Patented Mar. 30, 1948 2,438,754

UNITED STATES PATENT OFFICE 2,438,754 COPPER, CONTAINING DSAZO, DYESTUFFS Adolf Krebser, Riehen, near Basel, and Werner Bossard, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland No Drawing. Application March 1, 1943, Serial : No. 477,630. In Switzerland April 28, 1942 1. Claims. (C. 260-148) 2 - It has been found that valuable new Copper For the dyestuffs of the type (a): 2-amino containing disazo dyestuffs are obtained by 1-hydroxy-, -methoxy- or -benzyloxybenzene coupling a diazotised amino Sulfonic of the 4-Sulfonic acid, 4- or 6-methyl-2-amino-1-hy or series, which contains, in droxy- or ethoxybenzene sulfonic acid, 4- or o-position to the amino group, a 5 6-chloro-2-amino-1-hydroxy- or -methoxyben or a convertible into a hydroxy group Zene Sulfonic acid, 4- or 6-nitro-2-amino-1-hy. by coppering, with a 1:3-dihydroxy-benzene, droxy- or -methoxybenzene sulfonic acid, then causing a diazonium compound which is 1-amino-2-hydroxynaphthalene-4-sulfonic acid, free from sulfonic acid groups to react with the 6-nitro-2-amino-1-hydroxynaphthalene - 4 -sul said monoazo dyestuff and after-treating the 0. fonic acid. so-obtained disazo dyestuff with copper-yielding For the dyestuffs of the type (b) and (c) : agents, with the condition that at least one of 3-amino-4-hydroxy-, -methoxy- or -chloro-1:1'- the diazo components is substituted by a phenyl diphenylsulfone-5- or -3'-sulfonic acid, 3-amino nucleus bound by a non-basic bridge. The same 4-hydroxy- or methoxybenzene-1-sulfonic acid copper-containing disazo dyestuff is obtained by 5 ethylanilide-3- or -4'-sulfonic acid, 3-amino coppering the monoazo dyestuff obtained from . 4-hydroxy- or -methoxybenzene-1-sulfonic acid the first diazo component and the 1:3-dihydroxy phenylester-3'-sulfonic acid, 3-amino-4-hy benzene and coupling this copper compound with droxy-1:1'-diphenylether Sulfonic acid, the second diazo component and also by finally The second diazonium compound can be ob treating the completely formed disazo dyestuff 20 tained from the following : with copper-yielding agents. For the dyestuffs of the type (a) and (c): As non-basic bridges between two phenyl or 6-methyl- or -methoxy- or -chloro nuclei of the diazo components there may be 3-amino-1:1'-diphenylsulfone, 4- or 6-methyl-, enumerated for instance: -methoxy- or -chloro-3-aminobenzene-1-sulfonic -SO2-, -SO2NC2H5-, -OSO2-, -O-, 25 acid ethylanilide, 4- or 6-methyl-, -methoxy- or -CO-, and the like. From the above definition ; : -chloro-3-aminobenzene-1-sulfonic acid phenyl the following three types of dyestuffs may be Or cresyl , 2-, 3- or 4-amino-1-hydroxyben derived: Zene-benzene, -toluene- or -chlorobenzene sul (a) The first diazonium component is mono fonic acid ester, 2- or 4-amino-i:1'-dipheny nuclear, while the second diazonium body con 30 , its - or halogen substitution products. tains two nuclei linked together by a non- ; ; For the dyestuffs of the type (b): 2-methyl-, basic bridge, methoxy- or -chloro-4- or -5-nitro-1-amino benzene. (b) The first diazonium compound contains The dyestuffs obtained according to the present two aryl nuclei united together by a non-basic invention possess excellent drawing properties, bridge, while the second diazonium component 35 when applied to silk from a neutral dyebath. is mononuclear, and Beside good washing- and water-fastness prop (c) The first as well as the second diazonium erties they are especially distinguished by an compound contain two aryl nuclei bound to excellent light-fastness. - gether by a non-basic bridge. The present invention is illustrated, but not The first diazonium compound may be pre 40 limited, by the following examples, the parts pared from the following amines: being by Weight, unless otherwise stated. 