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Patented Oct. 8, 1946 2,408,961 -' UNITED .STATES' PATENT OFFICE 2,408,961 TRISAZO METALLIZABLE DYESTUFFS .Fritz Straub, Kaiseraugshnear Base1,-:and Jakob Brassel and. Hans Mayer,.Basel, Switzerland, assignors to the ?rm SocietyVof Chemical In dustry in Basic, Basel, Switzerland No Drawing. Application September 10, 1943, Serial No.. 501,868. In Switzerland September .12.,1942 '6 Claims. 1 2 '7 . _ diazo components, 1. e., para-nitraniline,- ll-ami The present invention is concerned with. azo dyestuffs containing at least two .azo groups. no-‘l'—nitrodiphenylamino-2'-sulfonic acid,» sul fanilic acid, metanilic acid, and the‘halogen sub stitution products thereof, aminophenols such as More particularly it provides valuable new dye stuffs of the type capable. of forming complex 5-nitro-2-amino-l-phenol, 4-nitro-, ~4-methyl and 4—chloro-2-amino-1-phenol-6-sulfonic acid, metal compounds. Further objects will appearas = .the speci?cation proceeds. 6-nitro- .or It is well known in-the art that resorcinol (i. e. 6-chloro~2-amino-1-phenol-ll-sul fonic acid, Z-amino-1-phenol-6-carboxylic acid Ll-sulfonic acid,A-nitro-Z-amino-l-benzoic acid, 4.: G-dinitro-Z-amino- l-phenol, v4--methyl-2-ami 1:3-dihydroxybenzene) is capable of coupling more than once, in View of the two hydroxyl ,groups. present, in thebenzene nucleus. .A con-: siderable number of azo-dyestuffs has been. pre pared in which resorcinol is used as a twice-cou no-l-phenol-B-sulfonic ~ acid, .3 : 6-.dichloro-2-ami . nod-phenol-li-sulfonic acid, l-amino-Z-hydroxy i cheap. product because it is easily ‘obtainable on . medium, e. g. alkaline with bicarbonates, car :naphthalene-4<-sulfonic acid and the-1 substitution pling azo component, comprising direct dyeing Coupling with .an 1:3-dihy _ products thereof. (substantive), mordant dyeing, and acid wool dyestu?s etc. Resor'cinol is r a comparatively $15 ,droxynaphthalene maybe effected in an alkaline bonatesor in a‘caustic alkaline medium. ‘If de sired two-molecular proportions of diazo com . an industrial scale, and therefore there .is noth ing to prevent its use in the manufacture of ‘dye - stuffs. 1In J contradistin'ction , to " this, 1‘: 3-dihydroxy _ ponents may be-combined in one step or succes 20 sively in .two steps - with 1:3-dihydroxynaph 0t‘ so ' easily obtainable'and has industrial use‘aslfar as is known. " It was to be expected ‘that-the 'fused-on‘benzene ring in > ‘the 1:3-dihydroxynaphth‘alene (:536 . thalenes. naphthalene is ' not found an benzo-lz3edihydroxy benzene) :would render cou pling reactions substantially more’ difficult than with resorcinol and it could-"not-be expected o? wheniusing twov identical or different diazo . components of the saidkind, ‘among which only one needs to possess .a lake-forming group, a 25' great number of very valuable disazo dyestuffs hand that 1:3-dihydroxynaphthalene ‘would be > capable at all of coupling twice. *MOI'GOVBI' there ~wasv nothing to induce any expert-to try 1:3 dihydroxybenzene in the manufacture of disazo and polyazo dyestuiis as component coupling twice. Contrary to every expectation, applicants have found it worth while doing so, because the‘ dyestuffs thus obtained have unexpected superior are obtained. ' In many instances there are preferably used dia-zo» components containing azo groups which are ‘obtainable; for-instance by couplingxa diazo compound with a middle component. ‘Particu larly valuable dyestuffs are in many cases ob tained by using diazo compounds which are ob tained by a one sided coupling of tetrazotized diamines, particularly of the benzidine series, with coupling components. In this case particu larly" also such coupling components come into properties in many respects. ' It has now been found that valuable disazo ' ' ' consideration which possess lake-forming groups and polyazo dyestuffs, and particularly trisazo such, as, the salicylic acid grouping, e. g., salicylic dyestuffs to which the appended claims are di acid and its substitution products capable of rected, may be obtained if for their synthesis 1:3-dihydroxy-naphthalene is used as twice cou coupling. pling azo component and if agents yielding metal ‘~ are-causedto. react with the dyestuffs thus; ob =tained, if desired. For the synthesis of ‘the dyestuffs the-known ‘ diazo components maybe used according‘ to the present’ process;’ for- instance such of the benzene, naphthalene and. particularly also of the benzi dine series. ' In‘ many cases also such diazo com pounds maybe used with advantage which