Reactive dyes

Abstract

Triphenodioxazine reactive dyes containing at least one fiber-reactive group, the dye, in the free acid form, having the formula: ##STR1## wherein each of T.sup.1 and T.sup.2, independently, represents H, Cl, Br, F, SO.sub.3 H or an optionally substituted alkyl or aryl radical;each of A.sup.1 and A.sup.2 represents alkyl, alkoxy, Cl, Br, COOH, SO.sub.3 H or optionally substituted sulphamoyl;n has a value of 0, 1 or 2;m has a value of 1 or 2;R.sup.1 represents H or a group of the formula: ##STR2## wherein Z represents a fiber-reactive group;each of R.sup.2 and R.sup.3, independently, represents H or an optionally substituted hydrocarbon radical;B represents an optionally substituted divalent hydrocarbon radical; andD represents a group of the formula ##STR3## wherein R.sup.4 represents H, an optionally substituted hydrocarbon radical free from fiber-reactive residues or an acyl radical;R.sup.5 represents H or an optionally substituted hydrocarbon radical;R.sup.6 represents H or an optionally substituted hydrocarbon radical free from fiber-reactive residues;Q represents O or S; anda has a value of 0 or 1,with the proviso that when D is NH.sub.2, B is an arylene radical.

Description

This invention relates to reactive dyes and more particularly to reactive dyes of the triphenodioxazine series and their application to textile materials.

Reactive dyes of the triphenodioxazine series are known and have been described in, for example, United Kingdom Patent Specifications 1349513, 1368158, 1450746, 1477071, 1559752 and 2059985 and in European Patent Specifications 212635, 260227 and 299328.

The present invention provides triphenodioxazine reactive dyes containing at least one fiber-reactive group which, in the free acid form, have the formula: ##STR4## wherein each of T.sup.1 and T.sup.2, independently, represents H, Cl, Br, F, SO.sub.3 H or an optionally substituted alkyl or aryl radical;

each of A.sup.1 and A.sup.2 represents alkyl, alkoxy, Cl, Br, COOH, SO.sub.3 H or optionally substituted sulphamoyl; n has a value of 0, 1 or 2; m has a value of 1 or 2; R.sup.1 represents H or a group of the formula: ##STR5## wherein Z represents a fiber-reactive group; each of R.sup.2 and R.sup.3, independently, represents H or an optionally substituted hydrocarbon radical; B represents an optionally substituted divalent hydrocarbon radical; and D represents ##STR6## wherein R.sup.4 represents H, an optionally substituted hydrocarbon radical free from fiber-reactive residues or an acyl radical; R.sup.5 represents H or an optionally substituted hydrocarbon radical; R.sup.6 represents H or an optionally substituted hydrocarbon radical free from fiber-reactive residues; Q represents O or S; and a has a value of 0 or 1, with the proviso that when D is NH.sub.2, B is an arylene radical.

Examples of optionally substituted alkyl radicals which may be represented by T.sup.1 and T.sup.2 particularly include C.sub.1-4 -alkyl radicals. Examples of optionally substituted aryl radicals which may be represented by T.sup.1 and T.sup.2 include optionally substituted phenyl radicals, for example phenyl, sulphophenyl, methylphenyl, disulphophenyl, dimethylphenyl, methoxyphenyl, dimethoxyphenyl, chlorophenyl, dichlorophenyl, methylchlorophenyl, methoxymethylphenyl, methoxychlorophenyl, aminophenyl and acetylaminophenyl.

It is preferred that each of T.sup.1 and T.sup.2 is Cl or Br.

Examples of alkyl and alkoxy radicals which may be represented by A.sup.1 and A.sup.2 particularly include C.sub.1-4 -alkyl and alkoxy radicals. In most cases, A.sup.1 and A.sup.2 will be identical.

It is preferred that n is 0 and that m is 1.

Fiber-reactive groups have been fully described in the prior art, for example in our GB-A-2063284. Such groups are capable, under suitable conditions, of reacting with the hydroxyl groups present in cellulosic fibers or with the amino groups present in natural and synthetic polyamide fibers to form a covalent linkage between the dye and the fiber.

As examples of fiber-reactive groups which may be represented by Z when R.sup.1 is a group of the formula: ##STR7## there may be mentioned aliphatic sulphonyl groups which contain a sulphate ester group in beta-position to the sulphur atom, e.g. beta-sulphato-ethylsulphonyl groups, alpha,beta- unsaturated acyl radicals of aliphatic carboxylic acids, for example acrylic acid, alpha-chloro-acrylic acid, alpha-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, beta-chloro and beta-bromopropionic acids and alpha,beta-dichloro- and dibromopropionic acids or radicals of vinylsulphonyl- or beta-chloroethylsulphonyl- or beta-sulphatoethyl-sulphonyl-endo- methylene cyclohexane carboxylic acids. Other examples of cellulose reactive groups are tetrafluorocyclobutyl carbonyl, trifluoro-cyclobutenyl carbonyl, tetrafluorocyclobutylethenyl carbonyl, trifluoro-cyclobutenylethenyl 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, 2,4-dicyano-3,5,6-trifluorophenyl, 2,4-dicyano-3,5,6-trichlorophenyl, 2,4,6-tricyano-3,5-difluorophenyl, 2,4,6-tricyano-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 reactive substituent these are usually referred to as heterocyclic reactive groups in this specification.

As example 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-1'-yl)benzoyl, 2-chlorobenzthiazole-6-carbonyl, 3,6-dichloropyrazin-4-carbonyl, 4-(4':5 '-dichloropyridaz-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-yl, 2,3,5,6-tetrafluoropyridin-4-yl, 2,4,6-trifluoro-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 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 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-chloro-2-methylsulphonyl-6-methylpyrimidin-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 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, e.g. SO.sub.3 H but the preferred reactive atoms or groups are F, Br or especially Cl; quaternary ammonium groups such as tri-lower alkyl ammonium, e.g. (CH.sub.3).sub.3 N.sup.30 - 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. C.sub.1-4 -alkoxy, e.g. methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy and lower alkoxy lower alkoxy, e.g. beta-methoxy-ethoxy, beta-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 SO.sub.3 H, e.g. beta-hydroxyethylamino, di(beta-hydroxyethyl)amino, beta-cyano- ethylamino, di(beta-cyanoethyl)amino, beta-sulphoethylamino, beta-hydroxypropylamino, (beta-hydroxybutyl)ethylamino and (beta-hydroxyethyl)methylamino; cycloalkylamino, e.g. cyclohexylamino; cyclic amino, e.g. morpholino or piperazino; naphthylamino substituted by 1,2 or 3 SO.sub.3 H groups and optionally substituted phenyl amino groups.

