DE1544552B2 - AZO DYES AND THEIR METAL COMPLEX COMPOSITIONS, PROCESS FOR THEIR PRODUCTION AND THEIR USE FOR COLORING - Google Patents

Description

correspond, where D is the radical of a diazo component, which can additionally contain water-solubilizing groups and / or other substituents of the type specified in the description, R is a hydrogen atom or an alkyl radical, η is the number 1 or 2, Z is a grouping of the formula

-SO ₂ -CH = CH ₂ (2)

-SO ₂ -CH ₂ -CH ₂ -X (3)

and X denotes an inorganic or organic radical which can be split off under alkaline conditions, and their metal complex compounds.

2. Process for the preparation of the dyes mentioned and defined in claim 1, characterized in that marked that one

a) Azo components, which in their acidic form of the general formula

HO

N-CO-NH
(SO ₃ H) _n .

35

(4)

correspond and where R, η and Z have the meanings given in claim 1, with the diazonium compounds of aromatic amines of the general formula

40

D-NH ₂

(5)

where D has the meaning given above, couples and optionally the metal-free dyes obtained of the formula (1), provided that this is a metal complex in the radical D in the ortho position to the azo bridge contain substituents capable of conversion directly or through treatment with metal donating agents, if necessary in the presence of an oxidizing agent, converted into their metal complex compounds or that man

b) metal-free azo dyes, which in their acidic form have the general formula

Have given meanings, with isocyanates of the general formula

NH

(SO ₃ H) _n

(6)

applies, where D, R and η are those in claim 1 OCN

wherein Z has the meaning given in claim 1, and, if appropriate, converts the metal-free obtained Dyestuffs of the formula (1), provided that these are the ones mentioned above under a) for metal complex formation Fulfill the established conditions, as stated there, converted into their metal complex compounds or that one

c) in the case of the preparation of metal complex compounds of dyes specified under b) of the formula (1) the metal-free dyes of the formula (6), provided that these are the above under a) for meet the conditions set out in the metal complex formation, initially as specified there in transfers their metal complex compounds and then reacts them with isocyanates of the formula (7), and furthermore with the resulting final dyes of the formula (1) or their metal complex compounds or in the case of the azo components of the formula (4) in which Z represents a grouping of the formula (2), these into one of the Convert formula (3) or, if Z stands for a grouping of the formula (3), the radical X in this Grouping can be replaced by another radical X of the same definition.

3. Use of those mentioned and defined in claim 1 or of those produced according to claim 2 Dyes for dyeing or treating silk, wool, leather, synthetic polyamides and polyurethanes, modified acrylonitrile, regenerated protein and cellulosic materials as well Cotton, linen and rayon rayon.

The subject of patent 12 89 930 is a process for the production of azo dyes which in their acidic form of the general formula

HO N

D-N = N

55

—CO - NH- / ~?

(SO ₃ H) _n

correspond, in which D is the radical of a diazo component which can additionally contain water-solubilizing groups and / or other substituents, R is a hydrogen atom or an alkyl radical, η is the number 1 or 2, Z is a grouping of the formula

or

- SO ₂ - CH = CH ₂ (2)

-SO ₂ -CH ₂ -CH ₂ -X (3)

and X denotes an inorganic or organic radical which can be split off under alkaline conditions, and optionally

of metal complex compounds of such dyes, characterized in that one

a) Azo components, which in their acidic form of the general formula

R Z

HO N - CO - NH

(SO ₃ H) ₁ ,

(4)

correspond and where R, η and Z have the meanings given above, with the diazonium compounds of aromatic amines of the general formula

D-NH ₂

(5)

where D has the meaning given above, couples and optionally the metal-free obtained Dyestuffs of the formula (1), provided they are in the radical D in the ortho position to the azo bridge for metal complex formation contain substituents capable of being converted directly or by conversion, by treatment with metal donating agents, optionally in the presence of an oxidizing agent, into their metal complex compounds convicted or that one

b) metal-free azo dyes, in which in their acidic form the general formula

HO NH

35

(SO ₃ H) _n (6)

comes, where D, R and π have the meanings given above, with isocyanates of the general formula

