GB1566921A

GB1566921A - Reactive dyestuffs

Info

Publication number: GB1566921A
Application number: GB4307877A
Authority: GB
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1976-10-20
Filing date: 1977-10-17
Publication date: 1980-05-08
Also published as: FR2368521A1; JPS5351230A; DE2647312A1

Description

(54) REACTIVE DYESTUFFS (71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Germany, of Leverkusen, Germany, 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:- The invention relates to reactive dyestuffs of the formula

wherein X denotes a group which can be split off under the conditions of reactive dyeing.

Y denotes

R1 denotes optionally substituted alkyl, R2 denotes hydrogen, or optionally substituted alkyl or aralkyl, F denotes the radical of an organic dyestuff, W and V denote a direct bond or a bridge member, Q denotes hydrogen or optionally substituted alkyl, D denotes hydrogen or optionally substituted alkyl or aryl, E denotes optionally substituted alkylene or arylene and n denotes 1, 2, 3 or 4.

Examples of suitable bridge members W are: -SO2-, -CO-, -alkylene- CO-, -arylene-, -arylene-SO2-, -arylene-CO-, -alkylene- or -amino-CO-.

Examples of suitable bridge members V are:-CO- arylene-N(R2)-, CO-alkylene-N(R3)-, -CO-aralkylene-N(R3)-, -CO-alkarylene N(R3)-, -SO2-arylene-N(R3)-, -SO2-alkylene-N(R3)-, -SO2 aralkylene-N(R3)-, -SO2-alkarylene-N(R3)-, alkylene-N(R3)-, aralkylene-N(R3)-, -alkarylene-N(R3)-, -arylene-N(R3)-, -CO aralkylene-O-, -CO-alkarylene-O-, -SO2-arylene-O-, -SO2 aralkylene-O-, -S02-alkarylene-O-, alkylene-O-, -aralkylene-O -alkarylene-O- or -arylene-O-, in which R3 denotes hydrogen or optionally substituted alkyl or aralkyl and the phenylene and arylene groups can carry further substituents.

Arylene and aryl D and E and in the bridge members W and V are, for example, phenylene and phenyl or naphthylene and naphthyl, which can be substituted, for example by sulpho, carboxyl, sulphonamide or carboxamide, which are optionally monosubstituted or disubstituted by C1-C4-alkyl, benzyl or phenyl, phenylsulphonylaminosulphonyl or phenylsulphonylaminocarbonyl which are optionally substituted in the phenyl nucleus by C1-C4-alkyl, C1-C4-alkoxy, chlorine, nitro, carboxyl or sulpho, C1-C4-alkylsulphonylaminosulphonyl, C1-C4- alkylsulphonylaminocarbonyl, C1-C4-alkylsulphonyl, phenylsulphonyl which is optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, sulpho or carboxyl, C1-C4-alkylamino, phenylamino or benzylamino which are optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, sulpho or carboxyl, nitro, cyano, halogen, such as chlorine and bromine, hydroxyl, C1-C4-alkylcarbonyloxy, benzoyloxy, C1-C4-alkoxy, C1-C4-alkylmercapto, C1- C4-alkyl, phenyl or benzyl which are optionally substituted by C1-C4-alkyl, C1- C4-alkoxy, chlorine, bromine, nitro, sulpho or carboxyl, trifluoromethyl, C1-Ca alkylcarbonylamino, C1-C4-alkylsulphonylamino or benzoylamino or benzenesulphonylamino which are optionally substituted by C1-C4-alkyl, C1-C4- alkoxy, chlorine, bromine, nitro, sulphor or carboxyl.

Aralkyl R2 and aralkylene and alkarylene in a bridge member are understood, in particular, as benzyl and benzylene which can optionally be substituted in the phenyl nucleus by C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, sulpho or carboxyl.

Suitable alkyl R1, R2, Q or D and alkylene E, and in a bridge member, are, in particular, C1-C4-alkyl and C2-C4-alkylene which can be substituted by halogen, such as fluorine, chlorine or bromine, hydroxyl or cyano.

The following groups may be mentioned in particular as groups X which can be split off under the conditions of reactive dyeing: halogen, such as fluorine, chlorine, bromine and iodine, C1-C4-alkylsulphonyl, or phenylsulphonyl or benzylsulphonyl which are optionally substituted by chlorine, bromine, C1-C4-alkyl, C1-C4- alkoxy, carboxyl or sulpho, thiocyanato, isothiuronium, tri-C1-C8- alkylammonium, phenyl- or benzyldialkylammonium which is optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, sulpho or carboxyl, pyridinium, N-C1-C4-alkylmorpholinium, N-C1-C4- alkylpiperidinium, N,N'-di-C,-C,-alkylpiperazinium or N,N-di-C1-C4- alkylhydrazinium.

Possible anions for the ammonium radicals mentioned are organic or inorganic colourless anions which have virtually no influence on the properties of the dyestuffs. Examples which may be mentioned are chloride, bromide, iodide, methosulphate, p-toluenesulphonate, benzenesulphonate, pchlorobenzenesulphonate, phosphate, acetate, formate and oxalate.

The new reactive dyestuffs can belong to very diverse categories, for example to the series of metal-free or metal-containing mono- or poly-azo dyestuffs, the metal-containing formazanes, the metal-free or metal-containing azaporphine dyestuffs, such as copper phthalocyanine or nickel phthalocyanine dyestuffs, the anthraquinone, oxazine, dioxazine triphenylmethane, nitro, azomethine, benzanthrone or dibenzanthrone dyestuffs and also the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrone.

Preferred dyestuffs correspond to the formula

wherein X, denotes halogen, especially fluorine, chlorine or bromine, Y, denotes

R4 denotes C1-C4-alkyl, Q1 denotes hydrogen or C1-C4-alkyl, D1 denotes hydrogen or C1-C4-alkyl, E1 denotes C2-C4-alkylene or m- or p-phenylene which is optionally substituted by sulphonic acid groups, W1 denotes a direct bond, C2-C4-alkylene or m- or p-phenylene which is optionally substituted by sulphonic acid groups, R5 denotes hydrogen or C1-C4-alkyl and n1 denotes 1 or 2 and F has the abovementioned meaning.

Very particularly preferred dyestuffs correspond to the formula

wherein F and n1 have the abovementioned meaning, W2 denotes -C112-CH2- or m- or p-phenylene which is optionally substituted by 1 or 2 sulpho groups, R8 denotes hydrogen or methyl, Y2 denotes

X2 denotes fluorine or chiorine, D2 denotes hydrogen or methyl and E2 denotes ethylene or m- or p-phenylene which is optionally substituted by 1 or 2 sulpho groups.

Within the formulae (I), (II) and (III), F, which in the text which follows is described as the dyestuff F-H without the reactive part, preferably corresponds to the following formulae.

1. Azo dyestuffs of the formula A-N=N-B (IV) wherein A represents the radical of a heterocyclic or carbocyclic diazo component, preferably of the benzene, naphthalene or triazole series, and B represents the radical of a heterocyclic, carbocyclic or CH-acid coupling component, especially the radical of an optionally further substituted phenol, naphthol, aniline, naphthylamine, 5-aminopyrazole, 5-pyrazolone, pyridone, aminopyridine, acetoacetic acid arylide, indole or pyrimidine.

The substituents W, W, and W2 are then linked to the azo dyestuff via a C atom of the diazo component and/or of the coupling component.

Particularly valuable dyestuffs of this series are those which contain watersoluble groups, such as sulphonic acid groups or carboxyl groups. The azo dyestuffs can be metal-free or can be in the form of metal complexes, in which case copper, chromium and cobalt complexes are preferred.

The metal complex-forming groups, preferably hydroxyl, carboxyl and amino groups, are in the ortho-position relative to the azo group.

The diazo components A and the coupling components B can be substituted, for example by the following substituents: sulpho, nitro, halogen, such as fluorine, chlorine and bromine, C1-C4-alkyl which is optionally substituted by chlorine, C1-C4-alkoxy, hydroxyl or cyano, C1-C4-alkoxy which is optionally substituted by C1-C4-alkoxy, hydroxy or cyano, C1-C4-alkylmercapto, C1-C4- alkylsulphonyl, or phenyl or naphthyl which are substituted by sulpho, amino, C1- C4-alkyl, C1-C4-alkoxy, nitro or halogen, trifluoromethyl, amino, hydroxyl, C1- C4-alkylcarbonylamino, C1-C4-alkylsulphonylamino, or benzoylamino or benzenesulphonylamino which are optionally substituted by sulpho, C1-C4-alkyl, C1-C4-alkoxy, nitro or halogen, phenyl-C1-C4-alkyl which is optionally substituted in the phenyl nucleus by sulpho, C1-C4-alkyl, C1-C4-alkoxy, nitro or halogen, phenylazo or naphthylazo which is optionally substituted in the phenyl nucleus or the naphthalene nucleus by hydroxyl, amino, sulpho, C1-C4-alkyl, C1 C4-alkoxy, nitro or halogen, C1-C4-alkylcarbonyloxy, benzoyloxy which is optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, nitro or halogen, aminocarbonyl, mono- or di-C1-C4-alkylamino, ureido, carboxyl, cyano, or carboxamide or sulphonamide which are optionally substituted on the nitrogen by C1-C4-alkyl, phenyl or benzyl, it being possible for alkyl to be further substituted by sulpho or sulphato and for phenyl and benzyl to be further substituted by sulpho, C1-C4-alkyl, C1-C4-alkoxy, halogen or nitro, or C1-C4-alkylsulphonyl- aminosulphonyl or phenylsulphonylaminosulphonyf which is optionally substituted in the phenyl nucelus by methyl, methoxy, chlorine or nitro.

