IL24729A - Reactive dyestuffs and process for their production - Google Patents

Description

PATENTS AND DESIGNS ORDINANCE SPECIFICATION REACTIVE OYBTUFFS AND PROCESS FOR THEIR PRODUCTION Ο-Χ Ρ "* I (we FARBE FABR I KEN BAYER AKT I ENGESELLSCHAFT , A GERMANY COM ANY , OF LE ERKUSEN— B A YERWERK , 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 :- The present invention relates to valuable new reactive dyeot ffs of the general ormula: in whic F represents, a grouping .-$-»'. -SO2-S - arylene-, -alkylene-, or : ¾ -^ : '1 -' ■ ■ ' -1*1-, flhie is linked directly wit the radical A and either directly or via a bridge member with the radical ¾ being hydroge or a subs ituent, and "arylene" standing for an arylene rad ical, "alkylene* for: a lower alkylene radical, A is the radical of a 6«mefflbered heterocyclic ring ¾hich contains at least one nitrogen atom in the ring and has at least one reactive sulphonyl eubstituent linked to carbon atom of the het©3?ocyc!ic ring whic is in an position to a nitrogen atom of t s: ring, and which ring may be fused to carbocyclic rings, and ra is a number from 0.5 to 8.

In the dyestuffs of the. general formula (I), the radical A is, by definition, linked to the dyestuff radical P by the especially -M- and -W(CH^ A)-groups and eulphonamide or carbonamide groups. S e amino or amide groups may carry further substituents, such as lower alkyl (preferably to C^), aralkyl, cyeloalkyl or aryl groups, but preferably they are present in the form -HH-, which is not further substituted.

She amino groups -N(H^)- are on the one hand linked directly to the radical A, and can on the other hand be linked directly or via a further bridge member, such as -SO,- or -CO- (as in the case of the amide grouping already, mentioned) , or via an alkylene group, an alkylene -CO— an arylene, arylene-S02, aryle-ne-CO, arylene amino or aralkylene-ainino group a urea grouping or a triazine or diazine ring, an arylene-amido-sulphonyl group or by members of different type to an aromatic radical F of the dyestuff. If such further bridge members contain heterocyclic ring systems, as in the case of triazinyl or pyrimidinyl radicals, these also may contai reactive atoms or groupings, such as halogen atoms or sulphonyl substituents.

The further possible bridge members -SOg-, alkylene and arylene are also on the one hand linked directly to the hetero- cycle A and can on the other hand be linked either directly or through a further bridge member with the radical P; in the case where bridge members stand between these radicals X and P, the following groupings may for example be present: -OC-arylene-A; -OC-alkylene-A; -OC-aralkylene-A; -OC-alkarylene-A; -O^S-arylene-A; OgS-alkyiene-A; -C^S-aralkylene-A; -C^S-alkarylene-A; -(R)N-alkylene-A; -(R)N-aralkylene-A; -(R)N-alkarylene-A; -(R)N-arylene-A; -(R)N02S-alkylene-A; -(R)N02S-aralkylene-A; -(R)N02S-alkarylene-A ; -(R)N02S-arylene- ; -( R)N-OC-aIk lene-A; -( R)N-OC-aralkylene-A ; -( )N-OC-alkar lene-A; -(R)N-OC-arylene-A; -N=N-aralkylene-A; -N=N-arylene-A ; -(R)N02S-A.

Suitable reactive sulphonyl substituents in the radical 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, jD-toluene-sulphonyl, £-chlorophenyl-sulphonyl radicals; aralkyl-sulphoriyl radicals, such as benzyl-sulnhonyl and £-toluylmethyl-sulphonyl radicals ; and also hetero-sulphonyl off under the known conditions for applying reactive d e-r^ stuffs, is for example a monoazine, diazine or triazine ring, such as a pyridine, pyrimidine, pyridazine, pyrazine, thiazine, . or an assymmetric or symmetric triazine ring, or a ring system of this type with one or more fused aromatic rings, such as a quinoline, phthalazine, cinnoline, quinazoline, · In the case where the bridge member X starts from the heterocyclic ring which contains the reactive sulphonyl substituent or substituents, X is linked either to a carbon atom or to a hetero atom, among the latter in general a nitrogen atom of the heterocylic 6-membered ring. Preferably X is joined to a carbon atom of the heterocyclic ring A.

As suitable heterocyclic rings A which contain at least in an a position to a ring ' nitrogen atom /*. one reactive sulphonyl substituent/and may contain further /*< fused rings, there may be mentioned, by way of Example: 2-carboxy-methylsulphonyl-4-pyrimidinyl, 2Hnethyl-sulphonyl-4- methyl-6-pyrimidinyl, 2-phenylsulphonyl-4-methyI-6-pyrimidinyl, 2-phenylsulpbonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-bis- methyls'ulphonyl-6-pyrimidinyl, 2,4-bis-methyleulphjanyl-5- sulphamidyl-pyrimidine, 3-phenylsulphonyl-6-pyridazinyl, ¾ ·> ·· methylsulphonyl-4-methyl-6-pyridazinyl, 2, 5-bis-methyleulphonyl- 6-pyrazinyl, l-methyl'suiph0nyl-3-triazinyl, l-methylsulphonyl- 3-( 3,-sulphophenyla'mino)-r5-triazinyl, l-methylsulphonyl-3-(2' - 8ulph0nyl-4-pyridazinyl, 1-phenyl-8ulphonyl-3-methoxy- 5-triazinyl, 1 ,3-bi8-phenylsulphonyl-5-triazinyl, 1-methyl- eulphonyl-3-phenoxy-5-trlazinyl , 1-methyl-eulp onyl- 3-pheny1-5-triaziny1.

The reactive sulphonyl substituen or substituents present in the nucleus. A may be further substituted in the aryl, alkyl or hetero" radicals by ionic or non-ionic groups, e.g. by carboxy (for example in the form of carboxy-methyl), sulpho, hydroxy, nitro or halogen (CI, Br) radicals, present for example in carboxy-methyl sulphonyl, chloromethyl sulphonyl, chloroethyl-sulphonyl, hydroxy ethyl sulphonyl, nitrophenyl sulphonyl or sulphophehyl sulphonyl groups.

Of the large number of groupings -X-A, the following may be mentioned by way of example: -NH-A, -N(CH^)-A, -N(C2H^)-A -NiC^J-A, -CO H-A, -S02NH-A, -NHOgS-A, -CON(CH3)-A, -S02N(CH3) Le. A 9111 -5- Israel Patent specification So. 14614 discloses organie dyastuffs containing the radical of a pyriisidine-5-sulfonic acid. h® sulfonyl radical in this group, however, is attached to the 5-eartoon atom of the pyrimidine ring, which carbon atom ie in the β-position to tooth nitroge atoms of the ring.

As a consequence this smlfonyl is stable and is not split off ia the dyeing process. Its function is not one of a reactive substit ent, but rather as a bridge member linking the pyrimidine t n ; o the dyestuff residue, or as a free -SO^H group contributing to th© ¾ater solubility of the dyes.

The new dyestuffs laay belong to a groat variety of classes, e.g. to the series of metal-free or metal-containing mono- o eiyazo dyestuffsf metal- ree or metal-containing azaporphin 24729/2 / the dyestuffs substituted by sulphonic acid groups have proved particularly suitable for this purpose. 3. Azo In this formula Pc stands for the radical of a phthalo- * cyanine, especially a copper- or nickel-phthalo-cyanine or a tetraphenyl-copper or -nickel-phthalo-cyanine, L stands for hydrogen or a substituent, the sulphonic acid group 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 -S02- grouping k for a 6-raembered heterocyclic ring which contains at least one nitrogen,a ora in the ring and has at least one reactive sulphonyl substituent linked to a carbon.atom of the heterocyclic ring which: is in an a position to a nitrogen atom of this ring and which ring may be fused to carbo- cyclic rings, and.m" 'stands, for a number of 0.5 - 4., The phthalo- cyanine radical Pc may obviously contain further substituents, especially sulphonic acid and sulphonamide groups such as -S02NH2- · . -S02KH-alkyl, -S02N(alkyl)2 and -S02KH(aryl) groups.

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

The selection of suitable azo, anthraquinone and aza- porphin "dyestuffs and heterocyclic ring systems A given above'-, represents no limitation of the general formulae, . either in is first condensed with the reactive component (VI), and the resultant intermediate product is subsequently converted into an azo dyestuff by diazotisation, and/or coupling, and/or condensation. This azo dyestuff can be subjected to further conversion reactions customary in azo dyestuffs, e.g. acylation, condensation, reduction, and metallisation. Also in the preparation of other dyestuffs, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (VI) can first be carried out with an intermediate product, e.g. with m-phenylene-diamine or a m-phenylene-diamine-sulphonic acid and the resultant reaction product subsequently further condensed, e.g. with bromoaminic acid ( l-amino-4-bromo-anthra- quinone-2-sulphonic acid) to form a reactive anthraquinone dyestuff, or with a copper- or nickel-phthalocyanine-sulphonic acid halide to form a reactive phthalocyanine dyestuff. anthraquinone and phthalocyanine dyestuffs.

Depending on the number of reactive groupings in the dye-stuff radical or dyestuff intermediates, preferably -HNR- groupings, which are suitable for the conversion, one or more groupings of the general formula -X-A can be incorporated in the dyestuffs. 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 -X-A, especially those of higher molecular structure, can also be synthetised.

If the dyestuffs prepared according to the invention contain groups forming metal complexes, then they can be converted into their metal complex compounds by the action of nietal-yielding agents, e.g. copperj nickel, chromium or cobalt salts. reacti densat with r d for ex of the wherei or aminoanthraquinone dyestuffs of the formula one amino group is protected, e.g. an acylamino compound, may be condensed at the second amino group with a reactive component (VI)-, the first, protected, amino group then converted into the : ee amino group for example by hydrolysis and the compound obtained condensed with for example l-amino-4-bromo-anthraquinone- 2-eulphpnic acid to a valuable type of anthraquinone dyestuff.

For the production of phthalocyanine dyestuffe, in a procedure similar to that iet forth for anthraquinone dyestuffe, there by be pro duded first a diaminoaryl oompound mono-condensed with the reactive oomponent A-Y, which is then condensed with, for example, copper- or nickel-phthalocyanine sulphonic acid halides; other amino compounds, such as ammonia, aliphatic amino compounds and/or aromatic amino compounds, can be employed as well, simultaneously or subsequently. In this way phthalocyanine sulphonamide dyestuffs are obtained which contain a certain proportion of sulphonarylamide groups, which carry reactive groups, besides a certain proportion of unreactive sulphonamlde groups and/or free sulphonic acid groups.

An especially preferred group of reactive dyestuffe within the scope of the compounds of formula I has the composition an amino group (X^). The amino group can carry further substituents, . such ae loi»'®r alky1- (p eferably to C^), aralkyl-, cycioalkyl- or aryl groups, but is preferably present . in the form -HH- not further substituted. The amino groups are on their part joined directly to an aromatic ring carbon atom of the dyestuff.

As reactive sulphonyl, substituents in the pyrimidine ring A-^» examples are lower alkyl sulphonyl radicals with preferabl 1 to 5 C-atome, such ae:,me hyi' ei';ilP^on 1~»: etb'yi' eulpfronyl-, ..'. or propylsulphonyl radicals aryl sulphonyl radicals, such as phenyl sulphonyl-, p-toluene sulphonyl-, p-chlorophenyl . sulphonyl radicals, aralkyl sulphonyl radicals such as benzyl sulphonyl- and p-toluyl methyl sulphonyl radicals, and also heterosulphonyl radicals such as 2-benzthiazolesulphonyl.

As suitable pyrimidine rings ^, which possess at least one reactive sulphonyl substituent, there may be named for example: 2-carboxy-methyl eulphonyl-4-pyrimidinyl, 2-methyl sulphonyl-4-methyl-6-pyrimidinyl, 2-phenylsulphonyl-4-methyl-6- pyrimidinyl, 2-phenylsulphonyl-4-methyl-5-chloro-6-pyrimidinyl, 2,4-bis-methylsulphonyl-6-pyrimidinyl, 2-methylsulphonyi-4- methyl-5-nitro-6-pyrimidinyl, 2-methylsulphonyl-5-cyano-4- pyrimidinyl, 2-methylsulphonyl-4-carboxy-6-pyrimidinyl or 2- e;thyleulphonyli-5-sulpho-4-pyrimidinyl, as well as further compounds already named on page 4.

The reactive substituents or substituents in the nucleus A1 can be further substituted by ionic or non-ionic groups, e.g. by carboxy^- (for example in the form of carboxymethyl-), hydroxy-, nitro-, halogeno- (CI, Br), sulphonic acid or sulphone radicals, or further groups already named on page 5.

The novel dyestuffs of the formula (XI) may belong to a wide variety of classes, for instance,, to the series of - - wherein B and D represent aromatic carbocyclic or heterocyclic radicals, for instance B the radical of a carbocyclic diazo component from the benzene or naphthalene series and D the radical of an enolic or phenolic coupling component, such as a 5-pyrazolone, an acetoaeetic acid arylamide, a hydroxy-naphthalene or an aminonaphthalene, etc. ; in addition, B and D may contain any of the substituents usual in azo dyestuffs including further azo groups* stands for a substituent or preferably a hydrogen atom; m' denotes an integer, preferably the integer 1 or 2; and A represents the radical of a pyrimidine ring, which contains at least one reactive sulphonyl substituent which is a to a arirvg nitrogen joined to a ring^carbon a¾oT-V Those dyestuffs in this series which are soluble in water are particularly valuable, and in particular those which contain sulphonic acid and/or carboxylic «cid groups. The azo dyestuffs may either be metal free or metal containing, preference beinggiven to the copper, chromium and cobalt complexes Important azo dyestuffs are-, for instance, hose rom the benzene-azo-naphthalene series, the benzene-azo-l-phenyl- fe-pyrazolone series,; the naphthaiene-azo-naphlthalene series, the naphthalene-azo-l-phenylpyrazolone-5 series and the stilbene azo-benzehe series, preference being again given to the dye-' stuffs containing suiphonic acid groups. In the case of metal complex azo dyestuffs, the groups complex linked to the metal are preferably in the o-positioos relative to the azo group, for instance in the form of OjO'-dihydroxy-, o-hydroxy-o β- carboxy-, o-carboxy-o' ÷amino--'and o-hyd oxy-o'-amino-azo ; groupings. 2. Anthraquinone dyestuffs wherein denotes hydrogen or substituents, which especially include a suiphonic acid group, £ is the integer 1, 2 or 3, R-j^ is a substituent or preferably hydrogen, and A-^ represents a pyrimidine ring which possesses at least one reactive · ' . . '. to a ring nitrogen >y sulphonyl substituent joined to a ring carbon atom, which is a/ Within the range of these dyestuffs, preference is again given to the water soluble products owing to their high suitability for dyeing and printing on fibres containing cellulose, the dyestuffs substituted by suiphonic acid groups having proved particularly suitable.

Le A 9111 -19- heterocyclic ring systems A^ does not represent any limitation of the general formulae, either in respect of the possible methods of preparation fo* the production of these dyestuffs within the scope of the general formula (I) or in respect of the valuable properties of these products with regard to the . technique for their application.

Prom the viewpoint of technical application especially or salphonamide.

Dyestuffs of outstanding importance are those of the formulae (XII), (XIII), and (XIV) in which the radical -N-A, t ■·■ Bl is a 2-methylsulphonyl-==5rachlo2,o°6-JB¾th l pyrisiidinyl-4 : radical. This radical is introduced by reaction of the dye-stuffs containing amino groups with, for example, 2-methyl-sulphonyl-4, 5-dichloro-6-methyl pyrimidinee In addition, the novel dyestuffs (XI) may contain any other substituents usual in dyestuffs, such as sulphonic acid, earboxylie acid, alkylamino, arylamino, aralkylamino, acylamino, nitro, eyaao, halogen, hydroxy, alkoxy,- thioether, azo groupings and th© like « Moreover, .th.© dyestuffs may. contain other fixable groupings such as mono- or di-halogenotriazinylamino, mono-, di- or tri-halogenopyrimidinylamino,2, 3~dihalogenoquinoxaline-6-carbonyi«- or -6-sulphonyl-amino, 1,4-dihalogenophthalazine- carbonyl- or -5rsulphonyl-amino, eaterified sulphonio acid oxalkylamide and oxalkylsulphone groups, sulphofluoride, halogenoalkylamino,: acryioylamino, halogenoacylamino groups and the like.

The new dyestuffs of the formula (XI) are obtained by introducing into ■'dyestuffs or dyestuff intermediates, by known processes, at least one. pyrimidinylamino group, which contains at least one. reactive sulphonyl substituent joined at a carbon atom of the pyrimidine ring and which is linked with the nitrogen atom of the amino group at a ring carbon atom of an aryl nucleus of the dyestuff or dyestuff intermediate, and in the-case where dyestuff intermediates are employed, converting the latter into. the desired final dyestuffs. The pyrimidinyl amino radioal containing at leas ile sulphonyl substituent can be introduced into the dyestuffs or dyestuff intermediates for example by reacting amino group-containing dyeatuffs or dyeetuff intermediates which have a reactive hydrogen atom on the amino nitrogen, with compounds of the general formula A^-Y (XVI) wherein A^ represents a pyrimidine ring which contains at least one reactive sulphonyl substituent linked to a carbon which is a to a, ring nitrogen atom of the heterocyclic ring/ and Y means an anionic radical which can be split off.

Among the anionic radicals which can be split off, reactive substituents Y, 01-, Br and sulphonyl aubstituents are of major interest. Further suitable anionic radicals capable of splitting off are, for example, SO^M-, (M=H or metal cation), quaternary ammonium groups, alkylmercapto, nitrile, alkoxy, or a yloxy groups. A most particularly favoured reactive component of the formula A-j^Y is 2-methylsulphonyl- f 5-dichloro-6-methyl pyrimidine, in the condensation of which with dyestuffs or dyestuff intermediates containing amino groups, the Heterocyclic compounds of the formula (XVI) suitajjp.e for the reaction are for example 2~earboxymethylsulphonyl-4-■ehloropyrimidine, " 2-me h lsulphonyl-6-methyl-4-^chloro-pyrimidine, 2, 4-bismethylsulphonyl-6-methyl-pyrimidine, 2,6-bis-phenylsulphonyl-4-methyl-5-chloro yrimidine, 2,4» 6-trismethyl-sulphonyl-pyjamidine, 2,4,5,6-tetramethylsulphonyl-pyrimidine, 2-iaethyl9ulphonyl-4-methyl»5-nitro-6-chlo3rpyrimidine, 2-methylsuiphonyl-4, 5-dimethyl-6-chloropyrimidine, 2-ethylsulpb.onyl 4-methyl-5, 6-dichloro yrimidine, 2-methylsulphonyl- , 6-dichloro-'.pyrimidine , 2 ,4 ,6°tri3methyleulphonyl-5-chloropyrimidine, 2-methyl-sulphonyl-4-carb0xy-6-chloropyrimidine, 2-methylsulphonyl- 4-chloro-pyrimidine-5-sulphonic acid or 4,6-bia-me hylsulphonyl pyrimidine and further compounds some of which have already been mentioned on pagee11. &ή& ΛΖ÷..

The reaction betwee dyestuffs or, dyestuff intermediates containing amino groups and heterocyclic compounds of the formula (XVI) is carried out. in an organic, aqueous organic or aqueous medium at temperatures of -10°C to 80°C, depending on the employed starting compounds, preferably in the presence of alkaline condensation agents such as pyridine, aqueous alkali metal carbonate or alkali metal hydroxide solutions.

When use, is made of dyestuff intermediates, the resultant condensation products are oonverted to the desired final dye- stuffs by the usual method. This procedure is of special interest for the production of azo dyestuffs, for instance by first condensing a diazo and/or coupling component containing a reactive amino group with the reactive component (XVI) and thereafter converting the resultant intermediate to an azo dyestuff by diazotising and/or coupling and/or condensing* Further, conversion reactions which are commonly applied to asso dyestuffs may afterwards be carried out on the product, for instance acylation, condensation, reduction and metallising an intermediate product oan also first be carried- out during the production of other dyestuffs, in particular of those from the phthalocyanine and anthraquinone series, for instance condensation with m-phenylene diamine or a m-phenylene diamine sulphonio acid, and the resultant reaction product can thereafter be further condensed to form a reactive anthraquinone dyestuff, for instance with bromamine acid (l-amino-4-bromo-anthraquinone-2-sulphonie acid) or condensed with copper or nickel phthalocyanine sulphonic acid halide to form a reactive phthalocyanine dyestuff.

Another modification of the process for the production of the novel dyestuffs of the formula (XI) consists in the reaction of dyestuffs or particularly of dyestuff intermediates which contain amino groups and have a exchangeable hydrogen atom on the amino group with compounds of the general formula Ai —■——(z)t (XVII) wherein represents a pyrimfiine ring, Z denotes, a radical which can be eliminated as an anion, other than the sulphonyl radical, and t stands for the number 2 or a number greater than 2, by replacement of one of the radicals Z which can be eliminated as an anion, followed by the conversion of the remaining radical or radicals Z to a sulphonyl substituent by a method known per se, and in the case of the use of dyestuff intermediates the transformation of the latter to give the desired final dyestuffs.

The exchange of one or more substituents Z which can be eliminated as an anion, for instance of halogen atoms, for sulphonyl substituents can for instance be effected by reacting the compounds with alkyl or aryl sulphinates or, when X for instance represents an alkylmercapto or arylmercapto group which can be eliminated as an anion, these are. converted to the The dyestuffs (XI) obtainable according to the various above described processes can be subjected to further reactions .commonly applied to dyestuffs,' as already mentioned in some instances, for instance by treating metallisable dyestuffs with metal discharging agents, in particular with chromium, cobalt, copper or nickel salts, by reducing dyestuffs which contain reducible groups, in particular nitro groups, by acylating dyestuffs which contain groups that can be acylated, in particular amino groups that can be acylated, or by the subsequent -treatment of dyestuffs with sulphonating agents such as chlorosulphonic acid, thionyl chloride, oleum or SO^ in chlorinated hydrocarbons in order to introduce further sulphonic acid groups into the products. The last mentioned process sometimes. has a special significance in the series of anthraquinone and phthalocyanine dyestuffs.

Depending on the number of HNR_j-groupings which are capable of being reacted (.R_j = hydrogen or a substituent such as lower alk l radical) available for the conversion reaction in the dyestuff radical or in the dyestuff intermediates, it is possible to incorporate one or several groupings of the general formula into the dye- stuffs. In the majority of instances, tho number m will not exceed 4, but it is possible to synthesise dyestuffs, particularly those with a higher molecular structure, having more tha 4, for instance up to 8 groupings of the formula -H-A, .

When the dyestuffs (XI) prepared according to the process contain groups which can form metal complexes, these can be converted to their metal complex compounds by the action of metal discharging agents, for instance of copper, nickel, chromium or cobalt salts. They can similarly be subjected to the dyestuffs, containing amino groups, of the formula: wherein Po, 1, B ¾» r and m" have the meanings already given The condensation products obtained correspond to the general formulae (I) and (XII) for the new dyestuffs. They can be subjected to further conversion reactions, in particular subsequent sulphonation being frequently of interest in the anthraquinone and phthalocyanine dyestuffs series. Instead products in the making of such dyestuffs, containing amino groups, can be employed, condensing them first with the reactive component A-^-Y and then further working them up in a customary manner to the final dyestuffs. Such a process via the dyeetuff intermediates has outstanding interest in the production of azo dyestuffs and anthraquinone and phthalocyanine dyestuffs.

.In the case of azo dyestuffs one proceeds for this purpose in such a way. that a diazo component or a coupling component, which possesses a reactive amino group is condensed with the reactive component of the formula (XVI) and the desired azo dyeetuff is then built up by coupling. The latter can then still be metallized or diazotized and changed into a disazo- or polyazo- dyestuff. In the case of anthraquinone dyestuffs, a diamino aryl compound whose one amino group is protected, e.g. an acylamino compound whose one amino group is protected, e.g. as a acylamino reactive component (XVI), the first, protected, amino group then, converted into the free amino group for example by hydrolysis and the compound obtained condensed with for example 1- amino-4-brom0-anttaraquirione-2-sulphonic acid to a valuable type of anthraquinone dyestuf . For the production of phthalocyanine dyestuffs, in a .procedure similar to that for anthraquinone, dyestuffs, there may be produced first a diaminoaryl compound mono-condensed with the reactive component A^-Y, that ; then being condensed with, for example, copper- or nickel- phthalocyanine sulphonic acid halides; other amino compounds, such as ammonia, aliphatic amino compounds and/or aromatic amino compounds, can be employed as well, simultaneously or subsequently. ' In this way phthalocyanine sulphonamide dyestuffs are obtained which contain a certain proportion of sulphonaryl- amide groups, which carry reactive groups, besides a certain proportion of unreactive sulphonamide groups and/or free sul An especially preferred group of reactive dyestuffs within the scope of the new compounds of formula I has the composition (XVIII) m In. this formula P represents the radical of an organic dyestuff, an amino group, Z a halogen atom, Y hydrogen or a optionally substituted alkyl substituent, R denotes an aliphatic, carbooyclic or heterocyclic, substituent and m is a number from 0.5 - 8.

