DE1644347C - Process for the production of waterless, copper-containing reactive dyes - Google Patents

Description

The invention relates to a process for the preparation of active, copper-containing disazo dyes of the formula

wherein the radical A or the radical B contains a group -NH- Z and the dye molecule with Inclusion of the group - NH - Z at least 5 sulfonic acid groups carries, one of the radicals A and B is an optionally further substituted phenyl radical or an optionally further substituted naphthyl radical bonded in the 2-position to the - N = N group, the other one optionally further substituted, bonded in the 2-position to the —N = N group Naphthyl radical and Z denotes a reactive group and the - O atom in each case in the rtho position to the azo group.

The process for the production of the new reactive dyes' is characterized in that the diazo compound from an amine of the formula

A-NH ₂

(H)

in which w is a hydroxyl or low molecular weight alkoxy group in the ortho position to the NH ₂ group, with a copper-containing dye of the formula

OH

HO ₃ S

(Hl)

- O - Cu - O

T N

couples and converted into the copper complex compound or that the diazo compound from an amine of the formula

Λ - NH,

(IV) acylamino or nitrophenyl or an acylamino or NUronaphthylrest, or a coupling component bearing an amino, nitro or aoylamino used and after coupling 5 or after coppering the amino, nitro or acylamino group through the group · - NH - Z replaced. Since the replacement of an acylamino or nitro group takes place in two stages (hydrolysis of the acylamino group or reduction of the nitro group

ίο and implementation of the amino group formed with the Reactive component), the process can also be carried out in the following order: coupling, Hydrolysis or reduction, coppering and reaction with the reactive component. In order to

If damage to the free amino group is to be avoided during oxidative copper plating, it is advisable to only perform normal copper plating when an unprotected amino group is present. For the hydrolysis of the acylamino group, one works advantageously

adhered in an alkaline medium, e.g. B. 2 to 10% sulfuric Alkajimetallhydroxidlösung, at 70 to 100 "C, while the nitro group is conveniently reduced with sodium sulphide or sodium hydrogen sulphide at temperatures of 20 to about 60 ⁰ C.

The copper-containing monoazo dyes of the formula (III) are prepared according to the German The method described in U.S. Patent 889,044.

The reactive radical Z is z. B. the remainder of at least one substituent which can be split off as an anion

and / or an acylating agent containing a C'-C multiple bond capable of addition. It is preferably the radical of at least one halogen atom which can be split off as an anion or a group which can be split off as an anion, e.g. B. - O - SO ₃ H, and / or a

acid bearing additive CC double bond, ζ B. chloroacetic acid c. Bromoacetic acid, / i-CliliH u..d;. ' Brompfupionsaure, "" (dichloro- or dibromopropionic acid, acrylic acid, methacrylsüuu α-chloro- and ii-bromoacrylic acid, ff- or j-chloro- or bromo-erotonic acid, a, (i- and / ^ - dichloro or -dibromoacrylic acid, / i- Chior- or / i-bromoilphonic acid, / f-sulphatopropionic acid, / i-sullato-iiiii, - »uiion acid, vinylsulphonic acid, / f-methylsulfonyloxydi / f-phenylsulfonyloxypropionic acid or 2,3- dichloro or 2,3-dibromoquinoxaiine-6- or -7-carboxylic acid, sulfonic acid or carbamic acid or the residue of a di- or triazine compound containing at least two mobile halogen atoms, /. B. de: cyanuric chloride, cyanuric bromide, a primary con c ' ensalionsproduktes met a Cyanurhalogcnids the For

Hal C

C ν

(V)

C "
Shark

with a dye of the formula (111) kuppeil and mil treated copper-donating agents in the presence of oxidizing agents.

A modification of the process according to the invention consists in the fact that a diazo component bearing an aylamino or Nilmgruppe is made from i amine of the formula (II) or (IV), in which Λ one in which Hal is chlorine or bromine and ν the optionally further substituted radical of a primary or secondary aliphatic, acyclic, aromatic or heterocyclic amine, see an aliphatic, alicyclic, aromatic or heterocyclic Ilydrox 'or thiol compound, but especially the Re of aniline, its alkyl and sulfonic acid odi