As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups of the formula: ##STR8## where G=H, methyl, ethyl, -sulphomethyl, beta-carboxy-, beta-hydroxy- or beta-cyanoethyl and Y and X are each independently selected from H, COOH, SO.sub.3 H, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 H.sub.5, Cl, Br, CN, NO.sub.2, NHCOCH.sub.3 and beta-sulphatoethylsulphonyl.

Optionally substituted hydrocarbon radicals which may be represented by R.sup.2, R.sup.3 and R.sup.5 include optionally substituted alkyl (especially C.sub.1-4 -alkyl), and optionally substituted aryl (especially phenyl) radicals.

Optionally substituted divalent hydrocarbon radicals which may be represented by B include optionally substituted alkylene, aralkylene and arylene radicals with the above-mentioned proviso that B must be arylene when D is NH.sub.2.

As examples of alkylene and aralkylene radicals which may be represented by R.sup.2, there may be mentioned:

ethylene 1,2- and 1,3-propylene 2-hydroxy-1,3-propylene 1- and 2-phenyl-1,3-propylene 2-(4'-sulphophenyl)-1,3-propylene 1,4-, 2,3- and 2,4-butylene 2-methyl-1,3-propylene 2-methyl-2,4-pentylene 2.2-dimethyl-1,3-propylene 1-phenylethylene 1-chloro-2,3-propylene 1,6-and2,5-hexylene 2,3-diphenyl-1,4-butylene 1-(methoxycarbonyl)-1,5-pentylene 1-carboxy-1,5-pentylene 2,7-heptylene 3-methyl-1,6-hexylene --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 - --CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 - --CH.sub.2 CH.sub.2 SSCH.sub.2 CH.sub.2 - ##STR9##

As examples of arylene radicals which may be represented by B, there may be mentioned 1,3- and 1,4-phenylene, 1,4-naphthylene and other divalent radicals containing one or more benzene and/or naphthalene nuclei which may optionallY be sulphonated.

Optionally substituted hydrocarbon radicals free from fiber-reactive residues which may be represented by R.sup.4 and R.sup.6 include aryl (especially phenyl), aralkyl, cycloalkyl and alkyl radicals, for example C.sub.1-4 -alkyl radicals. Thus, groups whch may be represented by R.sup.6 (Q).sub.6 - particularly include aryl, aryloxy, arylthio, benzyl, benzyloxy, benzylthio, alkyl, alkoxy and alkylthio.

Acyl radicals which may be represented by R.sup.4 include alkyl carbonyl radicals such as acetyl, arylcarbonyl radicals such as benzoyl and acyl radicals capable of conferring fiber-reactivity on the dyes of Formula 1.

As examples of fiber-reactive acyl radicals which may be represented by R.sup.4, there may be mentioned the fiber-reactive acyl radicals described above with reference to Z.

It is preferred that any fiber-reactive groups represented by R.sup.4 and/or Z are vinylsulphonyl groups or precursor groups thereof or, especially, halogenotriazinyl groups, for example monochlorotriazinyl, monofluorotriazinyl or dichlorotriazinyl groups. It is also within the scope of the invention for reactive groups to be present in the form of vinylsulphonyl groups or precursors thereof, for example hydroxyethylsulphonyl, sulphatoethylsulphonyl or chloroethylsulphonyl, attached directly to B, for example when B is arylene and R.sup.1 is H.

One valuable class of dyes within the scope of Formula 1 comprises the dyes which, in the free acid form, have the formula: ##STR10## wherein A represents alkyl, alkoxy, Cl, COOH, SO.sub.3 H or optionally substituted sulphamoyl;

R.sup.7 represents H or a group of the formula -NHZ; and Z, T.sup.1, T.sup.2, n, m, B and R.sup.4 have the meanings given above with the provisos that when R.sup.7 is H, R.sup.4 is an acyl group having fiber-reactive properties and when R.sup.4 is H, B is an arylene radical.

As examples of useful structures within the scope of Formula 2, there may be mentioned the following: ##STR11## wherein R.sup.8 is alkyl or aryl, ##STR12## wherein R.sup.9 is a fiber-reactive acyl radical, ##STR13## wherein R.sup.9 is as above.

In the compounds of formulae (3)-(7), T.sup.1, T.sup.2, A, Z, n and m have the meanings given above and the fiber-reactive groups Z and R.sup.9 are preferably mono- or dichlorotriazinyl or vinyl sulphonyl groups.

Another valuable class of dyes within the scope of Formula 1 comprises the dyes which, in the free acid form, have the formula: ##STR14## wherein T.sup.1, T.sup.2, A.sup.1, n, m, R.sup.2, R.sup.3, Z, B, Q, a and R.sup.6 have the meanings given above.

It is preferred that the fiber-reactive groups represented by Z in the dyes of Formula 8 are vinylsulphonyl groups or, especially, halogenotriazinyl groups, for example monochlorotriazinyl, monofluorotriazinyl or dichlorotriazinyl groups.

The dyes of the invention may be prepared by reactions conventional to triphenodioxazine chemistry. Thus, for example, dyes of the invention may be prepared by reacting an acylating agent capable of introducing a fiber-reactive group with an unsymmetrical triphenodioxazine of the formula: ##STR15## wherein T.sub.1, T.sup.2, A.sup.1, A.sup.2, n, m, R.sup.2 and B have the meanings given above, D.sup.1 represents a group of the formula R.sup.5 NH- or R.sup.6 (Q).sub.1 - and R.sup.10 represents H or a group of the formula -NR.sup.3 H wherein R.sup.3, R.sup.5, R.sup.6, Q and a have the meanings given above with the proviso that when R.sup.10 is H, D.sup.1 is R.sup.5 NH-. Suitable acylating agents particularly include cyanuric chloride and its primary condensation products with ammonia, primary or secondary amines, alcohols or mercaptans.