possess r lake-forming groupsjforexample, a 'hydroxyl group, a carboxyl group, an alkoxy' group or an alkoxy-carboxy groupin ortho-position to the A series of particularly valuble trisazo dyestuffs is-obtained ~if~a 1:3-dihydroxynaphthalene is coupled on the one hand with a diazotized amine of the aryl series containing in ortho-position to the diazo group a lake-forming group and on the‘ other :hand with a diazoazo compound, which is obtained byv one sided coupling of a tetrazo tized benzidine with an ortho-hydroXy-aryl car boxylic acid capable of coupling. The coupling may be conducted with advantage in ‘the said sequence or also in areverse order. In this manner there is obtained a series of predomi nantly brown 'dyestuiis of good fastness proper diazo group. Thus for example, benzidine and its 55 ties. substitution products come into consideration as 2,408,961 4 The dyestu?’s obtainable according to the 1/2 hour at 4-6“ C. to a solution of 8.5 parts of 1:3 present process may be used for dyeing and printdihydroxynaphthalene, 8 parts of sodium carbon ing the most various animal and in particular ate and 5 parts by volume of caustic soda solution cellulosic ?bers. Many of the disazo dyestuffs of 30 per cent. strength in 50 parts of water. produced according to the present process are 5 After stirring for 1 hour at 5-8° C. coupling is for example suitable for W001, silk and particucomplete. The dyestu?’ of the formula on on H OOH ' SOgNHg larly leather, whereas, when using substantive components, disazo and principally polyazo dye- is separated by addition of 30 parts of sodium chloride and ?ltered oif. It is introduced in the stu?s are obtained, which are predominantly form of a paste into the suspension of the diazo useful for cotton, linen, rayon and staple ?bers 15 azo compound prepared according to the ?rst from regenerated cellulose. paragraph. The whole is coupled for one hour If by a suitable choice of the components care at 11-12° C. and for 50 hours at 18-20° C., where has been taken that the dyestu? contains lakeupon the temperature is raised to 90° C. and the forming groups in the molecule, these dyestuffs trisazo dyestu? formed ?ltered from the hot re can be converted in substance, in the dye-bath 20 action mixture. When dry it is a dark powder or on the fiber into complex metal compounds. which dissolves in water and sodium carbonate In this case, for example, chromium, cobalt, iron solution to a yellow-brown, in dilute caustic and particularly copper are coming into consideralkalies to a brown-red and in concentrated ation as suitable metals. The conversion into sulfuric acid to a violet solution. Cotton is dyed such metal complex compounds may appro- 25 havana brown shades which are fast to washing priately be conducted in substance if the dyewhen dyed and coppered according to the one stu?, due to the presence of a su?icient number bath process. of groups promoting solubility, e. g. sulfonic acid Example 2 groups, possesses also in the metallized state still a su?lcient solubility. Many of the metal- 30 11-2, PM,“ "I f1‘°h1°r°'Z‘a‘mM'I'PheMI'G‘ merous dyestuffs thus obtained are remarkably sulfomc acid are diaaotized in the usual manner suitable for the dyeing of leather. Those dyewith hydrqchloric acld and sodium mtnte' The stu?s, the complex metal compounds of which dlazo solufmon is added within 1/2 hour at 4*60 C‘ are sparingly soluble to insoluble may with ad- to 3' 5011mm of 8'5 pains of lza'dlhydroxynaph' vantage be dyed according to a known after_ 35 thalene, 8 parts or sodium carbonate and 2 parts metallizing process, for example the after-copof S°diPm .hydroxlde m 50 parts of water‘ The pering method. Advantageous use, particularly in the dyeing oi’ cellulosic ?bers, may be made in whole is stirred for one hour at 5-8° C. and for 4 hours at 15400 C‘ The (.iyestu? is separated this case of the one-bath after-coppering process Py adding ,40 parts of sodmm chloride‘ It is known by the U. 5 Patent 2,148,659 (on also 40 introduced in the form of a paste into the diazo French patent'gog?gg), m which process dyeing azo compound from benzidine and salicylic acid followed by coppering is eil’ected in the same Prepared according to Example 1' The whOle bath. In this case complex copper tartrates or is coupled for 1 hour at 10—12° C. and for 50 hours similar metal compounds, stable towards alkalies, at 18-2? 