DE2037256A1 - Water-soluble metal complex disazo dyes and process for their preparation - Google Patents

Description

FARBWERKE HOECHST AG formerly Master Lucius & Brüning

File number: - HOE 70 / F

(Main) -Hochst, July 24, 1970 Dr Mü / B

Frankfurt

Water-soluble metal complex disazo dyes and processes for their preparation,

The present invention relates to new, water-soluble l: l copper, 1: 2 chromium and l ^ cobalt complex disazo dyes used in the metal-free form of the general formula (1)

A-N = N-K-N = N-B-X (1)

correspond, where A is the remainder of a diazo component of Benzene or naphthalene series is in the o-position to the azo group carries a hydroxy or carboxy group capable of forming metal complexes, K the remainder of the 1,3-dihydroxybenzene, B one substituted by one or two sulfonic acid groups Benzene radical, and X a grouping of the formula (2)

C CF ₂

l ²

NH - CO - CH - CH - CH - C - R ¹ (2)

R "

Or 3)

109886/1576

Ii I ²

- NH - CO - CH - CH - C - C - R ¹

■ I

R ¹¹

mean in which R 'represents a hydrogen atom or an alkyl group, R "represents a hydrogen atom or an alkyl or phenyl group, Y and Y ^{1 represent} fluorine or chlorine atoms, and processes for their preparation.

The new metal complex disazo dyes of the above general formula (1) can be prepared by

a) the monoazo dye, which in metal-free form of the general formula (4) · .. ·

A-N = N-K (4)

corresponds, in which A and K have the meanings given above, before or after the conversion into the l: l-copper, 1: 2 chromium or 1: 2 cobalt complex with a diazotized arylamine of the general formula (5)

H ₂ N - B - X (5)

where B and X have the meanings given above, couples and optionally metallizes the disazo dye obtained, or

b) the amino disazo dye of the general formula (6) ANNKN = NB - NH ₂ (6) ,

in which A, K and B have the meanings given above , before or after the conversion into the l: l-copper, 1: 2-chromium

10 98 86/16 76

ύ -

or 1: 2 cobalt complex compound with an acid halide of

(7)

Formula (7) Υ «- T
C -
I. = CH - Z-CO-CH = ■ ^CF 2 I ι
CH-C - R ¹
R "

or (8)

C-CF ₉

Il I- ²

Z-CO- CH = CH- CCR ¹ (8)

I R "

in which R ¹ , R ", Y and Y ^{1 have} the meanings given above, and Z is a chlorine or bromine atom, acylated and the disazo dye obtained is optionally metallized, or

c) the monoazo dye of the general formula (9)

K-N-N-B-X (9)

wherein K, B and X have the meanings given above, with a diazotized arylamine A of the above Meaning couples and metallized the disazo dye obtained.

The for producing the novel metallized bisazo dyes diazo component A used one of the above groups of the formulas (2) or (3) and / or customary in azo dyes may have substituents such as halogen atoms such as chlorine or bromine atoms _r alkyl, nitro , Alkoxy, alkylamino, arylamino, carboxylic acid, acylamino and / or especially sulfonic acid groups. In addition, the dye molecule can contain broad reactive groups, such as

10 98Of) / 1 5.76.- -.

for example mono- or dihalogenotriazinylaiainogruppen, di- or Trihalogenpyrimidy! Amino groups, also esterified with sulfuric acid Hydroxyalkylsulphonamide or hydroxyalkylsulphone groups, furthermore haloacylamino, acrylamino, urethane, haloalkyl, Epoxy and isothiocyanate groups.

1.3-dihydroxy-benzene (resorcinol) is a divalent azo component, which couples in the 2.4 or 4.6 position to disazo dyes. The first coupling generally takes place in the 4 position. When coupling to the disazo dye in the 4.6 position, positionally identical products are obtained, while the coupling in the 2,4-position with diazonium salts of different aromatic Amines can lead to positionally isomeric disazo dyes, the differ in their properties, for example in color, ^ divorce.

