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United States Patent Office 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 acid of the 4-Sulfonic acid, 4- or 6-methyl-2-amino-1-hy benzene or naphthalene series, which contains, in droxy- or ethoxybenzene sulfonic acid, 4- or o-position to the amino group, a hydroxy group 5 6-chloro-2-amino-1-hydroxy- or -methoxyben or a Substituent 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 amines: 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 ester, 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 ether, its alkyl- or halogen substitution products. tains two aryl 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-sulfone-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 acetic acid 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 salt in the usual manner. It azo dyestuff, which has been separated out in an dyes 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 sodium chloride. 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.
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