0-, heated after diluting the Coupling are used with advantage in a weakly alkaline 45 mixture with 100 parts of water to 85° C. and the medium. formed trisazo dyestu?' of the formula on OH H OOH 01 The following examples illustrate the inven“on, the Parts being by weight unless otherwise stated: Example 1 is then ?ltered off. When dry it is a dark powder which dissolves in water to a red brown, in dilute alkalies to a brown and in concentrated sulfuric acid to a violet solution, from which vegetable 9.2 parts of benzidine are tetrazotized as usual ?bers 9're dye (1 fast b r o wn shad es’ when dyed _ _ with hydrochloric acid and sodium nitrite. The and coppered accordin to the one bath rocess. A Similar dyestu? 1: obtained if in $1,115 ex clear tetrazo solution is then combined during 1 am 0 _ _ ple the 11.2 parts of 4-chloro-2-aminophenol hour “.545 C- Wlth *1 Solution Pf 8 Parts Of Sall6-sulfonic acid are replaced by 11.7 parts of 4 cylic acid and 20 parts of sodium carbonate in 70 nitm_2_a,mino_1_pheno1_6_su1fonic acid or by 80 parts of water. A brown-orange suspension of 9 5 ' - _ - ‘ the diazoazo compound is thus obtained. '4 parts of 2 ammo l phenol 4 sulfomc acid’ _9.4 parts of 2-amino-phenol-4-solfamide are diazotized with hydrochloric acid and sodium Example 3 13.8 parts of 1:3;6-trichloro-2-aminobenzene nitrite and the drama suspension added Within 75 4-sulfonic acid are diazotized in the usual man ner with hydrochloric-- acid and. sodium nitrite. x170. 85°. C. after diluting the. coupling mixture with Thesuspension of the vvdiazo compound is caused to react with 20 parts of crystallized sodium ace- .100 parts of water and the‘ formed .trisazodye stuff of the formula tateand the whole is stirred at. ordinary .temper- 15 is ‘then ?ltered o?. When dry it .isa.,_da'rk_ pow ature until the chlorine atom in one-position is replaced by the hydroxyl group, which generally is the case after afew hours. The thus dissolved ortho-hydroxy-diazo compound is added Within der which dissolves in water and in dilute sodi um carbonate solution to a Bordeaux red, in di lute caustic alkalies to a violet brown and in concentrated sulfuric acid to a blue-red solution, 20 from which vegetable ?bers are dyed fast brown ' shades,~when dyed and copperedv according to ‘the one ‘path process. If 3:3'-dichloro-4:4'-diaminodiphenyl is used instead of benzidine in preparing the d'iazoazo :5 compound mentionedabove, a similar rdyestuif is = Obtained I 1/2 hour at 5-8° C. to a solution of 8 parts of 1:3dihydroxynaphthalene, 18 parts of sodium car- bonate and 5 parts of caustic soda solution of 30 per cent. strength in 100 parts of water. The whole is stirred for 1 hour at 5—10° C-, then f0!‘ 20 hoursat 15-2090. and the monoazo dyestufiw thus vformed is separated by additionofisodium'chloride. It is, introduced,~while. still moist,‘into the v Example 5 suspension of the‘diazo compound from benzidine and salicylic acid, obtained according to Example @15 parts _of zfammoil'phfenol'§'ca'rboxync 1‘ The Whole is coupled fol-one hour at mama 1L ac1d-4-suliomc acid are vdiazotized in a hydro C. and then for 24v hours at 13_20° ‘(1 heated to ’ chloric acid medium in the usual manner with 90° C. and the trisazo dyestu?' thus formed of the formula Sodium nitrite at 15-20° C. The diazo compound is added within 1A2 hour at 4—6° C‘. to a solution 0H ‘i’H y, ‘ E ‘('30011 01 soan ?ltered from the hot reaction mixture after ad- of 8.5 parts of li3-dihydl‘oxynaphthalene_, 8 dition of sodium chloride. When dry it is a dark part5 0_f Sodium Carbonate and 2 Parts Of SOdHIIfI powder, which dissolves in Water and dilute alka- i5‘ hlfdroxlde m 50 parts of Water- The whole is lies to a brown, in concentrated sulfuricacid-to a violet solution and dyes vegetable ?bers brown Stlrred for 1 hour at 5'3 C- and for 14 hours at 10~15° C. and the monoazo dyestu?‘is separated . h. n 1. vi‘ h n shades Whlch are fast to was mg a d lght w e by addition of 60 parts of sodium ‘chloride. ~It is ‘ introduced in the form of a paste .into the diazo dyed and coppered according to the one ‘bath azo compound, prepared according to Example‘ 1. process‘ E Z 4 ’ L .The whole is coupled for one hour .at 10-12° C. .and for 50 hours at 18-22’ 0., heated to 85°C. “mp 6' 11.7 parts of 6-nit-ro-'2'-aminophenol-liesulfonic ; after diluting the coupling mixture with 100 parts acid’ are diazotized as usual at 10-15° "(L-'With of water, and the formed trisazo'dyestuff of the hydrochloric acid' and, sodium nitrite. The di- 55‘ formula , (‘m coon SOaH azo solution is added within 1/; hounat 4-6“,C. to a solution of 8.5 parts of 1:3-dihydroxynaphthalene, 8 parts of sodium carbonate andi2 parts of sodium hydroxide in 50 parts of water. The . is ?ltered on. »When ‘dry it is a dark powder, which dissolves inwater to ‘an orangeebrown, in dilute sodium carbonate solution toayellow brown, in‘ dilute caustic alkalies to a‘ brown red whole is stirred for one hour at 5—8° C. and the and in concentrated sulfuric acid to a violet so monoazo dyestuff separated by addition of 60 7O lution, Which dyes vegetable ?bers fast brown parts of sodium chloride. It is introducedin the shades; Whendyed and coppered according to the form of a paste into the diazoazo compound from "one ‘bath process' benzidine and salicylic acid prepared according ‘Emamplab‘ _ to Example 1. The whole is coupledforv 1' hour v7.7 parts of 5-nitro-2-amino-l-phenol are diaz ' at 10-120 C. and ior>50hours at ‘18--22° C'.'heated 75~otized as usualwithhydrochloric acid and sodium ‘2,408,961 8 nitrite. The suspension of the diazo compound which vegetable ?bers are dyed fast yellow brown is added within 1/2 hour at 4-6“ C. to a solution shades when treated and coppered according to of 8.5 parts of 1:3-dihydroxynaphthalene, 8 parts the one bath process. of sodium carbonate and 2 parts of sodium hyExample 8 droxide in 50 parts of water. The whole is stirred 5 for one hour at 5—8° C. and the monoazo dyestu? 22.7 Parts Of a Paste Containing 55 Per cent of is separated by addition of 40 parts of sodium chloride. It is introduced in the form of a paste diazotized 1-amino-2-hYd1'0Xynaphtha1ene-4—Su1 ionic acid (corresponding to 11-9 parts of 1 into the diazoazo compound, prepared according amin0—2—hyd1‘0XynaDhtha1ene - 4 - sulfonic acid) to Example 1. The whole is coupled for 1 hour 10 are introduced in the course of 1A» hour at 4—6° at 10-12° C. and for 24 hours at 18-22° C., heated 0. into a solution of 8.5 parts of 1:3-dihydroxy to 95° C. after diluting the coupling mixture with 100 parts of water and the formed trisazo dyestuff of the formula naphthalene, 8 parts of sodium carbonate and 2 parts of sodium hydroxide in 100 parts of water. The whole is stirred for one hour at 5-8” C., 10 COOH NO: is filtered off. When dry it is a dark powder ' parts of sodium chloride are added and stirring which dissolves in water and sodium carbonate 25 is continued for one hour at 10-15" C. The formed solution to a red brown, in dilute caustic alkalies monoazo dyestllif iS ?ltered off and introduced in to a violet brown and in concentrated sulfuric the form of a paste into the diazoazo compound acid to a violet solution from which vegetable from benzidine and salicylic acid, prepared ac ?bers are dyed fast brown shades when dyed and 30 cording to Example 1. The whole is coupled for coppered according to the one bath process. 1 hour at 1042’ C. and for 48 hours at 18-22° C., heated to 80° C. after diluting the coupling mix ture with 100 parts of water and the trisazo dye stuff of the formula Example 7 9.1 parts of 4-nitro-2-amino-l-benzoic acid are on Q on 0011 H0 | SOIH diazotized in a hydrochloric acid medium in the is separated by addition of 20 parts of sodium usual manner with sodium nitrite. The suspenchloride. When dry it is a dark powder, which $1011 of the diaZO Compound is added within 1/2 dissolves in water and sodium carbonate solution hour at 4-6° C. to a solution of 8.5 parts of 1:3to a brown,'in dilute caustic alkalies to an orange dihydroxynaphthalene, 13 Parts Of Sodium Car- 50 brown and in concentrated sulfuric acid to a bonate and 2 Parts Of Sodium hydroxide in 80 blue red solution, from which vegetable ?bers are Parts Of Water- The Whole is Stirred during 1 dyed fast orange brown tints, when dyed and coppered according to the one bath prgcesg 110111‘ at 5—8° C. and the formed 1110110310 dyestuff is ?ltered oil. It is introduced in the form of a _ paste into the diazoazo compound, prepared ac- 65 cording to Example 1. The whole is coupled for ' Example 9 25.5 parts of a paste containing 58 per cent of 1 hour at 5-8° C. and for 24 hours at Ill-22° C., 6-nitro-l-diazo-Z-hydroxy-naphthalene - 4 - sul heated to 95° C. after diluting with 100 parts of water and the formed trisazo dyestuff of the ionic acid (corresponding to 14.2 parts of 6-nitro 1-amino-2-naphthol-4-sulfonic acid) are intro formula _duced within 1/2 hour at 4—6° C. into a solution of V _ ' coon OH H00 COOH I r“ H \ No, is filtered o?. When dry it is a dark powder 8.5 parts of 1:B-dihydroxynaphthalene, 18 parts which dissolves in water and dilute sodium carbonate solution a yellow brown, in dilute caustic of sodium carbonate and 2 parts of sodium hy droxide in 100 parts of water. The whole is alkalies to an orange brown and in concentrated stirred for 1 hour at 5—8° C. 10 parts of common sulfuric acid to a Bordeaux red solution, from 75 salt are added and stirring is continued for 1 hour’at 10-15“ C. The formed monoazo dyestu?