DE2842640A1 - REACTIVE DYES - Google Patents

Description

BAYER AKTIENGESELLSCHAFT

5090 Leverkusen, Bayerwerk

Central area

Patents, trademarks and licenses My / kl

Reactive dyes

The present invention relates to reactive dyes of the formula

SO ₂ R ₂

η in which

D = residue of an organic dye,

Y = direct bond or link to an aromatic carbocyclic one or aromatic-heterocyclic carbon atom of the chromophore,

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V-

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= H, alkyl,

R ~ = vinyl, β-halovinyl or -CH ₂ CH ₃ -X where X = leaving group,

η = 1 or 2 and where ring B can contain further substituents.

Suitable alkyl radicals R and R- are, for example, those with 1-4 C atoms, which may be further substituted could be. Suitable bridge members are, for example, -N-alkylene-

CCH _o -h

< ^R 3> 0-2

^(R 3 ⁾ O-2

-N-CO

^(R 3> 0-2

-SO ₀ -NO

^(R 3> 0-2

where the phenyl radicals are preferably in the ρ or m position are linked

Alkylene = c.pC ^ alkylene and R ₃ = SO ₃ H, COOH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy.

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Suitable leaving groups X are, for example, —OSO ₃ H, —OH, —SSO ₃ H, dialkylaraino and quaternary ammonium groups.

Dyes with reactive groups -SO-R- are in the literature i. U. described in large numbers. A summary 'can be found in: Lit: E. Siegel in "The Chemistry of Synthetic Dyes", Vol. VI, "Reactive Dyes", K. Venkatararan. Academic Press, New York and London 1972, S. Iff.

Suitable organic dyes are in particular azo, anthraquinone, phthalocyanine and formazan dyes, especially water-soluble dyes.

Preferred dyes are generally those with η = 1, those with Y = direct bond, those with R and R ₁ = H and those with R2 = vinyl or β-sulfatoethyl.

Preferred dyes are those of the formulas

COOH _ττ

wherein

R ₄ = H, alkyl or aryl, in particular optionally substituted phenyl,

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SO ₃ H ₁ .;

NN -f \ NA R

III

wherein R ₁ - = H, alkyl, alkoxy, acylamino

Metal complexes of dyes of the formula

0.3Ep ₃ S ··> .- ■

- N.

VI

where Rg = H, halogen, -NO ₂ , alkyl

10 The metal atoms are Cu (1: 1 complexes) or Cr and Co (1: 2 complexes) preferred. Cr and Co complexes can

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contain the azo compound of the formula VI once or twice, i.e. they can be constructed symmetrically or asymmetrically with any other ligand groupings be.

SO ₃ H

SO ₃ H ₀ _,

VII

(R ₇ ) oi

SO ₃ H

wherein

RR ₇ = -NA

The condensed rings indicated by strokes represent alternative possible naphthalene systems.

Preferred anthraquinone dyes correspond to the general formula VIII:

wherein R ₈ = H, Ci-C ₄ -alkyl, C ₁ -C ₄ -AlkOXy.

VIII

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Preferred phthalocyanine dyes correspond to the general formula IX

IX

I -as I \ I / 4-r \ \ 0-2

Rg, R ₁₀ = H, C ₁ -C ₄ -AlCyI or together C ₄ -C ₅ -alkylene, optionally interrupted by N or 0,

Pc = residue of a Cu or Ni phthalocyanine and where the total number of substituents ^ .4.

In the formulas II-IX, A stands for radicals of the formula

preferably for those residues in which:

R, R ₁ = H, R ₂ = -OSO ₃ H or -CH = CH ₂ and the ring

B is not further substituted.

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The alkyl, aryl and alkoxy radicals in the formulas I IX can optionally have further substituents. In general, preference is given to the unsubstituted Residues, as well as those with 1-4 carbon atoms in the context of the alkyl and alkoxy radicals.

Of the large number of dyes described by the formulas I-IX, the following groups are whole particularly preferred:

'Vn- Ik. .-COOH

E ₁₁ - E, CH ₃ , Cl

₂ «E ₁ CH ₃ , OCH ₃ , NHCOCH ₃ , NH-CONH ₂

, SO ₃ H, NN - / ⁷ J ^) - NH ₂

NEA

SO ₅ H

XI

XII

XIII XIV

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XV

2-, 3- H, CE ₅ , C ₁ -C ₄ -AlkOXy, acylamino, especially -NIi-COGH ₃ , -NHCOC ₆ H ₆

XVI

O Cu-O SO, H

• NHA

SO ₃ H

SO ₈ H

HO NH ₂

- ΑΛ / Η - N Γ Il J

SO ₅ H ₀ ^ HO ₃ S "^^ - ^ SO ₃ H

XVII

XVIII

SO ₃ H

EN

R ₁₄ = H, C ₁ -C ₄ alkyl

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XIX

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-jr-

Ο NH ₂

XX

(SO ₃ E) _1-3

SO

SO ₂ NH

XXI

NHA COOH _0-1

where A has the meaning given above.

The dyes of these formulas are outstandingly suitable for printing and dyeing textiles made from native and regenerated cellulose as well as natural or synthetic polypeptides.

The dyeings obtainable in high yields with these dyes are distinguished by a high fiber-dye bond stability as well as excellent stability against oxidizing agents such as peroxide or detergents containing chlorine. The ability of the hydrolysis products formed during dyeing or printing to be washed out is excellent.

The formulas given are in each case those of the free acids. The synthesis generally gives

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the salts - especially the alkali salts - which are also used for dyeing.