i 644 347

Carboxylic acid derivatives, of low mono- and di denotes nlkyUiminen and the remainder of ammonia; of 2,4,6-TrichIorpyrimldins and 2,4,6-Tribromopyrimidins and their derivatives, which in the 5-position for example carry the following substituents: methyl, ethyl, carboxy, carboxylic acid methyl or ethyl ester, Chlorovinyl, substituted alkyl, ζ. B. carboxymethyl, Chloromethyl or bromomethyl; des 2,4,5,6-TeIrOChIOr- or ■ tetrabromopyrimidine, des 5-bromo-2,4,6-trichloipyrimidine, 2,4-dichloro-5-chloromethyl- or 2,4-dibromo-5-bromomethylpyrimidine, des 2,4-dichloro-S-chloromethyl-o -methyl- or 2,4-dibromo-5-bromomethyl-6-methylpyrimidine.

The coupling of the diazo compound from an amine of the formula (II) or (IV) with an azo component of the formula (III) is advantageously carried out in an alkaline medium, preferably at temperatures from 0 to 10 ° C.

The reaction of the starting materials or the disazo dyes obtained therefrom, which _{carry at least one —NH 2} group, with a functional derivative of an acid containing at least one halogen atom which can be split off as an anion or a group which can be split off as an anion or a C - C double bond capable of addition is preferably carried out with the acid halides or acid anhydrides. The work is carried out in an aqueous medium, preferably with good cooling and in the presence of acid-binding agents such as sodium carbonate, sodium hydroxide, barium hydroxide, calcium hydroxide or sodium acetate.

The carboxylic acid halide used is used for the acylation as such in twice to five times the amount of benzene, chlorobenzene, methylbenzene, dimethylbenzene or acetone dissolved and this solution in the aqueous solution of the amino group-bearing Body dripped at a temperature of 0 to 30 "C, preferably from about 2 to 5" C, in the presence an acid-binding agent, preferably at a pH of 7 to 3.

Introducing the 2,3-dihaloquinoxaiyl-6- or -7-earbonyl-, -sulfonyl-rnk-r -am.nn; nbon> l radicals ·. ·. ■> ends:;.:. ^ v \ .wwi.assig the acid halides, preferably the acid chlorides or the isocyanates. One can use the acid halides or isocyanates as use those in finely powdered form or in the form of a solution in benzene, toluene or chlorobenzene and the reaction in the temperature range from 0 to 50 ° C., preferably 20 to 45 ° C., and hot one pH between 3 and 8, preferably between 4 and 7, run.

The reaction with the di- or triazine compounds containing at least two mobile halogen atoms is also carried out in an aqueous medium. Here, the halide can be used as such brought to use in concentrated form or dissolved in an organic solvent will. Particularly suitable solvents are acetone, benzene, chlorobenzene or toluene.

The reaction temperature is to be adapted to the reactivity of the individual starting products and varies between 0 and! 0 (V ¹ C, e.g. 0 b: s 21) C for cyanuric chloride and cyanuric bromide, or 30 to 50 "C for the 2 mobile halogen atoms Monocondensation products of cyanuric chloride or bromide with ammonia, a primary or secondary amine, an alcohol, thioalcohol, phenol or thionhenol. Or 70 to KX) C for the dichloro-, dibromo-, trichloro-, tribromo-, tetrachloro- and tetrabromopyrimidines, must higher temperatures than about 40 "C are used, so it is with regard to the water vapor volatility of the halogenpyri-

s midine displayed, in a possibly with a Reflux condenser equipped vessel to work.

The reaction can be carried out in a weakly alkaline, neutral to weakly acidic medium, preferably but within the pH range from 7 to 3, through-

be guided. To neutralize the resulting one equivalent of hydrogen halide, the Reaction solution either add an acid-binding agent, for example sodium acetate, at the beginning or during the implementation in small portions of Na-

is triurn- or. Potassium carbonate or bicarbonate in Add in solid, powdered form or as a concentrated aqueous solution. As a neutralizing agent however, aqueous solutions of sodium or potassium hydroxide are also suitable.

The addition of small amounts of a wetting or emulsifying agent to the reaction mixture can Accelerate conversion reaction. The reaction is conducted so that only one halogen atom with one exchangeable hydrogen atom of the amino group reacted.

As already mentioned, the introduction of the reactive group Z can be used both as starting materials Diazo components, as in the disazo dyes, take place before or after coppering.

