1.2 parts of tetraphenoxy-1,4-benzo- quinone to a neutral solution of 1.9 parts of 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid in 30 parts of water. The mixture is heated at 65-70 C for 1 hour and at 100 C for 21 hours. The hot reaction mixture is filtered and the filtercake dissolved in 50 parts of water adjusted to pH 12.0 with sodium hydroxide, re-filtered and the filtrate acidified. The product is separated, washed with water and dried.

The foregoing condensation product is then treated with 23% oleum as described in Example 1 to produce the triphendioxazine dyebase.

Examples 340-349 Similar bright reddish-blue dyestuffs are obtained if the 2,4-dichlo-6-(3',5' disulphoanilino)-sctriazine in Example 339 is replaced by the following acylating agents: Example acylating agent 340 2,4-dichloro-6-(2',5'-disulphoanilino)-s-triazine 341 2,4-dichloro-6-(N'-sulphomethylanilino)-s-triazine 342 2,4-dichloro-6-(N'-sulphomethyl-3'-sulphoanilino)-s-triazine 343 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m-sulphoanilino-s triazinylamino)benzene-1,5-disulphonic acid 344 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(3",5"-disulphoanilino) s-triazinylamino]benzene-1,5-disulphonic acid 345 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro-4'-(2",5"-disulpho anilino)-s-triazinylamino]benzene-1,5-disulphonic acid 346 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(m-sulphoanilino)-s triazinylamino)benzene-1,4-disulphonic acid 347 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(3",5"-disulpho anilino)-s-triazinylamino]benzene-1,4-disulphonic acid 348 2-(2',4'-dichloro-s-triazinylamino)-5-[2'chloro-4'-(2",5"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid 349 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(2",4"-disulphoanilino) s-triazinylamino]benzene-1,4-disulphonic acid Examples 350-352 Similar bright reddish-blue dyestuffs are obtained if the 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid in Example 339 is replaced by equivalent amounts of the following diamines:: Example diamine 350 4-(2'-aminopropyl)aminoaniline-3-sulphonic acid 351 1,4-diaminobenzene-2-sulphonic acid 352 4-(3 '-amino-2'-hydroxypropyl)aminoaniline-3-sulphonic acid Examples 353-354 Similar bright reddish-blue dyestuffs are obtained if the tetraphenoxybenzo-1,4 quinone of Example 339 is replaced by the following quinones: Example quinone 353 2,3,5,6-tetra(4'-chlorophenoxy)-1,4-benzoquinone 354 2,3,5,6-tetra(3'-methyl-4'-chlorophenoxy)-1,4-benzoquinone Examples 355-364 If, as in the procedure of Example 114, an equivalent amount of 4,4'-diarnino- diphenylamino-2,3-disulphonic acid is used in place of the 4-(2'-aminoethyl)aminoaniline-3-sulphonic acid in the preparation of the dyebase there is obtained a dyebase of the structure::

This yields a bright reddish-blue reactive dye when reacted with 2,4-dichloro-6 (2',5'-disulphoanilino)-s-triazine as described in Example 21.

Similar bright reddish-blue reactive dyes are obtained by reacting the above dyebase with the following acylating agents:- Example acylating agent 355 cyanuric chloride 356 2,4-dichloro-6-methoxy-s-triazine 357 2,4,5,6-tetrachloropyrimidine 358 2,4,6-trichloropyrimidine 359 2,4,6-trichloro-5-cyanopyrimidine 360 2,4,6-tribromopyrimidine 361 2,4-dichloro-6-(3',5'-disulphoanilino)-s-triazine 362 2,4-dichloro-6-(3'-sulphoanilino)-s-triazine 363 2,4-dichloro-6-(4'-sulphoanilino)-s-triazine 364 2,4-dichloro-6-(N-sulphomethylanilino)-s-triazine Examples 365-379 An equivalent amount of a triphendioxazine dyebase of formula:-

is used in place of the triphendioxazine dyebase used in Example 1.

A blue dyestuff is obtained which yields bright blue shades with very good fastness to light and washing when applied to cellulose textiles.

The triphendioxazine dyebase used in the above Example is prepared as follows: A suspension of 1.14 parts of 2-(2'-chlorophenyl)-3,5,6-tribromo-1,4-benzo- quinone in 20 parts of water containing Calsolene Oil is added at 500C to a neutral solution of 1.15 parts of 1.15 parts of 4 < 2'-aminoethyl)aminoaniline-3-sulphonic acid in 30 parts of water. The mixture is stirred at 50-55 C at pH 6 for 2 hours. The condensation product of the quinone and the diamine is filtered off, washed with cold water and dried.