(7)

in which Z has the meaning given above, and, if appropriate, the metal-free dyestuffs obtained of the formula (1), provided that these are those set out above under a) for metal complex formation Meet conditions, as stated there, converted into their metal complex compounds or that one

c) in the case of the preparation of metal complex compounds of dyes of the formula (1) specified under b), the metal-free dyes of the formula (6), provided they meet the conditions set out above under a) for metal complex formation, first converted into their metal complex compounds as indicated there and then reacting them with isocyanates of the formula (7),
and where the final dyes of the formula (1) or their metal complex compounds or the azo components of the formula (4) in which Z is a group of the formula (2) are converted into a group of the formula (3) or, if Z stands for a grouping of the formula (3), the radical X in this grouping can be replaced by another radical X of the same definition.

In a further embodiment of the inventive concept, it has now been found that valuable new azo dyes can be obtained and their metal complex compounds obtained if, in modification of the method of Main patent azo dyes, which in their acidic form of the general formula

correspond, in which D is the radical of a diazo component which can additionally contain water-solubilizing groups and / or other substituents specified below, R is a hydrogen atom or an alkyl radical, η is the number 1 or 2, Z is a group of the formula

or

- SO ₂ - CH == CH ₂ (2)

-SO ₂ -CH ₂ -CH ₂ -X (3)

and X denotes an inorganic or organic radical which can be split off under alkaline conditions, and their metal complex compounds prepared in such a way that one azo components, which in their acidic form of the general formula

40

N - CO - NH

(SO ₃ H) ,,

correspond and where R, π and Z have the meanings given above, with the diazonium compounds of aromatic amines of the general formula

D-NH ₂

where D has the meaning given above, couples and optionally the metal-free dyes obtained of the formula (1), provided that in the radical D in the ortho position of the azo bridge, this leads to a metal complex formation directly or through a conversion capable substituents contain by treatment with metal-donating agents, if necessary in the presence of an oxidizing agent, into their metal complex compounds convicted or that one

b) metal-free azo dyes, which in their acidic form have the general formula

HO H

D-N = N

applies, where D, R and η are as specified in claim 1

have given meanings, with isocyanates of the general formula

OCN-

in which Z has the meaning given above, and, if appropriate, converts the metal-free dyes obtained of the formula (1), provided that these meet the conditions set out above under a) for the formation of metal complexes meet, as stated there, converted into their metal complex compounds or that one

c) in the case of the preparation of metal complex compounds of dyes specified under b) Formula (1) the metal-free dyestuffs of the formula (6), provided that these are the ones mentioned above under a) for metal complex formation meet the established conditions, initially as stated there in their metal complex compounds transferred and this is then reacted with isocyanates of the formula (7), and furthermore in the case of the final dyes of the formula (1) obtained or their metal complex compounds or in the case of the azo components of the formula (4) in which Z is a grouping of the formula (2), convert this into one of the formula (3) or, if Z is a group of the formula (3), the radical X in this group is replaced by another radical X the same definition can replace.

The use of the dyes produced in this way is dyeing or treating Silk, wool, leather, synthetic polyamides and polyurethanes, modified acrylonitrile, regenerated Protein and cellulosic materials as well as cotton, linen and rayon rayon are in question.

Under the radical D of a diazo component, that of the structure of the azo dyes obtainable according to the process of the general formula (1) is involved, a benzene, naphthalene, azobenzene, azonaphthalene Benzolazonaphthalene, diphenyl or stilbene series are understood.

In the case of the solubilizing groups which contain the said radical D of the diazo component can, they are acidic, water-solubilizing groups such as sulfonic acid or carboxylic acid groups and also to low molecular weight alkyl sulfone groups and also to sulfonic acid amide or carboxamide groups. In addition, additional substituents customary in azo dyes, for example halogen atoms, such as chlorine and bromine atoms, alkyl, alkoxy, acyl, acylamino, Arylamino, hydroxy, nitro, cyano and trifluoromethyl groups and heterocyclic radicals are represented be. These groups can be bonded to any point on the diazo component and possibly overlap Distribute condensed rings.

As inorganic or organic radicals X, which are split off when exposed to alkaline agents are the following: Halogen atoms, such as a chlorine or a bromine atom, an alkyl sulfonic acid ester or aryl sulfonic acid ester group, and also acyloxy groups, such as a Acetoxy group, furthermore a sulfuric acid ester or thiosulfuric acid ester group and a phenoxy group or a dialkylamino group such as a dimethyl or diethylamino group.