‘ is ?ltered off andfintroduced in the form‘of 'a» is'-?ltered"from--the =rot~ reaction mixture after ‘ addition'ofcommon-salt: When ‘dry it is a dark‘ paste into the diazoazo compound prepared 'ac- powdereewhic'h'dissolves-inwaterand diluteso cording to- Example 1. The mixture is coupled dium canbonate solutionto a brown,- iii-dilute for 1 hour at 10-12° C. and for 48 hours at 18-22° 5_ caustic alkalies "to a»v brown red- and in‘ concene (3., heated to 75° C. and the trisazo dyestuff 0f the formula trated sulfuric acid to a'violet-solution'from-which‘ vegetables ?bers are “dyed brown'shade's :fast" to COOH N03 | 303K is separated by the addition of 20 parts of com- 20 washing and to light when dyed and coppered ac mon salt. When dry it is a dark powder which cordingito the one bath process; dissolves in water and sodium carbonate solution to a brown, in dilute caustic alkalies to a, red Ewam_ple 11 tinged brown and in concentrated sulfuric acid 10-15 parts of 2—am1n0-4-methy1-l-hydroxy to a violet solution from which vegetable ?bers 25 benzene Sulfonic acid (Obtained by boiling 2-111 are dyed fast orange brown shades, when dyed 1'10-4=-me'0hy1-l-hydl‘oxybenzene With bisulfliie411+v and coppered according to the one bath process_ ‘ known manner) are "diazotized in ahydroohloric. acid medium in the-‘usual manner with sodiunr Example 10 nitrite. The .diazo compoundqobtained iStintI'O-g 9.2 parts of benzidine are vtetrazotized in the 30 duced in the course of l/z-hOLll‘ at 4-69‘ Cuint'oau usual manner with hydrochloric acid and sodium Solution of 8 parts of .1I3-dihydroxynaphthalene;.. nitrite. The clear tetrazo solution is mixed dur8 parts of anhydrous-sodium. carbonate ,-and <51, ing 1 hour at 4-6“ C. with a solution of 8 parts of parts by volume ‘of - caustic soda solution. of; 30... salicylic acid and 20 'parts‘of anhydrous sodium per cent. strength in ,50. parts of water. The: carbonate in 30 parts of water; There is -0b_ 35 whole is stirred for 1 hour .at 5-10? C.,.then:for.-1 tained a brown orange suspension of the intere hour at 10—15° C. and'theeformed. monoazodyeev mediate compound benZidjne—>sa,1icy1ic acid, stu? isseparated by ?ltration after addition of 11.65 parts of 6-nitro-2-amino-l-phenol-é-sulcommon salt- It is introduced in the form-of a». famide are diazotized in'a hydrochloric acid me- ' paste into the suspension Of the diaZoaZo com dium‘ in the usual manner with sodium nitrite. 40 pound from benzidine and salicylic acid. The The diazo compound obtained is introduced‘withmixture ‘is coupled 'for -1 hour‘at 10-12“ C. and for in 1/2 hour at 4-6" C. into ‘a solution vof 8.0 parts 2O1hours at'18—20° C., heated-to ‘YO-80°C.v andthe of 1:3-dihydroxy-naphthalene,‘ 3 parts of anhye formedv'triazo-dyestuif'of the formula H04 N—NNF_NP; vi, liq-N OOH drous sodium carbonate and 5 parts by volume of : caustic soda solution of 30 per cent. strength in '55 50 parts of water. The whole is stirred for 2 hours at 5-10° C., then for 15 hours at 15-20° C. and the formed monazo- dyestu? is separated by ?ltration, is ?ltered‘ from the hot reaction" mixture-‘after addition of ‘commonsalt.’ When‘dry‘it’is a dark" powder ‘which dissolves-in water ‘and ‘dilute’ see dium carbonate solution to a‘ yellow-"brown; in" dilute’ alkalies-toca ' red brown‘ and“ in concen if necessary after addition of common salt., It is trated ‘sulfuric’ acid ‘ to a violet ' solution from‘ introduced in the form of a paste into the sus- 60 which vegetable ?bers are dyed ‘brown shades > pension of the diazoazo compound from benzifast to washing and light, when dyed‘ and icop dine and salicylic acid, prepared as described pered according to theone bath-process. above. The mixture is coupled for 1 hour at Emm Z__12,_ 10-120 0. and for 24 hours at 1s_20° 0., heated to. p6 90° C. and the. formed triazo. dyestui’fv of the 65 9-45 parts of 2-amino-1-pheno1-4-sulfonic acid formula are diazotized with hydrochloric acid. and sodium NO: 801N111. 