Патент USA US3060191код для вставки
‘atent EQQ 3,060,18 Patented Oct. 23, 1962 1 2 3,060,180 As aryl-carboxylic acids there are advantageously used those of the formula ANTI-IRAQUINONE VAT DYESTUFFS CONTAIN ING CHLORO-TRIAZENYL GROUPS Max Staeuble, Base], and Kurt Weber, Bottmingen, Switz erland, assignors to Ciba Limited, Basel, Switzerland N0 Drawing. Filed May 26, 1959, Ser. No. 815,785 Claims priority, application Switzerland May 30, 1958 6 Claims. ((31. 260-249) This invention provides valuable new anthraquinone (3) N A lltt h vat dyestuffs which contain at least one aroylamino group 10 and at least one group of the formula in which aryl advantageously represents a benzene radi 1) cal, n and p each represent the whole number 1 or 2, and X represents a hydrogen atom or a substituent. As suit O-X 15 able substituents there may be mentioned chlorine atoms, ' alkyl, phenyl, hydroxyl, alkoxy, hydroxyalkoxy, aryloxy, especially phenoxy, primary and secondary amino groups, for example, an —NH2 group, a mono or di-alkylamino which is bound directly or through a bridge member to group, for example, mono- or di-methylamino group, an aroyl residue, and in which X represents a hydrogen 20 mono-or di-ethylamino group, a monobutyrylamino atom or a substituent. Advantageously, the new com group, ethylene-imino group, mono- or di-B-hydroxyethyl pounds correspond to the formula amino group, monochloroethylamino or monocyanethyl (2) i amino group, mono- or di-carboxymethylamino group, N or arylamino group, for example, an anthraquinonylamino 25 group, and especially a phenylamino group, which may be substituted in the phenyl radical, advantageously by a hydrophilic group, for example, a carboxylic acid, sulfonic acid, sulfonamido, alkyl-sulfone or alkoxy group, and El also groups capable of being converted into hydrophilic in which A represents an anthraquinone radical, m and n 30 groups, for example, sulfo?uoride, sulfochloride, car each represent the whole number 1 or 2, and X has the boxylic acid chloride, sulfonic acid ester or carboxylic meaning given above. acid ester groups. The symbol X may be an alkylmer~ \O/ (51 The invention also provides a process for the manu capto or arylmercapto group, for example, a methylmer facture of the above new dyestu?s, wherein an amino capto, carboxymethylmercapto, ethylmercapto or phenyl anthraquinone is reacted with a reactive derivative, more 35 mercapto group. especially a chloride, of an aryl carboxylic acid which As examples of suitable aryl carboxylic acids of the Formula 3 there may be mentioned: 2-carboxyphenyl contains at least one group of the Formula 1 bound directly or through a bridge member to an aroyl radical, and, when the resulting reaction product contains a di amino-4:6 - dichlorotriazines, chlorotriazine radical, if desired, exchanging one chlorine 40 atom for a substituent containing at least two atoms. ylarnino-6~chlorotriazines, 2-carboxyphenylamino-4-ethyl ene-imino - 6 - chlorotriazines, As aminoanthraquinones suitable for the process of this invention there may be mentioned monoamino- and 2 - carboxypheny1amino-4 amino-6-chlorotriazines, 2-carboxyphenylamino-4-dimeth 2:4 - di - (carboxyphenyl - amino) -6-chlorotriazines, 2 - carboxyphenyl-4:6-dichloro triazines, 2:4-di-(carboxyphenyl)-6-chlorotriazines and also diaminoanthraquinones, for example, l-aminoanthra 2 - (3':5' ~ dicarboxyphenylamino)~4-a1nino-6-chlorotri quinone and simple substitution products thereof, such, 45 azine. for example, as 1-amino-4-methoxy-anthraquinone, 1 The reaction of the aminoanthraquinones with the re; amino-4- or -5- or -8-acylamino- and especially -benzoy1 active derivatives, especially chlorides, of arylcarboxylic 4 amino-anthraquinones. The latter may be substituted in acids is advantageously carried out in an inert organic ‘the benzoyl radical, for example, by a halogen atom, methoxy, alkyl, tri?uoromethyl, sulfonamido or alkyl 50 solvent, for example, nitrobenzene, chlorobenzene or sulfone group. There may also be mentioned 1:5- and ortho-dichlorobenzene, at a raised temperature. Aryl 1 : S-diaminoanthraquinone and l :5-diamino-4 : 8-dioxy monocarboxylic acids of the Formula 3 are advanta~ anthraquinone. There may also be mentioned those geously reacted in the molecular ratio 1:1 with the mono aminoanthraquinones which contain a further fused-on aminoanthraquinones