[1]3,515,732 VAT DYESTUFFS CONTAINING SULFONAMIDE GROUPS Max Staeuble and Kurt Weber, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company 5 of Switzerland No Drawing. Continuatioii of application Ser. No. 202,959, June 18, 1962. This application Aug. 23, 1966, Ser. No. 574,474 Claims priority, application Switzerland, Dec. 31, 1959, 10 67,908/58; Mar. 2, 1959, 70,227/59 Int. Cl. C09b 3130 U.S. Cl. 260-354 4 Claims 15 ABSTRACT OF THE DISCLOSURE Vat dyestuffs are provided which contain at least one groiiping of the formula -SO2NH-R in which R represents a P-sulfatoalkyl group and especially a lower 6- sulfatoalkyl group. In addition to the said grouping the 20 dyestuffs may contain substituents that are customarily present in vat dyestuffs, for example, halogen atoms or alkoxy, acylamino or alkyl groups. A process for the preparation of such vat dyestuffs is also provided. The dyestuffs are suitable for dyeing a wide variety of mate- 25 rials, and especially, for the dyeing or printing of textile materials of natural or regenerated cellulose by the methods usual for the dyeing or printing of vat dyestuffs. The dyeings and prints produced possess excellent fastness to light and wet fastness. 30 0 3@515,7,32 Utiited States Patent Office Patented June 2, 1970 2 ing agent or (e) an aminoanthraquinone is reacted with an acylating agent which contains ae-sulfatoalkyl-sulfonamide group, and especially one of the formula - S O 2 N H C H , C H O - S O , H This is a continuation of copending application Ser. No. 202,959, filed June 18, 1962, now abandoned, which is a continuation-inpart of copending application Ser. 'o5 No. 860,628 filed Dec. 21, 1959, now abandoned. This invention provides vat dyesttiffs which contain at least one grouping of the formula (1) -SONH-R 40 in which R represents a p-sulfatoalkyl group, especially a lower psulfatoalkyl group. The term "lowee' in this connection means not more than 6 carbon atoms. R advantageously represents a radical of the formula 45 -CH,CH,OSO,H The term "vat dyestuffs" comprises dyestuffs which are capable of being ronverted by reduction into a socalled leuco-form or vat, possess a better affinity for 50 natural and regenerated cellulose fibers than in the nonreduced form, and can be reconnerted by oxidation iiito the original chromophoric system. As suitable vat dyestuffs there may be mentioned more especially those of the anthraquinone series, for example, those which con- 55 tain an unmodified 9: 10-oxoanthracene ring and also those anthraquinones which contain fused-on carbocyclic or heterocyclic rings or consist of a plurality of anthraquinone units, and also vat dyestuffs of perylene tetracarboxylic acid and naphthalene tetracarboxylic acid, 60 and indigoid vat dyestuffs. In addition to at least one grouping of the Form-ula 1, the. dyestuffs may rontain substituents that are customarily present in vat dyestuffs, for example, halogen atoms or alkoxy, acylamino or alkyl groups. 65 The invention also provides a process for the manufacture of the above new dyestuffs wherein (a) a vat dyestuff containing at least one sulfonic acid halide group is condensed with an amine of the formula NH2R, in which R has the meaning given in connection with Formtila 1, 70 or (b) a vat dyestuff containing at least one sulfonic acid-p-hydroxyalkylamide grotip is treated with a sulfator (d) an anthraquinone compound containing a mobile halogen atom is reacted with an amine containing a 6sulfatoalkylsulfonamide group. In the process as carried out under (a) there are advantageously used as starting materials vat dyestuffs containing at least one sulfonic acid chloride group. Of special iftterest are vat dyestuffs containing two such groups. As exa,tnples of suitable starting materials there may be irientioned more especially those of the anthraquinone series: 1:5-dibenzoylamino-anthraquinone disulfochloride, dibenzanthrone disulfochloride, isodibenzanthrone disulfochloride, and also the sulflochlorides of anthanthrone, dibenzpyrene-quinone, pyranthrone, acedianthrone, Ravanthrone, indanthrone, N:N'- diethyldipyra@zole-anthronyl, N:N'-diisopropyl-dipyrazole, anthronyl, anthraquinone2:1(N)I':2'-(N) naphthaeridone, 1:1'- dianthrimide-carbazole, 2'-2"-diphenyl - anthraquinone-1:2(N)- dithiazole, 2':2"-diphenyl-anthraquinone-5:7 (N) -dithiazole. In addition to sulfochlorides of the anthraquinone series there may be mentioned sulfochlorides of indigoid vat dyestuffs, perylene tetracarboxylic acid diimides; perinone dyestuffs and cobalt phthalocyanine. The aforesaid sulfochlorides can be obtained by treating the appropriate vat dyestuff with chlorosulfonic acid, or by reacting the appropriate sulfonic acids