[1]United States Patent @O 'ffice 21891,941 2,891,941 WATER SOLUBLE TRLAZM AZO DYESTUFFS Alfted Fasciati, Bottmingen, and Henri Riat, Arleshehn, Switzerland, assignors to Ciba Limited, Basel, Switzer5 land, a Swiss firm, N*Drawing. ApplicationJune27,1957- Serial No. 668,336 Claims priority, appucation Switzerland June 29, 1956 10 Claims. (Cl. 260-153) 10 This invention provides@ valuable new azo-dyestuffs, which contain at least two- strongly acid groups imparting solubility in water and, also. a monohalogen-triazine radical of the formula 15 N c C-Halogen 20 which,isboundto the,dyestuff-moleculethrough an amino bridge of the formula, -N- 25 in. which n- is a positive whole number, and Y represents an etherified hydroxyl group. Especially valuable among the dyestuffs of the above 30 formula are metal-free dyestuffs. of the formula (2) D-N=N-A , in which D represents the radical of a diazo-component which may contain -an azo-linkage, and A represents the radical of a coupling component, and in which one of 35 the radicals A and DI which together contain at least two strongly acid groups imparting solubility in water, contains bound thereto through an -NH- group a triazine radical of the formula 40 :@@N -0 C-Y k 45 iii, which Y represents a lower alkoxy group, and benzyloxy@ group@. or a phenoxy group which may cont@ain a carboxy lic acid or sulfonic acid, group. The aforesaid amino; bridge linking the characteristic 60 groupin g of, the Formula 1. to the dyestuff molecule may be connected directly; or through a bridge member, for example , through an alkylene radical or through an -SO2- group, to the radical of the coupling component or advantageously to: the radical@ D of a diazo-component, 55 which is advantageously at most bicyclic and is of the benzen e series. Accordingly, the said radical may be a substitut ed or unsubstituted@ phenyl radical or a radical of:highe r molecular weight, for example, a bicyclic or 60 naphthal ene radical which may contain an azo linkage. The dyestuffs of this invention contain, in addition to@ a triazine substituent of the F6rmula 1, at least two strongly aci(f groups imparting solubflity in water, such as carboxylic acid or preferably sulfonic acid groups. Advanta geously the dyestuffs contain more than one such 65 group per azo linkage, that is to say, at least two such groups in a monoazo-dyestuff and at least three such groi@ps in a disazo-dyestuff. These, groups imparting s olubility in water may be distributed in any desired man- 70 ner in the dyestuff molecule. The dyestuffs of this invention can be made by replacPatented June 23, 1959 ing in a trihalogen-triazine, especially in eyanuric chloride (2:4:6- trichloro-1:3:5-triazine), two halogen atoms by reacting one with an amino-azo-dyestuff, which contains at least two acid groups imparting solubility in water and an acylatable amino group and the other with an organic hydroxy-compound, for example,: benzyl alcohol or cyclohexyl alcohol, or a lower aliphatic alcohol or a phenol. As aniino,azo-dyestuffs, which contain at least two groups imparting solubility in water and an acylatable amino group, there may be used those which contain the acylatable amino group in the radical of the couplihg corilponent and/or advantageously in the radical of the diazo-component. For making dyestuffs@ which contain the acylatable amino group in the ra@dical of the coupling component, there may be used for example, coupling components of the benzene or naphthalene series, which owe their capacity for coupling to the presence of an at most secondary amino group or an aromatically bound hydroxyl group, or keto-methylene@ compounds which