The new dyes of the general formula I are customary in the synthesis of reactive dyes Manufacturing process accessible. For example, the corresponding dyes of the formula

XXII 1-2

which are known in large numbers from the literature, with 1 or 2 mol of a difluorotriazine of the formula

SO ₂ R ₂

XXIII

Il I '\' /

implemented.

Preferred compounds XXIII are, for example, 2- / 2'-, 3 ¹ - or 4 '- (β-sulfatoethylsulfonyl) -phenylamino7-4,6-difluoro-1,3,5-triazine.

You can also first XXIII with a dye precursor - e.g. a diazo or coupling component - convert and then produce the dye by coupling.

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The reaction with the triazine derivative XXlII takes place at weakly acidic to weakly alkaline pH value and at low temperature (O - 10 ° C). The one in condensation hydrofluoric acid released is reduced by adding dilute alkali hydroxide or carbonate or bicarbonate solution neutralized.

The preparation of dyes of the general formula I can generally be modified. For example Dyes containing amino groups, dye precursors or intermediates first with 2,4,6-trifluoro-1,3,5-triazine implement and then with compounds of the formula

XXIV

condense.

Other conversion reactions of the dyes or their precursors such as metallization reactions, sulphonations or the introduction of acylamino groups can generally be carried out in any stages of the dye syntheses be made.

The synthesis of dyes of the formula I with two reactive radicals A can be carried out completely analogously, with, for example In azo dyes, one reactive radical A is possible in each of the diazonium and coupling components.

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example 1

/ η

81 parts of 4-aminophenyl-.beta.-sulfatoethyl sulfone are suspended in 400 parts of water at pH 4, with 400 parts of ice to -2 to O ^e C and cooled under vigorous agitation with 27 parts by volume of 2,4,6-trifluoro -l, 3,5-triazine added. At the same time, a pH of 3.5 is maintained with 105 parts by volume of saturated sodium hydrogen carbonate solution. After about 3 minutes, no more amine can be detected.
The milk-like suspended condensation product (in the form of the free acid)

O) -SO ₂ -C ₂ H ₄ -OSO ₈ H

In this form it is suitable for reaction with dyes containing amino groups, dye precursors or intermediates.

In game 2 _

19 parts of 1,3-diaminobenzene-6-8ulfonic acid are used in 250 parts Stirred water and dissolved with 40 parts by volume of 20 # soda solution.

This solution is slowly poured into 40 parts of the condensation product described in Example 1 in the form of an aqueous solution

Suspension of ⁰ ° C. The temperature rises to 10-15 ^° C. A pH of 6-7 is maintained with 20% sodium carbonate solution. The reaction product obtained in this way (in the form of the free acid)

HO ₈ SO-H ₄ C ₂ -O ₈

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/ it

becomes after the addition of ice and 7 parts of sodium nitrite with 28 parts Hydrochloric acid diazotized directly.

30 parts by weight of l - ^ "'- methyl-4'-sulfophonyl7-3-carboxypyrazolone- (5) are added to this suspension of the diazonium compound and the coupling is completed by adding about 60 parts by volume of a sodium carbonate solution (20%) After the coupling is complete the separation of the dye is completed by adding 200 parts of potassium chloride or sodium chloride, then is isolated by filtration and dried at 50 ° C. Man contains a yellow powder that dyes or prints cotton in greenish yellow tones.

The prints or dyeings obtained in this way have excellent Wet fastness properties. If one replaces the coupling component l- (2'- Methyl-4'-sulfophenyl) -3-carboxypyrazolone- (5) by equimolar Amounts of the pyrazoles listed in the table below, so

yellow reactive dyes are also obtained.

E.g. acylated diamine Coupling component

3 l, 3-diaminobenzene-6-sulfone- 3-methylpyrazolone- (5) ■ acid

4 "1,3-dimethylpyrazolone- (5)

5 "l-carboxymethyl-3-ynethyl-

pyrazolone- (5)

6 ". 1- (4'-sulfophenyl) -3-c» rboxy-

pyrazolone- (5)

7 "l- (2'-5'-DiBulfophenyl) -3-

methylpyrazoloner

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Ex. Acylated diamine θ

Coupling component

l ^ -Diaminobenzene-ö-sulfonic _acid

1- (2'-Chloro-5'-sulfophenyl-3-methylpyrazolone- (5) 1- (3 '-. sulfophenyl) -3-methyl-5- aminopyrazole

Example 10

The solution of 21 parts of l, 3-diamino-2-methylbenzene-5-sulfonic acid sodium salt in 300 parts of water are added slowly to 40 parts of the condensation product described in Example 1 in the form of an aqueous suspension of 0 ⁰ C. The liberated hydrofluoric acid is neutralized by adding a 20% soda solution dropwise. After the condensation has ended, the reaction product is diazotized directly by adding ice, 7 parts of sodium nitrite and 28 parts of hydrochloric acid at 5-10 ° and then by adding 50 parts by weight of 1- (2'-methyl-4'-sulfophenyl) -3-carboxypyrazolone- (5) and about 80 parts of a 20 #Lgen soda solution to the azo dye of the formula

COOH

HO ₈ SO-S ₄ C ₈ -O ₈ S - ^ _

SO ₃ H

coupled. The separation of the dye is completed by salting out 150 parts of sodium chloride. It is then isolated by filtration and dried at 50-100 *. A yellow powder is obtained which is extremely suitable for printing and dyeing cotton.

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In this example, if you replace the coupling component with the pyrazole derivatives given in Examples 3-9, yellow reactive dyes with very good coloring properties are also obtained.