with an acid-halogenating agent, such as phosphorus halides, thionyl chloride or -chlorosulfonic acid, known methods being used for carrying out the aforesaid reactions. Another method of obtaining the sulfochlorides used as starting materials consists in acylating an aminoanthraquinone with benzoic acid-sulfonic. acid dichloride, whereby a chlorosulfonylbenzoylaminoanthraquinone is obtained. The reaction of the aforesaid sulfochlorides with an amine of the formula NH2R may be carried out in an inert organic sGIvent, for example, nitrobenzene, chlorobenzene or orthodichlorobenzene at a raised temperature. As, on working up, the sulfochlorides are generally obtained in the form of aqueous suspensions, it is of advantage to carry out the reaction with the amine of the formula NH2R in an aqueous medium, advantageously in the presence of an acid-binding agent, for example, sodium acetate, sodium hydroxide or sodium carbonate. The molar proportions of the components are preferably so chosen that for each sulfochloride group in the vat dyestuff at least one molecular proportion of an amine of the formula NH2R is used. In the form of the process described under (b) there are advantageously used as starting materials anthraquinone vat dyestuffs containing one or two sulfonic acid phydroxyethylamide groups, for example, mono- or disulfonic acid hydroxyethylamides of 1:5-dibenzoylaminoanthraquinone or of dibenzanthrone or of isodi@benzanthrone, and also sulfonic acid hydroxyethylamides of anthrathrone, dibenzpyrenequinone, pyranthrone, acedianthrone, flavanthrone, indanthrone, N:N'- diethyldipyrazole-athronyl, N:N' - diisopropyl-dipyrazole - anthronyl, anthraqi-iinone-2:1(N)-l':Z'(N)naphthacridone, 1:1'- dianthrimide-carbazole, or 2':Z"-diphenylanthraquinone1:2(N)- dithiazole, 2':2"-diphenylanthraquinone-5:7 (N)dithiazole. In addition to the aforesaid sulfonic acid hydroxyethylamides of the anthraquinone series, there may be mentioned sulfonic acid hydroxyethylamides of indigoid vat dyestuffs, perylene tetracarb(yxylic acid diimides, perinone dyestuffs or cobalt phthalocyanine. The aforesaid sul-
[2]3)5152732 3 4 fonic acid hydroxyeth3ilamides can be obtained by react- which products contain at least one exchangeable chlorine ing the appropriate sulfonic acid chloride with p-hydroxy- atom, for example, the compound of the formula ethylamine, or by reacting a vat dyestuff containing a mobile halogen atom, for example, an aminoantbra- N \ quinone of which the amino group is substituted 'by a 5 0 NH-0 C-Cl chlorotriazine radical, with an amine of the formula I 11 N N S 0,@,NII-CI12CI12-011 II2N-<= 10 The sulfating of the hydroxyethylsulfonamides is advantageously carried out in concentrated sulfuric acid in the cold, for example, within the range of 0-50' C., and adeach part of dyestuff. The sulfatin.- can also be carried out with oleum or chlorosulfonic acid or an - addition compound of chlorosulfonic acid with a tertitry base or amide, for example, pyridine, triethylamine or dimethyl- 2( formamide. In the form of the process described under (e) there are used as starting materials aminoanthraquinones, for example, 1:5-diaminoanthraquinone, I-ami no-5-benzoylaminoanthraquinone, 4 - aminoanthraqu inone-2:1(N)- )5 acridones, 4:4'- or 4:5'- or 5:5'-diamino-1: l '-dianthrimidecarbazole or 5-aminoantbraquinone-2: 1(N)-':2'(N)- naphthcarbazole. As acylating agents containnig a g-sulfatoalkylsulfonamide group there n-lay be mentioned more especially ben- 30 zoic acid halides and preferably the compound of the formula S02NHC11201-12OS03H cioc 35 -<= These compounds are advantageously obtained by reacting the appropriate sulfobenzoic acid with c hlorosulfonic acid to form the bedzoic acid sulfochloride, condensing 40 the latter with 6-sulfatoethylamine or 6- hydroxyethylamine to form benzoic acid-(,6-sulfatoethyl)- or -(g-hydroxyethyl)-sulfonaniide, and reacting the latter with a sulfating agent. As acylating agents there may be mentioned also, for example, compounds of the formula 45 Th- condensation product is reacted with an amine coii.taining a sulfonic acid-psulfatoalkylamide group, for exvantageously With at lepst 5 parts of sulfuric acid for 1,,3 ample, the amine of the formula N N [I ei- C-Cl 55 @-IN The reaction of the aminoanthraquinone with the acylating agent is advantageously carried out in an inert 60 organic solvent, for example, nitrobenzene, chlorobenzene or ortho-dichlorobenzene, at a raised temperature or in water. The molecular proportions of the coniponents are advantageously so chosen that for each amino .