In the dyestuffs of the general formula (XVIII) the pyrimidine . radical is by definition linked with the dyestuff radical F .via an amino, group. The amino group can carry further substituents, such as lower alkyl- (preferably to C^), aralkyl-, oycloalkyl- or aryl groups, but is preferably present in the form -NH- which -is not further substituted.

The amino group is on its part joined directly to an aromatic ring carbon a*tom of the dyestuff or to an alkylene group.

■As reactive sulphonyl substituents -SOgR, in 2-position of the pyrimidine ring, therey may be used lower alkyl sulphonyl radicals with preferably 1 to 5 C-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 radical such as benzyl sulphonyl- and The dyestuffs of the formula (XVIII) may belong to a wide Le A 9111 variety of classes, for instance, to the series of metal free or metal containing mono- or poly-azo dyestuffs, to the metal free or metal containing azaporphine dyestuffs such as copper or nickel phthalocyanine dyeetuffs, to the anthraquinone, oxazine, dioxazine, triphenylmethane, nitro, azomethine, benzanthrone and dibenzanthrone dyeetuffs as well as to the polycyclic condensation compounds of anthraquinone, benzanthrone and dibenzanthrone compounds.. The following general compositions have inter alia proved particularly valuable within the scope of these classes of dyestuffs: 1. Azo dyestuffs wherein B and I) represent aromatic,,carbocyclic or heterocyclic radicals, for instance B the radical of a carbocyclic diazo component from the benzene or naphthalene series and D the radical of an enolic or phenolic coupling component, such as a 5-pyrazolone, an acetoacetic acid arylamide, a hydroxynaphthalene or an aminonaphthalene, etc.; in addition, B and D may contain any of the substituents usual in azo dyestuffs including further azo groups? R^ stands for a substituent or preferably a hydrogen atom; m* denotes an integer, preferably the integer 1 or 2; and A? represents the radical si nificance s ecified for is a substituent or preferab y hydrogen, and g represents number 0, 1 or 2, whilst R^ represents a substituent or preferably hydrogen, and k0 a radical Z- C N ·< \ Y~ C C-SOJB (la) wherein Q denotes a radical which can be eliminated as an anion and R, Y and Z have the above specified significance.

Among the reactive substituents Q which can be eliminated as an anion radical, special importance attaches to CI, Br and sulphonyl substituents. Other suitable radicals which can be eliminated as an anion are, for instance, P, SO^M (M=H or metal cation), quaternary ammonium groups, alkylmercapto, alkoxy a reactive amino group with the reactive component (XXII) and thereafter converting the resultant int ermediate to an azo dyestuff by diazotising and/or coupling and/or condensing.

Further conversion reactions which are commonly applied to azo dyestuffs may afterwards be carried out on the product, for instance acylation, condensation, reduction and metallising reactions. The condensation of a reactive component (XXII) with an intermediate product can also first be carried out L.e A 9111 . during the production of other dyestuffs, in particular of those from the phthalocyanine and anthraquinone series, ""for •;4nB aneii: ; epijde'nea'.tion with m-phenylene diamine or a m-phenylene diamine sulphonic acid, and the resultant reaction product ca thereafter be further condensed to form a reactive anthraquinone dyestuff, for instance with "bromamine acid ( l-amino-4- bromo-anthraquinone-2-sulphonic acid) or condensed with copper or nickel phthalocyanine sulphonic acid halide to form a reactive phthalocyanine dyestuff.

- '.'· Another modification of the process for the production of the novel dyestuffa. of the formula (XVIII) consists in the reaction of dyestuffs or particularly of dyestuff intermediates which contain am drogen atom on the amin formula wherein Y, Z and Q have the above specified significance and T denotes a radical which can be eliminated as an anion, other than the sulphonyl radical, by replacement of the radical Q which can be. eliminated as an anion, followed by the conversion of the radical T to a sulphonyl substituent SOgB by a method known per se, and in the case of the use of dyestuff intermediates the transformation of the latter to give the desired final . dyestuffs.

The exchange of a substituent T which can be eliminated as an anion, for instance of a halogen atom, for sulphonyl substituents can for instance be effected by reacting the compounds with. alkyί or aryl sulphinates or, when T for instance represents an alkylmercapto or arylmercapto group which can be eliminated as an anion, these are converted to the correspond described processes can be subjected to further reactions commonly applied to- dyeatuffs, as already mentioned in some lihsta'nce'e · p'r''-i?is ance' by. treating metallisable dyestuffe with metal' .d acharging .agents,' in particular with chromium, cobalt, copper or nickel salts, by reducing dyeatuffs which contain reducible groups., in particular nitro groups, by acyiating dyesiuffs which contain groups that can be acylated, in particular miiiio groups that can be acylated, or by the subsequent treatment of dyeatuffs with sulphonating agents such as chlorsulphonic acid, thionyl chloride, oleum or SO^ in chlorinated hydrocarbons in order to introduce further 'sulphonic acid groups into the products. The last mentioned process sometimes has a special significance in the series of anthrequinone and phthalocyanine dyeatuffs.

Depending on the number of . -HNRg groupings which are capable of being reacted (It, = hydrogen or substituent such as a lower alkyl radical) available for the conversion reaction in the dyestuff radical or in the dyestuff intermediates» it is possible to incorporate one or several groupings of the general formula (lb) into the dyeatuffs.

In the majority of instances, the number m will not exceed 4, but it is possible to synthesise dyestuffs, particularly those with a higher molecular structure, having more than 4, for instance up to 8 groupings of the formula (lb).

When. the dyeatuffs prepared according to the process contain groups which can form metal complexes, these can be converted to their metal complex compounds by the action of metal discharging agents, for instance of copper, nickel, chromium or cobalt salts. They can similarly be subjected to the other usual conversion reactions such as^diazotisation, coupling, acylation and condensation reactione.

Th n w soluble compounds they are of special interes for the dyeing of textile materials containing hydroxyl groups or nitrogen, particularly of textile materials of natural and regenerated cellulose, as well as of wool, silk, synthetic polyamide and polyurethane fibres. Due to the reactive sulphonyl substituent .or substituents in the pyrimidine ring the products are especially suitable as reactive dyestuffs for the dyeing of cellulose materials according to the techniques recently disclosed for this purpose. The fastness properties obtained, particularly the fastness to wet processing, are excellent.

For the dyeing of cellulose, the dyestuffs are preferably used in a aqueous solution which can be mixed with compounds of alkaline reaction, such as alkali metal hydroxide or alkali metal carbonate, or with compounds convertible into substances of alkaline reaction, such as alkali metal bicarbonat Further adjuvants may be added to the solution, but these must not react with the dyestuffs in an undesirable manner.

Additives of this type are, for example, surface-active compounds such as alkyl-sulphates, or compounds preventing migration of the dyestuff, or dyeing auxiliaries, suc 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, fo example, by padding on the foulard (short bath) 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 salt baths, using these methods in an desired When a padding or dyeing liquor without alkali is used, the dry goods are subsequently passed through a solution of alkaline reaction to which sodium chloride or Glauber's salt s ..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, quently treated with a solution or paste of the dyestuff and finally fixed, as stated, at an elevated temperature.

For the dyeing from a long bath, the material is introduced into an aqueous solution of the dyestuff (liquor ratio 1 : 5 to 1 : 40) at room, temperature and dyeing is carried out, possibly while raising the temperature to 85°C, for 4-0 to 90 minutes with the portionwise addition of salt, e.g. sodium sulphate, and subsequently of alkali,, for example sodium phosphates, sodium carbonate, NaOH or KOH. The chemical reaction between the dyestuff and the fibre thereby οοο Γβ. After completion of the chemical fixation, the dyed material is rinsed hot and finally soaped, whereby non-fixed residues of the dye-stuff are removed. Dyeings of excellent fastness, especially to wet processing 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 20 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 hydroxy1 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 .■ acetate, or sodium and potassium . carbonate, 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.

Textile Materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibres are generally dyed by the dyeing methods customary for this purpose in the acidic to neutral range, and 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 polyamide 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 dyestuffs 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 from 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 on 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 arabic, etc. - prints obtained on fabrics of polyamide fibres is preferably carried out at a temperature of 50 - 110°C 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 djestuffs are characterised by good to very good fastness properties, especially by excellent fastness to wet processing.

Le A 9111 The following Examples are given for the purpose of illustrating the invention, the parts being parts by weight, unless otherwise stated.

Example 1 28 Farts by volume concentrated hydrochloric acid are added to a solution of 34*7 parts 2-aminonaphthalene-4, 8-disulphoaic aoid sodium salt and 7 parte 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 excess nitrous acid, 10.7 parte 3-aminotoluene dissolved in 10 parts by volume concentrated hydrochloric acid and 150 parts water are added, and coupling is completed by neutralising the mixture to pH 3 - 5. The resultant amlnoazo dyestuff is salted out, filtered off with suction, washed and then redissolved at pH 7 is 700 parts water with the addition of a sodium hydroxide solution. The aqueous solution is then mixed with 21 parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine and vigorously stirred. The temperature of the reaction mixture is maintained at. about 65°C by heating; the liberated hydrochloric acid is neutralised with a sodium carbonate solution, until the reaction is completed. The resultant dyestuff of the probable formu is salted out with 80 parts sodium chloride, pressed off, washed and dried at about 50°C in a vacuum. It is a yellow powder which dissolves in water with a yellow colour.

When a cellulose fabric is printed with a printing paste which contains er kilo ram 1 of the d t 100 300 ml water, 500 alginate thickener (60 g sodium alginate per kg thiokener), 2 g sodium hydroxide anilO g sodium carbonate) and which has been made up with water to 1 kilogram, the fabric is then dried, steamed at 105°C for 8 minutes, 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 (prepared according to the instructions of German Patent Specification No. 1,117,235 by coupling of diazotised 1-amino-8-(benzene-sulphonyloxy)-naphthalene-disulphonic acid-( 3,6)-in a soda-alkaline medium with the equivalent amount of 2-aoetylamino-5-hydroxynaphthalene-disulphonic acid-(4,8)-, conversion of the monoazo compound into the copper complex by oxidative ooppering, and hydrolysis of the acetyl and benzene-sulphonyl groups) is dissolved at pH 6 - 6*5 in 2500 parts by volume water at 60 - 65°C and mixed at this temperature with 0.12 mol 2,4-bis-methyl-sulphonyl-6-methyl-pyrimidine.

A pH of 7 - 7«5 is maintained during the condensation by the addition of a sodium carbonate solution. When the reaction is completed, the dyestuff is salted out and isolated. When dried, the dyestuff is a dark powder which dissolves in water with a blue colour. the dyestuff, 15 g/litre sodium bicarbonate and 150 g/ litre urea, subjected to intermediate drying, heated at 140°C for 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 of the monoazo dyestuff obtained in analogy with the instructions of Example 1 by coupling diazotised 2-aminonaphthalene-4»8-disulphonic acid with 3-methylamino-toluene, are dissolved at pH 7 - 8 in 400 parts water at 60 - 65°C, the solution is mixed portionwise with a total of 25 parts 2,4-bie-aethylsulphonyl-6-aethyl-pyrimidine 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 probable SO^Na is salted out, filtered off with suction, washed and dried.

A cotton fabric is impregnated with a solution at 20 -25°C, 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 poly-oxethylated oleyl alcohol) as well as 150 g urea and 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 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, The following Table gives the diazo components, coupling components, and the reactive components whioh can be linked to the amino group, from which dyestuffs can be syn- thetised 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: 2-methylsulphonyl-4-ehloro-6- the reactive components: methyl-pyrimidine B: 2,4-bis-methylsulphonyl-6- methyl-pyrimidine l-amino-3, 6 l-amino-3-methylbenzene A disulphonic 7 B 8 2-aminonaphthalene-5,7- 1-amino-3-methylbenzene A disulphonic acid 9 B 2-aminonaphthalene l-amino-3-niethylbenzene A disulphonic acid 11 B 4-aminoazobenzene-3»41"^ l-amino-3-methylbenzene A brown - disulphonic acid yellow 13 1-aminobenzene-4-sulphonic acid —> 1-aminonaphthalene- 6-sulphonic acid l-amino-3-methylbenzene B 14 2-( 3' -sulpho-4' -aminophenyl)- 6-methyl-benzothiazole-7- sulphonic acid " A yellow 2-aminonaphthalene-4»8-di- l-methylamino-3-methoxy- sulphonic acid benzene B 16 " l-amino-3-acetylamino- benzene 17 M aniline A Example 18 Parts 2,4-bis-methylsulphonyl-6-methyl-pyrimidine are introduced with good stirring at 50 - 60°C into a solution of 36.5 parts of the sodium salt of l-amino-8-hydroxy-naphthalene 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 o.btained 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 parte. Water. The dyestuff of the formula NaO.S S0,Na formed at a final pH of about 7, is salted out with 100 parts sodium chloride, filtered off with suction, washed and dried at 30 - 40°C in a vacuum. The dyestuff forms small red needles of metallic lustre, which readily 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 subsequently adding 20 g sodium carbonate and treating the material at this temperature for 60 minutes. After rinsing, soaping at the. oil and drying, a bluish red dyeing of good fastness to wet processing, rubbingand light is obtained.

The following Table gives the shades of further dye- stuffs which are synthetised from the likewise stated diazo components, coupling components, and reactive components which can be linked to the amino group in the latter, in analogy with the . instructions of Example 18, or also by reacting the 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 Diazo Coupling Reactive Shade No, component component componen l-aminobenzene-2-sulphonic l-amino-8-hydroxy- B red acid naphthalene-3, 6- disulphonic acid aminobenzene l-( 3' -aminobenzoyl- amino )-8-hydroxy- naphthalene-3» 6- disulphonic acid 21 B r22 1-amino-2-carboxybenzene■ l-amino-8-hydroxy- A 4-sulphonic acid naphthalene-3» 6- disulphonic acid 23 1-amino-4-methylbenzene- " A 2-sulphonic acid 24 l-amino-3-acetylamino- " B benzene-6-sulphonic acid l-amino-3-(2,-[4"- " A sulphophenylamino 1- ' -chloro- triazine-1' , 3',5,-yl-6' )- aminobenzene-6-sulphonic acid 26 l-aminobenzene-2-sulphonic 2-aniino-5-hydroxy- orange acid naphthalene-7-sulphonic acid component component componenj- 1-aminobenzene-2- 2-methylamino-5-hydroxy- A orange sulphonic acid naphthalene-7-sulphonic acid l-aminq-4-acetyl- scarlet amino-6-sulphonic acid ■ . 2-amino-5-hydroxy- A M naphthalene-7- sulphonic acid Example 30 .0 Parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine are introduced with good stirring into a solution of 21 parts of the sodium salt of 1, 3-diaminobenzene-6-sulphonic acid in 100 parts water, and the mixture is stirred at 60 - 65°C, while continuously neutralising the liberated hydrochloric acid to pH 7 - 8, until diazotisation of a sample and coupling with l-hydroxynaphthalene-4-sulphonic acid yields a clear yellowish red coloration. After the addition of ice, the resultant dyestuff 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 dyestuff of the whi shed 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. logy 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 Couplin Reactive pH of. Shade No. component component component coupling medium 1, 3-diaminobenze 2-aminoriaphthalene- A 4-5 orange sulphonic acid 5 , 7-disulphonic acid 2-aminonaphthalene- A 4-5 3, 6-di sulphonic acid 33 2-aminonaphthalene- B 4-5 6-sulphonic acid 34 2-N-methylamino-8- A 4-5 hydroxynaphthalene- 6-sulphonic acid l-O'^'-dichloro-l1 , A 7-8 red 2 ' -thiazole-4 ' -carbon- amido)-8-hydroxynaph- thalene-3» 6-disulphonic acid 36 l-( 2 , , 4'-dihydroxy- B 7-8 triazine-1 ' , 31 , 5'-yl- 6 ' -amino )-8-hydroxy- naphthalene-3» 6- dieulphonic acid 37 1- ( 3 , ! 5,-dichloro-l' , A 7-8 " 2 ' -thiazole-41 -carbon- amido)-8-hydroxynaphtha- lene-3» 6-disulphonic acid 38 2-hydroxynaphthalene- A 8 scarlet 3, 6-disulphonic acid 39 l-acetylaminb-8-hydroxy-B 7-8 red naphthalene-3» 6- disulphonic acid 40 l-( 3'-sulphophenyl)-3- A 6 yellow me hyl-pyrazolone-5- 41 1-( 2 · , 5'-dichloro-4 ' - A 6 yellow sulphophenyl)-3-methyl- - Example Dlazo Coupling Reactive pH of^ Sha^ No. component component componen coupling - medium · · 42 1, 3-diaminobenzene- l-CS'.^'-disulpho- A 6 yellow 4-sulphonic acid naphth l-2'-)-3- methyl-pyrazolone-5 1-(3'-sulphophenyl)-3-, B methyl-5-aminopyrazole 44 1, 4-diaminobenzene- 2-amino-8-hydroxynaph- A 4τ·4·5 red 3-sulphonic acid thalene-6-aulphonic acid 45 2-acetylamino-5-hydroxy- naphtha1ene-7-su1phonic , ' acid A 6-7 scariei 46 M l-acetylamino-5-hydroxy- naphthalene-7- . sulphonic acid B 6-7 red ■ Example 47 51.6 Parts. of the dyestuff of the formula obtained by diazotising l-hydroxy-2-aminobenzene-4-sulphonic acid and coupling with 2-amino-5-hydroxynaphthalene-7-sulphonic 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. 25.0 Parts 2-methylsul- phonyl-4-chloro-6-methyl-pyrimidine are added at 60 - 65°C with good stirring and the liberated hydrochloric acid is continuously neutralised to pH of 7 - δ with a sodium carbonate solution. When free amino groups can no longer be detected, the resultant reactive dyestuff of the formula with this dyestuff by one of the processes described above in ruby shades fast to wet processing, rubbing and light.

The following 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 aminoazo dyestuffs and of their metal complexes, and the reaction of the latter with the reactive components can be carried out according to the instructions of Example 47.

Abbreviations for the reactive components' as in "the Table following Example 3 xample Aminoazo Complex Reactive Shade Γ.9. dyestuff linked component ■ ' ' ' '■' . ' heavy metal 8 l-hydruxy-2-aminobenzene-4,6- Cu A ruby disulphonic acid —*· 2-amino-5- hydroxy-naphthalene-7-sulphonic acid 49 l-hydroxy-2-aminobenzene-4- Cu A ruby sulphonic acid —* 2-ethylamino- 5-hydroxy-naphthalene-7-sulphonic acid 50 l-amino-2-hydroxy-6-nitro-naphthalene- 4-sulphonic acid —» 2-amino-5-hydroxy- Cu A ruby naphthalene-7-sulphonic acid 51 „ . . · Cr A greenish grey 52 l-amino-2-hydroxy-6-nitronaphthalene- 4-sulphonic acid l-amino-8-hydroxy- naphthalene- -sulphonic acid . Co B reddish black 53 l-amino-2-hydroxy-5-methylsulphonyl- Cu A violet benzene —* l-amino-8-hydroxy- naphthalene-3> 6-disulphonic acid " Co A grey 55 Cr A greenish black 56 l-amino-2-methylbenzene-4-sulphonic Cu B blue acid -→ l-amino-2-hydroxy-5-methyl- benzene -→ l-amino-o~hydroxynaph- thalene-4, 6-disulphonic acid Example Aminoazo Complex Reactive Shade No. dyestuff linked component heavy metal ' 57 l-amino-2-methylbenzene-4-sulphonic Co B grey acid l-amino-2-hydroxy-5-methyl- benzene l-amino-8-hydroxynaphth- alene-4, 6-disulphonic acid 58 Cr greenis black 59 ( l-aminp-2-chlorobenzene-4-sulphonic acid l-hydroxy-2-acetylaminobenzene) , hydrolysed, l-amino-8-hydroxy- naphthalene-3, 6-disulphonic acid navy blue 60 Co A grey 61 1-amino-8-hydroxynaphthalene-4- Co A black sulphonic acid <~ l-hydroxy-2, 6- diaminobenzene-4-sulphonic acid —?> 1, 3-dihydroxybenzene 62 l^amin0-8-hydroxynaphthalene-3> 6- Co A w disulphonic acid l-hydroxy-2, 6- diaminobenzene-4-sulphonic acid 2-hydroxy-naphthalene 63 l-amino-8-hydroxynaphthalene-4- Co ; A " sulphonic acid l-hydroxy-2, 6- diaminobenzene-4-sulphonic acid 3-methyl-pyrazolone-( ) Example 64 96 Parts (referred to 100^ goods) of the copper- phthalocyanine tetrasulphochloride freshly prepared in the usual manner by the reaction of chlorosulphonic acid and thionyl chloride with copper-phthalocyanine, or of the isomeric copper-phthalocyanine tetrasulphochloride synthetised from l-sulphobenzene-3» 4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulphonic acid, are suspended in the form of the moist thoroughly washed filter cake in 500 parts water and 500 parts ice, a solution of 50 parts of the sodium salt of 1, 3-diaminobenzene-4-sulphonic acid 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 con tion product is precipitated at pH 1 - 2 by the addition of sodium chloride, filtered off with suction, washed, and then rediss lved neutral in 1000 parts water. 71 Parts 2,4-bis-methyl^sulphonyl-6-methyl-pyrimidine are introduced into the blue solution with intense stirring, and the reaction mixture is stirred at 60 - 65°C while continuously neutralising it to pH 7 - 8 by means of a sodium carbonate solution, until free ff 4-n n~2-3 thus obtained, is salted out, washed and dried at 30 - 40°C in a vacuum. It is a dark blue powder which dissolves in water with a blue colour and dyes cotton and regenerated cellulose 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 copper- or nickel-phthalocyanine, in the form of the moist 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 trisulpho-chloride and using 90 parts of the sodium salt of 4,4'-diamino- parts of the sodium salt of 1, 3-diaminobenzene-4-sulphonic a id, 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 41, 4", 4'"> 4HW-tetraphenyl-Cu-phthalocyanine is Used as starting material, sulpho-chlori ation and reaction with 1, 3-phenylene-diamine-4-sulphonic acid, followed by acylation with 2, 4-bis-methylsulphonyl-6-methyl-pyrimidine 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 l-amino-4-bromo-anthraquinone-2-sulphonic acid with an excess of 4,4l-diamino-diphenyl-2,2l-disulphonic acid are dissolved in 700 parts water, 25 parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine are added at 60 - 65°C with good stirring, . and a pH of 7 - 7.5 is maintained by the 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. sulphonic acid, similar dyestuffs are obtained, which likewise yield blue dyeings with fastness properties similar to those of the dyestuff obtained above: l-amino-4-( 4 ,-amino-2'-8ulphophenylamino)-anthraquinone-2-sulphonic acid, l-amino-4-( 4 · -aminophenylamino )-anthraquinone-2 , 6-disulphonic acid, isomer mixture of 1-amino-4-(4 ' -aminophenylamino )-an.thraquinone-2,5- and 2, 8-disulphonic acid, isomer mixture of 1-amino-4-( ' -amino-2 * -sulphophenylamino)-anthraquinone-2, 5- and -2, 8-disulphonic acid, isomer mixture of l-amino-4-( 3' -aminophenylamino )-anthraquinone-2, 5- and -2, 8-disulphonic acid, l-amino-4 -( 3' -aminophenylamino )-anthraquinone-2, 6-disulphonic acid, l-amino-4-(3'-amino-4'- sulphophenylamino)-anthraquinone-2-sulphonic acid. With 1-amino-4-(4,-l4H-amino-2H-sulphophenyl}aminophenyl)-anthraquinone-2,6-disulphonic acid there are obtained reactive dyestuffs which dye in bluish grey shades.

Example 66 When the procedure described in Example 47 is followed, but using, instead of the copper-containing amino-monoazo dyestuff there employed, the equivalent amount of the chromium complex of the aminoazo dyestuff obtained by coupling diazotised l-amino-2-hydroxy-3-chlorobenzene-5-sulphonic acid with 1- 3'-aminophe.nyl)7-3ulplionylimido-sulphonyLphenyl-3-methyl-pyrazolone-(5), a reactive dyestuff is obtained, which dyes cellulose materials by one of the processes described above in yellow-brown shades of good fastness to wet processing, rubbing and light.

Example 67 0.1 Mol of the copper complex compound of the formula is dissolved at pH 6 in 3000 parts by volume water and the solution is combined at a temperature of about 60°C, while stirring, with 21 parts (0.1 mol) 2-methyl-sulphonyl-4-chloro-6-methyl-pyrimidine.. 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 dye-stuff and 0.5 of a non-ionic wetting agent (e.g. a polyoxethy-lated oleyl alcohol), 150 g urea and 20 g sodium carbonate.

The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100$. After an intermediate dyring 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, rubbing 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 Le A 9111 which is obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene-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 25 parts 2,4-bis-methylsulphonyl-6-methyl-pyrimidine. The reaction mixture is stirred at 60 — 65°C, until the condensation is completed, while maintaining the pH of the reaction solution at 7 - 7.5 by the addition of sodium carbonate.