Unsymmetrical triphenodioxazines of Formula (9) may be obtained by methods described in the prior art, for example by ring closure of the corresponding unsymmetrical dianilides using strongly acid condensing agents, for example oleum with a persulphate. Sulphonic acid groups may be introduced into the dianilide during cyclisation, for example into any aryl groups represented by R.sup.6.

The unsymmetrical dianilides may be made in a stepwise manner by known methods, for example those described in United Kingdom Patent Specifications 509891 and 509893.

The dyes prepared as described above may be isolated by any conventional means, for example by spray drying or precipitation and filtration.

The dyes contain sulphonic acid groups which confer water-solubility and they may be isolated with such groups in the free acid form. However, it is usually found more convenient to isolate the dyes in the form of salts particularly alkali metal salts, especially sodium but sometimes lithium to improve the water-solubility.

The dyes of the present invention may be used for coloring a wide range of textile materials containing hydroxyl or amino groups, for example wool, silk, synthetic polyamides and natural or regenerated cellulose, for example cotton or viscose rayon materials, by conventional dyeing, padding or printing methods used for colouring such materials with water-soluble reactive dyes. In the case of cellulose, they are preferably applied in conjunction with a treatment with an acid binding agent, for example 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 dye.

The dyes of the present invention are valuable reactive dyes for cellulose. They yield bright blue colored textiles with good resistance to washing, chlorine and light. They are usually characterized by good strength and an ability to build-up to high depths of shade, the shades being somewhat redder than those of the corresponding symmetrical triphenodioxazine reactive dyes.

The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight unless otherwise indicated.

MONO-ANILIDES

Example 1

A solution of 4.6 parts of 5-amino-2-(2-aminoethylamino)benzene-sulphonic acid in 20 parts of water at pH 5 was added to a slurry of 4.8 parts of 2-methoxy-3,5,6-trichlorobenzoquinone in 100 parts of methanol at pH 5.6 and 40.degree. C. The mixture was stirred at 40.degree. C. for 1 hour whilst maintaininq the pH at pH 5. The mixture was cooled in ice, filtered and the solid washed with methanol and dried. 6.9 parts of compound I, 2-(4-(2-aminoethylamino-3-sulphoanilino)-3,6-dichloro-5-methoxy-1,4benzoquinone were obtained. ##STR16##

Example 2

15 parts of 5-amino-2-(2-aminoethylamino)-benzene-sulphonic acid was added portionwise to a slurry of 14 parts of 2-methoxy-3,5,6-trichlorobenzoquinone in 750 parts of methanol at pH 5.6 and room temperature. The mixture was stirred at room temperature for 16 hours whilst maintaining the pH at pH 5.4. The mixture was filtered and the solid washed with methanol, water and dried. 15.5 parts of compound I were obtained.

Example 3

19 parts of 4,4'-diaminodiphenylamine-2,3'-disulphonic acid was added portionwise to a slurry of 14 parts of 2-methoxy-3,5,6-trichlorobenzoquinone in 750 parts of methanol at pH 5.0 and room temperature. The mixture was stirred at room temperature for 16 hours whilst maintaining the pH at pH 5.4. The mixture was filtered and the filtrates were evaporated to dryness. 24.8 parts of compound II were obtained. ##STR17##

Example 4

A solution of 1.9 parts of aniline in 20 parts of methanol was added dropwise to a slurry of 4.8 parts of 2-methoxy-3,5,6-trichlorobenzoquinone in 100 parts of methanol at pH 5.5 and 40.degree. C. The mixture was stirred at 40.degree. C. for 1 hour whilst maintaining the pH at pH 5. The mixture was cooled in ice, filtered and the solid washed with methanol and dried, 4.9 parts of compound III were obtained. ##STR18##

Examples 5-21

Further mono-anilides were prepared using the methods of Examples 2 and 4 to react 2-methyoxy-3,5,6-trichlorobenzoquinone with the aromatic amines indicated below.

______________________________________Example Amine Method______________________________________5 5-amino-2-ethylaminobenzene sulphonic acid 26 5-amino-2-(2-hydroxyethylamino)benzene 2 sulphonic acid7 4-aminodiphenylamine-2-sulphonic acid 28 p-phenylenediamine sulphonic acid 29 metanilic acid 210 5-amino-2-phenoxybenzene sulphonic acid 211 p-anisidine 412 p-toluidine 413 3,4-dimethylaniline 414 4-aminodiphenyl 415 4-(ethylthio)aniline 416 5-amino-2-phenylthiobenzene sulphonic acid 217 4-aminodiphenylmethane 418 5-amino-2-benzyloxybenzene sulphonic acid 219 4-aminodiphenylamine-2,3'-disulphonic acid 220 4-aminobenzanilide 421 4-aminoacetanilide 4______________________________________

DIANILIDES

The following examples use monoanilides of Formula I, II or III as above or are from the monoanilide in Example 8 which has the Formula XXX: ##STR19## and produce dianilides of Formula IV: ##STR20##

Example 22

A solution of 2.1 parts of metanilic acid in 60 parts of water at pH 6 was added to a slurry of 5.1 parts of the monoanilide, I, in 175 parts of methanol at pH 6.5 and room temperature. The mixture was stirred at 50.degree. C. for 41/2 hours whilst maintaining the pH at 6.3.+-.0.2, cooled in ice and filtered. The solid was washed with methanol and dried. 4.8 parts of the unsymmetrical dianilide of Formula IV wherein W is --SO.sub.3 H, X is --NHC.sub.2 H.sub.4 NH.sub.2, Y is --SO.sub.3 H and Z is H, were obtained.

Example 23

A solution of 2.6 parts of 3-sulpho-4-phenoxyaniline in 40 parts of water at pH 6 was added to a slurry of 5.1 parts of the monoanilide, I, in 120 parts of methanol at pH 6.5 and room temperature. The mixture was stirred at 50.degree. C. for 31/2 hours whilst maintaining the pH at 6.3.+-.0.2, cooled in ice and filtered. The solid was washed with methanol and dried. 5.5 parts of the unsymmetrical dianilide of Formula IV wherein W is --SO.sub.3 H, X is --NHC.sub.2 H.sub.4 NH.sub.2, Y is --SO.sub.3 H and Z is phenoxy were obtained.