contain, in addition to a methylene group capable of coupliiig in a position vicinal to an enolizable keto group, an advantageously aromatically bound acylatable amino group. As such couplincomponents there may be mentioned, for example, w@-methanesulfonic acid derivatives of aniline, of ortho-methoxy-aniline and of ortho-carboxyaminobenzene (the w-methane sulfonic acidgroup being split off hydrolytically after reduction of the dyestuff to liberate the amino group),, and also meta-toluidine, 3 - acetylamino - 1 aminobenzene, 3-ureido - I - aminobenzene, I - aminobenzene@ - 21 methyl - 5 - niethoxibenzene, l@amino-2:5- dimethoxy- or -diethoxy@benzene, I - amino- 3 - methoxybenzene I - amino - Z - methoxy;. benzene-5-- isopropylbenzene, a-' or 6-naphthylamine and above all naphthylamine monosulfonic ac,'@d.9, such as Iaminonaphthalene-6- or -7-sulfonic acid, Z-aminb-naphthalene-6- sulfonic acid, 2-amino-8-hydroxypaphthalene-6sulfonic acid, 2-Nmethylamino-8-hydroxynaphthal6ne-6@ sulfonic acid, 2- alkylamino- or 2-arylamino-5,-hydroxy'naphthalene-7-stilfonic acid, 2-amino-5-hydrox-ynaphthalene-7-sulfonic acid, 2- (4'- aminobenzoyl-amino)-5-hydroxynaphthalene-7-sulfonic acid, 2- (4'-aminophenylamino) -5-hydroxnaphthalene-7-suffonic acid, @and alsfo 6-keto-carboxylic acid derivatives, e@pecially acetoacetic acid arylides, and above all pyrazolones, such as 1.@benzoylacetaniino-3- or -4-(4'-aminobenzoyl)-aminobenzene; I - acetoacetylamino - 4 - aminobenzene - 3 - carboxylic acid, Iacetoacetylamino-3-aminobenzene-4-sulfonic acid, I - acetocetylamino - 4 - aniinobenzene - 3 - sulfonic acid, Iacetacetylami-.io-4-aminobenzene, and also acetoacetyldiaminobenzenes, which may be substituted in thef ben7. zene nucleus by an alkyl or alkoxy group or a halogeii atom, 1 -acetoacetylamino-4' -aminodiphenylmoilo- or di@sulfonic acid, I-acetoacetylamino-4'-amiriostilbene-2:2'-@ disulfonic acid and monoacetoacetyl compounds of 1-4diaminodiphenyl-urea or of diamino-azobenzene@sulfonic acids, and al@so 5- pyrazolones such as 1-(3'- or 4'-amino)phenyl-3-methyl-5- pyrazolone and the corresponding, sul@ fonic acids, 1-[4'-(4" - aminophenyl)-phenyll-3-methyl-5@ pyrazolone and the corresponding sulfonic acid,s, 1-[4'(4" - aminophenyl) - phenyl] - 3 - methyl - 5 - pyrazloione; @and 1-[4-(4"-aminophenyl)- phenyl]-5-pyrazolone-3-carboxylic acid and the corresponding sulfonic acids, and, also the compound of the formula HO @-N -:@; He J03H Hogs C=
[2]2,891,941 or S03H HO 110 N@FT2 C=N I COOH and findy compounds obtainable by the nitrobenzoyla- 10 tion and redtiction of these 1-aminoary l-5-pyrazolones, which compounds contain an amino .-roup capable of condensing and which are capable of coupling in the 4-position of the pyrazolone nucleus. I The diazo-components to be coupled with these cou_ 15 pling components may contain substituents not impartin.@ solubility in water, and if desired, azo linkages, and they must contain strongly acid substittients capable of imparting solubility in water, such as sulfonic acid groups, if the coupling co@-nponents used as starting materials 20 contain only one or contain no such groups. These diazo-com onents may be relatively simple compounds, p for example, aminobenzene sulfonic acids, aminonaphthalene sulfonic acids, amino-pyrene sulfonic acids or aminochrysene sulfonic acids or aminonaphthol sul- 25 fonic acids or aminophenol sulfonic acids, or they may be more complex diazolizable compounds, which contain for example, one or two azo linkages. As examples of amines, whose diazo-compounds are coupled with the coupling components containing the 30 afore said acylatable amino groups, there may be mentioned