1 Part of the foregoing product is added to 20 parts of 24% oleum and stirred at 200C for 30 minutes. The mixture is heated to 550C over 25 minutes, maintained at 550C for 15 minutes, cooled to 300C and added to 50 parts of ice-water. The product is filtered off, washed with 200 parts of 10% brine and dried.

Similar bright blue dyestuffs are obtained if the diamines, quinones and acylating agents in Example 365 above are replaced by equivalent amounts of the following:- Example quinone diamine acylating agent 366 2-(2'-chlorophenyl) 3,5,6-tribromo benzo-1,4-quinone as in Example 104 as in Example 265 367 " " " " " 107 " " " " 368 " " " " " 110 " " " " 369 ,, ,, " " " 111 , > ., 370 " " " " " 105 " " " " Example quinone diamine acylating agent 371 2-(2'-chlorophenyl)- as in Example 365 2,4-dichloro-6-(2',5' 3,5,6-tribromo- disulphoaniline-s benzo-1,4-quinone triazine 372 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-4- [2'-chloro4'-(3 ",5 " disulphoanilino)-s triazinylamino] benzene 1,5-disulphonic acid 373 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-4 (2'-chloro-4'-m-sulpho anilino-s-triazinyl amino)benzene-1,5 disulphonic acid 374 " " ,, " " 365 2-(2',4'-dichloro-s- triazinylamino)-5 [2'-chloro-4'-(m sulphoanilino)-s triazinylamino]benze@ 1,4-disulphonic acid 375 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-5 [2'-chloro-4'-(3",5"@ disulphoanilino)-s triazinylamino]benze@ 1,4-disulphonic acid 376 2-(4'-chlorophenyl)- " " " " as in Example 365 3,6-dichloro-1,4 benzoquinone 377 2-(4'-nitrophenyl)- " " " " " " " " 3,6-dichloro-1,4- benzoquinone 378 2-(4'-nitrophenyl)- " " " " " " " " 3,5,6-trichloro-1,4 benzoquinone 379 2-phenyl-3,6-dichloro- " " " " " " " " 1,4-benzoquinone WHAT WE CLAIM IS: 1. Cellulose-reactive dyestuffs containing a triphendioxazine nucleus having an atom or group, other than chlorine, on one or both of the 6- and 13-positions of said nucleus.

2. Dyestuffs as claimed in claim 1 in which there is attached to one of the 6- and 13-positions of the triphendioxazine nucleus a hydrogen atom or an alkyl, aralkyl, aryl, alkoxy, aryloxy or aralkoxy group, all of which groups may optionally be substituted, or cycloalkyl, and in which the other of the 6- and 13-positions has attached one of the aforementioned groups or a hydrogen or halogen atom.

3. Dyestuffs as claimed in claim 1 or 2 and represented by the formula: TPD(NR7Q)n wherein TPD represents a n-valent triphendioxazine residue of the type defined in claim 1 or 2; R7 is H or an optionally substituted hydrocarbyl group, n is 1 or 2, and Q is a cellulose-reactive group.

4. Dyestuffs as claimed in claim 3 wherein the group or groups NR7Q are linked directly to a carbon atom in the triphendioxazine nucleus.

5. Dyestuffs as claimed in claim 3 wherein the group or groups NR7Q are linked to an optionally substituted alkylene, optionally substituted arylene or optionally substituted aralkylene group itself attached to the triphendioxazine nucleus by O or NH.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (35)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   Example quinone diamine acylating agent

   371 2-(2'-chlorophenyl)- as in Example 365 2,4-dichloro-6-(2',5' 3,5,6-tribromo- disulphoaniline-s benzo-1,4-quinone triazine

   372 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-4- [2'-chloro4'-(3 ",5 " disulphoanilino)-s triazinylamino] benzene 1,5-disulphonic acid

   373 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-4 (2'-chloro-4'-m-sulpho anilino-s-triazinyl amino)benzene-1,5 disulphonic acid

   374 " " ,, " " 365 2-(2',4'-dichloro-s- triazinylamino)-5 [2'-chloro-4'-(m sulphoanilino)-s triazinylamino]benze@ 1,4-disulphonic acid

   375 " " " " " " 2-(2',4'-dichloro-s triazinylamino)-5 [2'-chloro-4'-(3",5"@ disulphoanilino)-s triazinylamino]benze@ 1,4-disulphonic acid