Example 24

A solution of 3.8 parts of p-phenylene diamine-2-sulphonic acid in 65 parts of water at pH 6.5 was added to a slurry of 6 parts of the monoanilide,III, prepared as in Example 4, in 150 parts of methanol at pH 6.5 and room temperature. The mixture was stirred at 50.degree. C. for 3 hours whilst maintaining the pH at 6.3.+-.0.2, cooled in ice and filtered. The solid was washed with methanol and dried. 8.3 parts of the unsymmetrical dianilide of Formula IV wherein W and X are H, Y is --SO.sub.3 H and Z is --NH.sub.2 were obtained

Example 25

A solution of 4.8 parts of p-phenylene diamine-2-sulphonic acid in 125 parts of water at pH 7 was added to a slurry of 11 parts of the monoanilide,I, prepared as in Example 1 or 2, in 375 parts of methanol at pH 6.5 and room temperature. The mixture was stirred at 50.degree. C. for 3 hours whilst maintaining the pH at 6.3.+-.0.2, cooled in ice and filtered. The solid was washed with methanol and dried. 13.1 parts of the unsymmetrical dianilide of Formula IV wherein W is --SO.sub.3 H, X is --NHC.sub.2 H.sub.4 NH.sub.2, Y is --SO.sub.3 H and Z is --NH.sub.2 were obtained.

The following unsymmetrical dianilides were prepared by these methods using the appropriate amines. In all of the following examples W in the dianilide is --SO.sub.3 H.

__________________________________________________________________________Formula Dianilide of Formula IVExample of anilide X Y Z__________________________________________________________________________26 I --NHC.sub.2 H.sub.4 NH.sub.2 --SO.sub.3 H --NHC.sub.2 H.sub.527 I " " (3-SO.sub.3 H-4-NH.sub.2 --Ph)NH--28 I " H Ph29 I " --SO.sub.3 H --SPh30 I " H --NHCOC.sub.6 H.sub.531 I " --CH.sub.3 --CH.sub.332 II (3-SO.sub.3 H-4-NH.sub.2 --Ph)NH-- H --SC.sub.2 H.sub.533 II " --SO.sub.3 H --NHPh34 II " " --OPh35 II " " --NHC.sub.3 H.sub.4 OH36 II " H --CH.sub.2 Ph37 II " --SO.sub.3 H (3-SO.sub.3 HPh)NH--38 XXX NH.sub.2 --Cl --OCH.sub.339 I --NHC.sub.2 H.sub.4 NH.sub.2 H (3-SO.sub.2 C.sub.2 H.sub.4 OHPh)NH--__________________________________________________________________________

DYEBASES

The following examples produce dyebases of the Formula VIII ##STR21##

In Examples 40-68 inclusive V.sup.3 =H; V.sup.4 =H; V.sup.5 =SO.sub.3 H.

Example 40

4 parts of the unsymmetrical dianilide,IV, were added over 45 minutes to a mixture of 40 parts of conc. sulphuric acid and 32 parts of 65% oleum at room temperature. The mixture was stirred for a further 15 minutes to complete the dissolution. 2.9 parts of ammonium persulphate were added and the mixture was heated at 45-50.degree. C. for 2 hours. The mixture was drowned out into ice/water and filtered. The solid was washed acid free with 20% brine and dried. 2.8 parts of a dyebase of Formula VIII wherein V.sup.1 is N-(2-aminoethyl)amino, V.sup.2 is H were obtained (the solid also contains salt). The dyebase had lambda max 600nm in aqueous medium.

Example 41

2.1 parts of the unsymmetrical dianilide prepared in Example 26 were added over 45 minutes to a mixture of 22 parts of conc. sulphuric acid and 9.5 parts of 65% oleum at room temperature. The mixture was stirred for a further 15 minutes to complete the dissolution. 2.1 parts of ammonium persulphate were added and the mixture was heated at 40.degree. C. for 51/2hours. The mixture was drowned out into ice/water and filtered. The solid was washed acid free with 20% brine and dried. 1.6 parts of a dyebase of the Formula VIII wherein V.sup.1 is N-(2-aminoethyl)amino, V.sup.2 is ethylamino were obtained (the solid also contains salt). The dyebase had lambda max 616 nm in aqueous medium.

EXAMPLE 42

2 parts of the unsymmetrical dianilide,V, were added over 1 hour to 12 parts of 20% oleum keeping the temperature below 21.degree. C. The mixture was stirred at 20-22.degree. C. for 21/2hours. 2 parts of ammonium persulphate were added over 15 minutes and the mixture was stirred at 30.degree. C. for 11/2hours. The mixture was drowned out into ice/water and filtered. The solid was washed acid free with 20% brine and dried. 1.4 parts of a dyebase of Formula VIII wherein V.sup.1 is N-(2-aminoethyl)amino, V.sup.2 is sulphophenoxy, were obtained (the solid also contains salt). The dyebase had lambda max 580nm in aqueous medium.

Example 43

5.9 parts of the unsymmetrical dianilide,VII, were added over 45 minutes to a mixture of 59 parts of conc. sulphuric acid and 47 parts of 65% oleum at room temperature. The mixture was stirred for a further 15 minutes to complete the dissolution. 4.2 parts of ammonium persulphate were added and the mixture was heated at 45-50.degree. C. for 31/2hours. The mixture was drowned out into ice/water and filtered. The solid was washed acid free with 20% brine and dried. 7.4 parts of a dyebase of Formula VIII wherein V.sup.1 is N-(2-aminoethyl)amino, V.sup.2 is amino, V.sup.3 is H, were obtained (the solid also contains salt). The dyebase had lambda max 605 nm in aqueous medium.