The acylation according to process variant (b) can be carried out in purely aqueous, aqueous-organic or organic medium in the presence of acidic agents Medium between about 0 ° and 80 ° C at pH values between about 4 and about 10 take place. When working in aqueous or Aqueous-organic medium can be used as acid-binding agents, for example, hydroxides, carbonates or hydrogen carbonates Metals of the first to third groups of the periodic table, preferably the sodium compounds, are used. In the implementation In an organic medium, acid-binding agents can preferably be tertiary organic bases, such as dimethylaniline, Pyridine or picolines can be used.

For the preparation of the metal complex disazo dyes according to the invention the metal-free mono- or disazo dyes metallized by methods known per se. Copper, chromium or cobalt-releasing agents are used for metallization, preferably Salts such as copper acetate, copper carbonate, copper sulfate, cobalt acetate, cobalt sulfate or chromium chlorides or -sulphates. It is also possible to use metal donors which contain the metal bound in a complex, such as, for example complex chromium or cobalt compounds of aliphatic oxycarbon ~ acids or dicarboxylic acids and chromium complex compounds more aromatic o-Oxycarboxylic acids, such as salicylic acid, and complexes . Cobalt or copper compounds of the alkali salts are more aliphatic

1 0 9 8 8 ß / 1.5 7 6

■ - 5 -

Oxycarboxylic acids. The metallization can also be done in two stages take place so that the metal that entered the complex first is exchanged for another of the metals mentioned.

The ones used to make the new metal complex — disazo dyes Phenylenediaminesulfonic acids used in the form of the acyl compounds are obtained in a known manner. For example, the 1,4-diamino-benzene-2,5-disulfonic acid is sulfonated by 1,4-phenylenediamine with fuming sulfuric acid at 140 ° C (DRP 47 426, Frdl. 2, 312).

The novel dyes are suitable for dyeing and printing the most diverse materials such as leather, silk, wool, synthetic polyamide and polyurethane fiber materials, regenerated protein and cellulose fiber materials, such as INS i particular of cotton, linen and viscose. The new dyes are used in accordance with the dyeing and printing processes that are generally customary in the art.

The new dyes are particularly valuable as reactive dyes for dyeing cellulosic! Textile material. For this purpose, these dyes are applied to the cellulose textile material, for example after direct dyeing from a long liquor, by padding or in a printing paste, in conjunction with a treatment with an acid-binding agent, for example sodium hydroxide, sodium carbonate or bicarbonate, sodium metasilicate or trisodium phosphate . The acid-binding agent λ can be applied before, during or after the application of the dye. The dyes are fixed at ordinary temperature or by heating, for example by steaming. For dyeing cellulose fibers, the dyes are preferably used in the form of their aqueous solution, which can optionally contain inorganic salts such as sodium sulfate or sodium chloride. Further dyeing auxiliaries can be added to the dye solutions, such as thickeners, for example alginate, tragacanth or methyl cellulose, or surface-active compounds or substances that bind the migration of the dyes, as well as auxiliaries which improve the solubility and fixation of the dyes, such as urea or methylacetamide.

109086/1576

The dyeings obtainable on cellulose fibers with the water-soluble azo dyes of the type ¹¹ described are generally distinguished by the purity of their hues, good levelness and high dyeing power. In connection with a treatment with an acid-binding agent, strong color tones with good build-up are achieved on cellulose textiles, which have good to very good fastnesses to washing treatments and the action of light.

example 1

18.9 parts by weight of 2-aminophenol-4-sulfanic acid are known in Way diazotized. The diazo solution: is neutralized with sodium hydroxide solution and a solution of 11 parts by weight is added 1,3-dihydroxy-benzene and 50 parts by weight of calcium hydroxide and Add 10 parts by volume of 33% sodium hydroxide solution. After finished The coupling is acidified with 130 parts by volume of concentrated hydrochloric acid, salted out with sodium chloride and filtered off. The monoazo dye obtained is IGOO parts by volume Stirred water and neutralized the suspension with sodium hydroxide solution. After heating to 65 ° C., 12.4 parts by weight of copper carbonate are added and the mixture is stirred for 2 hours at 65 ° C., during which the pH value of 6.7 is maintained with sodium hydroxide solution or 2 normal hydrochloric acid. Then filtered the solution of the copper complex monoazo dye and allowed to cool.