or in the molecular ratio 2:1 with carbocyclic or heterocyclic ring, for example, 4-amino 55 the diaminoanthraquinones. Aryldicarboxylic acids of anthraquinone-2: 1- (N) -acridone, 5 -amino-1 :9-isothiazo leanthrone, 4- or S-aminoanthrapyrimidine, mono-amino the Formula 3 are advantageously reacted with mono or diamino-acedianthrones, 4- or 5-amino-1:1'-dianthri When there are used as starting materials those aryl carboxylic acids of the Formula 3, in which X represents aminoantharquinones in the ratio 1:2. mide-carbazole, 4:4'- or 5:5'-diaInino-l:1’-dianthrimide carbazole, 4- or S-amino-S’-benzoylamino-dianthrimide 60 carbazole or 4-amino-4'-benzoylamino-dianthrimide-car bazone, 4-amino-anthrapyridones, amino-dibenzanthrone, amino - isodibenzanthrone, aminodibenzpyrenequinone, aminoanthrathrone, aminobenzanthrone, amino?avan throne, and also the compound of the formula (I) NH“ 0 some“ I! a chlorine atom, that is to say compounds which contain a dichlorotriazine radical, a chlorine atom in the arylide so obtained may be exchanged for a substituent contain ing at least two atoms, for example, a hydroxyl, alkoxy, 65 hydroxyalkoxy or aryloxy group or one of the primary or secondary amino groups or mercapto groups men tioned above. The invention also includes a modi?cation of the proc~ ess described above, wherein an anthraquinone of the 70 formula 8,060,180 ' 4,. 3 Example 1 is condensed with a compound of the formula 3.9 parts of the triazine derivative of the formula (5) N Cl—-(|J//N\ \?—x /N 5 \‘f l 01 in which X has the meaning given above, and, when the reaction product so obtained contains two chlorine atoms in the triazine radical, one chlorine atom is exchanged for a substituent containing at least two atoms. Thus, or 10 are suspended in 100 parts of dry nitrobenzene and con verted into the corresponding dicarboxylic acid chloride with 4 parts of thionyl chloride by being stirred at 100 to 105° C. The excess thionyl chloride is removed from the clear solution in vacuo, and 6.9 parts of l-amino-S for example, one molecular proportion of the compound‘ 15 benzoylamino-anthraquinone are then added. The term of the Formula 4 may be reacted with one molecular perature is raised to 160 to 170° C. and the whole is proportion of cyanuric chloride, and the resulting dichlo rotriazine reacted, if desired, with a primary or secondary amine, or two molecular proportions of a compound of stirred on for 3 hours at the same temperature. After cooling, the orange-colored suspension of the new dye stu? of the formula C a A iIH-oC-O the Formula 4 may be reacted with one molecular pro portion of cyanuric chloride. The dyestu? so obtained may be isolated from the me dium in which they are produced and, notwithstanding the presence of an exchangeable halogen atom, they can be converted into useful dry dyestu? preparations; The dyestuff is advantageously isolated by ?ltration. The ?ltered dyestulf may be dried, if desired, after the addi tion of a neutral or weakly alkaline extender. Advanta geously the drying is carried out at not too high a tem perature, if desired, under reduced pressure. The new dyestulfs are suitable for dyeing a very wide variety of materials, and especially for dyeing or printing is ?ltered off, washed with nitrobenzene and then with alcohol and ‘dried in vacuo at 60 to 70° C. A dyestu?f powder is thus obtained which is yellowish 35 brown when dry; it dyes cotton and regenerated cellulose by the dyeing method described in Example 19 orange yellow tints of very good fastness properties. The dye stuif is so securely ?xed on the fiber that the strength of the dyeing is not substantially impaired even by a treatment with a hot organic solvent, such as dimethyl formamide or pyridine. The 2:4 - di - (carboxyphenylamino) - 6-chlorotriazine used as acylating component in this example can be pre pared, for example, by condensing equimolecular propor textile materials of natural or regenerated cellulose by 45 tions of the sodium salt of 4-aminobenzoic acid and cy the usual vat dyeing or printing methods. anuric chloride in the molecular ratio of 2:1 in an aque As the reactivity of the halogen atom in the triazine ous medium at a temperature ranging from 0 to 40° C., ring varies somewhat from compound to compound it by continuing the condensation at a slowly rising temper is of advantage to adapt the method