When the reaction is completed, the dyestuff is salted out, isolated and dried in a vacuum.

The dry dyestuff is a dark powder which dissolves in water with a violet colour and dyes cotton in 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 22 parts by weight 2-methylsulphonyl4-chloro-6-fliethyl. pyrimidine. A pH of 7 - 7.5 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 colour. Cotton fabrics are 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.25 parts 2, 4-bis-methylsulphonyl-6-methyl- pyrimtdine and stirred at 50 - 55°C, while continuously neutralising the methane-su-lphinic acid formed with a total of 34 parte b volume of a 16% sodium carbonate solution to pH 6-7. The acylatioii is completed after a short time, the pH is 6 and changes no more.

Parts sodium bicarbonate are then added, and the diazo suspension prepared from 34 parts of the disodium salt of 2-aminonaphthalerie-l,7-disulphonic acid in 200 parts water is added dropwise at 20°C within 15. minutes. The orange- coloured reactive dyestuff of the foririula which is immediately formed is completely separated, after further stirring for one hour, by the addition of 80 parts sodium chloride, filtered off, washed with a dilute sodium chloride solution, and dried at 35°C in a vacuum. The dyestuff dyes cellulose materials by the processes described above in reddish orange shades of very good fastness to wet processing and good fastness to chlorine.

When equivalent amounts. of 2-methylsulphonyl-4-chloro- 6-methyl-pyrimidine are used in this Example, instead of 25 parts 2,4-bis-raethylsulphonyl-6-methyl-pyrimidine, a reactive dyestuff is obtained which dyes in orange shades and whose of the bis-methylsulphonyl derivative.

Orange to red reactive dyestuffs are obtained in an analogous manner by a.cylating the aminonaphthol-sulphonic acids listed in Column 3 of the following Table with 2, 4-bis-methyl- sulphonyl-6-methyl-pyrimidine and coupling .the acylamino-naphthol sulphonic acids formed with the diazo components stated in Column 2.

Example Diazo Aminona hthol- Shade on No. component sulphonic acid cotton 2-aminonaphthalene-1,7- 2-ettaylamino-5-hydroxy- orange disulphonic acid naphthalene-7-sulphonic acid 72 2-(p-hydroxyethylamino)- " -bydroxynaphtha1ene-7- i sulphonic acid 73 2-amino-5-hydroxynaphtha- M lene-7-sulphonic acid 74 2-amino-5-hydroxynaphtha- " lene-l,7-disulphonic acid 75 2-amino-8-hydroxynaphtha- scarlet lene-6-sulphonic acid 76 2-amino-8-hydroxynaphtha- " . lene-3» 6-disulphonic acid 77 2-aminona phthalene-l, 5- 2-methylamino-5-hydroxy- orange disulphonic acid naphthalene-7-sulphonic acid 7i 2-ethylamino-5-hydroxy- " naphthalene-7-sulphonic acid 79 2-(fi-hydroxyethylamino)- " -hydroxynaphtha lene-7- sulphonic acid 80 2-amino-5-hydroxynaptha- " lene-7-sulphonic acid 81 2-amino-5-hydroxynaphtha- " lene-l,7-disulphonic acid 82 2-aminonaphthalene- 2-amino-8-hydroxynaphtha- Scarlet 1, 5-disulphonic acid lene-6-sulphonic acid 8.3 2-amino-8-hydroxynaphtha- " lene-3, 6-disulphonic acid 84. 2-aminonaphthalene-l, 5,7- 2-enino-5-hydroxynaphtha- orange Example Diazo Aminonaphthol- <&hade on No. component sulphonic acid cotton 85 2-aminonaphthalene-l, 5,7* 2-methylamino-5-hydroxy- orange trisulphonic acid naphthalene-7-sulphonic acid 86 2-amino-8-hydroxynaphtha- scarlet lene-6-sulphonic acid 87 2-aminobenzene-sulphonic 2-methylamino-5-hydroxy- orange acid napht¾alene-7-sulphonic acid 88 2-(0-hydroxyethyiamino)- w -hydroxynaphthalene-7- sulphonic acid 89 2-amino-8-hydroxynaphtha- scarlet lene-6-sulphonic acid 90 2-amino-8-hydroxynaphtha- lene-3, 6-disulphonic acid 2-amino-5-hydroxynaphtha- ttrange lene-l,7-disulphonic acid 92 2-aminonaphthalene-l- l-amino-8-hydroxyna htha- bluish sulphonic acid lene-3, 6-disulphonic acid red 93 l-amino-8-hydroxynaphtha «1 lene-4, 6-disulphonic acid 94 2-aminonaphthalene-l, 5" l-amino-8-hydroxynaphtha II disulphonic acid lene-3,6-disulphonic acid 95 l-amino-8-hydroxynaptha- lene-4 , 6-disulphonic acid 96 l-amino-8-hydroxynaphtha- lene-6-sulphonic acid 2-aminonaphthalene l-amino-8-hydroxynaphtha II disulphonic acid lene-3» 6-disulphonic acid 98 l-amino-8-hydroxynaptha- lene-4, 6-disulphonic acid 99 l-amino-8-hydroxynaphtha It lene-6-sulphonic acid 100 2-aminonaphthalene-l, 5,7- l-amino-8-h droxynaphtha trisulphonic acid lene-6-sulphonic acid 101 1-amino-4-chlorobenzene- l-amino-8-hydroxynaphtha II 2-sulphonic acid lene-3, 6-disulphonic acid 102 l-amino-2-methox -benzene- l-amino-8-hydroxynaphtha- 5-sulphonic acid lene-3, 6-disulphonic acid 103 l-amino-benzene-2-carboxylic l-amino-8-hydroxynaptha- acid-4-sulphonic acid lene-3, 6-disulphonic acid Example 106 ^ 56.8 Parts of the diaminoazo dyestuff obtained by coupling of diazotised l-amino-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.25.0 parts 2,4-bis-methylsulphonyl-6-meth lT-pyrimidine, the reaction mixture is stirred at 60°C for about one hour, while continuously neutralising the liberated sulphinic acid to pH 7 - 7.5 with a sodium carbonate solution. When the acylation is completed, the resultant reactive dye-stuff of the formula is salted out, filtered off, redissolved in 4000 jaarts 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 22 Parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine are added to a neutral solution of 60 parts of the trisodium salt of the amino azo dyestuff obtained by coupling diazotised 2-aminonaphthalene-3,6,8-trisulphonic acid with 3-ace¾rlamino-anilirie in an acetic acid medium, in 5Θ0 parts water, and the reaction mixture is stirred at 65°C for one hour, while maintaining a pH value of 7 - 7.5 by the continuous addition of a sodium hydroxide solution. The partially precipitated purification, the reactive dyestuff thus obtained can be re-dissolved in 2500 parts water at 30°C, clarified and separated again by salting out the filtrate with 350 parts sodium chloride. The dyestuff has the formula s ρΗ after filtering, drying at 35°C and grinding, it is a yellow powder 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 very fast reddish yellow shades. Fast yellow shades are also obtained on wool and polyamide fibres.

Similar dyestuffs are obtained by proceeding as described above, but using, instead of 60 parts 4'-amino-2'-acetylamino-phenyl-d' )-azo-naphthalene-(2 )-3, 6,8-trisuiphonic acid sodium salt, corresponding amounts of the aminoazo dyer 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 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine.

Le A 9111 -62- 117 3>-eminopb.enyl urea 118 l-amino-3-hydroxyacetyl- aminobenzene 119 1-aminona phthalene- l-amino-3-methyl-6- strongly 3, 7-disulphonic acid methoxybenzene reddish yellow 120 l-amino-3-methylbenzene reddish yellow 1-aminona phthalene- 1-aminonaphthalene-6 reddish 3, 7-disulphonic acid sulphonic acid yellow 122 2-aminonaphthalene-3 l-amino-3-methylbenz disulphonic acid 123 l-amino-3-methyl-6-methoxy- strongly benzene reddish yellow 124 l-amino-3-acetylamino- reddish benzene yellow 125 3-aminophenyl urea 126 l-amino-3-hydroxyacetyl aminobenzene 127 1-aminonaphtha lene-6- sulphonic acid 129 n l-amino-2-methoxynaphtha- Strongly lerie-6-sulphonic acid reddish yellow 130 H 1-aminonaphthalene-6- reddish sulphonic acid yellow 131 2-aminona hthalene-4, 8- ' l-aminonaphthalene-6- yellow disulphonic acid sulphonic acid 132 II l-aminonaphthalene-7- II sulphonic acid 133 2-aminonaphthalene-4, 8- l-amino-2-methoxynaphtha- strongly disulphonic acid lene-6-sulphonic acid reddish yellow 1 •34 l-methylamino-3-methyl- benzene yellow 135 2-aminonaphthalene-4,8- l-ethylamino-3-methyl'benzene " disulphonic acid 136 N-methylaniline I, 137 II N-ethylaniline 138 II N-(β-hydroxyethyl )-aniline 139 II N-butylaniline 140 2-aminonaphthalene- . aniline reddish 3, 6, 8-trisulphonic acid yellow 141 II l-amino-3-methylbenzene It 142 3-aminophenyl urea reddish yellow 143 l-amino-3-hydroxyacetyl- aminobenzene 144 1-amino-3-ace ylamino-6- yellowish methoxybenzene orange 145 l-amin6-3-acetylamino-6- reddish methylbenzene yellow 146 l-amino-3-methane-sulphonyl- aminobenzene 147 2 , -dimethoxyaniline yellowish orange 148 3-methyl-6-methoxyaniline 149 N-methylaniline reddish ellow Example Diazo Coupling S No. component component cotton 150, 2-aminonaphthalene- N-ethylaniline reddish 3,6i8-trisulphonic acid yellow 151 N-butylaniline 152 N-(p -hydroxyethyl )-aniline 153 3-( N-ethylamino )-toluene 2-aminotoluene l-amino-2, -dime hyl- strongly benzene reddish yellow 156 l-amino-2-methoxybenzene 157 1-amino-3-methoxybenzene reddish yellow l^ l-ethylamino-3-methoxy- benzene 159 . l-aminonaphthalene-6- sulphonic acid 160 1-aminonaphthalene-7- sulphonic acid 161 2-aminonaphthalene-4, 6,8- l-amino-3-methylbenzene reddish trisulphonic acid yellow 162 l-amino-3-acetylaminoben- zene 163 1-aminonaph halene-2, » 7- l-amino-3-methylbenzene yellow trisulphonic acid 164 l^-aminona hthalene-6- sulphonic acid 165 4-nitro- ' -aminostilbene- l-amino-3-acetylamino- reddish 2, 2' -disulphonic acid benzene yellow 166 3-aminophenyl urea 1167 l-amino-3-hydroxyacetyl- aminobenzene 168. 4-nitrb- 1 -aminostilbene- N-methylaniline 2, 2' -disulphonic acid 169 N-ethylaniline 170 N-butylanilaniline 171 N-(|?-hydroxyethyl )-aniline 172 1-(N-ethylamino )-3-methyl- benzene Example Diazo Coupling Sbyde on No. component component cotton 174 aniline-2 , 5-disulphonic l-aminonaphthalene-7- reddish acid sulphonic acid yellow 175 l-amino-3-methylbenzene yellow 176 l-amino-3-acetylamino- M benzene 177 l-amino-2-metbay-5-methyl- reddish benzene yellow 178 l-amino-2, 5-dimetboxy- M benzene 179 aniline-2, 4-disulphonic l-amino-2-methoxy-5-methyl " acid benzene Example 180 65 Parts of the dyestuff NaC S (prepared by coupling of diazotised l-hydroxy-2-aminobenzene- ,6-disulphonic acid with 2-amino-8-hydroxynaphthalene-6- sulphonic acid and coppering of the resultant azo dyestuff) are dissolved neutral in 700 parts water. 22 Parts 2-methyl- sulphonyl-4-chloro-6-methyl-pyrimidine are added and the reaction mixture is stirred at 60 - 65°C, while continuously neutralising the liberated acid to pH 7 - 7.5 with a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive dyestuff of the formula is salted out, filtered off, washed and dried at 30 - 40 C.

Dyestuffs 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-benzene- 2-methylamino-5-hydroxy- ruby 4-sulphonic acid naphthalene-7-suiphonic acid Ί82 2-ethylamino-5-^hydroxy- naphthalene-7-sulphonic acid 183 2-(ft-hydroxyethylamino)- 5-hydroxynaphthalene-7- sulphonic acid 184 2-amino-8-hydroxynaphtha- lerie-3» 6-disulphonic acid 185 l-hydroxy-2-amino-benzene- 2-amino-5-hydroxynaphtha- 4, 6-disulphonic acid lene-l,7-disulphonic acid 186 2-amino-8-hydroxynaphtha- lene-3, -disulphonic acid 187 2-methylamino-5-hydroxy- naphthalene-7-sulphonic acid 188 2—ethylamino-5-hydroxy- naphthalene-7-sulphonic acid 190 l-hydroxy-2-amino-benzene- l-amino-8-hydroxynaphtha- violet 4, 6-disulphonic acid lene-3» 6-disulphonic acid 191 l-amino-8-hydroxynaphthalene- " 4, 6-disulphonic acid 192 l-hydroxy-2-amino-benzene- l-amino-8-hydroxynaphtha- " -sulphonic acid lene-3» 6-disulphonic acid 193 l-amino-8-hydroxyna htha- " lene-4, 6-disulphonic acid 194 l-hydroxy-2-amino-4- l-amino-8-hydroxynaphthalene bluish acetylaminobenzene-6- 3, 6-disulphonic acid violet sulphonic acid Example Diazo Coupling Enade on No. componen component cotton 195 l-hydroxy-2-amino-4- l-ethoxy-8-hydroxynaphtha- bluish acetylaminobenzene-6- lene-3, 6-disulphonic acid violet sulphonic acid ■ ( 4-positioned acetylamino group subsequently hydrolysed) 196 l-amino-8-hydroxynaphthalene blue 2, 4-disulphonic acid 197 " l-amino-8-hydroxynaphthalene- " ' 2 4,6-trisulphonic acid 198 i-hydroxyr2-amino-6- l-amino-r8T-hydroxynaphthalene - " acetylaminobenzene-4- 2, 4-disulphonic acid sulphonic acid (6-positioned acetylamino group hydrolysed)' 199 l-amino-2-hydroxy-6- " " nitrona phthalene-4- sulphonic acid (6-positioned nitro group subsequently reduced to -NI^) 2££> l-amino-2-hydroxy-6- l-amino-8-hydroxynaphthalene- " nitronaphthalene-4- 2, 4, 6-trisulphonic acid . sulphonic acid (6-positioned nitro. group subsequently reduced to -NHg ) 201 -hydroxy-2-amino-6-ace¾rl- M " aminobenzene-4-sulphonic acid (6-positioned acetylamino group hydrolysed) , Example 202 The procedure is the same as that described in Example , but the diazotised, reactive group-containing intermediate product is coupled in a soda-alkaline medium with 40 parts of ^ the sodium salt of l-acetylamino-8-hydroxy-naphthalene-3,6- disulphonic acid, instead of with 47 parte of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3> 6-disulphonic acid, and the resultant dyestuff of the formula. is isolated in the manner described in Example 30. The water- soluble dyestuff dyes -cellulose materials by the pad-steam ° - Example 203 f ' " A solution of 19.5. parts of the sodium salt of 1-amino-benzene-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 diazb 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 mixture is" neutralised at 10 - 20°C to pH 4 by the careful addition of a 0 sodium hydroxide solution. The coupling is rapidly com-pleted; the resultant amino azo dyestuff is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redissolved in 500 parts water at 10°C and pH 6 - 7. The aqueous solution is mixed with 25.0 parts 2,4-bis-methyl-sulphonyl-6-methyl-pyrimidine and stirred at 55 - 60°C for one hour, while continuously neutralising the liberated acid to pH 7 - 7.5 with a sodium carbonate solution. When the amino-azo dyestuff can no longer be detected, the partially precipitated reactive dyestuff of the formula is salted out with 40 parts sodium chloride, filtered off and redissolved 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 dyeing processes described above in the presence of acid-binding agents in yellow shades of very good fastness to wet processing, light and chlorine. Past yello dyeings are also obtained on wool arid polyamide fibres.

By proceeding as described above, but coupling, 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-sulphonic acid, and acylating with 2, 4-bis-methylsulphonyl-6-methyl-pyrimidine, valuable yellow to brown reactive dyestuffs are also obtained.

Diazo component Shade on cellulose fibre 1-aminobenzene-2,5-disulphonic acid reddish yellow 2-amino-napthalene-4, 8-disulphonic acid strongly reddish yellow 2-amino-naphthalene-5»7-disulphonic acid 2-amino-naphthalene-6, 8-disulphonic acid 2-amino-naphthalene-3» 6,8-trisulphonic acid 2-amino-naphthalene-4, 6, 8-trisulphonic acid 4-amino-azobenzene-3» '-disulphonic acid yellowish brown 4-amino-2-acetylamino-azobenzene-2' ,5'- disulphonic acid orange-brown reddish brown ( l-aminobenzene-2, 5-disulphonic acid coupled in an acidic medium with 1- amino-naphthalene-6-sulphonic acid ) Le A 9111 -70- Diazo component Shade on cellulose fibre reddish brown ( l-aminobenzene2, 5-disulphonic acid coupled in an acidic medium with the technical mixture of 1-aminonaphthalene- 6- and -7-sulphonic acid) -NH violettish brown ( l-amino-naphthalene-2, 5 >7-trisulphonic acid coupled in an acidic medium with l-amino-naphthalene-6-sul honic acid) reddish brown ( l-amino-naphthalene-2, 5, 7-trisul honic acid coupled in an acidic medium with l-amino-2-methoxy-5-methylbenzene ) Example 204 When a cellulose fabric is printed with a printing paste which contains, per kilogram, 30 g of the dyestuff described in Example 18, 100 g urea, 300 g water, 5C0 g alginate thickener (60 g sodium alginate per kg thickener), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitrobenzene-sulphonic acid, and which has been made up with 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 bluish red print of good fastness to wet processing, rubbing and light is obtained.

Example 205 A mixture of the solutions of 65.5 parts each of the 2 : chromium complex and the 2 : 1 cobalt complex of the dyestuff of the in 400 parts water each time is stirred with 50 jiarts finely powdered 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine at 60 - 70°C for about 2 hours, while maintaining a pH of 7 - 8.

When no' more amino azo dyestuff can be detected chromato-graphically (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 following aminoazo dyestuffs: Diazo component Coupling component Coupling pH l-hydroxy-2-amino-4- l-hydroxy-8--amino-naph- 9 nitrobenzene thalene-3, 6--disulphonic acid l-hydroxy-2-amino-4- 9 nitronaphthalene-7-sulphonic acid Example 206 .0.Parts 2, 4-bis-methylaulphonyl-6-methyl-pyrimidine aire. added to a neutral solution of 53· 15 parts of the disodium sal of the aminoazo dyestuff obtained by coupling of diazo-tised l-amino-4-nitrobenzene-2-sulphonic acid with l-(2' -chloro-, ' -sulph phenyl)-3-methyl-pyrazolone-( )- and subsequent reduction of. the nitro group with sodium sulphide, in 300 parts water, and the mixture is stirred at 55 - 60°C for one hour, while continuously neutralising the liberated acid to a pH The separated 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 60°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, rubbin and light.

Valuable new reactive dyestuffs are also obtained by proceeding as described above, but using, instead of the stated aminoazo dyestuff, equivalent amounts of the aminoazo dye-stuffs synthetised from the components given in the following Table.

In the Table the ter "hydrolysed" means that an acylamine group contained in the aminoazo dyestuff is subsequently group contained in the diazo component 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 component coupling cellulose medium 207 1- amino-4-nitro-benzene- l-( 4' -sulphophenyl ) - 5 - 6 yellow 2- sulphonic acid 3-methyl-pyrazolone- (5) ( -positioned nitro group subsequently reduced) 208 l-( 4' -sulphophenyl )-3- 5 - 6 reddish carboxy-pyrazolone-( ) yellow 209 l-( 3' -sulphophenyl )-3- raeth l-5-amino-pyrazole 210 l-amino-3-acetyl-amino- 6 - 7 4 benzene-6-sulphonic acid ( 3-positioned acetylamino group subsequently hydrolysed) 211 l-(j? -hydroxymethyl)-3- 5 6 methyl-pyrazolone-( 5 ) 212 2 mol l-amino-3-acetyl- 1 mol bis-pyrazolone 5 6 amino-benzene-6-sulphonic from 4, 1 -bis-hydrazinorr acid (hydrolysed) dibenzyl-2, 2 · -disulphonic acid and acetoacetic ethyl ester 213 1 mol l-amino-3-acetyl- l-( 4' -sulphophenyl )-3- 5 - 6 amino-benzene-6-sulphonic carboxy-pyrazolone-( ) acid (hydrolysed) 214 l-amino-5-a cetyl-amino- l-( 4* -sulphophenyl)-3- 5 - 6 naphthalene-3»7-disulphonic carboxy-pyrazolone-( 5 )· acid (hydrolysed) l-amino-2-methyl-benzene- 2-acetylamino-5-naphthol-7 - 8 orange 4, 6-disulphonic acid 7-sulphonic acid (hydrolysed) 216 2-acetylaminO-3-na phthol- 6-sulphonic acid 7 8 red (hydrolysed) 217 l-amino-2-methyl-benzene-4 , 6- l-chloro-2-acetyl- 7 8 orange disulphonic acid amino-5-naphthol-7- sulphonic acid (hydrolysed) 218 l-aminobenzene-2-rsulphonic l-acetylamino-8-hydroxy- 7 - 8 red acid naphthalene-4, 6-disulphonic acid (hydrolysed) 219 2-aminonaphthalene 7 8 bluish disulphonic acid red 220 2-aminona hthalene 7 - 8 Example Diazo Azo pH of Shade οη No. componen component coupling cellulose medium 2-aminbnaphthalene- 1-acetylamino-8- 7 - 8 bluish 4, 8-disulphonic acid hydroxy-naphthalene- red 4.6-disulphonic acid ( hydrolysed) 2-aminonaphthalene-3» 6- l-acetylamino-8- 7. - 8 disulphonic acid : hydroxynaphthalene-3» 6- disulphonic acid (hydrolysed) 2-aminonapbthalene-4, 8- l-acetylamino-8-hydroxy- 7 - 8 disulphonic acid naphthalene-3» 6-disulphonic acid (hydrolysed) 1-amino-4-methoxy-benzene- 2-( N-acetyl-N-methyl- 7 - 8 yellowish 2-sulphonic. acid amino )-5-hydroxy- red naphthalene-7-sulphonic acid (hydrolysed) 2-( N-acetyl-N-methyl-amino )- 8-hydroxy-naphthalene-6- sulphonic acid, (hydrolysed) 7 - 8 red l-aminobenzene-2-sulphonic " 7 - 8 acid l-aminobenzene-3-sulphonic 7 - 8 acid l-aminobenzene-4-sulphonic acid 7 8 1-amino-4-methyl-benzene- 7 8 2-sulphonic acid l-amino-2, 4-dimethyl-benzene- 6-sulphonic acid 2-( N-acetyl-N-methyl- 7 - 8 amino )-8-hydro yna phtha- lene-6-sulphonic acid (hydrolysed) 2-acetylamino-8- 7 - 8 hydroxynaphthalene-6- sulphonic acid (hydrolysed) 2-acetylamino-8- 7 - 8 hydroxynaphthalene-3,6- disulphonic acid . (hydrolysed) 233 4-aminoazobenzene-3» 1 - l-amino-3-acetyl- 5 - 6 yellowish disulphonic acid aminobenzene bisown 234 l-amino-3-hydroxy- 5 - 6 acetylaminobenzene 235 l-amino-naphthalene-6- 5 - 6 sulphonic acid Diazo Azo pH of . Shade on componen component coupling cellulose medium -ami oazobenzerie- 1-amino-na hthalene- 5 - 6 yellowish , 4-di.sulphonic ac: 7-sulphonic acid- , brown l-amino-2-( 41 -amino- 2 · -sulphophenyl-( 1 ' )- azo )-8-hydroxynaphtha- lene-3, 6-disulphonic acid Example 238 52.4 Parts of the disodium salt of, 4-(; 4"-amino-phenyl - amino)-2*-nitrb-diphenylamine-3»4' -disulphonic acid are dissolved in 1000 parts water and the solution is stirred with 25.0 parts 2,4-bis-methylsulphonyl-6-methyl-pyrimidine at 55 - 65°C for one hour, while continuously neutralising the liberated acid to' a pH value of 6.5 - 7.5 with sodium carbonate. The resultant is salted out, filtered off, washed and dried. It dyes cellulose fibres from a long bath or by. one of the conventional padding processes in the presence of sodium carbonate as acid- binding agent in deep violet-brown shades fast to wet processing and" rubbing.