-roup of the anthraquinone radical approximately one 65 carboxylic acid chloride group or one -roup of the formula ci I -N@c- 70 of the acrylating agent is present. In the form of the process described under (d) there are used as starting materials, more especially reaction products of aminoanthraquinones with cyanuric chloride, 75 02NHCH2CH2OSo3H 50 II2N- <:D- S02NIICH2CH20SO311 The dyesttiffs so chosen can be isolated from the reaction mixture and, notwithstanding the presence of the reactive gro-uping of the Formula 1, they can be worked up, into useful dry dyestuff preparations. They can be isolated from the reaction mixture by filtration. The filtered. dyestuff, if desired after the addition of a neutral or weakly alkaline extender, may be dried. Drying is advantageotisly carried out at not too high a temperature, and if desired, under redticed pressure. The dyestuffs of this invention are suitable for dyeing a wide variety of materials, but especially for dyeing or printing textile materials of natural or regenerated cellil-; lose by the methods ustial for dyeing or printing with vat@ dyestuffs. The dyeings and prints so produced are distinguished by their excellent fastness to light and wet fastness. In view of the fact that, in contradistinction to rhe conventional vat dyestuffs, they can generally not be i-emoved to any substantial extent from the fiber by means of hot dimethylformamide, it must be assumed that, the dyestuffs are chemically bound on the fiber. The dyeings produced with the dyestuffs of this invention are therefore fast to dry cleaning and fast to migration. Fabrics dyed therewith can be coated with synthetic resins, for example, polyvinyl chloride, withotit the dyesttiff migrating into the plastic, which is especially important in the manufacture of artificial leather. The dyestuffs of this invention can generally be vatted very easily and freqiiently even at room temperature. The wate,r-soluble dyestuffs containing a radical of the Formula I can be vatted very rapidly, even with mild reducing agents such as glucose. As the reactivity of thei -OS03H groups in the sulfonic acid alkylaniide' radical may vary somewhat from dyestuff to dyestuff, it is of advantage to select the dyeing conditions, especially the concentration of alkali and reducing agent and also the duration and temperature of dyeing or steaming, depending on: the dyestuff used. The optimum conditions can easily be dete@rmined by preliminary tests. As compared with conventional vat dyestuffs, the vat dyes of the invention have the advantage of a better levelling and through-dyeing power. Moreover, in machinedyeing, even when foaming occurs, they do not cause faulty dyeings due to the precipitation of reoxidized dyestuff, and the pigmcntation necessary in dyeing wound, bodies, for exaniple, cross-wound spools or tricots on a reelin.- vat, with conventional vat dyestuffs is dispensed with when the dyestuffs of the invention are used.!They can also be used in the form of solutions in the fastrunning padding method, and there is no need for finely; dispersed commercial forms or special paste forms, so that the disadvantages connected with the latter, namelyi instability of the paste, dust and the necessity of one or more operations for producing finely dispersed powders, do not exist. Finally, they can usually be vatted very easily, frequently at @room temperature and, if desired, with mild reducing agents. They possess a very good solubility in
[3]3)5157732 5 6 th e vat, and especially on regenerated cellulose they proE XAMPLE 2 d uce strong and very level dyeings which have shades si milar to those of the corresponding. dyeings on cotton. 1 0.6 parts of the sulfochloride of the formula T he following examples illustrate the invention, the p arts and percentages being by weight unless otherwise 5 st ated, and the relationship of parts by weight to parts 0 by volume being the same as that of the kilogram to the 0 NH2 N F-XAMPLE I c 13.8 parts of I-aminoanthraquinone-6-(p-hydroxyeth- 10 yl)-sulfonamide (prepared by condensing 1-nitroanthraquinone-6-sulfochloride with monoethanolamine and reH duction with sodium hydrosulfide in an aqueous solution) are heated in 150 parts of nitrobenzene with 4.5 parts of 15 @o-c>-SO2CI 2-phenyl-4:6-dichlorotriazine-(1:3:5) for 5 hours with stirring at 150 to 155' C. After cooling, the dyestuff which crystallizes in orange needles is isolated in the usual manner. (prepared by condensing the appropriate amine with ben10 parts of the so-cibtained compound of the formula 20 zoyl chloride-4- sulfochloride in nitrobenzene at 140' C.) N N I II 0 NH-0 C-NH 0 N HO-CI12CI12-NH-SO2- 0 are slowly added at 0 to 5' C. to 180 parts of concentrated sulfuric acid and dissolved therein. The whole is then poured into about 800 parts of ice water and filtered. The moist filter cake is suspended in about 1000 parts of water and neutralized with sodium hydroxide solution. 