of dyeing, that is ature until aminobenzoic acid can no longer be detected. to say especially the concentration of the alkali or reduc 50 To isolate the dicarboxylic acid derivative it is advan ing agent, and the duration and temperature of the dyeing tageous to adjust the pH value of the aqueous suspension or steaming operation, to suit the dyestutf used. The with dilute hydrochloric acid to 2, ?ltering off the pre- _ most favourable conditions can easily be determined by preliminary tests. cipitate thus ‘formed, washing it with water until free In contradistinction to the conventional vat dyestu?’s, 55 from acid and drying it in vacuo at 70° C. the dyestuffs of this invention are substantially irremov Example 2 able from the ?ber with hot dimethyl formamide so that it is probable that they are chemically bound on the ?ber. 15.4 parts of 2:4-bis-(4'-carboxyphenylamino)-6-chlo Dyeings produced with the dyestu?s of this invention ro-1:3:5-triazine are heated in 300 parts of nitrobenzene are fast to dry cleaning and migration. The dyed fabrics can therefore be coated with synthetic resins, for example, 60 with 24 parts of thionyl chloride and 3 parts of dimethyl .formamide with stirring for 1 hour at 120° C. The excess polyvinyl chloride, without the dyestutf migrating into the thionyl chloride is distilled off in vacuo, at 100° C. 20 arti?cial resin. This is especially important in the manu~ parts of l-aminoanthraquinone are added, and the mix facture of arti?cial leather. ture is heated for 3 hours at 120° C. The dyestutf of The following examples illustrate the invention, the parts and percentages being by weight. 65 the formula N / N N 61 3,060,180 5 6 is isolated in the usual manner; it dyes cotton and regen- I Example 4 erated cellulose by the method described in Example 20 , yellow tints having good fastness- properties_ . _ _ _ 3.9 parts of the triazine derivatlve of the formula The corresponding dyestutl from l-amino-4-benzoyl aminoanthraquinone ‘gives red dyeings of similar, good '5 properties. HOOC_® I When in the above example the l-aminoanthraquinone is replaced by an equimolecular amount of 1-amino-6:7dichloroanthraquinone, an orange-yellow dyestu? of very good fastness properties is obtained. N 1lIH_O/ \C_NH_QOOOH II | N\ /N 10 0 Example 3 371 3.9 parts of the triazine derivative of the formula HOOC N / \ NH-fJ 000E are suspended in 100 parts of trichlorobenzene and con verted into the corresponding dicarboxylic acid chloride, 15 by being stirred at 100 to 105° C. with 4 parts of thionyl (|3—NH chloride. 6.9 parts of 1-amino-S-benzoylamino-anthra N \C% 6 1 quinone and 0.1 part of dimethyl formamide are added, the temperature is raised to 160—170° C. and the whole is stirred on at this temperature for 3 hours. 20 After cooling, the dyestu? of the formula H \O% Goo-11111 0 (‘J1 0 NH--O o-O are suspended in 70 parts of dry nitrobenzene and con-is ?ltered off, washed with trichlorobenzene and then with verted into the corresponding dicarboxylic acid chloride alcohol, and dried in vacuo at 70—80° C. by being stirred at 110° C. with 4 partsof thionyl chloThe dyestutf dyes cotton and regenerated cellulose by ride. The excess thionyl chloride is removed from the 40 the method described in Example 19 yellow tints having solution in vacuo, and 6.9 parts of l-amino-S-benzoylvery good fastness properties. aminoanthraquinone are then added. The temperature The acylating component used in this example can be is raised to 160° C., 0.1 part of pyridine is added, and made, for example, in the following manner: the mixture is stirred on for 1 hour at 160° C. After Equirnolecular amounts of the sodium salt of 3-arnin0 cooling, the new dyestutl of the formula 45 benzoic acid and cyanuric chloride are condensed in the ? NH-OOQ N C>O°~NH ? \ I1IH—-(“3/N\ /N\o-rlrn I <:>-oo—Nn b O/ 61 II o rim-00G is ?ltered off, washed with nitrobenzene and then with molecular ratio of 1:1 in an aqueous medium at 0-5° C. alcohol and dried in vacuo at 80° C. 60 On completion of the monocondensation, 1 molecular Cotton and regenerated cellulose are dyed by the proportion of 4-aminobenzoic acid is added in the form method described in Example 19 yellow tints having very of a neutral aqueous solution of the sodium salt and con good fastness properties. densation is performed at a temperature rising to 40° C. The acylating component used in this example can be until aminobenzoic acid can no longer be detected. To prepared, for example, by condensing equimolecular 65 isolate the asymmetrical dicarboxylic acid derivative the amounts of the sodium salt of 3~aminobenzoic acid and reaction mixture is acidi?ed, and the product is ?ltered cyanuric chloride in the molecular ratio of 2:1 in an aqueous medium at a temperature ranging from 0 to 45° C., o?, washed with water and dried in vacuo at 70° C. Example’ 5 by continuing the condensation at a slowly rising tempera- - . ture until aminobenzoic acid can no longer be detected. 