The transfer of disazo dyes in which the substituent w capable of forming metal complexes is a hydroxyl group, in its copper complex compounds is advantageously carried out in weakly acidic aqueous Solution. A disazo dye containing one atom of copper is advantageously allowed on one molecule of disazo Act with the amount of a copper-releasing agent.

When the substituent w is an alkoxy group, the Küpfrrrung under such conditions, e.g. Am ammoniacal medium in the presence of hydroxyalkylamines, such as mono-, di- or triethanolamine, at temperatures from So to about 100 C, after the method of Swiss patent 261 365, carried out that the alkoxy group is split.

Suitable compounds of copper are, for. B.

Cupric sulfate, cupriformate, cupric acetate or cupric chloride.

The obtained copper complex compounds can from their aqueous solutions by adding Table salt deposited, then filtered off, if necessary washed and dried.

The new copper-containing reactive dyes are not very sensitive to salt and have, as they at least have five water-solubilizing groups, good solubility in water, so that after fixation the non-chemically bound part can easily be washed out. They are therefore well suited to zurr Dyeing leather, for dyeing or padding fibers made from natural or regenerated cellulose especially after the pull-out bar procedure.

*> o The obtained, an alkaline post-treatment Färbu-.igen unc Blocking on cellulose fiber !! have good light and wet fastness properties, e.g. B. water, washing, welder * Rubbing and alkali fastness, and are resistant to crease-proof finishes.

The oxidative coppering of the disazo dyes from the diazo components of the form! (IV) is at

I 644

for example according to the method of German patents 807 289, 889196 or 893 699, preferably but according to the> in Examples 1 and 4 to 10 of German Patent 807 289 described Method using a water-soluble copper salt and s hydrogen peroxide.

Compared to the closest comparable dicopper complex dyes known from French Patent 1,329,112, the dicopper complex dyes obtainable according to the invention are distinguished by the fact that they have a different shade (navy blue instead of dark green) and their colorations are based on cellulose fibers! have better wash fastness at 9S ⁰ C and in particular better lightfastness.

Compared with those from the Swiss patent specification 374132 known, navy blue monocopper complex dyes the dicopper complex dyes obtainable according to the invention have the. Advantage that their colorations both in the dry and in the When wet, they are better lightfast and that they have a significantly better boiling fastness and a much greater one Show resistance to anti-crease finishes.

In the following examples, parts are parts by weight, percentages are percentages by weight, and the temperatures are given in degrees Celsius.

solution entered. The solution is heated to 90 ° for 7 hours in order to split off the acetyl group, neutralized Then the solution with Satatlure, the aminodisazo precipitates with sodium chloride, sucks them off, washes them with sodium chloride solution and dissolves them again in 1000 parts of hot water. 19.5 parts of 2,4,5,6-tetrachloropyrimidine are added to the solution and stir it for a few hours at a pH of 5 to 6 and a temperature of 70 to 75 °, until none Aminoazo dye is no longer present. The dye is precipitated and isolated with sodium chloride. The dried dye is a dark powder that dissolves in water with a blue color and cotton and dyes regenerated cellulose fibers in navy blue tones. The colorations are excellent Light and wet fastness properties, in particular they are well suited for anti-crease finishes.

A similar dye is obtained if the 24, (5 parts of the diazo component replaced by the same amount of 4-acetylamino-2-amino-1-hydroxybenzene-6-sulforic acid.

Coloring prescription

example 1

80 parts of the tetrasodium salt of the dye of the formula

OH

SO ₃ H (VI)

SO, H

SO, H 2 parts of the dye described above dissolved in 4000 parts of softened water at 40 °.

100 parts of pre-wetted mercerized cotton fabric are placed in the bath, 110 parts of calcined sodium sulfate and 30 parts of calcined sodium carbonate are added, and the bath is heated in 30 minutes to 100 °, after 10 or 20 minutes 110 or

100 parts of calcined sodium sulfate are added. After the boiling temperature has been reached, 50 parts of calcined sodium carbonate are added and the bath is kept at the high temperature for 1 hour. The dye is then removed from the liquor.; · ,, washed with water and dried. The navy blue coloration obtained is soft and wet

In the following table 1 there are other methods produced according to ? Contain dyes which are obtained if, in Example 1, instead of 2,4,5,6-tetrachloropyrimidine, the acylating agents listed in column A are mixed in the same way with the amino disazo dyes condensed.

are dissolved in 500 parts of warm water with the addition of 6 parts of sodium hydroxide. After cooling to 10 ^r , an ice-cold, aqueous suspension of the diazo compound from 24.6 parts of 6-acylamino-2-amino-1-hydroxybenzene-4-sulfonic acid is added over the course of 2 hours. By sprinkling in about 10 parts of powdered calcium hydroxide, the pH is kept at 10.5 to 11.0. After coupling is complete, the solution of the disazo dye is neutralized with the aid of 12 parts of glacial acetic acid and, at 60 ", about 85 parts of an aqueous 1 molar copper sulfate solution are added dropwise until a little excess inogenic copper can be detected.

