IL24444A - Reactive dyestuffs and process for their production and use - Google Patents

Description

PATENTS AND DESIGNS ORDINANCE SPECIFICATION Reactive dyestuffs and process for their production and use I ( we ) PARBEHPABRIKBH BAYER AKTIEKGESELLSGHAPT , a German Company of Leverkusen-Bayerwerk, Germany do hereby declare the nature of this invention and in what manner the same is to be performed, to be particularly described and ascertained in and by the following statement : - REACTIVE DYESTUFFS AND PROCESS FOR THEIR PRODUCTION AND USE The present invention relates to valuable new reactive dyestuffs of the general formula in which F de dyestuff, X is a direct bond or a bridge member, A is a 5-membered hetero-oyolio ring which contains at least one reactive sulphonyl eubstituent linked to a carbon atom of the heterocyclic ring, and m is a number of 0.5 to 8.

In the dye stuffs of the general formula (I), the rraaddiiccaall AA iiss,, bbyy ddeeffiinniittiioonn,, lliinnkkeedd ttoo tthhee ddyyeessttuuffff rraaddiiccaall FF eeiitthheerr bbyy aa ddiirreecctt bboonndd oorr vviiaa aannyy bbrriiddggee mmeemmbbeerr.. AAss bbrriiddggee mmeemmbbeerrss,, tthhoossee ccoonnttaaiinniinngg nniittrrooggeenn aarree pprreeffeerrrreedd,, eessppeecciiaallllyy aammiinnoo oorr aammiiddee ggrroouuppss.. TThhee aammiinnoo oorr aammiiddee ggrroouuppss mmaayy ccoonnttaaiinn ffuurrtthheerr ssuubbssttiittuueennttss,, ssuucchh aass lloowweerr aallkkyyll ((pprreeffeerraabbllyy C^ ttoo CCgg)),, aarraallkkyyll,, ccyyoollooaallkkyyll oorr aarryyll ggrroouuppss,, bbuutt tthheeyy aarree pprreeffeerraabbllyy pprreesseenntt iinn tthhee ffoorrmm --NNHH-- wwhhiicchh iiss nnoott ffuurrtthheerr ssuubbssttiittuutteedd.. TThhee aammiinnoo ggrroouuppss mmaayy,, iinn ttuurrnn,, eeiitthheerr bbee lliinnkkeedd ddiirreeccttllyy ttoo aann aarroo¬mmaattiicc rriinngg ooff tthhee ddyyeessttuuffff,, oonn tthhee oonnee hhaanndd^^aanndd ttoo tthhee rraaddiiccaall AA,, oonn tthhee ootthheerr hhaanndd,, oorr tthheeyy mmaayy bbee lliinnkkeedd vviiaa aa ffuurrtthheerr bbrriiddggee mmeemmbbeerr,, ssuucchh aass --SSOOgg-- oorr --CCOO-- ((aass iinn tthhee ccaassee ooff tthhee aammiiddee ggrroouuppiinngg aallrreeaaddyy mmeennttiioonneedd)),, oorr aann aallkkyylleennee ggrroouupp,, aann aarryylleennee,, aarryylleennee--SSOOgg,, aarryylleennee--CCOO,, aarryylleennee--aammiinnoo oorr aarraallkkyylleennee--aammiinnoo ggrroouupp,, oorr aa ttrriiaazziinnee oorr ddiiaazziinnee rriinngg,, aann aarryylleennee--aammiiddoo-- ssuu y on the other hand. If these further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, these may also contain reactive atoms or groupings, suoh as halogen, atoms or sulphonyl eubstituents.

Suitable reactive sulphonyl substituents in the radioal A are lower alkyl-sulphonyl radicals, preferably with 1 - 5 carbon atoms, such as methyl-sulphonyl, ethyl-sulphonyl or propyl-sulphonyl radicals; aryl-sulphonyl radicals, such as phenyl-sulphonyl, p_-toluene-sulphonyl, p_-chlorophenyl-sulphonyl radicals; aralkyl-sulphonyl radicals, suoh as benzyl-sulphonyj. and p_-tolylmethyl-sulphonyl radicals; and also hetero-sulphonyl radicals such as 2-benzothiazole-sulphonyl.

The 5-membered heterocyclic ring A which contains at least one reactive sulphonyl substituent, carries no further fused rings. The ring system A can be, for example, an imidazole, thiazole, 1,2,4-trlazole, 1,2,4-thiadiazole, 1,5,4-thiadiazole radical. or 1 ,2-isothiazole radical.

The linkage of the heterocyclic 5-membered ring A toX, or in the case where X is a direct bond, to P, starts either from a carbon atom of the heterocyclic 5-membered ring or from a hetero atom of this ring, particularly a nitrogen atom.

As hetero atoms, the heterocyclic 5-membered ring A preferably contains oxygen, sulphur and/or nitrogen atoms in the 0 form of the groupings or atoms -0-, -S-, -S-, »N-, -N- or -N- i I 0 0 X in which X is hydrogen or a substituent, e.g. an alkyl, aralkyl or aryl radical which may^ in turn, contain further substituents or bridge members. aromatio, but it may also be hydro-aromatie. Groups of preferred heterocyclic rings A are those which oontain at least two heterocyclically linked nitrogen atoms or at least one heterocyclically linked nitrogen atom and one heterboyclically linkedsulphur atom.

Besides at least one reactive sulphonyl substituent and the direct bond or bridge member by whioh the 5-membered ring is linked to the dyestuff molecule, the heterocyclic -membered ring A may contain further substituents, such as aLkyl, e.g. methyl or ethyl groups; aralkyl, e.g. benzyl groups aryl, e.g. phenyl groups whioh may, in turn, oontain any desired further substituent; furthermore hydroxyl, mercapto. amino, acylamino, substituted amino, alkyloxy, aralkyloxy, aryloxy, alkylthio, aralkylthio, arylthlo, halogeno, particularly chlorine or bromine, oarboxy, oarbalkoxy, carbonamido, alkylcarbonyl, aralkylcarbonyl, arylcarbonyl, sulphlnio acid, sulphonio acid, sulphonamide, nitro or nitrlle groups.

Examples of suitable 5-membered heterocyclic rings A are, in particular, the following: 2-methylsulphonyl-l-methyl- imidazol-yl-5, 2-methylsulphonyl-l-phenyl-imidazol-yl-5, 2- methyl-aulphonyl-4-phenyl-thiazol-yl-5, l-methyl-5-methyl- sulphonyl-lH-triazol-l,2,4-yl-5, 3-methylsulphonyl-5-phenyl-4H- triazol-l,2,4-yl-4, 3,5-dimethylsulphonyl-4H-triazol-l,2,4-yl-4, 2-methylsulphonyl-thladiazol-i,5,4-yl-5, 1-ethyl- -methylsul- phonyl-4-methyl-imidazol-yl-5, l,4-dimethyl-2-ethylsulphonyl- iraidazol-yl-5, 5-methylsulphonyl-thiadiazol-l,2,4-yl-5, 5- methylsulphonyl-thiadiazol-l,2,4-yl-3, 3-methylsulphonyl-l,2,4- thiadiazolyl-5, 3-hydroxy-5-methylsulphonyl-isothiazolyl-4, 2-methyl-5-methylsulphonyl-isothiazolin-3-one-yl-4, 2,5-bis-methylsulphonyl-4-methyl-4H-lmidaz01-yl-4 or 4-methyl-2-methyl-sulphonyl-thlazolyl-5.

Of the great number of possible and useful bridge members X the following may be mentioned by way of example: -NH-, -N(CH3)-, -NfCgHg)-, - (C3H7)-, -CONH-, -HNOC-, -SOgNH-, -NHOgS-, -CON(CHg)-, -(CH3)N0C-, -S0gN(CH3)-, -(CH3)N0gS- and the corresponding N-ethyl- and N-propyl-amides, -NH-CO-NH-, -HN-CHg-CO- H-, -N(CH3)-CHg-G0 H-, -HN-CH -CH -NH-, N-alkyl(l-5 C) -amides or -amines as well as the. corresponding N-alkyl-(l - 5 C)-amides or -amines of the said compounds.

A further suitable bridge, member is the azo grouping -N=N-. In a special case the new dyestuffs correspond to the formula Ρχ : — H-N=N— A)k (II) in which represents the residual constituent of an azo dyestuff; A stands for the radical of a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring; k denotes the number Γ or 2; is in thie formula, 'for example, the radical of a coupling component, but may also represent any other aromatic carbocycllc or heterocyclic radical which serves for the synthesis of the azo dyestuff (II), e.g. by condensation.

, He new dyestuffs may belong to a great variety of classes, e.g..to the series of metal-free or metal-containing mono- or polyazo dyestuffs; metal-free or metal-containing azaporphin dyestuffs, such as copper- or nickel-phthalocyanine dyestuffs; anthraquinone, oxazine, dloxazine, triphenyl-methane, nitro, azo e thine, benzanthrone and dibenzanthrone dyestuffs; and to the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds.

In the range of these dyestuff classes, dyestuffs of -fee following general formulae are particularly valuable, for example:. 1. Azo dyestuffs β preferably the number 1 or 2; A stands for the radical of a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring.

Particularly valuable dyestuffs of this series are those which are water-soluble, especially those containing sulphonic acid and/or carboxylic acid groups. The azo dyestuffs may be metal-free as well as metal-containing, the copper, chromium and cobalt complexes being the most Interesting metal complexes.

Important azo dyestuffs are, for example, those of the benzene-azo-naphthalene,. benzene-azo-l-phenyl-5-pyrazolone , benzene-azo-aminonaphthalene, naphthalene-azo-naphthalene, stuffsy the groups linked to the metal complex are preferably in the' o-positions to the azo group, e.g. in the form of ο,ο'- dihydroxy, σ-hydroxy-o'-carboxy, _-carboxy-o_' -amino , and o-hydroxy-o ' -aminoazo grou ings. heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring.

Also in the range of these dyestuffs the water-soluble products are preferred because of their excellent suitability for the dyeing and printing of cellulose-containing fibres; the dyestuffs substituted by sulphonic acid groups have proved especially suitable for this purpose. . 3. Azaporphin dyestuffs (V) In this formula Pc. stands for the radical of a phthalocyanine, e.g. a copper- or nickel- phthalocyanine , or a tetraphenyl-copper- -nickel-phthalocyanine , L stands for hydrogen or a subs ituent, the sulphonic acid grou being preferred as substituent, r stands for the number 1 or 2, for the number 0, 1 or 2, for a substituent or, preferably, hydrogen, Q for a direct bond or a grouping -CO- or -SOg-, A for the radical of a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring, and m" for a number of 0.5 to 4. The phthalocyanine radical Pc may obviously contain further substituents , especially sulphonic acid and sulphonamide groups.

Water-soluble phthalocyanine dyestuffs of the formula (V) which are preferred for application to cellulose-containing materials, are particularly those containing sulphonic acid groups in the radical Pc and optionally, in addition, as the substituent L.

Examples of suitable 5-membered heterocyclic radicals A in dyestuffs of the formulae (I), (II), (III), (IV), and (V) The selection of suitable azo, anthraquinone and azaporphln dyestuffs and heterocyclic ring systems A given above represents no limitation of the general formulae, either in respect of the possibilities of preparing such dyestuffs within the soope of the general formula (I), or with regard to the valuable technical properties of applying these products. The new dyestuffs may moreover contain any substituent oustomary in dyestuffs, such as sulphonic aoid, carboxylio aoid, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogeno, hydroxyl, alkoxy, thloether, azo groupings, and the like.

The dye8tuffs may also contain further groupings capable of fixation, such as mono- or . dihalo-triazinyl-amino, mono-, di-or trihalo-pyrlmidinyl-amino, 2,5-dihalo-quinoxaline-6-carbonyl-or -6-sulphonyl-amino, l,4-dihalo-phthalazine-6-earbonyl- or -6-sulphonyl-amino, S-halo-benzothiazole-5-carbonyl- or -5-sulphonyl-amino, esterified sulphonic acid oxalkylamide and oxalkylsulphone groups, sulpho-fluoride, haloalkylamino, acryloylamino, haloacylamino groups, and the like. Ί¾β new dyestuffs of the formula (I) are obtained by introducing into dyestuffs or dyestuff intermediates by known methods at least one 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring, and in the case where dyestuff intermediates are used, converting these into the desired end dyestuffs, Ώιβ introduction of the 5-membered heterooycle containing at least one reactive sulphonyl substituent into dyestuffs or dyestuff intermediates can be carried out by various methods. For example, amino or amide group-containing dyestuffs or dyestuff intermediates which carry a reactive hydrogen atom at the amine or amide nitrogen, can be reacted with compounds of the general formula A — Y (VI) in which A represents a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substi- tuent linked to a carbon atom of the heterocyclic ring, and Y denotes a radical which can be split off as anion, and in the case where dyestuff intermediates are used, these converted in a suitable manner into the desired end dyes tuffs. Of the reactive substltuents Y which can be split off as anionic radicals,. chlorine, bromine and sulphonyl substltuents are preferred. Further suitable radicals which can be split off as . anions arej for' example, F-, SO^M- ( being H or a metal cation), quaternary ammonium groups, alkylraercap o, nitrile, alkoxy or aryloxy groups.