Example 11

19 parts of 1,4-diaminobenzene-2-sulfonic acid are used as sodium alkali dissolved in 250 parts of water and 40 parts of the in Example 1 product described selectively condensed in aqueous suspension. By adding 30 parts of a 20% soda solution a pH value of 5> 8 - 6 is maintained.

After the condensation has ended, the suspension is by adding Ice, 7 parts of sodium nitrite and 28 parts of hydrochloric acid directly diazo-

animals.

The suspension of the diazonium compound is with a solution of the

Sodium salt of 29 parts of 1- (4'-sulfophenyl) -3-carboxypyrazolone- (5) in 150 parts of water and the coupling by addition of 50 parts of a 20 # soda solution to the end. It is then salted out with 200 parts of potassium chloride, isolated and dried. A yellow powder is obtained that contains cotton in shades of golden yellow. The dye corresponds to the formula »

HO ₃ SO-S ₄ C ₂ -0 ₂ S- / ~

SO ₅ H

Similar shades of color are obtained if, in this example, the ^{1- (4 f} -sulfophenyl) -3-caxboxypyrazolone- (5) is replaced by squinolar amounts of the pyrazoles given in Example 3-9.

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Example 12

The solution of 0.1 mol of the aminoazo dye of the formula prepared by customary methods

SO ₃ H

in 600 parts of water is slowly added to 40 parts of the product described in Example 1, while the pH is kept in the range of 6-8 by adding dilute sodium hydroxide solution or a sodium carbonate solution. When the condensation has ended, it is salted out, isolated and dried. The color of the formula, obtained as a yellow powder

NN - // \ VnH- / ^N

/ VsO ₂ -C ₈ H ₄ -OSO ₃ H

SO ₃ H dyes cotton in lightfast and chlorinefast yellow shades.

If in this example the 2-aminonaphthalene-4,6,8-trisulfonic acid is replaced by 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-3 »6,8-trisulfonic acid, amino - If benzene-2,4-disulfonic acid or iminobenzene-2,5-disulfonic acid is replaced, yellow reactive dyes are also more excellent Preserved light and wet fastness.

Yellow reactive dyes of this type can be obtained in an analogous manner if, in this example, this is the coupling component iniline used by 3-methylaniline, 2-methoxyaniline, 3-

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Acetylaminoaniline, 3-ureidoaniline or is replaced by 2-methoxy-5-oethylaniline.

Example 15

To dissolve the diazonium to be obtained by conventional methods from 0.1 mol of 2-aminonaphthalene-4,6,8-trisulfonic acid Binding is 0.1 mol of the condensation product to be obtained according to Example 2 from 19 parts of 1,3-diaminobenzene-6-sulfonic acid and 40 parts of the product described in Beisp.l given and the coupling carried out by neutralization with a dilute soda solution to the end.

After salting out, filtering and drying, the dye has the formula

SO ₃ H

SO ₂ -C ₂ H ₄ -OSO ₃ H

obtained in the form of a yellow powder. It is ideally suited for dyeing and printing tree-filled In Golden yellow hues.

Example 14

A solution of 24 parts by weight of 2-amino-5-hydroxynaphthalene-7-sulfonic acid as the sodium salt in 200 parts of water is at pH 2Q added to 40 parts of the product described in Ex. With 15-20 · and simultaneous neutralization with dilute sodium hydroxide solution or a 20/6 strength soda solution, the condensation can be completed within an hour with vigorous stirring.

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Lie suspension of the condensation product is with the after customary methods produced suspension of a liazonium compound from 2-naphthylamine-l, 5-disulfonic acid combined and the Coupling ended by adding 10 parts of lithium carbonate guided. Ler orange reactive dye of the formula

-P

HO ₃ S

SO, H

is salted out, isolated and dried. An orange powder is obtained which is used for dyeing and printing cotton the process customary for reactive dyes is eminently suitable.

Will be the product of condensation described in this example from the product prepared according to Example 1 and 2-amino-5-hydroxynaphthalene-7-eulfonic acid by methods known per se with the Diazonium compounds are coupled from the amines listed below, so are also excellent reactive dyes with receive the specified color shades:

Liazonium compound aust

hue

2-aminonaphthalene-1,5 »7-trisulfonic acid · orange

Aniline-2-sulfonic acid orange

l-l-lmino-3-acetylaminobenzene-6-sulfona acid orange

l-Amino-3-triazinylaminobenzene-6-sulfonic acid * orange

l-imino-4-methoxybenzene-2-8ulfonic acid scarlet fever

l-Amino-4-methoxybenzene-2,5-dieulfonic acid scarlet fever

2-aminonaphthalene-3,6,8-triulfonic acid · scarlet fever

l-lmino-4-acylaminobenzene-2-sulfonic acid scarlet fever

l-lmino-4-acylaainobenzene-2,5-dieulfonsäux · scarlet fever

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Example 15

The solution of 32 parts by weight of 1-amino-8-hydroynaphthalene-3,6-disulfonic acid as the sodium salt in 200 parts of water, 40 parts of that prepared according to Example 1 are added with vigorous stirring Product is dripped and the acid released is neutralized by dilute sodium hydroxide solution or soda solution. After about an hour, the condensation has ended under these conditions.

The condensation product obtained in this way is then with the diazonium compound to be obtained by customary methods from 0.1 Moles of aniline-2-sulfonic acid combined and the coupling at pH 7 brought to the end. After salting out, isolating and drying, a dark powder of the dye of the formula is obtained

HN-P ^ -SO ₂ -Cg H ₄ -OSO ₃ H

HO ₃

the Bich dissolves in water with red paint and dyes or prints trees in brilliant red tones.