The solution of the dicopper complex compound is made alkaline at 60 to 70 "with the aid of 25 parts of calcined sodium carbonate and then freed from calcium carbonate formed by filtration. The dye is then precipitated with sodium chloride, filtered off and divided into 800 parts of 7% sodium hydroxide.

Table 1

example A. hue
on cotton 2 2,4,6-trichloropyrimidine Navy blue 3 2,4,6-tribromopyrimidine Navy blue 4th 2,4,5,6-tetrabromopyrimidine Navy blue 5 2,4,6-trichloro-5-methyl
pyrimidine Navy blue 6th 2,4,6-trichloro-5-chloromethyl-
pyrimidine Navy blue 7th 2,4,6-trichloro-5-bromo
pyrimidine Navy blue

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Example 8

65 parts of the trisodium salt of the dye of the formula

OH (VlI)

HO ₃ S

Cu-O SO ₃ H

SO ₃ H

are dissolved in 500 parts of warm water and the solution is then cooled to 0 to 5. At this temperature, the diazo compound from 37 parts of 2-amino-6-acetylaminonaphthaliri-4,8-disulfonic acid and the amount of 20% sodium carbonate solution necessary to maintain a pH between 9 and 10 are added and the mixture is kept at 0 to 5 ° in an alkaline medium (pH about 9.5) stirred until the coupling is complete, which is the case after a few hours. The disazo dye formed is precipitated with sodium chloride, filtered off with suction and redissolved in 2000 parts of warm water. 100 parts of a 50% strength sodium acetate solution are added to the solution and the pH is adjusted to 5.5 with acetic acid. After adding a solution of 25 parts of CuSO ₄ · 5H ₂ O in 140 parts of water, 283 parts of 3% hydrogen peroxide are added dropwise at 30 to 40 "with stirring in about 3 hours and the mixture is stirred for a further 1 hour at 30 °. The coppered dye is deposited, filtered off with suction, hydrolyzed by treatment with 5% sodium hydroxide solution at 80 to 90 ° to the aminodisazo compound and this is reacted with 19.5 parts of 2,4,5,6-tetrachloropyrimidine as described in Example 1. The dye obtained is deposited with sodium chloride and The dried dye is a dark powder which dissolves in water with a blue color and dyes cotton and fibers from regenerated cellulose in dark blue shades. The dyeings are characterized by excellent light and wet fastness properties. A dye whose coloration is navy blue is obtained if, in the above example, the 65 parts of copper-containing monoazo dye are replaced by 80 parts of monoazo dye from Example l 1 replaced.

Example 9 5 <>

72 parts of the trisodium salt of the dye of the formula _OH (VIII)

HO ₁ S-Λ \) - ° -C "- ° ? Ο'Η

Kl == M -, ·

SOjH

are dissolved in 500 parts of water and then cooled to IO to 15 ". It gradually adds a cis" S cold and acidic to Congo red solution of the diazo compound of 2-39Teilen Aminonuphthalin-4,6,8-tnsulfonsäure hinm. simultaneously being by

A portion-wise addition of about 100 parts of a 20% aqueous sodium carbonate solution Maintains pH between 8 and 9. After stirring for half an hour, the coupling to the disazo dye is completed. It is separated in the warmth with the help of sodium chloride and sucked off. The se The aminodisazo dye obtained is redissolved and following the procedure described in Example 1 Condensed manner with 19 parts of 2,4,6-trichloropyrimidine and then isolated. The still moist dye is according to that described in Example 8 Oxidatively coppered way and then deposited with the help of sodium chloride and filtered off. the Dried dye dyes cotton and regenerated cellulose fibers in navy blue tones of good light and wet fastness properties.