Preferred azo dyestuffs F-H correspond to the formula

wnerem A1 denotes a phenyl or naphthyl radical which can be substituted by sulpho, nitro, chlorine, C1-C4-alkyl, C1-C4-alkoxy, or phenyl or naphthyl which are optionally substituted by sulpho, amino or C1-C4-alkyl, amino, acetylamino, benzyl which is optionally substituted by amino, sulpho or C1-C4-alkyl, phenylazo or naphthylazo which are optionally substituted by amino, C1-C4-alkyl, sulpho, C1-C4-alkoxy or hydroxyl, or trifluoromethyl, Z denotes hydroxyl, alkoxy which is optionally substituted by hydroxyl or C, C4-alkoxy, or amino which is optionally substituted by C1-C4-alkyl, phenyl or benzyl, it being possible for alkyl to be further substituted by cyano, hydroxyl or C1-C4-alkoxy and for phenyl and benzyl to be further substituted by methyl, methoxy, chlorine, nitro or sulpho, and R7, R8 and R9 independently of one another denote hydrogen, C1-C4-alkyl, C1-C4-alkoxy, amino, C1-C4-alkylcarbonylamino, phenyl which is optionally sub- stituted by C1-C4-alkyl, or amino, hydroxyl or sulpho. Further preferred azo dyestuffs correspond to the formula

wherein A1,R7, R8, R9 and Z have the abovementioned meaning.

Further preferred azo dyestuffs correspond to the formula

wherein A1 has the abovementioned meaning, Z1 denotes amino or hydroxyl, R10 denotes C1-C4-alkyl, preferably methyl, or carboxyl and R11 denotes phenyl or naphthyl which are optionally substituted by chlorine, C1-C4-alkyl, sulpho, C1-C4-alkoxy or amino.

A further preferred group of azo compounds corresponds to the formula

wherein A1 has the abovementioned meaning.

Dyestuffs of the formula wherein

A1, R7, R8 and R9 have the abovementioned meaning, are also especially valuable.

Azo dyestuffs of the formula

wherein R.2 denotes C1-C4-alkyl or hydroxyl, R,3 denotes cyano, sulpho-C1-C4-alkyl or aminocarbonyl and A, has the abovementioned meaning, and of the formula

wherein R13 and A1 have the abovementioned meaning, R14 denotes C1-C4-alkyl or amino and R15 denotes hydrogen or C -C4-alkyl, are also preferred.

Preferred dyestuffs within the formulae (V) to (XI) are those in which A1 represents the radical of an amine of the formula wherein

R16 denotes hydrogen, sulpho, hydroxyl, carboxyl or amino, R17 denotes hydrogen, chlorine, nitro, aminosulphonyl, C1-C4-alkyl, C1-C4- alkoxy, amino, sulpho, hydroxyl or phenylazo or naphthylazo which are optionally substituted in the phenyl nucleus or naphthyl nucleus by hydroxyl, sulpho or amino, and R18 denotes hydrogen, chlorine, nitro, C1-C4-alkyl or C1-C4-alkoxy, and of the formulae

wherein R15,R17 and R18 have the abovementioned meanings and R19 denotes hydrogen, chlorine, nitro, aminosulphonyl, C1-C4-alkyl, C1-C4- alkoxy, amino, sulpho, hydroxyl or phenylazo or naphthylazo which are optionally substituted in the phenyl nucleus or naphthyl nucleus by hydroxyl, sulpho or amino.

2. Anthraquinone dyestuffs of the formula

wherein L denotes hydrogen or a substituent, R20 denotes hydrogen, alkyl or aralkyl and p denotes an integer from 1 to 6 and the reactive radical is bonded to the amino group in the 4-position via the bridge member W.

Preferably, L represents hydrogen, halogen, especially chlorine, amino or hydroxyl or particularly preferentially represents sulpho, R20 represents hydrogen, C1-C4-alkyl or benzyl and p represents I or 2.

3. Azaporphine dyestufffs of the formula Pc-[-So2-NH-R21 ] m (XVI) wherein Pc denotes the radical of a copper phthalocyanine or nickel phthalocyanine which is optionally substituted by C1-C4-alkyl, C1-C4-alkoxy or sulpho or sulphonamide which is optionally monosubstituted or disubstituted by C1-C4-alkyl, benzyl or phenyl, and R21 denotes hydrogen, alkyl or aralkyl, preferably hydrogen, C1C4-alkyl or benzyl, and m denotes 1 to 4.

The reactive group is bonded to the nitrogen atom of the sulphonamide group via the bridge member W.

Those azoporphine dyestuffs in which Pc represents a copper phthalocyanine or nickel phthalocyanine radical which is optionally substituted by 1--3.5 sulphonic acid groups or sulphonamide groups are preferred.

4. Formazane dyestuffs of the formula wherein

M denotes a heavy metal atom, preferably a copper atom, G1 and G2 denote aromatic carbocyclic or aromatic heterocyclic rings which carry the substituents a and b in the o-position relative to the formazane nitrogen atoms, a and b denote hydrogen, hydroxyl, carboxyl or aminosulphonyl, W3 denotes a direct bond or a bridge member, R22 denotes alkyl or aryl and the aromatic carbocyclic or aromatic heterocyclic rings G1 and G2 can contain further substituents, such as C1-C4-alkyl, C1-C4- alkoxy, chlorine, bromine, amino or, preferably, sulpho.

Suitable aromatic carbocyclic and aromatic heterocyclic rings G1 and G2 are, preferably, benzene rings and naphthalene rings.

Suitable bridge members W3 are, for example, -CONH-, -CO- or 502.

Suitable alkyl R22 is C1-C4-alkyl which is optionally substituted by C1-C4- alkoxy.

Suitable aryl R22 is phenyl or naphthyl which are optionally substituted by C1 C4-alkyl, C1-C4-alkoxy, chlorine, bromine, sulpho, amino or phenylazo, it being possible for the phenylazo groups to be further substituted by C1-C4-alkyl, C1- C4-alkoxy, nitro, chlorine, sulpho or amino.

The dyestuffs of the formula (I) are obtained by reacting dyestuffs or dyestuff precursors which contain at least one amino, amide or hydroxyl group which has at least one reactive hydrogen atom with compounds of the formula

wherein U is a radical which can be split off and X and Y have the indicated meaning.

In the case of dyestuff precursors, these are converted after the reaction with (XVIII), into the desired dyestuffs in a suitable manner, for example by diazotising and coupling.

Preferred radicals U which can be split off are fluorine, chlorine, bromine, sulphonate, C1-C4-alkylsulphonyl, tri-C1-C4-alkyl-ammonium, benzyl-di-C1-C4- alkyl-ammonium, C1-C4-alkoxy or phenoxy which is optionally substituted by methyl, methoxy, chlorine, bromine or nitro.

Preferably, dyestuffs or dyestuff precursors which contain amino or amide groups are reacted with the compounds (XVIII). Depending on the nature of the starting compounds used, the reaction is carried out in an organic, organic-aqueous or aqueous medium at temperatures of -10 to 800C, preferably in the presence of alkaline condensing agents, such as pyridine or aqueous alkali metal carbonate or alkali metal hydroxide solutions.

U preferably represents halogen, such as fluorine, chlorine or bromine.

A further variant for the preparation of the new dyestuffs (I) consists in reacting dyestuffs or dyestuff precursors which contain amino or amide groups and have at least one replaceable hydrogen atom on the amino group or the amide group with a compound of the formula

wherein U1 denotes a radical which can be replaced by an anionic mechanism, preferably halogen, such as fluorine, chlorine or bromine, and X and U have the meaning already indicated.

The resulting product is reacted in any desired sequence with the compound of the formula Y-H (XX) wherein Y has the meaning already indicated, and, in the case of dyestuff precursors, the desired dyestuff is prepared, for example by diazotising and coupling.

The compound of the formula (XX), if it corresponds to the formula

is prepared in a manner which is in itself known by a condensation reaction in any desired sequence from the primary amine R1-NH2 wherein R1 has the meaning already indicated, the aldehyde Q-CHO wherein Q has the meaning already indicated, and sodium bisulphite or sulphur dioxide.

The compound of the formula (XX) which corresponds to the formula

is prepared by a condensation reaction of a compound of the formula (XIX), a diamine of the formula

wherein D and E have the meaning already indicated, and an amine of the formula

wherein R1 and Q have the meaning already indicated, in the customary manner by a condensation reaction in any desired sequence.