40 20 parts of sodium chloride are added, the mixture is suctionfiltered and the filter residue is dried in vacuo at 60 to 701 C. In the form of its free acid and the new dyestuff corresponds to the formula 45 02-NH-CH2-CU2-011 are pasted at 120' C. with 120 parts of nitrobenzene. 1.8 parts of monoethanolamine are added, and the mixture is stirred for 4 hours at 120 to 125' C., then allowed to cool, and the product is filtered off, washed successively with benzene, alcohol and water, and dried. 10 parts of the resulting condensation product are stirred into 180 parts of concentrated sulfiiric acid at 0 to 5' C., and dissolved therein. The working up is carried out as described in Example 1. The new dyestuff corresponds to the forrnula N N I 0 NH-C 8-NH 0 11 N H03SO-OH2CH2-NH-SC)2- 02-NH-CH2CH2-OS.03H 0 and is completely soluble in water, giving a yellow solu0 tion. 0 NH2 N A solution of 10 parts of the dyestuff in 1000 parts of water is used to impregnate a cotton fabric so that its C weight shows an increase of 75%, and the fabric is then 65 dried. The fabric is then impregnated with a solution cons taining per liter 40 cc. of sodium hydroxide solution of 36' B6., 30 grams of Rongalite and 200 grams of sodium chloride, squeezed to a weight increase of 75%, and the @o S02--NH-CH2- CH2OSO3Na dyeing is steamed for I to 5 minutes at 100' C., thor70 -C>- oughly rinsed in cold water, treated with a 0.5% solution and gives a blue solution in water. of sodium bicarbonate, rinsed with water, soaped for 20 minutes at the boil with yellow soap-suds, again rinsed, Dyeing Process A and finally dried. A yerow dyeing is obtained which has 1.5 parts of dyestuff are dissolved in 500 parts of water good pro_perties of fastness. 75 at 60' C. The dissolved dye is vatted in a dyebath contain-
[4]3)5153732 7 8 ing 20 parts of sodiuni hydroxide solution of 30% -are slowly added at 0 to 51 C. to 180 parts of sulfuric strength and 12 parts of sodium hydrosulfite in 3500 parts acid of 100% strength and dissolved therein. @ The dyeof water. At 50' C., 100 parts of well wetted cotton are stuff is isolated as described in Example 1; in the form of introduced into this dyebath, and dyeing is carried @out its free acid it corresponds to the formula c i N N 0 NH C-NII Iz@ N 0 2 - N I I - C H 2 - C H 2 - O S O a T T co- 0 for 45 minutes at that temperature. After the first 10 and dyes cotton and re,-enerated cellulose by the followminutes, 60 parts of sodium chloride are added, and after ing method fast yellow tints. the first 20 minutes, another 60 parts of sodium chloride are added. The cotton is then taken out of the bath, oxiDyeing Process B dized, neutralized, thoroughly soaped at the boil, rinsed 20 in warm water and then in cold water, and dried. A greenish blue dyeing having good fastness properties 3 parts of dyestuff are suspended in 500 parts of water is obtained. at 60' C. The suspended dyestuff is vatted in @a dyebath EXAMPLE 3 25 containing 20 parts of sodium hydroxide solution of 30% When in Example 2 there is used instead of the sulstrength and 12 parts of sodium hydrosulfite in 3500 parts fochloride first mentioned the sulfochloride of the formula of water. 1 00 parts of well wetted cotton are entered into 0 NH2 NIT.2 0 this dyebath at 50' C and dyeing carried out for 45 / 0 \ minutes at that temperature@ After ithe.first ilO iminutes, C C30 60 parts of sodium chloride are added, and after the first NN 20 minutes, another 60 parts of sodium chloride, are add-! ed. The cotton is then removed from the bith, oxidized, neutralized, thoroughly soaped at the boil, rinsed in warm clo2s--<:D-@ 0- <@D-so2cl 35 water and then in cold water, and dried. A yellow dyeing having good fastness properties is ob,- and the same procedure followed, there is obtained the tained. dyestuff of the formula 0 NH2 NH2 0 0 0 ,II N-@ H 0 1 NII-so@-<@::)-Ico Co-<:D-SO3-NII I @Hn-CH20SOSNTa CH2-CH2OSO3Na When used according to Dyeing Process A, this dyestuff yields strong reddish blue dyeings having good fastness properties. EXAMPLE 4 55 14.7 parts of 4:6-dichloro-2- [ (5) -benzoylaminoanthraquinonly-(l)-aminol-1:3:5- triazine are pasted at 100' C. with 200 parts of nitrobenzene and 15 parts of N-Ndiethylaniline. 6.5 parts of 3-aminobenzene-p-hydro x@,ethylsulfonamide are then strewn in, and the mixture is stirred 60 for 6 hours at 100 to 105' C. The dyestuff crystallizes out in very fine, small needles; it is filtered off, washed with alcohol and then with water, and dried. 10 parts of the soobtainedcompound of the formula ci EXAMPLE 5 22.4 parts of the condensation product from 2 molecular proportions of Iaminoanthraquinone and I molecular proportion of cyanuric chloride in 250 paxts of nitrobenzene are stirred in the presence of 26 parts of3-aminobenzene-sulfonic acid - N -,3 - hydroxyethylamide for 10 hours at 180 to 185' C. The whole is allowed to cool, filtered, and the filter residue is washed successively with benzene, alcohol and water, and then dried. 10 parts of the resulting condensation product are slowly stirred at 0 to 5' C. into 180 parts of sulfuric acid of 96% strength and dissolved therein. Working up is' N N 0 NH-c@ Icl-NH II N 02-@NH-CH2CHz-OH