The following unsymmetrical dyebases are prepared by these methods using the appropriate dianilides:

__________________________________________________________________________Example V.sup.1 V.sup.2 V.sup.3 V.sup.4 V.sup.5 Shade__________________________________________________________________________44 2-aminoethylamino ethoxy Reddish-blue45 " 3-methyl sulphoanilino "46 " ethylthio "47 " sulphophenylthio "48 " 2-hydroxyethylamino Blue49 " benzoylamino Reddish-blue50 " p-toluenesulphonylamino "51 " sulphobenzyl "52 " methyl "53 4-amino-3-sulphoanilino sulphoanilino Blue54 " propoxy Reddish-blue55 " ethylamino Blue56 " 2-hydroxyethylamino "57 " 4-chlorosulphophenoxy Reddish-blue58 " ethylthio "59 " sulphophenylthio "60 " ethyl "61 " acetylamino Blue62 " benzoylamino Reddish-blue63 " p-toluenesulphonylamino "64 " 3-chloro sulphoanilino Blue65 amino ethylamino "66 " 4-amino-3-sulphoanilino "67 " 3-sulphoanilino "68 " 2-aminoethylamino "69 NH.sub.2 EtNH-- Me H --SO.sub.3 H Me Reddish-blue70 NH.sub.2 EtNH-- EtNH-- H H --SO.sub.2 NH--PhSO.sub.3 H Blue71 --NH.sub.2 --NH--Ph--NH.sub.2 H H --SO.sub.2 NHEt Blue72 4-NH.sub.2 -3-SO.sub.3 HPhNH-- --OMe Cl H SO.sub.3 H Reddish-blue__________________________________________________________________________

In the above: Me is methyl: Et is ethyl; Ph is phenyl.

DYESTUFFS

Example 73

(i) To 3.8 parts of aniline 2,5-disulphonic acid stirring in 35 parts water at pH7 was added 0.1 parts of mixed phosphate buffer. After cooling to 0-5.degree. C., 2.4 parts of cyanuric chloride was added and the mixture stirred at 0-5.degree. C. and pH 6-7 until dissolved. After screening, this solution was added to a solution of 3.8 parts of the dyebase, VIII from Example 40, dissolved in 210 parts of water at pH9-10. The reaction mixture was heated to 50-55.degree. C. at pH 8.5-9.0 for 2 hours, salted to 35% w/v with sodium chloride/potassium chloride and filtered. The product was washed with brine and dried to give 12.6 parts of a reactive dyestuff,XII, which dyes cellulose textile materials in bright reddish blue shades. ##STR22##

(ii) 4 parts of cyanuric chloride and a few drops of Calsolene oil were added to 7.3 parts of the dyebase, VIII,dissolved in 600 parts of water at 10.degree.-20.degree. C. The mixture was stirred at 10.degree.-20.degree.C. and pH 6-7 for 2 hours, then warmed to 40.degree. C. for 2 hours. 20 parts of aniline-2,5-disulphonic acid dissolved in 100 parts of water were added and the pH adjusted to pH 7-8. The mixture was stirred overnight at 45.degree. C., salted to 30% w/v with sodium chloride and filtered. The product was washed with brine and dried to give 16.6 parts of the same reactive dyestuff described in (i).

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 73 is replaced by an equivalent amount of the following amines:

______________________________________Example Amine______________________________________74 2-carboxyaniline-4,5-disulphonic acid75 metanilic acid76 aniline-3,5-disulphonic acid77 N-sulphomethylaniline78 aniline-2,4-disulphonic acid79 2-carboxyaniline-4-sulphonic acid80 3-aminoaniline-4-sulphonic acid81 4-aminoaniline-3-sulphonic acid82 3-aminoaniline-4,6-disulphonic acid83 4-aminoaniline-2,5-disulphonic adid84 sulphanilic acid85 orthanilic acid86 1-aminonaphthalene-6-sulphonic acid87 1-aminonaphthalene-7-sulphonic acid88 2-aminonaphthalene-5,7-disulphonic acid89 2-aminonaphthalene-6,8-disulphonic acid90 2-aminonaphthalene-8-sulphonic acid91 2-aminonaphthalene-7-sulphonic acid92 1-aminonaphthalene-3,8-disulphonic acid93 1-aminonaphthalene-3,6,8-trisulphonic acid94 2-methylaniline-5-sulphonic acid95 4-chloroaniline-3-sulphonic acid______________________________________

Following the procedure in Example 73 similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 74-95 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________ 96 2,4-dichloro-6-beta-hydroxyethylamino-s-triazine 97 2,4-dichloro-6-di-beta-hydroxyethylamino-s-triazine 98 2,4-dichloro-6-beta-hydroxypropylamino-s-triazine 99 2,4-dichloro-6-methoxy-s-triazine100 2,4-dichloro-6-amino-s-triazine101 2,4-dichloro-6-methylamino-s-triazine102 2,3-dichloroquinoxaline-6-sulphonyl chloride102 2,4,5,6-tetrachloropyrimidine104 2,4,6-trichloro-s-triazine105 2,4-dichloro-6-n-butoxy-s-triazine106 2,4-dichloro-6-dimethylamino-s-triazine107 2,4,6-trichloropyrimidine108 1,4-dichlorophthalazine-6-carbonyl chloride109 2,4,6-trichloro-5-cyanopyrimidine110 2,4-dichloro-6-p-sulphophenoxy-s-triazine111 2,4,6-trifluoro-5-chloropyrimidine112 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone113 2,4,6-tribromopyrimidine114 2,4-dichloro-6-beta-sulphatoethylamino-s-triazine115 2-(2',4'-dichloro-s-triazinylamino-5-(2'-chloro-4'-m- sulphoanilino-s-triazinylamino)benzene sulphonic acid116 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino- s-triazinylamino)benzene sulphonic acid117 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino)benzene sulphonic acid118 2,4-dichloro-6-(3'-sulphatoethylsulphonylanilino)- .sub.- s-triazine119 2,4-difluoro-6-(3'-sulphoanilino)- .sub.- s-triazine120 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-m- sulphoanilino-s-triazinylamino)benzene-1,5-disulphonic acid121 2-(2',4'-dichloro-s-triazinylamino)-4-(2'-chloro-4'-amino- s-triazinylamino)benzene-1,5-disulphonic acid122 2-(2',4'-dichloro-s-triazinylamino)-4-[2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino]benzene- 1,5-disulphonic acid123 2-(2' ,4'-dichloro-s-triazinylamino)-4-[2'-chloro- 4'-(2",5"-disulphoanilino)-s-triazinylamino]benzene- 1,5-disulphonic acid124 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'- methoxy-s-triazinylamino)benzene-1,4-disulphonic acid125 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'- amino-s-triazinylamino)benzene-1,4-disulphonic acid126 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4'-(m- sulphoanilino)-s-triazinylamino]benzene-1,4-disulphonic acid127 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid128 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(2",5"-disulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid129 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(4"-sulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid130 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(2",4"-disulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid131 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-bromo- 4'-(2",4"-disulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid132 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(2"-methyl-5"-sulphoanilino)-s-triazinylamino] benzene-1,4-disulphonic acid133 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(o-sulphoanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid134 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(N"-sulphomethylanilino)-s-triazinylamino]benzene- 1,4-disulphonic acid135 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(3",6",8"-trisulphonaphthyl-1"-amino)-s-triazinyl- amino]benzene-1,4-disulphonic acid136 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(4",6",8"-trisulphonaphthyl-2"-amino)-s-triazinyl- amino]benzene-1,4-disulphonic acid137 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(N"-methyl-3"-sulphoanilino)-s-triazinylamino] benzene-1,4-disulphonic acid138 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(2"-methyl-4",5"-disulphoanilino)-s-triazinylamino] benzene-1,4-disulphonic acid139 2-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro-4-sulpho- methylamino-s-triazinylamino]benzene-1,4-disulphonic acid140 2-(2',4'-dichloro-s-triazinylamino)-6-[2'-chloro- 4'-(3",6",8"-trisulphonaphthyl-1"-amino)-s-triazinyl- amino]naphthalene-4,8-disulphonic acid141 2-(2',4'-dichloro-s-triazinylamino)-6-[2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino]naphthalene- 4,8-disulphonic acid142 2-(2',4'-dichloro-s-triazinylamino)-6-[2'-chloro- 4'-(4",6",8"-trisulphonaphthyl-2"-amino)-s-triazinyl- amino]naphthalene-4,8-disulphonic acid143 1-(2',4'-dichloro-s-triazinylamino)-5-[2'-chloro- 4'-(3",6",8"-trisulphonaphthyl-1"-amino)-s-triazinyl- amino]naphthalene-3,7-disulphonic acid______________________________________