The coupling of the azo components of the formula (4) mentioned with diazotized amines according to the process can be carried out by methods known per se, preferably under weakly acidic, neutral or weakly alkaline conditions. Especially when it is carried out in the weakly alkaline range, it is advisable to carry out the coupling at as low a temperature as possible - preferably below ^40.degree. C. - in order to prevent undesired side reactions, in particular the loss of the substituent X or the addition of water

ίο to the double bond of the vinyl sulfone group to Can have consequences.

The above-mentioned diazonium compounds of primary aromatic amines used as starting materials for the method of the present invention use are based on the lying amines by methods known per se, for example by treatment with sodium nitrite in Presence of mineral acids, especially hydrochloric acid, available. The diazotization can also by means of nitrosylsulfuric acid as well as in the presence of u-naphthalenesulfonic acid.

The following can be listed as examples of diazotizable amines which are suitable according to the process:

1-aminobenzene, l-aminobenzene-2- or -3- or - 4 - sulfonic acid, 1-aminobenzene-2,5-disulfonic acid,

1 - amino - 4 - chlorobenzene - 2 - sulfonic acid, 1 - amino-4 - methyl - 5 - chlorobenzene - 2 - sulfonic acid, 1 - amino-4-methylbenzene-2-sulfonic acid, 1-amino-3-trifluoromethylbenzene-6-sulfonic acid, 1-amino-3,4-dichlorobenzene-6-sulfonic acid, 1-amino-4-methoxybenzene-6-sulfonic acid, 1-amino-S-methoxybenzene-o-sulfonic acid, l-Amino-3-methylbenzene-4-sulfonic acid, also o-, m- and p-toluidine, o-anisidine, chlorine and Nitroaniline, l-aminobenzene-3- or -6-carboxylic acid.

1-Amino-3- (2 ', 4'-dichlorotriazinyl-6' -) - aminobenzene-6-sulfonic acid, l-aminonaphthalene-4-, -5-, -6- or -7-sulfonic acid, 2-aminonaphthalene-1-, -4-, -6-, -7- or - 8 - sulfonic acid, 1 - aminonaphthalene - 3,6 - disulfonic acid, 2-aminonaphthalene-l, 5-, -3.6-, -4.8-, -5.7- or -6,8-disulfonic acid, l- (3'- or 4'-aminobenzoyl) -aminobenzene-3-sulfonic acid, 3-aminopyrene-5,8- or -5,10-disulfonic acid, 4-nitro-4'-aminostilbene-2,2'-disulfonic acid and dehydrothiotoluidinsulfonic acids and primary aromatic amines containing azo groups.

for example 4-aminoazobenzene- (l, l ') ~ 2,4-disulfonic acid.

Is the transfer that can be produced according to the process Metal-free azo dyes are intended in their metal complex compounds, so are given as examples for diazotizable amines to be mentioned further:

2 - aminobenzene -1 - carboxylic acid - 4- or - 5 - sulfonic acid, 2 - aminobenzene -1 - carboxylic acid, nitroaminobenzenecarboxylic acid or aminohydroxybenzenes such as 4-methyl-, 4-chloro- or 4-nitro-2-amino-1-hydroxybenzene, 6-acetylamino-, 6-chloro- or 6-nitro-2-amino-1 -hydroxybenzene-4-sulfonic acid, 2-aminol-hydroxybenzene-4- or - 5 - sulfonic acid, 4-nitro-6 - acetylamino - 2 - amino -1 - hydroxybenzene, 4 - nitro-6-chloro-2-amino-1-hydroxybenzene, 4-chloro- or 4-nitro-2-amino -1-hydroxybenzene-6-sulfonic acid, 4,6-dinitro- or 4,6-dichloro-2-amino-1-hydroxybenzene, 2-amino-1-hydroxybenzene-4- or -5-sulfonic acid amide and 3 - amino - 2 - hydroxybenzene carboxylic acid-5-sulfonic acid.