2,408,961‘ 11 12 nitrite and the diazo suspension is introducedin aminoazobenzene sulfonic acid orv 4'-nitro-4-' the course of 1/2 hour at 4—6° C. into a solution of amino-diphenylamine-Z'-sulfonic acid, there are obtained dark brown to black brown dyeing prod ucts. The dyestuff obtained when using the 8.0 parts of 1:3-dihydroxynaphthalene, 8 parts of anhydrous sodium carbonate and 5 parts by vol ume of caustic soda solution of 30 per cent. 5 last named diazo component has the formula strength in 50 parts of water. The whole is stirred for 2 hours at 510° C., then for 15 hours at 15-20° C. and the formed monoazo dyestu? is separated by addition of common salt and dilute acetic acid. OH OH It is introduced in the form of a paste into the i0 OH suspension of the diazoazo compound from benzi dine and salicyclic acid obtained as described in Example 10. The mixture is coupled for 1 hour at l0-12° C. and then for 24 hours at 18-20° 0., heated to 90° C. and the formed trisazo dyest of the formula N=N ——Fl SOSH N01 - When replacing part of the iron by other metals, OH OH | COOH $0111 is ?ltered from the rot reaction mixture after for example copper, the shade of the dyestu?f is displaced to red tinged dark brown to reddish black brown. The order of succession of the diazo components to be used can also be reversed addition of common salt. When dry it is a dark powder which dissolves in water and dilute so dium carbonate solution to a brown, in dilute caustic alkalies to a brown red and in concen 30 and similar dyestuffs are then obtained. ¢ trated sulfuric acid to a violet solution from which Example 14 vegetable ?bers are dyed brown shades fast to washing and light, when dyed and coppered ac If 3 : 3’-dimethyl-4 :4'-diaminodiphenyl or 3 :3’ - A mixture consisting of 11.7 parts of 4-nitro Z-amino-l-phenol—6-sulfonic acid and 15.5 parts dimethoxy-4:4'-diaminodiphenyl is used instead of benzidine in preparing the diazoazo compound, acid is diazotized in usual manner and coupled cordinglto the one bath process. of 4'- intro-4-aminodiphenylamine - 2’- sulfonic in the presence of 2.1 parts of freshly precipi tated iron-(IID-hydroxide and 0.6 part of cop per hydroxide with 8.0 parts of 1:3-dihydr0xy naphthalene in a medium alkaline with sodium carbonate. When the dyestu? formation is com plete, the whole is heated for some time to 60-70° C. and the formed metal compound of the for mula similar dyestuffs are obtained. ' Example 13 23.4 parts of 4-nitro-2-amino-l-phenol-B-sul fonic acid are diazotized in usual manner and coupled with 16 partsof 1:3-dihydroxynaphtha lene in a solution alkaline with sodium carbonate and in the presence of 5.5 parts of freshly pre cipitated iron-(III) -hydr0xide. When coupling is complete, the whole is heated for some time to 60-80° C. and the formed iron compound sep HOI SOzH arated in a‘neutral medium and dried; ' It dyes vegetable tanned and chrome tanned leather 50 brown violet shades. 22 parts of the above iron compound (of the dyestuff from diazotized 4-nitro-2-amino-1-phe nol-?-sulfonic acid and 1:3-dihydroxynaphtha lene) are dissolved. in 200 parts of water and 15 NO: SOIH parts of caustic soda solution of 30 per cent. 55 ' strength, mixed with 15 parts of anhydrous so is then precipitated in usual manner and dried. dium carbonate and coupled with the diazo com A product is obtained which dyes leather power pound from 6.9 parts of para-nitraniline pre ful black brown shades. pared in the usual manner. The disazo dyestu? of the formula 60 Example 15 The dyestuif obtained from 29.5 parts of 6 nitro-l-diazo-2-hydroxynaphthalene- 4 -sulfonic 5 acid and 16 parts of 1:3-dihydroxynaphthalene is heated to the boil in 800 parts of water and ' boiled for 24 hours in a re?ux apparatus with a quantity of chromium sulfate corresponding to‘10 parts of CI‘zOa. The whole is then ?ltered ‘7 70 to remove the precipitated chromium compound NO: is precipitated in the usual manner and dried. It dyes leather olive-tinged, brown shades. When using instead of para-nitraniline for example which-is then dried at a moderate temperature. The dyestu? dyes leather red tinged blue shades. 50.7 parts of the above chromium compound are coupled in a solution alkaline with sodium 1-aminonaphthalene-4-sulfonic' acid, 75 carbonate with the diazo compound from 20.7 231683361? 133 ‘7.6 parts Eofgfreshly precipitated chromium: hya parts, of 4 -chloro-1-aminobenzene-3=sulfonic'~ droxide; 15v partsof ‘tartaric acid and 2'7 parts ofv caustic soda solution-of. 30.per:cent. strength; The dyestu?f- is salted out, ?ltered and dried. The; chromium compound dyes vegetable tanned-and-Z chrome tanned leather deep blue shades. The " leather is dyed with a good penetration. acid. A- product isthus obtained of .theiormula _ SOsH OH ClON=N _Y, HUN 1.. 19 parts of the above chromium compound are coupled in‘ a medium alkaline/with. sodium car V. 10 bonate with the diazo compound from 8.7 parts of ——G: In?” I ‘-—OH 4-aminobenzenesulfonic acid. . The dyestuff ob tained of the formula - NO 155 S0313?