The following examples produce dyes of the Formula XIII ##STR23##

Example 144

If dyebase from Example 41 is used in place of dyebase from Example 40 in Example 73 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is ethylamino and V.sup.2 is a group of Formula XXV: ##STR24## and which dyes cellulose in bright greenish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 144 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________145 2-carboxyaniline-4,5-disulphonic acid146 metanilic acid147 aniline-3,5-disulphonic acid148 N-sulphomethylaniline149 aniline-2,4-disulphonic acid150 2-carboxyaniline-4-sulphonic acid151 3-aminoaniline-4-sulphonic acid152 4-aminoaniline-3-sulphonic acid153 3-aminoaniline-4,6-disulphonic acid154 4-aminoaniline-2,5-disulphonic acid______________________________________

Following the procedure in Example 144, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 145-154 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________155 2,4-dichloro-6-beta-hydroxyethylamino-s-triazine156 2,4-dichloro-6-di-beta-hydroxyethylamino-s-triazine157 2,4-dichloro-6-beta-hydroxypropylamino-s-triazine158 2,4-dichloro-6-methoxy-s-triazine159 2,4-dichloro-6-amino-s-triazine160 2,4-dichloro-6-methylamino-s-triazine161 2,3-dichloroquinoxaline-6-sulphonyl chloride162 2,4,5,6-tetrachloropyrimidine163 2,4,6-trichloro-s-triazine164 2,4-dichloro-6-n-butoxy- .sub.- s-triazine______________________________________

Example 165

If dyebase in Example 42 is used in place of dyebase in Example 40 in Example 73 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is sulphophenoxy and V.sup.2 is a group of Formula XXV and which dyes cellulose in bright reddish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 165 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________166 sulphanilic acid167 orthanilic acid168 1-aminonaphthalene-6-sulphonic acid169 1-aminonaphthalene-7-sulphonic acid170 2-aminonaphthalene-5,7-disulphonic acid171 2-aminonaphthalene-6,8-disulphonic acid______________________________________

Following the procedure in Example 165, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 166-171 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________172 2,4-dichloro-6-dimethylamino-s-triazine173 2,4,6-trichloropyrimidine174 1,4-dichlorophthalazine-6-carbonyl chloride175 2,4,6-trichloro-5-cyanopyrimidine176 2,4-dichloro-6-p-sulphophenoxy-s-triazine177 2,4,6-trifluoro-5-chloropyrimidine178 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone179 2,4,6-tribromopyrimidine______________________________________

EXAMPLE 180

If dyebase from Example 54 is used in place of dyebase from Example 40 in Example 13 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is propoxy and V.sup.2 is a group of Formula XXVI: ##STR25## and which dye cellulose in bright reddish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 180 is replaced by an equivalent amount of each of the following amine.

______________________________________Example Amine______________________________________181 2-aminonaphthalene-8-sulphonic acid182 2-aminonaphthalene-7-sulphonic acid183 1-aminonaphthalene-3,8-disulphonic acid184 1-aminonaphthalene-3,6,8-trisulphonic acid185 2-methylaniline-5-sulphonic acid186 4-chloroaniline-3-sulphonic acid______________________________________

Following the procedure in Example 180, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 181-186 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________187 2,4-dichloro-6-beta-sulphatoethylamino-s-triazine188 2-(2',4'-dichloro-s-triazinylamino-5-(2'-chloro-4'-m- sulphoanilino-s-triazinylamino)benzene sulphonic acid189 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino- s-triazinylamino)benzene sulphonic acid190 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino)benzene sulphonic acid______________________________________

Example 191

If dyebase from Example 59 is used in place of dyebase from Example 40 in Example 73 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is sulphothiophenoxy and V.sup.2 is a group of Formula XXVI and which dyes cellulose in bright reddish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 191 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________192 2-carboxyaniline-4,5-disulphonic acid193 metanilic acid194 aniline-3,5-disulphonic acid195 N-sulphomethylaniline196 aniline-2,4-disulphonic acid197 2-carboxyaniline-4-sulphonic acid198 3-aminoaniline-4-sulphonic acid199 4-aminoaniline-3-sulphonic acid______________________________________

Following the procedure in Example 191, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 192-199 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________200 2,4-dichloro-6-beta-hydroxyethylamino-s-triazine201 2,4-dichloro-6-di-beta-hydroxyethylamino-s-triazine202 2,4-dichloro-6-beta-hydroxypropylamino-s-triazine203 2,4-dichloro-6-methoxy-s-triazine204 2,4-dichloro-6-amino-s-triazine205 2,4-dichloro-6-methylamino-s-triazine206 2,3-dichloroquinoxaline-6-sulphonyl chloride207 2,4,5,6-tetrachloropyrimidine______________________________________