Heterocyclic 5-membered ring compounds of the formula (VI) which are suitable for the reaction, are, for example, 2-methylsulphonyl-l-methyl- .——N imidazole-5-carboxylic acid c loride Cl-CO SOgCH 2-methylsulphonyl-l-phenyl- itnidazole-5-carboxylic acid chloride 2-methylsulpbonyl-4-phenyl- 5-aminothiazole 2, 5-bis-me thylsulphonyl - 1 ,3,4-thiodiazole 2 -me ttiyl sulphonyl - 5 -am ino - 1, 3, 4-thiodiazole 1 -me ttiyl -2 -me thyl sulphonyl- 5-amino- imidazole The reaction of the amino or amide group-containing dyestuffs or dyestuff intermediates with heterocyclic compounds of the formula (VI) is carried out, depending on the type of starting compounds employed; in an organic, aqueous-organic in wh ch A1 represen s a -membere he erocy c r ng, Z is a radical which can be split off as anion, with the exception of a sulphonyl radical, and t denotes the ,nu¾ber' 2 or a . number greater than 2, while, replacing' one -o .the radicals Z which can be split off as anion, that the remaining radical or radicals Z are subsequently converted, in 'know manner into sulphonyl . substituents and, if dyes tuff "intermediates are used, these transformed into the' desired end dyestuffs.

The exchange of one or more substituents Z capable of being split off as anion, e.g. of halogen atoms, for sulphonyl substituents can be effected e.g. by reacting the compounds with alkyl- or aryl-sulphinates or, if Z represents, for example, an alkylmercapto or arylmereapto group, which can be split off as anion, by transforming this group by means of suitable oxidising agents, such as hydrogen peroxide, hypohalites, chlorine or permanganates, into the corresponding sulphonyl radicals.

The dyestuffs obtainable by the various processes described above can be subjected, as has already been mentioned for some cases, to further reactions customary for dyestuffs, in . that, for example, metallisable dyestuffs are treated with metal-yielding agents, especially chromium, cobalt, copper or nickel salts; dyestuffs containing reducible groups, especially nitro groups, are reduced dyestuffs containing acylatable groups, especially acylatable amino groups, are acylated; or dyestuffs are subsequently treated with sulphonatlng agents, such as chlorbsulphonic acid, thionyl chloride, oleum or SO-in chlorinated hydrocarbons, in order to introduce further sulp onic acid groups into the products. The last^mentioned process is: sometimes of particular importance in the series of anthraquinone and phthalocyanine dyestuffs.

Depending on the number of reactive groupings ' : in the dyestuff radical or dyestuff intermediates, preferably -H R-r groupings, which are suitable for the conversion, one or more groupinge of the general formula (II) can be incorporated in the dyestuf s. In the majority of cases the number m will not exceed 4, but dyestuffs with more than 4, e.g. up to 8 groupings of the formula (II), especially those of higher molecular structure, can also be synthetised.

If the , dyeetuffs prepared according to the invention contain groups forming metal complexes, then they can be converted into their metal complex compounds by the action of metal-yielding agents, e.g. copper, nickel, chromium or cobalt salts. They can also be subjected to other customary conversion reactions, such as diazotisation, coupling, acylatlo , and condensation.

The new dyestuffs are highly valuable products which are suitable for a great variety of applications. As water- soluble compounds they are of special interest for the dyeing of textile materials containing hydroxy! groups or nitrogen, particularly of textile materials of natural and regenerated oellulose, as well as of wool, silk, synthetic polyamide and polyurethane fibres. . Due to the reactive sulphonyl substituent or substituents in the heterocyclic ring A, the products are especially suitable as reactive dyestuffs for, the dyeing of cellulose materials according to the techniques reoently disclosed for this purpose. The fastness properties obtained, particularly the fastness to wet processing, are excellent.

For the dyeing of cellulose, the dyestuffs are compounds such as alkyl-sulphates, or compounds preventing migration of the dyestuff, or dyeing auxiliaries, such as urea (for improving the solubility and fixation of the dyestuffs), or inert thickeners, such as oil-in-water emulsions, tragacanth, starch, alginate, or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example, by padding on the foulard or by printing, and subsequently heated for some time at an elevated temperature, preferably at 40 to 150°C. Heating can be · carried- out in the hot flue, in a steaming apparatus, on heated rolls, or by introduction into heated concentrated alkaline salt baths, using these methods in any desired sequence or any of them alone.

When a padding or· dyeing liquor without alkali is used, the dry goods are subsequently passed through a solutio of alkaline reaction to which sodium chloride or Glauber's salt is -added. The addition of salt reduces the migration of the dyestuff from the fibre.

The material to be dyed can also be previously treated with one of the above-mentioned acid-binding agents, subsequently treated with a solution ot paste of' the dyestuff and finally fixed, as stated, at an elevated temperature.

For the dye ing; from a long bath, the material is introduced into an aqueous solution of the dyestuff at room temperature and dyeing is carried out, possibly while raising the temperature, to 95°C, for 40 to 90 minutes with the portionwise addition of salt, e.g. sodium sulphate or sodium chloride, and subsequently of alkali, for example sodium phosphates, sodium carbonate or alkali hydroxide. The chemical reaction between the dyestuff and the fibre thereb occurs. After completion of the chemical fixation, the dyed material is rinsed hot and finally soaped, whereby non-fixed residues of the dyestuff are removed. Dyeings of excellent fastness, especially to wet processing, washing, . perspiration, solvents and. light, are thus obtained. '. -.

In the so-called- cold batch-pad process,, subsequent . heating of the padded fabric' can be dispensed with if the fabric is stored at room temperature for some time, e.g. for 2 to 40 hours. A stronger alkali is used in this process than in the dyeing process from a long bath described above.

For printing materials containing hydroxyl groups, a printing paste is used which consists of the dyestuff solution, a thickener, such as sodium alginate, and a compound of alkaline reaction or splitting off alkali upon heating, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate, or sodium and potassium bicarbonate, 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 an after-treatment with metal-yielding agents, such as copper salts, e.g. copper sulphate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulphate or nickel sulphate.

Materials containin amide groups, such as wool, silk, synthetic polyamlde and polyurethane fibres are generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, arid it is sometimes of advantage finally to raise the pH value of the dyebath, e.g. to pH 6.5 to pH 8.5.

The- dyestuffs are applied, for example, to synthetic polyamlde fabrics in the form of solutions or, preferably, in a dispersed form and subsequently after-treated, possibly together with acid-binding' agents, such as sodium carbonate (preferably in smaller amounts). Especially advantageous results are achieved with those dyes tuffs which are insoluble or only hardly soluble in water. These are worked up by known methods and with the addition of the known adjuvants into a dyestuff dispersion and applied as such in a dyebath and/or padding liquor, or in. a printing paste.. Suitable adjuvants for this', application are, inter alia, compounds which prevent the migration of the dyestuff ori the fibre, such as cellulose ethers, alkali metal chlorides and sulphates, wetting agents, such as condensation products from ethylene oxide and fatty alcohols or phenols, sulphonated fatty alcohols, solvents, such as thiodiglycol , as well as thickening agents, such as starch, tragacanth, alginate thickening, gum arable, etc.

The after-treatment of the dyeings, impregnations and prints obtained on fabrics of polyamlde fibres is preferably carried out at a temperature of 50 - 110°G for a period of 5 to 60 minutes. Also in this case the fastness properties of the dyeings can. sometimes be improved, provided the dyestuffs employed contain metal complex-forming groupings, by means of metal-yielding agents, such as copper salts, e.g. copper sulphate, or chromium, cobalt and nickel salts,, such as chromium acetate, cobalt sulphate or nickel sulphate.

In general, the dyeings which can be obtained with the new dyestuffs are characterised by good to very good fastness properties, especially by excellent fastness to wet processing.

The following Examples are given for the purpose of illustrating the invention, the parts being parts by weight, unless otherwise stated.

Example 1 28 Parts b volume concentrated hydrochloric acid are added to a solution of 34.7 parts 2-aminonaphthalene-4, 8- , disulphonic acid sodium salt and 7 parts sodium nitrite in 300 parts water while cooling with ice, and the mixture is stirred at 0 - 10°C for 30 minutes. After removing the •xoess nitrous acid, 10.7 parts 3-aminotoluene dissolved in 10. parts by volume concentrated hydrochloric acid and 150 parts water are added, and ooupling is completed by neutralising the mixture to pH 3 - 5. The resultant aminoazo dyestuff is salted out, filtered off with suction, washed and then redissolved at pH 7 in 700 parts water with the addition of a sodium hydroxide solution. The aqueous solution is then mixed with 24 parts 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride pasted with a wetting agent and some water, and vigorously stirred. The temperature of the reaction mixture is maintained at about 20°C; the liberated hydrochloric acid is neutralised with a sodium carbonate solution until free amin nt dyes is salted out with 80 parts sodium chloride, pressed off, When a cellulose fabric is printed with a printing paste which contains, per kilogram, 15 g of the dyestuff, 10 g m-nitrobenzene-sulphonic acid sodium salt, 100 g urea, 300 ml water, 500 g alginate thickener (60 g sodium alginate per kg thickener), 2 g sodium hydroxide and 10 g sodium carbonate, and which has been made up with water to 1 kilogram, the fabric is then dried, steamed at 105°C for one minute, rinsed with hot water, and soaped at the boil, an intense, reddish yellow print of good fastness to washing and light is obtained.

Example 2 0.1 Mol of the copper complex compound of the formula ( repared ac rman Patent Specification No. 1,117,235 by coupling diazotised 1-amino- 8-(benzene-sulphonyloxy)-naphthalene-disulphonic acid-(3,6) in a soda-alkaline medium with the equivalent amount of 2-acetylamino-5-hydroxynaphthalene-disulphonic acid-(4,8) , conversion , of the monoazo compound into the copper complex by oxidative coppering, and hydrolysis of the acetyl and benzene- sulphonyl groups ) is dissolved at pH 6 - 6.5 in 2500 parts by volume water at 20°C and mixed at this temperature with 0.1 mol 4-me thyl-2-methyl- sulphonyl-thiazole-5-carboxylic acid chloride, which is pasted with a wetting agent and some water. A pH of 6 - 6.5 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, When dried, the dyestuff is a dark powder whic dissolves in water with a blue colour.

A ootton f brio is treated on the foulard with an aqueous solution at 20°C, which contains 20 g/litre of the dyestuff, 10 g/litre m-nitrobenzene-sulphonic acid sodium salt, 15 g/litre sodlua hydrogen carbonate and 150 g/litre urea, subjected to an intermediate drying at 60-70eC, heated at 140°C for 10 minutes, then rinsed and soaped at the boil. The fabric is dyed in very clear blue shades fast to wet processing.

Example 3 46 Parts bf the monoazo dyestuff obtained in analogy with ttie instructions of Example 1 by coupling diazotised 2«aminonaphthalene-4,8-disulphonic acid with 3-metiiylamino- toluene, are dissolved at pH 7 - 8 in 400 parts water at 20°C, the solution is mixed portionwise with a total of 26.4 parts 4-isopropyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride in the presence of excess sodium acetate or calcium carbonate and stirred at the same temperature, until acidification of a sample no longer leads to a change of colour. The resultant dyestuff of the formula is salted out, filtered off with suction, washed and dried.

A cotton fabric is impregnated with an aqueous solution at 20 - 25°C, which contains, per litre of liquor, sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 80$ of the weight of the fabric. After an intermediate drying at 60 - 70°C, the fabric is heated at 140°C for 1 - 3 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and ■ ' treated for 20 minutes at the boil with a solution containing, per litre, 5 g Marseilles soap and 2 g sodium carbonate.

After rinsing and drying, an intense, reddish yellow dyeing of good fastness to wet processing, 'rubbing and light is obtained.

.·'. ' . .· The following Table gives the diazo components, coupling components, and the reactive components which can be linked to the amino group, from which dyestuffs can be synthetised in analogy with Examples 1 - 3; the shades obtained by one of the methods of application described above are also specified in the Table.

Abbreviations for A: 4-methyl-2-methylsulphonyl- the reactiv components: thiazole-5-carboxyllc acid chloride B: 4-isoprooyl-2-methylsulphonyl- thiazole-5-carboxylic acid chloride Example Diazo Coupling Reactive Shade No. component ■ ·.··' component , . " component 4 2-aminonaphthalene-4, 8- l-amino-2-methoxy-5- A yellow dieulphonio acid methylbenzene " w B " 6 l-aminonaphthalene-3, 6- l-amino.r3-methylbenzene A " disulphonic acid Example Diazo Coupling Reactive Shade No. Component component component 11 2-aminoriaphthalene-6, 8- . 1-amino -3-methyl- B yellow diaulphonic acid benzene 12. 4-aminoazobenzene-3, 41 - 1-amino-3-me thyl- brown- yellow disulphonic acid benzene 13 1-aminobenzene-4-sulphonic acid —*■ 1-aminonaphthalene 1-amino-3-methy1- brown- 6-sulphonic acid benzene B yellow 14 2-( 3' -sulpho-4 ' -amine-phenyl )- 6-me thyl-benzothiazole-7- sulphonic acid n A yellow 2-aminonaphthalene-4, 8-di- l-methylamino-3- B sulphonic acid me thoxybenzene 16 1-amino-3-ace tylamino- benzene A 17 aniline A n Example 18 24 Parts 4-me thyl-2-me thylsulphonyl-thiazole-5- carboxylic acid chloride are introduced with good stirring at °C into a solution of 36.5 parts of the sodium salt of 1- amino-8-hydroxynaphthalene-3, 6-disulphonic acid in 100 parts water, and the reaction mixture is stirred, while continuously neutralising the liberated hydrochloric acid to pH 6 - 7, until free amino groups can no longer be detected. The dyestuff intermediate thus obtained is coupled, after dilution with 600 parts water and addition of 12 parts sodium carbonate, at 5 - 10°C with 17,5 parts diazotised 2-aminobenzene-sulphonic acid dissolved in 200 parts water. The dyestuff of the formula needles of metallic lustre, which readil dissolve in water with a red colour.