-~ HO'aSON-éN ‘ 0H _ whichfdyes leath'ergrey, tinged blue shades.- It the disazo dyestu?is?rst produced and subse-1 quently coupled, thereis obtained a similar dyea 20. stu?. By replacing. 4-chloro-l-aminobenZene-3sulfonic acid. by é-nitro-l-aminobenzene-izesul is freely soluble in water and dyes leather green ionic acid, 2? -nitr0-4-aminodiphenylamine-4' --v tinged blue shades. By replacing "the sulfanilic sulfonic acid or 4’-nitro-ll-aminodiphenylamine- ~ acid for example‘by aniline-2:5;disulfonic acid; a“ 2’-sulfonic acid, dyestu?s are obtained which dye, ’ similar dyestu? is obtained.v leather green tingedgrey blue or black o-r-olive blackshades. Example 18 Other metals, foriexample iron or manganese, lead to violet brown to dark brown . shades. ' from diazotized 4-nitro-“2‘-amino-l-phenol" and i ' Example 16-‘ 19.9 parts of 4:6-dinitro-2eamino-l-phenol are diazotized in usual manner and coupled in a me dium alkaline with bicarbonate with 16 parts of l:3-dihydroxynaphthalene. ls-partsof the iron compound ‘of theidyestuffi 30 1:3-dihydroxynaphthalene are‘coupled- in a me-'‘ dium alkaline with sodium carbonatewith the-4 diazo-i compound from' 11.7 parts of-‘ll-nitro-Z-l amino-‘l-phenol'-6-sulfonicI acid.’ When the for: mat-ion ' of dyestuff ‘is » complete; the " solution“ is 35 neutralized at 60° C. and treated for‘some-timea with a mixturev of '4 parts of copper sulfate and’ The monoazo-dye stuii is precipitated in crystalline form, then ?l 1.3 parts ‘of iron-(IID-chloride. The dyestu? of} tered and Washed. . 18.5 parts of this dyestu? are suspended in 200 the‘ formula parts of water and 15 parts of calcined sodium carbonate and mixed with the diazo compound 40 from 15.4- parts of 2' - nitro- d-aminodiphenyl amine-4'-sulfonic acid. When coupling is com plete, the disazo-dyestu? is separated in usual manner. 34.5 parts of thedisazo dyestu? are dissolved in .water and. heated for some timeat v70—90° C. with 12.5 parts of copper sulfate and 14' parts of " sodium acetate. The copper compound is then separated with common salt anddried at a mod ‘ . .V then‘ filtered-and vdried at ‘a moderate tempera-‘ ture. There is obtained a'brown black‘ powder‘v 55 5 which dissolves in water and dilute sodium car: bonate solution‘ to a deep'brown'solution and N02 N=N / N02 isprecipitated by addition" of sodium‘ chloride, on NO P 1 H018 erate temperature. A dyestuff is thus obtained of the formula ‘ --0 u dyes leather ‘powerful red tinged dark‘ brown" shades. When replacing the copper sulfate'by'nickel" sulfate, a slightly more yellow dyestuffds *ob 60 tained. N02 1 which dyes leather brown violet shades. When using as second diazo component l-aminonaph thalene-ll-sulfonic acid andinstead of the. cop per sulia'tea mixture of manganese and nickel sulfate,there is obtained a red brown dyestuff. Example 17 The dyestuff obtained from 15.4.- parts of diazo tized 5-nitro-2'-amino-1-phenol and 16 parts of 1:3-dihydroxynaphthalene in a medium alkaline with sodium carbonate is suspended in 500 parts of Water and boiled for 15 hours in a re?ux ap paratus with a ‘chromium solution consisting of When'using'the corresponding quantityof 4:6‘ dinitro-2-amino-1-phenol instead "of the ,4-‘nitro-" aminophenol; a blackish violet brown dyestu?'ls obtained; ' Example v19 22 'parts 'of the iron compound of thevdyestuff' from’ diazotized 6-nitro-2-amino-l-phenol;4= sulfonic acid and 1:3-dihydroxynaphthalene are coupled in a medium alkaline with sodium car bonate with the diazo compound from 9.9 ‘parts of 4 : 6-dinitro-2-aminoel-hydroxybenzene. The whole is mixed with a solution consisting of ‘4.5 parts- I of iron»v (III) ‘chloride;- 2‘ lparts :aof" tartaric 2,408,961 15.. acid and 16 parts of caustic soda solution of 30 per cent. strength and heated for some hours to 60—'IO° C. After neutralizing, ?ltering and drying there is obtained a black powder which dyes leather black brown shades. The dyestu? has 5 the formula r" (IJH. NO . 