If, in this example, the diazonium compound from iniline- 2-sulfonic acid is replaced by the equimolar amounts of the diazonium compounds obtainable from the following amines , brilliant 2Q red reactive dyes are also obtained »

aniline

Aniline-2,5-diulfonic acid
4-methylaniline-2-sulfonic acid
4-methoxyaniline-2-sulfonic acid
5 4-methoxyaniline-2, 5-di-sulfonic acid

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AS

3-pyrimidinylamino-aniline-6-sulfonic acid
4-triazinylaminoaniline-2-sulfonic acid
2-aminonaphthalene-1-sulfonic acid
2-aminonaphthalene-1,5-disulfonic acid
2-aminonaphthalene-1,5 »7-trisulfonic acid

Example 16

Condensation is carried out under the conditions given in Example 15 in each case 0.1 mol of the product described in Example 1 and 1-amino-8-hydroxynaphthalene-4 »6-disulfonic acid and the condensation product is coupled by analogous methods with the diazonium compound of aniline-2- sulfonic acid, the dye of the formula is obtained after salting out, isolation and drying

SO ₂ -C ₂ H ₄ -OSO ₃ H

as a dark powder that turns yellowish red in water in water dissolves and is ideal for printing and dyeing cotton in brilliant red shades.

If in this example the diazonium compound is replaced from aniline 2-sulfonic acid by equimolar amounts of the diazonium compound of amines listed in the table in Example 15 are obtained also brilliant red reactive dyes.

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Example 17

The solution of the sodium salt of 32 parts by weight of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 200 parts of water, as stated in Example 15, 40 parts of that in Example 1 given product and condensed at 15-20 °.

The solution of the condensation product is then mixed with the diazonium compound combined from 0.1 mol of 2-aminonaphthalene-4,6,8-trisulfonic acid in 200 parts of water and the addition of alkali Coupling carried out at pH 7.

After coupling has ended, 35 parts by weight of copper sulfate are added to the red dye solution and a mixture of 50 parts of a 30% hydrogen peroxide solution and 130 parts of a 20 % sodium acetate solution is added dropwise _{at 15 ° and pH 4 f 6.} The temperature is kept in the range of 10-15 * by adding approx. 200 g of ice. After the oxidative coppering has ended, the copper complex dye has the formula

- ^ VsO ₂ -C ₂ H ₄ -OSO ₃ H

HO ₃ !

SO ₃ H SO ₃ H

salted, isolated and dried. A dark powder is obtained which dissolves in water with a blue color and is suitable for printing and dyeing cotton in navy blue shades with good lightfastness.

The diazonium compound from 2-naphthylamine-4,6,8-trisulfonic acid can be replaced in this example by the diazonium compounds from the mines in the table below. The oxidative copper plating is carried out in the same way.

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2 B A 2 6 4 Q

Diazonrum compound

hue

Aniline-4-sulfonic acid

Aniline-3,5-disulfonic acid aniline

2-aminonaphthalene-4ι8-disulfonic acid 2-aminonaphthalene-6,8-disulfonic acid 2-aminonaphthalene-1,5,7-trisulfonic acid

violet

violet

Red-violet

blue

blue

blue

Example 18

In the solution obtained by the process described in Example 14 for the preparation of the condensation product from 2-amino-5-hydroxynaphthalene-7-sulfonic acid and the product from Example 1, a suspension of the diazonium compound from 0.1 mol of 2-aminonaphthalene-4,6 , 8-trieulfonic acid is added to 250 parts by volume of water and the coupling is completed by adding 20 parts of sodium bicarbonate. The coupling solution thus obtained is mixed with 250 parts of a 20% strength sodium acetate solution and 500 parts of a 3% strength hydrogen peroxide solution. The oxidative copper plating is then achieved by adding dropwise 250 parts of a 20/6 copper sulfate solution. When the copper plating is complete, the dye becomes of the formula

Ή «

HO ₃

HO ₅ S

SO ₂ -C ₂ H ₄ -OSO ₃ H

salted out with a mixture of 400 parts of sodium chloride and 100 parts of potassium chloride then isolated and dried. A dark powder is obtained which turns violet in water Dye dissolves and dyes cotton in clear blue-violet hues.

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If, in this example, the diazonium compound of 2-aminonaphthalene-4,6,8-trisulfonic acid is replaced by diazonium compounds of the following aromatic amines, violet reactive dyes are also obtained:

Aniline-4-sulfonic acid

Aniline-3-sulfonic acid

Aniline-3,5-disulfonic acid 2-aminonaphthalene-4,8-disulfonic acid 2-aminonaphthalene-6,8-disulfonic acid 1-aminonaphthalene-4 »6-di8ulfonic acid 1-aminonaphthalene-4f7-disulfonic acid 2-aminonaphthalene-3,6,8-trisulfonic acid.

Example 19

0.1 Get the aminoazo compound of the formula

SO, H

HCj ₈ S - (\

which can be obtained by coupling l-aminonaphthalene-4,6-disulfonic acid with 2-acetylamino-5-hydroxynaphthalene-4,8-di8ulphonic acid, followed by oxidative coppering and saponification of the acetylamino group, are dissolved in 1500 parts by volume of water at pH 6.5 - Dissolves and added dropwise to 40 parts of the condensation product described in Example 1, the acid released being neutralized with a soda solution so that a pH of 6.5 is maintained during the condensation time of about 2 hours.

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- * 4 When the reaction is complete, the dye of the formula

E - ^ \ - SO ₂ - C ₂ H ₄ -OSO ₃ H

HO ₃ E ι V N I. fr Λ
H HO ₃ S- - N ^ -Cu ( 3O ₃ H Ό ΓΤ ) SO ₃ H

salted out, isolated and dried at about 50 ° in a vacuum. A dark powder is obtained which dissolves in water with a blue color and dyes cotton in reddish-tinged blue shades.

