DE834882C - Process for the preparation of copper-containing disazo dyes - Google Patents

Description

Process for the preparation of copper-containing disazo dyes 1? S was refuti (len, that valuable copper-containing 1) isazb dyes can be prepared by mixing a Mo (tetrazotized 3, 3'-dialkoxy-4,. -Diami, nodiplieilyl with one mole of an oxynaphthalenesulfonic acid and with a Moles of an azine of the formula where \ C = C is part of an aryl radical, couples and treats the dyes obtained with copper-donating agents.

The new copper-containing disazo dyes dye space wool and fibers made of regenerated cellulose in blue to pale gray tones of excellent light, Wash and water fastness and have a very good draw power.

The production of the azo dyes to be converted into the copper compounds is preferably carried out in an alkaline medium using the usual coupling methods, where either the oxynaphthalenesulfonic acid or the azine comes first with the tetrazotized 3, 3'-dialkoxy-4, 4'-d-iaminodiphenyl can be combined '.

As 3,3'-dialkoxy-4, 4-diaminodipihenyls there are mainly 3,3'-dimethoxy- or 3, 3'-diethoxy-4, 4 ', diaminod-iphenyl in question.

An addition can be added to both the coupling and the Kupferurig of pyridine bases have a beneficial effect. .11s, suitable oxynaphthalenesulfonic acids Koninien all couplingable sulfonic acids of t- or 2-Oxynaphthlialins in Btracht, for example i -Oxynaphtlialin-3, 6, 8-trisulfonic acid, i -Oxynap'lithalin-3, 8-disulfonic acid, i-Oxynaplitlialin-3, 6- (lisulfonic acid, i-Oxynaphthlialin-4, 8-disulfoiisäur.e, i-Oxynal), htlialin-3-s, sulfonic acid, i-OxynaplitIialin-4-sulfonic acid, i-Oxynaphth, lialin-5-stilfonic acid, 2-Oxynaphthalin-3,6-disulfonic acid, 2-Oxynal) ht'halill-4-sulfonic acid, 2-Oxynal) lithalin-6-sulfonic acid.

Also sulfonic acids of dioxynaplithalins such as t, 8-Dioxynaphfhalin-3, 6-disulfotic acid are suitable coupling components.

Suitable azines are e.g. 13. 2-Sttlfo-4-oxy-a, ßnaplithophenazin, 2-sulfo-4-oxy-a, ß-liapilithoio-methylplienazin, 2-sulfo-4-oxy-a, ß-nap @ litlioi0-nietlioxypbenazin, 2-sulfo-4-ox5 # -a, ß-naphtlio-carl) oxyphenazine, 5, 5'-dioxy-7, 7'-disulfo-i, i ', 2 '2-dinaphthaz, iti, 5, 5'-dioxy-7, 7'-disulfo-i, 2, 2', i'-ditiaphthazine, their Production is described in part in French patent 679 164. In question also come from 5-oxy-1, 2-napIitliylenediamine-7-sulfonic acid by condensation azines which can be prepared with ortho-diketones, such as plienanthrenequinone.

The conversion into the copper complexes can be carried out by known methods take place, the complete or extensive splitting of the alkoxy groups in the remainder of the 3, 3 '- Dialkoxy-4, 4'-diaminodipheliyls letvirken, z.13. by heating with a ammoniacal solution of a copper salt.

The dyes that have not yet been coppered are also used to dye cotton and regenerated cell silose. After treatment with copper salts -the fiber the colorings obtainable with it are improved in the light fastness died.

In the following examples, parts mean parts by weight. Example 1 24.4 parts 4, 4'-Dianiilio-3, 3 '- (liniet: lioxydipliellyl are tetrazotized as usual, and the tetrazolization is with ice cooling with 30.4 parts of i-Ox3, nal) lithalin-4, 8-disulfonic acid combined in the presence of sodium bicarbonate. After education the intermediate compound is an alkaline solution of the sodium salt of 32.6 parts 2-sulfo-4-oxy-a, ß-naplithophenazine added. To transport the clutch can to add 5 to 10 percent by volume of pyridine bases. After the coupling is complete the dye is isolated. It dissolves in water with a reddish blue and in more concentrated Sulfuric acid with a gray-blue color.