When a fabric of cotton or regenerated cellulose is dyed or printed with this dyestuff according to one of the processes described in Examples 1 - 3, clear bluish red dyeings and prints of good fastness to wet processing, rubbing and light are obtained.

Equally good results are obtained according to the following process: 50 Grams cotton skein are dyed in 1 litre of a dyebath which is heated to 50°C and contains 1.5 g of the above dyestuff, by raising the temperature within 30 minutes from 50°C to about 85°C while adding a total of 100 g sodium chloride in several portions, subsequently adding 20 g sodium carbonate and treating the material at 85°C for 60 minutes. After rinsing, soaping at the boil and drying, a bluish red dyeing of good fastness to wet processing, rubbing and light is obtained.

The following Table gives the shades of further dyestuffs which are synthetised from the likewise stated diazo components, coupling components, and reactive components which can b i k d corresponding aminoazo dyestuffs with the reactive components, and which can be applied to cellulose materials by dyeing or printing according to one of the processes, described above.

Abbreviations for the reactive components as in Table following Example 3.

Example Dlazo Coupling Reactive shade No. , component componen Component l-aminobenzene-2 1-amino-8-hydroxy B red sulphonic acid naphthalene-3, 6- disulphonic acid l-(3'-aminobenzoyl- 'amino ) -8-hydroxy- naphthalene -3,6- disulphonic acid 21 " B 22 1-amino-2-carboxybenzene- 1-amino -8-hydroxy■ A 4-sulphonic acid naphthalene-3,6- disulphonic acid 23 l~amino-4-methylbenzene- 2-sulphonic acid 24 1-amino -3-acetylamino- B benzene-6-sulphonic acid 1-amino-?3-( 2» -j' l- sulphophenylamino/-4' -chloro- trlazine-l',3',5'-yl-6' )- aminobenzene-6-sulphonic acid 26 l-aminobenzene-2-sulphonic 2-amino-5-hydroxy- orange acid naphthalene-7- sulphonic acid 6a l-amlno-3-(2'- ¾» '-sulpho- 2-amino-5-hydroxy- Example Dlazo Coupling Reactive Shade No. component component component triazine-l' ,3' ,5' -yl-6' )- sulphonic acid aminobenzene-6-sulphonic acid 27. l-aminobenzene-2- 2-methylamino-5- A orange sulphonic acid hydroxy-naphthalene 7-sulphonic acid 28 1-amino-4-acetyl- " A scarlet amino-6-sulphonic acid 29 " 2-amino-5-hydroxy- A " naphthalene-7- sulphonic acid Example 30 24.0 Parts 4-methyl-2-methylsulphonyl-thiazole-5- carboxylic acid chloride are introduced with good stirring into a solution of 21 parts of the sodium salt of l,3-diamlnobenzene- 6-sulphonic acid' in 100 parts water, and the mixture is stirred at 20°c, while continuously neutralising the liberated hydrochloric acid to pH 6 - 7, until diazotisation of a sample and couplin with l-hydroxynaphthalene-4-sulphonic acid yields a clear yellowish red coloration. After the addition of ice, the resultant dye'stuff intermediate is directly diazotised with 7 parts sodium nitrite and 28 parts concentrated hydrochloric acid and the product is subsequently added to a solution of 47 parts of the sodium salt of l-benzoylamino-8-hydroxy- naphthalene-3, 6-disulphonic acid and 12 parts sodium carbonate in 200 parts water, whereupon coupling takes place giving the dye stuff of the formula which is salted out; filtered off with suction, washed and dried at 30 - 40°C in a Vacuum. The dyestuff readily dissolves in water with a red colour and yields clear bluish red dyeings and prints on cellulose materials by one of the processes described above.

The following Table gives the shades and the pH, value of the coupling medium of dyestuffs which are prepared in analogy with the instructions of Example 30 from a diazo component containing a further, preferably acylatable, amino group, a coupling component and a reactive component which can be linked to the diazo component The processes, described above can be used for dyeing' and printing cellulose materials with the dyestuffs of the Table.

Abbreviations for the reactive components as in the Table following Example 3 Example Diazo Coupling Reactive pH of No. component component component coupling medium 1 , 3-diaminobenzene 2-aminonaphthalene- . A 4-5 orange 4-sulphohic acid '5,7-disulphonic acid tl 2-aminona hthalene A 4-5 3, 6-disulphonic acid 2-aminonaphthalene^ · B 4-5 6-sulphonic acid 2-N-methylamino-8- ϋ 4-5 hydroxynaphthalene- 6-sulphonic acid. l-(3.« ,5'-dichloro-l» , A 7-8 red 2* -thiazole-4' -carbon- amido ) -8-hydroxynaphtha- Plazo. Coupling Reactive pH of Shade component componen componen coupling ..medium , 5-diaminobenzene 1- ( 2· , ' -dihydroxy- B 7-8 red -sul honic acid triazine-l1 ,3' ,5' ,-yl- 61 -amino ) -8-hydroxy- naphthalene-3, 6- disulohonic acid 1-iS'^'-dichioro-l', A 7-8 2 » -thiazole- ' -carbon- amido )-8-hydroxynaphtha- lene-3,6-disulphonic acid 2-hydroxynaphthalene - A 8 scarlet 3,6-disulph.onic acid l-acetylamino-8-hydroxy- B · . 7-8 red ■naphthalene-3,6- disulphonic acid l-(3' -sulphophenyl)-3- A 6 yellow methyl-pyrazolone-5 l-(2',5'-dichloro-4'- A 6 yellow sulphophenyl )-3-methyl- pyrazolone-5 l-(5' ,7 · -disulphonaph- A 6 yellow thyl-2'-)-3-methyl- pyrazolone-5 1- (3'-sulpho;ohenyl)-3- B 6 methyl-5-aminopyrazole l,4-diaminobenzene' 2-aminor8-hydroxynaphtha- A 4-4.5 red 3-sulphonic acid lene-6-sulphonlc acid n 2-acetylainino-5-hydroxy- A 6-7 scarlet naphthalene-7-sulphonic acid.

Example 47 . 51.6 Parts of the dye stuff of the formula obtained by diazotising l-hydroxy-2-aminobenzehe-4-sulphonlc acid and coupling with 2-amino-5-hydroxyriaphthalene-7-sulphonlc acid in water/pyridine in the presence of sodium carbonate, followed by treatment with a copper-yielding agent, are dissolved in 1500 parts water, at pH 7. 24.0 Parts 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride' are added at'20°C with good stirring and the liberated hydrochloric: acid is continuously neutralised to pH of ,5 - 7 with, a sodium carbonate solution. When free amino groups can no longer be detected, the resultant reactive dyestuff of the formula is vacuum at 30 e dyed or printed with this dyestuff by one of the processes described above in ruby shades fast to wet processing, rubbin and light.

The followin Table gives the heavy metal complexes of further aminoazo dyestuffs and the reactive components · linked to the amino group, as well as the shades of these dyestuffs on cellulose materials. The preparation of the reaction of the latter with the reactive components can be carried out in analogy with the inetructions of Example 47.

Abbreviations for the reactive components as in the Table following Example 3 Example Aminoazo Complex Reactive Shade No. dye stuff linked component ^ heavy me tal · 48 l-hydroxy-2-aminobe.nzene-4, 6- Cu ruby disulphonic acid —2-amino-5-hydroxy- naphthalene'-7-sulphonic acid 49 1-hydroxy-2-aminobenzene-4- Cu ruby sulphonic acid →2-ethylam1no 5-hydroxy- naphthalene-7-sulphonlc acid 50 1-amino-2-hydroxy-6-nitro-naphthalene -4- Cu ruby sulphonic acid —>2-amino-5-hydroxy- naphthalene-7-sulphonic acid 51 Cr greenish grey 52 l-amino-2-hydroxy-6-nitronaphthalene-4- Co B reddish black sulphonic acid —*1-amino -8-hydroxy- naphthalene -4-sulphonic acid 53 1-amino- -hydroxy-5-me thy1su1phony1- Cu violet benzene —*·1-amino-8-hydroxy- naphthalene-3,6-dlsulphonic acid 54 Co A grey 55 Cr A greenish black 56 l-amino-2-methylbenzene-4-sulphonic Cu B blue acid «— 1-amino-2-hydroxy-5-methylbenzene —>l-amino-8-hydroxynaphthalene-4,6- disulphonic acid Example Amino a zo Reactive , shade No. dye s tuff component 58 l-amino-2-me thylbenzene -4-sulphonic Cr A .; greeniab black acid-→l-amino-2-hydroxy-5-methylbenzene -→ l-amin0-8-hydroxynaphthalene -4, 6- disulphonic acid 59 ( l-amino -2-chlorobenzene-4-sulphonic acid Cu A navy blue — »-l-hydroxy-2-acetylaminobenzene ) , hydrolysed, — *l-amin6-8-hydroxy-naphthalene - 3, 6-disulphonic ac id 60 " Co A . : grey 61 l-amino-8-hydroxynaphtbalene-4-sulphonic Co A black acid l-hydroxy-2, 6-diaxninobenzene-4- sulphonic acid-→-l, 3-dihydroxybenzene 62 l-amino-8-hydroxynaphthalene-3, 6-disulphonic Co A n acid «*— l-hydroxy-2, 6-diaminobenzene-4- sulphonic acid 2-hydroxy -naphthalene 63 l-amino-8-hydroxynaphthalene-4-sulphonic Co A " ac id * — l-hydroxy-2, 6-diaminobenzene-4- sulphonic ac id — »3-me hyl-pyrazolone - ( 5 ) Example 64 : . 96 Parts (referred to 100$ goods ) of · the copper- phthalocyanine te trasulphochloride freshly prepared in the usual' manner by the reac tion of chlorb sul honic ac id and thiohyl chloride with copper-phthalocyanine , or o the isomeric copper- phthalocyanine te trasulphochloride synthetised from 1-sulpho- benzene-3;4-dicarboxylic acid via the corresponding; cqpper- phthalocyanine tetrasulphonic acid, are sus pended in the form of the mo is t^ thorough ly washed filter cake in 500 parts , water, is added and the pH is adjusted to 8.5 with sodium carbonate. The suspension is stirred at room temperature for 24 hours, while maintaining a constant pH of 8.5 by the continuous addition of sodium carbonate. , The resultant condensation product is precipitated at pH 1 - 2 by the addition of sodium chloride, filtered off with suction, washed, and then redissolved neutral in 1000 parts water. A suspension of 72 parts 4nne thyl-2-methyl-sulphonyl-thiazole-5-carboxylic acid chloride in. water and a wetting agent are introduced into the blue solution, and the reaction mixture is stirred at 20°C while continuously neutralising the liberated hydrochloric acid to 5 -·7 by means " of. a . sodium carbonate solution, ' until free amino groups can no longer be detected. The reactive, dyestuff of the' formula Cu-Pht .thus obtaine a vacuum. with a blue by one of the dyeing or printing processes described above in .. clear blue shades of good fastness to wet processing, rubbing, and light.

Instead ,of 96 parts copper-phthalocyanine tetra- sulphochloride, there may also be used 87 parts' (referred to 100 goods) of the copper- or nickel -phthalocyanine trisulpho^ chloride obtainable by the reaction of chlorosulphonic acid with filter cake thoroughly washed with ice water, the procedure being otherwise the same as in -Example 64; reactive dyestuffs yielding clear blue dyeings are thus, likewise obtained.

' . ' '.- ; ' When, the procedure described in Example 64 is followed, but •starting' from 87 parts copper -phthalocyanine trisulph.o-chioride and usin 90 parts of the sodium salt of 4, 1 -diamino-diphenyl-2, 2 ' -disulphonic acid or 90 parts of the sodium salt of ' 4,4','rdiamino-stilbene-2;2' -disulphonic acid, instead of 50 parts of the sodium salt of l,.3-diaminobenzene-4-sulphonic acid, reactive dyestuffs are again obtained which dye cellulose materials by one of the processes described above in clear blue shades fast to wet processing, rubbing and light.

• When 4' ,4",4" ' ,4""-tetraphenyl-Cu-phthalocyanine isused as, starting' material , sulpho-chlorination and reaction with l,3-phenylene-diamine-4-sulphonic acid, followed by acylation with 4-me thyl-2-mettiylsulp onyl-thiazoie-5-carboxylic acid chloride yield a reactive dyestuff which dyes cellulose materials in the presence ;of acid-binding agents in clear green shades fast to wet processing and light.

Example 65 71 Parts of the amino -anthraquinone dyestuff obtained by reacting 1-amino -4-bromo-anthraquinone-2-sulphonic acid with an excess of 4,4,-diamino-diphenyl-2,2T-disulphojnic acid are dissolved in 700 parts water, 24 parts 4-methyl-2-methyl-sulp'onyl-thiazole-5-carboxylic acid chloride are added at °C with good stirring, and a pH of 6 - 7 is maintained by Vne continuous addition of a sodium carbonate solution. When amino groups can no longer be. detected, the resultant dyestuff of the formula is salted out, filtered off; with suction, washed and dried at 30 - 40°C in a vacuum. The dyestuff dyes cotton and regenerated cellulose by one of the processes described above in blue shades fast to wet processing, rubbing. and light.