2,438,754 3. 4. w 1:3-dihydroxybenzene in 50 parts of water and Eacample 1 14 parts of sodium hydroxide. After 4 hours 32.9 parts of 3-amino-4-hydroxy-1:1'-di the monoazo dyestuff thus formed is precipitated phenyl--3'-sulfonic acid are dissolved by means of hydrochloric acid, filtered off and with 6 parts of sodium carbonate in water, then 5 coupled in an suspension. With the intermixed with 6.9 parts of sodium nitrite and diazo body from 19.6 parts of 2'-methyl-2-amino diazotised by allowing to run into 23 parts of 1:1'-diphenyl ether. In order to convert the hydrochloric acid at 5°C. The diazo compound disazo dyestuff into the copper complex compound thus partly precipitated is combined with 11 it is treated at 90° C. with 25 parts of crystallised parts of 1:3-dihydroxybenzene in a caustic alka- 10 copper sulfate, then precipitated and converted line medium. For the conversion of the mono into the sodium in the usual manner. It azo dyestuff, which has been separated out in an wool and silk in vivid brown shades of good acid medium, into the copper complex compound light and wetting fastness. it is stirred at 90° C. for 30 minutes with 25 parts of crystallised copper sulfate, then salted out, 15 Eacample 5 separated and again suspended. Now, it is coul 20.3 parts of 2-amino-1-methoxybenzene-4- pled in an acetic acid medium. With the diazo sulfonic acid are diazotised in the usual manner, compound from 24.7 parts of 4-methyl-3-amino coupled in a soda, alkaline solution with 11 parts . 1:1'-diphenylsulfone and the copper-containing of 1:3-dihydroxybenzene and separated out b disazo dyestuff is finally precipitated by means 20 acidifying ythe solution.y For thesep conversion ofy of . This dyestuff dyes animal the monoazo dyestuff into the copper complex fibres in yellowish-brown shades of excellent compound the same is dissolved in Water and light-When, and on Washing-fastneSS. the other hand, the coupling of the - boiled for several hours in the presence of 20 coppered monoazo dyestuff is carried out. With 25 partsallised of coppersodium sulfate. acetate Thewith copper-containing25 parts of crys the diazonium compound from 16.8 parts of 5-nitro-2-amino-1-methoxybenzene instead of o-hydroxythe diazo confound azo dyestuff from is 247 finally parts coupled of 4-methyl with with diazotised 4-methyl-3-amino-1:1-diphenyl 3-amino-1:1'-diphenylsulfone in an acetic acid sulfone, a dyestuff of equally good fastness prop- - suspension thus giving the disazo dyestuff. The erties is obtained which gives dark-brown shades so fórmation of the dyestuff can be accelerated by on fibres. gradually neutralising the solution with dilute. sodium carbonate solution. The dyestuff so, ob Eacample 2 tained dyes silk in reddish-brown shades of good The diazo compound from 18.9 parts of 2 aminé-1-hydroxybenzene-4-sulfonic acid is com- 35 fastness properties. . - bined with a caustic alkaline solution of 11 parts Eacample 6 of 1:3-dihydroxybenzene. When the coupling has completed, the monoazo dyestuff is pre The monoazo dyestuff obtainable according to cipitated by means of hydróchloric acid, then Example 1 from 32.9 parts of 3-amino-4-hy isitaia copied in actic acid solo 11EEEEEE parts of resorcinol is coppered, as mentioned tion with the diazo body obtained from 21.9 in the said Example 1, by means of 25 parts of parts of 4-chloro-2-amino-1:1'-diphenyl ether. crystallised copper sulfate and coupled in an The disazo dyestuff precipitated by means of acetic acid solution with the diazo compound sodium chloride is dissolved in 2000 parts of from 26.1 parts of the p-toluene sulfonic acid water at 80° C., treated with 25 parts of crys- 