The dyestuffs obtainable by the processes described above can be subjected to further reactions customary for dyestuffs, for example by treating metallisable dyestuffs with metal donors, especially with chromium salts, cobalt salts, copper salts or nickel salts. Dyestuffs which contain groups which can be reduced, and especially nitro groups, can be reduced, dyestuffs which contain groups which can be acylated, and in particular amino groups which can be acylated, can be acylated and dyestuffs which can be sulphonated can be sulphonated with chlorosulphonic acid, thionyl chloride, oleum or sulphur trioxide.

Preferably, dyestuffs which contain amide groups or amino groups and are of the formula

wherein A, B, W1, R5 and n1 have the indicated meaning,

wherein L,R20, W1, R5 and p have the indicated meaning,

wherein Pc, R21, W1, R5 and m have the indicated meaning, and

wherein G1, G2, a,b,W3, R22, W1 and R5 have the indicated meaning and m denotes 1 or 2, are reacted with compounds of the formulae (XVIII) or (XIX) and, in the case of the latter reaction, this is followed by the reaction with compound (XX).

Preferably, the products of the formulae (XXI) to (XXIV) are reacted with compounds of the formula

wherein X1 and Y1 have the indicated meaning and U2 denotes fluorine, chlorine or bromine, or with compounds of the formula

wherein U2, X2 and Y2 have the meaning already indicated.

The new dyestuffs are valuable products which are suitable for very diverse applications. As water-soluble compounds they are of preferred interest for dyeing and printing hydroxyl group-containing and nitrogen-containing textile materials, especially textile materials made of natural and regenerated cellulose and also made of wool, silk and synthetic polyamide and polyurethane fibres.

The products are particularly suitable as reactive dyestuffs for dyeing cellulose materials by the techniques known for this purpose.

For dyeing cellulose, the dyestuffs are preferably employed in an aqueous solution to which substances having an alkaline reaction, such as an alkali metal hydroxide or alkali metal carbonate, or compounds which are converted into substances having an alkaline reaction, such as an alkali metal bicarbonate, can be added. Further auxiliaries can be added to the solution but these auxiliaries should not react with the dyestuffs in an undesirable manner. Such additives are, for example, surface-active substances, such as alkyl sulphates, or substances which prevent migration of the dyestuff or dyeing auxiliaries, such as urea (in order to improve the solubility and fixing of the dyestuffs) or inert thickeners, such as oil-inwater emulsions, tragacanth, starch, alginate or methylcellulose.

The solutions or pastes prepared in this way are applied to the material to be dyed, for example by padding in a pad (short liquor) or by printing, and then heated for some time to an elevated temperature, preferably 40 to 1500C. Heating can be carried out in a hot flue, in a steaming apparatus, on heated rollers or by introducing the material into heated concentrated salt baths and these measures can be used on their own or in any desired sequence after one another.

When a padding or dye liquor without alkali is used, this treatment is followed by passage of the dry goods through a solution which has an alkaline reaction and to which sodium chloride or Glauber salt is added. The addition of a salt reduces the migration of the dyestuff from the fibre.

It is also possible to pre-treat the material to be dyed with one of the abovementioned acid-binding agents and then to treat it with a solution or paste of the dyestuff and finally, as indicated, to fix the dyestuff at elevated temperature.

For dyeing from a long liquor, the material is introduced into an aqueous solution of the dyestuff (liquor ratio 1:5 to 1:40) at room temperature and dyed for 40 to 90 minutes, if necessary whilst increasing the temperature up to 850C, with the addition, in portions, of a salt, for example sodium sulphate, and then alkali, for example sodium phosphates, sodium carbonate or alkalis. The chemical reaction between the dyestuff and the fibre then takes place. After chemical fixing has taken place, the dyed goods are rinsed hot and then soaped and by this means residues of the dyestuff which have not been fixed are removed. Dyeings with excellent fastness, especially fastness to wet processing and light, are obtained.

In the so-called cold pad-batch process, subsequent heating of the padded fabric can be saved by storing the fabric at room temperature for some time, for example 20 to 40 hours. In this process a stronger alkali is employed than in the case of the dyeing process from a long liquor, which has been described above.

For printing materials which contain hydroxyl groups a printing paste made from the dyestuff solution, a thickener, such as sodium alginate, and a compound which has an alkaline reaction or which splits off an alkali on heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium bicarbonate and potassium bicarbonate, is used and the printed material is rinsed and soaped.

If the dyestuffs contain groupings which form metal complexes, the fastness properties of the dyeings and prints can frequently be improved by after-treatment with metal donors, such as copper salts, for example copper sulphate, or chromium salts, cobalt salts and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Textile materials which contain amide groups, such as wool, silk and synthetic polyamide and polyurethane fibres, are generally dyed in an acid to neutral range by the dyeing methods customary for these materials and it is sometimes advantageous, as a final step, to increase the pH value of the dye bath, for example to pH 6.5 to pH 8.5.

The dyestuffs are applied, for example to a synthetic polyamlde fabric, in the form of solutions or, preferably, in a dispersed form and then after-treated, optionally together with (preferably small amounts of) acid-binding agents, such as sodium carbonate. Particularly advantageous results are achieved with those dyestuffs which are insoluble or only sparingly soluble in water. These are processed by techniques which are in themselves customary, and with the addition of the known auxiliaries, to a dyestuff dispersion and used as such in the dye bath and/or padding bath or in a printing paste.The auxiliaries suitable for this use are, inter alia, compounds which prevent the migration of the dyestuff on the fibre, such as cellulose ethers, alkali metal chlorides and alkali metal sulphates, wetting agents, such as condensation products of ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols, solvents, such as thiodiglycol, and also thickeners, such as starch, tragacanth, alginate thickener, gum arabic and the like.

The after-treatment of the dyeings, impregnations and prints obtained on polyamide fibre fabrics is preferably carried out at a temperature of 50110 C and for a time of 5 to 60 minutes. In this case also, if the dyestuffs used contain groupings which form metal complexes, the fastness properties of the dyeings can sometimes be improved by the use of metal donors, such as copper salts, for example copper sulphate, or chromium salts, cobalt salts and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

The dyeings obtainable with the new dyestuffs are in general distinguished by good to very good fastness properties and especially by outstanding fastness to wet processing.

The invention also relates to compounds which, in the form of the free acid, correspond to the formula wherein

Q, and R4 have the meanings indicated above, and to the use of these compounds as intermediate products for the preparation of reactive dyestuffs.

The compounds (XXVII) are used in particular as alkali metal salts and ammonium salts. They are obtained by subjecting cyanuric chloride to a condensation reaction with amines of the formula

wherein Q1 and R4 have the meaning indicated above.

Example 1 13.7 g of methylaminomethanesulphonic acid (MAMS) are added to a suspension, which has been cooled to OOC, of 19.4 g of cyanuric chloride in 100 ml of water. The condensation reaction is brought to completion at 0--50C in the course of 2 hours, with the addition of sodium carbonate solution (200/, strength).

The solution is clarified to remove small residues of cyanuric chloride and 18.8 g of 2,4-diaminobenzenesulphonic acid are then added. The condensation reaction is carried out at 45-500C and the pH is kept constant at 7 by adding 20% strength sodium carbonate solution. This condensation reaction lasts about 2+ hours. The end product is a dark brown solution. The pH of this solution is adjusted to 1 with concentrated hydrochloric acid and the mixture is diazotised with an aqueous solution of sodium nitrite (consumption 7 g of sodium nitrite dissolved in 25 ml of water). The diazotisation mixture is stirred for about a further 1 hour and the excess nitrite is then removed (potassium iodide/starch paper) with amidosulphonic acid.

30.8 g of l-(2,5-dichloro-4-sulphophenyl)-3-methyl-5-pyrazolone are dissolved in 100 ml of water with sodium hydroxide solution to give a neutral solution and the latter is cooled to OOC. The diazonium salt solution described above is added at this temperature and the coupling reaction is brought to completion by adding sodium acetate solution. The resulting dyestuff is salted out with sodium chloride, filtered off and dried in a vacuum drying cabinet at a temperature of about 30"C. Cotton and rayon staple are dyed by this dyestuff, in accordance with the printing and dyeing instructions customary for reactive prints or reactive dyeings, in clear greenish-tinged yellow shades which are fast to light and wet processing.

In the form of the free acid, the dyestuff corresponds to the following formula

If, in Example 1, 2,4-diaminobenzenesulphonic acid, l-(2,5-dichloro-4sulphophenyl)-3-methyl-5-pyrazolone and methylaminomethanesulphonic acid (MAMS) are replaced by the compounds indicated in the table under A, B and C, further valuable dyestuffs with the indicated colour shades are obtained. In the table, EAMS stands for ethylaminomethanesulphonic acid.