When the procedure described in Example 65 is followed, but using, Instead of the 71 parts of tiie starting dyestuff there employed, equivalent amounts of one of the following derivatives of l-amin0-4-(aminoarylamino )-anthraquinone-2-sulphonic acid, similar dyestuffs are obtained, which likewise yield blue dyeings witii fastness properties similar to those of the dyestuff obtained above: l-atnlno-4-(4'-amino-2' -sulphophenylamino )-anthraquinone-2-sulphonic acid, 1-amlno-4-(4' -amino phenylamino ) -an hraquinone-2,6-disulphonic acid, isomer mixture of l-amino-4-( 4' -amino phenylamino )-anthraquinone-2,5- and -2,8-disulphonic acid, isomer mixture of l-amlno-4-(4'-amino-21 -sulphophenylamino )-anthraquinone -2, 5- and -2,8-disulphonic acid, isomer mixture of l-amino-4-(3' -amino phenyl-amino) -an thraquinone -2, 5- and -2,8-disulphonic acid, l-amino-4- (3· -aminophenylamino )-anthraquinone-2,6-disulphonic acid, l-amino-4-(3' -amino -4' -sulphophenylamino ) -an thraquinone -2-sulphonic acid. Witti l-amino-4-(4 » -/ n-amino-2"-sulpho-phenyl7aminophenyl)-anthraquinone-2,6-disulphonic acid there are obtained reactive dyestuffs which dye in bluish grey shades. Example 66 is dissolved at pH 6 in 3000 parts by volume water and the solution is..combined at a temperature of about 50°C, while stirring, with 24 parts (0.1 mol) 4-methyl-2-methylsulphonyl- thiazole-5-carboxylic acid chloride. The mixture is stirred, until the condensation is completed, the dyestuff is separated by the addition of a little sodium chloride, and isolated.

The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which dissolves in water with a green colour and dyes cotton by the methods described in Examples 1 - 3 in green shades.

A cotton fabric is impregnated with a solution at 20 - 25°C, which contains, per litre liquor, 25 g of the above dyestuf f and 0.5 g of a non-ionic ; wetting a gent (e.g. a rubber rollers to a moisture content of about 100$. After an intermediate drying at 50 - 60°C;, the fabric is heated at 140°C for 10 minutes, the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 20 minutes with a solution containing, per litre, 5 g Marseilles soap and 2 g sodium carbonate. After rinsing and drying, a green dyeing of good fastness to wet processing, rubbin and light is obtained.

Clear green shades of good fastness' properties, are also obtained on cellulose materials by one of the other dyeing or printing processes described in Examples 1 to 3, 18 and 30.

Example 68 0.1 mol of the paste of the aminoazo compound of the formula which is obtained by coupling the diazonium compound from 6-acetamino-2-aminqnaphthalene-4, 8-disulphonic acid. with 2- hydroxynaphthalene-3,6-disulphonic acid, hydrolysis and conversion of the monoazo' compound into the copper complex, is dissolved at pH 6.5 in 2000 parts by volume water and combined with 24 parts 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride. Ihe reaction mixture is stirred at 20°C, until the condensation is completed, while maintaining the pH of the reaction solution at 6 - 7 by the addition of sodium carbonate.

The dry dyes uff is a dark powder which dissolves in water with, a violet colour and dyes cotton i the presence of alkali in bluish violet shades. . ·.

Example 69 An aqueous solution of 0.1 mol of the copper complex of the formula , prepared according to the instructions of German Patent Specification No. 1,061,460 or 1,085,988, is reacted in the usual manner with a solution of 23.6 parts trlchloro-pyrimidino-pyrimidine in acetone. A pH 'of 6 - 7 is maintained by the addition of sodium carbonate, and when the reaction is completed, the dyestuff is isolated by salting out. In the dry state the dyestuff is a dark powder which dissolves in water wit a violet colour. Cotton fabric is dyed in violet shades fast to light and wet processing.

Example 70 27.5 Parts 2-methylamino-5-hydroxynaphthalene-7- sulphonic acid sodium. salt are dissolved in 150 parts water, the solution is mixed with 24.0 parts 4-methyl-2-methylsulphonyl- thiazole-5-carboxylic acid chloride and stirred at 20°C, while continuously neutralising the hydrochloric acid formed to pH 4 - 6 with a total of 34 parts by volume of a 16% sodium carbonate solution.: The acylation is completed after a short time, the pH is 6 and changes no more. reddish orange shades of very good fastness to wet processing and good fastness to chlorine.

When equivalent amounts of 4-isopropyl-2-methyl- sulphonyl-thiazole-5-carboxylic acid chloride are used in this Example, instead of 24 parts 4-methyl-2-methylsulphonyl-thiazole- 5-carboxyllc acid chloride, a reactive dyestuff is obtained which dyes in orange shades and whose dyeing properties are similar to the corresponding 4-methyl derivative.

Orange to red reactive dyestuffs are obtained in an analogous manner by acylating the aminonaphthol-sulphonic acids listed in Column 3 of . the following Table with 4-meth l-2-methyl- sulphonyl-thiazole-5-carboxylic acid chloride and coupling the acylamino-naphthol sulphonic acids formed with the diazo components stated in column 2.

Example Diazo Aminonaphthol- Shade on No. component sulphonic acid' cotton 71 2-aminonaphthalene- 2-ethylamino-5-hydroxy- orange Example Dlazo Aminona htho1- Shade on No. componen au1ohon1c- ac.Id cotton 72 2-aminonaphthalene- 2-(6-hyd oxyethylamino ) - orange 1,7-disulphonlc acid 5-hydroxynaph thalene-7- sulphonlc acid 75 2-amino-5-hydroxynaphtha- n lene-7-sulphonic acid, 74 2-amino-5-hydroxynap tha- n lene-l,7-disulphdnic acid 75 2-amino-8-hydroxynap tha- scarlet lene-6-aulphonic acid 76 2-amino-8-hydroxynaphtha- " lene-3, 6-disulphonic acid 77 2-aminonaphthalene- 2-methylamiho-5-hydroxy- orange 1, 5-disulphonic acid naphthalene-7-sulphonic acid 78 2-ethylamino-5-hydroxy- " naphthalene-7-sulphonic acid 79 2-(^-hydroxyethylamino)- 11 -hydroxynaohthalene-7- sulphonic acid 80 -amino-5-hydroxynaphtha- M lene-7-aulphonic acid 81 2-amino-5-hydroxynaphtha- n lene-l,7-disulphonic acid 82 2-aminonaphthalene- 2-aminO-8-hydroxynaphtha- acarlet 1, 5-disulphonic acid lene-6-aulphonic acid 83 2-amino-8-hydroxynaphthar n lene-3, 6-disulphonic acid 84 2-aminonat>hthalene- 2-amino-5-hydroxynaphtha- orange 1,5,7-trisulphonlc acid lene-7-aulphonic acid " Example Dlazo Aminonaphthol- Shade on No. component sulphonic acid cotton 86 1,5,7-trisulpiionic acid 2-amino-8-hydroxynaphtha- Ιβηβ-6-a lphonic acid 87 2-amino enzene- 2-methylamino-5-hydr0xy- sulphonio acid naphthalene-7-aulphonic acid 88 2-( -hydroxyethylamino )- 5-hydroxynap thalene-7- sulphonic acid 89 2-amino-8-hydroxynaphtha- lene-6-sulphonic acid 90 2-amino-8-hydroxynaphtha- lene-3, 6-disulphonic acid 91 2-amino-5-hydroxynaphtha- lene-l,7-disulphonio acid 92 2-amlnonaphthalene- l-amino-8-hydroxynaphtha- 1-sulphonlc acid lene-3, 6-disulphonic acid 93 1-amino-8-hydroxynaphtha- lene-4, 6-disulphonic acid 94 2-aminonaphthalene- l-amino-8-hydroxynaphtha- 1,5-disulphonic acid lene-3, 6-disulphonic acid 95 1-araino-8-hydroxynaphtha- lens-4,6-disulphonlc acid 96 1-amino-8-hydroxynaphtha- lene-6-sulphonic acid 97 2-aminohaphthalone- 1-amino-8-hydroxynaphtha- 1,7-disulphonic acid lene-3, 6-disulphonic acid 9a l-amino-8-hydroxynaphtha- lene-4, 6-disulphonic acid 99 1-amino-8-h drox na htha- Example Diazo Aminonaphthol- Shade on No. component sulphonic acid cotton 100 2-aminonaphthalene- l-amino-8-hydroxynaphtha- bluish 1, 5,7-trisulphonic ac id Ιβηβ-6-sulphonic aci d red 101 . l-amino-4-chlorobenzene- l-amino-8-hydroxynaphtha- 2-sulphonic acid lene-3, 6-disulphonic acid 102 l-amino-2-raethoxy- l-amino-8-hydroxynaphtha- w benzene-5-sulphonic acid lene-3, 6-disulphonic ac id 103 l-amino-benzene-2- l-amino-8^hydroxynaphtha- ' " carboxylic. ac id-4- :. lene-3, 6-disulphonic acid ■ sulphonic acid 104 l-amino-4-acetyl- " violet aminobenzene -2-sulphonic acid 105 " l-amino-8-hydroxynaphtha- bluish lene-4, 6-disulphonic acid red Example 106 • 56.8 Parts of the diamlnoazo dyestuff obtained by couplin of dlazotised lramino-3-acetylaminobenzene-6-sulphonic acid with 2-aminonaphthalene-5,7-disulphonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are dissolved at pH 7 in 450 parts water. After the addition of 24,0 parts 4-me thyl-2-methyl- sulphonyl-thiazole-5-carboxylic acid chloride, the reaction mixture is stirred at 50°C for about one hour, while continuously neutralising the liberated hydrochloric acid to pH 4 - 6 with a sodium carbonate solution. When the acylation is completed, the resultant reactive dyestuff of the formula is salted out, filtered off, redissolved in 4000 parts water at 30°C, filtered and separated from the filtrate in a completely pure form by the addition of 400 parts sodium chloride. The dyestuff is dried as usual at 35°C in a vacuum. It dyes cellulose materials by one of the processes described above in fast yellowish orange shades.

Example 107 24 Parts 4-methyl-2-methylsulphonyl-thiazole-5- oarboxylic acid chloride are added to a neutral solution of 60 parts of the trisodlum salt of the aminoazo dyestuff obtained by coupling dlazotised 2-aminonaphthalene-3,6,8- trieulphonic acid with 3-acetylamino-aniline in an acetic acid described above in the presence of acid-binding agents in very fast reddish yellow shades. Fast yellow shades are also obtained on wool and polyamide fibres.

Similar dye stuffs are obtained by proceeding as described above, but using, instead of 60 parts 4' -amino -2'- acetylamino -phenyl-( 1 » ) -azo-naph halene- ( ) -3,6,8-trisulphonic acid sodium salt, corresponding amounts of the aminoazo dye- stuffs obtained from the amino compounds stated in Column 2 and the coupling components stated in Column 3 in the usual manner by diazotisation and coupling in an acetic acid medium, and acylating with 4-methyl-2-methylsulphonyl-thiazole-5- carboxylic acid chloride.