Example 239 A neutral solution of 54.7 parts of the disodium salt of l-araino-4-( ' -methyl-3' -aminophenyl j-amino-anthraquinone- 2, -disulphonic acid in 1000 parts water is stirred with 22.0 parts 2-methylsulphonyl-4-chloro-6-methyl-pyriniidine at 65°C for one hour, while continuously neutralising the liberated hydrochloric acid to a pH value of 6.5 -7.5 with a sodium carbonate solution. When the reaction is completed, 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 dyestuffs 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 2-methyl-sulphonyl-4-chloro-6-methyl-pyrimidine: Example tfater-soluble amino-anthra uinone derivative No. l-amino-4-( 3' -aminophenyl )-amino-anthraquinone, 2, 5' - disulphonic acid. l-amino-4-( 2 ' -chloro-31 -aminophenyl )-amino-anthraquin one-2, 51 -disulphonic acid l-amino-4-( 2 · -methyl-3 ' -methylaminophenyl )-amino- anthraquinone-2, 5 ' -disulphonic acid l-amino-4-( 4 ' -aminophenyl )-amino-anthraquinone-2 ,6,3' trisulphonic acid l-amino-4-( 3' -aminophenyl )-amino-anthraquinone-2, 6, 4 ' trisulphonic acid ' 1-amino-4-( 4 '-aminophenyl )-amino-anthraquinone-2, 5, 3' trisulphonic acid l-amino-4-( 3 ' -aminophenyl )-amino-anthraquinone-2 , 5» 4 ' trisulphonic acid mixture of l-amino-4-( 3' -aminophenyl )-amino-anthra- quinone-2, 4', 5- and 2, 4 ' , 8-trisulphonic acid furthermore the derivatives subsequently sulphonated at 20 - 30°C Example Water-soluble amino-anthraquinone derivative^ No. W 249 l-anatio-i-C^'-methylaminophenylJ-amino-anthraquinone^^ sulphqnic acid 250 l-amino-4-( 3,-niethylam nophenyl)-amino-anthraquinone- 2-sulphonic acid 251 l-amino-4-( 2 · -mettaylaminophenyl-amino-anthraquinone- 2-sulphonic acid 252 l-amino-4-(7 ' -amino-naphthyl-rf ? · j )-amino-anthraquinone- 2-sulphonic acid 253 the condensation product obtained from 1 mol cyanuric chloride with 1 mol 1, 4-diamino-anthraquinone-2- sulphonic acid, 1 mol aniline-2, 5-disulphonic acid and 1 mol ethylene-diamine (one-sided), yields, after acylation with 2,4-bis-methylsulphonyl-6-methyl pyrimidine, a violet reactive dyestuff.

Example 25 * A solution of 107 g of a mixture of equal molar proportions of copper-phthalocyanine-trisulphonic acid-( 3, 3' , 31' )-mono-(m-amino-£-sulphophenyl)-amide and copper-phthalocyanine-trisulphonic acid-( 3, 3' , 3" )-di-(m-amino-£-sulphophenyl)-amide is adjusted to 1-3 litre and pH 7; 40 parts 2,4-bis-methyl-sulphonyl-6-methyl-pyrimidine are introduced at 50 - 55°G.

While stirring, the temperature is raised every hour by 5°C and finally maintained at 65 - 70°C for several hours. At the same time, a pH of about 6.5-7.5 is maintained by the dropvnse addition of 3N NaOH, until, on average, each dyestuff molecule is provided with at least one pyrimidine radical; this can easily be ascertain by the consumption of sodium hydroxide solution, on the one hand, and by an amino group determination, on the other hand. For working up, the dyestuff solution can also be slightly heated at the stated pH, without substantially, reducing the reactivity of the dyestuffs towards cellulose. The separation of the unreacted 2, 4-bis-methylsulphonyl-6-methyl-pyrimidine tated by introducing 150' g sodium chloride per litre dye-stuff solution. The product is filtered off with 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 starting materiel 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-phthalocyanine-trisulphonic acid chloride at 0 - 20°C and at a pH of about 6.5 and simultaneously catalysing the 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 i a molar ratio of 4- : 1 is used as starting material. This mixture is obtained from the same copper-phthalocyanine-trisulphonic acid chloride and 2 mol 2,4-diaminobenzene-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 ' , 4M ) or from the phthalocyanine-tetrasulphonic acid chlorides -( 3,4' ,4", 4" ' ) or -(4,4' ,4" ,4" ' ), or with the use of other arylene-diamine-eulphonic acids, such as toluylene-diamine-(2,4)-sulphonic acid-(5); 4,4'-diamino-dibenzyl-disulphonic acid-(2,2'), naphthylene-diamine-(l,5)-disulphonic acid-(3»7)-. Products of this type sulphonyl-6-methyl-pyrimidine or 3>6-bis-methylsulphonyl-; pyridazine can always be carried out in the same manner. .

This applies also to the reaction of 2-methylsulphonyl 4-chloro-6-methyl-pyrimidine with the copper- and nickel-phthalocyanine intermediates leading to green reactive dyestuffs such as can be obtained e.g. by polysulphdchlorination of tetra-( 3t 3' » 3" , 3" ' )-(j>-tolylmercapto )-copper-phthalocyanine with chiorosulphonic acid, condensation of 1 to 2 sulphochloride groups per molecule with 1, 3-pbenylene-diamine-4-sulphonic acid or l,4-phenylene-diamine-3-sulphonic acid, and hydrolysis o 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 nickel-)-phthalo cyanine can be converted into valuable green reactive dyestuffs in an analogous manner by acylation of their amino group with 2, -bis-methylsulphonyl-6-methyl'-pyrimidine .

Example 25 .

When the procedure described in Example 18 is followed, with the difference that the resultant dyestuff intermediate is not coupled with the diazo compound obtained from 17.5 parts 2-aminobenzene-sulphonic acid, but with the 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 dyestuff of the formula with which cellulose materials can be dyed or printed from a long bath at 40°C or according to one of the padding or print fast to wet processing.

In an analogous manner there are obtained from the coupling components stated in the following Table, by acylation of their amino groups with 2-methylsulphonyl-4-chloro-6-methyl- pyrimidine and coupling of the resultant dyestuff intermediates with the stated diazo components, valuable reactive dyestuffs with which cellulose materials can be dyed or printed, preferably in the presence of sodium carbonate, in the specified shades : Example Diazo Coupling Coupling Shade No. component component __J>H l-amino-4-methoxy-benzene· 1-amino-8-h droxy- 7 - 8 violet 6-sulphonic acid naphthalene-3, 6- disulphonic acid 1-amino-8-hydroxy- 7 - 8 reddish naphthalene-4, 6- violet disulphonic acid 2-amino-5-hydroxy- scarlet. naphthalene-1,7- disulphonic acid l-amino-5-chloro-benzene-2- 2-?aminb-5-hydroxy- orange sulphonic acid naphthalene-l, 7- disulphonic acid l-aminobenzene-3-sulphonic acid l-aminobenzene-4-sulphonic 7 acid 2-amino-8-hydroxy- 7 - 8 scarlet naphthalene-3» 6- disulphonic acid 4-aminobenzoic acid l-amino-8-hydroxy- 7 - 8 red sulpho-ethyl )-amide naphthalene-3, 6- disulphonic acid l-amino-4-sulpho-acetylamino- 7 - 8 violet benzene-6-sulphonic acid l-amino-3-sulpho-acetylamino- 2-amino.-5-hydroxy- benzene-6-sulphonic acid naphthalene-1^7- ' orange disulphonic acid l-amino-4-sulpho-acetylamino- 2-amino-5-hydroxy-naph- benzene thalene-1, 7-d sulphonic scarlet acid Example 269 When the instructions of Example 30 are followed, but the dyestuff intermediate obtained from i, 3-diaminobenzene-6-sulphonic acid and 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine is coupled after diazotisation at 10°C and pH 7.5 to 6.5 with a solution of 40.5 parts of the disodium salt of wed, but instead of the aminoazo dyestuff there are employed 53.15 parts of the disodium salt of the aminoazo dyestuff obtained by coupling of diazotised l-amino-4-nitrobenzene-2-sulp onic acid with l-(2'-chloro- l-sulphophenyl)-3-methyl-pyrazolone-(5) and subsequent reduction of the nitro group with sodium sulphide, are acylated with 2,4-bis-methylsulphonyl-6-methyl-pyrimidine, a valuable reactive dyestuff is likewise obtained with which cellulose materials can be printed by the usual 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 dye-stuff synthetised from the components stated in the following Example Diazo Azo Shade No. component component 271 l-amino-4-nitro-benzene-2- l-( 2' -metbyW -sulpho- yellow sulphonic acid (reduced) phenyl )-3-methyl-pyraz- olone-(5) 272 M l-(2 · , 5 ' -disulphophenyl)- yellow 3-methyl-pyrazolone-(5) 273 " l-(2'-methyl-4,-sulpho-6'- . yello chlorophenyl)-3-methyl- pyrazolone-(5) 274 yellow 275 l-amino-3-acetylamino- greenis benzene-6-sulphonic acid yellow (hydrolyaed) 276 l-( '-sulphophenyl )-3-methyl pyrazolone-( 5 ) 277 l-( 2·-methyl-41 -sulphophenyl) 3-carboxy-pyrazolone-( 5) 278 l-( 21 -chloro-4 '-sulphophenyl ) 3-carboxypyrazolone-( 5 ) Example' 279 58 Parts of the dyestuff of the formula (prepared by coupling dlazotised l-hydroxy-2-amino-4-chloro- benzene-5-sulphonic acid with 2-methylamino-8*-hydroxynaphthalene- 6-sulphonic acid and coppering of the resultant azo dyeatuff) are dissolved neutral in 700 parts water. 22.0 Parts of finely powdered 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine are added, and' the reactio mixture is stirred at 60 - 65°C, while continuously neutralising the liberated hydrochloric acid to pH 7 - 7.5 with a sodium carbonate solution, until free amino groups can no longer be detected. The resultant reactive " Dyestuffs with similar properties are obtained by a method analogous to that described above from the copper complexes, obtained by simple demethylating or oxidising coppering, of the mono- and disazo dyestuffs prepared from the diazo and azo components stated in the following Table : Example Diaz Azo Coupling Shade No. component component H 280 l-hydroxy-2-amino-4- 2-amino-8-hydroxy- 10 reddish chlorobenzene-5-sulphonic naphthalene-3, 6- violet acid disulphonic acid 281 1-amino-8-hydroxy- 10 bluish naphthalene-3, 6- violet disulphonic acid 282 2-amino-naphthalene-4, 6,8- 2-hydroxy-6-acetyla - 8 - 9 reddish trisulphonic acid (coppered mino-napthalene-4- blue with oxidation) sulphonic acid (hydrolysed) 283 l-amino-2-hydroxy-6-nitro- 1-hydroxy-8-ethoxy- 10 blue naphthalene-4-sulphonic naphthalene-3, 6- acid (reduced) disulphonic acid 284 l-hydroxy-2-amino-benzene- 2-hydroxy-3-amino- 10 red 4,6-disulphonic acid naphthalene-5, 7- diaulphcnic acid 285 2-amino-naphthalene-4, 8- disulphonic acid (coppered 8 - 9 blue with oxidation) 286 2-aminonaphthalene-4, 6,8- 2-hydroxy-3-amino- 8 - 9 blue trisulphonic acid (coppered naphthalene-7- with oxidation) sulphonic acid 287 3-methoxy-4-amino-6-methyl- 2-methylamino-5- 10 navy azobenzene-21 ,4*-disulphonic hydroxynaphthalene- blue acid (coppered with de- 7-sulphonic acid methylation) 292. 2-amino-5-hydroxy- 10 naphthalene-l,7-di- sulphonic 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-)-anthraquinone- 2, 5-disulphonic acid there mentioned, 63· 5 parts of the tri- sodium salt of l-amino-4-( ( 3' -aminophenyl )-amino )-anthraquinone- 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 .4 Parts 2-amino-8-hydroxynaphthalene-3,6-disulphonic acid are dissolved neutral in 300 parts water, heated to 60 - 65°C, and 20 parts 2, 4-bis-methylsulphonyl-6-methyl-pyrimidine 6 and 7. 5. The acylation product is in part precipitated. ' A diazonium salt solution freshly prepared from 13 · 6 parts p_-aminobenzyl-sulphonic acid is added drop ise at 0 - 5°C to the suspension of the acylation product, which has been mixed with 12.5 parts sodium carbonate. After further stirring at ice-bath temperature for five hours, the product is salted out with- sodium chloride, filtered off with suction, washed with a dilute sodium chloride solution and dried at 30°C in a o the formula When the procedure described above is followed, but instead of 30.4 parts 2-amino-8-hydroxynaphthalene-3 , 6- disulphonic acid, 30.4 parts 2-amino-5-hydroxynaphthalene-l,7- ° disulphonic acid are acylated with 2-methylsulphonyl-4-chloro- 6-methyl-pyrimidine , and the reactive group-containing coupling component is coupled with diazotised £-aminobenzyl-sulphonic acid, a readily soluble reactive dyestuff is obtained which dyes fabrics containing cellulose fibres in brilliant reddish orange shades.

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 fabri is squeezed to a moisture content of about 100 , and the moist fabric is rolled up again. After standing at room temperature for 24 hours, the fabric is rinsed, soaped at the boil in the usual manner and dried. A brilliant scarlet dyeing of good fastness to wet processing and light is obtained. 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 of about 100^ and steamed at 103°C for 30 seconds. After rinsing, soaping at the boil and drying, a brilliant scarlet dyeing of good fastness to wet processing and light is likewise obtained.

A cotton fabric is impregnated with a solution at 20 -25°C, which contains, per litre liquor, 20 g of the dyestuff obtainable according to Paragraph 1 of the present Example and 0/5 g of the non-ionic wetting agent (e.g. a poly-oxyethylated oleyl alcohol), as well as 150 g urea and 15 g sodium bicarbonate. The fabric is subsequently squeezed between two rubber rollers to a moisture content of about 100$. After an inter1-mediate drying at 50 - 60°C, the fabric is heated at 14-0°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 soa 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, 5OO g alginate thickener (60 g sodium alginate per kg thickener), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitro-benzene-sulphonic acid, and which has been made up with water to 1 kilogram, the fabric is subsequently subjected to an intermediate drying and thas steamed in a suitable steaming apparatus at 103 - 115°C for 30 seconds, rinsed and soaped at the boil, an intense scarlet dyeing of good fastness properties is obtained. 100 Parts wool are introduced at 4-0°C into a bath which parts 30$ acetic acid and 0.5 part of a polyoxethylated hydr.oxyl group-containing stearylamine derivative. The dyebath is brought to the boil within 30 minutes, and dyeing is then carried out 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-3, 5-disulphonic acid (monos diam 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 immediately in solution without isolation, and coupled in an alkaline medium with 25.3 parts 2-methylaiidno-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 copper sulphate, 40 parts diethanolamine, 50 parts ammonia (d 0.88) at 95 - 100°C within 5 hours. The dyestuff is isolated from the coppering solution by the addition of salt and careful acidification.

The coppered amino-disazo dyestuff is then acylated in an aqueous solution at pH 7 - 8 and at a temperature of 60 -65°C with 22.0 parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine, while maintaining the pH within the stated range by the addition of sodium carbonate. When the acylation is completed, the dyestuff is isolated by means of sodium chloride and dried at 35°C. In the form of the free sulphonic acid the dyestuff corresponds to the formula The dyestuff dyes cellulose fabrics by the processes known for reactive dyestuffs in navy blue shades fast to wet processing and light.

Further dyestuff according to the invention can be prepared in a similar manner, when the above monoazo dyestuff obtained from 2-amino-i-methylbenzene-3» 5-disulphonic acid and 1-amino-2-methoxy-5-methylbenzene is oombined according to the instructions given above with the aminonaphthol-sulphoHic acids stated in the following Table and with 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine.

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

Example 296 0.1 ol 4-ureido-2-amino-l-hydroxybenzene-5-8ulphonic acid id diazotised and coupled in a soda-alkaline medium with 0.1 mol l-amino-8-hydroxynapthalene-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 hydro-lyse 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 7 - 7.5 and at temperatures of 60 - 70°G with 0.1 mol 2-methylsulphonyl-4-chloro-6-methyl- rimidine. The resultant d estuff of the formula is salted ut. A blue dyeing is obtained on cotton.

Example 297 A neutral paste of copper-phthalocyanine-3, 3'-3 - trisulphonic acid chloride, 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 N- methyl-N-(4'-amino-2,-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 then distilled off with steam at pH 9.0 from the resultant solution of copper-phthalo-cyanine- disulphonic acid-monoaulphonic acid-( 3' -sulpho-4' -methyl- aminomethyl-anilide) . The solution is heated to 60°C, and 330 g finely powdered 2,4-bis-methylsulphonyl-6-methyl-pyrimidine 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 sodium 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 ood ield and ver ood fastness to washin .

When Ν1Ρο-3,3·τ3β-ΐΓΐβμ1ρ]ιοη1ο aoid chloride le used as starting material, a turquoise blue is obtained which is only slightly more greenish and has equally valuable properties.

Example 298 0.1 Mol of the aminoazo dyestuff of the formula (prepared according to the instructions of German Patent Specification No. 1,115,865 (Application P 27466 IVb/22 a) by coupling of the diazoni m compound from 2-aminonaphthalene- .. 4,8-disulphonic acid with 1-aminohaphthalene-6-sulphonic acid, further diazotisation of the resultant aminoazo dyestuff, coupling with the equivalent amount of 2,5-diaminonaphthalene- 4, 8-disulphonic acid, and conversion into the aminotriazole are dissolved at pH 6 in 1000 parts by volume water and mixed with 21 parts 2-methylsulphonyl-4-chloro-6-methyl-pyrimidine at a temperature of 60 - 65°C, while stirring. The slowly liberated hydrochloric acid is neutralised with a sodium carbonate solution, until the reaction is completed. The dyestuff is subsequently separated by the addition of sodium chloride, isolated, and dried at about 50°C in a vacuum. The dyestuff is a yellow powder which dissolves in water with a yellow colour. 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 parts water Example 1:1 Chromium complex Metal-free dyestuff Shade No. on cotton 315 4-chloro-2-amino-l-hydroxybenzene- 4-nitro-2-amino-l- navy 6-sulphonic acid——> l-amino-8- hydroxybenzene —-4 blue hydroxynaphthalene-3>.6-disulphonic 1-amino-8-hydroxy- . acid :;'":.·:: * ' ·':"",·''· Γ· naphthalerie-2 ,4-dieul- phonic acid 316 blue- 6-nitro-l-amino-2- black hydroxynaphtbalene- 4-suiphonic acid —> 2-hydroxynaphthalene 317 2-aminobenzene-l- grey- carboxylic acid-5- green sulphonic acid — 1-phe 1- 3-meth 1-5- pyrazolone 318 4-nitro-2-amino-l-hydroxybenzene-6- 6-nitro-l-amino-2- black sulphonic acid —> l-amino-8-hydroxy- hydroxynaphthalene- naphthalene-3> 6-di-sulphonic acid 4-sulphonic acid—■) 2-hydroxynaphthalene 319 4-chloro-2-amino-l-hydroxybenzene-6- 4-chloro-2-amino-l- violet sulphonic acid — l-amino-8-hydroxy hydroxybenzene — naphthalene-3t 6-disulphonic acid 1-( 41 -sulphophenyl ) 3-methyl-5-pyrazolone 320 4-methyl-2-amino-l-hydroxybenzene-6- 4-chloro-2-amino-l- sulphonic acid —^ l-amin0-8-hydroxy- hydroxybenzene —·+ naphthalene-3> 6-disulphonic acid 2-hydroxyna hthalene- 6-sulphonic acid 321 4-nitro-2-amino-l-hydroxybenzene-6- 5-nitro-2-amino-l- black sulphonic acid * l-amino-8- hydroxybenzene —^ hydroxynap¾halene- 3» 6-disulphonic acid 2-hydroxynaphthalene- 6-sulphonic acid 322 4-nitro-2-amino-l- hydroxybenzene —> 2-hydroxynaphthalene- 8-sulphonic acid 323 4-nitro-2-amino-l- hydroxybenzene —→ 1-hydroxynaphthalene- 5-sulphonic acid 6-nitro-4-chloro.-l- hydrox benzene — 1-hydroxyna h halene- 5-sulphonic acid Le A 9111 -94- 62.0 Parts of the .trisodium salt of the dyestuff obtai ned by soda-alkaline coupling from diazotised 4-chloro-2-amino-l-hydroxybenzene-6-sulph.onic 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 dye stuff f rom 6-nitro-l-diazo-2-hydroxynap¾halene-4-sulphonic acid and 2-hydroxynaphthalene . A deep blue solution has formed after 10 minutes.

The mixed complex is acylated within about one hour at 60 - 65°C and a pH of 6.5 - 7. 5 with 25 pa rts 2-metbylsulphonyl 4-chloro-6-methylr-pyrimidine, while maintaining a constant pH by the dropwise addition of a sodium carbona te soluti on . The acylated dyestuff is separated with 20 sodium chloride , fi lt ered off with suction and dried at 30°C.

A blue^black print of excellent fastness to light and washing is obtained on cotton by the proc ess described in Example 3.

Example 325 6 Grams l-amino-4-^- ( 4 ' -aminophenylamino )-anthraquinone-2 , 5 , 8-trisulphonic acid are dissolved in the form of the sodium introduced in small portions at 65 - 70°G..At. the same time a dilute sodium hydroxide solution is added dropwise in such a manner that a pH of 7.5 - 8.5 is maintained. during the reaction, Stirring is continued at 65 - 70°C, until the starting material has completely disappeared, the product is filtered off with suction from the. excess pyrimdine derivative, and salted out at 10°C with sufficient- solid sodium chloride for a 10 sodium chloride solution to result. After filtering off with suction and washing with a little sodium chloride solution, the resultant dyestuff of the formula is dr of the dyestuff are obtained in the form of blue-green needles.

The dyestuff dyes cotton by the- processes customary for reactive, dyestuffs in intense blue-green shades of good fastness to wet processing and light. . ■ The l-amino-4-l4'-aminophenylamino)-anth aquinone-2, 5,8-trisulphonic acid used as starting material was obtained as follows: 31.2 g _-phenylene-diamine are introduced under nitrogen into a solution of 62 g l-amino-4-bromo-anthraquinone-2,5,8-trisulphonic acid sodium salt and 12 g sodium carbonate, and stirred with the addition of a CuGl paste at 40°C until disulphonated bromoaminic acid can no longer be detected. The 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 ► sodium salt; the product is then washed and dried.

In the above Examples the reactive components employed can be interchanged under the same or similar reaction conditions. It is also possible to use with equally good or similar results the reactive/components stated on page 11, paragraph 2, Examples, instead of d of the fprmula cification No.599, 581, water and mixed at the ulphonyl-4-i;ehloro-6- ■ ·· methyl-pyrimidine, while stirring. The slowly liberated hydrochloric acid is neutralised with a sodium carbonate solution while maintaining a pH value between 5 and 6. When the condensation is completed, the dyestuff is salted out by the addition of 150 parts potassium chloride, isolated, and dried at about 50°C in a vacuum. A dark powder is obtained, which dissolves in water with. a blue colour and dyes cotton in reddish blue shades of excellent fastness to light and washing.

In the following Examples, the "parts" specified are parts by ..weight, unless otherwise stated.

Example 527; 28 Parts by volume of concentrated hydrochloric acid are added to a solution of 54.7 parts sodium 2-aminonaphthalene-4,8-disulphonate and 7 parts sodium nitrite in 500 parts water, whilst cooling with ice, and the mixture is stirred at O-10°C for half an hour. When excess of nitrous acio has been removed a solution of 10*7 -parts .5-aminotoluene in 10 parts by volume of concentrated hydrochloric acid and 150 parts water is added, and coupling is completed oy buffering the mixture to pH 3-5. The resultant aminoazo dyestuff is salted out filtered off with suction, wasned and then redissolved in 700 parts water at pH 7 by the addition of sodium hydroxide solution. The aqueous solution is thereafter, treated with 2.4 parts 2-met'h lsulphonyl-4,5-dichloro-'6-rcethyl-pyrimi ine and. stirred; vigorously. The temperature of the reaction mixture is maintained at about 65°C by heating; the liberated hydrochloric acid is buffered with sodium carbonate solution until the reaction has gone to completion. a SQ Na is salted out with 80 parts sodium chloride, pressed off, washed and dried in vacuo at about 50°0. It consists of a yellow powder soluble in water with a yello colour.

When a cellulose fabric is printed with a printing paste whiTfh contains, per kilogram, 15 grams of the dyestuff, 100 g urea* 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg of thickening) , 2 g sodium hydroxide and 10 g sodium carbonate and which ; had been made up to 1 kg with water, it is then dried, steamed at 105 °C for 8 minutes, rinsed with hot water and soaped with boiling, a strongly reddish yellow obtained. ound of the. (prepared according to the directions in German Patent Specification No.l 117255 by coupling diazotised i-amino-8-(benzene-sulphonyl-oxy)-naphthalene-disuiphonic acid- (3, 6) in a medium rendered alkaline by sodium carbonate with an equivalent amount of 2-adetylamino-5-hydroxy-naphthalene-disulphonio aoid- (4,8), conversion of the monoazo compound to the copper complex by oxidative coppering and hydrolysis of the acetyl and benzene-sulphonyl group) are dissolved at pH 6-6.5 in. 500 parts by volume of water at 60 to 65°C, and treated at this temperature with 0.12 moles 2-methylsulphon l-4,5-dichloro-6-methyi-pyrimidine.