Colour shade on No. A B C cotton 2 2,4-diaminobenzenesulphonic acid 5-amino-3-methyl-1-(2-methyl-4- EAMS yellow sulphophenyl)-pyrazole 3 2,4-diaminobenzenesulphonic acid 5-amino-3-phenyl-1-(2-methoxy-5- MAMS yellow sulphophenyl)-pyrazole 4 2,4-diaminobenzenesulphonic acid 5-amino-3-phenyl-1-(2-methoxy-5- EAMS yellow sulphophenyl)-pyrazole 5 2,5-diaminobenzenesulphonic acid 5-amino-3-phenyl-1-(2-methoxy-5- MAMS yellow sulphophenyl)-pyrazole 6 2,4-diaminobenzenesulphonic acid 1-(ss-carboxyethyl)-5-pyrazolone-3- MAMS greenish-tinged carboxylic acid yellow 7 2,4-diaminobenzenesulphonic acid 1-(ss-cyanoethyl)-5-pyrazolone-3- MAMS greenish-tinged carboxylic acid yellow 8 2,4-diaminobenzenesulphonic acid 6-hydroxy-1,4-dimethyl-3-sulpho- MAMS greenish-tinged methyl-2-pyridone yellow 9 1,4-diaminobenzene-2,5- 6-hydroxy-1,4-dimethyl-3-sulpho- neutral yellow disulphonic acid methyl-2-pyridone 10 2,4-diaminobenzenesulphonic acid 4,6-dihydroxy-1-methyl-3-(N- EAMS yellow methylaminocarbonyl)-2-pyridone 11 2,4-diaminobenzenesulphonic acid 1-naphthol-4,7-disulphonic acid MAMS orange-red 12 2,5-diaminobenzenesulphonic acid 2,4-diamino-5-cyano-6-(3-sulpho- MAMS yellow phenyl)-pyridine 13 2,4-diamino-5-chlorobenzene- (4-amino-3,5-disulphophenyl)- MAMS greenish-tinged sulphonic acid acetoacetanilide yellow 14 2,4-diaminobenzenesulphonic acid 6-ureido-1-naphthol-3-sulphonic acid MAMS orange 15 2,4-diaminobenzenesulphonic acid 7-(4-sulphophenylamino)-1-naphthol- EAMS brown 3-sulphonic acid 16 2,4-diaminobenzenesulphonic acid 8-acetylamino-1-naphthol-3,6-di- MAMS red sulphonic acid 17 1,4-diaminobenzene p-cresol MAMS yellow 18 2,5-diaminobenzenesulphonic acid 1-(4-sulphophenyl)-3-carboxy-5- MAMS reddish-tinged pyrazolone yellow 19 2,5-diaminobenzenesulphonic acid barbituric acid MAMS greenish-tinged yellow 20 2,5-diaminobenzenesulphonic acid 7-phenylamino-1-naphthol-3,6- MAMS brown disulphonic acid 21 2,4-diamino-5-methoxybenzene- 7-phenylamino-1-naphthol-3,6- EAMS brown-red sulphonic acid disulphonic acid Colour shade on No. A B C cotton 22 2,5-diaminobenzenesulphonic acid 7-amino-1-naphthol-3-sulphonic acid MAMS red (coupled under acid conditions) 23 2,5-diaminobenzenesulphonic acid 7-methylamino-1-naphthol-3- EAMS red sulphonic acid (coupled under acid conditions) 24 2,5-diaminobenzenesulphonic acid 7-amino-1-naphthol-4-sulphonic acid EAMS red-violet (coupled under acid conditions) 25 4,6-diamino-1,3-benzenedi- 1-(4-sulphophenyl)-3-sulphomethyl- MAMS yellow sulphonic acid 5-pyrazolone 26 2,5-diaminobenzenesulphonic acid 5-(2-sulphophenylazo)-6-phenyl- MAMS red amino-1-naphthol-3-sulphonic acid 27 2,5-diaminonaphthalene-1- 8-benzoylamino-1-naphthol-3,6- MAMS bluish-tinged red sulphonic acid disulphonic acid 28 2,8-diaminonaphthalene-1- 8-benzoylamino-1-naphthol-3,5- MAMS bluish-tinged red sulphonic acid disulphonic acid 29 2,-amino-5-aminomethylnaphthalene- 8-benzoylamino-1-naphthol-3,5- MAMS red 1-sulphonic acid disulphonic acid 30 2-amino-5-aminomethylnaphthalene- 8-acetylamino-1-naphthol-3,6- MAMS red 1-sulphonic acid disulphonic acid Example 31 29.2 g of cyanuric chloride are subjected to a condensation reaction with 22.5 g of MAMS as in Example 1, at pH 7 and 3"C. After the condensation reaction, 54.5 g of the disodium salt of 8-amino-l-naphthol-3,6-disulphonic acid are added and the condensation reaction is carried out at 500C and pH 2.5 (20% strength sodium carbonate solution).After the condensation reaction, the pH is adjusted to 6 and the suspension of the diazonium salt of 25.1 g of 2-aminobenzenesulphonic acid is added. The coupling reaction is brought to completion at this pH value (sodium carbonate solution) and the product is salted out (sodium chloride), filtered off and dried in vacuo. Using this dyestuff, deep red prints and dyeings are obtained on cotton and rayon staple. In the form of the free acid, this dyestuff corresponds to the formula

Comparable dyestuffs are obtained when 2-aminobenzenesulphonic acid, 8 amino-l-naphthol-3,6-disulphonic acid and MAMS are replaced by the compounds listed under A, B and C in the Table which follows.

colour shade or No. A B C cotton 32 6-aminobenzene-1,3-disulphonic acid 3-methyl-1-[6-amino-4,8- MAMS yellow disulphonaphthyl-2]-5-pyrazolone 33 2-aminonaphthalene-4,8-disulphonic m-toluidine MAMS yellow acid 34 2-aminobenzenesulphonic acid 6-amino-1-naphthol-3-sulphonic acid MAMS orange 35 2-amino-5-(4-sulphophenylazo)- 6-amino-1-naphthol-3-sulphonic acid MAMS bluish-tinged benzenesulphonic acid red 36 2-amino-1-sulphomethylnaphthalene- 6-amino-1-naphthol-3-sulphonic acid MAMS red 5-sulphonic acid 37 2-amino-5-(4-sulphophenylazo)- 1-aminonaphthalene-6-sulphonic acid EAMS yellow-brown benzenesulphonic acid 38 1-amino-4-(2,5-disulphophenylazo)- 1-aminonaphthalene-7-sulphonic acid EAMS red-brown naphthalene-6-sulphonic acid 39 1-amino-4-(2,5-disulphophenylazo)- 3-ureidoaniline MAMS reddish-tinged naphthalene-6-sulphonic acid brown 40 2,5-dimethoxy-4-(2,5-disulpho- N-ethyl-3-ureidoaniline MAMS brown phenylazo)-aniline 41 4-[4,8-disulphonaphthylazo-2]- 1-aminonaphthalene-6,8-disulphonic EAMS brown naphthalene-7-sulphonic acid acid 42 1-aminonaphthalene-7-sulphonic acid 43 1-amino-4-[4,8-disulphonaphthylazo- 1-aminonaphthalene-8-sulphonic acid MAMS brown-red 2]-naphthalene-6-sulphonic acid 44 3-aminopyrene-5,8,10-trisulphonic 2,4-diaminobenzenesulphonic acid MAMS scarlet-red acid 45 aniline 8-amino-1-naphthol-3,6-disulphonic MAMS bluish-tinged acid red 46 2-amino-5-methylbenzenesulphonic 8-amino-1-naphthol-3,6-disulphonic MAMS red acid acid 47 2-aminonaphthalene-1-sulphonic acie 8-amino-1-naphthol-3,6-disulphonic MAMS claret acid 48 2-aminonaphthalene-1,5-disulphonic 8-amino-1-naphthol-3,6-disulphonic MAMS red acid(1,5) acid 49 2-aminonaphthalene-1,5-disulphonic 8-amino-1-naphthol-3,5-disulphonic EAMS red acid(1,5) acid 50 2-amino-1-sulphomethylnaphthalene- 8-amino-1-naphthol-3,5-disulphonic MAMS ruby 5-sulphonic acid acid 51 2-methoxy-4-(2-sulphophenylazo)-5- 8-amino-1-naphthol-3,6-disulphonic MAMS blue methylaniline acid Example 52 The diazonium salt, prepared as in Example 1, of the condensation product of 57 g of 2,4-diaminobenzenesulphonic acid and 58 g of cyanuric chloride and also 45 g of MAMS is subjected to a coupling reaction, at pH 2.5, with 0.3 mole of the disodium salt of 8-amino-1-naphthol-3,6-disulphonic acid.

The solution of the aminoazo dyestuff is subjected to a coupling reaction with the diazonium salt of 52 g of 2-aminobenzenesulphonic acid at pH 7 to 8 (sodium hydroxide solution). The dyestuff is salted out, filtered off and dried and corresponds to the formula

Cotton and rayon staple are dyed in blue-grey shades which are fast to light and washing.