[5]3)515)732 9 carried out as described in Example 1. The new dyestuffcorresponds in the form of its free acid to the formula 02-NH-CH2CH2-OSOaH NIT I L; N N I 11 0 NH-C C-NH 0 N It dyes cotton and regenerated cellulose by the method B described in Example 4 yellow tints having excellent properties of fastness. The corresponding derivative of 2-phenyl-4:6-dichlo rotriazine-(1:3:5) dyes cotton and regenerated cellulose greenish yellow tints of similarly good properties. It can be prepared in the following manner: A solution of 18.9 parts of 2-phenyl-4:6-dihydroxyt riazine-(1:3:5) in 175 parts of chlorosulfonic acid is heated for I hour at 130 to 135' C. and then for 4 hours at 140 to 145' C., poured over a@bout 1000 parts of ice, filtered, and the precipitate is suspended in 500 parts of C102s-<::>c O-NH-<=>-N / co\co ice water, accurately neutralized with sodium hydroxide solution, suction-filtered and dried under reduced pressure. 14.4 parts of the resulting sulfochloride are refluxed for 3 hours with 84 parts of phosphorus oxychloride and 45 parts of phosphorus pentachloride, then cautiously poured over about 1500 parts of ice, maintained for 30 minutes at O' C. with energetic stirring, suction-filtered, and the filter residue is washed neutral with ice water, dried and recr-ystallized from trichlorethylene; the product melts at 142' C. 6.5 parts of the resulting sulfochloride of the phe nyldichlorotriazine are mixed with 100 parts of nitrobenzene and 9.3 parts of I-a minoanthraquinone, and the mixture H03SOCH2-CH2-NH-02S-<@@-C O-N]I-CD-N is heated for 4 hours at 140 to 145' C. The sulfochloride, which crystallizes in the form of needles, is filtered off, washed with benzene, and dried in vacuo. 13 parts of the resulting dyestuff sulfochloride are pasted at 120' C. with 140 parts of nitrobenzene,. At the same temperature 4.6 parts of monoethanolamine are slowly added dropwise, and the whole is stirred for 2 hours at 120' C. and then for I hour at 140' C., and allowed to cool. The dyestuff, which crystallizes in the form of fine small needles, is filtered off, successively washed with benzene, alcohol and water, and dried. 10 parts of the resulting condensation I)roduct are added at 0 to 5' C. to 180 parts of sulfuric acid of 96% strength and dissolved therein. The whole is poured over ice and then worked up as described in Example 1. 10 In the form of its free acid the new dyestuff corresponds to the forn-iula S02-NH-OTT2-CH2-OS03H N N 10 0 NH-@ 8-NH 0 N 0 When the condensation is performed with - 1-amino-5- 20 benzoylaminoanthraquinone instead of with I-amin oanthraquinone, a dyestuff is obtained which dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat golden orange tints having excellent properties of fastness. When 1- amino-4-benzoylaminoanthraquinone 25 is used, red tints are obtained, and with 1:4-di amino-2acetylanthraquinone blue tints result, both shades having similarly good properties offastness. EXAMPLE 6 30 19.6 parts of the disulfoebloride of the formula co \ N-<@:D-NIT-CO-<@@>-SO2CI co/ (prepared from the appropriate diamine by condensation with benzoylehloride-4- sulfochloride in nitrobenzene) are pasted at 140' C. with 300 parts of nitrobenzene. 10 40 parts of mono-ethanolamine are then added dropwise within 1 hour at 140 to 145' C., and the mixture is heated for 5 hours at the same temperature, then allowed to cool, and the product is filtered off, washed successively with benzene, alcohol and water, and dried. 45 10 parts of the resulting condensation product are stirred at 0 to 5' C. into 180 parts of concentrated sitlfuric acid and dissolved therein. The solution is cautiously poured into ice water and isolated in the usual manner. In the form of its free acid the new dyestuff corre50 sponds to the formula / co co \ N \co co/ NH-C O-C>-SO2-NH-CH2CH2OSO3II It dyes cotton and regenerated cellulose from an alkaline hydrosulfite vat red tints. EXAMPLE 7 65 11.4 parts of isodibenzanthrone are added at 20 to 25' C. to 210 parts of chlorosulfonic acid, and the whole is stirred for I hour at the same t.-mperature, and then heated at 70 to 75' C. until a test portion dissolves in aqueous pyridine of 10% strength, which is the case 70 after about 5 hours. The mixture is then cautiously poured over ice, the precipitated sulfochloride is suctioned off and washed with ice water. The isodibenzanthrone disulfochloride so obtained is sus ended in the form of a moist press cake in 700 parts 75 of @ ice water and at 0 to 5' C. treated with 300 parts