To convert into the copper compound, 96.2 parts of dye are dissolved in 3000 parts of water and 20 parts of sodium carbonate. At 80 ° to 90 °, 500 parts of a copper oxide ammonia solution containing 50 parts of crystallized copper sulfate and 85% concentrated aqueous ammonia solution are gradually added with stirring. The mixture is stirred at 90 ° for 5 hours and then 18 hours under reflux gckoclit. The The copper complex is isolated, filtered and dried. It dyes cotton and fibers regenerated 'cellulose in blue-gray tones from very good light and \\ 'asclieclitlieit. When transferring the metal-free disazo dye into the complex copper compound can iti the conditions given above wide limits. If one uses instead of the 1-OxN, naplitlialin- 4, 8-disulfonic acid the same amount of t-oxynaplite: halin- 3, 6- (lisulfonic acid # so a slightly greenish tint is blue-gray coloring agent from excellent quality Achieved lightfastness. Xlinliclie l, arl) fabrics be obtained when using i-Ox \, nal) litlialiii- 3, 8-disulfonic acid and of 2-oxnaphthalene-3, 6-di- sulfonic acid. 13eisl) iel d 24.4 parts 4. 4'-l) iainino-3, 3 '- (Iinletlioxy (1ipllell \ l are tetrazotized like iil) licll, and the Tetrazover- The binding is made up of 38.4 parts with ice cooling i-Oxynal) htlial, in-3, 6, 8-tristilfonsiiui-e in counter- were united by Natritiincai-lx) nat. After he subsequent formation of the interconnection becomes a alkaline solution of the atrium salt of 32.6 parts of 2-sulfo-4-oxy-a, j -) '- nal) litliophenazill to- joined. In the presence of 3% oluin percent I'yri (Iin is stirred at 25 to 30 ° until the substance formation is finished. Then the 1) isazofarl) stoft is isolated. It dissolves in water with a greenish blue color and in concentrated sulfuric acid with green l, 'arlve. He dyes "rayon in greenish gray blue tones, the d @ urcli \ aclikupfern on greed l, 'aser Hardly changed in the nuance, in the 1_ichteclitlieit but much to be improved. To clverfiilirun (-, in the copper compound 10.6.4 parts of dye are divided into 2,000 parts Water and 20 parts of atriunicarbonate dissolved. At about 90 °, the agitation is gradual 500 parts of a copper oxide ammonia solution, lialtend 5o parts of crystallized copper sulfate and 85 T 1 concentrated w: ilirige: \ inmoniaklösung, added. It is then heated to the boil and about 15 hours on the back with stirring cooks. The resulting copper complex is isolated, filtered and dried. It dyes cotton and other cellulose fibers in lively grayish blue tones of exquisite licher light and \\ 'asclieclitlieit. When fulfilling the metal-free disazo dye into the complex copper compound the above conditions can be found in wide limits. Instead of 32.6 '' parts, 2-piece 4-oxy-a, ß-naplitliol) lienazill 3.5.6 parts 2-Su] fo- 4-oxy-α, β-naphtho-to-methoxyphenazine, thus obtained one even livelier 1 # dye of very similar nuance. When using 34 parts 2-Stllfo-4-oy-x. / 3-tial) litlio-io-niet] ivl- phenazine or of 37 Te11Cti 2-Su] fo-4-oxy- a, 'ß-nal) litho-io-cai-1) () xvl) lienazin become equivalent Obtain dyes. If, in this example, instead of 24.4 parts, 4,. -Diamiilo-3, 3'-dimethoxydiphenyl 2 parts 3, 3'-1) Iitll () xv-4, 4'-diamiiiodiphenvl, so 7 one obtains dyes with the same properties. Example 3 24.4 "heal 4, 4'-uianiino-3, 3'-dimethoxydil> lienyl are tetrazotized as usual, and the tetrazo compound is, while cooling with ice, with 32 parts of 1,3-dioxnal> htli @ alin-3, 6-disulphonic acid When the intermediate compound has formed, an alkaline solution of the sodium salt of 32.6 parts of 2-sttlfo-4-oxy-α, @ -nalilitlioplienazine is added Stirred until the formation of the dyestuff has ceased, then the dyestuff is isolated and dissolves in water with a greenish blue color and in concentrated sulfuric acid with a greenish grayish blue color.

The same dye is obtained when the tetrazOtated .4,. -I) iamino-3, 3 '@ dimethoxydiphenyl first with the 2-sulfo-4-oxy-a, ß-naphthophenazine and then is coupled with the t, 8-dioxynaphthalene-3, 6-disulfonic acid.

For conversion into the copper complex, 97.8 'files are used dissolved in 3ooo parts of water and .2o parts of \ atritiiiicarlxj # nat. Be at 9o ° with stirring gradually 500 parts of a copper oxide ammonia solution containing 5o Parts of crystallized copper sulfate and 85 parts of concentrated aqueous ammonia solution, added. At 90 ° is stirred for 5 hours, heated to the boil and 18 hours cooked on the condenser while stirring. The resulting copper complex is isolated, filtered and dried.