Example Diazo Coupling Shade on No. component component cotton 108 2-aminohaph thalene- 1-amino -3-me hyl-6-me thoxy- strongly l, 5-disulphonic ac id benzene reddish yellow 109 1-amino -3-me thylbenzene yellow 110 1-amino naphthalene -6- reddi sh sulphonic acid yellow 111 1-amino -3-acetylamino- n benzene 112 3-am ino henyl urea 113 n l-amino-3-hydroxyacetyl- aminobenzene 114 2 -a inonaph thalene ^ 1-amino - 3-me th yl -6 -me thoxy « strongly 5,7-disulphonic acid benzene reddish yellow 115 1 -am i no na ph th ale ne -7 - reddish sulphonic acid yellow 116 1-amino -3-acetylamino benzene 117 3-aminophenyl urea 118 l-amino-3-hydroxyacetyl- aminobenzene 119 l-aminonaphthalene- 1-amino -3-me thyl-6- strongly 3,7-disulphonic ac id me hoxybenzene reddi sh yellow 120 1-amino -3-me thylbenzene reddi sh yellow 121 1- aminonaph thalene - 1-aminonaph halene -6- reddi sh 3,7-disulphonic acid sulphonic ac id yellow 122 2- aminonaph thalene - l-amino-3-me thylbenzene n 3,6-disulphonic acid Example Dlazo Coupling Shade on No. component component cotton 124 2-amlnonaphthalene- l-amino-3-acetylamino- reddish 3, 6-disulphonic ac id benzene yellow 125 3 -amino phenyl urea it 126 l-amiho-3-hydroxyacetyl- n aminobenzene 127 1-am ino naphthalene -6- sulphonic ac id 128 2-aminonaphthalene- l-amino-3-acetylaminoben 6,8-disulphonic ac id 129 l-amino -2-methoxynaphthalene - strongl 6-sulphonlc aci d reddish yellow 130 1-amlno naphthalene -6- reddish sulphonic acid yellow 131 2 -am inonapb th al ene - l-aminonaphthalene-6- yellow 4, 8-disulphonic ac id sulphonic ac id 132 l-aminonaphthalene-7- suljfeonic acid 133 2-aminonaphth al ene - l-amino-2-methoxynaphthalene - strongly 4, 8-disulphonic acid 6-sulphonic acid reddish yellow 134 l-me thylamino -3-me thylbenzene yellow 135 2-aminonaphth alene- l-e thylamino -3-me thylbenzene n 4, 8-diaulphonic acid 136 . N-methylaniline n 137 " N-ethylaniline it 138 " N- ( I -hydroxye thyl ) -aniline n 139 w N-butylaniline it Example Diazo Coupling Shade No. component component cotton 142 2-amirionaphthalene- 3-amlnophenyl urea reddi sh 3,6,8-trisulphonic acid yellow 143 1-amino -3-hydroxyacetyl- amino benzene 14 l-amino-3-acetylamino-6- yellowish me thoxybenzene orange 145 l-amino-3-acetylamino-6- reddish methylbenzene yellow rt 146 lramino - 3-me thane - sulphonyl - amino benzene 147 2, 5-dime thoxyaniline yellowish orange 3-me th 1 - 6 -me th o xyan il ine n 148 149 N-me thylanil ine reddish yellow 150 2-aminonaphthalene- N-ethylaniline 3,6,8-trisulphonic acid 151 n N-butylaniline 152 N-(S-hydroxyethyl)-aniline " 153 3- (N-e thylamino ) -toluene " 154 2-amino toluene B 155 1-amino -2 , 5-dime thylbenzene s trongly reddish yellow 156 1-amino -2 -me thoxybenzene n 157 l-amino-3-me thoxybenzene reddish yellow 158 1-e thylamino -3-me thoxybenzene n 159 H l-aminonaphthalene-6- Example Diazo Coupling Shade on No. component component cotton 161 2-aminonaphthalene- l-amino-3-methylbenzene reddish 4,6,8-trisulphonic , acid yellow 162 w l-amino-3-acetylaminobenzene 163 l-aminonaphthalene- l-amino-3-methylbenzene yellow 2,4,7-trisulphonic acid 164 w l-aminonaphthalene-6- " sulphonic acid 165 4-nitro-4' -aminostil- l-amino-3-acetylaminobenzene reddish bene-2, 1 -disulphonic acid yellow 166 " 3-aminophenyl urea w 167 " l-amino-3-hydroxyacetylamino- " benzene 168 4-nitro-4' -aminostil- N-methylaniline " bene-2,2' -disulphonic acid 169 " N-ethylaniline w 170 " N-butylanilanlline " 171 " ■ N-(/3-hydroxyethyl) -aniline " 172 " l-(N-ethylamlno.) -3-methylbenzene n 173 aniline-2,5-disulphonlc l-aminonaphthalene-6-sulphonic " acid acid 174 " l-aminonaphthalene-7-sulphonic " acid 175 " l-amino-3-methylbenzene yellow 176 M l-amino-3-acetylaminobenzene n 177 ", l-amino-2-methoxy-5-metfiyl- reddish benzene yellow 178 " l-amino-2,5-dimethoxybenzene n 179 aniline-2,4-disulphonic l-amino-2-methoxy-5-methyl~ " Example 180 (prepared by coupling of diazotised l-hydroxy-2-aminobenzerie-4,6-disulphonlc acid with 2-amino-8-hydroxynaphthalene-6-sulphonic acid and coppering of the resultant azo dyestuff) are dissolved neutral in 700 parts water. 24.0 Parts 4-methyl 2-me hylsulphpnyl-thiazOle-5-carboxylic acid chloride are added and the reaction mixture is stirred at 20°C, while continuously neutralising the liberated hydrochloric acid to o . ses described above in very fast ruby shades.

Dye stuffs with similar properties are obtained by a method analogous to that described above from the copper complexes of the azo dyestuffs prepared from the diazo and azo components stated in the following Table: Example Diazo Coupling Shade on No, component component cotton 181 l-hydroxy-2-amino - 2 -me th y lamino -5-h ydr oxy - benzene -4-sulphonic naphthalene-7-sulphonic ac id 182 2-ethylamino-5-hydroxy- . naph ti al ene-7-sulphonic acid 183 2- ( 3-hydroxyethylamino ) - 5-hydroxynaph halene -7- sulphonic acid 184 2 - am i no - 8-h ydr o xynaph th 1 e ne ■ 3.6- disulphonic acid 185 l-hydroxy-2-amino - . , 2» am ino - 5 -h y dr o xyn aph th al e ne · benzene-4, 6-disulphonic 1.7- disulphonic acid acid 186 f! 2-amino-8-hydroxynaphthalene 3, 6-disulphonic acid 187 2-me thylamino-5-hydroxy- naphthalene-7-sulphonic ac id 188 2-ethylamino -5-hydroxy- naphthalene-7-sulphon c acid 189 2- ((3-hydroxye thylamino ) -5- * hy dro xynaph h ale ne -7- sulphonic acid 190. l-hydroxy-2-amino- l-amino-8-hydroxynaphthalene< benzene-4, 6-disulphonic 3, 6-disulphonic acid acid 191 n 1 - am ino - 8 -h y dr o x yn aph th al ene ■ 4, 6-disulphonic ac id 192 l-hydroxy-2-amino- l-amino-8-hydroxyna h halehe- benzene-5-sulphonic acid 3, 6-disulphonic acid Example Dlazo Coupling Shade on No. oomponent component cotton 194 l-hydroxy-2-amino-4- 1l--aammiinnoo--88--hhyyddrrooxxyynnaapphhtthhaalleennee-- bluish acetylaminobenzene-6- 33,.66--ddiissuullpphhoonniicc aacciidd violet aulphonic acid 195 l-hydroxy-2-amino-4- l-ethoxy-8-hydroxynaphthalene acet laminobenzene-6- 3,6-disulphonic acid sulphonio acid (4-positioned acetylamlno group subsequently hydrolysed) 196 " " '" ." ·' .. · /.; l-amino -8-hydroxynaphthalene- blue 2 , 4-disulpho nic acid 197 " l-amino -8-hydrdxynaphthalene- n 2,4,6-trisulphonic acid , 198 l^ydroxy-2-amino- l-amino-8-hydroxynaphthalene- blue 6-acetylaminobenzene- 2,4-disulphonic acid 4-sulphonic acid (6-pos tioned acetylamlno group hydrolysed) 199 l-amino-2-hydroxy-6- " n nitronaphthalene-4- sulphonic acid (6-positioned nitro group subsequently reduced to -NH0) 200 l-amino-2-:hydroxy-6- 1-amino-8-hydroxynaphthal nitronaphthalene-4- 2,4,6-trisulphonic acid , sulphonic acid (6-positioned nitro group subsequently reduced to 201 l-hydroxy-2-amino-6- " acetylaminobenzene-4- sulphonic acid (6-positioned acetylamlno group hydrolysed) Example 202 The procedure is the same as that described in Example 30, hut the diazotised, reactive group-containing th f rubbing and light.

Example 203 A solution of 19.5 parts of the sodium salt of 1- aminpbenzene-4-sulphonic acid and 6.9 parts sodium nitrite in 200 parts water is allowed to run into a mixture of 100 parts ice and 28 parts by volume concentrated hydrochloric acid; the reaction mixture is then stirred at 0 - 10°C for 30 minutes, and the excess nitrous acid is subsequently removed. To the diazo suspension thus obtained there is added at 0 - 10°C the cooled and thus partially recrystallised solution of 26.2 parts of the potassium salt of l-aminonaphthalene-8-sulphonic acid in 250 parts hot water, and the strongly acidic coupling rapidly completed; the resultant amino azo dyestuff is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redis solved in 500 parts water at 10°C and pH 6 - 7, One aqueous , solution, Is mixed with 24.0 , parts 4-methyl-2rmethylsulphonyl-thiazole-5-carboxylic acid chloride, and stirred at 10°c for one hour, while continuously neutralising the liberated hydrochloric acid to pH 5 with a sodium carbonate solution. When the aminoazo dyestu f can no is salted out with 40 parts sodium chloride, filtered off and redlseolved in 800 parts warm water for purification. After clarification of the solution, the pure dyestuff is separated from the filtrate by the addition of 80 - 100 parts sodium chloride. After filtering off, drying at 35°C and grinding, a yellow powder is obtained which readily dissolves in water with a yellow colour and dyes cellulose fibres by one of the dyeing processes described above in the presence of acid- binding agents in yellow shades of very good fastness to wet processing, light and chlorine. Pas yellow dyeings are also obtained on wool and polyamide fibres.

By proceeding as described above, but ooupling, instead of 19.5 parts of the sodium salt of l-aminobenzene-4- sulphonic acid, equivalent amounts of the diazo components stated in the following Table with l-aminonaphthalene-8- Shade on Diazo ,component cellulose fibre reddish yellow acid strongly reddish yellow acid acid nic acid nic acid acid yellowish brown , 5 f - orange-brown reddish brown SOJTa (l-aminobenzene-2, 5-disulphonic acid coupled in an acidic medium with l-amino-naphthalene-6-sulphonic ac id) reddish brown (l ic acid coupled in an acidic medium with the technical mixture of l-aminonaphthalene- 6- and -7-sulphonic acid) Shade on Diazo component oellulose fibre wn water to 1 kilogram, the fabric is subsequently subjected to an intermediate drying, then steamed in a suitable steaming apparatus at 103 to 115°C for 30 seconds, rinsed and soaped the ly acid of 4.5 - 5.5. When no more amino azo dyestuff can be detected chromatographically (Co-complex: blue; Cr-complex: blue- green), the resultant mixture of the two reactive dyestuffs is salted out with potassium chloride, filtered off and dried.

The dyestuff yields on cellulose materials by the pad-dyeing processes or by printing in the presence of acid- binding agents intense black shades of very good fastness to wet processing and light.

Valuable black dyestuffs are also obtained by proceeding in an analogous manner, but using a mixture of the 2 : 1 chromium and 2 : 1 cobalt complexes of the followin 'aminoazo dyes uffs: Diazo component . Coupling component Coupling pH l-hydroxy-2-amino-4- l-hydroxy-8-amino-naphthaI- 9 nitrobenzene ene-3,6-disulphonic acid l-hydroxy-2-amino-4- " 9 nitronaphthalene-7- Example 206 24.0 Parts 4-me thyl-2-me thylsulphonyl-thiazole-5-< carboxyli.c acid chloride are added to a neutral solution of 53.15 parts of the disodium salt of the aminoazo dyestuff obtained by coupling of diazotised l-amino-4^nitrobenzene-2-sulphonic acid with l-(2 ' -chloro-5 ' -sulphophenyl)-3-methyl-pyrazolone-(5) and subsequent reduction of the nitro group with sodium sulphide, in 300 parts water, and the mixture is stirred at 25°C for one hour, while continuously neutralising the liberated hydrochloric acid to a pH value of 4 - 6 with a sodium carbonate solution. "Jhe separated dyestuff of the formula is filtered off, dissolved warm in 3000 parts water at pH 6 - 7, and reprecipitated from the filtered solution by the addition of sodium chloride. After filtering off, drying and pulverising, a yellow powder is obtained, which is readily soluble, in water and dyes · cellulose materials from a long bath at 85°C or by the cold batch pad process with the use of sodium carbonate as acid-binding agent in clear yellow shades fast to washing, rubbing and light.

Valuable new reactive dyestuffs are also obtained by proceeding as described above, but using, instead, of the following Table.

.In the Table the term "hydrolysed" means that an acylamino group contained i . the aminoa .o dye stuff is subsequently hydrolysed, whereas 'the term "reduced" indicates that a nitro group contained in the diazo com onent is reduced, after coupling, to form the amino group, whereby the desired aminoazo dyestuff is formed.

Example Diazo Azo pH of Shade on No. component comoonent coupling cellulose medium 207 l-amino-4-nitro- ' . l-( 4 ' -sulphophenyl ) -3- 5 - 6 yellow benzene-2-sulphonic . me thyl-oyrazolone- ( 5 ) acid ( 4-positloned nitro group subsequently reduced) 208 " l-(4' -sulphophenyl)-3- 5 - 6 reddish ' carboxy-pyrazolone-(5) yellow 209 " l-(3 sulpho.phenyl)-3- 6 - 7 " meth l-5-amino-pyrazole 210 l-amino-3-acetyl- " 6. - 7 . " amino -be zene -6- sulphonic acid ■ · ' ' ( 3-positioned acetylamino group subsequently hydrolysed) . 211 " l-0#-hydroxyethyl)-2- 5 - 6 ' " meth l-pyrazolone - ( 5) 212 2 2 mmooll ll--aammiinnoo--33-- 1 mol bis-pyrazolone 5 - 6 " . ac etyl-amino -ben ene · from 4,4 ' -bis-hydrazino - 6-sulphonic acid dibenzyl-2, ' -disul honic (hydrolysed) acid and acetoacetic ethyl ester 213 1 1 mmooll l1--aammiinnoo--.33-- l-(4 « -svilphoohenyl )- . 5 - 6 " ' Example Diazo Azo pH of S kde on No. component component coupling cellulose medium 214 1-amino-5-acetyl- 1- ( 4 ' -sulphophenyl ) 6 reddish, amino-naphthalene■ carboxy-pyrazolone- yellow disulphonlc acid (hydrolysed) 215 1-amino-2-methyl- 2-acetylamino -5-naphtho1 benzene -4,6- 7-sulphonic acid disulphonic acid (hydrolysed) : 216 2-ace tylamino-8-naphthol 6-sulphonic acid (hydrolysed) 217 1-amino -2-me thyl- l-chloro-2-acetyl-amino- benzene-4,6- 5-naphthol-7-sulphonic disulphonic acid acid (hydrolysed) . 218 l-aminobenzene -2- l-acetylamino-8-hydroxy- 8 red sulpho c acid naphthalene-4,6- . disulphonlc acid (hydrolysed) 219 2-aminonaphthalene- - 8 bluish 3.6-disulphonic acid red 220 2-a inonapht a1ene- 7 - 8 bluish 3.7-disulphonic acid red 221 2-aminonap thalene- 7 - 8 bluish 4.8-disulphonic acid red. 222 2-aminonaphthalene-3,6 l-acetylamino-8- 7 - 8 bluish disulphonlc acid _ hydroxynaphthalene - red 3,6-disulphonic acid (hydrolysed) 223 2-aminonaphthaiene- l-acetylamino-8- bluish 4,8-disulphonic acid hydroxynaphthalene- red Example Diazo . Azo pH of Shade on Νο· componen component coupling cellulose medium 224 1-amino-4~methqxy- ' 2-(N-acetyl-N-methyl- 7 - 8 yellowish benzene-2-sulphonic amino ) -5-hydroxyr- red acid haphthalene-7 -sulphonic acid (hydrolysed) 225 2-(N-acetyl-N-methyl- 7 - 8 red amino ) -8-hydroxy- naphthaiene-6-sulphonic acid (hydrolysed) 226 l-aminobenzene-2- 7 - 8 sulphonic acid 227 l-aminobenzene-3- 7 - 8 sulphonic acid 228 l-aminobenzene-4- 7 - 8 sulphonic acid 229 l-amino-4-meth l- 7 - 8 benzene-2-sulphpnic acid 230 1-amino-2, 4-dime thyl- 2-(N-acetyl N-methyl- 7 - 8 red benzene-6-sulphonie amino )-8-hydroxynaphtha- acid lene-6-sulphonic acid (hydrolysed) 231 2-acetylamino -8- 7 - 8 hydroxynaphthalene- 6-sulphonic acid (hydrolysed) 232 l-amino-2, 4-dimethyl- 2-acetylamino -8- 7 - 8 red benzene-6-sulphonic hydroxynaphthalene- acid 3,6-disulphonic acid (h drol sed Example Diazo Αζό· pH of Shade on No. componen component coupling cellulose medium '4-aminoazobenzene- Ί- amino -3.- acetyl 5 - 6 yellowish 3, 4* -dlsulphonic acid aminobenzene brown " l-amino-3-hydroxy- 5 ^ 6 " acetyiamino benzene " 1-amlno -naphthalene- 5 - 6 " 6- sulp ohic acid " l-amino-naphthalene- 5 - 6 " 7- sulphonic acid ic ¬ cellulose fibres from a long bath or by one of the conventional is salted out, filtered off, washed and dried at 30 - 40°C. The dyestuff dyes cellulose materials in clear blue shades of very good fastness to wet processing, rubbing and light.