26.8 parts by weight of 1,4-diarainobenzene-2,5-disulfonic acid become in 600 parts by volume of water by adding sodium hydroxide solution dissolved at pH 6. 24.2 parts by weight of β- (2.2.3.3-tetrafluoro-4-methyl-cyclobutyl) acrylic acid chloride are added dropwise with stirring over the course of 1 hour and holds the during the acylation by adding sodium carbonate pH 6 upright. It is stirred for 1 to 2 hours. After neutralization, the solution becomes 20 parts by volume 5 normal sodium nitrite solution are added and added dropwise to a mixture of 300 parts by weight of ice, 200 parts by volume Added water and 30 parts by volume of concentrated hydrochloric acid.

10 9 8 8 6/157 6 ^Bm

After the pH has been set, 4 is then added to the diazo solution with sodium carbonate the above solution of the copper complex monoazo dye and couples with the addition of sodium carbonate at pH 7.5. After the coupling is complete, acidification is also carried out Acetic acid up to pH 5.5. The obtained copper complex disazo dye is salted out with sodium chloride, filtered off and dried at 60 C under vacuum. The dye found in Form of the free acid of the formula

-Cu F F

0 ^H0 3S II

^υ 'FC CF

ι ι

NH-CO-CH-CH-CH-CH-CIU

corresponds to, delivers in the presence of alkaline compounds brown prints and dyeings on cellulose fiber fabric of good light and wet fastness properties.

Example 2

18.9 parts by weight of 2-aminophenol-4-sulfonic acid are known in Way diazotized. A solution of 11 parts by weight of 1,3-dihydroxybenzene is added to the neutralized diazo solution 50 parts by weight of calcium hydroxide and 10 parts by volume of 33% sodium hydroxide solution. When the coupling is complete, 130 parts by volume are used concentrated hydrochloric acid and acidified with sodium j Salted out chloride. The filtered monoazo dye becomes 1000 Stirring parts by volume of water. After neutralization with sodium hydroxide solution, 14 parts by weight of crystalline are added. Cobalt sulfate and a mixture of 2.5 parts by volume of 30% strength hydrogen peroxide and 7.5 parts by volume of water are added and provided a pH value of 5.5 with sodium hydroxide solution. The reaction solution is stirred for 1 hour at 60 ° C, the pH value ' 5.5 is maintained with sodium hydroxide solution and then let cool down, '

109886/1576

26.8 parts by weight of 1,4-diamino-benzene-2,5-disulfonic acid
in the manner described in Example 1 with 24.2 parts by weight of β- (2.2.3.3 ~ tetrafluoro-4-methyl-cyclobutyl) acrylic acid chloride
acylated and then diazotized. The diazo solution is adjusted to pH 3.5 with sodium carbonate, the above-mentioned solution of the cobalt complex monoazo dye is added and the coupling is carried out with the addition of sodium carbonate at pH 7.5. After the coupling has ended, the mixture is acidified with acetic acid to pH 5.5, salted out with a mixture of sodium and potassium chloride and filtered off. The cobalt complex disazo dye obtained is dried at 60 ° C. under vacuum. The 'dye, in the form of the free acid of the formula

HO ₃ S

N = N \ v /> - NH-CO-CH = CH-CH-CH -. CH,

SO ₃ H

CV - CV

i 2 T 2

H-CO-CH = CH-CH-CH-CH

corresponds, results in the presence of alkaline reacting
Connections on cotton fabric, brown prints and dyeings
of good wet fastness properties.

109 8 86/1576

Example 3

25 parts by weight of l-diazo-2-naphthol-4-sulfonic acid are in 1000 parts by volume of water suspended. After neutralization with sodium hydroxide solution, 11 parts by weight of 1,3-dihydroxy are added benzene and 50 parts by weight calcium hydroxide and 10 parts by volume 33% sodium hydroxide solution is added and stirring is continued. After finished The coupling is acidified with 130 parts by volume of concentrated hydrochloric acid, salted out with sodium chloride and filtered off. The isolated monoazo dye is suspended in 750 parts by volume Water, neutralized with sodium hydroxide solution and 13.3 parts by weight of crystalline. Chromium (III) chloride and 30 parts by weight of crystalline. Sodium sulfate too. It will be at 100 ° C for 5 hours stirred and then cooled.