45 ester of the 4-aminophenol. The completely tallised copper sulfate and the whole is main formed dyestuff is precipitated by means of so tained for 1 hour at 90° C. The copper-contain dium chloride. It dyes silk and wool in fast ing dyestuff thus precipitated is filtered off and yellowish-brown shades...... cófiverted into the sodium salt by means of known When, instead of the monoazo dyestuff ob methods. It dyes silk in deep brown shades of 50 tained according to Example 1, there is used that very good fastness properties. obtainable according to Example 2 from 18.9 parts of diazotised 2-amino-1-hydroxybenzene Eacample 3 4-sulfonic acid and 11 parts of 1:3-dihydroxy 11 parts of 1:3-dihydroxybenzene are com benzene and worked up as indicated above, a bined at 0° C., in the presence of 14 parts of so dyestuff is obtained which dyes animal fibres in dium hydroxide, with the diazo compound ob reddish-brown shades of similar fastness prop tained from 37.2 parts of 3-amino-4-hydroxy erties. - benzene-i-sulfonic acid ethylanilide-4'-sulfonic Ecample 7 acid. The monoazo dyestuff isolated in an acid 34.5 parts of 3-amino-4-hydroxybenzene-1- medium and again dissolved in water is treated 60 sulfonic acid phenyl-ester-3'-sulfonic acid are for 1 hour with 25 parts of crystallised copper diazotised indirectly and coupled at 0°C. in the sulfate. The monoazo dyestuff thus coppered is presence of exceeding caustic soda, lye with 11. then separated, dissolved in water and coupled - i. parts of 1:3-dihydroxybenzene. The monoazo in ah acetic acid suspension withwi the diazo coin- is dyestuff isolated by acidification is converted at p6th d from 16.8 parts of 5-rhitro-2-amin - 80° C. into the copper complex compound by methoxybenzene. The dyestuff, worked up as adding 25 parts of crystallised copper sulfate and is:brown in shadesExample of excellent2, dyes wool fastness arid propersilk in coupled with the diazo compound from 24.7 parts ------, ------S-9 p ofsoon 4-methyl-3-amino-1:1'-diphenylsulfone. as the dyestuff formation is completed, theAs - - - - Ecample 4 mixture is salted out with sodium chloride and

234 parts of 4-nitro-2-amino-1-hydroxyben then filtered off. The copper-containing disazo Zene-6-sulfonic acid diazotised according to usual dyestuff dyes wool and silk in brown shades of methods are combined at 6 c. with 11 parts of 75 good fastness properties. 2,438,754 5 6 In the following table further examples illus airylamine of the benzene series, with the condi trating the present invention are enumerated: tion that, at east. One of the radicals A and C is

dyeing of the Example 1st diazo coalpound middle component 2nd diazo compound copper complex COLpound

6-methyl-2-amino-I-hydroxybenzene-4-sul- 1:3-dihydroxyben- 4-aminophenyl-4-methylbenzene sul brown. fonic acid. Zee. fonic acid ester. 3-amino-4-hydroxybenzene-i-Sulfonic acid------do------4-methyl-3-amino-1:1'-diphenyl-sulfone-- yellowish-brown. methyl-anilide4-sulfonic acid. 3-amino-4-hydroxy-1:1-diphenylsulfoner ----- do------4-amyl-2-amino-1:1-dipheny ether----- Do. 3'-sulfonic acid. 4: to-3-hydroxynaphthalene-6- - - - do------6-methyl-3-amino-1:1'-diphenyl-sulfone.-- violet brown. SOC 4- ligamino-1-hydroxybenzene-6------do------4-methoxy-3-amino-i:1'-diphenylsulfone. brown. On 8 2-amino-1-methoxy-benzene-4-sulfonic acid.....dio -- 6:chloro-3-amino-i:1'-diphenylsulfone.---- reddish-brown, 3-amino-4-hydroxybenzene-1-sulfonic acid- --do-- ... 2'-methyl-2-aminori:i-diphenyl ether.-- brown. ethylanilide-3-sulfonic acid. 6-methyl-2-amino-, -hydroxybenzene-4- 3-resorcylic acid---- 3-amino-6-phenylaminori:i-diphenyl red-brown. sulfonic acid. Sulfone. 