The same dye can be obtained by coupling the diazonium compound from 1-aminonaphthalene-4,6-disulfonic acid with the condensation product from 2-amino-5-hydroxynaphthalene-4,8-disulfonic acid and the product from Example 1 and then oxidative Copper plating can be obtained.

Dyes similar to cotton in reddish-tinged blue hues color, can be obtained if, in this example, the diazonium compound from l-aminonaphthalene-4,6-disulfonic acid replaced by the following amines:

1-aminonaphthalene-4,7-disulfonic acid

l-aminonaphthalene-4-sulfonic acid

2-aminonaphthalene-6,8-disulfonic acid

2-aminonaphthalene-4,6,8-trisulfonic acid 2-aminonaphthalene-3,6-disulfonic acid
1-amino-8-hydroxynaphthalene-4,6-disulfonic acid.

Example 20

0.1 mole of the 1: 2 chromium complex of the formula

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HO ₃

which can be obtained by coupling diazolated 5-nitro-2-aminophenol bit 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and subsequent conversion into the 1: 2-Cr complex are in 1000 parts of water at pH 7 dissolved and condensed with 80 parts of the difluoro product from Example 1. The acid released is neutralized by adding a dilute soda solution dropwise. When the condensation has ended, the dye is salted out, isolated and dried. It is obtained in the form of a dark powder that dyes or prints cotton in green-tinged gray tones.

Is replaced in this example, the pure chromium complex by «· 1: 1 mixture of the Cr complex and the corresponding co-complex, so obtained mixture a Färbstoff, dyes cotton in neutral, lightfast black or grays, or prints.

Example 21

0.1 mole of the Co complex of the formula

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are dissolved in 800 parts by volume of water at pH 6 and condensed with Θ0 parts of the product from Example 1 with vigorous stirring. The released acid is through Adding a 20 $ solution of soda neutralized. After the condensation has ended, the reactive dye obtained is salted out, isolated and dried. It comes in the form of a dark powder that dissolves in water with a brown color and cotton in colors lightfast brown tones.

Example 22

0.1 mol of the dye obtained by the alkylic coupling of diazotized 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 300 parts of water at 70-80 ° and a pH of 8-9 with 0.1 mole of 1: 1 chromium complex of the dye of 6-nitro-l-diazo-2-hydroxynaphthalene-2-hydroxynaphthalene and 4-8ulfonsäure offset · After a short time has a dark blue solution formed. The 1: 2 Cr mixed complex obtained in this way is acylated with 45 parts of the condensation product from Example 1 at a pH of 6.5-7.5 in about 2 hours. The pH is kept constant by adding a 20 % soda solution dropwise. The reactive dye is salted out with 20 μ6 sodium chloride, isolated and dried. The dye of the formula

EO ₈ p

VsO ₈ -C ₈ H ₄ -OSO ₈ H

HO ₈

SO ₈ H

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dyes cotton in lightfast blue-gray shades. Example 25

0.1 mol of the condensation product of 1,3-diaminobenzene-6-sulfonic acid and the product from Example 1 is how described in Example 2 and diazotized the suspension at pH 2-3 with 0.1 mol of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid coupled. After the coupling has ended, the diazotization suspension from aniline-2,5-disulfonic acid is added to the dark red dye solution. For the second coupling, the pH of the reaction mixture is increased by adding dropwise a 20 # strength soda solution 7-Θ posed. When the coupling is complete, the dye has the formula

SO ₅ H

salted, isolated and dried. It then makes a dark one Powder that dissolves in water with a blue color and dyes cotton in dark blue to black shades.

Example 24

The coupling carried out in a weakly acidic pH range of 0.1 mol the diazonium compound from aniline-2,5-dieulfonic acid with 0.1 hol l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid leads to a dark red solution of the monoazo dye, which at pH 6-7 with 0.1 mol of the diazonium compound from the condensation product of 1,3-diaminobenzene-6-sulfonic acid and the product from Example 1 can be coupled to a dark blue dye. According to JLus-

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salting, isolating and drying drops the dye of the formula

SO ₃ H HO ₃

as a dark powder that dissolves in water with a blue color and cotton in dark blue to black Shades of color.

Example 25

12.6 g of 4-aminophenyl-ß-sulfatoethyl sulfone are in 250 ml Dissolved in water. After cooling the solution to 0-5 ° C., a pH of 4.5 is set. 4.2 ml of cyanuric fluoride are left drop to the solution within 15 minutes and keeps the pH value at 4.0-4.5 with 2N soda solution. The reactive component obtained is added to the suspension in the course of of 30 minutes a neutralized solution of 19.0 g of 1-amino-4- (3'-amino-2'-methylphenylamino) -anthraquinone-2,5'- disulfonic acid was added dropwise in 350 ml of water. The temperature in the reaction solution is kept at 0-5 ° C. and the pH with soda solution to 6.0-6.5. After 2 hours, the temperature is allowed to rise gradually over the course of 15 hours increase to 10. When the condensation is complete, the dye becomes of the formula

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28A2640

-CH ₂ -CH ₂ -OSO ₅ H

salted out of the solution with 10% sodium chloride, filtered off with suction, washed with 10% sodium chloride solution and dried at 45 ° C in a vacuum.

The dye provides strong, blue prints with excellent fastness properties on cotton and rayon.

Example 26

12.6 g of 4-aminophenyl-ß-sulfatoethyl sulfone are in the manner described in Example 25 with 4.2 ml of cyanuric fluoride at pH 4.1-4.5 and 0-5 ° to give 4- (2 ', 4'-difluoro-6'-triazinylamino) -phenyl-ß-sulfatoethylsulfone condensed.