26.8 parts by weight of 1,4-diamino ~ benzene-2,5-disulfonic acid are in in the manner described in Example 1 with 24.2 parts by weight of β- (2.2.3.3-tetrafluoro-4-methyl-cyclobutyl-acrylic acid chloride acylated and then diazotized. The hydrochloric acid diazo solution if blunted with sodium carbonate (pH 4), the above-mentioned solution of the chromium complex monoazo dye is added ' and couples with the addition of sodium carbonate at pH 7.5. After the coupling has ended, the mixture is acidified with acetic acid up to pH 5.5, salted out with sodium chloride, filtered off and dries at 60 ° C under vacuum. The obtained chromium complex disazo dye, that in the form of the free acid of the formula

HO ₃ S-

CF ₉ -CF ₉ , 2.2

NH-CO-CH = CH-CH -CH-CH,

HOoS

NH-CO-CH = CH

₉ -CF ^, 2.2

-CH -CH-

CH,

10988S / 15 76

corresponds, gives gray prints and dyeings of good wet fastness properties on cotton fabric in the presence of alkaline agents.

Example 4

36 parts by weight of the monoazo dye, which is in the form of the free Acid of the formula

OH

■ N = N-

are converted into the cobalt complex in the manner described in Example 2.

18.8 parts by weight of 1,4-diamino-benzene-2-sulfonic acid v / earth in 750 parts by volume of water suspended. After neutralizing with sodium hydroxide solution, the mixture is left for 3 hours 24.2 parts by weight of β- (2.2.3.3-tetrafluoro-4-methyl-cyclobutyl) acrylic acid chloride add dropwise and maintain the pH value 6 with sodium carbonate during the acylation. The mixture is then stirred and neutralized the solution with sodium carbonate solution, add 20 parts by volume of 5 normal sodium nitrite solution and leave the solution dropwise flow to a mixture of 300 parts by weight of ice, 100 parts by volume of water and 30 parts by volume of concentrated hydrochloric acid. After adjusting the pH to 3.5 with sodium carbonate, the above-mentioned solution of des is then added to the diazo suspension obtained Cobalt complex monoazo dye and couples with addition of sodium carbonate at pH 7.5. After coupling has ended, the mixture is filtered and acidified with acetic acid up to pH 5.5. Of the The cobalt complex disazo dye obtained is salted out with sodium chloride, filtered off and dried at 60 ° C. under vacuum. The dye in the form of the free acid of the formula

109886/1576

-XJ-

HO ₃ S

N = N - <\ /) - NH-CO-CH = CH-CH -CII-CH,

J,

I -

-Cl? 2 ι

CF ₉ CF _0, 2.2

NH-CO-CH = CH-CH -CH-CH,

, delivers alkaline in the presence of cotton fabrics reacting compounds brown prints and dyeings with good wet fastness properties.

The dyes in the following table can be used in a similar way, as described in the previous examples and deliver when applied to cellulose fibers in Presence of alkaline agents, prints and dyeings of similarly good fastness properties.