70 3.4 parts of 2-(4'-carboxyphenylamino)-4-amino-6 To isolate the dicarboxylic acid derivative the pH value chloro-1z3z5-triazine are suspended in 50 parts of dry of the solution is advantageously adjusted to 2 with dilute nitrobenzene and 1.0 part of dirnethyl formamide, and hydrochloric acid, and the precipitate formed is ?ltered 3.0 parts of thionyl chloride are stirred The mixture off, washed until free from acid and dried in vacuo at 60 is heated at 90-100° C. until a clear solution of the acid to 70° C. 75 chloride is obtained. 3.4. parts of l-amino-S-benzoyl 3,060,180 8 amino-anthraquinone are then added. The temperature ' is raised to 125 to 130° C., and the whole is stirred for a further'6 hours at this temperature, cooled to room tem I 11 111 perature and the dyestutt of the formula 0 N o 5 NH-O O-ONH-O/ \C—Cl NH, H 1 """ " C1 °’§§§§;,_ 1'l\ g. (I3/ NH: ' 1 ‘ 0 l C>~o o-NH o ' H ' 0 2 ______ __ p H 7 yellow. (I; / \ is ?ltered o?f, washed with methanol, and dried at 70° C. 1E1 III The dyestu? produces on cotton and regenerated cellu- 15 lose by the method described in Example 21 very fast orange-yellow prints. The 2-(4'-carboxyphenylamino)-4 - amino - 6 - chloro lz3z5-triazine used in this example can be prepared by condensation in an aqueous medium of a ?ne suspension 20 of 2-amino-4z6-dichloro-l z3z5-triazine and the sodium IT II Hm O . 3 ------ -- yellow salt of 4-aminobenzoic acid in the molecular ratio of 1:1 ([1) NH‘O C®—NH” at 30—40° C., or by ?rst condensing cyanuric chloride and the sodium salt of 4-aminobenzoic acid in an aqueous 25 medium at 0-4° C. to form 2-(4'-carboxyphenylamino) 4:6-dich1oro-l : 3:5-triazine and reacting a further chlorine atom at 30-40° C. with a slight excess of ammonia. g Equally good results are obtained by using as the acylat ing component 2-(4’-carboxylpheny1amino)~4-dimethyl- 3o ‘1------ -arnino-6-chloro-1z3z5-triazine of the formula N ? I‘IIH? 0 / \ “it \ HOOO@—~NH—(§/ \(!:—o1 N \ // N Ted ‘iONm N—N 35 ii ‘i ‘ _ N(CH3)”_ Example 6 $3.25- (t4- - Farbogytgheélylamlmo)A'dlethylammoé'chlom‘ ' ' ' ' nazme o 6 0mm a . p 40 chloro-1:3:5-triazine are converted into the correspond /N\ HOOC—<:>~NH—-G IL]; 3.2 parts of 2-(4'-carboxyphenylamino)-4-amino-6 ing carboxylic acid chloride in 100 parts of nitrobenzene C—Cl 11; with 2.5 parts of thionyl chloride at 95—100° C. The solution is treated with 0.2 part of pyridine and then with \ // 1.4 parts of l:5-diarnino-4:S-dihydroxyanthraquinone, ('3 45 and the temperature is maintained at 120—125‘’ C. for N03213:): 2 hours with stirring. The mixture is then heated for 1 These acylating components can be prepared in a manner hour at 150~l55° C., cooled to room temperature, and similar to that described in this example for the prepara- _ the dyestu? of the formula tion of .2-(4'-carboxyphenylamino)-4-amino-6 - chloro- is ?ltered o? and dried. 1:3:5-triazine, by condensing the sodium salt of 4-amino- 65 a The; dy?stu? dyes Cotton and regenerated cellulose benzoie acid in an aqueous medium with Z-dimethylamiriO4:6-dich1orotriazine or with 2-diethylamino-4:6-dichloro- blue-violet‘ tints having very good fastness to solvents. _ 1 Example 7 triazine respectively. 16.4 parts’ ‘of 2-(4'-carboxyphenylamino)-4-amino-6 "Similar dyestu?s which dye cotton and regenerated cel 70 chloro-lz3zr5etriazine are converted into the correspond iulose 'theetints shown in column III of the following ing carboxylic acid chloride in 100 parts of nitrobenzene table are obtained when in the above example l-aminq- with .5 parts of thionyl chloride in the presence of 0.5 5-benzoylaminoanthraquinone is replaced by an equlpart of pyridine at 90 to 100° C. The excess thionyl molecular amount of the starting materials listed in cOlI chloride is expelled in vacuo and 2.4 parts of lzi-diamino um 11 of'the following table: 75 anthraquinone are added to the solution. The tempera 3,060,180 9 l0 ture is raised in the course of 1 hour to 150-155° C. and the mixture is stirred for 3 hours at this temperature. The yellow-brown suspension of the dyestuff of the formula The acylating component used in this example can be prepared in an aqueous medium by condensing the so dium salt of 4-aminobenzoic acid with cyanuric chloride at 0 to 5° C. in the molecular ratio of 1:1 and by fur /N\ t IrH-OCGNH-t \‘f-m , N N \(f 11TH: /N\ | Ol—(|]/ IC—NH—<:>—CO—NH 0 N\ A \C.’ NH: is isolated by ?ltration, washed with nitrobenzene and then ther adding one molecular proportion of the sodium with alcohol, and dried in vacuo at 70° C. salt of sulfanilic acid; this second condensation is per The dyestuff dyes cotton and regenerated cellulose by 20 formed at 30-40° C. by adding sodium hydroxide solu the method described in Example 19 orange tints having tion dropwise at pH=6.0 to 7.5 until a solution is ob good fastness properties. The dyeing is fast even to hot tained and sulfanilic acid can no longer be detected. organic solvents. The condensation product can be precipitated from its When in this example 2-(4'-carboxyphenylamino)-4'solution in the form of the crystalline disodium salt by amino-6-chloro-l:3:5-triazine is replaced by an equi- 25 the addition of sodium chloride and then isolated by ?l molecular amount of 2-(4’-carboxyphenylamino)-4-ditration. methylamino-6-chloro-l :3z5-triazine, or of 2-(4'-carboxyExample 9 phenylamino)-4-diethylamino-6-chloro-1 :3 : S-triazine, or ‘j ~ 10.7 parts of 2:4-bis-(4’carboxyphenyl)-6-hydroxy of 2- (3 ’-carboxyphenylamino ) -4-amino-6-chloro-l : 3 : 5 1:3:5-triazine are slowly heated with stirring to 110° C. triazine, dyestu?fs are obtained that have similar proper- 30 in 100 parts of nitrobenzene with the addition of 24 parts hes‘ of thionyl chloride and 2 parts of dimethyl formamide. Example 8 The resulting clear solution is maintained for 45 min 5.1 parts of the condensaton product from 4-aminoutes at 110° C. and then cooled, whereupon the product benzoic acid, cyanuric chloride and sulfanilic acid of the 35 crystallizes out in the form of long, ?ne needles. It is formula ?ltered oif, washed with dry petroleum ether and dried N in vacuo at room temperature. / \ H 0 0 C—C>—NH—-(HJN The product of the formula (|3—NH—®~S 03H 01 N \C// 4° | 01 . . are converted for use as an acylatmg component mto the / <'1\ N/ N C C I Cl—OC-— § / ll 00-01 N corresponding carboxylic acid-sulfonic acid dichloride with 5.0 parts of thionyl chloride and 1.0 part of di- 45 crystallizes from acetone in long, ?ne needles melting at methyl formamide by being heated for 2 hours at 90212° C. (uncorrected). 100° C. in 100 parts of nitrobenzene. 3.0 parts of 14 parts of this acid chloride are made up at 60° C. amino-5-benzoylamino-anthraquinone are then added, into a clear solution in 150 parts of nitrobenzene. 6.9‘ and the whole is heated for 3 hours at 130 to 135° C. 50 parts of 1-amino-5-benzoylarnino-anthraquinone are then After cooling to room temperature, the orange-colored added, the whole is slowly heated to 120° C. and main dyestuff suspension is ?ltered 01f, washed with alcohol, tained at this temperature for 5 hours. The dyestufl of and dried in vacuo at 70-80° C. the ‘formula /N\ l M05“ N\ It I \o/ I The dyestulf of the probable formula is isolated in the usual manner; it dyes cotton and re N (I) NH-ooONn-o/ \(|3—NH~<:>—SO2C1 l\ )1 0 61 | || dyes cotton and regenerated cellulose yellow tints of very generated cellulose clear yellow tints of good fastness good fastness to washing. 75 properties. The corresponding dyestulf from l-amino 3,060,186 11‘ i2 anthraquinone yields a greenish yellow dyeing, and the corresponding dyestu? from 1-amino-4-benzoylaminoanthraquinone produces red tints. is ?ltered off, washed with‘alcohol, and dried in vacuo at 90 to 1000 Q , The analogous dyestu?- of the formula NH_ The dyestuff dyes cotton and regenerated cellulose by NH 0 dyes cotton and regenerated cellulose vfrom an alkaline the method described in Example 19 greenish blue tints hydrosul?te vat greenish blue tints of ‘good ‘fastness 20 having good fastness properties. properties. 