Example 10

72 parts of the trisodium salt of the dye of the formula

(VIII)

HO, S

SO, H

NH,

SO ₁ H

are dissolved in 500 parts of water with the addition of 6 parts of sodium hydroxide and coupled at a temperature of 10 to 15 ° with a suspension of the diazo compound of 27 parts of 2-amino-1-hydroxybenzene ^ o-disulfonic acid. The pH value is kept at 1 * 0.5 to 11.0 by gradually adding about 10 parts of powdered calcium hydroxide. After coupling is complete, the solution of the disazo dye is neutralized glacial acetic acid using 12 parts and mixed at 50 to 60 ^C and as much of a 1 molar solution of copper sulfate, can be detected until excess ionic copper The solution as described in Example 1, free of calcium carbonate; then the copper-containing amino disazo dye is salted out with the aid of sodium chloride and filtered off. The moist paste is dissolved in water and the amino group is condensed in the manner described in Example 1 with 19.5 parts of 2,4,5,6-tetrachloropyrimidir. The dye obtained is precipitated and filtered off in the heat with the aid of sodium chloride. In the dried and ground state, it is a dark powder that dissolves in water with a blue color and dyes cotton and regenerated cellulose fibers in navy blue shades with good light and wet fastness properties. The practitioners are particularly well suited to wrinkle-proof equipment.

The same dyestuff is obtained if the di-diao compound is obtained from 25.3 parts of i-aminobenzene 3.5 disulfonic acid at about 10 ° and in the pH range from 8 to 9 with 72 parts of the trisodium salt dei Coupling of the dye of the formula (VIII), then the aminodisazo dye with 19 parts of 2,4,6-trichloro pyrrnidine converts and oxidatively copper

i 644

example

10

55 parts of amino disazo dye of the formula

, Cu

Ο — Cu-O SO ₃ Na

SO ₃ Na

SO ₃ Na

obtained according to Example 1 in the form of the pentasodium salt are dissolved in 600 parts of water at room temperature solved. Within 1 hour, the solution is left with stirring in an ice-cold aqueous suspension of Run in 9.3 parts of cyanuric chloride. By simultaneous dropping of a dilute sodium hydroxide solution keeps the pH value at 5.5 to 6.5. After finished In the reaction, the resulting dichlorotriazinyl dye is salted out, filtered off and in vacuo dried at 3 ° to 40 °. It dyes cotton and regenerated cellulose fibers according to the following described dyeing instructions in very real dark blue tones.

Staining instructions

2 parts of dye are dissolved in 3000 parts of softened water at 40 °. Bring 100 parts pre-wetted Cotton or cellulose tissue in the bath, add 100 parts of calcined sodium sulfate within 30 minutes closed and heated to 60 ° at the same time. Then 6 parts of sodium hydrogen carbonate are added added and held for another half hour at 60 °. Then add 6 parts in portions within 10 minutes calcined sodium carbonate and keeps at the same temperature for 15 minutes. On this takes the dyed fabric is taken from the liquor, rinsed with hot water, soaped with 0.3% boiling water Solution of a non-ionic detergent, rinses it again and dries it. A dark blue one is obtained lightfast and wetfast coloring. so

Example 12

The dichlorotriazine dye solution obtained according to the information in Example 11 is stirred for 2 hours at 40 "with 20 parts of a 25% strength aqueous ammonia solution. After the reaction has ended, the monochlorotriazine dye formed is salted out, filtered off and dried. It dyes cotton and fibers regenerated cellulose according to the described in example I dyeing method ^fi ° in dark blue shades.

B e i s ρ i e I 13

The solution of the Dichlortriazinfarbstoffes the information obtained according to Example 11 during ⁶ S of some hours at 45 to 50 "with the solution of 9.75 parts of I ^ -aminobenzol- sulfonsaurcm Nutrium in QO parts of water with F.inhaltung a pH of 6 to 6.5 stirred by the dropwise addition of 15% strength sodium carbonate solution.After the reaction has ended, the monochloririazine dye is salted out, filtered off and dried.It dyes cotton and fibers from regenerated cellulose according to the dyeing method given in Example 1 in dark blue shades.

The same dye is obtained if 55 parts of the amino disazo dye of the formula (IX) dissolves as the pentasodium salt in 600 parts of water at room temperature, with the solution of 17.5 parts 4 - (4,6'-diochloro-1 ', 3', 5 '- triazinyl - 2' - amino) - benzene-1 - Sodium sulfonic acid is added to 180 parts of water and the whole thing is stirred for a few hours at 45 to 50 °, the pH value being kept at 5 to 6 by adding a 15% sodium carbonate solution dropwise.