Example 53 If the components used are the same as in Example 52 but 2aminobenzenesulphonic acid is first subjected to a coupling reaction at pH 2.5 with 8-amino-l-naphthol-3,6-disulphonic acid and the diazonium salt of the condensation product of 2,4-diaminobenzenesulphonic acid, cyanuric chloride and MAMS is then subjected to a coupling reaction at pH 7 to 8 with the monoazo dyestuff, a dyestuff which dyes cotton or rayon staple in blue-grey shades is obtained.In the form of the free acid it corresponds to the formula

Example 54 A solution of 13.8 g of sodium nitrite and 41.6 g of the disodium salt of 4,4' diamino-5,5'-dimethyldiphenyl-2,2'-disulphonic acid in 450 ml of water is cooled to 0--5"C and then added slowly, whilst stirring, to 70 ml of concentrated hydrochloric acid which has been cooled to 0--50C. The mixture is stirred for a further 2 hours and the excess of sodium nitrite is then destroyed by adding amidosulphonic acid.

38.4 g of acetoacetic acid 4-aminoanilide are added to the solution of the condensation product of 38.7 g of cyanuric chloride and 27.5 g of methylaminomethanesulphonic acid and the condensation reaction is carried out at pH 7 and about 50"C with the addition of 20 ^ strength sodium carbonate solution. After the condensation reaction, the solution is cooled to 0--50C and the diazonium salt solution is added. The coupling reaction is brought to completion with the addition of sodium carbonate solution and the dyestuff is salted out, filtered off and dried. In the form of the free acid it corresponds to the formula

and dyes cotton and rayon staple yellow.

Example 55 The diazonium salt of the condensation product of 75.2 g of 2.5-diaminobenzenesulphonic acid, 77.5 g of cyanuric chloride and 60 g of methylaminomethanesulphonic acid is prepared according to Example 1.

72.6 g of the disodium salt of 8-amino-l-naphthol-3,6-disulphonic acid are first subjected to a coupling reaction at pH 2.5 with one half of the diazonium salt prepared above and then subjected to a coupling reaction at pH 8 with the second half of the said salt. The dyestuff is then salted out, filtered off and dried in vacuo.

Using the dyestuff, cotton and rayon staple are dyed or printed in bluish-tinged grey shades. In the form of the free acid the dyestuff corresponds to the formula

Example 56 The solution of the diazonium salt obtained according to Example 1, paragraph 1, from the amine obtained by a condensation reaction of cyanuric chloride, MAMS and 2,4-diaminobenzenesulphonic acid is subjected to a coupling reaction at OOC and pH 7 with the solution of the coupling component which is obtained by a condensation reaction of l-(4-aminophenyl)-3-sulphomethyl-5pyrazolone, cyanuric chloride and MAMS, analogously to Example 31. The dyestuff of the formula

which is obtained after bringing the coupling reaction to completion, salting out, filtering off and drying, dyes cotton in yellow shades which are fast to wet processing.

Radical on cyanuric Colour shade on No. Diazo component Coupling component chloride cotton 57 2,4,-diaminobenzenesulphonic 1-(3-aminophenyl)-5-pyrazolone- EAMS reddish-tinged acid carboxylic acid yellow 58 2,5-diaminobenzenesulphonic 1-(3-aminophenyl)-5-pyrazolone- MAMS reddish-tinged acid carboxylic acid yellow 59 2-(3-sulpho-4-aminophenyl)-5,9- 1-(4-aminophenyl)-5-pyrazolone- MAMS yellow disulpho-7- 3-carboxylic acid aminonaphthotriazole 60 2,6-diaminonaphthalene-4,8- m-touidine MAMS golden yellow disulphonic acid 61 2,5-diaminobenzenesulphonic 6-amino-1-naphthol-3-sulphonic acid MAMS yellowish-tinged acid red 62 2,5-diaminobenzenesulphonic 7-amino-1-naphthol-3-sulphonic acid MAMS red-brown acid 63 2,5-diaminobenzenesulphonic 8-amino-1-naphthol-3,6-disulphonic MAMS red acid acid 64 2,4-diaminobenzenesulphonic 8-amino-1-naphthol-3,6-disulphonic MAMS red acid acid 65 2,4-diaminobenzenesulphonic 8-amino-1-naphthol-3,5-disulphonic EAMS red acid acid Example 66 137.7 g of the copper complex azo dyestuff obtained from the diazonium salt of 2-amino-5-sulphobenzenecarboxylic acid by a coupling reaction with 3-methyl-l [6-amino-4,8-disulphonaphthyl-2]-5-pyrazolone and complexing the reaction product with copper in an acetate-buffered solution using copper-II sulphate solution, are dissolved in 3.5 1 of water at pH 5 and the solution is cooled to 20C.

38.8 g of cyanuric chloride are added and the pH and temperature are kept constant. After the condensation reaction, 30 g of MAMS are added, the mixture is warmed to 50"C and the pH is adjusted to 7 with 20% strength sodium carbonate solution. The dyestuff is salted out at room temperature, filtered off and dried. The dyestuff, which in the form of the free acid, corresponds to the formula

S03H o=c , NH/ N Ho; CH3 503M N-CH5 Cu-Complex CH2SCt3H dyes cotton and rayon staple in yellow which is very fast to light and fast to washing.

Example 67 18.9 g of 2-aminophenol-4-sulphonic acid are diazotised and the diazo compound is subjected to a coupling reaction at pH 8 with 31.9 g of 8-amino-l- naphthol-3,5-disulphonic acid. After the coupling reaction, the mixture is warmed with 16 g of copper sulphate to 900C for 1 hour, at pH 5. The copper complex azo dyestuff is salted out and filtered off. The moist paste is dissolved in 600 ml of water and subjected to a condensation reaction, first at pH 4.5 and 2"C with 19.4 g of cyanuric chloride and then at pH 7 and 50"C with 13.7 g of MAMS, with the aid of 20% strength sodium carbonate solution in each case. The product is salted out, filtered off and dried in vacuo. Cellulose fibres are dyed blue-violet by this dyestuff.

In the form of the free acid, the dyestuff corresponds to the formula:

Cu-Complex Further copper complex reactive dyestuffs are obtained when the components A, B and C listed in the Table which follows are used in place of 2-aminophenol-4sulphonic acid, 8-amino-l-naphthol-3,5-disulphonic acid and MAMS. Colour shade on No.A B C cotton 68 2-amino-5-sulphobenzoic acid 6-amino-1-naphthol-3-sulphonic acid MAMS brown-red 69 2-amino-5-sulphobenzoic acid 6-(ss-aminoethylamino)-1-naphthol-3- MAMS bluish violet sulphonic acid 70 2-amino-5-sulphobenzoic acid 6-(3-amino-4-sulphophenyl)-1- MAMS bluish violet naphthol-3-sulphonic acid 71 2-aminonaphthalene-4,8- 8-amino-1-naphthol-3,5-disulphonic MAMS reddish-tinged disulphonic acid acid blue 72 2-aminonaphthalene-4,8- 8-amino-1-naphthol-3,6-disulphonic MAMS bluish-tinged disulphonic acid acid red 73 2-amino-6-nitronaphthalene-4,8- 6-amino-1-naphthol-3-sulphonic acid MAMS blue disulphonic acid 74 2,4-diaminophenol-6-sulphonic acid 8-(3-sulphophenylaminocarbonyl- bluish-tinged amino)-1-naphthol-3,5-disulphonic violet acid 75 2,4-diaminophenol 8-amino-1-naphthol-5,7-disulphonic MAMS bluish-tinged acid violet 76 6-amino-2-naphthol-4-sulphonic acid 8-amino-1-naphthol-5,7-disulphonic MAMS blue acid 77 2,4-diaminophenol-5-sulphonic acid 1-(4-sulphophenyl)-5-pyrazolone-3- EAMS brown carboxylic acid 78 4-(2-sulphophenyl)-2-methoxy-5- 6-amino-1-naphthol-3,5-sulphonic EAMS blue methylaniline acid 79 2,5-diaminobenzenesulphonic acid 4-(2-hydroxy-4-sulphophenylazo)- MAMS brown resorcinol Example 80 109 g of the copper complex azo dyestuff obtained from the diazonium salt of 8-amino-l-phenylsulphonyloxynaphthalene-3,6-disulphonic acid by a coupling reaction at pH 8 with 6-acetylamino- 1 -naphthol-4,8-disulphonic acid, oxidative complexing of the reaction product with copper, using copper sulphate and hydrogen peroxide and hydrolysis of the N-acetyl and O-phenylsulphonyl groups, are dissolved in 4 1 of water to give a neutral solution and subjected to successive condensation reactions with 29.5 g of cyanuric chloride at pH 6 and 0 to 50C and with 20.5 g of MAMS at pH 7 and 55"C. In the form of the free acid, the dyestuff corresponds to the formula

Cu-Complex and dyes cotton and rayon staple blue.

Example 81 If, in Example 80, 8-amino-1-phenylsulphonyloxynaphthalene-3,6-disulphonic acid is replaced by the equivalent amount of 8-amino-l-phenylsulphonyl- naphthalene-3,5-disulphonic acid, a dyestuff which dyes cotton and rayon staple in very fast blue shades is obtained.