3-amino-4-hydroxybenzee-Esfonie acid- 1:3-dihydroxy-ben ----- do------Do. ethyl-anilide-4'-sulfonic acid. 28 2-amino-1-hydroxybenzene-4-Sulfonic acid.-----do------3-aminobenzophenone.------brown, 3-amino-4-hydroxy-1:1-diphenylsulfone-3'------do------4-methoxy-3-amino-1'-diphenylsulfone. nigger-brown. sulfonic acid. 19------do------'a - a as a w- a war raw wr- - - rs arvax w - - us r or r-wm war--a war r- do------2-methyl-5-nitro-1-aninobenzene.------yellowish-brown, do. 2-chloro-5-nitro--aminobenzene.------Olive-brown. --do------2:4'-dichloro-2-amino-i:1-diphenylether reddish-brown. 22------do------do------3-aminobenzene-sulfonic acid-2'cresyl Do. ester. 28------2-amino-1-methoxybenzene-4-sulfonic acid.------do------4-chlorobenzene-sulfonic acid-4'-amino Do. - phenyl ester. 24------2-amino-1-hydroxybenzene-4-sulfonic acid 6-resoreylic acid...: Gielgiano-benzene-sulfonie acid Do. Y ethylanllide. 25------|----- do------i:3-dihydroxyben-4-imethylbenzene-sulfonic acid-2-amino brown. fee. phenyl ester. 26------2-amino-i-ethoxy-beitzeae-4-Sulfonic acid------do------3-aminobenzoyl-ethylanilide------reddish-brown. 27------1-0-2-hydroxy-naphthalene 4-sulfonie - - - - do------2-amino-2-methyl-1:1-diphenyl ether--- grey. 8. 28------3-amino-4-hydroxy-lit-diphenylsulfone-5------do------4-methyl-3-amino-1:diphenyl-sulfone. brown, sulfonic acidi. - 29------do------do------4-aminobenzophenone.------DO. What we claim is: linked to a benzene radical by means of a mem 1. A process for the manufacture of copper 35 ber Selected from the group consisting of -SO2-, containing disazo dyestuffs of the general formula, -SO iN-alkyl Wherein. A stands for a Sulfonated aryl radical -SO2-O-, -O-, and -CO-. of the benzene series containing in O-position to 40 3. A process for the manufacture of copper the azo group a group capable of being coppered, containing diazo dyestuffs of the general for B stands for a radical of a 1:3-dihydroxybenzene nula, Y and C stands for an unsulfonated aryl radical of the benzene series, which comprises diazottising an aminoarylsulfonic acid of the benzene series 5 NaN-B-NetN-- C containing in o-position to the amino group a group capable of being coppered, coupling the dia Zo compound with a 1:3-dihydroxybenzene and coupling the monoazo dyestuff with a diazotised UnSulfonated arylamine of the benzene series, 50 With the condition that at least one of the radi SOH calls A and C is linked to a benzene radical by means of a member selected from the group cgn. sisting of -SO2-, a Wherein B stands for a radical of a 1:3-dihy droxybenzene, C stands for an unsulfonated aryl -S on-alkyl radical of the benzene series and X stands for a -SO2-O-, -O-, and -CO-, an Wei member selected from the group Consisting of the dyestuff2 into its copperd complexand compound.ConVerting Of-SOg-, 2. A process for the manufacture of copper -so-N-alkyl containing disazo dyestuffs of the general formula 60 -SO2-O-, -O-, and -CO-, while Y rep A-NRN-B-NeN-C resents a group capable of being coppered, which wherein. A stands for a sulfonated aryl radical of Comprises coupling a 1:3-dihydroxybenzene with the benzene series containing in o-position to the a dia2Otised of the formula, aZO group a group capable of being coppered, B stands for a radical of a 1:3-dihydroxybenzene and C stands for an unsulfonated ary radical of NH the benzene series, which comprises diazottising an anninoarylsulfonic acid of the benzene Series containing in o-position to the amino group a 70 group capable of being coppered, coupling the diazo compound with a 1:3-dihydroxybenzene, converting the monoazo dyestuff into its copper SOH complex compound and coupling the coppered monoazo dyestuff with a diazotised unsulfonated 75 2,488,754 7 8 wherein X and Y have the above mentioned sig - 6. A process for the manufacture of a copper nifications, converting the monoazo dyestuff into containing diazo dyestuff of the formula, its copper complex compound and coupling the O * O. monoazo dyestuff with a diazotised unsulfonated arylamine of the benzene Series. 4. A process for the manufacture of copper containing disazo dyestuffs of the formula. OE O CH O OE . 10 NN-B-NEN-C