Blue dye stuffs with similar properties are obtained by. proceeding as described above, but acylating, instead of the stated water-soluble amino-anthraquinone derivative, equivalent amounts of the amino-anthraquinone-sulphonic acid derivatives mentioned below with 4-me thyl-2-methylsulphonyl-thiazole-5- carboxylic acid ch oride. .

Example Water-soluble amino-anthraquinone derivative ■ 240 l-amino-4- ( 5 ' -aminophenyl ) -amino-anthraquinone-2, 5 ' -di- sulphonic acid 241 l-amino-4-(2' -chloro-3' -aminophenyl )-amino-anthraquinone- 2, 51 -disulphonic acid 242 l-amino-4- (2 ' -me thyl-3 ' -me thylaminophenyl ) -amino -anthraquinone--^, 5' -disulphonic acid 243 l-amino-4-( 4 ' -aminophenyl ) -amino-an hraq inone-2, 6, 5 r - trisulphonic acid 244 l-amino-4- ( 3 ' -aminophenyl ) -amino-anthraquinone-2, 6, 4 ' - trisulphonic acid 245 l-amino-4-(4' -aminophenyl ) -amino -anthraquinone-2, 5,3' - trisulphonic acid 246 l-amino-4-.( 3· -aminophenyl ) -amino-anthraquinone-2, 5,4' - trisulphonic acid 247 mixture of l-amino-4- (3· -aminophenyl ) -amino-anthraquinone-2, 4 ' , 5- and 2,4' ,8-trisulphonic acid furthermore the derivatives subsequently sulphonated at 20 - 30°C with 5% oleum 248 · l-amirio-4-^4"1 - ( 4 ' 1 -raminobenzyl )-phenyls-amino -anthra- quinone-2-sulphonic acid 249 1-amino- -( 41 -me th 1aminophen l ) -amino-anthraquinone-2- sulphonic acid 250 l-amino-4-( 3' -methylaminophenyl ) -amino-anthraquinone-2- sulphonic acid 251 l-amino-4-( 2' -methylaminophenyl )-amino.-anthraquinone-2- sulphonic acid 252 l-amino-4-(7'-amino-naphthyl-^~2'_/) -amino-anthraquinone- 2-sulr»honic acid 253 the .'condensation product obtained from 1 mol cyanuric chloride .with 1 mol l,4-diaminc-antbraquinone-2- sulphonic acid, : Γ ίηόΐ aniline-2,5-disulphonic acid and 1 mol ethylene-diamine ( onersided) , yields, after a c la t i on wl t,h 4 -me: hy 1 - 2 -me th y 1 s u 1 ph o n y 1 - th i a z o 1 e - 5 - carboxylic. acid chloride, a violet reactive dyestuff. Example 254 '.·..

A solution of 107 g .of a mixture of equal molar proportions of copper-phthalocyanine-trisulphonic βο1ά-(3,3', 3" ) -mono- (m-amino-p_-sulphophenyl) -amide and copper phthalo-cyanine-trisulphonic acid-(3,3' ,3" )-di-(m-amino-p_-sulphophenyl) amide is adjusted to 1.3 litiee and pH 6; 37.1 g 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride are introduced at 10°C. While stirring, the temperature is raised every hour by 5°C and finally maintained at 20 - 25°C for several hours. At the same time, a pH of about 6.1 - 6.9 is maintained by the dropwise addition of 3N NaOH, until, on average, each dyestuff molecule is provided with at least one 4 -me th 1 - 2 -me thylsulphonyl-thiazole-5-carbonamido radical; this can easily be ;ascertained by' the consumption of sodium hydroxide solution, on: the one hand, and by a amino group determination, on the other hand. The 4-me thyl-2-me thyl-sulphonyl-thiazole-5-carboxylic acid chloride can also be.

Introduced dissolved in acetone. For working up, the dyestuff solution can also be slightly heated at the stated pH, without substantially reducing the reactivity of the dyestuff towards cellulose. The separation of the unreacted thiazole-carboxyiic acid chloride and of the hydrolysis products formed therefrom is effected by filtration or in a separator. The reaction product is precipitated b Introducing 150 g sodium chloride per litre dye3 uff solution. The product ia filtered off. ith suction and dried at about 30°C under normal pressure or in a vacuum. . There are obtained 195 - 200 g crude dyestuff which still contains about 30 sodium chloride.

The sodium chloride can be substantially removed by stirring the crude dyestuff with 250 ml water and again filtering it off with suction.

The dyestuff dyes cellulose materials by the pad-thermofixing process at 140°C and by the pad-steam process in turquoise shades fast to wet processing, rubbing and light.

The dyestuff mixture used as startin material can be obtained by known methods, e.g. by adding 3 mol 2,4-diamino-benzene»sulphonic acid to an aqueous suspension of sulphonic acid group-free copper-phthaloc anine-trisulphonic acid chloride at 0 - 20°C and at a pH of about 6.5 and simultaneously catalysing tiie hydrolysis with 3 mol pyridine, the above-mentioned mixture of Pc^sulphonamides being thus formed.

A similar product is obtained, when a mixture containing the said components in a molar ratio of 4 : 1 is used as starting material.' This mixture, is obtained from the same coppe,r-.ph1¾alocyanine-trisulphonic acid chloride and 2 mol .2,4-diaminobenzerie-sulphonic acid according to the same process.

; Instead of the said starting materials, there may also be used those which contain nickel instead of copper as the central atom, or which are prepared from copper-phthalo.cyanine-trisulphonic acid chloride-(4,4' ,4" ) or from the phthalocyanine-tetrasulphonic acid chlorides -(3, 4' , ",4"' ) or -(.4,4' ,4", 4" · ), or with the use of ottier arylene-dlamine-sulpho.nic acids, such as toluylene-diamine- (2,4)-sulphonic acid-(5) ; 4,4' -diamino-dibenzyl-disulphonlc ac i d- ( , 2 · ) ," naph thylen e - diamine -(1,5) -disu lphonlc ac 1 d- ( 3 , 7 ) . Products of this "type and their preparation have frequently been described in the patent literature. The reaction thereof with 4-me t3,y'l-2-me thylsulphonyl-thiazole-5-carboxylic acid chloride can always be carried out in the same manner J This applies also to the reaction of 4-methyl-2-methylsulphonyl-thlazole-5-carboxylic acid, chloride with the copper- and nickel -phthalocyanine intermediates leading to green reactive dye stuffs, such as can be obtained e.g. by polysulphochlorination of tetr -(Z,51 ,3", 3" ' )-(p_-tolylmercapto ) copper-phthalocyanine . with ch lor osu Iphonic ,acid, condensation of 1 to 2 sulphochloride groups per molecule with 1,3-phenylene diamine-4-sulphonic acid or l,4-phenylehe-dlamine-3-sulphonlc acid, a d' hydrolysis of the remaining sulphochloride groups; also the homogeneous or mixed amino and sulpho group -containing arylation and alkylation products of tri- and tetra-mercapto-copper- (or ickel-) -phthalocyanine can be converted into valuable green reactive dyestuf fs in an analogous, manner b acylation of their amino group with 4-methyl T2-methylsulphonyl thiazole-5-carboxylic acid chloride.

Example 255 When the procedure described in Example 18 is followed, · with the difference that the resultan t.. dyestuf f intermediate is not coupled with the diazo . compound obtained from 17.5 parts 2-aminobenzene Sulphonic acid, but with he diazo compound from 20.8 parts 3-chloro -aniline -6-sulphonic acid in the presence of 12 parts sodium carbonate at a final pH of 7, there is obtained a reactive dyestuf f of the formula e red e onyl- e materials can be dyed or printed, preferably in the presence of sodium carbonate, in the specifled. shades: Example Diazo Coupling Coupling Shade No. component component PH 256 1-amino- -me thoxy- 1-amino-8-hydroxy· 7 - 8 violet benzene-6-sulphonic naphthalene-3, 6- acid disulphonic acid 257 .1-amino-8-hydroxy- 7 - 8 reddish naphthalene -4,6- violet disulphonic acid 258 2-amino-5-hydroxy- 7 scarlet naphthalene-1,7- disulphonic acid Example Diazo Coupling Coupling Shade No. component component PH 259 l-amino-5-chloro-ben- 2-amino-5-hydroxy- orange zene-2-sulphonic acid naph th al ene - 1 , 7 - . disulphonic acid 260 l-aminobenzene- · ·.·-..·.' " 3- sulphonic acid. ..· \ 261 l-aminobenzene— : " 4- sulphonic acid, 262 " . 2-amino-8-hydroxy- 7 - 8 scarlet naphthalene-3,6- disulphonic acid 263 4-aminobenz0'ic ' acid- 1 -am In o - 8 -hydroxy - 7.-.8, red Q3-sulpho -ethyl ).-amide naphthalene -3, 6- . disulphonic acid 264 l-amino-4-sulpho- : 7 - 8 violet ac e tylamino -benzene- 6-sulphonic acid 265 l-amino-3-sulpho- 2-amino-5-hydroxy- 1 orange ac e ylamino -benzene - naph thalene -1,7- 6-sulphonic acid disulphohic acid 266 l-amlno-4-sulpho- 2-amino-5-hydroxy- ' scarlet ace tylamino -benzene na ph thalene -1,7- disulphonic acid 267 l-aminobenzene -2, 4- l-(2»-methyl-3'-amino- 6 yellow disulphonic acid 5· -sulphophenyl)-3-methyl- pyrazolone-(5) 268 2 - amino -naph thai en e- yellow 4, 8-disulphonic acid Example 269 followed, but instead of the aminoazo dyes tuff there employed, 53.15 parts of the disodium salt of the aminoazo dyestuff obtained by coupling of diazotised l-amino-4-nltrobenzene- sulphonic acid with l-(2' -chloro-5' -sulphophenyl)-3-me hyl- pyrazolone-( 5) and subsequent reduction of the nitro group with sodium sulphide, are acylated with 4-methyl-2-methyl- sulphonyl-thiazole-5-carboxylic acid chloride, a valuable reactive dyestuff is likewise obtained with which cellulose materials can be dyed or printed by the visual dyeing and printing processes in fast yellow shades.