the following aminostilfonic acids: (A) 1-aminobenzene-2-, -3- or -4-sulfonic acid, 35 2-amino-l-methoxybenzene-4-sulfonic acid, 3-amino-2-hydroxybenzoic acid-5-sulfonic acid, 3-amino-6-hydroxybenzoic acid-5-sulfonic acid, 2-aminophenol-4-sulfonic acid, 5-acetylamino-2-aminobenzene-l-sulfonic acid 40 5-acetylamino- or 5-benzoylairino-2-ami nobenzene-l-carboxylic acid, 2-aminobenzoic acid-4- or -5-sulfonic acid, I-aminonaphthalene-4-, -5-, -6- or -7-stilfonic acid, 2-aminonaphthalene-4-, -6-, -7- or -8-sulfonic acid, I-aminonaphthalene-3:6-disulfonic acid, 45 I-aminobenzene-2:5-disulfonic acid, 2-aminonaphthalene-4:8- or -6:8-disulfonic acid, 1-(3'- or 4'-aminobenzoyl) - aminobenzene - 3 - sulfonic acid, 3-aminopyrene-8- or -10-monosulfonic acid, 50 3-aminopyrene-5:8- or -5:10-disulfonic acid, or 4-nitro-4'-aminostilbene-2:2'-disulfonic acid, and the 0- acyl-derivatives of I-amino-8-hydroxynaphthalene-3:6- or -4:6-disulfanic acid, 65 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, or 2 - (4'-aminobenzoylamino) -5-hydroxynaphthalene-7-sul fonic acid. 60 Dehydrothiotoluidine mono- or di-sulfonic acid, etc. There may also be used as diazo-components amino-azodyestuffs such as those obtainable by coupling o-iie of the above-mentioned coupling components containing -NH2 groups, with the diazo-cornpounds of the above- 65 rnentioned amino-sulfonic acids. For producing starting materials which contain the acylatable amino group in ti'ie diazo-component, there may be used, for example, diazo-compounds of monoacyl-derivatives of aromatic diamines, for exarr@ple, mono- 70 acyl-derivatives of 4:4'-diamino-diphenyl-3-sulfonic acid, 4:4@-di@minostilbene-2:2'-disulfonic acid, 4-(4'-aminobenzoYlamino)-l-aminobenzene-2-sulfonic acid, 1:3- or 1:4-diaminobenzene, 1:4-diaminobenze iie-2-carboxylic 4cid, 1.,3-diaminobeiizene-4-sulfonic acid or 1:4-diamino- 7,5@ benzene-3-sulfonic acid, 2-methoxy-1:4-diaminobenzene5-sulfonic acid, the acyl radicals of which are saponified after coupling to liberate the amino group. As coupling components there may be used in this case compounds capable of coupling which are free from acylatable amino groups, for example, (B) g-Keto-carboxylic acid esters or amides which are capable of coupli:lg in the a-position, for example, acetoacetic acid arylides, pyrazolones, especially 5-pyrazolones capable of coupling in the 4-position, such as 3-methyl5-pyrazolone, 1-phe nyl-3-methyl-5-pyrazolone, I-phenyl3- methyl-5-pyrazolone-2'- or -3'- or -4'-sulfonic acid, 1phenyl-5-pyrazolone-3-carboxylic acid, 5-pyrazolone-3carboxylic acid amide, barbituric acids, hydroxyquinolines or phenols, such as 8- hydroxyquinoline, 2:4-dihydroxyquinoline, paracresol, 2-carboxy-l-hydroxybenzene, naphthols slich as a- or p-naphthols, a- or p-naphthylamine, 2tiydroxynaphthalene-sulfonic acid amides, and especially amino- and/or hydroxy-naphthalene sulfonic acids or their N-alkyl-, N-aryl- or N-acylderivatives, such as 1-hydroxynaphthalene-3- or -4- or -5- or -8-sulfonic acid, 2-hydroxynaphthalene-4- or -5- or -6- or -7- or -8-suffonic acid, 1:8-dihydroxynaphthalene-3:6- disulf(>nic acid 2i'lydroxynaphthalene-3:6- or -6:8-disulfonic acid, droxynaphthalene-3:6- or 3:8-disulfonic acid, 2-aminonaphthalene-6-sulfonic acid, 1-amino-8-hydroxynaphthalene-2:4- or -3:6- or 4:6-disulfonic acid and the N-acylderivatives of aminonaphthol sulfonic acids, which contain as the acyl radical, for example, an acetyl, propionyl, butyryl, chloracetyl, pchloropropionyl, benzoyl, ortho-, meta- or para-chlorobenzoyl, nitrobenzoyl, tertiary butylbenzoyl, 3'- or 4'-aminobenzoyl, methane- or e thane-sulfonyl, para-toluene-sulfonyl or chlorobenzene