The azo components of the general formula (4) identified above, which are used in the process according to the invention Coupling can optionally also be used in the form of their alkali metal salts, can be carried out in a simple manner

from naphthalene derivatives of the general formula

Ν — Η
- (SO ₃ H) ₁ ,

HO H

in which an acylatable amino group is available, by reaction with isocyanates or carbamic acid derivatives of the formulas

OCN-

S VO-CO-NH- / ^ J (7)

produce, where R, Z and η have the meanings described above.

The isocyanates of the formula (6) and carbamic acid derivatives of the formula (7) used represent new ones Compounds are, in turn, from corresponding arylamines, for example by implementing the Amino group can be obtained with phosgene or by condensation with phenyl chloroformate.

The group of suitable naphthalene derivatives of the formula (5) includes, for example, 2-amino-8 - hydroxynaphthalene - 6 - sulfonic acid, 2 - amino-8 - hydroxynaphthalene - 3,6 - disulfonic acid, 2 - amino-5 - hydroxynaphthalene - 7 - sulfonic acid, 2 - amino-5 - hydroxynaphthalene -1,7 - disulfonic acid, 1 - amino-5 - hydroxynaphthalene - 7 - sulfonic acid, 1 - amino-5 - hydroxynaphthalene - 3,7 - disulfonic acid and am Nitrogen monoalkylated derivatives of these compounds such as. B. 2 - (N - methylamino) - 8 - hydroxynaphthalene-6-sulfonic acid.

From the class of suitable isocyanates and carbamic acid derivatives of the formula (6) and (7), for example, 4-vinylsulfonylphenyl-1-isocyanate, 3-vinylsulfonylphenyl-1-isocyanate, 4- (β - chloroethylsulfonyl) - phenyl - 1 - isocyanate, 3 - (ß - chloroethylsulfonyl) - phenyl - 1 - isocyanate, 2- (ß- chloroethylsulfonyl) - phenyl -1 - isocyanate, also such β - hydroxyethylsulfonyl - phenyl isocyanates, their ^ - positions Hydroxyl group e.g. B. is esterified with methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or acetic acid, 3- or 4 - (/ 3-Phenoxyäthylsulfonyl) -phenyl-1-isocyanate and condensation products of one mole of phenyl chloroformate with one mole of 3- or 4-aminophenyl (jS -sulfatoäthylsulfon) can be used.

Contain the amines, their diazo compounds for the production of metal-free dyes Formula (1) can be used, in o-position to the amino group one for metal complex formation directly or after conversion capable substituents, z. B. a carboxyl group, a hydroxyl group or a Alkoxy group, such as a methoxy group, the resulting metal-free dyes of the formula (1) into their metal complex compounds, for example into their copper, nickel, chromium or cobalt complex compounds - be converted in a manner known per se. For the production of the metal complex compounds the ο, ο'-dihydroxyazo dyes or o-carboxyo'-hydroxy-azo dyes obtainable according to the process implemented with a metal donor. The metal complex compounds mentioned of ο, ο'-dihydroxyazo dyes can optionally also be obtained indirectly by o-Alkoxy-o'-hydroxyazo dyes dealkylating copper, or by using o'-hydroxyazo dyes, the contain a hydrogen atom in the radical D in the o-position to the azo bridge, in weakly acidic solution with Treated with copper salts and an oxidizing agent. Leave the copper complex compounds thus obtained possibly then, z. B. decopper by treating with mineral acids and then with another metal donors into the desired metal complex compounds of o, o'-dihydroxy-azo dyes convict.

According to the method, copper, nickel, chromium or cobalt-donating agents are used as metal donating agents Connections into consideration. For this task you can z. B. use salts of the metals mentioned as Chromium sulfate, cobalt sulfate, cobalt acetate, copper acetate or copper sulfate. However, this can be done also use those metallizing agents which contain the metal bound in a complex, for example complex chromium or cobalt compounds of aliphatic hydroxycarboxylic acids or dicarboxylic acids and chromium complex compounds of aromatic o-hydroxycarboxylic acids, such as. B. salicylic acid, as well as complexes Cobalt or copper compounds of the alkali salts of aliphatic hydroxycarboxylic acids. As examples Aliphatic hydroxycarboxylic acids can include citric acid, lactic acid, and glycolic acid in particular Tartaric acid.