[6]3;5152732 12 of monoethanolamine. The mixture is stirred on for about In the form of its free acid the new dyestuff corre2 hours at 0 to 5' C., then allowed to heat up to room sponds to the formula temperature, and stirred for a further 15 hours. Finally, the whole is heated for I hour at 60 to 65' C., suctionfiltered while still warm, and the filter residue is washed 5 with water until it is neutral, and then dried. 7 parts of the resulting condensation product are added at 0 to 5' C. to 190 parts of sulfuric acid of 96% strength 0 and dissolved within 4 hours. The sodium is then cautiously poured over about 800 parts of ice, and the 10 precipitate is suctioned off, pasted with 1000 parts of water at 30 to 40' C., and neutralized with sodium hy02N]ICH2CI12OS03H droxide solution. 50 parts of soditim chloride are added, the whole is suction-filtered, and the filter residue is dried in vacuo at 60 to 70- C. 15 In the form of its free acid the new dyestuff corresponds to the formula 02NHCH2CH20soall 20 25 02NIrCH2CT420so3n It dissolv es compl etely in water, giving a blue solutio n, 30 and produ ces by the metho d C descri bed in Exarn ple 7 strong reddis h blue dyeing s having excell ent prope rties of '02N]EICH2CH20803TT fastness. E X A M P L E 9 13.3 p a r t s o f 3 : 4 : 8 : 9 - d i b e n z p y r e n e q u i n o n e - ( 5 : 1 0 ) a r e 35 added to 250 parts of chlorosul fonic acid, and the whole is heated for I hour at 60 to 65' C., then for 4 hours at 80 to 85' C. and finally for 9 hours at 100 to 1031 C. The reaction mixture is then poured over ice, isolated in the 40 @sual manner, condens ed with monoeth anolamin e accordin g to Example 7, second paragra ph, and then esterifie d with concentr ated sulfuric acid acccordi ng:to Example and is completely soluble in water, giving a blueviolet third paragraph. solution. For dyeing it is used in the following manner. The new dyestuff gives a yellow aqueous solution and Dyeing Process C 45 dyes cotton froni an alkaline vat yellow tints. 1.5 parts of dyestuff are dissolved in 500 parts of water EYAMPLE 10 i at 60o C. The dissolved dyestuff is vatted in a dyebath When in Example 7 there is used, instead of 300 @parts containing 60 parts of sodium hydroxide solution of 30% of monoethanolamine, the same quantity of 11-aminostrength and 12 parts of sodium hydrosulfite in 3500 parts propanol-(2), the procedure being otherwise the same, of water. 100 parts of well wetted cotton are entered at 50 there is obtained the dyestuff of the formula 60% C. into this dyebath, and dyeing is carried out for 10 minutes at that temperature with the addition of 60 parts of sodium chloride. The teniperature is then raised to 70' C., and another 60 parts of sodium chloride added. After 15 minutes, the dyeing temperature is raised to 80' C. and 5,1 maintained at that level for 15 niinutes. The cotton is then removed from the bath, oxidized, neutralized, thoroughly 0 soaped at the boil, rinsed in warm water and then in cold water, and dried. There is obtained a brilliant reddish blue dyeing having 60 good fastness properties. EXAMPLE 8 CII3 11.4 parts of dibenzanthrone are added at 20 to 25' C. @(SO2-NH-CH2-CHOSOaNa to 210 parts of chlorosulfonic acid, and the mixture is 65 )2 stirred for 1 hour at the same temperature and then heated at 60 to 65' C. until a test portion is soluble in aqueous pyridine of 10% strength, which is the case after about 8 hours. Working up is carried out as described in Exarnple 7. 70 Tite dibenzanthrone disulfo-dichloride so prepared is 0 condensed, as @described in the second paragraph of Example 7, with monoethanolamine and theii esterified with concentrated sulfuric acid according to Example 7, third paragraph. 75