Example 208

If dyebase from Example 62 is used in place of dyebase from Example 40 in Example 73 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is N-(benzoyl)amino) and V.sup.2 is a group of Formula XXVI and which dyes cellulose in bright reddish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 208 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________209 3-aminoaniline-4,6-disulphonic acid210 4-aminoaniline-2,5-disulphonic adid211 sulphanilic acid212 orthanilic acid213 1-aminonaphthalene-6-sulphonic acid214 1-aminonaphthalene-7-sulphonic acid215 2-aminonaphthalene-5,7-disulphonic acid______________________________________

Following the procedure in Example 208, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 209 to 215 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________216 2,4,6-trichloro-s-triazine217 2,4-dichloro-6-n-butoxy-s-triazine218 2,4-dichloro-6-dimethylamino-s-triazine219 2,4,6-trichloropyrimidine220 1,4-dichlorophthalazine-6-carbonyl chloride221 2,4,6-trichloro-5-cyanopyrimidine222 2,4-dichloro-6-p-sulphophenoxy-s-triazine223 2,4,6-trifluoro-5-chloropyrimidine______________________________________

Example 224

If dyebase from Example 66 is used in place of dyebase from Example 40 in Example 73 a dyestuff is obtained which is believed to be of Formula XIII wherein V.sup.1 is amino and V.sup.2 is a group of Formula XXVI and which dyes cellulose in bright reddish blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 224 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________225 2-aminonaphthalene-6,8-disulphonic acid226 2-aminonaphthalene-8-sulphonic acid227 2-aminonaphthalene-7-sulphonic acid228 1-aminonaphthalene-3,8-disulphonic acid229 1-aminonaphthalene-3,6,8-trisulphonic acid230 2-methylaniline-5-sulphonic acid231 4-chloroaniline-3-sulphonic acid______________________________________

Following the procedure in Example 224, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 225 to 231 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________232 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone233 2,4,6-tribromopyrimidine234 2,4-dichloro-6-beta-sulphatoethylamino-s-triazine235 2-(2',4'-dichloro-s-triazinylamino-5-(2'-chloro-4'-m- sulphoanilino-s-triazinylamino)benzene sulphonic acid236 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino- s-triazinylamino)benzene sulphonic acid237 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino)benzene sulphonic acid______________________________________

Example 238

To 3.8 parts of aniline-2,5-disulphonic acid stirring in 35 parts water at pH7 was added 0.1 parts of mixed phosphate buffer. After cooling to 0-5.degree. C., 2.4 parts of cyanuric chloride was added and the mixture stirred at 0.degree.-5.degree. C. and pH 6-7 until dissolved. After screening, this solution was added to a solution of 1.5 parts of the dyebase from Example 65, dissolved in 150 parts of water at pH 9. The reaction mixture was stirred at pH 8.5-9.0 and 35.degree. C. overnight, salted to 15% w/v with sodium chloride and filtered. The product was washed with brine and dried to give 2.1 parts of a reactive dyestuff of Formula XIII wherein V.sup.1 is N-(ethyl)amino and V.sup.2 is a group of Formula XXVII: ##STR26## which dyes cellulose textile materials in bright mid blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 238 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________239 aniline-2,4-disulphonic acid240 2-carboxyaniline-4-sulphonic acid241 3-aminoaniline-4-sulphonic acid242 4-aminoaniline-3-sulphonic acid243 3-aminoaniline-4,6-disulphonic acid244 4-aminoaniline-2,5-disulphonic adid245 sulphanilic acid246 orthanilic acid247 1-aminonaphthalene-6-sulphonic acid248 1-aminonaphthalene-7-sulphonic acid______________________________________

Following the procedure in Example 238, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 239 to 248 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________249 2,4-dichloro-6-methylamino-s-triazine250 2,3-dichloroquinoxaline-6-sulphonyl chloride251 2,4,5,6-tetrachloropyrimidine252 2,4,6-trichloro-s-triazine253 2,4-dichloro-6-n-butoxy-s-triazine254 2,4-dichloro-6-dimethylamino-s-triazine255 2,4,6-trichloropyrimidine256 1,4-dichlorophthalazine-6-carbonyl chloride257 2,4,6-trichloro-5-cyanopyrimidine______________________________________

Example 258

To 7.6 parts of aniline-2,5-disulphonic acid stirring in 70

at pH7 was added 0.2 parts of mixed phosphate buffer. After cooling to 0.degree.-5.degree. C., 4.8 parts of cyanuric chloride was added and the mixture stirred at 0.degree.-5.degree. C. and pH 6-7 until dissolved. After screening, this solution was added to a solution of 1.5 parts of the dyebase from Example 68, dissolved in 150 parts of water at pH 9. The reaction mixture was stirred at pH 8.5-9.0 and 35.degree. C. overnight, salted to 15% w/v with sodium chloride and filtered. The product was washed with brine and dried to give 2.4 parts of a reactive dyestuff of Formula XIII wherein V.sup.1 is a group of Formula XXVII and V.sup.2 is a group of Formula XXV which dyes cellulose textile materials in bright mid blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 258 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________259 2-aminonaphthalene-5,7-disulphonic acid260 2-aminonaphthalene-6,8-disulphonic acid261 2-aminonaphthalene-8-sulphonic acid262 2-aminonaphthalene-7-sulphonic acid263 1-aminonaphthalene-3,8-disulphonic acid264 1-aminonaphthalene-3,6,8-trisulphonic acid265 2-methylaniline-5-sulphonic acid266 4-chloroaniline-3-sulphonic acid______________________________________

Following the procedure in Example 258, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 259 to 266 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________267 2,4-dichloro-6-beta-hydroxyethylamino-s-triazine268 2,4-dichloro-6-di-beta-hydroxyethylamino-s-triazine269 2,4-dichloro-6-beta-hydroxypropylamino-s-triazine270 2,4-dichloro-6-methoxy-s-triazine271 2,4-dichloro-6-amino-s-triazine272 2,4-dichloro-6-p-sulphophenoxy-s-triazine273 2,4,6-trifluoro-5-chloropyrimidine274 1-(4'-chlorocarbonylphenyl)-4,5-dichloro-6-pyridazone275 2,4,6-tribromopyrimidine______________________________________

Example 276

To 7.6 parts of aniline-2,5-disulphonic acid stirring in 70 parts water at pH7 was added 0.2 parts of mixed phosphate buffer. After cooling to 0.degree.-5.degree. C., 4.8 parts of cyanuric chloride was added and the mixture stirred at 0.degree.-5.degree. C. and pH 6-7 until dissolved. After screening, this solution was added to a solution of 1.8 parts of the dyebase from Example 66, dissolved in 150 parts of water at pH 9. The reaction mixture was stirred at pH 8.5-9.0 and 35.degree. C. overnight, salted to 15% w/v with sodium chloride and filtered. The product was washed with brine and dried to give 2.3 parts of a reactive dyestuff of Formula XIII wherein V.sup.1 is a group of Formula XXVII and V.sup.2 is a group of Formula XXVI which dyes cellulose textile materials in bright mid blue shades.