Example 82 18.9 g of diazotised 2-aminophenol-4-sulphonic acid are subjected to a coupling reaction with 64.7 g of the copper complex azo dyestuff obtained from the diazonium salt of 6-amino-l-naphthol-4,8-disulphonic acid by a coupling reaction with 6-amino-l-naphthol-3-sulphonic acid and subsequent oxidative complexing of the reaction product with copper. After salting out and filtering off, the moist dyestuff paste is dissolved in 1.8 1 of water, complexed a second time with copper for one hour at pH 5 and 50"C, using 25 g of copper sulphate, and isolated again.

The dyestuff paste is stirred into 1.9 1 of water and subjected to a condensation reaction, first with 19.4 g of cyanuric chloride at pH 5 and 3"C and then with 13.7 MAMS at pH 7 and 550C. The dyestuff, which in the form of the free acid corresponds to the formula

9 a1 OH N N = N =+ ic; NH OH OH I I 503H ti K N N-CH3 Bis-copper complex CH S03H dyes cotton and rayon staple blue.

Example 83 47.4 g of 1:1 complex obtained by a coupling reaction of the diazonium salt of 2-amino-4,6-dinitrophenol with 2-aminonaphthalene-6-sulphonic acid and subsequent complexing of the product with cobalt at pH 5 and room temperature, using cobalt sulphate heptahydrate, are reacted in 1,250 ml of water at pH 11 and 45"C with 55.4 g of the azo dyestuff obtained by a coupling reaction of the diazonium salt of 2-amino-4-nitrophenol-6-sulphonic acid with 6-amino-l- naphthol-3-sulphonic acid, to give the 1:2 cobalt complex. This reaction takes about 2.5 hours. The product is then salted out with sodium chloride and filtered off.

The paste is suspended in 1.5 1 of water and subjected to a condensation reaction at pH 7 and 50"C with 27.3 g of the condensation product of cyanuric chloride and MAMS.

The product is then salted out, filtered off and dried in vacuo. The asymmetrical 1:2 cobalt complex prepared in this way dyes cotton and rayon staple in dark brown shades. In the form of the free acid, the complex corresponds to the formula

Symmetrical 1:2 cobalt complex azo dyestuffs are obtained when the compounds A in the Table which follows are used as the diazo component and the compounds B in the Table which follows are used as the coupling component.

Colour shade on No. A B cotton 84 2-aminophenol-4-sulphonic acid acetoacetic acid 4-aminoanilide yellow 85 2-amino-4-nitrophenol-6-sulphonic 4-aminophenol brown acid 86 2-amino-4-nitrophenol-6-sulphonic 3-amino-2-naphthol-5,7-disulphonic reddish-tinged acid acid brown 87 2-amino-4-nitrophenol 8-amino-l -naphthol-3,6-disulphonic grey acid 88 l-amino-6-nitro-2-phenol-4- 2-amino-5-naphthol-7-sulphonic acid grey sulphonic acid Example 89 If, in Example 83, the metal-free azo dyestuff is replaced by the equivalent amount of the azo dyestuff prepared from the diazonium salt of 2-amino-4,6dichlorophenol by a coupling reaction at pH 8 with 8-amino-l-naphthol-3,6- disulphonic acid, a dyestuff which dyes cotton and rayon staple navy-blue is obtained.In the form of the free acid, this dyestuff corresponds to the formula

Example 90 77.8 g of the dyestuff prepared from 2-amino-6-nitro-phenol-4-sulphonic acid and 2-naphthol by diazotisation and a coupling reaction are stirred into 500 ml of water at 800C.

The 1:1 chromium complex which is obtained by diazotising 44.7 g of 2-amino4-chlorophenol-6-sulphonic acid, coupling the diazo compound at pH 8 with 72.6 g of 8-amino-l-naphthol-3,5-disulphonic acid, complexing the reaction product with chromium, using 32 g of chromium trichloride in acid solution, salting out and filtering off, is introduced into this suspension in the course of 1 hour.

The asymmetrical 1:2 chromium complex azo dyestuff is isolated as an intermediate product and subjected to a condensation reaction with 38.8 g of cyanuric chloride at pH 5 and 3"C and with 27.4 g of MAMS at pH 6.5 and 45"C.

The product is salted out, filtered off and dried. The dyestuff, which in the form of the free acid corresponds to the formula

dyes cotton and rayon staple blue-grey.

Example 91 If, in Example 90, 2-amino-4-chlorophenol-6-sulphonic acid is replaced by the corresponding amount of 2-amino-4-nitrophenol-6-sulphonic acid, this gives an asymmetrical 1:2 chromium complex dyestuff with which cellulose materials can be dyed or printed in blue-grey shades.

The symmetrical 1:2 chromium complex azo dyestuffs in the Table which follows are obtained when the compounds indicated in column A are used as the diazo component and the compounds indicated in column B are used as the coupling component, in accordance with the instructions of Example 90, and the reaction product is subjected to a condensation reaction with cyanuric chloride and, finally, with the compounds indicated in column C.

Colour shade on No. A B C cotton 92 2-aminobenzoic acid 6-amino-l-naphthol-3-sulphonic acid MAMS brown 93 2-aminobenzoic acid 6-amino- 1 -naphthol-3,5-disulphonic acid MAMS brown 94 2-amino-4-chlorophenol 8-amino-l-naphthol-3,6-disulphonic acid MAMS blue-grey 95 2-amino-4-chlorophenol 8-amino-l-naphthol-3,5-disulphonic acid EAMS blue-grey 96 2-amino-4-nitrophenol 8-amino- 1 -naphthol-3 ,5-disulphonic acid EAMS blue-grey 97 2-amino-5-nitrophenol 8-amino-1-naphthol-3,5-disulphonic acid MAMS blue-grey 98 2-amino-5-nitrophenol 8-amino-l-naphthol-3,6-disulphonic acid MAMS blue-grey 99 2-amino-4-nitrophenol 8-amino-I -naphthol-3,6-disulphonic acid MAMS blue-grey 100 1 -amino-6-nitro-2- 2-amino-5-naphthol-7-sulphonic acid MAMS grey naphthol-4-sulphonic acid Example 101 If, in Example 90, 8-amino-l-naphthol-3,5-disulphonic acid is replaced by the equivalent amount of 8-amino-l-naphthol-3,6-disulphonic acid, this gives a dyestuff with which cotton and rayon staple can be dyed or printed blue-grey.

Further outstanding grey to black dyestuffs are obtained by mixing cobalt complex dyestuffs with chromium complex dyestuffs, for example by mixing Example 100 with Example 88 and also Example 99 with Example 87, and the mixing ratio can vary between 30:70 and 70:30.

Example 102 19.4 g of cyanuric chloride in 100 ml of water are subjected to a condensation reaction with 18.8 g of 2,4-diaminobenzenesulphonic acid at pH 5 and 3"C. The reaction mixture is then acidified with concentrated hydrochloric acid and diazotised with an aqueous solution of sodium nitrite. The mixture is stirred for a further one hour and the excess sodium nitrite is removed with amidosulphonic acid.

30.8 g of 1-(2,5-dichloro-4-sulphophenyl)-3-methyl-5 > pyrazolone are dissolved in 150 ml of water with the aid of sodium hydroxide solution to give a neutral solution and the latter is cooled to OOC. The diazonium salt solution is added and the coupling reaction is carried out at pH 4 to 5.

After the coupling reaction, the reaction product is subjected to a condensation reaction, first with 6.1 g of ethylenediamine at 400C and pH 6, then with 19.4 g of cyanuric chloride at pH 6 and 3"C and finally with 13.7 g of MAMS at 50"C and pH 7. The dyestuff is salted out, filtered off and dried in vacuo. In the form of the free acid it corresponds to the formula

Cellulose materials are dyed greenish-tinged yellow, which is outstandingly fast to washing, by this dyestuff.

Further valuable bis-reactive dyestuffs are obtained when the compounds indicated under A, B, C and D in the Table which follows are employed in place of 2,4-diaminobenzenesulphonic acid, l-(2,5-dichloro-4-sulphophenyl)-3-methyl-5- pyrazolone, ethylenediamine and MAMS Colour shade No.A B C D on cotton 103 2,4-diaminobenzenesulphonic (2,5-dichloro-4-sulphophenyl)- N-methyl- EAMS yellow acid 3-methyl-5-pyrazolone ethylenediamine 104 2,4-diaminobenzenesulphonic (2,5-dichloro-4-sulphophenyl)- p-phenylene- MAMS yellow acid 3-methyl-5-pyrazolone diamine 105 2,5-diaminobenzenesulphonic (2-methyl-4-sulphophenyl)- N,N-dimethyl- MAMS yellow acid 3-methyl-5-aminopyrazole ethylenediamine 106 2-amino-5-methoxybenzene- 6-amino-1-naphthol-3- 4,6-diamino- MAMS scarlet sulphonic acid sulphonic acid benzene-1,3disulphonic acid Example 107 159.9 g of the disodium salt of the condensation product obtained from equivalent amounts of l-amino-4-bromoanthraquinone-2-sulphonic acid and 2,4diaminobenzenesulphonic acid are dissolved in 4 1 of water, the solution is cooled to 0 C and a solution of 58.1 g of cyanuric chloride in 240 ml of acetone is added at pH 5-5.5 and 05 C. After the condensation reaction, 45 g of MAMS are added and the second condensation reaction is carried out at 500C and pH 7. The dyestuff is salted out, filtered off and dried in vacuo. The dyestuff dyes cotton and cellulose in reddish-tinged blue shades which are fast to washing and light. In the form of the free acid the dyestuff corresponds to the formula

Further valuable anthraquinone dyestuffs are obtained when 2,4diaminobenzenesulphonic acid is replaced by the diamino compounds indicated in the Table which follows.