A pH value of 7-7.5 is maintained during the condensation by the addition of sodium carbonate solution.

When the reaction has gone to completion, the dyestuff is salted out and isolated. Whe dried, the dyestuff consists of a dark ethoxylated oleyl alcohol) as well as 150 g urea and 15 g sodium bicarbonate. The fabric is thereafter squeezed out between two has been subjected, to intermediate drying at 50-60°C, it is heated at 140°G for .10 minutes, and the resultant dyeing is thoroughly rinsed with hot water and boiled for 20 minutes with a. solution which contains, per litre, 5 g Marseilles soap and 2 g sodium carbonate.. A strongl reddish yellow dyeing of good fastness to wetting, abrasion and ; light, is obtained after rinsing and drying.' . · . . · The following Table lists the diazo components, coupling components and the reactive components which can be linked to the amino group from which dyestuffs can be synthesieed by analogy with the statements in Examples 327-329 whose colour shades, as obtained aocording to one of the above described methods of application, are also specified in the Tahle^ Abbreviations for the reactive components: A = 2-Methylsulphon l-4,5-dichloro-6«.methyl-pyrimidine.

B = 2, 4-Bis-me hylsulphonyl-5-c loro-6-methyl-pyrimidine Exam le Diazo component pling component Reactive Colour Compon- Shade No. ent 330 2-Aminonaphthalene- 1- mi o- -methox -5« A Ye llow 4,8-disulphonic acid methylbenzene •l B. 332 1-Aminonaphthalene- l-Amino-3-methylbenzene A 3,6-disulphonic acid 333 B 334 2-Aminonaphthalene- 1-Amino-3-meth lbenzene A , 7-disulphonic acid 335 B 336 2-Aminonaph alene- l-Amino-3-methylbenzene A 6,8-disulp onic acid 337 B 338 4-Aminoazobenzene- l-Amino-3-met ylbenze e Brown-yellow 5 , 4,-di3ulprio:ic acid Examp la iaz o ' component. Coupling component Reactive Colour 'C ompon- Shade ■No.'. ont 339 1-Ami nob enze ne- 4- . ' 1- Ami no- 3-me t h lbe nz e ne B Brown-yellow sulp onic acid — — ^ 1- aminonaphthalene- 6-sulphonic acid 340 2- ( 3' -Sulpho-4' -amino- l-Amino-3-methylbenzene A Yellow phenyl )-6-methy l-be'nz- thiazoie-7-3Ulphonic ' acid.. 341 2-Aminonaphthalene- l-Met ylamino- 3- B 4,8-disulp onic acid met hoxy-benzene 342 1-Ami no- 3-acety lamino- benzene φ3 " · " Aniline A " Example 344; 29 Parts 2,4-Dis-methylsulphonyl-5-chloro-6-methyl- pyrimidine are introduced at 50-60° into a solution of 36·5 parts of the. sodium salt of 1 -ami no-8- ydroxy naphthalene -3, 6- disulp onic acid in 100 parts wator whilst stirring well and with constant buffering of , the liberated hydrochloric acid to pH 6-7 until no free amino group can any longer be detected.

The dye stuff intermediate thus obtained is diluted with 600 parts water and 12 part 3 sodium carbonate are added before coupling at 5-lO°C with a solution of 17,5 parts diazotised 2-aminobenzene-sulphonic acid in 200 parts wator. The dyestuf of the formula formed at a final pH value of about 7 is salted out with 100 parts sodium chloride, filtered off with' suction, wasned and dried in vac uo at ¾0-4O°C . , Τ,ηβ- dyestuff forms small red • ^needles with a metallic glose which are, readily soluble in water with a red colour, · .

; When a fabric of cotton or re enerated cellulose ' is dyed or printed with this dyestuff according to one of the ■ methods described in Examples 327-529, full bluish red dyeinrs and, prints are obtained which, have good fastness to wetting, abrasion and light, .· Equally good results are obtained according to the following method: 50 g Cotton skein are dyed in 1 litre of a dyeing liquor containing 1.5 g of the above dyestuff by raiBing the temperature from 20°C to about 80°C within 30 minutes, adding a total of 50 g sodium chloride by portions during' his operation and finally adding 20 g sodium carbonate before treating at this temperature for 60 minutes. A bluish red dyeing having good fastness to wetting, abrasion and light is obtained after rinsing, soaping by boiling and drying.

The following' Table lists the colour shades of other dyestuffs synthesised according to the statements in Example 544 from the diazo components, coupling components and the reactive components which can be linked to the amino group of the latter, as also specified there, or a ain by the reaction of the corresponding aminoazo dyestuffs with the reactive components, and which. can be dyed or printed on cellulose , materials according to one o the above described processes.

Abbreviations for the reactive components as in the Table of Example 529.

Example Diazo component '.' ..Coupling component Reactive Colour No. ' .'· · . , ;'... ., ' component shade 345 l-Aminobenzene-2- l-Amino-8-hydroxy- B Red sulphonic acid napht ale e-3, 6- disulphonic acid 346 l-Aminobe zene .1- ( 3' -Aminobenzoy1- sulphonic acid amino )-8-hydroxy- naphthalene-3, 6- · disulohonic acid 347 Ami obenze e B: 348 1 -Amino-2- 1-Amino-8-hydroxy* carDoxyben ene-4- naphthalene-3,6- sulphonic acid disulphonic acid 349 l-Amino- -methyl- benzeime-2-3ulphonic . acid 350 l-Amino-3-acetylamino B benzene-6-sulphonic acid 351 l-Amino-3-(2«- 4"- A sulpho enylaminp_7-4' chlorotriazin -1« , 3' , yl-6' )-aminobeazene-6 sulohonic acid 352 l-Aminobenzene-2- 2-Amino-5-hydr A Orange sulohonic acid naphthalene-7- suiphonic ac id 352a l-Amino-3-(2'- "4"-sulpnophe.nyl aminj'-41 -methy1- amino-triazin-1' , 3» ,5' -yl-6' )- aminobenzene-6- sulphonic acid 353 l-Aminobenzene-2- 2-Methylamino~5- 3ulphoriic acid hyά oxynaphthalene- 7-3ulphonic acid 354 l-Amino-4-ac etyl- scarlet amino-6-3ul ncnic acid 555 2-Amino-5-hydroxy- na hthalene-7- suiphonic acid Example 356 ; . 24.0 Parts 2-methylsulphonyl-4 ,5-dic hloro-6-methyl-pyrlmidlrie. ;a're Introduced into a' solution of 21 parts of the sodium salt of l,3-diaminobenzene-6-sulphonic acid in 100 parts waterj whilst stirring well,'and the mixture is stirred at 60-65°C- with\constant buffering of the liberated hydrochloric acid to pH 7-8 until a sample produces a full yellowish red colour when diazotised and coupled with lrhydroxynaphthalene- -sulpnonic, acid . The resultant dyestuff intermediate is treated with ice and.then directly diazotised with 7 parts sodium nitrite and 28 parts of concentrated hydrochloric acid before it is added to a previously prepared solution of 47 le e- arts in s and The following Table lists the colour s ades an the pH value of the coupling medium for dyestuffs which are prepared by analogy with the statements in Example 356 from a diazo component containing another amino group which ca preferably be ac lated, from a coupling componen and from a reactive component which.' can be linked to the diazo component.

The above mentioned: processes can be em loyed for dyeing and printing the. dyestuffs in the Table on cellulose materials.

Abbreviations for the reactive components as in the Table of Example .329· Diazo component Coupling component Reactive pH of Colour compon- coupling shade ent . medium 1, 3-Diaminobenzene 2-Aminonaphthalene- A -5 Orange 4-aulphonic aoid 5,7-disulphdnio acid - 1 II it 2-Aminonaphthalene- 3, A 4-5 6-d.isulphonic acid 2-Aminonaphthalene- B 4-5 6-sulphonic acid 360 2-N-methylamino-8- A 4-5 hydroxynapht ale e- 6-sulphonic acid 361 l-(3« ,5'-Dic loro-l» , A 7-8 Red 1 - thiazole- ' -carta oxy lamid o ) - 8 -hyd r oxy- naphthalene- 3, 6-disulphonic acid 362 l-(2' ,4'-Dihydroxy- B 7-8 triazin-l',3« ,5«-yl- 6 · -ami no ) -8-hyd roxy- naphthalene-3, 6-disulphonic acid 1- (3' ,5»-Dichloro-l» , A 7-8 2' -thiazole-4' -ca b oxy lamid o ) -8-h d roxy- naphthalene- 3, 6-disulphonic acid 364 2- Hydroxynaphthalene- A 8 Scarlet 3, 6-disulphonic acid 365 l-Acetylamino-8- B Red hyd roxynaph hale ne- 3, 6-disulphonic acid 366 l-(3«-Sulphophenyl)-3- A Yellow me t hy lpy r a z o lo ne- 5 367 l-(2«,5'-Dichloro-4»- A sulphophenyl)-3- methylpyrazolone-5 Example . Diaz o component Coupling component Reactive pH of Colour compbn- coupling, shade No. ent medium 368 1, 3-Diaminobenzene- l-(5» ,7'-Disulpho- Yellow 4-sulphonic acid naphthyl-2' )-3- rneth>y 1pyraz olone-5 •369 t» n 1- ( 3 ' -Sulpnppheny1) -3- B methyl-5-aminopyrazole 370 .1,4-piaminobenzene- 2-Amino-8-h droxy- 4-4.5 Red 3-aulphonic acid naphthalene-6- aulphonic acid 371 n. 2-Acetylamino-5- 6-7 Scarlet hydroxynaphthalene- 7-sulphonic acid 372 l-Acetylamino-5- B 6-7 Red hydroxynap t ale e- 7-3uiphonic acid Example 373; 51.6 Parts of the dyestuff of the' formula obtained by diazo ising - y roxy- -aminobenzene-4-aulphontc- aoid and coupling with 2-amino-5-hydroxynaphthalene-7-3ulphonio acid in water/ yridine i the presence, of sodium carbonate followed by treatment with a copper dischargin agent are dissolved a pH 7 in 1500 parts water. 24.0 Parts 2-methyl- 3ulph.onyl-4,5-diohloro-6-methyl-pyrimidine are introduced at 60-65°C whilst stirring well and constantly buffering the liberated hydroc hloric ' acid to pH 7-8 with sodium carDonate solution. When a free amino group can no longer be detected, the resultant reactive dyestuff of the formula S03Na is salted out, pressed off, washed and dried in vac uo at 30-40°C.

Fabrics from cellulose materials can be dyed or printed with this dyestuff to ruby shades fast to wetting, abrasion and light φ according to. one of: the above mentioned processes.

The following Table lists the heavy metal complexes of other aminoazo' dyestuffs and the reactive components linked to the amino group as well as the colour shades of these dyestuffs on cellulose materials. The preparation of these aminoazo dyestuffs and of their metal complexes, as well as their reaction with the reactive components can be carried out by analogy with the statements i-n, Example 373.

Abbreviations for the reactive components as in t he Table of Example 329, xample Aminoazo dyestuff Heavy metal Reactive Colour combined in component shade No. \ _ complex . 374 l-Hydroxy-2-aminobenzene- Cu Ruby 4,6-disulphonic acid 2-amino-5-hydroxynapnthale e 7-sulphonic acid 375 l-Hydroxy-2-aminobenzene- Cu A " 4-sulphonic acid 2-ethylamino-5-hydroxy- napht'aalene-7- sulphonic acid 376 l-Amino-2-hydroxy-6-nitro- Cu A " naphthalene-4-sulphonic acid —> 2-amino-5-hydroxynaphth le e- 7-sulphonic acid Exam le Aminoazo dye stuff Heavy metal Reactive Colour c ombined in component shade complex 577 1- Amino-2-hydroxy-6-nitro~ Cr Greenish naphthalene-4-sulphonic acid -> grey 2- amino-5-hydroxynapht alene-. 7-sulphonic acid 385 (l-Amino-2-chlorobenzene- Cu A Navy blue 4-sulphonio acid >· 1 -hydroxy-2-acetylamino- benzene) hydrolysed ^ l-amino-8-hydroxynaphthalene« 3,6-disulphonic acid 386 Co A Grey 387 1- Ami n o -8 - hy d r oxy na phthalene- Co A Black 4-sulphonic acid 1-hyd r oxy- , 6-d iaminobenzene- 4-sulpi onic acid ^ 1, 3-dihydroxybenzene 388 l-Amino-8-hydroxynaphthale ne- Co A 3,6-disulptionic acid 4 1- hyd roxy-2, 6-diaminobenzene- 4-sulphonic acid > 2- hyd roxynaphthalene 389 1-Ami n o-8 -hy d r oxynap t ha le ne - Co A 4-sul honio acid Example 390; , 96 Parts ( referred to 100 product) of the copper phthalocyanine; .tetrasulphochloride freshly prepared as usual by the action of chlorsiilphonic acid and thionyl chloride on copper phthalocyanine or the isomeric copper phthaloc anine tetrasulphochloride synthesised from l-sulphobenzene-3, -dicarboxylic acid via the corresponding copper pht alocyanine tetrasulphonio acid. are suspended, in the form of the moist, well washed suction filter cake, in 500 parts water and 500 parts ice, a solution of 50 parts- of. the sodium salt of 1,3rd iaminobenzene-4-sulphpnic acid in 500 parts water is added and the pH value adjusted to 8·5 with sodium carbonate. The suspension is stirred at room temperature for 24 hours and the pH value is constantly maintained at 3.5 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 in 1000 parts of water until neutral. 80 Parts 2, -bis-methylsulphonyl-5-chloro-6-methyl-pyrimidine are introduced into , this blue s olution, with intensive stirring, and the mixture is stirred at 60-65°C whilst constantly buffering to pH 7-8 with sodium carbonate solution until no free amino gr reactive dyestuff of t 0u-Ph alocyanin thus obtained is salted out, washed and dried in vacuo at .30-40 C . It consists of a dark blue powder soluble in water with a' blue colour, and it dyes cotton and regenerated cellulose to full blue shades of good fastness to wetting, abrasion and light . according to one of the above specified dyeing or printing processes..

It is also possible to replace the 96 parts of copper phthalo yanine tetrasulphochloride during the operation, which is otherwise identical to that described in Example 390, by the use of 87 parts (in terms of the 100$ product) of the copper or nickel phthaloc anlne trisulphoc hloride , as obtained by the action of chlorsulphonic acid on the copper or nickel phthalocyanlne, in the. form of its moist suction filter cake thoroughly washed with ioe water: reactive dyestuffs which produce full blue dyeings are then also obtained.

When the procedure is again as described in Example 390 except that the starting material is 87 parts of copper phthalocyanlne trisulphochloride and the 50 parts of the sodium, salt of 1, 3-diaminoben2ene-4-sulphonic acid are replaced by the use of 90 parts of the sodium salt of 4,4' -diamino-diphenyl-2,2» -disulphonic acid or by. the use of 90 parts of the sodium salt of 4, 4,-diamino-stilbene-2, 2' -disUlphonic acid, reactive-dyestuffs are obtained which dye cellulose materials to full blue shades fast to wetting, abrasion and light according to one of the above described processes.

When the start ing material is 4« , 4" ,4" · ,4" "-tetra- phenyl-Cu-phthalpcyanine , sulphochlorinatiori,. reaction with 1, 3-phenylene-diamine-4-sulphonic acid and acylation with 2,4- bis-methylsulphpnyl-6-methyl-pyrimidine produces a reactive dye stuff which in the presence of acid binding agents dyes cellulose materials to full green shades fast to wetting and · is salted out, filtered off with suction, washed and dried in vacuo at 30-40°C. It dyes cotton and regenerated cellulose to blue shades fast to wetting, abrasion and light according to one of the above specified processes.

When the procedure is as specified in Exam le 591 but the 71 parts of the starting dyestuff there employed are replaced by the use of equivalent amounts of one of . the following derivatives of l-amino-4-— (amino-arylamino )-anthra- quinone-2-sulpnonic acid, similar dyestuff s are obtained whose dyeings are also blue and have similar fastness properties as the dyestuff obtained above: . l-amino-4-(4'-airiino-2»- aulphophenylaminoj-antliraquinone-S-sulphotic acid., l-amino-4-( 4» -amino-phenylamino )-anthraquihone-2, 6-disulphonic acid , an isomer mixture of l-amino-4-(4,-amino-phenylainino)-antb,raquinone-2,5- and-2,8-disulphonic acid, an isomer mixture of l-amino-4-(4,,-amino-2,-sulphophenylamino)-anthraquiri0ne-2,5- and -2,8-disulphonic acid, an isomer mixture of l-amino-4- ( 3' -amino-phenylamino)-anthraquinone-2, 5- and -2,8-disulphonic acid, 1-amino-4- ( 3» -amino-phenylamino )-anthraquinone-2, 6-disulphonic acid, and 1 -amino-4-(3 '-amino-41 -sulphophen lamino )-anthraquinone- 2-sulphonic acid'.Reactive dyestuffs producing "bluish grey dyeings are obtained from 1-amino-4-( l-Z?ll-amino-2w-sulphOj-henyl7-amino-phenyl)-anthraquinone-2, 6-disulphonic aoid.

Example 392; Whe the. procedure is as stated in Example 373 but the amino-monoazo dyestuff containing copper which is employed as the startin mater ial in that Example is replaced by an equivalent amount of the chromium complex of the aminoazo dye-stuff obtained by coupling diazotised l-amino-2-hydroxy-3-chloro-benzene-5-sulphonic acid with l- "3'-(3"-aminophenyl} -3Ulphonyl-imido-sulphonylphenyl-3-methylpyrazolone- (5 ), a reactive dyestuff is obtained which dyes cellulose materials to yellow-brown shades with good fastness to. wetting, abrasion and light according to one of the above specified processes.

Example 593; 0.1 Mole of the copper complex compound of the formula are dissolved at pH 6 in 3000 parts by volume of water . and combined at a temperature of about 60°C with 24 parts by weigh " (Oil mole) of 2-methylsulphonyl-4,5-dic loro-6-methyl-pyrimidine whilst stirring. The mixture is stirred until the condensation has gone to completion, and, the dyestuff is separated by the addition of a little sodium chloride and isolated. The residue is , ashed with acetone and dried at room temperature under reduced pressure. A dark powder is obtaine which dissolves in water with a green colour and dyes cotton to green shades according to the procedures stated in Examples 327-329.

A cotton fabric is impregnated at 20-25°C with a solution which contains, per litre of liquor, 25 g of the above dyestuff and 0.5 g of a non-ionic wetting agent (for instance a polyethoxylated oleyl alcohol), 150 g ureaand 20 g sodium carbonate. The fabric is thereafter squeezed out between two rubber rollers,to a moisture content of about 100b. After it has been subjected to intermediate drying at 50-60°C, it is heated at 140°C for 10 minutes, and the resultant dyein is thoroughly rinsed with hot water and. boiled for 20 minutes w-ith a solution which contains, per litre, 5 g Marseilles soap and 2 g sodium carbonate.. A green dyeing of good' fastness to wetting, abrasion and light is obtained after rinsing and drying.

Pull green shades of good fastness properties are also obtained on cellulose materials according to one of the other dyeing or printing processes described in Examples 327-329, 344 and 356.

Example 394; 0.1 Mole of a paste of the a inoazo compound of the formula HOsS 0 — Cu S03H obtained by coupling the diazonium compound from 6-acetamino-2-aminonaphthalene-4,8-disulphonic acid with 2-hydroxynaphthale e-3, 6-disulphonic acid, hydrolysis and conversion of the monoazo compound, to the copper complex, is dissolved at pH 6.5 in 2000 parts by volume of water and combined with 29 parts by weight of 2, 4-bis-methylsulphonyl-5-c hloro-6-methyl-pyrimidine .... The reaction mixture is stirred at 60-65°C until the condensation has been completed,, whilst the pH value of the reaction solution is maintained at 7-7.5 by the addition of sodium carbonate.

When the reaction has finished, the dyestuff is salted out, isolated and dried in vacuo.

The dried dyestuff consists of a dark powder which dissolves in water with a violet colour and dyes cotton to bluish violet shades in the presence of alkali.

Example 395 ; An aqueous . solution of 0.1 mole of the copper complex of the formula prepared according to the statements in German Patent Specification No. 1 061 460 and 1 085 988 is reacted as usual with 24 parts by weign of 2-methylsulphonyl-4,5-dichloro-6-methyl-pyrimidine . The pH value is maintained at 7-7.5 by the addition of sodium carbonate and when the reaction has gone to completion the dye-stuff - is isolated b salting out. In the dry state, it consists of a dark powder which' dissolves in water with a violet , c olour. Cotton fabric -is dyad by it to violet shades fast to light and wetting.

Exam le 5961 27.5. Parts sodium 2-methylamino-5-hydroxynaphthaiene- 7-sulphonate are dissolved in 150 parts water, treated with 29 parts 2, 4-bis-methylsulphonyl-5-chloro-6-me.thyl-pyrimidine and stirred at 50-55°C whilst constantly buffering the liberated methane-sulphi ic acid to pH 6-7 with a total of 34 parts by ■volume of 16% sodium carbonate solution. Acylation is completed within a short while, when the pH value is 6 and no longer changes any more.

Parts sodium bicarbonate are then added, and a diazo suspension from 34 parts of the disodium salt of 2-amino- naphthalene-l, 7-disulphonio acid in 200 parts water is added dropwise at 20°C during 15 minutes. After stirrin ; for one hour, the orange coloured reactive dyestuff of the formula which iz formed. at once, is completely separated by the addition,of 80 parts sodium, chloride, filtered off, washed dilute sodium chloride solution and dried in vacuo at 35°C . dyes cellulose materials to re.ddish orange shades of very good fastness to wetting and good resistance to chlorine according to the above mentioned processes.

When in this Example, the 29 parts by weight of 2.4- bis-methylsulphotiyl-5-chloro-6-methyl-pyrimidine are replaced by the use of an equivalent amount .of 2-Tnethylsulphonyl- ,■· 4, 5-dichloro-6-methyl-pyrimidine, a reactive dyestuff is obtained which produces orange dyeings, and whose dyeing behaviour corresponds to that of the reaction product of the bis-methyl- sulphonyl derivative* ^ Apylation of the aminonaphthol-sulphonic acids listed in Column 3 of the following Table with 2,4r.bis-methyl- sulphonyl-5-chloro-6-methyl-pyrimidine or 2-methylsulphonyl- 4.5- dichloro-6-niethyl-pyrimidine and combination of the resultant ac laminonaphthol-sulphonic acids with the diazo . components specified in Column 2 produces orange to red reactive dyes tuffs by an analogous method.