2:4-bis-(4'-carboxyphenyl)~6-hydroxy - 1:3:5 - triazine Exwiwle 12 can be prepared from 2:4-'bis-(4’-tolyl)-6ihydmxy-1;3;5triazine by oxidation with potassium permanganate in an alkaline aqumus Salution, _ 4.2 parts of aminoacedrnanthrone are acylated with 3.2 Parts Of the CaPbOXYIiC 301d chloride of 2-(4'-°'¢1Ib0XY 25 phenylamino)-4-arnino-6-chloro - 1:325 - triazine in 100 parts of nitrobenzene and 0.2 part of pyridine by being Example 10 9.4 parts of 2-(4'-car-boxyphenylamino)-4:6-'dichloro- stirred for 6 hours at 140 to 150° C. After cooling to room temperature, the dyestutf of the formula 1 : 3:5-triazine are heated in 350 'parts of nitrobenzene with O 12 parts of thionyl chloride and 1.5 parts of dimethyl 30 A formamide for 2 hours at 110° C. The excess thionyl chloride is distilled oif in vacuo, 10.2 parts of 4-amino anthraquinone-Z:1(N)-acridone ‘are added at 50° ‘C., and the whole is heated ‘for 16 hours at 80° C. and for 6 hours at 100° C. The resulting dyestu? of the formula 01 35 l ! _ 0 N I L smegma am. NH \A/ ' 1 40 CO ([31 N O / \ N /0\N NH_CO_®_NH__<|§ N% (|;__C1 (‘l 4 is ?ltered off, washed with nitrobenzene and then with 5 alcohol, and dried in vacuo at 70° C. The dyestu? dyes cotton and regenerated cellulose fast brown tints_ Similar good results are obtained when in this example is isolated in the usual manner; it dyes cotton and regenel'ated Cellulose greenish blue tints having gOOd 'PIOPeIties 0f fast?ess- 2-(4’-carboxyphenylarnino)-4-arnino-6-chloro - 113:5 - tri Example 11 50 azine is replaced by an equimolecular amount of 2-(4' 88 parts of z_(4,_carboxyphenylamino) _ 4 _ amino _ 6_ chlor0-1:3:5-triazine are slowly heated in 350 parts of clarbfoxyphlenylamino)-4-phenyl-6-chloro-1.3.5-tr1azine of 6 0mm 3’ nitrobenzene with 12 parts of thionyl chloride and 1.5 ([31 parts of dimethyl formamide with stirring to 120° C., 55 g whereupon the compound dissolves with evolution of hydrochloric acid. N/ \N After 15 minutes the excess thionyl H chloride is distilled off in vacuo at 70° C., 10.2 parts | HOO0—®‘NH_C\ //C—® of 4-aminoanthraquinone-2:1(N)-acridone are added, and N the mixture is heated for 2 hours at 100° C. and for 1 60 hour at 120° C. After cooling, the blue dyestuff of the formula I . 01‘ of 2'(4 -¢aTb°XYPheI1Y1alI11I10)-4-Phen0XY-6-°h10r0-1I 3 :S-triazine of the formula or I u 65 NH CO HOOC-ONH-C \ // o—o—® N N (H) NH_O0 /C\ ll‘? 1}‘ 70 The aeylating components can be prepared in crystalline NH_C/ \C__C1 | form by condensing in an aqueous medium equimolecular H amounts of the sodium salt of 4-aminobenzoic acid and a ?nely dispersed suspension of 2~phenyl-4:6-dichlorotria O NHZ V zine, or 2-phenoxy-4:6-dichlorotriazine respectively, at 75 40° C. 8,060,180 13. 14 Example 13 is prepared in an analogous manner and gives golden-' yellow dyeings from an alkaline hydrosul?te vat. 3.2 parts of 2-(3’-carboxyphenylamino) - 4- amino-6 Example 15 chloro-1:3:5-triazine are suspended in 100 parts of dry nitrobenzene and 2.0 parts of thionyl chloride are stirred 7 parts of 2-(4'-carboxyphenyl)-4:6-dihydroxy-123:5 in. The whole is heated to 90—100° C., and in the ’ triazine are heated in 250 parts of nitrobenzene, while course of 2 hours a clear solution of the corresponding being stirred, with 24 parts of thionyl chloride and 3 carboxylic acid chloride is formed. 3.45 parts of 1 parts of dimethyl formamide to 105° C. and maintained amino-S-benzoylamino-anthraquinone are then added and at this temperature for 2 hours. The excess thionyl the temperature is raised to 135 to 140° C., the mixture chloride is then distilled off in vacuo. At 80° C., 13.7 is stirredv on for 6 hours at this temperature and then 10 parts of l-aminoanthraquinone are added, and the whole cooled to room temperature. The dyestu? of the formula is raised to 100° C. within 30 minutes, and then heated for 4 hours at 100° C., for 2 hours at 120° C. and for 3 hours at 140° C. The dyestutf of the formula 15 // IiI | OCO-NH o 01 I] is ?ltered off, washed with alcohol, and dried in vacuo at 70° C. The dyestuff dyes cotton and regenerated cellulose very fast orange-yellow tints. The 61 20 ll 0 o is isolated in the usual manner; it dyes cotton and regen erated cellulose by the method described in Example 19 or 20 clear yellow tints having good fastness properties. The dyestu? of the formula 2-(3’-carboxyphenylamino)-4-amino - 6 - chloro O I 013 It Go 0~1lu1 0 1:3:S-triazine used in this example can be prepared by is prepared in an analogous manner; it dyes cotton and’ condensing in an aqueous medium a ?ne suspension of 2 amino-4z6-dichloro-1:3:5-triazine and the sodium salt of 3-aminobenzoic acid in the molecular ratio of 1:1 at 30 _to 40° C. Example 14 regenerated cellulose from an alkaline hydrosul?te vat 40 gold-orange tints of good fastness properties. Equally fast, red dyeings are obtained with the analo gous dyestu? from 1-amino-4-benzoylamino - anthra quinone, While the dyestuif from 4-arninoanthraquinone 6.1 parts of the carboxylic acid chloride of 2-(4'-car 2: 1 (N)-acridone yields greenish blue tints. 