Similar reactive dyestuffs are obtained when instead of the amino azo dyestuff mentioned above, one of the aminoazo dyestuffs synthetieed from the components stated in the following Table is acylated with 4-methyl-2-methylsulphonyl- thiazole-5-carboxylic acid chloride: Example Diazo Azo Shade No. component component 271 1-amino-4-nitrol-( 2' -methyl-4 ' -sulphophenyl )- yellow benzene-2-sulphon 3-methyl-pyrazolone-( 5) acid (reduced) 272 " l-(2',5'-disulphophenyl)- yellow 3-methyl-pyrazolone-( 5) 273 " '. l-(2'-methyl-4'-sulpho-6«- yello chlorophenyl ) -3-me hyl- pyrazolone-( 5) 274 " l-(2» ,5'-dichloro-4'-sulpho- yellow phenyl )-3-me hyl-pyrazolone-( 5) 275 l-amino-3-acetylamino- l-( 2 ' -methyl-4 ' -sulphophenyl )- greenish benzene-6-sulphonic 3-methyl-pyrazolone-(5) yellow acid (hydrolysed) 2 6 l-( 4' -sulphophenyl ) -3-methyl- pyrazolone- ( 5) 277 l-(2« -methyl-4' -sulphophenyl) 3-carboxy-pyi'azolone-( 5) 278 1-( 2 ' -chloro-4 ' -sulphophenyl ) 3-carboxypyrazolone-( 5) Example 27,9 rmula (prepared by coupling of dlazotised l-hydroxy-2-amino-4-chloro. benzene-5-sulphonic acid with 2-methylamino-8-hydroxynaph- Parts of finely powdered 4-methyl-2-methylsulphonyl-thiazole / 5-carboxylic acid chloride are added, and the reaction; mixtu' is stirred at 20°C,. while continuously neutralising the liberated hydrochloric acid to pH 5 - 6 with a sodium carbon solution, until free amino groups can no longer be detected. - 40 C. rocesses ined by copper complexes, obtained by simple demethylating or oxidising coppering, of the mono- and disazo dyestuff s prepared from the diazo and azo comOonents stated in the following Table: Example Diazo Azo Coupling Shade No. component component PH. 280 l-hydroxy-2-amino■ 2-amino-8-hydroxy- reddish 4-chlorobenzene-5- naphthalene-2, 6- violet sulphonic acid disulphonic acid 281 1-amino-8-hydroxy- bluish naphthalene-5, 6- violet disulphonic acid 282 2->amino-naphthalene- 2-hydroxy-6-ac tylamino 4,6,8-trisulphonic naphthalene-4-sulphonic 9 reddisi c d c Example Diazo Azo .. Coupling Shade No. component component H 283 l-amino-2-hydroxy- · 1-hydroxy-8-ethoxy- 10 blue 6-nltronaphthalene- naphthalene-3,6- 4-sulphonic acid .·. ..disulphonic acid (reduced) 284 1-hydroxy-2-amino-; 22--hhyyddrrooxxyy--33--aammiinnoo-- 10 red benzehe-4, 6-disul- naphthalene-5,7- phpnic acid di.sulphonic ac id 285 2-amino-naphthalene- 8 - 9 blue 4, 8-disulphonic acid : . (coppered with . oxidation) •286 2-aminonaphthalene- 2-hydroxy-3-amino- 8 - 9 blue 4, 6,8-tr.isulphoni.c naphthalene -7-sulphonic acid acid (coppered with , oxidation) · 287 3-methoxy-4-amino-6- 2-methylamino-5- . . 10 navy methyl-azobenzene-2' , hydroxynaohthalene-. blue 4' -disulphonic acid ..7-sulphonic acid (copoered with demethyla11on ) 288 it 2-amino-8-hydroxy- 10, naphthalene-3,6-di- sulphonic ' acid 289 2-amlno-5-hydroxy- 10 naphthalene-l,7-di- sulphonic acid 290 -methoxy- -amino- 2-methylamino-5- 10 navy -methyl-azobenzene hydro:r,ynaphtha1ene- blue Example Diazo Azo · . Coupling Shade No. component component pH 291 3-methoxy-4-amino- 2-amino-8-fhydroxy- . 10 navy 6-methyl-azpbenzene- naphthalene-3, 6-di- blue .. '2 ',5' -disulphonic acid sulphonic acid (coppered with demethylation) 292 ·. n. 2-amino-5-hydro y- 10 " naphthalene-1,7-disulphonic acid . Example 293 When the procedure described in' Example 239 is followed, but using, instead of the 54.7 parts of the disodium salt of l-amino-4-( (2' -methyl-3' -aminophenyl')-amino*- )-anthra- quinone-2,5-disulphonic acid there mentioned, 63.5 parts of the trisodium salt. of l-amino-4-( (31 -aminophenyl )-amino )-anthra- quinone-2,4' ,6'-(or 2,2» ,6' )-trisulphonic acid, a reactive dyestuff is obtained, which dyes cellulose fibres by one of the usual dyeing processes in clear reddish blue, shades of very good fastness to wet processing.

When equivalent amounts of l-amino-4-(3' -aminophenyl- amino )-anthraquinone-2,5, 8-trisulphonic acid are used, a valuable reactive dyestuff is again obtained, which dyes cotton in fast greyish blue shades.

Example 294 ■ 30.4 Parts 2-amino-8-hydroxynaphthalene-3, 6- disulphonic acid are dissolved neutral in 300 parts water, ' and 18,6 parts 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride are added. 30 Parts of a 15% sodium carbonate solution are added in the course of one hour so that the pH A cotton or staple fibre fabric is impregnated on the foulard at 20 - 25°C with a solution containing, per litre liquor, 30 g of the dyestuff described in Paragraph 1 of the present Example, 100 g urea and 20 g sodium carbonate, the fabric is squeezed to a moisture content standing at room temperature for 24 hours, the abric is rinsed, soaped at. he boil in the usual manner and dried. A brilliant scarlet dyeing of good fastness to wet processing and light is obtained.

A cotton or staple fibre fabric is impregnated on the foulard at 20 - 25°C with a solution containing, per litre liquor, 50 g of the. dyestuff described in paragraph 1 of the present IJxample , 100 g urea and 20 g sodium carbonate, the fabric is squeezed to a moisture content of about 100 and steamed at 103°C for 10 -120 seconds. After' rinsing, soaping at the boil and drying, a brilliant scarlet dyeing of good fastness to wet processin and light is likewise obtained.

A cotton fabric is impregnated with a solution at -· 25°C, which contains, per litre liquor, 20 g of the dyestuff obtainable according to Paragraph 1 of the present Example, 100 g m-nitrobenzene-sulphonic acid sodium salt and 0.5 g of a non-ionic wetting agent (e.g. a pblyoxethylated oleyl alcohol), as well as 150 g urea arid 15 g sodium bicarbonate. The- fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100$.

After an intermediate drying at 50 - 60°C, the fabric is heated at 140°C for 10 minutes, and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boil for 10 minutes with a solution containing, per litre, 5 g Marseilles soap and 2 g sodium carbonate. After rinsing and drying, an intense scarlet dyeing of good fastness to wet processing and light is obtained.

When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestuff described in Paragraph 1 of the present Example, 100 g urea, 300 g water, 500 g alginate thickener (60 g sodium alginate per kg thickener), 10 g sodium carbonate and 10 g of the sodium salt of S-riitrobenzene-sulphonic acid, and which has been made-u with water to 1 kilogram, the fabric is subsequently subjected to an intermediate drying and then s eamed in a suitable steaming apparatus a 103 - 115°C for 30. seconds, an intense scarlet dyeing of good fastness properties is obtained after rinsing' and soaping at the boi 100 Parts wool are introduced at 40°C into a bath which contains, in 5000 parts water, 1.5 parts of the dyestu. described in Paragraph 1 of the present Example, as well as 6 parts 30 acetic acid and 0.5 part of a polyoxethylated hydroxy! group-containing stearylamine derivative.- The dyebath is brought to the boil within 30 minutes, and dyeing is the carried put at the boil for one hour. After, rinsing and drying, a" brilliant scarlet dyeing of good fastness to-washing, milling and light is obtained* Example 295 28.9 Parts 2-amino-l-methylbenzene-iJ, 5-disulphonic acid (monosodium salt) are diazotised and the diazo compound is coupled with 13.7 g l-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The monoazo dyestuff obtained is isolated and subsequently diazotised, or diazotised immediate; in solution without isolation, and coupled in an alkaline medium with 25.3,parts 2-methylamino-5-hydroxynaphthalene-7~ sulphonic acid. The resultant disazo dyestuff is salted out by the addition of sodium chloride, filtered off with suction and the isolated product is metallised with about 50 parts crystalline copoer sulphate, 40 parts die ha"iolamine, 50 parti - ° d and light.

Further dyestufife according to the invention can be prepared in a similar manner, when the above monoazo dyestuff obtained from 2-amlno-l-methylbenzene-3,5-disulphonic acid and 1-amino-2-methoxy-5-methylbenzene is combined according to the instruction given above with the aminonaphthol-sulphonic acids stated in the following Table and with 4-methyl-2- methylsulphonyl-thiazole-5-carboxylic acid chloride.

Coupling component 2-amino-5-hydroxynaphthalene-l,7-disulphonic acid 2^amino.-8-hydroxynaphthalene-3, 6-disulphonic acid The dyestuffs obtained have a blue colour.

Example 296 . . 0.1 Mol 4-ureido-2-amino-l-hydroxybenzene-5-sulphQ.nic acid is diazotised and coupled in a soda-alkaline medium with 0.1 mol i-amino-8-hydroxynaphthalene-2,4-disulphonic acid. The coupling solution is adjusted to a content of 2 mol/litre with caustic soda and then boiled under reflux for 3 hours to hydrolyse the ureido group. After cooling, the reaction mixture is neutralised with hydrochloric acid. The. dyestuff is metallised at 45°C and a pH value of 4 - 6 by the addition of 25 parts copper sulphate and 100 parts 2N sodium hydroxide solution and, after 30 minutes, acylated at pH 4 - 6 and at a temperature of 20°C with 0.1 mol 4-methyl-2-me hylsulphonyl- thiazole-5-carboxylic acid chloride. The resultant dyestuff "- r su phon c ac d ch or de, prepared from 600 g technical 96$ copper-phthalocyanine, is slurried with a little water, adjusted to 4 litres and reacted at a pH of 3.5 - 6.0 with 216 g limethyl-N-( 4» -amino-21 -sulphobenzyl ) -amine , initially at 0 - 3°C, finally at 20 - 35°C, with the addition of 300 ml (295 g) pyridine, and the pyridine is the distilled off with steam at tion of copper-phthalo-cyanine- aminomethyl-aniiide ). The solution is cooled to 10°C, and 305 g finely, powdered -methyl-2-me hylsulphonyl-ttiiazole-S-carboxylic acid chloride are strewn in portionwise in the course of 1 - 2 hours, while maintaining a pH of 7,5 - 8,5 by the addition of a dilute 3odium hydroxide solution. At the same time the reaction mixture is diluted, as required, with sufficient water for the dyestuff to remain constantly dissolved, "■ .■ : > Litres of a dyestuff solution are thus obtained, which is separated from the excess acylating agent, adjusted to pH 7,0 by the. addition of acetic acid, and precipitated by adding 2,5 litres of a concentrated sodium chloride solution while stirring.

After filtering off with suction and drying at 30°C, a clear turquoise-blue dyestuff is obtained, which is fixed on cotton from, a soda-alkaline solution at 40 - 60°C with a very good yield and very good fastness to washing.

When NiPc-3»3 ' ,3"-trisulphonic acid chloride is used as starting material, a turquoise blue is obtained which is only slightly more , reenish and has equally valuable .properties. Example.298 12,5 Parts 3-amino-4-sulphobenzyl-N-methylamine are dissolved in 150 parts by volume cone entrated hydrochloric acid. 4 Parts sodium nitrite in 20 parts by volume water are added dropwise to the solution. The resultant clear diazonium salt solution is added dropwise at 30 - 35°C to an aqueous solution of the equimolar amount of l-N-benzoylamino-8-hydroxynaphthalene-4,6-dlsulphonic acid and 16 parts sodium bicarbonate in 200 parts by volume water, ΏΙΘ dyestuff is in part precipitated and redissolved by the addition of 2000 parts by volume water. 17.6 Parts 4-methyl-2-me hylsulphonyl-thiazole-5-carboxylic acid chloride are then added a 20PC. A pH value between 6 and 7 is maintained by the dropwise addition of a sodium carbonate solution. When .the acylation is completed, as can be recognised from the consumption of sodium carbonate, the dyestuff is separated with 10 per. cent sodium chloride, filtered off .with' suctioh,- pressed off arid dried in a. vacuum: drier at 30°C. · Ίη the' :fbrrn of the free, acid, the bluish red dyestuff obtained corresponds to the formula Example 299 38.9 Parts of the dyestuff obtained by soda-alkaline coupling from 6-nitro-2-diazo-l-hydroxybenzene-4-sulphonic acid and 2-hydroxynaphthalene are slurried in 200' arts water at pH 8 and at, a temperature of 70 - 80°C. 67.9 Parts of the chromium complex compound of the azo dyestuff from 4-chloro 2-diazo-l-hydroxybenzene-6-sulphonic acid and l-amino-8-hydroxy-naphthalene-3, 6-disulphonic acid, containing 1 chromium atom per dyestuff molecule, are added to this suspension, while maintaining the pH. between 7 and 9 by. the · dropwise addition of a sodium carbonate solution. After 20 minutes at 70 - 80°C, a dark blue solution has formed. The paper chromatogram shows that a unifo formed. ■ The mixed complex is within the s ated range by the dropwise addition of a sodium carbonate solution. The acylated dye stuff is salted out with 20%, potassium chloride, filtered off and dried at 30°C. A dark powder is obtained which dissolves in water with a blue- grey colour. d er Example No. 1: 1 Chromium complex Me tal-fr 300 4-nitro-2-amino-l-hydroxybenzene-6- riitro- sulphonic ac id. — l-amino-8-hydroxynapb.thalene ■ -^2-hy 3, 6-disulphonic acid 301 302 303 4Tn itr'o- — — 2-hy sulphoni 304 n 305 tr 4-hltrq- —> l-hy sulphoni 306 6-ni rp - 307 308 6-ni t r o - 4-sulpho . 509 4-nitro-2-amino-l-hydroxybenzene-6-sulphonic 4-nltro-2 acid — l-amino-8-hydroxynaphthalene-4,6- 6-sulphon disulphonic acid 310 4-chloro-2-amino-l-hydroxybenzene-6-sulphonic 4-nitro-2 acid — l-amino-8-hydroxynaphthalene-3,6- —» 2-hyd disulphonic acid 311 312 4-nitro-2 ^ 2-hyd 313 4-chloro- » 2-hyd 314 4-nitro-2 — l-ace 3,6-disul 315 4-nitro-2 1-ami 2,4-disul 316 6-n ltro-l 4-sulphon 317 2-aminobe acid —^ l Example No. 1 : 1 Chromium complex Metal-free 318 4-nitro-2-amino-l-hydroxybenzene-6-sulphonic 6-nitro-l-amin acid ^ l-amino-8-hydroxynaphthalene—3, 6-di- 4-sulphonic ac sulphonic acid 319 4.-chloro.-2-amino-l-hydroxybenzene-6-sulphc)nic 4-chloro-2-ami acid-— l-amino-8-hydroxynaphthalene- —-> 1-( 4 ' -sulp 3,6-dlsulphoTiic acid 5-pyrazolone 320 4-methyl-2-amino-l-hydroxybenzene-6-sulphonic 4-chloro-2-aml acid — 1-amino-8-hydroxynaphthalene-3,6- 2-hydroxyna disulphonic acid 321 4-nitro-2-amino-l-hydroxybenzene-6-sulphonic 5-nitro-2-amln acid —- l-amino-8-hydroxynaphthalene-3, 6- —■> 2-hydroxyn disulpho ic acid 322 n 4-nitro-2-amin — 2-hydroxyn 323 4-nitro-2-amin —> l-hydrbxyn 324 6-nitro-4-chlo — l-hydroxyn 62.0 Parts of the trisodium salt of the dyestuff obtained' by soda-alkaline coupling from diazotised 4-chloro- 2-amino-l-hydroxybenzene-6-sulphonlc acid and l-amino-8-hydroxynaphthalene--3,6-disulphonic acid are mixed in 300 parts water at 70 - 80°C and pH 8 - 9 with 54.2 parts of the 1 : 1 chromium complex of the dyestuff from" 6-nitro-l-diazo-2-hydroxynaphthalene-4-sulphonic acid and 2-hydroxynaphthalene . A deep blue solution has formed after 10 minutes.