Example Diazo component Aminonaphthol-sulphonic Colour shade No. acid on cotton 397 2-Aminonaphthalene-. " 2-Ethylamino-5-hydroxy- Orange < 1,7-disulphonic acid naphthalene-7-sulphonio aci 398 " " 2-(t>-Hydroxyethylamino)- . °" - hydroxynaphthalene- 7-sulphonic acid 399 " n 2-Amino-5-hydroxynaphthalene- " 7-sulphonic acid 400 " n 2-Amino-5-hydroxy naphthalene- " 1,7-disulphonic acid 401 " " 2-Amino-8-hydroxynaphthalene- Scarlet 6- sulphonic acid 402 " " -2-Amino-8-hydro.xy naphthalene- " 3,6-disulphonic acid 403 2-Aminonaphthalene- 2-Methylamino-5-hydroxy- Orange 1,5-disulphonic acid naphthalene- 7-sulphonic acid Exam le Diazo component Amino naphthol-sulphon Colour shade Νο.·' acid on cotton 40 2 -Ami no ha p h t ha le ne - 2— Bthylamino-5-hydroxy- " Orange 1, 5-d isulphohic acid naphthalene-7-sulphonio acid 405 2- (l^-Hydroxyeth lamino )- 5- hydr oxynapht halene- 7-sulphonic acid 406 2-Amino-5-hyd r oxynapht hale ne 7-sulphonic acid 407 2-Amino~5- hyd r oxynapht ha lene 1,7-disulphonic acid 408 2-Ami no-8- hyd r oxynapht hale ne Scarlet 6- sulphonic acid' 4^ 2-Amino-8-hydroxynaphthale e 3.5- disulphonic acid 410 : 2-Amihonaphthalene- 2-Amino-5-hydr oxynapht hale ne Orange 1,5 , 7-tri3ulphonic acid 7- sulphonic acid 411 2-Met ylamino-5Th.ydroxy- · . . aphthalene- 7-3Ulphonic acid 412 2-Amino-8-hy r oxynapht alene Scarlet 6- sulphonic acid 413 2-Aminobenzene- 2-Met ylamino-5-h d roxy- Orange sulphonic acid naphthalenc-7-sulphonic acid 414 2-( -H cίro yθth lam o)- 5- dro yna t alθnθ- 7- sulphonic acid'' W 2-r-Amino-8- h r oxynapht hale ne Scarlet 6-sulphcnic acid 416 2-Amino-8-hydroxynaphthalene 3.6- disulphonic acid 417 2-Amino-5-hydroxynaphthale e Orange 1.7- disulphonic acid : 418 2r-Ami nona pht ha le ne ■ 1-Ami o-8-hydroxynapht ale ne Bluish red 1-sulphonic acid 3,6-disulphonic acid . 419 l-Amino-8-hydroxynaphthale e 4, 6-d isulphonic acid 420 '2-Aminonaph ale ne- 1-Ami no- 8- hyd r oxynap t hale ne .1,5-disulphonic acid 3,6-disulphonic acid 421 l-Amino-8-h d r oxynapht ha le ne 4,6-disulphonic acid Example Diazo component , Aminonaphthol-sulphonic Colour shade No. acid on cotton 423, 2-Aminonaphthalene-. l-Amino-8-hydroxynaphthalene- Bluish refl 1, 7-disulphonic acid 3,6-d.isulptionic acid 423a l-Amino-8-hydroxynaphthalene- 4,6-disulphonic acid 424 l-Amino-8-hydroxynaphthalene- 6-sulphonic acid 425 2-Aminonapht alene- l-Amino-8-hydroxynaphthalene- 1, 5, 7-trisulphonic acid 6-sulphonic acid 426 l-Amino-4-chlorobenzene- l-Amino-8-hydroxynaphthalene- 2-sulphonic acid 3, 6-disulphonic acid 427 1-Amino-2-methoxy-ben- l-Amino-8-hydroxynaphthale e- zene-5rSulphonic acid 3,6-disulphonic acid l-Aminobenzene-2-oar- l-Amino-8-hydroxynaphthalene- boxylic acid-4- 3, 6-disulphonic acid sulphonio aold 42Θ 1-Amino-4-acetylamino- l-Amino-8-hydroxynaphthalene- Violet benzene-2-sulphonic aoid 3,6-disulphonic acid 430 " " 1-Amino-8-hydroxynaphthalene- Bluish red 4, 6-disulphonic acid Example' 4311 56.8 Parts of the diaminoazo dyestuff obtained by coupling diazotised l-amlno-3-acetylamino-benzene-€-aulphonio acid with 2-amlnonaphthalene-5., 7-disulphonio acid in an acetio acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are dissolved at pH 7 in 450 parte water.

.After 24.0 parts 2-methylsulphonyl-4,5-dichloro-6-methyl-> pyrimidine have been added, the mixture is stirred at 60°C for about one hour whilst constantly buffering the. liberated hydrochloric acid to pH 7-7.5 with sodium carbonate solution.

When the acylation has been 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 an entirely pure state by the addition of 400 parts sodium chloride. The dyestuff Is dried in vacuo at 35°C , as usual. It dyes cellulose materials to fast yellowish orange shades according to one of the above mentioned processes.

Example 43a: 24 Parts 2-methylsulphonyl-4,5-dichloro-6-methyl-pyrimidine are added to a neutral solution of 60 parts of the trisodium salt of the aminoazo dyestuff, obtained by coupling diazotised 2-aminonaphthalene-3,6,8-trisulphonia acid with 3-acetylamino-aniline in an acetic acid medium, in 500 parts water and the mixture is stirred at 65°C for one hour, whilst its pH value is maintained at 7-7.b by the constant addition of sodium hydroxide solution. The partially precipitated acylation product is completely separated at pH 7 by the addition of 100 parts sodium chloride and filtered off. In order to purify it, the reactive dyestuff thus obtained can be redissolved in 2500 parts water at 30°C , clarified and separated again by salting out the filtrate with 350 parts sodium chloride. The dyestuff has the formula of the following Table by diazotising and coupling in an acetic acid medium, and by acylating them with 2-methylsulphonyl- 4, 5-dichloro-6-methyl-pyrimidine .

Example Diazo component Coupling component . Colour shade No. on cotton 433 2-Aminonapnthalene- l-Amino-3-met hyl- Strongly 1,5-disulphonic aoid 6-me t h oxy-be nz e ne reddish yellow 434 l-Amino-3-methy lbenzene Yellow 435 l-Aminonapiithalene- Reddish yellow 6-sulphonio acid 436 1- mi no- 3- ace t lami o- be zene 437 3-Ami o-phenylurea . tt 8 Example Diaz.o component Coupling component Colour shade NoV on cotton 438 2-Ami npnapht ha le ne- 1- Ami n o- 3- hy d roxy a c e t y 1- Reddish yellow 1,5-disulpnonic acid aminobenzene 439 -Ami n onaphtha le ne - 1-Amino- 3-mat hy 1- Strongly red5, 7-disu phonic acid 6- me t oxy-b e nz e ne dish yellow 440. 1-Ami nonapnt ha le ne - Reddish yellow 7- sulphonic acid 441. l-Amino-S-acetylamino benzene 442 3-Amino-phenylurea 443 l-Araino-3-b.ydroxyacetyl- aminobenzene ,4 .l-Asai nonapht ha le ne- l-Amino-3-methyl- Strongly red3,7-disulphonio acid 6-ΪΤΙΘ t hoxy-be nze ne dish yellow 445· ■ 1- mino-3-Βΐβ t hy lbe nz e ne Reddish yellow 446 1- Ami nonapht ha le ne- 1-Amino nap t ha le ne- 3, 7-dlaulphonic acid 6-sulphonio acid 447 2 - Ami no naphtha le e - 1-H m i no - 3-rne t hy lb e nz e ne 3,6-diaulphonic acid 448 l-Amino-5-met hy 1- Strongly red6-methoxy-benzene dish yellow 449 l-Amlno-3-acetylami Reddish yellow benzene 450 3-Ami o-phenylurea J1 1-Amino- 3-hyd roxyac e ty 1- aminobenzene 452 l-Aminonaphthale e-6- sulphonic acid 453 2-Ami nonapht ha le ne- l-Amino-i-ac etylamino- 6,8-fl isulp cnic acid be zene 454 tr l-Amino-2-me t b oxy- Strongly red- naphthalene-6-sulph.onic acid di3h yellow 455 l-Aminonaphthalene-6- Reddish yellow sulphonio acid .456 .2-Aminonaphthalen'e-.. 1-Ami no na p h a le ne-6- Yellow 4, 8-disulpho ic acid sulp onic acid 457 l-Aminonaphthale ne-7- sul honic acid Example Diazo c omponent Coupling component Colour shade No . ' on c otton 458. ' 2-Aminonaphthalene- l-Amino-2-methoxy-naphthal- Strongly red4,8-d isulphonic aoid ene-6-sulphonlc acid dish yellow 459 , it n l-Me t hy lami no - 3-me t hy 1- yellow benzene 460 tt 1-Ethy lamino-3-met hy 1- tl i benzene 461 , . it '■ · N-methyl-aniline II 462 '' » . tt N-ethyl-aniline It 463 t» t> N- ( β- hydroxy et yl) -aniline tt 464 It t» N-butyl-aniline tl 2-Aminonaphthalene- Aniline Redd ish yellow 3, 6,8-triaulpnonio aoid 466 II It l-Amino-3-methylbenzene It tt 467 II It 3-Amino- phe ny lurea tt ir 468 II • tt l-Amino-3-hydroxyacetyl- tl It aminobenzene 469 n . tt l-Amino-3-acetylamino- Yellowish, 6-methoxy-benzene orange 470 tl It l-Amino-3-acetylamino- Reddish yellow 6-methylbenzene 471 II II 1- Ami no- 3-me thane - ft It sulphonyl-aminobenzene II It 2,5-Dimethoxy-aniline . Ye llowish orange 473 tl II 3-Methyl-6-raet oxy-aniline It It 474 It n N-me t hy 1-a n i 11 ne Redd ish yellow 475 tt N-ethyl-aniline It tl 476 II It N-butyl-aniline It tt 477 It II 11- (β-hydroxy ethyl) -aniline II II 478 II It 3- ( -et hylamino )- toluene If ft 479 It II 2-Aminotoluene II It 480 It tt l-Amino- , 5-d ime t hy 1- Strongly redbenzene d ish ye llow ' i.

Example Diazo component Couplin component Colour shade No. on cotton 482 2-Am nona p t ha le ne - 1-Ami no- 3-methoxy-benzene Reddish yellow 3i,6,8-tri3ulphonic acid 483 1-Et h lamino-3-me t ho - benzene 484'· ' : · l-Aminonaphthalene- 6- sulphonic acid 485 1-A mi no na p n t ha le ne - 7- sulphonic acid 486 2-Ami nonapht ha le ne- 1-Ami no-3-ae hylbe nz e ne 4,6,8-triaulphohic aoid 487 l-Amino-3-aoetylamino- benzene QQ l-Aminonapht alene- 1-A.mi no- 3-me t hy lbe n z e ne Yellow 2,4, 7-triaulphonic aoi 489 l-Aminonaphthalene- 6-sulphonic acid 490 4-Ni ro-4 ' -amin o s t i 1- l-Amino-3-acetylami Reddiah yellow bene-2,2'-disulphonio benzene acid 491 3-Amino-phenylurea . 492 1- Ami n o- a-h d r oxy ac e t y 1- aminobenzene 493 N-me hy 1-ani line ^494 N-ethyl-aniline 495 - II N-but 1-anilaniline .496 ·. N- ( -hydroxyethyl)-aniline tl 497 : 1- (N-ethylamino)-3-methyl- II It benzene 498 Aniline-2,5- l-Aminonaphth le ne- disulohonic acid 6- sulphoriic acid 499 1-Ami ona ut ha le ne - 7- aulphonic acid 500 l-Amino-S-methylbenzene Yellow tt 501 l-Amino-S-acetylamino- benzene 502 1-Ami n o- 2 -me t h oxy- 5 - Reddish yellow 8-hydroxy-naphthalene-3,6-disulphonic acid, and' the . resultant dyestuff of the formula ia isolated by the method stated irv Example 30» The dyestuff via ch is .soluble -in water dyes cellulose materials to bluish red shades dischargeable to white and fast to wetting, abrasion and light, according .to the padding-steaming or- paddi ng-thermo- fixing process. (at 140°C ) * Example 528 ϋ solution of 19.5 parts of the sodium salt of l-aminobenzehe-4-3.ulphonic 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 of concentrated hydrochloric acid the mixture is then stirred at 0-10°C for half an hour and excess of nitrous ac id is then removed.- A cooled and thereby partially crystallised solution of 26.2 parts of the potassium salt of l-aminonaphthalene-e-sulphonic acid in 250 parts of hot water is added at 0-lC C to the diazo suspension thus obtained, and the strongly acidic cc pl.'ng mixture is buffered at 10-20 C tc a pH value of 4 by the careful addition of sodium hydroxide solution. Coupling is rapidly completed; the resultant aminoazo dyestuff is completely salted out with ·: 100 parts sodium chloride, filtered off with suction, washed and redissolved at pK 6-7 in 500 parts water at 10°C . The aquebus soluti on is treated with 29.0 parts 2, -bis-methyl- sulphonyl-5-c hl0ro-6,-m.ethyl- yrimidine arid stirred .at 55-60°C for one hour whilst constantly buffering the liberated acid to H 7-7.5 by means of sodium carbonate solution. When no amino'azd dyestuff can any longer be detected, the partially is salted out with 40 parts sodium chloride, filtered off and redissolved in.800 parts warm water, for purification.

After the solution has been clarified, the pure dyestuff is separated from the filtrate by the addition of 80 to 100 parts sodium chloride. When the product has been filtered off, dried; at 35°C and ground, a yellow powder is obtained which readily dissolves in water with a yellov/ colour and which dyes cellulose fibres in the presence of acid binding agents to yellow shades of very good fastness to wetting, light and chlorine according to one of the above mentioned dyeing processes. Fast yellow dyeings are also obtained on wool and polyamide fibres.

When the procedure is as described above but the 19.5 parts of the sodium 3alt of l-aminobenzene-4-sulphonic acid are replaced by the use of equivalent . amounts of the diazo components listed in the following Table for coupling with l-aminonaphthalene-8-sUlphonic acid, valuable yellow to brow reactive dyestuffs are also obtained after acylation with 2-methylsulphon l-4, 5-dichloro-6-me h l-?yrimidine# Diazo component ' Colour shade on ■· '.'■· cellulose fibres l-Aminobenzene-2, 5-disulphonic acid Redcish yellow 2-Aminona hthalene-4 8-disul honic acid . Stron l reddish Dia o component : . Colour shade on cellulose fibres -Aminonapnthalene-5, 7-disulphonic acid trongly reddish yellow -Aminonaphthale e-6, 8-d isulphonic acid " " " -Aminonapnthalene-3,6, 8-trisulphonic acid " " " rAminonaphthalene-4, 6,8- tr isulphonic acid " " " -Amino-azobenzene-3, 4' -d isulphonic acid Yellowish brown -Amino-2-acetylamin'o-azObenzene- 1 , 51 - d isulphonic acid Orange-brown .

Reddish brown ( 1-Arni nobenz e ne-2 , 5-d is ulp ho n ic ac i d coupled in ac id with 1-aminonaphthal- ene-6-sulphonic acid) Reddish, brown ( l-Arainoben ene-2,5-ciisulphonic acid coupled in acid with a technical mixture of l-aminonaphthalene-6- and -7-sulp onic acid) Violettish brown (l-Aminonaph hale e-2,5, 7- tr isulphonic Colour shade on cellulose fibres Reddish brown ( l-Aminonaphthalene-2', 5, 7-tr.isUlph0nic acid coupled in acid wit l-amiho-2-methoxy-5- methylbenzene) Example 529 t When a cellulose fabric is printed ith- a printing paste whioh contains, per kilogram, 30 g of the dyestuff described in Example 18, 100 g urea, 300 g water, 500 g alginate thickening (60 g sodium alginate per kg of thickening), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitro-benzene-sulphonic acid and which had been made up to 1 kilogram with water, when it is thereafter' su jected to intermediate drying and then steamed at 103 to 115°C for 30 seconds in a suitable steamer, a strongly bluish red print of good fastness to wetting, abrasion and light is obtained after rinsing and soaping by boiling* ' -' ' ■ ·.· Example 530t A mixture o the solutions, one containing 65,5 parts of the 2il ohromium complex and the other 65.5 parts of the 2j the formula each in 400 parts water, is stirred at 60-70°G for about 2 hours 'with 60 parts of finely powdered 2-methylsulphonyl-4,5-dichloro-' 6-methyl-pyrimidine whilst maintaining a pH value of 7-8.

When. o more aminoazo dyestuff can-any longer be detected by chromatography (Co complex: blue; Cr complex: blue-green), the resultant mixture of the two reactive dye stuffs is salted .out with potassium chloride, filtered off and dried.

'. · , Strong black shade.s of very good fastness to wetting, and light are produced when the dyestuff is applied on cellulose materials in the presence, of acid binding agents according to the padding dyeing process or by printing.

When the procedure is similar except that a mixture of the 2:1 chromium and 2:1 cobalt complexes of the following aminoazo dyestuffs is employed, valuable black, dyestuffs are again obtained.

Dlazo component Coupling component pH during coup- ling ; l-Hydroxy-2-amino- l-Hydroxy-8-aminonaphthal- 9 4-nitrqbenzene - ene-3,6-disulphonic acid · l-Hydroxy-2-amino- " " 9 4-nitronapb.thalene- 7-sulphonic acid Example 551: .0 Parts of 2-meth lsulphon l-4,5-d ichloro-6-meth l- pyrimidine are added to a neutral solution. of 53.15 parts of the disodium salt of the aminoazo dyestuff, obtained by coupling diazotised l-amino-4-r.itrobenzene-2-sulphonic acid with l-(2»- chloro-C-sulphopher-ylJ-S-methyl-pyrazolone-iS) followed b reduction of the nitro group with sodium sulphide, . in 300 parts water, and the mixture is stirred at 55-60°C for one hour whilst the liberated acid is constantly buffered to a pH value of 6.5-7 by means of sodium carbonate solution. The separated ΐ ^ . has been reduced to the amino group after coupling so as to form the deeired aminoazo dyestuff.

Example Diazo oomponent Azo component pH value Colour shade o coupling on No, ■ medium cellulose 532 l-Amino-4- nitrobenzene- l-(4' -Sulphophenyl)- 5-6 Yellow 2-sulphonio aoid 3-methyl-pyrazolone- (5) Example Diazo oomponent Azo oomponent pH value Colour shade of coupling on No. medium cellulose 533 1- Amino-4-nitrobenzene- 1- ( 4» -Sulphophenyl)- 5-6 Keddish 2- sulphonic acid 3-carboxy-pyrazolone- ye llow ; (5) (Nitro group in 4-position is subsequently reduced) 534 ; " " l-( 3' -Sulphophenyl)- 6-7 it 3-methyl-5-amino- · pyrazole 535 l-Amino-3-acetylamino- l-(3' -Sulphophenyl) 6-7 benzene-6-sulphonio 3-methyl-5-amino- acid pyrazole (Aoetylamlno group in 3-position is subsequently hydrolysed) 536 it n 1- ( -Hyd r oxy e t hy 1)- 3- 5-6 methy 1- pyrazolone- (5 ) * 2 Moles l-amino-3-acetyl- 1 Mole bis- yrazolone 5-6 amino-benze ne-6- from 4,4'-bis-hydra- suiphonio aoid zinb-dibenz l-i-:,2i- (hydrolysed ) disulphonic acid and ethyl aoetoacetate 538 1 Mole l-amino-3- l-( 4'-3ulphophenyl)- 5-6 aoe ylamino-benze 3-carboxy-pyrazolone- 6-sulphonic acid (5) (hydrolysed ) 539 l-Amino-5-acetylamino- l-(4» -Sulphophenyl)- 5-6 Kedd ish naphthalene-3, 7-diaul- 3-carboxy-pyrazolone^ yellow phonic acid (hydro(5) lysed) 540 l-Amino-kJ-methylbe - 2-Ace ty lamino-5- 7-8 Orange zene- , 6-disulphonic naphthol-7-sulphonic aoid acid (hydrolysed) 541 2-Acetylamir o-8- 7-8 Red. napht ol-6-aulphonic acid (hydrolysed) 542 1-Amin o-2-rcet hy lbe n- l-C loro-2-acetylamino- 7-8 Orange zene-4, 6-disulphonic 5-naphthol-7-sulphonic acid acid (hydrolysed) 543 1- Aminobenzene- l-Acetylamino-O-hydroxy- 7-8 Red 2- sulphonic acid naphthalene-4,6-d isul- phonic acid (hydrolysed) 544 2-Aminonaphthalene- » » 7-8 Bluish red 3.6- disulphonic acid 545 2-Aminonaphthalene- 11 7-8 3.7- disulphonic acid Example Diazo oomponent Azo component pH ¾ralue Colour shade of coupling on No. medium oellulose 2-Aminonaphthalene- .1-Aoe tylamino-8-hy dr oxy- Bluish red 4,8-diaulphonic aoid haphthalene-4,6-d isulphonic acid (hydrolysed) 2-Aminonaphthale e 1-Ac et y lamino-8-hy d r oxy- 3,6-diauiphonic acid hapht hale er 'ό, 6-d isulphonic acid ( ydrolysed ) .546 2-Aminonaphthalene- .. It 4, 8-d isulphonic acid 549. l-Amino-4-met oxy-' •2-(N-aoetyl-N-inethyl- 7-8 Yellowish benzene-2-aulphonio amino )-5-hydroxynaphth- red acid aiehe-7-sul nonic acid (hydrolysed) 550 2- ( N-aoetyl-N-me thyl- 7-8 Red amih o ) - 8 - hyd r ox ynap n t h- alene-6-sulphonic acid (hydrolysed) ,551 1- Aml nobe nze ne - . 7-8 2- sulphonio aoid 552 l-Aminobenzene- 7-3 3- aulphonio acid 553 l-Aminobenzene- 7-8 4- sulpnonio acid 554 1-Ami no-4-Bie thy 1- 7-8 benzene-2-sulphonio acid 555 l-Amino-2, 4-dime thyl- 7-8 benzene-6-sulphonic acid 556 2-Acetylamino-8-hydroxy- 7-8 naphthalene-6-sulphonic acid (hydrolysed) 557 -Acetylamino-8-hydroxy- 7-8 naphthalene- 3, 6-disul- phonic acid (hydrolysed) 558 4-Ami noa z obe nz e ne · l-Amino-3-ace ylamino- 5-6 Ye I low- rown 3, 4'rdisulphonio benzene aoid 559 l-Amino-5-hydroxy- 5-6' aoetylamino-be zene 560 n l-Amihonaphthalene-6- 5-6 sulphonic aoid salt of l-amino-4-(2l-methyl-3'-aminopnenyl)-aminoanthraquinone- 2,5l-disulptionic acid in 1000 parts water is stirred at 65°C .for one hour with 24.0 narts 2-methylsulphonyl-4,5-dichloro-6- methyl^pyrimidine.The hydrochloric acid liberated during this reaction is constantly buffered to a pH value of 6.5-7.5 by means of sodium carbonate solution. When the reaction has been completed, the resultant reactive dyestuff of the formula is salted out, filtered off, washed and dried at 30-40°C. It dyes cellulose materials to full blue shades with very good fastness to wetting, abrasion and light.

Blue dyestuTfs of similar properties are obtained when the procedure is as described above but instead of the water soluble amino anthraquinone derivative specified, equivalent amounts of the aminoanthraquinone-sulphonic acid derivatives listed below are acylated with 2-methL8ulpho.n l-- » 5-dichloro-6-methyl-pyrimidine : Example Water soluble aminoanthraquinone derivative No. 565 l-Amino-4- ( 3» -aminopheny1 ) -aminoanthraquinone- ,51 - disulptionic acid 566 l-Amino-4- ( 2 » -c nloro-3' -aminopnen 1) -aminoanthraquinone- 2,5'-disulphonic acid 567 l-Amino-4- ( 2» -methy1-5' -methylaminopnenylj-aminoanthra- quinohe-2,5'-disulphonic acid 568 l-Amino-4-( 4· -aminophenyl) -aminoan thraquinone-2,6, 3' - trisulphonic acid Example' Water soluble aminoanthraquinone derivative No. 569 l-Amino-4- ( 31 -aminopne yl)-aminoanthraquinone-2, 6, 4 ' - trlsulptionic acid 570 l-Amino-4- (4'-aminopnenyl)-aminoanthraquinone-2, b, 31- jbrisulpnonic acid 571 l-Amino-4- (3» -aminopnenyl)-aminoa.nthraquinone-2, 5, 4'- triaulpnonic acid .72 Mixture of l-amino-4- ( 3» ~aminophenyl)-aminoanthraquinone- 2, 4», 5- and 2, 4 , 8-trisulphonic acid as well as the derivatives af ter-sulphonated at -30°C with 5f oleum: 573 . l-Amino-4-j t1 - ( 4"-aminobenzyl)-pnenyl7-aminoanthra- quinone-2-sulp.nonic acid 574 l-Amino-4- (4' -methylaminopnenyl)-aminoanthraquinone-2- sulphonic acid 575 l-Amino-4- (3' -methylaminopnenyl)-aminoanthraquinone-2- sulphonic acid 578 Condensation product of 1 mole cyanuric chloride with 1 mole 1,4-d iamino-anthraquinone-'-i-sulo onic acid, ■ 1 mole aniline-2,5-disulptionic acid and 1 mole ethylene diamine (one-sided) produces a violet reactive dyestuff after acylation with 2,4-bis-methyl- sulphonyl-5-chloro-6-met1iyl-pyrimidin9.

Example 579: Δ solution of 107 g of a mixture of equal molar proportions of c opper phthalocyanine-trisulphonic acid- (3,3' ,ΰ")- mono- (m-ami o-^sulphophenyl) -amide and copper phthalocyanine- trisulphonic acid- (3, 3«', 3 )-di-(m-amino-£-sulphophenyl)-amide is made up to 1.3 litres and adjusted to pH 7; 50 parts 2,4- bisHmethylsulphonyl-5-ehloro-6-methyl-pyrimidine are introduced into it at 50-55°C. The temperature is raised at a rate of 5°C per hour whilst stirring and it is finally left at 65-70°C for several hours. At the same time, a pH value of about 6.5-7.5 is maintained by the dropwise addition of 3N sodium hydroxide solution, until each dyestuff molecule has on average been provided, with at least one pyrimidine radical which can readily be determined b the consumption of sodium hydroxide solution as well as by a determination of amino groups. For working up, the dyestuff solution can also be heated a little at the specified pH value without appreciably reducing the reactivity of the dyestuff with oellulose. The separation from unreacted 2, 4-bis-methylsulphonyl-5-chloro-6-methyl-pyrimidine and the hydrolysis products formed from it is carried out by filtration or in a separator. The reaction product is precipitated by the introduction of 150 g sodium chloride per litre of dyestuff solution. It is filtered off with suction and dried at about 30°C in vacuo or at ordinary pressure. 195-200 g of the orude dyestuff are obtained, which still contains about 30% sodium chloride. Stirring of the crude dyestuff with 250 ml water and repeated filtration with suction largely removes the sodium chloride.