ORIGINAL INSPECTED

109886/1576

Bex- 1st diazo component game

2, diazo component

Metal hue

6-Xitro-2-aminophenol-4-sulfonic acid

₉ 2

-NH-CO-CH = CH-CH -CH-CH,

l-diazo-2-naphthol ~ 4-sulfonic acid

2-Aniino-5-sulfo-benzoic acid

2-Ä! Nino-4-acetaminophenol-6-sulfonic acid

2-amino-phenol-4 ~ - sulfonic acid

likewise

likewise

likewise

• CF,

II

NH-CO-CH = CH-C - CH,

Co

Cu

• Co

Cu

Brown

gray-violet

yellow-brown

Brown

Brown

ro ο co

Bfei> - I. Diazo component game __ ^^

2 »Diazo component

Metal hue

10 2-Amxno-phenol-4 ~ -sulfone

acid

^H0 3f

SH-CO-CH = CH-CH -CH
i

CF _rt ~ CF,

SO ₃ H

oraun

IX 6-chloro-2-aminophenol-4-sulfonic acid

NH-CO-CH = CH-CH-CH

Cu

Brown

12th

6-nitro-2-aminophenol-4-sulfonic acid

Γ2-Γ2

: -C0-CH = CH-CH -CH ₀

SO ₃ H

Co

Brown

Example 1. Diazo components game ^

2. Diazo components

Metal hue

6-nitro-2-aniino-

phenol-4-sulfonic acid

HO ₃ S ^H 2 ^N - {\ ff

ϊ ¹

CF - CF _r I i -

-NH-CO-CH = CH-CH-CH _r

Co

Brown

14th

.es it-

2-Ami no-phenol-4 sulfonic acid

HO ₃ S

CF_ CF ₀ , 2 j 2

NH-CO-CH = CK-CH-CH-CH.

Cu 'brown

«· * 15,

2-ARii no-phen oil-4-sailfonic acid

H ₂ N HO ₃ S

-NH-CO-CH = CH-CH - CH - CH,

- CF

Cu brown

2i-amino-phenol-4-sulfonic acid

H ₂ N-HO ₃ S-

NH-CO-CH = CH - CH - CH -

CF ₂ -CF ₂

Co.. Brown

Example 17 ΟΠΟΠΟΓΓ

Z U 7 Z b

23.4 parts by weight of 6-nitro-2-aminophenol-4-sulfonic acid diazotized in a known manner. 11 parts by weight of 1,3-dihydroxybenzene are added to the weakly hydrochloric acid (pH 4) diazo solution couples with the addition of sodium carbonate at a pH value between 6.5 and 7.0. After the coupling has ended, it is acidified with hydrochloric acid, axially salted with sodium chloride and the monoazo dye filtered off.

26.8 parts by weight of 1,4-diamino-benzene-2. 5-disulfonic acid are acylated in the manner described in Example 1 with 24.2 parts by weight of β- (2.2.3.3-tetrafluoro-4-methyl-cyclohutyl) -acrylic acid chloride and then diazotized. The hydrochloric acid diazo solution to set with sodium carbonate to pH 3.5, outputs to (the above-mentioned monoazo dye and coupling at pH 7. After coupling is acidified with acetic acid (pH 5.5), the disazo dye is salted The dye is then stirred in 2000 parts by volume of water, the suspension is heated to 60 ° C., a solution of 25 parts by weight of crystallized copper sulfate is added and the pH is adjusted to 5 _f 5 with sodium hydrogen carbonate stirred for a long time at 60 ° C. and the stated pH value and then admixed with acetic acid (pH 5). After cooling, it is salted out with sodium chloride, filtered off and dried under vacuum at 60 ° C. The dye obtained is in the form of the free acid the formula *

Cu. ™

CF ₉ -CF ₉

I ² J ²

- N = N ~ <v, V-NH-CO-CH-CH-CH-CH-CH ₁ -OH ^{XV / f}

corresponds to, delivers in the presence of alkaline compounds brown prints and dyeings of good wet fastness properties on cotton fabric.

109886/1576 BATH ORIGINAL

Example 18

26.8 parts by weight of 1,4-diamino-benzene-2, 5-disulphonic acid are mixed with 24.2 parts by weight of β "(2", 2.3, 8-tetrafixior-4-methyl -cyclobutyl) -srylic acid chloride aeylated and then diazotized. The hydrochloric acid diazo solution to set with sodium carbonate to pH 3, a, are 11 parts by weight of 1.3-dihydroxy-benzene, and coupling to the addition of sodium carbonate at a pH between 6.0 and 6.5. Then acetic acid is added (pH 5), salted out with sodium chloride and the monoazo dye is filtered off «