[7]32515)732 13 This dyestuff, when used according to Dyeing Process C, yields vigorous reddish blue dyeings harving good fastness properties. EY-AMPLE 11 When, in Example 7, 13.1 parts of dichloroisodibenzanthrone are used instead of 11.4 parts of isodibenzanthrone, and the sulfochlorination is performed at 80-85' C., there is obtained the dyestuff of the formula 0 12 S02NH-CH2-CH20SOaNa o@ According to Dyeing Process C, this dyestuff yields vigorous violet dyeings having good fastness properfies. EXAMPLEIZ 11.4 parts of isodibenzanthrone are introduced into 210 parts of chlorosulfonic acid and stirred for one hour at 20-30' C. The reaction mixture is then heated to 80' C. and stirred at that temperature for 4 hours. After cooling, the mixture is poured very carefully on to ice-water while stirring thoroughly. The precipitated sulfochloride is rapidly filtered off and washed with ice-water. The moist sulfochloride is then introduced into a mixture of 100 parts of 6-aminoethyl-sulfuric acid semi-ester, 300 parts of water and 22 cc. of sodium hydroxide solution of 30% strength (pH of the solution 9.5) at 5-10' C., and the reaction mixture heated in the course of 3 hours to 20' C., the pH of the solution being kept constant by the dropwise addition of concentrated sodium hydroxide'solution. Stirring is continued overnight at room temperature; the reaction mixture is then heated for 2 to 3 hours at 40-50' C. The product is isolated by filtration and dried in vacuo at 40- 50' C. The new dyestuff in the form of the free acid corresponds to the formula 14 0 5 02-N]EI-C :5-CH2o-so3H 2 1 0 15 0 20 25 EXAMPLE 13 When the condensation described in Example 8 is performed with 2-aminobutanol-(I) instead of with mono30 ethanolamine, the dyestuff of the formula 35 0 40 C TT3 @H2 45 A@SO.-NII-611:-CH2OSO3Na 2 50 0 55 ;s obtained. 60 ' Bly the Dyeing Process C (see Example 7), this dyestuff yields vigorous reddish blue shades on cotton. The dyeings have excellent fastness properties. EXAMPLE 14 65 6.2 parts of the compound of the formula <=>-<=>-N / C 0 C 0 \N \CO CO/
[8]325152732 15 are introduced into 150 parts of chlorosulfonic acid and dissolved. The solution is stirred at room temperature for 15 minutes, then carefully poured onto ice, the sulfochloride which precipitates is filtcred off with suction, and washed with some ice-water. The moist sulfochloride is then qtiickly introduced into a mixture of 50 parts of p-aminoethyl-sulfuric acid semiester, 150 parts of water, and 11 parts by volume of 30% sodium hydroxide solution (pH 9.4), the pH value being kept constant by the dropwise addition of sodium hydroxide solution of 30% strength. The batch is then stirred at room temperature for 15 hours. It is then beated at 40-50' C. for 2 hours, the product isolated by filtration, and dried under vacuum at 40-50' C. T'he resulting dyestuffcorresponds to the formula ,co /\C o NaOBSOCHz-CH2--NHSO2 Dyeing Process D 2.2 parts of dyestuff are suspended in 500 parts of water of 60' C. The suspended dyestuff is vatted in a dyebath containing 20 parts of sodium hydroxide solu@- tion of 30% strength and 12 parts of sodium hydrosulfite in 3500 parts of water. 100 parts of well wetted cotton are introduced at 60' C. into this dyebath, and dyeing carried out at that temperature for 10 miiiutes with the addition of 60 parts of sodium chloride. The temperature is then raised to 70' C., and another 60 parts of sodium chloride added. After 15 minutes, the temperature is raised to 80' C., and dyein.- continued for 15 minutes at that temperature. The cotton is then rer.noved from the dyebath, oxidized, neutralized, thoroughly soaped at the boil, washed in warm water, then in cold water, and dried. A vigorous red dyeing having good fasteners properties is obtained. EXAMPLE 15 13.6 parts of the compound of the formula 0 0 are introduced into 260 parts of chlorosulfonic acid and the resulting solution stii-red for 24 hours at room temperature. It is then carefully poured onto ice, the 16 with some ice-water, and condensed with monoethanolamine according to Example 7. YTte resulting sulfonamide is esterified with concentrated sulfuric acid as described there, The resulting new dyestuff corresponds to,the.formula, s s I I 02NI-I-CH2-CH2Oso3Na )2 C=C 0 20 It dissolves completely in water to give a blue-green coloration. When used for Dyeing Process D, @ it gives 25 vigorous blue-green dyeing having good fastness prop-! erties. CO\ CO/ SOz-NH-CH2-CH20SOaNa EXAMPL-E 16 10.3 parts of the dyestuff of the formula N ?N 50 C)O 0 55 \N/ 60 65 are introduced into 220 parts of chlorosulfonio acid and the mixture stirred for I hour at room temperature. It is stirred while being heated to 40' C., and main tained at that temperature for 2 hours. After that ' it is stirred at 50-55' C. for 3 hours. After cooling, t@e 70 mixture is carefully poured onto ice, the sulfochloride which precipitates is filtered off, washed with some @ice water, and condensed with monoethanolamine according to Example 7. Esterification is performed according to Example 7 with concentrated sulfuric acid for 10 sulfochloride whicb precipitates is filtered off, washed 7,5 hours at room teriiperature.