The dyestuff dyes cellulose materials to turquoise shades fast to wetting, abrasio and light according to the padd ing-thermofixin process at 140°C and according to the padding-steaming process.

The dyestuff mixture employedas the starting material can be obtained by methods known per se, for instance by adding 3 moles 2, -d iaminobenzenersulphonic acid at a pH value of about '6.5 and at 0-20°C to an aqueous suspension of copper phthalo-cyanine-trieulphonic acid chloride free from sulphonic. acid groups and simultaneously, catalysing the hydrolysis with 3 moles pyridine, the above mentioned mixture of the phthalocyanine- sulphonamides. being, formed.

A similar produc is obtained when the mixture employed as the starting material' contains .the above- specified components .'.'in- a molar proportion of 4:1. This mixture is obtained from the same copper phthalocyanine- risulpnonic acid chloride and 2 moles 2.4-diaminobenzene-sulphonic acid according to the same method.

The above mentioned starting materials may also be replaced by the use of those containing nickel instead of copper as the central atom or those prepared from copper phthalocyanine- trisulphonic acid chloride-(4,41 , 4" ) or from phthalocjranine- tetrasulpnonic acid chlorideM'3, 4« , 4", 4"' ) or -'(4,4' ,4", 4"» ) or with the use of other arylene-diamine-sulphonic acids such as toluylene-diamine-(2,4)-sulphonic acid-(5); 4, 4 '-diamino- dibenzyl-disulphonic acid-(2,ii' ); or napnthylene-diamine-( 1,5)- disulphonic acid-(3,7). Such products and their preparation have many times been described in the patent literature. Their reaction with 2, 4-bis-methylsulphonyl-5-chloro-6-methyl- pyrimidine or 2-met yls.ulpnon l-4,b-dic hloro-6-methyl-pyrimidine: can in every case be carried out by the same method.

This also applies to the reaction of 2-methylsulphonyl- 4.5-dichloro-6-methyl-pyrimidine with the copper and nickel phthalocyanine : itvbermediate products producing green reactive dye stuff s, such as are for instance obtainable by. the poly- sulphoc hlorination of te tra- ( 3 , 3 * , 3 " , 3" 1 ) - Cp_- 1 o ly l-me rc apt o ) - copper phthalocyanine with c lorsulphphic acid, condensation of 1 to 2 sulphochloride groups per molecule with 1,3-phenylene- diamine-4-sulpnonio acid or 1, 4-phenylene-diamine-3-sulphonic acid and hydro iy s is. of the residual sulphochloride groups the homogeneous or mixed arylation and alky lat ion products of tri- a d tetrarmercapto copper (or nickel) phthalocyanine whioh contain amino and sulpho groups can also be converted to valuable green reactive dyestuffs by an analogous process, by means of the acylation of their amino "group with 2, 4-bis-methy 1- sulphonyl-5-chloro-6-methyl-pyrimidine.

Example 580: ' · ■' ", '. . ■ When the procedure is in accordance with the stdatements of Example 344, but the resultant dyestuff intermediate product is coupled with the diazo compound from 20.8 parts 3-chloroaniline-6-sulphonic acid instead of the diazo compound from 17*5 parts of 2-aminobenzene-sulphonio acid, at a final pH value of 7 in the presence of 12 parts sodium 'is obtained, which can be used for dyeing or printing cellulose materials to brilliant red shades fast to wetting from a dilute liquor at 40°C or according to one of the usual padding or printing processes for reactivedyestuffs, with sodium carbonate as the acid binding agent.

Valuable reactive dyestuffs are also obtained by an analogous method from the coupling components listed in the following Table by the acylation of their amino group with 2-methylsulphony1-4, 5-dichloro-6-me hyl-pyrimidine and coupling of the resultant dyestuff intermediates with the specified diazo. components, and these can be used for dyeing or printing cellulose materials to the stated shades, preferably. in the presence of sodium carbonate: Example Diazo component Coupling componen pH value Colour of coupling shade, ^^^^ medium 581 1-Amino-4-methoxybenzene- l-Amino-8-hydroxy- 7-8 Violet 6-sulphoriie acid naphthalene- . 3, 6-disulphonio acid 582 1-Amino-8-hydroxy- 7-8 Reddish naphthalene- violet 4.6-disulphonic acid 583 2-Amino-5-hydroxy- Scarlet naphthalene- 1.7-disulphonic acid 584 1-Amino-5-c lprobenzene- 2-Amino-5-hydroxy- Orange 2-sUl honic acid naphthalene- 1, 7-d.isulp onic acid «5 l-Aminobenzene- 7 3-sulphonic acid 586 1-Aminobenzene- 7 4-sulphonic acid 587 2-Amino-8-hydroxy- 7-8 Scarlet naphthalene- 3,6-disulphonic acid 588 4-Aminobenzoic acid- 1-Amino-8-hyurox - 7-8 Red (P-sulphoethy1) -amide naphthalene- 3, 6-disulphonic acid 589 l-Amino-4-sulptio- 7-8 Violet acetylaminobenzene- 6-sulphonic aoid 590 l-Amino-3-sulpho- 2-Amino-5-hydroxy- Orange acet laminobenzene* naphthalene- Example Diazo component ; Couplin component pH value Colour of o'oupling o . , ■ ' ;'/' medium shade l-Amino-4-sulphq- 2-Amino-5-hydroxy- Scarlet aoe ylaminobenzene napht alehe- 1,7-disulphonic aoid 592 l-Aminobenzene- 1- ( » -Met hy 1-3 » -amino- Yellow 2,4-disulptionlo 5'-aulphophenyl)-3- acid met hyl- pyrazolone- (5 ) .593 2-Amlnonaphthalene- 6 Ye How , ■ 4,8-disulphonio aoid Example 594 i When the procedure is as stated in Example 356 except that the dyestuff intermediate obtained from 1,3-diamino- benzene-6-aulphonic acid and 2-methylaulphonyl-4,5-dichloro-6- methyl-pyrimidi e ia diazotiaed at 10°C and pH 7.5-6.5 before being coupled with a aolution of 40.5 parta of the disodiunr aalt of 2-aulphoaoetylamino-5^hydroxynaphthalene-7-sulphonic acid, a reactive dyestuff of the formula ia obtained which dyea celluloae materials to fast orange shades according to the usual methods of application, with the use of sodium oarbonateas the acid binding agent.

Example 595: When the procedure is as stated in Example 531 except that the aminoazo dyestuff there employed is replaced by the use of 53.15 parts of the disodium salt of theaminoazo dyestuff, obtained by coupling diazotiaed l-amino-4- nitrobenzene-2-sulphoni'c acid with l-(2 '-chloro-5 '-sulphophenyl)- 3«methyl-pyrazolone-(5) followed by reduction of. the nitro group with sodium sulphide, for acylation wi.th 2,4-bis-methylsulphonyl- 5-c hloro-'6-meth l- yrimidihe,. a valuable reactive dyestuff is again obtained which prints cellulose materials to fast yellow shades according to the usual dyeing and printing processes.

Similar reactive dyestuffs are obtained when the above mentioned aminoazo dyestuff is replaced by the use of one ..of the aminoazo, dyestuffs; synthesised from the components . listed in the. following Table, for acylation with 2-methyl- sulphonyl-4, 5-dichloro-6-methyl-pyrimidine : ^cample Diazo component Azo component Colour No. ; ; shade 596 l-Amino-4-nitrobenzene- 1- (2 '-Methy1-4' -sulphophenyl)- Yellow 2-sulphonic acid (re- 3-methyl-pyrazolone- (5) duced ) 597 " " l-(2» ,5«-Disulphophenyl)~ Yellow 3-met 1-pyraz olone- ( 5 ) 598 n " l-(2» -Methy1-4' -sulpho-6'- Yellow chlorophenyl)-3-methyl- pyrazolone-(5) 599 " " l-(2» ,5'-Dichloro-4«-sulOho- Yellow Dhe yl)-3-methy1-pyraz olone-φ (5) OO l-Amino-3-acetylamino- l-(2« -Meth 1-4' -sulphophenyl)- Greenish benzene-6-sulpnonic 3-methyl-pyrazolone- (5) yellow acid (hydroiysed ) ' : 601 " " 1- (4' -Sulphophenyl)- " " 3-methyl-pyrazolone- (5 ) 602 " " 1- (2' -Meth 1-4' -sulphophenyl)- " " 3-carboxy-pyrazolone- (5) 603 " " l-(2'-Chloro-4'-3ulp!ophenyl)- " " 3-carboxy- yrazolone- (5 ) Example 604: 58 Parts of the dyestuff of the formula - is salted out, filtered off, washed and dried at 30-40°C . It dyes cellulose materials to .very fast violet shades according to one of the above specified processes.

Dyestuffs of similar properties are obtained by analogy with the above described procedure from the copper complexes (obtained by simple, demethylating or oxidative ooppering) of the monoazo and disazo dyestuffs prepared from the diazo and. azo components listed in the following Table: Example Diazo component Δζο component pH value Colour of coupling Ηο· ■ medium shade 617 3-Me hoxy-4-amino- 2-Amino-5-hydroxy- 10 Navy 6HBiethyl-azobenzene- naphthalene-1, 7- blue 2' ,5· -disulphonio disulphonio acid aoid (coppered with demethylation) Example 618: When the procedure is in accordance with the statements in Example 564 but the 54.7 parts of the disodium salt of l-amino-4-^"(2|-methyl-3,-aminophen l7-amino)-anthra- quinone-2,5-disulphonio acid specified there are replaced by the use of 63.5 parts of the trisodium salt of l-amino-4- ^ 5'-aminophenyl)-aminor-aBthraquinone-2,41 ,6'-(or -2, 2', 6'-) trisulphonio acid, a reactive dyestuff is obtained, which dyes oellulose fibres to full reddish blue shades having very good fastness to wetting, according to one of the usual dyeing processes.

When an equivalent amount of l-amino-4 (3'-amino- phenyl)-amino^-anthraquinone-2, 5,8-trisulphonio acid is employed, a valuable reactive dyestuff is again obtained, which dyes cotton to fast greyish blue shades.

Example 619; . 30*4 Parts 2-amino-8-hydroxynaph alene-3,6- disulphonio acid are dissolved neutral in 300 parte of water heated to 60-65°G, and 25 parts 2,4-bis-methylsulphonyl-5- chloro-6-methyl-pyrimidine are added. 40 Parts of a 15$ sodium oarbonate solution are added during one hour so that the pH value remains between 6 and 7.5. The acylation product is partially precipitated.

A freshly prepared diazonium salt solution from are acylated with 2-methylsuiJ.phonyl-4,5-dichloro-6-methyl~ pyrimidine instead of the 30.4 parts of 2-amino-8-hydroxynaphth- alene-3, 6-disulphonic acid before the coupling component containing the reactive groups is coupled with diazotised £- aminobenzyl-sulphonic acid,- a readily soluble reactive dyestuff is obtained which dyes fabrics containing cellulose fibres to brilliant reddish orange shades.

Cotton or cellulose staple fabric is impregnated at 20-25°G on a foularding machine with a solution which, contains, per litre of liquor, 30 g of the dyestuff described in Paragraph 1 of this Example, 100 g urea and 20 g sodium carbonate, it is squeezed out to a moisture content of about 100 and the moist fabric is rolled up again. After the fabric has been left to stand at room temperature for 24 hours, it is rinsed, soaped by boiling as usual and dried. A brilliant scarlet dyeing of good fastness to wetting and light is obtained.

Cotton or cellulose staple fabric is impregnated at 20-25°C on a foularding maohine wit a solution which contains, per litre of liquor, 50 g of the dyestuff described in Paragraph 1 of this Example, 100 g urea and 20 g sodium carbonate, it is squeezed out to a moisture content of about 100$ and steamed at l03°C for 30 seconds. After rinsing, soaping b boiling and drying, a brilliant scarlet dyeing of good fastness to wetting and light is again obtained.

Cotton fabric is impregnated at 20~25°C with a solution which contains, per litre of liquor, 20 g of the dyestuff obtainable according to Paragraph 1 of this Example and 0.5 g of a non-ionic wetting agent (for instance a polyethoxy-lated ole l alcohol) as well as 150 g ureaand 15 g sodium bicarbonate. The fabric is thereafter squeezed out between two rubber rolls to a moisture content of about 100 . after it has been subjected to intermediate drying at 50-60°C, the fabric is heated at 140°C for 10 minutes, and the resultant dyeing is thoroughly rinsed with hot water and boiled for 10 minutes with a solution which contains, per litre, 5 g of Marseilles soap and 2 g sodium carbonate. A strong scarlet dyeing of good fastness to wetting and light is obtained after rinsing and drying.

When cellulose fabric is printed with a printing paste which contains, per kilogram, SO g of the dyestuff described in Paragraph 1 of this Example, 100 g urea, 300 g water, 500 g alginate thickening (60 g eodium alginate per kilogram of thickening), 10 g sodium carbonate and 10 g of the sodium salt of 3-nitrobenzene-sulphonic acid and which had been made up to 1 kilogram with water, when it is thereafter subjected to intermediate drying and then steamed at 103-115°c for 30 seconds, in a suitable steamer, a strong scarlet dyeing of good fastness qualities is obtained after rinsing and soaping by boiling. 100. Parts wool are( introduced, at 40°C into a liquor which contains 1.5 parts of the dyestuff described in Paragraph 1 of this Example in 5000 parts water as well as 6 parts of 30$ acetio acid and 0.5 parts of a polyethoxylated stearylamine derivative containing hydroxyl groups. The dyeing liquor is brought to the boil during 30, minutes and dyeing is then carried out at the boiling point for. one hour. A brilliant scarlet dyeing of good fastness to washing, fulling and ligh is obtained after rinsing arid drying.

Example 620: 28.9 Parts 2-amino-l-methylb§nzene-3,5-disulphonic acid (as the monosodium salt) are diazotised and the diazo compound is coupled in a weakly aoidic medium with 13.7 g l-amino-2-methoxy-5-methylbenzene. The resultant monoazo dyestuff is either isolated" and diazotised or not isolated and its solution- directly diazotised, 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 and filtered, off with suction, and the isolated product is metallised at.95-lG0°C for 5 hours with about 50 parts copper sulphate crystals, 40 parts diethanol-amine, 50 parts aminoniurn hydroxide solution ( d_ = 0.88). The dyestuff is isolated from the coppering solution by the addition of salt and careful acidification.

. The aqueous solution of the coppered amino-disazo dyes uff is now acylated at a temperature of 60 to 65°c and at a pH value of 7-8 with 24.0 parts 2-methylsulphonyl-4,5-dichloro-6-niethyl-pyrimidine , whilst the pH value is maintained within the specified range "b the addition of sodium carbonate. When acylation has been completed, the dyestuff is isolated with wetting and light according to the processes known for reactive dyestuff a.

Further dyestuff s according to the invention can be prepared by an analogous method when the above mentioned monoazo dyestuff from 2-amino-l-methylbenzene-3,5-disulphonic acid and l-amino-2-methoxy-5-methylbenzene is combined in accordance with .the above directions with 2-methylsulphonyl-4,5-dichloro-6-methyl-pyrimidine and the aminonaphthol-sulphonic acids listed in the following Table: Coupling component; 2-Amino-5-hydroxynaphthalene-l, 7-disulphonic acid 2-Amino-8-hydroxynaphthalene-¾,6-disulphonio acid The resultant dyestuff s have a blue colour.

Example ,621: .0.1 Mole 4-ure ia -2-amino-l-hyuroxybenzene-5-sulphonic acid are diazotised and coupled with 0.1: mole 1-amino-C-hydroxy-naphthalene-2,4».disUiphonic acid in a medium made alkaline with aodium carbonate . The . coupling solution is made up to a content of 2 moles/litre with caustic soda a.nd then refluxed for 3 hours in'' order to hydrolase the ureido group. After cooling, it is neutralised with hydrochloric acid. The dyestuff is metallised' at 45°C and a a pH value of 4-6 by the addition of 25 parts copper sulphate and 100 parts of 2 N sodium hydroxide solution, and after 30 minutes the product is acylated at a temperature of 60-70°C and at a pH value of 7-7#5 with 0·1 mole 2-methylsulphonyi-4,5-r5ichloro-6-methyl-pyrimi<-iine» The resultant dyestuff. of the formula "- al made 216 g 0-3°C g) pyridine, and the pyridine is thereafter steam distilled at pH 9.0 from the resultant solution of copper phtiialoc anine- disulphonio acid-mqnosulphonic acid-(3,-sulpho-4l-me hyl-aminomethyl-anilide). .330 g of finely powdered 2-methyl-sulpho yl-4, 5-di0nloro-6-methyl*pyrimidine are added by portions during 1 to 2 hours to the solution, which had been heated to 60°C, whilst a pH value of 7.5-8.5 is maintained by the addition of dilute sodium hydroxide solution. At the same time, the .reaction mixture is diluted with water, as required in order to keep the dyestuff in solution throughout. 1 of a dyestuff solution are obtained, which is separated from excess of the acylation agent, adjusted to pH 7.0 by the addition of acetic acid and precipitated by stirring in 2.5 1 of a concentrated sodium chloride solution.

A full turquoise-blue dyestuff is obtained after filtering with suction and drying at 3G°C, and this is fixed at a very good yield on cotton at 40-60°C from a solution made alkaline with sodium carbonate and exhibits, very good fastness to- washing.

A turquoise-blue dyestuff of only a little less green shade and equally valuable properties is obtained by the use of nickel phthalocyanine-3,3' , 3"-trisulpbonic acid chloride as the starting material.

Example 625: the aminoazo dyestuff of the formula as prepared according to the statements In German latent Specification' No.. 1 115 865 (Application F 27466 IVb/22a) by couplin the diazo ni urn compound from 2-aminonaphthalene-4,8-disulphonic acid- with. l-aminonaphthalene-6-sulphonic acid, further. diazotisation of the resultant aminoazo dyestuff, coupling with an equivalent amount of 2, 5-diaminonaphthalene-4,'8-disulphonic acid and conversion to the aminotriazole, is dissolved at pH 6 In.lOOO parts by volume of water and treated at a temperature' of 60-65°C with 24 parts 2-meth lsulphonyl-4,5-dichloro-6-methy¾.-pyrimidine, whilst stirring. The hydroohloric acid which is slowly liberated is buffered with sodium carbonate solution until the reaction has ,οζοηβ to completion. The' dyestuff is thereafter separated b the addition of sodium chloride, isolated and dried in vacuo at about 50°C. It consists of a yellow .powder which dissolves in water with a yellow colour.

Example 624; 38.9 Parts of the dyestuff obtained by coupling. 6-nitro-2-diazo-l-hydroxybenzene-4-sulphoriic acid with 2-hydroxynaphthalene in a medium" made alkaline with sodium carbonate are stirred at pH 8 and at a temperature of 7O-80°C with 200 parts water. 67.9 Parts of the chromium complex compound of the azo dyestuff from 4-chloro«2-diazo-l-hydrozy-benzene-6-sulphonic acid and l-amino-8-hydroxynaphthalene-3,6-disulphonic acid, which contains 1 chromium atom per 1 molecule of dyestuff, are introduced into this suspension whilst the pH value is maintained between 7 and 9 by the dropwise addition of sodium carbonate solution. A dark blue solution has been f earned after 20 minutes at 70-80°C · . Λ paper c roma to gram indicates that a homogeneous mixed complex has been formed* and dyes cotton to grey to black shades according to the processes stated in Examples 327-329.

Valuable dyestuffs can also be obtained by the method described in this Example from the starting components specified in the following Table. The azo dyestuff which has the reactive group in the 2:1 mixed complex was always introduced in the form of the 1:1 chromium complex for the preparation of these dyestuffs.

Example 1:1 Chromium complex Metal-free dyestu No. 625 4-Nitro-2-amino-l-hydroxybenz 4-Nitro-2-amino-l~ 6-sul honic acid :—^ 2-hydrox naphthale l-amino-8-hydroxynaphthalene- 3, 6-disulphonic acid 626 627 628 4-Nitro-2-a ino-l- 2-hydroxyna hthale 629 630 4-Nitro-2-anjino-l- 1-hydroxyn phtha 1e 631 6-Nitro-2-amino-l- 4-sulpho.nic acid 2-hydroxyna phtha le 632 4-Ni ro-2-amino-l- l-acetylamino-7-hy 633 6-Nitro-l-amino-2- 4-sui honic acid 2-h droxynaphthale 634 4-Ni ro-2-anino-l-hydroxybenzene- 4-Ni ro-2-amino-l- 6-sulphonic acid :—^ ό-sulphonic acid l-amino-8-hydroxyna hthalene- 2-hy rox na hthale 4, 6-di sulphonic scid 1:1 Chromium complex Me al-free dyes o 635 4-Chloro-2-araino-l-hydroxybenz 4-Nitro-2-amino~l-hyd 6-sulphonic acid : =■ ^ 2-hydroxyna hthalene 1-amiήο-8-h droxynaphthal ene- 3,6-disulphonic acid 636 637 4-Nitro-2-amino-l-hyd 2-hydroxynaphthalene- 638 4-Chioro-2-amino-l-hy 2-hydroxy a hthalene 639 4-Nifcro-2-amino-l-hyd 1- acetylamino-8-hydr o 3, 6-di sulphonic acid 640 4- i ro-2-amino-l-hyd 1- amino-8-hydroxyna ph 2,4-: disulphonic aci 641 o- itro-l-amino-2-hyd 4-sulphonic acid 2-hydroxynaphthalene Example 1:1 Chromium complex Metei-f No. 4-Chloro-2-amino-l-hydrbx benzene 2-Aminobenzene-l- 6-sulphonic acid —: ^ 5-sulphonic acid l-amino-8-hydroxynaphthalene- l-Phenyl-3-meth l 3, 6-disul honic acid 4-Nitro-2-amino-l-hydroxybenzene- 6-Nitro-l-ami o-2 6-sulp onic acid : ^ thalene-4-sulphon l-amino-8-hydroxynaphthalene- 2-hydroxynaphtha l •3,6-disulphonic acid 4-Ghloro-2-amiio-l-hydroxybenzene 4-Chloro-2-amino- 6-sulphonic acid — 1- (41 -sulphopheny l-amlno-8-hydroxynaphtha.lene- 5- yrazolone -'. 3, 6-disulphonic acid 4-Methyl-2-amino-l-hydroxyber)zene 4-Chloro- -amino- 6-sulphcnic acid : — > 2-hydroxyna^ii ha1 l-amino-8-hyd oxynaphthal ene- acid 3, 6-disulphonic acid 4-Nitrp-2-ami o-l-hydroxybenzene- 5-Nitro-2-amino-l 6-suiphonic acid ■ ϋ-hyaroxynapht hal l-amino-8-hyaroxyna h a iene- 3,6-disuIphonic acid .

Example 1:1 Chromium complex Metal-free dy No. 647 4-Nitro-2-amino-1 - ' 6-sulphonic acid l-amino-8-hydroxyn 3,6-disul'phonic ac 648 11 649 6-Nitro-4-chioro- 1-hydr xynaphthal — I_ I 62.0 Parts of the trisodium salt of the dyestuff obtained from diazotiaed 4^chloro-2-aminp-1-hydroxy-benzene-6-sulpho.nic acid with 1-amino-8-hydroxynaphthalene-¾,6-disulphonl» acid by couplin in a medium made alkaline with sodium carbonate are treated in 300 parts water at 90 - 80°C and at a pH value of D-0 wi h 54.2 oar c of the 1:1 chromium complex of the dyestuff from 6-nitro-l-diazo-'^-hydroxynaphthalene-4-sulphonic acid and- 2-hyd roxynaphthalene .. A deep "blue solution', has formed af er 10 minutes.

The mixed comple is acylated at 60-65°C and at a pH value of 6.5-7.5 with 26 parts 2-methylsulphonyl-4,5-dichloro- 6-metnyl-pyrimidine. during about one hour. During this operation, the pH value is kept constant by the dronwise addition of sodium carbonate solution. The acylated dyestuff is separated with 20 ■ sodium chloride, filtered off with suction and dried at 30°C .

It produces a blue-black print of excellent fastness to light and washing on cotton according to the process ctated in Example 329.

Example 650: 6 g i-Amino-4-(4'-aminophenylamino)-anthraquinone-2,5,8-trisulphonic acid, in the form of its sodium 3alt, are dissolved in 180 mi water. at 40°C, the solution is adjusted to pH 8, and 3.0 g 2-methylsulphonyl-4,b-dichloro-6-methyl-pyrimidine are introduced at 65-70°C by .small portions. At the same time, dilute sodium hydroxide solution is added dropwise at a rate to ensure the maintenance of a pH value of 7.5-8.5 during the reaction. Stirring at 65- 0°C is continued until all the starting material, has disappeared, excess o the pyrimidine derivative is filtered off with suction, and the product is salted out at 10°C with sufficient solid. sodium chloride for an approximately 10$ sodium chloride solution to be formed. It is filtered off with suction and was ed with some sodium cnloride solution, and the resultant dyestufr of the formula is dried in vacuo below 400C · About 8.5 g of the dyestuff are obtained, in the form of blue-green needles.