Colour shade No. Diamino compound on cotton 108 1,4-diamino-2,3,5,6-tetramethylbenzene blue 109 4,4'-diaminobiphenyl-3-sulphonic acid blue 110 4,4'-diaminostilbene-2,2'-disulphonic acid blue Example 111 106.5 g of the copper complex dyestuff of the formula

in which Cu-Pc denotes copper phthalocyanine and the sulphonic acid groups and sulphonamide groups are in the 3-position, are subjected to a condensation reaction with 58 g of cyanuric chloride at 0--50C and pH 6.5 and the reaction product is then reacted with 41 g of MAMS at 450C and pH 7. After salting out, filtering off and drying, this gives a dyestuff with which cotton and rayon staple can be dyed or printed in brilliant blue shades.In the form of the free acid the dyestuff corresponds to the formula

Example 112 If, in Example 111, 2,5-diaminobenzenesulphonic acid is replaced by the equivalent amount of ethylenediamine, this gives a corresponding dyestuff with which cotton or cellulose can be dyed in brilliant blue shades.

Example 113 63.1 g of 3,1 0-di-(p-aminoethylamino)-6, 1 3-dichlorotriphenyldioxane-4, 11 - disulphonic acid are suspended in 1.5 1 of water and reacted at pH 6-7 and a 30 35"C with the condensation product of 18.4 g of cyanuric chloride and 12.5 g of MAMS. The product is salted out, filtered off and dried in vacuo. The dyestuff dyes cellulose fibres blue.

Example 114 The diazonium salt of 22.1 g of 2-aminophenol-4-sulphonic acid is subjected to a coupling reaction, at pH 8, with 19.2 g of a-formylphenylacetic acid ethyl ester.

The reaction mixture is boiled for 30 minutes at pH 10 and the solution of the saponification product is subjected to a coupling reaction, at pH 5, with the diazonium salt of 23.0 g of 2-amino-5-acetylaminobenzenesulphonic acid.

The acetylamino group is then saponified by warming the mixture for one hour at 9.5 and the formazane dyestuff is salted out and isolated and reacted, at pH 3, 'with 25.0 g of copper-II sulphate pentahydrate. The product is salted out and isolated. The moist phase is subjected to successive condensation reactions with 19.4 g of cyanuric chloride atpH 5 and 2"C and 13.7 g of MAMS at pH 7 and 50"C.

Cotton and rayon staple are dyed blue, which is fast to light and washing, by the dyestuff of the formula

CL 1 HCSSNH-4 H03S' N N cn2-cn Cu-Complex Example 115 The diazonium salt of 73.8 g of 2-amino-6-acetylaminophenol-4-sulphonic acid is subjected to a coupling reaction, at pH 9, with the hydrazone prepared from 31.8 g of benzaldehyde and 45.6 g of 2-hydrazinobenzoic acid. The acetylamino group is then saponified, at pH 10, by warming the reaction mixture to 950C for one hour. The pH is adjusted to 3 with concentrated hydrochloric acid and the formazane is reacted with 75.0 g of copper-II sulphate pentahydrate.

After salting out and filtering, the moist phase is stirred into 1.5 1 of water and subjected to successive condensation reactions with 58.2 g of cyanuric chloride at pH 6.5 and 3"C and with 41.1 g of MAMS at pH 7 and 50"C. Using the dyestuff, which in the form of the free acid corresponds to the formula

LA'uII LI -1 N | SO3H Od2SO3H N CSc t Cu-Complex cotton and cellulose can be dyed or printed in blue shades which are fast to light and fast to washing.

Example 116 0.1 mol of the hydrazone prepared from 2-hydrazino-4-sulphobenzoic acid and 4-amino-2-formylbenzenesulphonic acid are dissolved in 500 ml of water to give a neutral solution and the solution is acidified and diazotised at 0--5"C with an aqueous solution of sodium nitrite. The mixture is stirred for a further one hour, excess nitrite is destroyed with amidosulphonic acid and 12.6 g of barbituric acid are sprinkled in. The coupling reaction is carried out at pH 6-7.

The dyestuff is isolated as an intermediate product and dissolved in 600 ml of water. The diazonium salt of 36.0 g of 2-amino-6-[4-chloro-6-(N-methyl-Nsulphomethylamino)-triazinyl-2]-phenol is added at pH 8-9 and the coupling reaction is brought to completion at pH 8-9. The reaction product is then reacted with 75.0 g of copper sulphate pentahydrate at pH 11 and the dyestuff is salted out, isolated and dried in vacuo.Cotton and rayon staple can be dyed or printed dark green using the dyestuff, which in the form of the free acid corresponds to the formula

CL ~ NH Gt)OH HO MN/CSO5H > NM N \CH3 1 II Ho= N N N\C t N = N t Cu-Complex N HO Example 117 If, in Example 116, barbituric acid is replaced by the equivalent amount of 5 amino-3-methyl-1-(4-methyl-2-sulphophenyl)-pyrazole, this gives a dyestuff which dyes cotton and rayon staple olive.In the form of the free acid, the dyestuff corresponds to the formula

CL ~ N SNH N t N-ChH NH zN CH3 ~~ N N H03Sb, /--7 Cu-Complex NH2 SOBH Example 118 137 g of MAMS are reacted with a suspension of 2.5 1 of water and 184.5 g of cyanuric chloride for 2 hours at pH 7 and 0--5"C.

Small amounts of residue are then filtered off, potassium chloride is added to the filtrate and the precipitate is filtered off and dried in vacuo at roon temperature. This gives a colourless crystalline precipitate which corresponds te the formula

Elementary analysis gives the following values: calculated: 19.30/, C 1.6% H 22.8% Cl 18.0% N 10.3% S found: 19.5e C l.77o H 22.40/,C1 18.1% N 10.5% S WHAT WE CLAIM IS: 1.A reactive dyestuff of the general formula

in which X denotes a group which can be split off under the conditions of reactive dyeing, Y denotes a group of the general formula

R, denotes an optionally substituted alkyl group, R2 denotes a hydrogen atom, or an optionally substituted alkyl or aralkyl group, F denotes a radical of an organic dyestuff, W and V independently denote a direct bond or a bridge member, Q denotes a hydrogen atom or an optionally substituted alkyl group, D denotes a hydrogen atom or an optionally substituted alkyl or aryl group, E denotes an optionally substituted alkylene or arylene group and n is 1, 2, 3 or 4.

2. A reactive dyestuff according to claim 1, in which radical W is any of those bridge members hereinbefore specifically mentioned.

3. A reactive dyestuff according to claim 1 or 2, in which radical V is any of those bridge members hereinbefore specifically mentioned.

4. A reactive dyestuff according to claim 1, of the general formula

in which X, denotes a halogen atom, Y, denotes a radical of the general formula

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

Claims

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

Elementary analysis gives the following values: calculated: 19.30/, C 1.6% H 22.8% Cl 18.0% N 10.3% S found: 19.5e C l.77o H 22.40/,C1 18.1% N 10.5% S WHAT WE CLAIM IS: 1.A reactive dyestuff of the general formula

in which X denotes a group which can be split off under the conditions of reactive dyeing, Y denotes a group of the general formula

R, denotes an optionally substituted alkyl group, R2 denotes a hydrogen atom, or an optionally substituted alkyl or aralkyl group, F denotes a radical of an organic dyestuff, W and V independently denote a direct bond or a bridge member, Q denotes a hydrogen atom or an optionally substituted alkyl group, D denotes a hydrogen atom or an optionally substituted alkyl or aryl group, E denotes an optionally substituted alkylene or arylene group and n is 1, 2, 3 or 4.
2. A reactive dyestuff according to claim 1, in which radical W is any of those bridge members hereinbefore specifically mentioned.
3. A reactive dyestuff according to claim 1 or 2, in which radical V is any of those bridge members hereinbefore specifically mentioned.
4. A reactive dyestuff according to claim 1, of the general formula

in which X, denotes a halogen atom, Y, denotes a radical of the general formula

R4 denotes a C1 to C4 alkyl group, Q, denotes a hydrogen atom or a C, to C4 alkyl group, D1 denotes a hydrogen atom or a C1 to C4 alkyl group, E, denotes a C2 to C4 alkylene or m- or p-phenylene radical which is optionally substituted by one or more sulphonic acid groups, W1 denotes a direct bond, a C2 to C4 alkylene or m- or p-phenylene radical which is optionally substituted by one or more sulphonic acid groups, R5 denotes a hydrogen atom or a C, to C4 alkyl group and n1 is 1 or 2 and F has the same meaning as in claim 1.
5. A reactive dyestuff according to claim 4, in which X1 denotes a fluorine, chlorine or bromine atom.
6. A reactive dyestuff according to claim 1, of the general formula

in which F and n, have the same meanings as in claim 4, W2 denotes a -CH2-CH2- or m- or p-phenylene group which is optionally substituted by 1 or 2 sulpho groups, R8 denotes hydrogen or methyl, Y2 denotes a

group or a radical of the formula

X2 denotes a fluorine or chlorine atom, D2 denotes a hydrogen atom or a methyl group and E2 denotes an ethylene or m- or p-phenylene radical which is optionally substituted by I or 2 sulpho groups.
7. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1,.