21.7 parts by weight of 2-amino ~ 5-sulfobenzoesäuro are known in Way diazotj.ert. The diazo suspension is provided with Sodium carbonate to pH 4, add the above-mentioned monoazo dye and couple with the addition of sodium carbonate at pH 7. After the coupling is complete, it is acidified with hydrochloric acid, salted out with sodium chloride and the disaao dye is filtered off, The filter residue is stirred in 2000 volume parts of water, neutralized with sodium carbonate solution and heated to 60 C. Then a solution of 25 parts by weight of crystallized Küpfersuliat is added and the pH is adjusted with sodium hydrogen carbonate 5.5 a. Ils is for 1 hour at 60 ° C and the specified pH value stirred, after cooling it is salted out with sodium chloride, filtered off and the copper complex disazo dye at 60 ° C dried under vacuum. The dye, in the form of the free acid of the formula

Cu ^.

N-N

OTI-CO-CH = CH-CH-Cli-CIL

SO ₃ H

corresponds to, in the presence of alkaline agents on Gellulosofasergewebo gives brown prints and dyeings of good Wet fastness properties.

109BB6 / 1S7ß · H:

23 parts by weight of 3-amino-acetylaminobenzene-4-sulfonic acid diazotized in a known manner. After the free acid has been blunted (pH 5) with sodium carbonate, 11 parts by weight of 1,3-dihydroxybenzene are added and couples with the addition of sodium carbonate at a pH between 6.0 and 6.5. When the coupling is complete, press Salt out sodium chloride and filter off. The monoaza dye obtained is stirred. in 1000 parts by volume of water and neutralizes the suspension with sodium hydroxide solution. 55 parts by weight of sodium hydroxide are added and the mixture is stirred for cleavage of the acetylamino group for 1 hour at 100 ° C. After cooling, the mixture is acidified by the dropwise addition of concentrated hydrochloric acid and the precipitated amino-monoazo dye is filtered off away. The filter residue is dissolved neutrally in 500 parts by volume of water. To this is added in a known manner from 21.7 Parts by weight of 2-amino-5-sulfo-benzoic acid obtained diazo suspension and couples with the addition of sodium carbonate at pH 7.5. After the coupling is complete, the acetic acid is used pH 6 adjusted. 29 parts by weight of β- (2.2.3. 3-tetrafluoro-4-methyl-cyclobutyl) acrylic acid chloride are then added over the course of 3 hours drop by drop, keeping the pH at 6 with sodium carbonate, and stirring. the neutralized and filtered solution of the disazo dye is mixed with a solution of 25 parts by weight of crystallized Copper sulphate, after adjusting the pH to 5.5 with sodium carbonate is stirred for 1 hour at 60 ° C while maintaining the specified pH with sodium hydrogen carbonate. After cooling, it is salted out with a mixture of potassium and sodium chloride, filtered off and the Copper complex disazo dye dried at 60 C under vacuum. The dye in the form of the free acid of the formula

109886/1576

Cu

C.0

-N = N-

HO

N = N HO ₃ S

CF-CF

NII-Co-CH = CII-CH

- CH-CIL

corresponds to, delivers in the presence of alkaline compounds brown prints and dyeings of good wet fastness properties on cotton fabric.

109886/1576

Claims (1)