Similar dyestuffs are obtained if the aniline-2,5-disulphonic acid used in Example 276 is replaced by an equivalent amount of each of the following amines.

______________________________________Example Amine______________________________________277 2-carboxyaniline-4,5-disulphonic acid278 metanilic acid279 aniline-3,5-disulphonic acid280 N-sulphomethylaniline281 aniline-2,4-disulphonic acid282 2-carboxyaniline-4-sulphonic acid283 3-aminoaniline-4-sulphonic acid284 4-aminoaniline-3-sulphonic acid285 3-aminoaniline-4,6-disulphonic acid286 4-aminoaniline-2,5-disulphonic acid______________________________________

Following the procedure in Example 276, similar dyestuffs are obtained if the 2,4-dichloro-6-arylamino-s-triazines used in Examples 277 to 286 are replaced by equivalent amounts of the following acylating agents.

______________________________________Example Acylating Agent______________________________________287 2,4-dichloro-6-amino-s-triazine288 2,4-dichloro-6-methylamino-s-triazine289 2,3-dichloroquinoxaline-6-sulphonyl chloride290 2,4,5,6-tetrachloropyrimidine291 2,4-dichloro-6-beta-sulphatoethylamino-s-triazine292 2-(2',4'-dichloro-s-triazinylamino-5-(2'-chloro-4'-m- sulphoanilino-s-triazinylamino)benzene sulphonic acid293 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro-4'-amino- s-triazinylamino)benzene sulphonic acid294 2-(2',4'-dichloro-s-triazinylamino)-5-(2'-chloro- 4'-(3",5"-disulphoanilino)-s-triazinylamino)benzene sulphonic acid______________________________________

The following dyebases prepared by the methods outlined above function as reactive dyes without further modification, these are of Formula XIII:

______________________________________Ex-ample Dyebase Shade______________________________________295 V.sup.1 is N-(2-aminoethyl)amino Greenish-blue ##STR27##296 V.sup.1 is ethoxy Reddish-blue ##STR28##297 V.sup.1 is sulphophenoxy Reddish-blue ##STR29##298 ##STR30## Greenish-blue ##STR31##299 V.sup.1 is amino Reddish-blue ##STR32##______________________________________

Claims

1. A triphenodioxazine reactive dye containing at least one fiber-reactive group, the dye, in the free acid form, having the formula: ##STR33## wherein each of T.sup.1 and T.sup.2, independently, represents H, Cl, Br, F, SO.sub.3 H or an optionally substituted alkyl or aryl radical;

each of A.sup.1 and A.sup.2 represents alkyl, alkoxy, Cl, Br, COOH, SO.sub.3 H or optionally substituted sulphamoyl;

n has a value of 0, 1 or 2;

m has a value of 1 or 2;

R.sup.1 represents H or a group of the formula: ##STR34## wherein Z represents a fiber-reactive group;

each of R.sup.2 and R.sup.3, independently, represents H or an optionally substituted hydrocarbon radical;

B represents an optionally substituted divalent hydrocarbon radical; and

D represents a group of the formula ##STR35## wherein R.sup.4 represents an optionally substituted hydrocarbon radical free from fiber-reactive residues or an acyl radical;

R.sup.5 represents H or an optionally substituted hydrocarbon radical;

R.sup.6 represents H or an optionally substituted hydrocarbon radical free from fiber-reactive residues;

Q represents O or S; and

a has a value of 0 or 1.

2. A reactive dye according to claim 1 wherein each of T.sup.1 and T.sup.2 is Cl or Br.

3. A reactive dye according to claim 1 or claim 2 wherein A.sup.1 and A.sup.2 are the same.

4. A reactive dye according to any preceding claim wherein n is 0 and m is 1.

5. A reactive dye according to any preceding claim wherein the fiber-reactive groups are selected from vinylsulphonyl groups or precursors thereof and halogenotriazinyl groups.

6. A reactive dye according to claim 5 wherein the fiber-reactive groups comprise monochlorotriazinyl, monofluorotriazinyl or dichlorotriazinyl groups.

7. A reactive dye according to claim 1 having the structure: ##STR36## wherein A represents alkyl, alkoxy, Cl, COOH, SO.sub.3 H or optionally substituted sulphamoyl;

R.sup.7 represents H or a group of the formula --NHZ;

and Z, T.sup.1, T.sup.2, n, m, B and R.sup.4 have the meanings given above with the provisos that when R.sup.7 is H, R.sup.4 is an acyl group having fiber-reactive properties.

8. A reactive dye according to claim 1 having the structure: ##STR37## wherein T.sup.1, T.sup.2, A.sup.1, n, m, R.sup.2, R.sup.3, Z, B, Q, a and R.sup.6 have the meanings given in claim 1.

9. A method for the preparation of a reactive dye as defined in claim 1 which comprises reacting an acylating agent capable of introducing a fiber-reactive group with an unsymmetrical triphenodioxazine of the formula: ##STR38## wherein D.sup.1 represents a group of the formula R.sup.5 NH-- or R.sup.6 (Q).sub.a --and R.sup.10 represents H or a group of the formula --NR.sup.3 H with the proviso that when R.sup.10 is H, D.sup.1 is R.sup.5 NH--, the symbols T.sup.1, T.sup.2, A.sup.1, A.sup.2, n, m, R.sup.2, R.sup.3, R.sup.5, R.sup.6, Q, a and B having the meanings given in claim 1.

10. A process for colouring textile materials which comprises applying thereto a reactive dye as defined in claim 1.