sulfonyl gioup, or a carbomethoxy or carbethoxy group, or an acyl radical derived from a cyanuric acid, for example, a radical of the formula N -C) C-Y y in which the two substituents Y represent halogen atoms or amino groups, and especially substituted amino groups. There may also be used as coupling components 5:5'd ihydroxy-2'-dinaphthyl-urea-7:7'-sulfonic acid and 5:5'dihydroxy-2:2'-dinaphthylamine-7:7'-disulfonic acid, which like I-amino-2- hydroxynaphthalene-3:6-disulfonir, acid can be coupled twice with the aforesaid diazocomponents, and also compounds capable of coupling which co-iitain azo-linkages, for example, monoazo-compounds, which can be made, for example, by coupling in an acid medium a simple diazo-compound of the benzene or naphthalene series (for example, a diazotized naphthylamine, an aniline such as chloraniline or nitro. an;]iTie, a toluidine, a 2-aminobenzoic acid, a 5-nitro-2aminobenzoic acid or a nitro-aminophenol, or a chloroaminophenol etc.) with 2-amino5-hydroxynaphthalene7-sulfonic acid or with 1-hydro xy-8-aminonaphthalene3:6-disulfoilic acid, In this case also only those starting materials should be coupled together, which lead to the formation of amino-azo-dyestuffs containing at least two groups imparting solubility in water. The condensation of the amino-azo-dyestuffs obtained from these components with cyanuric chloride is carried out in such mannr that two exchangeable halogen atoms remain in the condensation product obtained, and of which halogen atoms one is exchanged for.the radical of an organic hydroxy-compound. As such hydroxy-com. -oounds there may be used aliphatic or aromatic hydroxy@QQmpounds, sucli a@ rRp thyl alcoho e alcohol, iso - thyl
[3]propyl alcohol, butyl alcohol, cyclohexanol, m'ethoxvethvi alcohol, or phenols free from sulfonic acid groups, su@h as phenol, ortho-, meta- or para-cresol, 4-secondary butylphenols or especially 1-hydroxybenzene-2- or -3- or -4-sulfonic acid or salicylic acid, and also heterocyclic or araliphatic alcohols, such as furyl alcohol or benzyl alcohol. Good results are generary obtained with the corresponding alkali metal alcoholates or phenolates. The condensation of these alcohols or phenols or their alkali metal compounds with the dihalogentriazine dyestuffs in the process of this invention is advantageously carried out in the presence of an acid-binding agent, such as sodium acetate or sodium carbonate and under conditions such that an exchangeable halogen atom remains in the product, that is to say, for example, in an organic solvent or at a relatively low temperature in an aqueous medium. Instead of condensing the eyanuric chloride first witb the amino-azo-dyestuff and then with the alcohol, the procedure may be reversed ' by first condensing an alcohol or a phenol with eyanuric chloride to form a dihalogentriazine of the formula -@-I \ Y-0 0-Halogen @alogen in which Y has the meaning given in connection with Formula 1, and subsequently condensing the primary condensation product of the Formula 3 with the aminoazodyestuff, which contains at least two strongly acid groups imparting solubility in water and also an acylatable amino group, for example, with an amino-azo-dyestuff obtainable from the components mentioned above. The dyestuffs of this invention can also be made by a modification of the above process. In this modification of the process the aforesaid monohalogentriazine radical is not incorporated into the finished dyestuffs or into the components used for making them. Thus, a dihalogentriazine of the Formula 3 may be condensed with a coupling component or diazo component suitable for making the dyestuff by