5 which comprises coupling 1:3-dihydroxybenzene SO with diazotised 3-amino - 4 -hydroxy-11'-di phenylsulfone-3-sulfonic acid, converting the dyestuff into its copper complex compound and SOE coupling the monoazo dyestuff with diazotised 2 20 anino-1-methoxy-5-nitrobenzene, 7. A process for the manufacture of a copper containing disaZO dyestuff Of the formula whereini B stands for a radical of a 1:3-dihy droxybenzene and C stands for an unsulfonated O gh aryl radical of the benzene series, which con prises coupling a 1:3-dihydroxybenzene With a -N=N- diazotised 3-amino-4-hydroxy-1'-diphenylsul - OE fone Sulfonic acid of the formula, 30 SO3. N-N-( )-0-so-g X-ch, O which comprises coupling 1:3-dihydroxybenzene with diazotised 2-amino-1-hydroxybenzene-4-sul NH fonic acid, converting the monoazo dyestuff into its copper complex compound and coupling the monoazo dyestuff with diazotised 4-amino-1-hy droxy-benzene-p-toluenesulfonic acid ester.. 8. The copper-containing dyestuffs of the gen eral formula, O wherein. A stands for a sulfonated aryl radical of the benzene Series containing in o-position to the a2O group a group capable of being coppered, converting the monoazo dyestuff into its copper B stands for a radical of a 1:3-dihydroxybenzene complex compound and coupling the monoazo 45 and C stands for an unsulfonated aryl radical of dyestuff with a diazotised unsulfonated arylamine the benzene series and wherein at least one of Of the benzene Series. the groupSA and C. is linked to a benzene radi 5. A process for the manufacture of a copper cal by means of a member selected from the group Containing disaZO dyestuff of the formula 50 consisting of -SO2-, --SO -N-alkyl 9H OE -SO-O-, -o-, and -CO-, being dark pow Ne ders dissolving in Water with brownish color, in 55 concentrated with Orange to red color and dyeing fibres in brown shades of ex O Ca cellent fastness if coppered. SO N=N 9. The copper-containing dyestuff of the for mula, 60 0. SO 65 which comprises coupling i:3-dihydroxybenzene 70 With diazotised 3-amino - 4 - hydroxy - 1:1'-di phenylsulfone-3-sulfonic acid, converting the dyestuff into its copper complex compound and coupling the monoazo dyestuff with diazotised 3 amino-4-methyl-1:1-diphenylsulfone, is 2,488,754 O being a dark powder dissolving in water with yel 11. The copper-containing dyestuff of the for lowish brown color, in concentrated sulfuric acid mula with Orange color and dyeing fibres in yellowish OE OE brown shades of excellent fastness to light and Washing if COppered. 5 sN 10. The copper-containing dyestuff of the for mula, OH

OE OE O 2 N-N-C-O-so-g X-ch, being a dark powder dissolving in water with yell lowish brown color, in concentrated sulfuric acid With Orange color and dyeing fibres in reddish brown shades of very good fastness if coppered. 5 ADOF KREBSER. WERNER BOSSARD. -NO REFERENCES CTED The following references are of record in the SOs 20 file of this patent: UNITED STATES PATENTS being a dark powder dissolving in Water With Number Name Date olive-brown color, in concentrated Sulfuric acid 2,117,731 Kollmann ------May 17, 1938 with red color and dyeing fibres in dark brown 25 2,135,433 Delfs et al. ------Nov. 1, 1938 shades of very good fastness to light and washing 2,160,448 Wehrli ------May 30, 1939 if coppered. 2,257,165 Fellmer ------Sept. 30, 1941