The dyestuff dyes cotton to strong blue-green shades of good fastness to wetting and light according to the normal processes for reactive dyestuf s.

. The l-amino-4-(4,-aminophenylamino)-anthraquinone-2, 5, 8-trisulphonic acid employed as the starting material was o a ne as o ows: . g p_-p eny ene- am ne are ^ introduced under nitrogen into a solution of 62 g of the sodium salt of l-amiho-4-bromo-anthraquinone-2, 5,8-trisulphonic acid and 12 g sodium carbonate and stirred at 40°C with added cuprous chloride paste until no more disulpnonated bromoamine acid oan any longer be detected. The solution is then treated with dilute, hydrochloric acid, and the dyestuff which separates during this operation is filtered off with suction, washed with dilute hydrochloric acid, mixed in 300 ml water with a dilute sodium hydroxide solution in such an amount that dissolution just takes place and the dyestuff is precipitated in the heat in the form of its sodium salt; the product is then washed and dried.

In the above described Examples, the employed reactive components may in every case be interchanged under the same or similar reaction conditions. Moreover, the reactive components listed in Paragraph 2 , on page 11 can be used in the reactions according to the preceding Examples with equally good or similar results instead of the reactive components indicated therein.

Example 651: 79.9 Parts of the aminoazo. compound of the formula H03S as prepared according to Belgian Patent Specification No.599 581, are dissolved at 60-65°C in 500 parts water and treated at this temperature with 24 parts 2-methyl-sulphonyl- 4,5-dichloro-6-methyl-pyrimidine, whilst stirring. The hydrochloric acid which is slowly liberated is buffered with sodium' carbonate solution so as to maintain a pH value at between 5 and '6. Whe n the - condensation has been completed, the dyestuff is. salted, out by the addition of 150 parts potassium chloride, •isolated and dried in vacuo at about 50°C. A dark powder, is . obtained, which dissolves in water with a. blue colour arid 'which dyes . cot ton to' redd ish blue shades of excellent fastness to light and' ashing.

As is evident from the introductor description and is known in practical technology, the dyeing, agents according to the" .invention still contain salts in addition to the dyestuff; someofthese salts originate from the process of preparation of the dyestuffs and/or may possibl have been added as adjusting agents, and the dyeing agents can also concain other adjusting agents and assistants, as required.

Example 652 : 12.5 Parts 3-amino-4-sulpnobenzyl-N-meth lainine are dissolved in 150 parts by volume of concentrated .hydrochloric aoid . A solution of 4 parts sodium nitrite in 20 parts by volume of water is added dropwise to this solution. The resultant, c lear diazonium salt solution is added dropwise at 30-35°C to an aqueous solution of an equimolar amount of 1-N- benzoylamino-8-hydroxynaphthalene-4,6-disulphonic acid and 16 parts sodium bicarbonate in 200 parts by volume of water.

The dyestuff is partially precipitated and is redissolved by adding 2000 parts by volume of water. 20 Parts 2,4-bis-mothylsulphonyl-6-methyl-pyrimidine are then added at 55-60°C . Tne pK value is maintained at between 7 and 8 by the dropwise addition of sodium carbonate solution. When the acylation has been completed, as recognised by the consumption of sodium carbonate, the dye-stuff is separated, with 10 percent sodium chloride, filtered off with suction and pressed off, and dried at 50°C in a vacuum drying cabinet. The resultant bluish red dyestuff, in the form of the free acid, corresponds to the formula Example 655; .1500 par s by volume of an aqueous solution of 56,8 parts of the tris odium salt of. an aminoazo compound, which had bee obtained by coupling diazotised l-aminobenzene-2». sulphonic acid with. l-acetylamino-8-hydroxynaphthalene-3, 6-disulphonic acid in the presence of sodium carbonate and eliminating the acetyl group by heating at 80 to 85°G in an aqueous solution containing about 4% caustic soda, are added dropwise at about 0°C to an ice cold aqueous-methanolio suspension of 50.1 parts by weight of 2, , e-tris-phenylsulphonyl-triazine-d, 3, 5) containing 2 parts by weight of the condensation product of oleyl alcohol with 20 moles ethylene oxide, whilst the liberated acid is continuously buffered to pH 5 to 6· The solution is stirred at 0 to 5°C and pH 5 to 6 for a few minutes and then adjusted to a pH value of about 6.5 with 100 parts by volume of a solution of 185 parts KH2PO and 262 parts NagHP04.12 HgO in 1000 parts water.

The resultant dye stuff of the formula is salted out with 200 parts by weight of sodium chloride, filtered off with suction and washed with acetone. The dark powder is then mixed with 10 parts by weight of a mixture of 42 pants Na2HP04 and 75 parts KHgPO^ and it is dried in vacuo at 20 to 30 °C. It dissolves in water with a red colour.

The same dyestuff is obtained when l-amino-8- b^droxynaphttialene-3,6-disulphonic acid acylated with tris-phenylsulpnonyl-triazine is coupled with diazotised 2-amino-benzene-sulphqnic- acid at pH 5 to 6 and at a temperature of 0 to 5°C.

When printed on cellulose fabrics with sodium carbonate as the acid-binding agent, the dye stuff obtained, according to one of the above directions produces a strong bluish red print having good fastness to wetting and light.

Similar dyeings are obtained on cotton fabrics from a dilute liquor according to the .thermal fixing process or according to the short term cold padding process.

Example 654: solution of 19.2 parts by weight of the dyestuff of the formula in 1000 parts water neutralised with sodium carbonate is aaded dropwise to an ice cold aqueous-methanolic suspension of 18.5 parts by weight of 2,4,6-tris-phenylsulphonyl-triazine-(l, 3,5) containing 1 part by weight of the condensation product of oleyl alcohol with 20 moles ethylene oxide, whilst the liberated acid is continuously buffered to pH 5 to 6. The mixture is stirred at 0 to 5°C and pH 5 to 6 for a few minutes and then adjusted to a pH value of about 6.5 with 50 parts by volume of a consists of a dark powder which dissolves in water with a blue colour, and which produoes a blue dyeing, on oellulose fibres whe it is applied at room temperature from a solution made alkaline with sodium carbonate, or from an aqueous solution by padding and after-treatment of the padded material, optionally after drying, with an aqueous solution containing sodium hydroxide solution and sodium chloride, or by printing with a printing paste containing urea and sodium carbonate. The dyeings are characterised by high fastness to washing and light* Valuable reactive dyestuffs corresponding to the following formulae: which also dye oellulose fibres to blue shades, are obtained by reacting 2,4,6-tris-phenylsulphonyl-triazine-(l,3,5) , with other anthraquinone dyestuffa containing amino groups.

Example 655: When 54.4 parts by weight 2,4, 6- tris- ( -methylphenyl) sulphonyl- triazlne-( 1,5,5) are reacted by analogy with the directions in Example 653 with 49.7 parts of the disodium salt of the deacetylated amiribazo compound from diazotised 4-amino-anisole-sulphdnic acid-(3) and 2-acetylamino-5-hydroxynaphthal-ene-7-sulphonic acid, the dyestuff of the formula is obtained* This consists of a red-brown powder soluble in water with a red colour which dyes cellulosemate rials to fast scarlet coloured shades* When 2,4, 6-tria-phenylsulphonyl-triazine-(l,5,5) is reacted with other aminoazo compounds by analogy with the directions in Example 655, the dye stuffs specified in the following Table are obtained which dye cellulose materials to the given colour shades* S03H OH orange orange orange orange OH orange orange OH OH orange scarlet scarlet let let red red olet Other red or orange coloured dye stuffs are obtained b employin the dyestufi's made up from the components specified in Examples 19 to 29 and not mentioned here.

Example 656 : When In Example 653 the amlnoazo dyestuff specified there is replaced by 0.1 mole of the coupling product of diazotised 2-aminonaphthalene-4,8-disulphonic acid and 5-amino-toluene but the procedure is otherwise the same, the dyestuff of the formula is obtained. It consists of a yellow powder which dissolves in water with a yellow .colour and dyes cellulose materials to fast yellow shades.

Yellow dyeings on cellulose materials are also obtained with the dyestuffs of the following formulae available by an analogous method* Other yellow dye stuffs of this type can be obtained with the corresponding use of the dyestuffs in Example's -4 to 17 by condensation with 2, 4,6-tris-paenylsulphonyl-triazine-(l,3, 5) · Example 657; When 45.4 parts Dy weignt of ^,4, 6-tris- (£-methyl-phenylj-sulphonyl-triazine- ( 1, 3, 5) are reacted according to the directions in Example 653 with 48.3 parts by weight of the deacetylated amlnoazo compound from diazotised 4-(N-acet lamino)-2-amino-benzene-sulphonic acid and 1- (4 '-sulphojihenyl) -pyrazolone-5-carboxylic acid-(3), the dyestuff of the formula is obtained. It consists of a yellow powaer which dissolves in water with a yellow colour and dyes cotton to greenish yellow shades naving good fastness^properties.

Dyestuffs with a similar colour shade on cotton and prepared by an analogous method are as follows: Example 658: 0.1 Mole of the copper oomplex compound of the formula Na0„S is' dissolved at pH 6 in 1500 parts water and condensed at 0 to 5°C with a met hanolic -aqueous suspension of 0.1 mole 2,4, tris-phenylsulphonyl-triazine-(l, 5,5) containing 2 parts by weight of an emulsifying agent, whilst buffering with sodium carbonate solution and stirring vigorously. The reactive dyestuff thus obtained dyes cellulose materials to ruby shades fast to wetting, abrasion and light.

The metal complex compounds specified in Examples 48 to 63 can be converted to reactive dyestuffs in the sulphonyl- triazino series under analogous conditions.

Very brilliant blue dyeings on cotton are obtained with the dyestuff of the formula syntheslsed by an analogous method.

Example 659: A solution of 50.1 parts by weigh . of 2,4, 6-tris- phenylsulphonyl-triazine-( 1, 3,5) in aqueous methanol is added to a solution of 2 parts of the sodium salt of 1, 3-diaminoben- zehe-6-sulphonlc acid in 100 parts water, whilst stirring well, and the mixture is stirred at 0 - 5°G whilst continuously buffering the liberated acid to pH 5 - 6 until a sample produces a clear yellowish red colour when diazotised and coupled with 1-hydroxynaphthalener4--sulphonic acid. After addition of ice the resultant dyestuff intermediate is directly diazotised with 7 parts sodium nitrite and 28 parts of concentrated hydrochloric acid, and finally combined with a previeuely prepared solution o 47 parts of the sodium salt of 1-benzoylamino-8-hydroxy-naphthal ne-3,6-disulphonic acid and 12 parts sodium carbonate in 200 parts water, resulting in coupling to form the dyestuff of the formula C whioh is salted out, filtered, with suction, washed, and dried in vaouo at 20 - 30°C · The dye stuff dissolves in water with a red colour and produces clear bluish red dyeings and prints on cellulose materials, with good fastness properties.

Dyeatuff s with the stated shades can be obtained by an analogous method from the combinations specified in Examples 31 to 46.

Example 660; Condensation of the reaction products of copper phthalocya ine sulphochiorides and 1, 3-diami obenzene-4-3ulphonIc acid described in Example 64 with 2,4, 6-tris-phenylsulOhonyl-triazine-( 1, 3,5) at 5 - 10°C and at a pH value of 6 - 7 produces dyestuffs which dye cotton and regenerated cellulose to clear turquoise shadee having good fastness to wetting, abrasion and light according to one of the above specified dyeing or printing processes.

A particularly valuable type of dyestuffs is obtained when the condensation product of copper phthalocyanine tetrasulphochloride and 1, 3-diaminobenzene-4-sulph0nic acid is reacted with a solution of ammonium hydroxide so that a compound of the following composition is obtained CuPc wherein a = ' 2,7-2 and b = · ' 0,3-1. i'ne condensations with the reactive components, for instance' 2-methylsulphon l-4, 5-dichloro-6-me hylpyrimidine, 2-moth isulphoriyl-4-chloro-6-methy lpyriniid ine , 2,4, 6-tris-phenylsulp onyl-trioxine-( 1, 3,5) , 2-methylsulphonyl-4-c loro-5-bromo-6-raet hylpyrimidine , 2-methylsulphonyl-4-c hloro-5-cyano-pyriiuidine etc. are in each case carried out under the normal conditions.

Example 661; .

When those dyestuffs or dyestuff intermediates described in Examples 65 - 326 which contain amino groups are condensed with 2,4, 6-tris-phenylsulphonyl-triazine-(l,3,5) as specified in Examples 653 - 660 and optionally further reacted in an appropriate manner, fixation dyestuffs are obtained which produce dyeings with excellent wet fastnesses.

Example 662; YJhe the dyestuffs described in Examples 653 - 661, each having two phenylsulpnonyl groups per triazine ring, are reacted at 20 - 70° in a molar proportion of 1 : 1 with colourless amino, hydroxy or mercapto derivatives whilst buffering the liberated' acid, such derivatives for instance being N-methylaniline, aminobenzene-3-3ulphonic acid, amino-benzene-4-sulphonic acid, aminobenzene-3-carbox lic acid, sulphonyl-S-c loropyrimidine , dyestuffs with similar good properties are again obtained.

Example 666: When 'in. 'Sample a 1 - 326, the 2-methylsulphonyl-4-chloro-6-methylpyrimidine i3 replaced by 2-carboxymethyl- -181- 24729/2

Claims (17)

1. CLAIMS 1. Reactive dyestuffs of the general formul Ϊ -EX-AI in which F denotes the radical of an organic dyestuff, X represents a grouping -M-, -S0 -, -arylene-, -alkylene-, or which is linked ¾directly with the radical A and either directly or via a bridge member with the radical F, Rjbeing hydrogen or a substituent, and "arylene" standing for an arylene radical, "alkylene" for a lower alkylene radical, A is the radical of a 6-membered heterocyclic ring which contains at least one nitrogen atom in the ring and has at least one reactive sulphonyl substituent linked to a carbon atom of the heterocyclic ring which is in an a position which ring / to a nitrogen atom of this ring, and/may be fused to carbo- cyclic rings, and m is a number from 0,.5 to 8.

2. Reactive dyestuffs of formula I in Claim 1, in which A is a pyrimidine ring and X is an amino group.

3. Reactive dyestuffs according to Claims 1 and 2, of the general formula: wherein F denotes the radical of an organic dyestuff, ^ is an amino group, Z is a halogen atom, T ie hydrogen or an -182- 24729/2

4. Reactive dyestuf s of formula la in Claim 3, wherein P denotes the radical of an azo, anthraquinone or phthalocyanine dyestuff containing sulphonic acid groups, R is methyl, is -HH-, Z is 01 or Br, Y is hydrogen or CK, , and m is the number 1 or 2. 3 -

5. Dyestuffs according to any of the preceding Claims, wherein A is the 2-methylsulphonyl-5-chloro-6^methylpyrimidinyl-4 radical.

6. Reactive dyestuffs of the formula I in Claim , wherein P contains one or more sulphonic acid groups.

7. Reactive dyestuffs according to Claim 1, of the general formula: P. (H = H - A)k II 1 in which P^ represents the residual constituent of an azo dyestuff, A has the same meaning as in Claim 1, and k is the number 1 or 2.

8. Reactive dyestuffs of formula II in Claim 7, in which A is a pyrimidine ring.

9. Dyestuffs according to Claim 8, wherein A is the 2-methylsulphonyl-5-chloro-6-methylpyrimidiny1-4 radical.

10. Reactive azo dyestuffs according to Claim 1, of the general formula: B - N = N - D (Q) A III -183- 24729/2 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 ehollc or phenolic coupling component, B and D may moreover contain any further substltuents, including further azo groups, stands for a subatituent or, preferably, for hydrogen, Q denotes a direct bond or a group -SO,,-, m* is an integer, preferably 1 or 2 and A has the same meaning as in Claim 1.

11. Reactive azo dyestuffs of formula III in Claim 10, wherein Q is a direct bond and A in a pyrimidine ring.

12. Reactive azo dyestuffs according to Claim 11, of the general formula: in which m' , B, D and ^ have th© same meaning as in Claim 10 and R, Y and Z have the same meaning as in Claim 3.

13. Dyestuffs according to Claim 11, wherein A is the 2-methylsulphon 1-5-chlo o-6-methylpyrimidinyl-4 radical.

14. Dyestuffs according to Claims 10 to 13, wherein B and/or D contain one or more sulphonic acid groups.

15. Reactive anftraquinone dyestuffs according to Claim 1, of the general formula: -184- 24729/2 in which I is hydrogen or a substituent, preferably a s lphonic acid group, £ denotes the number 1, 2 or 3, A has the same meaning as in Claim 1 and R^ and Q have the same meaning as in Claim 10.

16. Reactive anthraquinone dyestuffs of formula IV in Claim 15, in which A is a pyrimidine ring.

17. Dyestuffs according to Claim 16, wherein A is the 2-methylsulphonyl-5-chloro-6-methylpyrimidinyl-4 radical. 18* Reactive anthraquinone dyestuffs according to Claim 16 of the general formula: wherein I and p have the same meaning as in Claim 15, m* and ^ have the same meaning as in Claim 10 and Y, Z and R have the same meaning as in Claim 3. -185- 24729/2 · 20. Reactive azaporpiiin dyestuffs according to Claim 1, of the general formulas in which Pc stands for the radical of a phthalocyanine, preferably a copper- or nickel-phthalocyanine or a tetra-phenyl copper- or nickel-phthalocyanine, A has the same meaning as in Claim 1, L has the same meaning as in Claim 15, and Q have the same meaning as in Claim 10, r is the number 1 or 2, is the number 09 1 or 2 and m" is a number of 0.5 to 4. 21. Reactive dyestuffs of formula V in Claim 20, in which Q is a direct bond and A is a pyrimidine ring. 22. Dyestuffs according to Claim 21, wherein A is the 2-methylsulphonyl-5-chloro-6-methylpyrimidinyl-4 radical. 23. Reactive azaporphihe dyestuffs according to Claim 21, of the general formulas in which Pc, r, g and m" have the same meaning as in Claim -186- 24729/2 24. Dyestuffs according to Claims 20 to 23, which contain one or more sulphonic acid groups. 25. Reactive dyestuffs according to Claim 1, substantially as herein described and exemplified. 26. Process for the production of reactive dyestuffs of formula I in Claim 1, wherein at least one group -X-A, in which X and A have the same meaning as in Claim 1, is introduced into dyestuffs or dyestuff intermediates, and in the case where dyestuff intermediates are used, these are converted into the desired end-dyestuffs. 2?· Process according to Claim 26, wherein a dyestuff or dyestuff intermediate containing at least one amino- or amide-group with a reactive hydrogen atom attached to the amine or amide nitrogen, is reacted with a compound of the general formulas A Y» VI in which A has the same meaning as in Claim 1 and Y' is a radical which can be split off as an anion. 28. Process according to Claim 27, wherein a diazo or coupling component which contains a reactive amino or amine group is condensed with a compound of formula VI in Claim 27. and the intermediate products thus obtained are converted into azo dyestuffs by diazotisation and/or coupling. 29. A modification of the process according to Claim 27, wherein a compound of the formula: A m2 Via -187- 24729/2 30. Process according to Claim 27, wherein as a compound of formula VI there are used 2»carboxy-methylsulphonyl-4- ehlo opy imidine, 2-methylsulphonyl-6-methyl-4-chloro-pyrimldine, 2,4-bis-methylsulphonyl-6-meth l-pyrimidlne, 2 ,6-.bis-phenylsulphonyl-4-methyl~5-chloropyrimidine, 2,4,6-1ris-methylsulphonyl-pyrimidine, 2, 4-bis-methylsulphonyl-pyriffiidine- 5-sulp onic acid chloride, 3i6-bis-phenylsulphonyl-pyridazlne, 3-methylsulphoi.yl^6«chloropyridazine, 3 ,6-bis-methylsulplionyl- 4-methyl«pyridazine, 2,5,6-tris-methylsulphonyl-pyrazine, ¾ 3-bis-methylsulphonyl-2, 4,6-triazine, 1, 3-bis-methylsulphonyl^ 5- (3» «sulphophen 1-amino )-2,4,6-triazine, 1, 3 bis-methylsulphonyl-5-phenoxytriazine, l,3-bis-methylsulphonyl-5- trichloroethoxy triazine and numerous further 1,3-bis-methylsulphonyl- , ,β-triazines substituted in 5-positionj 2 , 4-bis-methylsulphonyl-quinazoline, 2, -bis-phenylsulphonyl- ¾uinoline, 2-methylsulphonyl-4^chloropyrimidine, 2-chloro- methylsulphonyl-4-chloropyrimidine, 2-phenylsulphonyl-4-chloro- pyrimidine, 2,6-bis-methylsulphonyl-4-∑Dethyl-5-chloropyriiaidine, 2-methylsulphonyl-4-methyl-5 ,6-dichlorop rimidine, 2,6-bis- ffiethylsulphonyl-4-methyl-.5-bromopyriiaidine, 2-methylsulphonyl- 4-chloromethyl-5 ,6-dichloropyrimidine, 2-methylsulphonyl-4- methyl-6-chloropyriiaidine-5-sulphonic acid chloride or 4,6-bls- methylsulphonyl-5-chloropyridazine· 31. Process according o any one of Claims 26 to 28, wherein A is a pyrimidine ring and X is an amino group:. 32. Process according to Claims 27 and 31, vjherein as the compound of formula VI in Claim 27 there are used 2-carboxy- methyl-eulphonyl-4-chloropyrimidine, 2-methylsulphonyl-6-methyl- ~ l 2 - - - - - ι 4, 6-tris-methylsulphonyl-pyrimidine, 2,4,5 ,β-tetr. me hylsulphonyl-pyrimidine, 2-methyl3ulphonyl-4-meth;rA-5-nitro-6«ehlorop rimidine, 2-methylsulphonyl- , 5-dimethyl-6-chloropyrimidine, 2-eth lsulphon l- -methyl-5 , 6-dichloro-pyrimidine, 2-methylsulphonyl- , β-diehloro-py imidine, 2,4, 6- ris-methylsulphonyl-5-chloro-pyrimidine, 2-methy1-s lphonyl-4-carboxy-6-chlorop imidine, 2-methylsulph.onyl-4-chloropyrimidine-5-sulphonic acid or 4,6-bis-methylsulphonyl-pyrimidine,*,, 33. Process according to Claims 27, 28 and 31, wherein 2-methylsulphonyl- , 5-dichloro-6-methylpyridine is used as the compound Via in Claim 29, 34. Process according to Claims 27, 28 and 31, wherein the compound of formula VI in Claim 27, has the general formula: y I in which R, Y and Z have the same meaning as in Claim 3; and Y' has the same meaning as in Claim 27. 35. Process according to Claim 34, wherein as a compound of formula VIb there are used 2-methylsulphonyl- , 5-dichloropyrimidine, 2-methylsulphonyl-4-ehlor -5-bromo-p rimidine, 2-methylsulphonyl- , 5-dichloro-6-methylpyrimidine, 2-methylsulphony1-4-chloro-5-broiao-6-methylpyrimidine, 2 , 4- s-methylsulphonyl- -chlorop rimidine , 2, 4-bis-methyl-sulphonyl-5-chloro-6-methylpyrimidine, 2, 4-bis-methylsulphonyl- -189- 24729/2 * 56. Process according to Claims 28 and 34, wherein a diazo or coupling component which contains a group of the formulas in which R, Y and Z have the same meaning as in Claim 3 , is converted to an aao dyestuff by dia¾otisation and/or coupling. 37. Process according to any one of Claims 26 to 36, wherein after the condensation the dyestuffs obtained are subjected to conventional further conversion reactions, especially metallisation, acylation, reduction and/or sulphonation. 38. Process according to any one of Claims 26 to 37» wherein the dyestuff or dyestuff intermediate used as starting material and/or the dyestuff product contain one or more sulphonic aeid groups. 39. A process for the production of reactive dyestuffs of formula I in Claim 1, substantially as hereinbefore described with reference to the Examples. 40. 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 dye-stuffs according to Claim 1, are applied to these materials in any sequence, and the material thus treated is subjected to the action of an elevated temperature, if desired. 42. Process according to Claim 40, wherein at least on© dyestuff according to Claim 3 is used. 43. Process for the dyeing of nitrogen-containing materials, preferably of wool, silk, synthetic superpolyamide and -poly-urethane fibres, characterised in that these materials are dyed with one or more dyestuffs accordiag to Claim 1 from an acidic to neutral bath, and that the pH value of the dye-bath is subsequently increased, preferably to pH 6.5 to 8.5, if desired. 44. Process according to Claim 43, wherein at least one dyestuff according to Claim 2 is used. 45. Process according to Claim 43, wherein at least one dyestuff according to Claim 3 is used. 46. Materials containing hydroxyl groups which are dyed or printed by a process according to any one of Claims 40 to 42. 47. Materials containing nitrogen which are dyed or printed by a process according to any of Claims 43 to 45. 48. Dyeing agents containing a reactive dyestuff according to any one of Claims 1 to 25. ND:ea