Example 14

65 parts of the trisodium salt of the dye of the formula (VII) are dissolved in 500 parts of warm water dissolved and the solution then cooled to 10 to 15 °. At this temperature the diazo compounds from 50 parts of 2-amino-6- (2 ', 4', 5'-lrichloropyrimidyl-6'-amino) -naphthalene-4,8-disulfonic acid and which is used to maintain a pH between? and 10 necessary amount of 20% sodium carbonate solution added and the mixture stirred at K to 15 "until the coupling is complete. The ent Disazofarbsioff is made with sodium chloride deposited, filtered off and dissolved in 20 (X) parts of Wassei. The dye is according to the example fr described way oxidatively coppered. After separation with sodium chloride, filtration and dry A dye is obtained which is identical that of example K.

Example I S

HO parts of the Tetranaliiunisal / es of the dye; of formula (Vl \ S are dissolved in (H) parts of warm Wassei with the addition of miles Natriumhydioxid After it has cooled UUF IO, add all gradually an aqueous suspension of the slide / bindunguus over 26 parts of 6-acetylamino-2-amino- l-Melh added oxybenzene-4-sulfonic acid. By /.ulrupfen 2 ()% sodium carbonate solution, the pH If ¹ * J ₁ O j'fhiilten at KO Hi. After completion Kupplmij

the resulting disazo dye is made with the help of Sodium chloride deposited and filtered off. For coppering, the dye cake is divided into 800 parts dissolved in hot water, crystallized with 20 parts of diethylamine and a solution of 25 parts Copper sulfate in 100 parts of water and 30 parts of 20% ammonia solution are added and then refluxed for 12 hours. After the reaction has ended, the dicopper complex is exposed and bottled. The procedure is then as described in Example 1 by using Sodium hydroxide splits off the acetyl group and then condenses with 2,4,5,6-tetrachloropyrimidine. The dye is identical to that of Example 1.

Example 16

55 parts of the amino-disazo dye of the formula (IX) as the pentasodium salt are dissolved in 600 parts of water solved at about 40 °. A solution of 14 parts of 2,3-dichiorquinoxaline-6-carboxylic acid chloride is added dropwise in 50 parts of benzene and stir vigorously at 40 to 45 ° with the addition of 15% sodium carbonate solution, to keep the pH at 6 to 6.5. When no more free amino group can be detected is, the dye is salted out, filtered off and dried at 40 to 50 "in a vacuum after grinding it is a dark blue powder which dissolves in water with a navy blue color and dyes cellulose fibers in light and wetfast navy blue shades.

If the 2,3-dichloroquinoxaline-6-carboxylic acid chloride is replaced by the corresponding amount of 2,3 - dichloroquinoxaline - 6 - sulfonic acid chloride or -6-isocyanate, similar dyes are obtained.

OH

HO ₃ S

112
B is ρ) ie 1 17

72 parts of the trisodium salt of the dye of the formula (VIII) are dissolved in 500 parts of water and the solution is cooled to 10 ° to 15 °. An ice-cold solution of the diazo compound made from 30.5 parts of 2-aminonaphthalene-4,8-disulfonic acid is gradually added; maintains. After stirring for half an hour, the coupling is complete. The amino-disazo dye is deposited in the heat with the help of sodium chloride and suctioned off. It is redissolved in 2000 parts of water at room temperature, the solution is cooled to O ¹ to 2 ° and 14 parts of I-chloropropionic acid chloride are added dropwise, the pH being kept at 5 to 6 by adding 20% strength sodium carbonate solution . When the acylation has ended, the dyestuff is isolated by salting out and suction, redissolving it in 2000 parts of water at 40 °, adding 100 parts of a 50% sodium acetate solution to the solution and adjusting the pH to 5.5 of concentrated acetic acid. After adding a solution of 25 parts of crystallized copper sulfate in 150 parts of water, 285 parts of 3% hydrogen peroxide are added dropwise at 35 to 40 ° with stirring in about 3 hours and the mixture is stirred for a further 1 hour at 35 to 40 °. The coppered dye is salted out, filtered off, dried and ground. It is a dark blue powder that dissolves in water with a dark blue color and dyes cellulose fibers in light and wet-fast navy blue tones.