[9]3,515,732 17 The new dyestuff so obtained corresponds to the formula Os-NH-CH2-.CH20SOaNS)a \Nl 0 and dissolves completely in water. In the dyeing Process D of Example 14, it yields orange dyeings. EXAMPLE 17 13.4 parts of the dyestuff of the formula 0 0 N 0 N@EE 0 are dissolved in 280 parts of chlorosulfonic acid. The solution is stirred for 14 hours while being heated at 100 to 105' C. After cooling, it is carefully poured onto ice, and the sulfochloride which precipitates is filtered off, washed with ice @water, and condensed with monoethano amine according to Example 7. Esterification is p formed in a maner analogous to that of Example 7 w 100% sulfuric acid for 3 hours at room temperature. In Dyeing Process D, the new water-soluble dyestuff yields vigorous olive-gray dyeings having good fastness properties. EXAMPLE 18 6 parts of the compound of the formula 0 NH-co S02NH-CH2-CH20H H 0 H-C 0 -CD>- S02NH-CHz-CH20H are introduced at 5-12' C. and into 150 parts of 100% sulfuric acid, and for complete dissolution, the mixture is stirred for 4 hours at 0-5' C. The product is worked up as described in Example 10. 18 The new water-soluble dyestuff corresponds to the formula 0 NH-C 0 SOz-NH-CHr-CH20SOsNa 10 15 H-C 0 S02--NH-C]E[2-CH2OSO3Na and in Dyeing Process A gives golden orange dyeings having good fastness properties. 20 The first-mentioned compound can be obtained as foll,ows, 24.4 parts of benzoic acid-para-sulfoehloride in 250 parts of nitrobenzene are stirred and heated to 100-110' C. 'for I hour together with 20 parts of thionyl chloride 25 and 0.5 part of dimethylformamide. From the resulting clear solution, the excess thionyl chloride is distilled off under reduced pressure. 22.9 parts of 5,5'-diamino-1,1'4ialithrimide-carbazole are then added, and the whole kept at 120-125' C. for 21 hours. The product is isolated 30 by filtration. 8.6 parts of the sulfochloride of the formula 0 NH 0 35 clo2s-<:@>CO H co 40 2 45 so obtained are stirred in 130 parts of nitrobenzene at 120' C. After the addition of 6.2 parts of monoethanolamine, the mixture is stirred while being heated at 120125' C. for 4 hours and at 140-154' C. for 6 hours. After cooling, the product is isolated by filtration and triturated 50 in a dish with alcohol, filtered off, and washed with alcohol. When in this example the benezoic acid-para-sulfochloride is replaced by the same quantity of benzoic acidmeta-sulfochloride, and the resulting sulfochloride is treat55 ed as described, there is obtained the dyestuff of the formula S02NH-CH2-CH2oso3Na 60 0 NH-CO-C-> 65 H 0 70 S0 2NH-CH2-CH20SOSNa I co -<-@ which likewise yields golden orange dyeings having good 75 fastness properties.
[10]19 3)515,732 20 2. The vit dy6stuffs 6f @ the formula 0 - (so2 NH CH2 CH2 OS O3 H)2 EX AMPLE 19 whe rein t!be substituent groups occupy,the,positions of the ring system which are occupied by sulfonic@ acid 10.1 parts of pyranthrone are introduced into 175 parts chlo ride groups when the di-chlorosuffonating step is of chlorosulfonic acid and the resulting solution heated 10 con ducted under conditions wherein the ratio, of isodito 80-85' C. for 22 hours, then carefully poured onto ben zanthrone to chlbrosulfonic acid is about 1: 18.4 by ice. The sulfoebloride which precipitates is filtered off, weig ht. was hed with some ice water, and condensed with mono3. The vat dyestuffs of the formula 0 0 ( S O 2 N H C j l 2 C T r 2 O S O 3 H ) 2 ethanolamine according to Example 7. The resulti.ng sul- 20 wherein the substituent groups occupy those positions of fonamide is esterified with concentrated sulfuric acid, as the ring system which are occupied iby sulfonic acid described there. chloride groups when. the dich.lorosulfonating step is The water-soluble dyestuff so obtained corresponds to conducted under -conditions wherein the -ratio, of dithe formula benzanthrone to chlorosulfonic acid is about 1: 18.4 by 0 25 weight. 11 4. A vat dyestuff of the formula /,SOa--NH-CH2- CH2,OS03Na K-(-SO2NH-R)2 30 wherein R is 6-sulfato lower alkyl and K is' the isodi.@ benzanthronyl cbronlophore, wherein the substituent groups occupy those positions of the ring systemiwhich are occtipied by sulfonic acid chloride-groups when the 3,5 dichlorosulfonating step is carried out under conditions wherein the ratio of isodibenzanthrone to chlorosulfonic. acid is about 1:18.4 by weight. When used for Dyeing Process D it yields golden orange References Cited dyeings. 40 UNITED STATF@"5 PATENTS What is