coupling and containing, in addition tO the @group cape@ble of leading to dyestuff forination, an acylata,@ble amino group. As examples of coupling and diazo-components obtainable as described above, which contain a radical of the Formula 1, there may be mentioned (a) As diazo-components the secondary condensation products of I mol of cyanuric chloride with I mol of methyl alcohol, isopropyl alcohol, methoxyethyl alcohol or an hydroxybenzene sulfonic acid and I mol of4:4'-diaminod.iphenyl-3-sulfonic acid, 4:4'-diaminostilbene-2:2', disulfonic acid, 4-(4'@a niinobenzoyl-amino)-l-aminobenzene-2- sulfonic acid, 1:3- or 1:4-diamino-benzene-1:4-diam inobenzene-2-carboxylic acid, 1:3- diaminobenzene-4sulfonic acid or 1:4-dianiinobenzene-3-sulfonic acid, 2methoxy-1:4- diaminobenzene-5-sulfonic acid and the secondary condensation products of the formulae .OBH N ci-C c N 0 CH3 H N N=X- 03H 2)891,941@ and 5 CH3 ci-c c k Z@@0 / 10 Hk'o r-N OSH 15 (b) As coupling components the secondary condensation products of I mol of cyanuric chloride, 1 mol of methyl alcohol, phenol or hydroxybenzene sulfonic acid and I mol of 2-amino-8-hydroxy-naphthalene-6-sulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid or 20 2-(4'-aminobenzoylamino)-5-hydrpxynaphthalene-7-sulfonic acid, Iacetoacetylamino-4-aminobenzene-3-carboxylic acid or -3-sulfonic acid, 1- acetoacetylamino-4-aminostilbene-2:2'-disulfonic acid, 1-(3'- or 4'-aniinophenyl)- 5pyrazolone-3-carboxylic acid or I mol of tlle compound 25 of the formula HO HO CH= 30, c I c HO"] C @S -N]E[2 or HO 35 SO&H HO C=l -N= I 40 COOH In making the dyestuffs of the invention by condensing one of the aforesaid amino-azo-dyestuffs with cyanuric chloride and one of the aforesa-id hydroxycompounds in 45 gneral the condensation may be carried out in either order of succession, and the condensations necessary for making the secondary condensation products to be used as. dyestuff components are advantageously carried out by first making the dihalogen-triazine of the:Formula 3 and r)O subsequently condensing the latter with the dyestuff component necessary for the coupling. Thee ondensations are advataneogusly carried out in the presence of an acid-binding agent, such as sodium acetate or sodium carbonate, in such manner that the 55 resulting dyestuff condensation product contains one of the three exchangeable halogen atoms of cyanuric chloride, for example, by working in a weakly acid or weakly alkaline to neutral medium and/or by maintaining the temperature as low as possible. 6( Without losing their valuable properties the dyestuffs of this invention can be isolated and worked up into useful dry dyestuff preparations. The dyestuffs are isolated preferably. at as low a temperature as possible by salting out and filtration. After being filtered off the dyestuffs 05 may be dried, ff desired, after the addition of extenders or buffers for example, a niixture@ of equal parts of a monoalka 'ii phosphate and a dialkali phosphate. The drying is preferably carried out at not too high a temperature and under reduced pressure. In certain cases 70 it is.possible by spray drying the whole mixture resulting from the dyestuff manufacture to produce dry preparations directly, that is to say, without intermediate isolation of the dyestuff. The new dyestuffs of this invention are suitable for 75 dveinly or nrintinc, n vpru @l",I. -f -.+..4.1. --