He dyes cotton and rayon in greenish blue-gray tones of good washfastness and excellent lightfastness.

Instead of 32.6 parts of 2-sulfo-4-oxy-x, #inaplithcrp: henazine, 38.6 parts of 2-sulfo-4, to-dioxy-a. ß-nalihtltol> lrenazin-9- or -ii-car-) xric acid can be used. This compound is obtained, for example, from an azo dye represented by the following formula by treating with acid. 13example4 2; I, 4 parts 4,. -Diamiilo-3, 3'-dimethoxydiphenyl are tetrazotized as usual, and the tetrazole> indung with 38.4 parts of i-oxalilitlialin-3 with ice cooling. 6, 8-trisulfonic acid combined in the presence of sodium carbonate. After the intermediate compound has formed, an alkaline solution of the sodium salt of 42.6 parts of the compound of the formula. which can be prepared, for example, by condensation of 1,2-diamino-5-oxynaphthalene-7-sulfonic acid with phenanthrenequinone, added. In the presence of 7 percent by volume of pyridine, the mixture is stirred at 15 to 20 ° until the formation of the dye has ended. The dye is then isolated. It dissolves in water with a greenish blue color and in concentrated sulfuric acid with a greenish blue-gray color.

For conversion to the copper complex, 1 16.4 parts of dye are used dissolved in 2500 parts of water and 2o parts of sodium carbonate. At 9o ° are below Gradually stir 500 parts of a copper oxide, ammoniacal solution, containing 50 parts crystallized copper sulfate and 85 parts of concentrated aqueous ammonia solution added. The mixture is stirred for 5 hours at 90 °, brought to the boil and cooked while stirring about 18 hours on reflux. The resulting copper complex is deposited and filtered and dried.

It dyes cotton and regenerated cellulose fibers in lively, greenish blue tones of excellent lightfastness and washfastness. Example 24.4 Parts 4, 4-diamino-3, 3'-dimethoxydiplienyl are tetrazotized as usual and the tetrazover bond is cooled with 38.4 parts of i-Oxynap.hthalin-3, 6, 8-trisulfonic acid combined in the presence of sodium carbonate. After education the intermediate compound is an alkaline solution of the sodium salt of 47.2 parts 5, 5'-Dioxy-7, 7 ', disulfo-i, 1'-2', 2, dinaphthazine added. In the presence of io volume percent Pyridine is stirred at 25 ° until dye formation is complete. Then the Dyestuff isolated and, if necessary, purified by turning it around. It dissolves in Water with greenish blue and in concentrated sulfuric acid with blue green Colour. 123.2 parts of dye are used for conversion into the copper complex dissolved in 2,000 parts of water and 2o parts of sodium carbonate. At 8o to 9o0 will be with stirring gradually 500 parts of a copper oxide ammonia solution containing 5o Parts of crystallized copper sulfate and 85 parts of concentrated aqueous ammonia solution, added. The mixture is then heated to the boil and with stirring on the reflux condenser for 20 hours cooked. The resulting copper complex is deposited, filtered and dried.

It dyes cotton and fibers from regenerated cellulose in lively, greenish blue tones of good lightfastness and washfastness.

Is used instead of 38.4 parts of i-oxynaphth: alin-3, 6, 8-trisulfonic acid 30.4 parts of i-oxynaphthalene-3, 6-disulfonic acid or 30.4 parts of i-oxynaphthalene-3, 8-disulfonic acid or 22.4 parts of i-oxynaphthalene-3, sulfonic acid or 22.4 parts of i-oxynaphthalene-4-sulfonic acid, in this way, dyes of a similar hue and properties are obtained.

If in this example the same is used in place of the azine mentioned Amount of 5, 5'-dioxy-7, 7'-disulfo 1, 2, 2 ', i'-dinaphthazine and proceed as above stated, a copper complex which stains blue-gray cotton is obtained.

Since the azines used in this example have two couplable per molecule Have places, the dyes described are capable of before or after Conversion into the copper compound with a further mole of any diazo compound to be coupled.

Claims (1)

PATEN TANS JIRUC II: Process for the production of copper-containing 1) isazo dyes, characterized in that 1 mol of tetrazoti.ertes 3, 3'-dialkoxy-4, 4'-diaminodiphen_vl with t \ lol of an Oxvnapli-thal @ insulphonic acid and with 1 \ tol of an azine of the formula where / C = CI "is for an aryl radical, couples and treats the disazo dyes obtained with copper-releasing agents.