A blue-black print of excellent fastness to light and washing is obtained on cotton by the process described in Example 3. solution is then mixed with dilute hydrochloric acid, the dyestuff thus precipitated is filtered off with suction, washed with dilute hydrochloric acid, mixed in · 300 ml water with just sufficient dilute sodium/hydroxide solution to form a solution, and the dyestuff is precipitated in the hot in the form of the sodium salt; the product is then washed and dried.

Example 326 s .4 Grams 2-N-methylamino-5-hydroxynaphthalene-7- sulphonio acid are dissolved neutral in 150 ml water. 26.6 Grams 2,5-bis-methylsuiphonyl-thiodiazole-l,3,4 (m.p. 171 - 173°C; prepared by oxidation of 2, 5-bis-methylthio-thio- diazole-1,3,4 with performic acid or peracetic acid), pasted with a wetting agent and water, are added and the reaction mixture is stirred at 50°C. T!he sulphinic acid split off is neutralised with a sodium carbonate solution so that the pH is - 6. When the reaction is completed, the precipitated intermediate product is iltered off wi h suotioh, stirred in 150 ml water and mixed with 17.3 g diazotised l-aminobenzene- 2-sulphonic acid. TSie red solution is neutralised to pH 6 and the preoipitated orange dyestuff of the formula is filtered off with suction and dried at 50°C in a vacuum.

The dyestuff dyes cotton in orange shades of excellent fastness properties.

Dyestuffs with similar properties are obtained by the above method from, the following diazo and coupling components: Example Diazo Coupling Shade Ho, component component 327 l-aminobenzene-2- 2-amino-5-hydroxy- orange sulphonic acid naphthalene-7-sulphonic acid - n Example 329 31.9 Grams l-amino-8-hydroxynaphthalene-4,6-disul-phonlc acid are dissolved neutral in 150 ml water. 29 Grams 3,5-bis-methylsulphonyl-thiodiazole-l,2,4 (m. o. 140 - 141.5°c.f prepared by oxidation of 3, 5-bis-methylthio-thiodiazole-l,2, 4 with performic acid or peracetic acid), pasted with a wetting agent and water, are added at 20eC. The liberated methyl-sulphinic acid is neutralised while stirring to pH 5 - 6 with a sodium carbonate solution. When the reaction is completed, the intermediate product is filtered off with suction, suspended in 100 ml water and mixed with 17.3 g diazetieed 1-aminobenzene-2-sulphonic acid. Coupling is performed at pH 6.5 and the product is salted out with 15 sodium chloride. The bluish red dyeetuff of the formula is filtered off with suction and dried at 50°C in a vacuum.

The dyestuff dyes cotton in red shades of good fastness properties.

Dyestuffs with similar properties are obtained with the following diazo and coupling components: Example Diazo Coupling No. component component Shade 530 1-aminobenzene-2- 1-amino-8-hydroxy- bluish sulphonic acid naphthalene-3,6-*disul- red phonic acid SSI 2-amino-5-hydroxy- drange naphthalene-7-sulphonio acid 352 2-methylamino-5-hy- orange droxy-naphthalene-7- sulphonic acid Example 333 50.3 Grams of the dyestuff obtained by coupling of l-acetylamino-3-aminobenzene-4-sulphonic acid with 2-hydroxy-naphthalene-6,8-disulphonic acid and hydrolysis, are dissolved neutral in 160 ml water. 25.6 Grams 3,5-bis-methylsulphonyl- thiodiazole-1,2,4 pasted with a wetting agent and water, are added. Ihe mixture is stirred at 55 - 60°C and pH 5 - 6, until no more sodium carbonate solution is consumed for neutralising the methylsulphinio acid split off. The orange dyestuff of the formula SOgCflg is filtered off with suction and dried at 40°C in a vacuum.

Example 334 46 Parts of the monoazo dyestuff obtained by coupling diazotised 2-aminonaphthalene-4, 8-disulphonic acid with 3-methyl amino-toluene, are dissolved at pH 7 - 8 in 300 parts water at 50°C and mixed, in the presence of excess sodium acetate or calcium carbonate at 5 - 40°C, portionwise with a total of 31 parts 3> 5-di-(methyl-sulphonyl) - 1 , 2-isothiazole-:4-carboxylic acid chloride and stirred at the same temperature until a sample no longer shows a change of colour when acid is added. The resultant dyestuff of the formula is sa dried.

A cotton fabric is impregnated at 20 - 25°C with a solution which contains, per litre of liquor, 20 g. of the above dyestuff and 0.5 g of a non-ionic wetting agent (e.g. a polyethoxylated oleyl alcohol), as well as 150 g urea and I 5 g sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100 After an intermediate drying at 50 - 60°C, the material is heated at 140°C for 10 minutes and the dyeing thus obtained is thoroughly rinsed with hot water and treated at the boll for 20 minutes wi h a solution containing, per litre 5 g Marseilles soap and 2 g sodium carbonate. After rinsing and drying, an intense reddish-yellow dyeing of good fastness to wet processing, rubbing and light is obtained.

Claims (1)

1. 2. , - Process for the production of reactive dyestuffs, which contains at least one reaotive sulphonyl aub- stituent linked to a carbon atom of the heterocyclic benzoyl chloride, 4-^3' -methylsulphonyl-S' -phenyl-4fH-triazol-ll,2!,4,-yl-(4«'i} -benzoyl chloride, 4-^3"» ,5' -bis-methyl-aulphonyl-4'H-triazol-l' ,2' ,4'-yl-(4' jj-oenzoyl chloride, 3. ,5-bis-methylsulphonyl-l,2,4-thiodiazole, 2,5-bis-methylsul-phonyl-l,3,4-thiodiazole, 2-methylsulphonyl-5-amino-l,3,4 thiodiazole, l-methyl-2-methyl3ulphonyl-5-amino-imidazole# -ethyl-4-methyl-2-methylsulphonyl-imidazolyl- ( 5j7"-acetyl chloride, l,4-dimethyl-2-ethylsulphonyl-imidazole-5-carb©xylic aoid ohloride, 3-methylsulphonyl-5-chloro-l,2,4-thiodiazole, S*^5-methylsulphonyl-l,2,4-thiodiazolyl-(3j7'-mercaptoacetyi chloride, 3-hydroxy-5-methylsulphonyl-isothiazole-4-carboxylic aoid chloride, 2-methyl-5-methylsulphonyl-isothlazolin-3-one-4-carboxylic acid chloride or 4-methyl-2-methylsulphonyl-thiazole-5-carboxylic acid chloride. 4. Process according to Claims 1 and 2, characterised in that the dyestuffs obtained after condensation are subjected to customary conversion reactions, especially metallisation, acylation, reduction, and/or sulphonation. 5. Process according to Claim 2, characterised in that aminoazo dyestuffs of the formula in rtilch B and D represent aromatic carbocyclic or heterocyclic radicals, B is preferably a radical of a oarbocyclio diazo component of the benzene or naphthalene series and D is preferably the radioal of azo groups, R^ stands for a substituent or, preferably, hydrogen, and m1 denotes an integer, preferably the number 1 or.2f are condensed with compounds of the formula A Y in which A and Y have the meaning specified in Claim 2. 6. ; Process according to Claim 2, characterised in that amino-anthraquinone dyestuffs of the formula in which L denotes hydrogen or a substituent, the sulphonic acid group being preferred as substituent, p_ is the number 1, 2 or 3, and R^ denotes a aubstituent or, preferably, hydrogen, are reacted with compounds of the formula .* A y in which A and Y have the meaning specified in Claim 2, and the dyestuffs thus obtained are sulphonated, if desired. 7. Process according to Claim 2, characterised in that azaporphin dyestuffs of the formula in which Pc stands for the radical of a phthalocyanine, especially a copper- or nickel-phthalocyanine or a tetra- phenyl-copper- or -nickel-phthalocyanine, L stands for hydrogen or a substituent, the sulphonic acid group being preferred as substituent, r is the number 1 or- 2, CL is the number 0, 1 or 2, and denotes a substituent or, preferably, hydrogen, and mM stands for a number of 0.5 to 4, are oondensed with compounds of the formula A —— Y in which A and Y have the meaning specified in Claim 2, and the dyes tuffs thus obtained are sulphonated, if desired. 8. Process according to Claim 2, characterised in that a diazo or coupling component which contains a reaotive amino or amide group, is oondensed with a compound of the formula A Y in which A and Y have the meaning specified in Claim 2, and that the intermediate products thus obtained are converted into azo dyestuffs by diazotisation and/or coupling. 9. Modification of the process acoording to Claim 2, characterised in that a compound in whioh A has the meaning specified in Claim 2, is diazotised and combined witti a coupling component P^, in which represents the residual constituent of an azo dyestuff. 10. Process according to Claims 1 to 9, characterised in that those azo dyestuffs are synthetised or those starting components are used, which contain one or more sulphonic acid 1. Reactive dyes tuffs of the formula in which F denotes the radical of an organic dyestuff, X represents a direct bond or a bridge member, A stands for a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring, and m represents a number of 0.5 to 8. 12, Reactive dyestuffs according to the formula of Claim 11, in which F contains one or more sulphonic acid groups. 13. Reactive dyestuffs of the formula in which F^ represents the residual constituent of an azo dyestuff, A has the meaning specified in Claim 11 , and k stands for the number 1 or 2. 14. Reactive azo dye stuffs of the formula in which B and D represent aromatic carbocyclic or heterocyclic radicals, B is preferably the radical of a carbocyclic diazo component of the benzene or naphthalene series and D is preferably the radical of an enolic or phenolic coupling component, B and D may moreover contain is a direct bond or a group -CO- or -SOg- m' represents an integer, preferably the number 1 or 2, and A stands for a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbo atom of the heterocyclic ring. · 15. Reactive anthraquinone dyestuffs of the formula in which L stands for hydrogen or a substituent, the sulphonic acid group being preferred as substituent, p_ is the number 1» 2 or 3, R^ represents a substituent or, preferably, hydrogen, Q denotes a direct bond or a grouping -CO- or -S02*> nd A represents a 5-membered heterocyollo ring which contains at least one reactive eulphonyl eubetituent linked to a carbon atom of the heterocyclic ring. 16. Reactive azaporphin dyestuffs of the formula Po -SOft H in which Pc stands for the radical of a phthalocyanine, preferably a copper- or nickel-phthalocyanine or a - - - - and for the number 0, 1 or 2, R, is a substituent or, preferably, hydrogen, Q is a direct bond or a grouping -CO- or -SO -, A represents a 5-membered heterocyclic ring which contains at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring, and mn stands for a number of 0.5 to 4. 17. Dyestuffs according to Claim 14, in which B and/or D contain one or more sulphonic acid groups. 18. Dyestuffs according to Claim 15, which contain one or more sulphonic acid groups. 19. Dyestuffs according to Claim 16, which contain one or more sulphonic acid groups. 20. Process for the dyeing and printing of hydroxyl group-containing materials, especially textile materials of natural or regenerated cellulose, characterised in that one or more dyestuffs according to Claim 11 are applied to these materials in any sequence, and the material thus treated is subjected to the action of an elevated temperature, if desired. 21. Process for the dyeing of nitrogen-containing materials, preferably wool, silk, synthetic superpolyamide and -polyurethane fibres, characterised in that these materials are dyed with one or more dyestuffs according to Claim 11 from an acidic to neutral bath, and that the pH value of the dyeba^th is subsequently increased, preferably to pH 6.5 to 8.5, if desired. 22. . Materials which are dyed or printed according to the processes of Claims 20 and 21, Dated this 10th day of October, 1965 For the Applicants DR. RBIKH0LB C0IIN &C0. : [\ C) /;