16 compound from 6.9 parts or para-nitraniline. When the formation of dyestu?f is complete, the solution is worked up in the usual manner. There is obtained a product which dyes leather power ful, medium brown shades. When using the 4'-nitro-4-aminodiphenyl amine-2'-sulfonic acid instead of the para " nitraniline, there is obtained a disazo dyestu? which dyes leather powerful red tinged dark N=N OH brown shades. Example 23 NO; OH HO —-F6 100 parts of cotton are introduced at 50° C. into a dye-bath which contains in 2500 parts 01' water 15 2 parts of sodium chloride and 1.5 parts of the dyestuff prepared according to Example 3, and the temperature of the bath is gradually raised to 90-95" C. 30 parts or Glaubers salt are added after M; hour and dyeing is continued for 3/4 hour 20 at this temperature. The bath is then cooled to _ 0.11 J about 70° C., the necessary quantity or a solution Example 20 made feebly alkaline with sodium carbonate of A mixture consisting of 23.4 parts of 4-nitro-2 complex copper tartrate is added and the mate amlno-l-phenol-S-sulfonic acid and 22.3 parts of rial is coppered at 80-90° C. for 1/2 hour. The 4-chloro-2-amino-l-phenol-?-sulfonic acid is di 25 cotton is thoroughly rinsed and soaped for a short N0 N=N azotized in usual manner and coupled with a so time, if necessary. It is dyed fast brown shades. lution alkaline with sodium carbonate of 16 parts The expression “benzene series” in the follow of 1:3-dihydroxynaphthalene. When the forma ing claims will be understood to encompass the tion of dyestuff is complete, the solution is neu tralized with hydrochloric acid, the reaction solu 30 benzidine series. What We claim is: tion heated to 80° C. and mixed with iron-(III) - chloride solution corresponding to 5.6 parts of iron, and 30 parts of crystallized sodium acetate. 1. Trisazo dyestu?s of the general formula The whole is boiled for some time in a reflux ap paratus. After salting out, ?ltering and drying 35 there is obtained a metal complex which dyes leather olive tinged black brown shades. When replacing a part, for example half of the iron by copper, there is obtained a red tinged dark. brown shade. 40 Example 21 29.5 parts of 6-nitro-l-diazo-2-hydroxynaph HO Iii-N=N wherein R3 stands for the radical of a coupling component containing the salicyclic acid group ing and R2 stands for the radical of a diazo com ponent containing a, member selected from the thalene-‘l-sulfonic acid are coupled with 16 parts of 1:3-dihydroxynaphthalene in a feebly alkaline 45 group consisting of OH and COOH in ortho posi tion to the diazonium group, the said diazo com medium. 13.3 parts of caustic soda solution and ponents being selected from group consisting of a neutralized diazo solution from 14.35 parts of 4-chl0ro-2-amino-l-phenol are then added. When coupling is complete, the whole is heated to 50° C. and the disazo dyestuif is separated in diazo components oi.’ the benzene and naphtha lene series. 2. Trisazo dyestu?s of the general formula usual manner. 30.5 parts of the dyestu? are mixed in 500 parts of water with a quantity or basic chromium sul fate corresponding to ‘7.6 parts of CrzO: and heat ed to boiling in a re?ux apparatus for 24 hours.v After this time the formed chromium compound is salted out, ?ltered and dried. A blue black HO Iii-N=N powder is obtained which dyes leather red tinged blue grey shades. wherein R3 stands for the radical of an ortho When using instead of the 4-chloro-2-amino-l hydroxy benzoic acid and R2 stands for the radi phenol as second diazo component for example cal of a diazo component of the benzene series containing a hydroxyl group in ortho-position to the diazonium group. 4-chloroaminonaphthol-6-sulfonic acid, 4-nitro aminophenol-G-sulfonic acid, sulfoanthram'lic acid, G-nitro-1-amino-2-hydroxynaphthalene-4 ‘ 3. The trisazo dyestu?? oi the formula sulfonic acid, or instead of the chromium a mix 65 ture of chromium and iron, there are obtained products which dye leather navy blue to blue black shades. When using iron instead of chro mium there are obtained dark brown to black brown dyestu?s. 70 Example 22 24 parts of the dyestu? from diazotized 4’-nitro 4-aminodiphenylamine-2’-sulfonic acid and 1:3 dihydroxynaphthalene are coupled in a solution alkaline with sodium carbonate with the diazo 75 0 OH OH IHO HOOC N=N 2,408,961 17 ther with one molecular proportion of the diazo azo compound obtained by one-sided coupling of tetrazotizccl benzidine and salicylic acid. 6. Process for the manufacture of trisazo dye OH c0011 ‘ OH | 18 tized 2-amino-LhyrlroxyA-sulfamide and fur‘ 4. The trisazo dyestu? of the formula ><\ \ stu?s, comprising coupling 1:3-dihydroxynaph E0 thalene with one molecular proportion of diazo tized Z-amino-l-hydroxybenzene-B-carboxylic-4 -N:N sulfonic acid and further with one molecular 10 proportion of the diazoazo compound obtained by one-sided coupling of tetrazotized benzidine and SO2NH2 salicylic acid. 5. Process for the manufacture of trisazo dye stuffs, comprising coupling 1:3-dihydroxynaph thalene with one molecular proportion of (ham 15 ‘‘ FRITZ STRAUB. JAKOB BRASSEL. HANS MAYER.