PATENT PRESS 9 ΓΠ 7? RR 1) Water-soluble 1: 1 copper, 1: 2 ~ chromium and 1: 2 cobalt complex disazo dyes, those in the metal-free form of the general Formula 1) A-N = N-K-N = N-B-X (1) correspond, where A is the remainder of a diazo component of Benzene or naphthalene series, which is in o ~ position to the azo group carries a hydroxy or carboxy group capable of forming metal complexes, K the remainder of 1,3-dihydroxybenzene, B one substituted by one or two sulfoic acid groups Benzene radical, and X a grouping of the formula (2) C-CF _n y ι. -NH - CO - CH = CH -CII-CR ¹ (2) Or 3) C-CF ₀ HI ² -NH-CO-CH-CH-C - C - R '(3) R " mean in which R 'a hydrogen atom or an alkyl group, R "a hydrogen atom or an alkyl or phenyl group., Y and Y ^{1 may represent} fluorine or chlorine atoms. 2) Water-soluble 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex disazo dyes, those in the metal-free form of the general Shape] AN = NKNNB-NH-CO-OH-CH-CH -CII-CH ₃ " _1MAY 1ü9i ?? & / 1576 .. BAD ORtGiNAU in which A, K and B have the meanings given in claim 1 to have. 3) dye of the formula ^H0 3 ^S , - N = N - N = N OH NII-CO-CH = CH-CH - CH-CH, SO ₃ H SO ₃ H 4) dye of the formula SO ₃ H N = N HO ₃ S f2 ~ ^CF 2 .NH-CO-CH = CH-CH-CH-CIL .0 SO ₃ H Co N = N OH NH-CO-.CH = CH-CH-CH-CH - CH- ( SO ₃ H SO ₃ H 0 9, ß; 8, ß ./, 1.5,76 ... ■ .-,: - "5) Dye your Förhiel 20372BÖ -ff % —NNi f ² ~ f T NH-CO-CH = CIi-CH - CiI-CH, • i "" ~ "~ CF, NH-CO-CH = CII-CH - • J ) FariDstoff dbiForiiiei HO ₃ S - N = N CF ₂ -CF ₂ NH-CO-CH = CH-CH - CH-CH, Dye of formula HO ₃ S L "TZ" ol ^{N =} \ _ι -CF, ; -icb-CH = CH-b - ORIGINAL· 8) dye of the foriÜei SO ₃ H «INSPECTED 9) Process for making water-soluble l: l copper, 1: 2 chromium and 1: 2 cobalt complex disazo dyes used in the metal-free form of the general formula (1) A-N-N-K- N = N-B-X (1) correspond, where A stands for the rust of a diazo component of the benzene or naphthalene series, which is in o-position to the azo group Hydi'oxy or carboxy group capable of forming metal complexes carries, K the remainder of the 1,3-dihydroxybenzene, B one by one or two sulfonic acid groups substituted benzene radical, and X a grouping of the formula (2) Y
Y'-G CF ₀ ι ι - NII - CO - CH = CH - CH - C - R ¹ R "or (3) C-CF ₂ Il Γ -CC-R ' - NH - CO - CH = CH - C - C - R '(3) R " mean, in which R * is a hydrogen atom or an alkyl group, R "is a hydrogen atom or an alkyl or phenyl group, Y and Y 'represent fluorine or chlorine atom, characterized in that that he a) the monoazo dye, which is in the metal-free form of the general Formula (4) A-N = N-K (4) 10 9.88 G / 1 57.6 .. corresponds, in which A and K have the meanings given above, before or after the conversion into the l: l-copper, 1: 2 chromium or 1: 2 cobalt complex with a diazotized arylamine of the general formula (5) H ₂ N - B - X (5) wherein B and X have the meanings given above, couples, and optionally metallized the disazo dye obtained, or
b) the amino-disazo dye of the general formula (6) AN = NKN = NB- NH ₂ (6) in which A, K and B have the meanings given above, before or after the conversion into the 1: 1 copper, 1: 2 chromium or 1: 2 cobalt complex compound with an acid halide of the formula (7) YY ¹ -C CF ₀ I I Z-CO-CH-CH-CH-CR ¹ (7) R "or (8) Y ι C CF ₀ II I ² Z - CO - CH = CH - C - C - R '(8) R " 109886/1576 ■ - 25 ■ - in which R ', R ", Y and Y ^{1 have} the meanings given above and Z denotes a chlorine or bromine atom, acylated and the disazo dye obtained optionally metallized, or c) the monoazo dye of the general formula (9) K-N = N-B-X (9) in which K, B and X have the meanings given above, with a diazotized arylamine A of the above Meaning couples and metallized the disazo dye obtained. 10) Use of the dyes mentioned in claim 1 for dyeing and printing of native or regenerated cellulose fibers, wool, silk or polyamide fibers. 11) Leather or fiber materials made from native or regenerated Cellulose fibers, wool, silk, polyamide fibers, polyurethane fibers or regenerated protein fibers which have been dyed or printed with the dyes mentioned in claim 1. 10 9886/1576