A neutralized solution of 20.0 g of 1-amino-4- (4 ¹ -5 methylamino-phenylamino) -anthraquinone-2,2'-disulfonic acid in 300 ml of water is added dropwise to this reactive component in 20 minutes at such a rate that the temperature adjusts itself to 0-5 ° in the mixture. The pH value is kept at 6.0 - 6.5 with 2N soda solution. After the reaction has ended, the temperature is allowed to rise to 20 °. The dye of the formula obtained is salted

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28A2640 zs

_0Η, -CH ₁ -OSO ₅ H

with 5% sodium chloride, sucks it off, washes the filter cake with 5% sodium chloride solution and
dry it at 45 ° C in a vacuum.

From a long liquor at 40 ° it gives very real blue dyeings to cotton.

Example 27

If, in Example 25, 4-aminophenylß-sulfatoethylsulfone is used instead 12.6 g of 3-amino-ß-sulfatoethyl sulfate and the rest of the procedure is as described there, this gives a dye of the formula

-CH, -CH, -OSO ₅ H

the one on cellulose fabric, which is also strong, blue
Provides prints with very good fastness properties.

Further analogous dyes are obtained if the anthraquinone components listed in the table below are used and reacts reactive components.

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Tabs

Bap.

lnthraquinone component

Reactor component "

hue

28

SO ₃ H SO ₃ H is green.

blue

SO ₂ CH ₂ CHgOSO ₃ H

HO ₃ S

blue

SO ₃ H

HO ₅ S

HH

SO ₃ H SO ₃ H

HH ₂

SO ₃ H

HO ₃ S

HO ₃ S

HO ₃ S

CH ₂ CHg OSO ₃ H

grttnvt.

blue

, CH ₂ CH ₂ OSO ₃ H

blue

CH ₂ CH ₂ OSO ₃ H

greenery

blue

Q-SO _f CH ₁ CH ₄ OSO ₃ H

blue

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BeisDiel 34

14.7 g of i-amino-4- (3 ¹ -amino-phenylamino) -anthraquinone-2,4'-disulfonic acid are dissolved in 250 ml of water at pH 5 and 0-5 °. 2.8 ml of cyanuric fluoride are allowed to drip into the solution of the color component over a period of 5-10 minutes and the pH is kept at 4.2-4.7 with 2N soda solution. The condensation to give the difluorotriazinyl dye has ended after a short further stirring.

9.4 g of 4-aminophenyl-ß-sulfatoethyl sulfone are added to the The solution of the reactive dye component was slowly added while the pH was kept at 5.0-5.6. The pH is then kept at 6.0-6.5 and the temperature is gradually increased over the course of 15 hours increase, after which the condensation has ended. The dye will now develop over the course of 2 hours salted out with 8% potassium chloride. The precipitated dye of the formula is filtered off with suction

[-0H ₁ -CHj-OSO ₃ H HO ₅ S

and washes it with 10% potassium chloride solution until the light runs off. After drying in vacuo at 45 ° a product is obtained with the cellulose fabric in strong shades of blue, which has excellent fastness properties have, can be printed.

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Example 35

If in Example 34 the specified anthraquinone component is replaced by 14.7 g of 1-amino-4- (4'-aminophenylamino) -anthraquinone-2,3'-disulfonic acid and if the rest of the procedure is as described there, one obtains a Dye of the formula

-CH ₁ -CH ₁ -OSO ₅ H

the cellulose fabric dyes in greenish blue tones or prints.

Example 36

13, Og 4-aminophenyl-ß-sulfatoethyl sulfone are dissolved in 260 ml of water. The solution is cooled to 0-5 ° and the pH is adjusted to 4.5. 4.4 ml of cyanuric fluoride are added dropwise over a period of 10 minutes and the pH is kept at 4.0-4.5 with 2N soda solution. A neutralized solution, cooled to 0-5 °, of 19.6 g of 1-amino-4- (6 ^l -aminomethyl-4'-phenylamino) anthraquinone-2,2'-disulfonic acid is added all at once to the reactive component obtained keeps the pH value in the mixture at 7.0 - 7.5. After the condensation has ended, the temperature is adjusted to 20 ° and the resulting dye of the formula

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, -CH ₁ -CH ₁ -OBO ₃ H 'CH ₅

salted out with sodium chloride. The dye crystals obtained are suctioned off, washed with 15% sodium chloride solution and dried at 45 ° in a vacuum.

With the dye obtained, strong, clear, reddish-tinged blue prints can be made on cotton and rayon with excellent fastness properties.

Example 37

If, in Example 36, a neutralized solution is used instead of the anthraquinone component specified there of 20.4 g of 1-amino-4- (4'-methyl-aminomethyl-phenylamino) -anthraquinone-2,2'-disulfonic acid with the condensation product of 13.0 g of 4-aminophenyl-ß-sulfatoethyl sulfone and 4.4 ml of cyanuric fluoride at 0-5 ° and pH 6.5-7.0 um and works on, as described there, this gives a dye of the formula

IH - ^ - SO, -CH ₁ -CH ₁ -OSO ₅ H

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which produces strong blue dyeings on cotton from a long liquor or when printed.

Other dyes are obtained by using the anthraquinone components listed in the table below Reactive components analogously to the information in Examples 36 and 37.

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Example no.