[4]7 pecially cellulosic materials having a fibrous structure, such as linen, cellulose, regenerated cellulose and above aR cotton, They are especially suitable for dyeing by the so-called padding dyeing process, in wi-iieh the goods are impregnated with an aqueous dyestuff solution which -0 may contain a high concentration of salt, and the dyestuff is fixed by treatment with alkali, advantageously at a raised temperature. When the dyestuffs contain groups capable of forming complexes, for example, an ortho:ortho'- dihydroxy-azo- 10 grouping or an ortho-hydroxy-carboxy-groupinsuch as is present in salicylic acid esters, the dyeings produced with such dyesttiffs may be treated with an a.-ent yield;r@g metal, for example, an agent yielding cliromium, but preferably one yieldin- copper. The treatment with 15 the agent yielding metal may be carried out in the ustial manner. In many cases very valuable dyeings are obtained by usin.- the process in which a dyeing produced with the metal-free dyestuff is after-treated with an aqueous solution which contains a water-soluble, preferably 20 complex, copper c-ompound and a basic condensation product of forrpaldehyde with a compound which contai.ns at least orce the atomic groupin-. -N=C N '30 or a compound, such as cyanamide, that is easily convertible into a cornpound containing the said grouping. Dyeings produced with the new dyestuff preparations on cerulosic fibers are generally distinguished by the purity of their tints, by their good fastness to light and ,5 above afl by their excellent fastness to washing. The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated, and the relationship of parts by wei-,bt to parts by volume being the same as that of the kilogram to the 40 liter. Example I 18.4 parts of eyanuric chloride are dissolved in 400 parts by volume of methanol at 20-25' C. and the solution is cooled to O' C. Then 2 parts of water axe added and 9.3 parts of finely powdered sodium carbonate are strewn in. The whole is stirred for 2 hours at 0-5' C., the temperati-i@-e is allowed to rise to 20-25' C., and the whole is further stirred for 2 hours at that temperature. It is theii cooled to 5' C. and a solution of 18.8 parts of 1:3diaminobenze-@ie-4-sulfonic acid (in the form of its sodium salt) in 700 parts by volui-ic of water is added. A further 200 parts by volume of a 4 N-solution of sodiuni acetate is added and the whole is stirred for 3 hours at 30-35' C. The dissolved reaction product is precipitated by the additioai of hydrochloi-ic acid and 15% by volume of sodium chloride, and filtered off. 31.5 parts of the condensation product so obtained are stirred in 300 parts of water, 300 parts of ice and 20 pai-ts of hydrochloric qcid of 30 percent strength, and diazotizati--n is carried out at 0-2' C. with 25 parts by. volume of a 4 iNT-solution of sodiim nitrite. To the diazo-suspension so obtained, which is still acid to Congo, are added 15 parts of sodium bicarbonate, and then the mixture is added to a solution, cooled to 0-2- C., of 42.3 parts of 1-benzovlamino-8-hydroxynaphthalene3:6disulfonic acid (as the alkali salt) in 400 parts of water and 15 parts of cale-ined sodium carbonate. Wben the coupling is finished, the dyestuff is precipitated by the addition of potassitir@i ehloride, filtered off, washed with potassilim chloride solution, and dried at 70' C. in vacuo. It dissolves in cold water with a bluish red coloration, and dyes celluicse fibers fast bluish red tints by the padding dyei-.ig process. Ti,@ere are also obtained by this method by coupling the secondary condensatioii products given in column I of the following table with the coupling components given in column 11 similar dyestuffs, which dye cotton by the padding dyeing process the wet fast tints -.iven in column 111. N HO NH-COCH3 H300- 0 CNH SOSH bl uish I 1 1 r ed. ,N N -C@>- NHI H03s-@ S03H N ci HO TT300-C S03H greenish yellow. N N -:@> 2------ C-NH-<- NH3 RC C= N C TT3 H 0 3------ Hac 0-0 C -NH--<@@@s 0 2H C N--<@D-so3H Do. N N Ho C C=N T T 3 N H 0 NH-COCH3 4------ Haco-C C -N S03H red. N N 0 XH2 HOBS-