   376 2-(4'-chlorophenyl)- " " " " as in Example 365 3,6-dichloro-1,4 benzoquinone

   377 2-(4'-nitrophenyl)- " " " " " " " " 3,6-dichloro-1,4- benzoquinone

   378 2-(4'-nitrophenyl)- " " " " " " " " 3,5,6-trichloro-1,4 benzoquinone

   379 2-phenyl-3,6-dichloro- " " " " " " " " 1,4-benzoquinone WHAT WE CLAIM IS: 1. Cellulose-reactive dyestuffs containing a triphendioxazine nucleus having an atom or group, other than chlorine, on one or both of the 6- and 13-positions of said nucleus.
2. 2. Dyestuffs as claimed in claim 1 in which there is attached to one of the 6- and 13-positions of the triphendioxazine nucleus a hydrogen atom or an alkyl, aralkyl, aryl, alkoxy, aryloxy or aralkoxy group, all of which groups may optionally be substituted, or cycloalkyl, and in which the other of the 6- and 13-positions has attached one of the aforementioned groups or a hydrogen or halogen atom.
3. 3. Dyestuffs as claimed in claim 1 or 2 and represented by the formula: TPD(NR7Q)n wherein TPD represents a n-valent triphendioxazine residue of the type defined in claim 1 or 2; R7 is H or an optionally substituted hydrocarbyl group, n is 1 or 2, and Q is a cellulose-reactive group.
4. 4. Dyestuffs as claimed in claim 3 wherein the group or groups NR7Q are linked directly to a carbon atom in the triphendioxazine nucleus.
5. 5. Dyestuffs as claimed in claim 3 wherein the group or groups NR7Q are linked to an optionally substituted alkylene, optionally substituted arylene or optionally substituted aralkylene group itself attached to the triphendioxazine nucleus by O or NH.
6. 6. Dyestuffs as claimed in any one of claims 3 to 5 in which R7 is H or C14

   alkyl optionally substituted by OH, OSO3H, CN or SO,H.
7. 7. Dyestuffs as claimed in any one of claims 3 to 6 in which Q is or contains a heterocyclic cellulose-reactive group having a cellulose reactive substituent on a carbon atom of the heterocyclic ring.
8. 8. Dyestuffs as claimed in claim 7 in which the heterocyclic group contains 2 or 3 nitrogen atoms in the heterocyclic ring.
9. 9. Dyestuffs as claimed in claim 8 in which the heterocyclic ring is a triazine or pyrimidine ring.
10. 10. Dyestuffs as claimed in claim 9 in which the triazine ring has one or two substituents selected from F, Br, Cl, quaternary ammonium or pyridinium groups.
11. 11. Dyestuffs as claimed in claim 10 in which the pyridinium group is derived from a pyridine carboxylic acid.
12. 12. Dyestuffs as claimed in any one of claims 9, 10 or 11 in which the triazine ring has a substituent not reactive to cellulose.
13. 13. Dyestuffs as claimed in claim 12 in whih the substituent not reactive to cellulose is selected from C1-4 alkoxy, C1-4 alkoxy C1-4 alkoxy, phenoxy, sulphophenoxy, amino, C1-4 alkylamino, di(C1-4 alkyl)amino and groups of the last two types in which one or both of the alkyl groups is substituted by OH, CN or SO3H; cycloalkylamino, morpholino, piperazino, mono-, di- or trisulphonaphthylamino or a group of the formula

    where G is H, methyl, ethyl, #-sulphomethyl, ss-carboxyethyl, ss-hydroxyethyl or ss-cyanoethyl and Z and X are each independently selected from H, COOH, SO3H, CH3, C2H5, OCH3, OC2H5, Cl, Br, CN, NO2, NHCOCH3, NH2, phenylamino and methylamino.
14. 14. Dyestuffs as claimed in claim 7 in which Q is of the form -Ht-Dm-Q' 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 Q' to a cellulose-reactive group having the meaning hereinbefore defined for Q.
15. 15. Dyestuffs as claimed in any one of claims 3 or 6 to 14 having the formula:

    wherein (R6)m represents m substituent groups R6 where each R6 is independently halogen, C1-4 alkyl, C1-4 alkoxy or COOH, m is 0 to 3 a+b is 1 to 4 X is 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 Y together are a direct link X1 is H, cycloalkyl or AR8 where A is 0, or a direct link and R8 is alkyl, aryl or aralkyl all of which may be optionally substituted, X2 is an atom or group of the type defined for X1 or halogen and one of Z and Z' is a cellulose reactive group Q as hereinbefore defined and the other is H or a second cellulose reactive group of the type defined by Q and R7 has the meaning hereinbefore defined.
16. 16. Dyestuffs as claimed in claim 15 in which m is 0 and a and b are each 1.
17. 17. Dyestuffs as claimed in claim 15 in which each X is joined to a position para to a heterocyclic nitrogen.
18. 18. Dyestuffs as claimed in daim 15 of the formula:

    wherein X, X1, X2, Y, R?, Z and Z' have the meanings stated in claim 15.
19. 19. Dyestuffs as claimed in any one of claims 15-18 in which Xis NH.
20. 20. Dyestuffs as claimed in any one of claims 15-18 in which X and Y together are a direct link and R is H.
21. 21. Dyestuffs as claimed in any one of claims 15-19 in which Y is a benzene or naphthalene linking group optionally substituted by 1,2 or 3 SO3H groups.
22. 22. Dyestuffs as claimed in any one of claims 15-19 in which Y is an aliphatic or araliphatic linking group either of which may be optionally substituted.
23. 23. Dyestuffs as claimed in any of claims 3 or 6-15 having the formula:

    wherein X1, X2, Z and Z1 have the meanings stated in claim 15.
24. 24. Dyestuffs as claimed in any one of claims 15-23 in which one or both of X1 and X2 are selected from H, cyclohexyl, cyclopentyl, and groups of the formula AR8 wherein A has the meaning stated in claim 15 and R5 is alkyl optionally substituted by OH, halogen, alkoxy or aryloxy; naphthyl or phenyl each of which may be optionally substituted by halogen, nitro, alkyl, alkoxy, acyl or alkoxycarhonyl; benzyl or phenylethyl.
25. 25. Dyestuffs as claimed in claim 24 in which AR8 is C1 4 alkyl, C1 alkoxy; or phenoxy or phenyl in each of which the nucleus may optionally be substituted by a, NO2 or C1, alkyl.
26. 26. Dyestuffs as claimed in any one of claims 15-25 in which one of X1 and X2 is Cl or Br.
27. 27. Dyestuffs as claimed in claim 1 and described in any one of the Examples.
28. 28. A process for the manufacture of dyestuffs as claimed in claim 3 which comprises reacting an aminotriphendioxazine of the formula: TPD(NR7H)n where TPD, R7 and n have the meanings stated in claim 3 with n moles of carbyl sulphate or a compound of the formula Qhal where Q is a cellulose-reactive group as hereinbefore defined other than ss-sulphatoethylsulphonyl and hal represents halogen.
29. 29. A process for the manufacture of dyestuffs as claimed in claim 3 in which Q is a s-triazine nucleus substituted by a Cl, Br or F atom and an amino or substituted amino group which comprises reacting a dyestuff as claimed in claim 3 in which Q is a dichloro-, dibromo- or difluoro-s-triazine group with ammonia or an amine.
30. 30. A process for the manufacture of dyestuffs as claimed in claim 3, in which Q is of the form -Ht-Dm-Q1 where Ht is a chloro-, bromo- or fluoro-triazinyl group, Dm is the residue of a diamine linking Ht and Q1 by its two amino groups, and Q1 is a cellulose-reactive group which comprises reacting 1 mole of a diamine DmH2 in either order with 1 mole of a dyestuff as claimed in claim 3 in which Q is a dichloro-, dibromo- or difluorotriazinyl group and one mole of carbyl sulphate or a compound Qhal where Q is a cellulose-reactive group other than ,ss-sulphatoethyl- sulphonyl and hal is halogen.
31. 31. A process for the manufacture of dyes as claimed in claim 3 in which Q is a triazinyl group having quaternary ammonium or pyridinium substituents as the cellulose-reactive substituent which comprises reacting the corresponding chloro-, bromo- or fluorotriazinyl dyestuff with the appropriate tertiary amine or pyridine compounds
32. 32. A process as claimed in any of claims 28 to 31 and substantially as described in any one of the Examples.
33. 33. Dyestuffs as claimed in claim 3 whenever produced by a process as claimed in any of claims 28-32.
34. 34. A process for the colouration of cellulose textile materials which comprises contacting the textile material with a dyestuff as claimed in claim 1 in conjunction with a treatment with an acid-binding agent.
35. 35. Textile materials whenever coloured by a process as claimed in claim 34.