Anthraquinone component Realctivlcoraponente

hue

NH,

SO ₃ H

39

CH ₂ -NH

SO ₃ H

CH ₂ -NH ₂ SO ₅ H

NE ₂

SO ₃ H

CH ₂ -NH ₂

HO ₃ S rotit.blau

CH ₂ CH ₂ OSO ₃ H

reddish blue

^CH 2 ^ch « ^0S0 3 ^h

green.blue

^CH 2 ^CH * ^0S0 3 ^H

rotat.blue

^ VsOj CH ₁ CH ₂ OSO ₃ H

blue

,? SO ₂ CH ₂ CH ₂ OSO ₃ H

^ NH

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Example 43

20.0 g of a dye component of the formula

(SO ₅ H) ₃
Cu-Pc-O)

which was obtained by reacting equimolar amounts of copper phthalocyanine 3,3 ', 3 ", 3"' - tetrasulfochloride and 3-aminoacetanilide, subsequent saponification of the unreacted sulfochloride groups at pH = 10 and 50 ° C and subsequent saponification of the acetylamino group in hot 5% hydrochloric acid, at pH 6 - 7 in 400 ml of water dissolved. The solution is cooled to 0-5 °.

A solution of 4- (2 ', 4'-difluoro-6'-triazinylaminophenyl) -ß-sulfatoethyl sulfone is added dropwise to the solution of the color component, which according to the information in Example 25 from 6.5 g of 4-aminophenyl-ß-sulfatoethylsulfone and 2.0 ml Cyanuric fluoride was produced.

The pH value in the reaction mixture is kept at 6.5 - 7.0, lets the temperature rise gradually to 20 ° C. after 5 hours and, after the reaction has ended, salts the dye with sodium chloride. The product of the formula

. (SO ₅ H) ₃

Cu-Pc-O) ~

^ SO ₁ -ΗΗγΓγ ΒΗγΝ- ^ ΗΗ - ^ - ΒΟ, -CH, -CH ₁ -OSO ₃ H

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is filtered off with suction, washed with sodium chloride solution and dried at 45 ° in a vacuum.

The dye obtained gives strong, turquoise-blue prints with very good fastness properties on cotton.

If, instead of the above phthalocyanine component, the following phthalocyanine components are used, further dyes are obtained with which cotton is used in
can be printed in the specified colors.

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• μ »

E.g. Mr. Phthalocyanine component hue 44 ^ (SO ₃ H) ₃
Cu-Pc- (3)
^v S0, -HH γί ^ turquoise 45 / (SO ₃ H),
Cu-Pc- (3)
^x S0, -HH-CH ₁ -CH, -HH, turquoise 46 ^ (SO ₃ H) ₃
Cu-Pc- (3) ^, turquoise COOH 47 / (SO ₃ H) ₃
Hi-Pc- (3)
^N S0, -ΗΗνί ^ ΝΉΗ, bluish green 4β ^ (SO ₃ H) ₃
Hi-Pc- (3) _
^s S0, -ΗΗ-ζ ^ -ΗΗ, with a tinge of green 49 / (SO ₃ H),
Cu-Po- (5 J-SO ₁ -HH,
^ SO, -HH-CH, -CH, -HH, turquoise 50 (SO ₃ H) ₁
Cu-Pc- (3 J-SO ₁ -IH ₁
^ SO, -HH Y ^ V * H, turquoise 51 / (SO ₃ H),
Cu-Pe- (3) -S0, -HH-CH ₃
SO ₁ -HH γ ^ γ-ΗΗ, turquoise

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2842B40

Example 52

21.2 g of a dye component of the formula

/ (SO ₃ H),

Cu-Pc- (3J-SO ₄ -IH ₁
SO ₂ -IH

are dissolved in 300 ml of water at pH 5. After cooling to 0-5 °, 2.1 ml of cyanuric fluoride are left in 5 10 Add dropwise minutes and keep the pH value at 4.0-4.5 with 2N soda solution. After condensation has ended a neutralized solution of 6.7 g of 4-aminophenyl-ß-sulfatoethyl sulfone is gradually added to the dye solution and keeps the pH at 5.5 - 6.0. After 4 hours, the temperature is allowed to rise slowly to 20 and after the end of the reaction it salts the dye, which is in the form of the free acid of the formula

/ (SO ₅ H) ₁ Cu-Pc-O) -SOj-HH,

^X SO, -ΙΗγ ^ ΙΗγΙ ^ ΙΗ - ^^ - βΟ, -CH, -CH ₁ -OSO ₃ H

corresponds to, with sodium chloride. The precipitated dye is filtered off with suction and the filter cake is washed with sodium chloride solution and the product is dried at 40 ° C. in vacuo.

The dye gives a clear turquoise color to cotton ne prints and dyeings.

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The dye component mentioned in Example 52 is obtained by adding equimolar amounts of copper phthalocyanine-3-tetrasulfochloride and 2,4-diaminobenzenesulfonic acid condensed in an aqueous medium under pH control, the implementation product further with an equimolecular amount of ammonia and 1.5 equivalents of sodium hydroxide solution added and then saponified the remaining sulfochloride groups at pH 10 and 40 °.

Other reactive dyes that print or dye cellulose in the specified nuances are obtained if the phthalocyanine components indicated in the table below with cyanuric fluoride and then with the aminophenyl-ß-sulfatoethyl sulfones as the 2nd reactive component condensed.

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E.g.
No.