A denotes a radical of a heterocyclic or carbocyclic diazo component and B represents the radical of a heterocylic, carbocyclic or CH-acid coupling component, and the substituent W is linked to the azo dyestuff via a carbon atom of the diazo component, and/or of the coupling component.
8. A reactive dyestuff according to claim 7, in which A denotes a radical of the benzene, naphthalene or triazole series.
9. A reactive dyestuff according to claim 7 or 8, in which B denotes a radical of optionally further substituted phenol, naphthol, aniline, naphthylamine, 5aminopyrazole, 5-pyrazolone, pyridone, aminopyridine, acetoacetic acid arylide, indole or pyrimidine.
10. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1 and A, denotes a phenyl or naphthyl radical which is optionally substituted by sulpho, nitro, chlorine, C, to C4 alkyl, C, to C4 alkoxy, or by a phenyl or naphthyl radical which is optionally substituted by sulpho, amino or C, to C4 alkyl, by amino or acetylamino, by a benzyl radical which is optionally substituted by amino, sulpho or C, to C4 alkyl, by a phenylazo or naphthylazo radical which is optionally substituted by amino, C, to C4 alkyl sulpho, C, to C4 alkoxy or hydroxyl, or by trifluoromethyl, Z denotes hydroxyl, alkoxy which is optionally substituted by hydroxyl or C, to C4 alkoxy, or amino which is optionally substituted by C, to C4 alkyl, phenyl or benzyl, it being possible for alkyl to be further substituted by cyano, hydroxyl or C, to C4 alkoxy and for phenyl and benzyl to be further substituted by methyl, methoxy, chlorine, nitro or sulpho, and R7, R8 and R9 independently of one another denote a hydrogen atom or a C, to C4 alkyl, C1 to C4 alkoxy, amino or C, to C4 alkylcarbonylamino group, a phenyl radical which is optionally substituted by C, to C4 alkyl, or an amino, hydroxyl or sulpho group and the substituent W is linked to the azo dyestuff via a carbon atom of the diazo component or of the coupling component.
11. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1 and A1,R7, RB, R9 and Z have the same meanings as in claim 10.
12. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1, A, has the same meaning as in claim 10 and Z, denotes an amino or hydroxyl group, R10 denotes a C, to C4 alkyl or carboxyl group and R" denotes a phenyl or naphthyl group which is optionally substituted by chlorine, C, to C4 alkyl, sulpho, C, to C4 alkoxy or amino, and W is linked to the azo dyestuff via a carbon atom of the diazo component or of the coupling component.
13. A reactive dyestuff according to claim 12, in which R10 denotes a methyl group.
14. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1 and A, has the same meaning indicated in claim 10 and W is linked to the diazo component via a carbon atom.
15. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1 and A1,R7,R8 and RB have the same meanings as in Claim 10 W is linked to the azo dyestuff via a carbon atom of the diazo component or of the coupling component.
16. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meaning as in claim 1 and A, has the meaning as in claim 10, R12 denotes a C, to C4 alkyl or hydroxyl group and R13 denotes a cyano, sulpho-C, to C4 alkyl or aminocarbonyl group and W is linked to the azo dyestuff via a carbon atom of the diazo component or of the coupling component.
17. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1, A, and R,3 have the same meaning as in claim 16, R,4 denotes a C1 to C4 alkyl or amino group and R,s denotes a hydrogen atom or a C, to C4 alkyl group and W is linked to the azo dyestuff via a carbon atom of the diazo component or of the coupling component.
18. A reactive dyestuff according to any of claims 11 to 17, in which A, denotes a radical of an amine of the general formula

in which R.6 denotes a hydrogen atom or a sulpho, hydroxyl, carboxyl or amino group, R,7 denotes a hydrogen or chlorine atom or a nitro, aminosulphonyl, C, to C4 alkyl, C, to C4 alkoxy, amino, sulpho or hydroxyl group or a phenylazo or naphthylazo group which is optionally substituted in the phenyl nucleus or naphthyl nucleus by hydroxyl, sulpho or amino, and RIB denotes a hydrogen or chlorine atom or a nitro, C, to C4 alkyl or C, to C4 alkoxy group.
19. A reactive dyestuff according to any of claims 11 to 17, in which A, denotes a radical of the general formula

in which Rr6, R,7 and RIB have the same meanings as in claim 18, and RIB denotes a hydrogen or chlorine atom or a nitro, aminosulphonyl, C, to C4 alkyl, C, to C4 alkoxy, amino, sulpho or hydroxyl group or a phenylazo or naphthylazo group which is optionally substituted in the phenyl nucleus or naphthyl nucleus by hydroxyl, sulpho or amine.
20. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1 and L denotes a hydrogen atom or a substituent, R20 denotes a hydrogen atom or an alkyl or aralkyl group and p is 1, 2, 3, 4, 5 or 6.
21. A reactive dyestuff according to claim 20, in which L denotes a hydrogen or halogen atom or an amino, hydroxyl or sulpho group, R20 denotes a hydrogen atom or a C, to C4 alkyl or benzyl group and p is 1 or 2.
22. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the same meanings as in claim 1, Pe denotes a radical of a copper phthalocyanine or nickel phthalocyanine which is optionally substituted by C, to C4 alkyl, C, to C4 alkoxy or sulpho, or sulphonamide which is optionally monosubstituted or disubstituted by C, to C4 alkyl, benzyl or phenyl, and R2, denotes a hydrogen atom or an alkyl or aralkyl radical and m is 1, 2, 3 or 4.
23. A reactive dyestuff according to claim 22, in which R2, denotes a hydrogen atom or C, to C4 alkyl or benzyl group.
24. A reactive dyestuff according to claim 1, of the general formula

in which V, W, X, Y, R2 and n have the meanings indicated in claim 1, M denotes a heavy metal atom, G, and G2 denote aromatic carbocyclic or aromatic heterocyclic rings which carry the substituents a and b in the o-position relative to the formazane nitrogen atoms, a and b independently denote a hydrogen atom or a hydroxyl, carboxyl or aminosulphonyl group, W3 denotes a direct bond or a bridge member, R22 denotes an alkyl or aryl group and the aromatic carbocyclic or aromatic heterocyclic rings G, and G2 optionally contain further substituents.
25. A reactive dyestuff according to claim 24, in which one or both of the rings G, and G2 are substituted by C, to C4 alkyl, C, to C4 alkoxy, chlorine, bromine, amino or sulpho.
26. A reactive dyestuff according to claim 24 or 25, in which M denotes a copper atom.
27. A reactive dyestuff according to claim 1, as hereinbefore specifically identified.
28. A process for the production of a reactive dyestuff as claimed in claim 1, in which a dyestuff, or dyestuff precursor, which contains at least one amino, amide or hydroxyl group which has at least one reactive hydrogen atom is reacted with a compound of the general formula

in which U is a radical which can be split off under the reaction conditions and X and Y have the same meanings as in claim 1, and, in the case of a dyestuff precursor, the reaction product is converted into the dyestuff.
29. A process for the production of a dyestuff as claimed in claim 1, in which a dyestuff, or dyestuff precursor, which contains an amino or amide group and has at least one replaceable hydrogen atom on the amino group or the amide group is reacted with a compound of the general formula

in which U, denotes a radical which can be replaced by an anionic mechanism, U is a radical which can be split off under the conditions of reaction with the dyestuff or dyestuff precursor and X has the same meaning as in claim 1, and the resulting product is reacted in any desired sequence with a compound of the general formula Y-H (XX) in which Y has the same meaning as in claim 1, and, in the case of dyestuff precursors, the dyestuff is then prepared.
30. A process according to claim 29, in which radical U, denotes a fluorine, chlorine or bromine atom.
31. A process for the production of a reactive dyestuff as claimed in claim 1, when carried out substantially as described in any one of the Examples.
32. A reactive dyestuff according to claim 1, when produced by the process of any of claims 28 to 31.
33. A process for dyeing or printing a hydroxyl group-containing or a nitrogencontaining textile material comprising treating the material with a dyestuff as claimed in any of claims 1 to 27 and 32.
34. A hydroxyl group-containing or nitrogen-containing textile material when dyed or printed by the process of claim 33.