The same dye is obtained if the 72 parts of the trisodium salt of the dye are used instead of formula (VIII) 81 parts of Trinalriumsal / es of the dye of the formula

SO, H

(X)

NH-OC-C ₂ H ₄ CI

OH

C) H

I. B.

and the resulting pisiizofur material oxidatively residues copper.

The following table contains further copper-containing reactive disazo dyes, which according to the information

of Examples I to 17 are available. They correspond to Z and by the color of the color on cotton of the formula I and are identified in the table by the.

example

OH

I.
Λ

2-HydroxyO, 5-disuirophenyl-! I) the same

on

I. H

I -hydroxy-6-Z-umino-4,8-disulfonaphthyl- (2) the same

Z - RcM uus

2,4,6 irichloropyrimidine

^ -Dichloro-S-chloromelhyl-6-methylpyrimidine

hue

Navy blue Navy blue

13th OH the same 1,644,347 the same 14th Color ion I. the same continuation the same A - OH Z = remainder off Navy blue game 1 -hydroxy-SJ-disulfo- I. the same Navy blue naphlhyl- (2) B - Acrylic acid chloride 20th 1 -hydroxy-o ^ -disulfo- the same 2,4-dichloro-6 - // - hydroxy- Navy blue 21 naphthyl (2) ethylamino-1,3,5-triazine 2-hydroxy-3-Z-amino- 1 -hydroxy- ^ ö ^ -trisulfo- the same Navy blue 22nd 5-sulfophenyl- (l) naphthyl (2) the same the same the same Navy blue 23 the same the same 2,4-dichloro-6- (3'-sulfo- Navy blue 24 phenylamino) -l, 3,5-triazine 2,4-dichloro-6-methoxy- Navy blue 25th 1,3,5-triazine 2,4-dichloro-6-dimethyl- 26th amino-1,3,5-triazine

example

100 parts of the tetrasodium salt of the amino disazo dye of the formula

SO ₃ H

O-Cu O SO ₃ H

SO ₃ H

as obtained in Example 1, when the equivalent amount of 2-aminonaphthalene-4,8-disulfonic acid is used in place of 2-aminonaphthalene-4,6,8-trisulfonic acid, are dissolved in 1500 parts of water at 50 to 60 " and a solution of 40 parts of 2,4 - dichloro - 6 - phenylamino -1,3.5 - triazine - 3 '- sulfonic acid sodium is added. By adding 20% sodium carbonate solution to a pH of 8.0 to 9, 0, the mixture is stirred until there is no more amino dye.After the reaction is complete, the resulting dye is separated off with the aid of sodium chloride, filtered off and dried. It re-dyes cotton and fibers from regenerated cellulose the dyeing method indicated in Example I in navy blue shades of good lightfastness and washfastness.

Claims (2)

Claims: 6s 1. Process for the preparation of water-soluble, copper-containing reactive dyes of the formula O Cu wherein the radical A or the radical B contains a group of the formula - NH-Z and the dye molecule including the group - NH - Z has at least 5 sulfonic acid groups, one of the radicals A and B has an optionally further substituted phenyl radical or an optionally substituted one in the 2-position on the - N = N group bonded naphthyl radical, the other an optionally substituted, in 2-position to the -N = N group bonded naphthyl radical and Z denotes a reactive O group, where the - O atom is in the ortho position to the azo group, thereby gckennzeich- IS η ψ} that the diazo compound from an amine of the formula A-NHj (Π) where w is an ortho-position ssur NR group standing hydroxy or low molecular weight alkoxy group means / with a copper-containing dye of the formula OH / γ \ (IH) HO ₃ SI 1 J- O - Cu - O ^V Y / r N = ~ N B couples and into the copper complex compound You can do this or you can use the diazo compound an amine of the formula NH ₁ (IV) with a dye of the formula (111) and with copper donating agents in the presence of Treated oxidizing agents. 2. Modification of the method according to claim 1, characterized in that a diazo component bearing an acylamino or nitro group is obtained from an amine of the formula (II) or (IV). in which A denotes an acylamino or nitrophenyl or an acylamino or nitronaphthyl radical, or a coupling component bearing an amino, nitro or acylamino group is used and, after coupling or after coppering, the amino, nitro or acylamino group through the group - NH - Z replaced.