[5]27891,941 9@ 10 N ------ H300-C C-NH S02H HO N"-Co-c:> bluish II -<::@> red. @H3 H03S 0 v ST-T N CH2--C-OOOH 6 ------ HSCO-C CNH SOSH 0=@ greenish \Nl yellow . c ol HOSS N H2c-o-cHB :;@-I \ 1 7------ H2co-c C-NH-C>-SOSH O=c Do. / @H, N c N CH-C-COOH 8 ------ H3CO-C@ CHN NH2 0=, N ollen N' @- / - <@o@ll@ \,X/ y@@110,@'. c 61 Hoas H20-CH2 N CH-C-COOH 9------ @H-CH,-O-C'-' \C-NIE[-< S03H 0=@ greeiaish \0/ 4 ::@>- @NI yellow. H2 c 61 ci H03 S ci HO NH-COCHB 0-0 C-N.U-<@@@SOBT-T blue-red. Ik r-ross- -SOSH c @l CH3 N HO NH-C 0 CHS I - 5:-, \ TTC O-C CNH S03H Do. c / 'N' -<@II2 H03s[: -S 0 3TT N 110 12 ----- CH,-O-c C-Nil<@D-SOSH orange. HOBS] -NH-C O-Nff2 N II2C-C-CHs 13 ----- O-C C-NH S03H 0=6 greenish I yellow. N \Nl c -ci oil SH
[6]Example 2 30.3 parts of 2-aminonaphthalene-4:8-disulfonic acid are diazotized in the presence of hydrochloric acid with 6.9 parts of sodium nitrite. The diazo-compound is coupled in acetic acid solution with 15 parts of I -amino3-acetyl-aminobenzene. The monoazo-dyestuff so formed is salted out, filtered off, and dissolved in 2000 parts of water. The solution, after being neutralized with sodium carbonate, is run -into an icecold suspens@@'on of 18.4 parts of cyanuric chloride, and -Lhe ivhole is stirred for 30 minutes at 0 to 5' C. Then about 50 parts by volume of a 2 N-solution of sodium carboiiate are added dropwise so that the reaction mixture is maintaiiied at a slightly acid reaction (pH value of 5.5 to 6). When free amino groups can no lon,@er be detected, an aqueous solution of 9.4 par-ts of phenol and sufficient sodium carbonate to produce a pH value of 8.5 to 9 are added, and the -@vliole is stirred for a few hours at room t,,mperature, the reactio-ii mixture b,-ing maintained wea'.-ly alkalir,.o by the addition of furth--r sodium carbonate. The dyestuff so formed is then salted out, i5ltered off, and dried in vacuo at a moderately raised temperature. it dyes cotto-.1 from baths having a high salt concentration and in the presence of alkali, or by th.- padding dyeing pr@-cess, yellow tints that are very fast to light and washing. Similar dyestuffs are obtained by using 10.8 parts of ortho- or para-cresol, instead of 9.4 parts of phenol. Example 3 Ls of 2 24.1 par' -phenoxy-4:6-dichloro-1:3:5-triazine are slispended in 1000 parts of water, and a neutralized solution of 18.4 parts of 1:4-d;ami-@lobenzerie-2-sulfonic acid is added. About 50 -oarts by volume of Ei 2 N-solution of sodium carbonate are gradiially added, and the whole is stirred for a few hours at 30-40' C. The secondary condensation product so obtained is separated by the addition oihydrochloric acid aDd sodium chloride. The product so obtained is diazotized in the usual manner with sodium nitrite in hydrochloric acid solution and the diazo-compound is colipled in acetic acid solut;on with 29.3 parts of 2-amino-8-hydroxy-r,.aphthalene-6-sulfonic acid. The dyestuff so obtained dyes cotton fast bluish red tints. Similar dyestuffs are obtained by using 2-methoxy-4 :6dichloro-1:3:5-triazine and 1:3- diaminobenzene-4-sulfonic acid instead of the indicated2-phenoxy-2:4-dichloro1:3:5- triazine and of the 1:4-diaminobenzen.--2-sulfonic acid mentioned in this example. Example 4 62.7 parts of the dyestuff of the formula S03H HO ci N N Go 11 I I H03s- iN IL-U U-Ul u.ti3 are suspended in 2000 parts of water and an aqueous solution of 9.4 parts oj' phenol is added. Such a quantity ol. an aqueous solution of sodium carbonate is then added dropwise in the course of 4 hours that the pl-I value o'L the reaction mixture -is maintain-.d between 8 and 9. Tjae dyestuff -o formed is then salted out and filtered off. It dyes cotton by the padding dyeing process fast scarlet red tints. A very easily soluble dyestuff havin.