55

57

58

Phthalocyanine component a

/ (SO ₃ H) J Cu-Pc- (3) -S0 ₂ NH ₂ ^N SO ₂ -NHn

/ (SO ₃ H) ₃ Cu-Pc- (3)

Cu-Pc- (3) "

SO ₃ H

, (SO ₃ H) ₃

SO ₃ H

Cu-Pc- (3) -S0 ₂ -NHj

Ni-Pc- (3) '

^N SOg-NH

^ SO ₃ H

Ni-Pc- (3) '

'(SO ₃ H) ₃

SO ₃ H

2. Reactive component

H ₂ NY ^ f SO ₂ CH ₂ CH ₂ OSO ₃ H

NH ₂ - ^ 3 ^"S0 2 ^CH 2 ^{CH '0S0} 3 ^H

NHj - ^ v-SO ₂ CH ₂ CH ₂ OSO ₃ H NH, - ^ jVsOj CHg CH ₁ OSO ₃ H

SOjCHgCHgOSO ₃ H

NHg N ^ y SO ₂ CH ₂ CH ₂ OSO ₃ H

hue

turquoise

turquoise

turquoise

turquoise

bluish green

bluish green

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Example 59

14.7 g of i-amino-4- (3'-aminophenylamino) -anthraquinone-2,4'-disulfonic acid are dissolved in 250 ml of water at pH 5 and 0-5 °. 2.8 ml of cyanuric fluoride are left inside from 5-10 minutes to the solution of the color component and keep the pH value with 2N soda solution at 4.2-4.7. To The condensation to the difluorotriazinyl dye is followed by brief stirring completed.

9.4 g of 4-aminophenyl vinyl sulfone are added to the solution added to the reactive dye component while maintaining the pH at 5.0-6.0. Then you hold the pH to 6.0-6.5 and leaves the over the course of 15 hours Gradually increase the temperature to 20, after which the condensation is over. The dye solution will now Salted out with 10% sodium chloride over the course of 2 hours. The precipitated dye of the formula is sucked off away

HO ₃ S

and washes it up with 10% sodium chloride solution to the bright flow. After drying in vacuo at 45 °, a product is obtained with the cellulose fabric in strong shades of blue, which have excellent fastness properties, can be printed.

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284V640

The same dye is obtained if the dye of Example 34 is used for a few hours at pH 9 and 20 ° treated, the splitting off of the ß-sulfato group being followed by chromatography.

Similar dyes can be synthesized if, in Example 59, instead of 4-aminophenylphenylsulfone the following sulfone components are used:

3-aminophenyl vinyl sulfone
2-aminophenyl-ß-chloroethyl sulfone
3-aminophenyl-ß-chloroethyl sulfone
4-aminophenyl-ß-chloroethyl sulfone
4-aminophenyl-ß-bromoethyl sulfone

Example 60

13.0 g of 4-aminophenyl vinyl sulfone are dissolved in 260 ml of water suspended. The suspension is cooled to 0-5 ° and the pH is adjusted to 4.5. Leave within 10 minutes Add 4.4 ml of cyanuric fluoride and keep the pH value 2n soda solution to 4.0-4.5. To the reactive component obtained is added all at once a cooled to 0-5, neutralized solution of 19.6 g of 1-amino-4- (6'-aminomethyl-4'-methyl-phenylamino) -anthraquinone-2,2'-disulfonic acid and keeps the pH in the mixture at 7.0-7.5. When the condensation has ended, the temperature will rise to 20 set and the resulting dye of the formula

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salted out with sodium chloride. The dye crystals obtained are sucked off with 1oX_iger sodium chloride solution washed and dried at 45 ° in vacuo.

With the dye obtained, strong, clear, reddish-tinged blue prints can be made on cotton and rayon with excellent fastness properties.

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Claims (5)

Claims 1. Reactive dyes of the formula wherein SO ₂ R ₂ —Ί1 D = residue of an organic dye, Y = direct bond or link to an aromatic carbocyclic one or aromatic-heterocyclic carbon atom of the chromophore, R, R ₁ = H, alkyl, R ₂ = vinyl, ß-halovinyl or -CH ₂ CH ₃ -X where X = leaving group, η = 1 or 2 and where the ring B can contain further substituents. 2. Colorants of the formulas Le A 19 165 030015 / 03U INSPECTED Ii - K COOH worm = H, alkyl or aryl, in particular optionally substituted phenyl, N-W - / yyV N-A wherein R ₅ = H, alkyl, alkoxy, acylamino EO ₃ SO ₃ H SO ₈ H ₀ -, Metal complexes of dyes of the formula "-A HO ₃ S"*>. ·· Le A 19 165 030015 / 03U wherein Rg = H, halogen, -NO ₂ , alkyl, especially the 1: 1-Cu Complexes and the 1: 2 Cr and 1: 2 Co complexes, SO ₃ H _0-2 HO NF-, SO ₃ H ₀ . ₂ 5 in which = -N-A wherein H _f C ₁ -C ₄ -AlCyI, C ₁ -C ₄ -AlkOXy, 10 0-8 SO ₅ H x- O ₃ H µ -K-A COOH (p 1-2 Le A 19 030016 / 03U wherein R _g , R ₁ = H, C ₁ -C ₄ -Al] CyI or together C ₄ -C ₅ -Al] Cylene, optionally interrupted by N or 0 / Pc = radical of a Cu or Ni phthalocyanine and where the total number of substituents - ==. 4, and where with the substituent meanings given in claim 1 and R ₁ = H or C ₁ -C ₄ AlCyI. 3. Dyes of claims 1 and 2 with R, R ₁ = H, Y = direct bond, R ₂ = -CH ₂ CH ₂ OSO ₃ H or -CH = CH ₂ and not further substituted ring B. 4. Dyes of claims 1-3, wherein D = residue of an azo, anthraquinone, phthalocyanine or formazan dye. Le A 19 165 O30016 / Q3U 5. Use of the dyes of claims 1-4 for dyeing and printing cellulosic materials. Le A 19 165 03001S / 03U