2- (4'-carboxyphenyl ) -4 : 6-dihydroxy-1 : 3 :S-triazine can solved at 100° C. in 200 parts of nitrobenzene, 9.6 parts 45 be prepared from 2-(4’-tolyl)-4:6-dihydroxy-1:3z5-tria zine by oxidation with potassium permanganate in an al of l-aminoanthraquinone are added, the mixture is raised kaline aqueous solution. in the course of 45 minutes to 160° C. and stirred at this temperature for 5 hours. Example 16 The dyestu? of the formula 6.5 parts of 2-(4’-carboxyphenylamino)-4-phenyl-6 50 chloro-1:3:5-triazine in 120 parts of nitrobenzene are heated in the presence of 4.8 parts of thionyl chloride for 1 hour at 110° C. The excess thionyl chloride is removed boxyphenylamino)-4:6-dichloro - 1:3 :5 - triazine are dis from the resulting clear solution by distillation under reduced pressure. At 80° C., 4.6 parts of l-aminoanthra 55 quinone are added and the whole is maintained for 24 hours at 80° C. The dyestutf of the formula 0 II dyes cotton and regenerated cellulose by the method described in Example 20 yellow tints of very good fast ness properties. $1 ' The dyestuif of the formula C1 5 %\ N I ll ii NH-COQ 3,060,180 15 ' is isolated in the usual manner; it dyes cotton and regen-i 16‘ The dyestu? dyes cotton and regenerated cellulose very fast blackish green tints. When in this example aminoisodibenzanthrone is used instead of aminodibenzanthrone, a dyestuff results which erated cellulose by the method described in Example 19 clear yellow tints of good fastness properties. The dyestu? of the formula N 5 dyes cotton violet tints of similar properties. / o" NH-C 0C>NH-o/ i \O—O© i. Exam” 1e 18 \O/ 2.3 parts of 4:5'-diamino-1:1'-dianthramide carbazole A 10 are acylated with 3.2 parts of the carboxylic acid chloride 1 1 of 2-(4' - carboxyphenylamino) - 4 - amino - 6 - chloro ' 1:3:5-triazine as described in Example 7 and then isolated. 0 The dyestu? of the formula /N\ mN-(IJ/ <HJ-HN-OOQ_NH oI N N \ o 51 0 °1 NH 1 31 II N/ \N l I o NH-O oONn-cl \ % harm N is obtained by using in the above example 7.6 parts of dyes cotton and regenerated cellulose brown tints having 2 - (4' - carboxyphenylamino) - 4 - phenoxy - 6 - chloro~ very good properties of fastness. 1_:3:S-triazine; it gives similar, slightly more greenish tints. When 2-(4'-carboxyphenylamino) - 4 ~ amino-6-chloro 1:3:5-triazine is replaced by an equimolecular amount of Example 17 40 2 - (4’ -_carboxyphenylamino-4-phenylamino - 6 - chloro 3.2 parts of 2-(4'-carboxypheny1arnino)-4-amino-6chloro-l:3 :S-triazine are converted into the corresponding 1:3 zs'tnazule of the formula carboxylic acid chloride in 100 parts of nitrobenzene with _ 4 parts of thionyl chloride with addition of 0.5 part of dimethyl formamide at 100 to 110° C. The excess thionyl 45 HOOC N / \ NH_(1]3 (‘J-NEH N\ /N chloride is distilled oi the solution in vacuo, and 4.7 parts 0l of aminodibenzanthrone are added. 0.5 part of pyridine (III is then added and the whole is heated With stirring for 6 hours at 140 to 150° C., and then for 3 hours at 160 to 170° C. After cooling, the dyestu? of the formula 01' 0f 2-(4'-¢arb0Xyphenylamin0)-4-cyclohexylamino-6 50 Chl0r0-1I3I5-triaZine 0f the formula . /N\ N _O v 55 N \G// (‘11 0 dyestuffs of similar properties are obtained. |1 O\ These acylating components can be prepared in an 60 aqueous medium by condensing the sodium salt of 4 N/ \N aminobenzoic acid with cyanuric chloride in the molecular ll ratio of 121 at 0 to 5° C. and adding one molecular pro l NH_O OONH~C\ /C_NH2 portion of aniline hydrochloride or of cyclohexylamine N/ hydrochloride respectively; the second condensation is car 65 ried out at 30—40° C. and a pH value of 6.5 to 7.5 by the dropwise addition of sodium hydroxide solution until a primary amino group can no longer be detected. The free carboxylic acid is then precipitated quantitatively with di 0 lute hydrochloric acid and ?ltered off. 70 Example 19 14 parts of the dyestutf obtained as described in Exam ' ple 1 are ?nely ground in a ball mill with 126 parts of a is ?ltered o?