- otherwise similar properties is obtained by using for forming the dyestuff 19.8 parts of sodium 3-hy droxybenzene-l-sulfonate, instead of 9.4 parts of pheiaol. Example 5 60.7 parts of the amino-azo-dyestuff (obtained by coupling diazotized 4-amino1:1'-azobenzene-3:4'-disulfonic acid with 2-acetyla mino-5-hydroxynaphthalene-7- sulfonic acid in the presence of sodium carbonate followed by splitting off of the acetyl group by means of a warm dilute solution of sodium hydroxide) are dissolved in 2000 p-,irts of water. The resulting solution is run into an icecold suspension of 18.4 parts of cyanuric chloride. The whole is stirred for one hour at 0-5' C., and then a solution of 10% stren@th of sodium carbonate is added dropwise until the reaction is neutral. When free amino -roups can no longer be detected 9.4 parts of phenol and 10 such a quantity of sodium carbonate are added that the mixture is maintained at a pH value of 8 to 8.5. After sti.-ring the mixture for 4 to 6 hours at 40' C. the dyestuff formed is salted out, filt,-red off, and dried in vacuo. It dissolves in water with a red coloration, and dyes cotton 15 'oy the padding dyeing process in the presence of alkali very pure red tints. Exomple 6 2 parts of the dyestuff obtained as described in the first and second paragraphs of Example I are dissolved in 20 100 parts of water by boiling. A cotton fabric is impregnated at 80' C. with the solution, and squeezed to remove the excess of solution until the increase in the weight of the fabric is 70 percent. The fabric is dried, and then passed throu.-h a solution of 10 parts of sodium 25 hydroxide and 300 parts of sodium chloride ;n 1000 parts of cold water, squeezed unt;l its increase in weight is 70%, steamed for 60 seconds, rinsed, neutralized in a solution of 0.5 percent streiagth of bicarbonate, rinsed, soaped for 10 15 minutes in a boiling solution of 0.3 percent strength of an ion-.Lree detergent, rinsed and dried. There is obtained a red dyein,-, which is fast to washing and light. Siniilar results are obtained by using 20 or 30 parts of sodium carbonate, instead of 10 par-ts of sodium hydroxide, and steaming for 3 minutes instead of 60 seconds. 35 Example 7 2 parts oi- the dyestuff obtained as described in the first and second paragraphs of Example 1 are dissolved in 100 parts of water by the addition of I part of sodium hydrox40 ide. A cotton fabric is impregnated with the solution at room t-,mperature, then squeezed until its increase in weight is 70%, and dried. The fabric is then steamed for 160 seconds, rinsed, and fiwshed in the manner described in Example 6. There is obtained a red dyeing 45 that is fast to washin.- and light. Example 8 2 parts of the dyestuff obtained as described in the first paragraph of Exqmple 4 are dissolved in 4000 parls 50 of water. To the solution are added 40 parts of trisodium phosphate and 80 parts of sodium chloride, and 100 parts of a well wetted cotton fabric are entered into th-@ dyebath. In 45 minutes the temperature is raised to 90' C., a further 80 parts of sodium chloride being added to the r)5 dyebath after 30 minutes. The temperature is maintained at 90' C. for 30 minutes, and the dyeing so produced is rinsed and soaped for 15 riinutes in a boilin.@ solution of 0.3% strength of an ion-free detergent, rinsed again, and dried. There is obtained a scarlet red dyei-@ig that is 60 fast to washing. What is