‘, washed with nitrobenzene and then with neutral solution of 125 parts of dinaphthyl-methane alcohol, and dried in vacuo at 70° C. 75 disulfonic acid in 1000 parts of water. 3,060,180 17 18 7.5 parts of the resulting paste are suspended in 250 parts of warm water. The dyestu? suspension thus ob stirred until cold. 1 part by volume of aqueous formal dehyde solution of 30% strength is added as preserva tive. tained is added to a solution heated at 50° C. of 10‘ parts by volume of sodium hydroxide solution of 30% strength and 6 parts of sodium hydrosul?te in 1750 parts of water and vatted for 1 minute. The printing paste is printed on a fabric of‘cotton or staple ?bers of regenerated cellulose on a roller printing machine. The fabric is dried, impregnated with a solu tion containing per liter 24 grams of sodium hydroxide, 70 grams of sodium hydrosul-?te, 50 grams of sodium sulfate and 20 grams of borax, squeezed to a weight in 50 parts of cotton are dyed for 45 minutes in the dyebath prepared in this man ner at 50 to 60° C. with addition of 60 parts of sodium chloride. After the dyeing the cotton is washed, oxidized, acidi?ed, again thoroughly rinsed and soaped at the boil. An orange-yellow dyeing is obtained which has very good 10 fastness properties. crease of 70% and ?xed for 24 seconds at 120° C. in a Monforts reactor, thoroughly rinsed in cold water, oxidized at 40° C., in a solution containing per liter 5 parts by volume of hydrogen peroxide of 30% strength Example 20 and 3 parts by volume of acetic acid of 40% strength, 14 parts of the dyestu? obtained as described in Exam 15 rinsed, soaped at the boil for 15 minutes, rinsed and dried. ple 2 are ?nely ground in a ball mill with 126 parts of a A clear, yellow-orange‘ print of excellent fastness neutral solution of 125 parts of dinaphthyl-methanedi— properties results. sulfonic acid in 1000 parts of water. 10 parts of the What is claimed is: resulting paste are suspended in 100 parts of water. A 1. An anthraquinone vat dyestuif of the formula cotton fabric is impregnated with this suspension to a 20 N weight increase of 75% and then dried. The fabric is then impregnated with a solution containing per liter 16 grams of sodium hydroxide, 10 to 300 grams of sodium ' AHNOO N r GONHA chloride and 30 grams of Rongalite (trade name for sodi um sulfoxylate formaldehyde), squeezed to a weight in 25 crease of 75%, the dyeing is steamed for 1 to 9 minutes at 100 to 101° C., thoroughly rinsed in cold water, treat in which. A represents anthraquinonyl. ed with a sodium bicarbonate solution of 0.5% strength, 2. The dyestu? of the formula rinsed, soaped for 20 minutes in a boiling 0.3% solution 3. The dyestuif of the formula of a non-ionic detergent, rinsed and dried. A clear yel low dyeing of good fastness properties is obtained. Example 21 4. ‘The dyestuff of the formula 28 parts of the dyestu? obtained as described in Exam 60 ple 5 are ground in a ball mill with 112 parts of a neutral solution of 125 parts of dinaphthyl-methanedisulfonic acid in 1000 parts of water. A printing paste is prepared from 100 parts of the dyestuff paste described above 65 300 parts of water 600 parts of thickening KB 1000 parts PREPARATION OF THICKENING KD 70 (a) 20 parts of locust bean flour are strewn into 450 parts of water. (b) 15 parts of wheat starch are pasted in 20 parts of water and diluted with 495 parts of boiling water. (a) and (b) are combined, boiled for 20 minutes and 75 0 mI l I I l 31 / §N if NH-O o-O-rrn-o \ & N ll 0 éFNHz 3,060,180 19 > 5. The dyestu? of the formula ’ TV I . J . . ‘ V , _ 20_ G1 i V N OH NEE-COONH-é] §N/Hl-NH E1 I ' o . Goo-11m o’ ' g I1TH—-OO~C> 6. ‘The dyestu? of the formula N References Cited in the ?le of this patent ' UNITED STATES PATENTS 2,235,480 2,391,164 2,824,093 2,835,663 Graenacher et a1 ______ __ Mar. Kaiser _____________ __ Dec. Benz et a1. __________ __ Feb. Benz _______________ __ May 18, 18, 18, 20, 1941 1945 1958 1958 OTHER REFERENCES Bergmann: The Chemistry of Acetylene and Related -Compounds, page 80,‘ 'Interscience Publishers Inc., New York (1948).v ' Hess et 21.: Nature, vol. 183, pages 260 to 261 (Jan. 24, 1959).