The reaction of the metal-free azo dyes of the general formula (1) with the metal donating agents is advantageously carried out with heat. The procedure is expediently such that the aqueous Metallisierungsgemisch in weakly acidic or neutral range to temperatures of 20-130 ⁰ C, optionally under reflux, or in a closed vessel, heated. If necessary, organic solvents, such as alcohol or dioxane, can be added, or the reaction can be carried out in the presence of other agents which promote complex formation, such as. B. of salts of organic acids.

The metal complex dyes obtainable according to the process can be based on 1 or 2 dye molecules each contain 1 atom of metal in a complex bond. In the presence of the metals chromium or Cobalt, the molar ratio of metal and azo dye is preferably 1: 2, while at Use of copper or nickel releasing agents creates complex compounds in which 1 atom of metal is bound to 1 dye molecule.

The structure of the dyes according to the invention

General formula (1) can furthermore also be achieved by using metal-free azo dyes the general formula

HO H

D-N = N

NH
(SO ₃ H) _n (8)

where D, R and η are those given above

609 540/401

Have meanings and in which an acylatable amino group is available with isocyanates of the formula (6). The required starting materials of the formula (8) can be passed through in a simple manner Coupling of the diazonium compound of any aromatic amine with an azo component of Win formula (5).

According to a special variant of the process described for the production of metal complex compounds of the formula (1), the metallization can already be carried out in an advantageous manner for the starting dyes of formula (8) - provided this is in the o-position to the azo bridge in the radical D for metal complex formation Contain capable substituents - be made according to known methods before the reaction with the isocyanates of the formula (6) is carried out.

The above-described reaction is expediently carried out in such a way that the aqueous solution is stirred vigorously Solution of the metal-free starting dye of the formula (8) containing an acylatable amino group or its metal complex compound if it is weakly alkaline or weakly acidic, but preferably in the case of a neutral reaction with an isocyanate of the formula (6) at relatively low temperatures, expediently between 0 and 50 ° C, offset. The acylation components of the formula (6) can either as such, for example in the form of a powder, optionally with the addition of an emulsifier for Achieving better distribution in the aqueous phase, or dissolved in a suitable organic solvent, such as benzene, toluene, chlorobenzene or acetone, are used.

Another embodiment of the method of the present invention is that the Group Z within the scope of the metal-free azo dyes of the formula (1) obtainable according to the process and their metal complex compounds, or above all the azo components used for their production of formula (4) before coupling, within the limits imposed by the groups of formulas (2) and (3) are mapped out, subject to further reactions. For example, the vinyl sulfone group of formula (2) by reaction with salts of thiosulfuric acid in a weakly acidic aqueous medium in a ß-Thiosulfato-ethylsulfongruppe, which the corresponds to formula (3) above, as well as the substituent X in formula (3) itself can be changed, for example by replacing a halogen atom present in the case of X with a Dialkylamino group or a thiosulfato group as a result of treatment with dialkylamine or with Salts of thiosulfuric acid.

The process products can be isolated in their metal-free form or as complex compounds from the medium in which they were formed by customary methods, for example by salting out with sodium or potassium chloride or by spray-drying the neutralized reaction mixture in the form of an alkali metal salt.
The dyes obtainable according to the invention are compounds which are soluble in water in the form of their alkali salts and which are used for dyeing and printing a wide variety of materials such as silk, wool, leather, synthetic polyamides and polyurethanes, regenerated protein and cellulose materials and, above all, cotton, linen and viscose rayon can be.

The application of the new dyes to cellulosic material is general in accordance with those in the art customary printing and dyeing methods carried out in the presence of acid-binding agents. By dyeing according to the usual dyeing processes from weakly acidic, neutral or weakly alkaline dye solutions You can also use the dyes on wool, silk, regenerated proteins, polyamides and modified acrylonitrile materials be applied. The dyeings and prints are usually characterized by high Color strength and the purity of the shade, good lightfastness and good wetfastness, in particular due to its very good resistance to washing treatments.

If the dyes contain groups capable of forming metal complexes, e.g. B. o-carboxy-o'-hydroxy or ο, ο'-dihydroxy groups and o-hydroxycarboxy groups, such as those in salicylic acid derivatives occur, the metal-free colorations obtained can also be applied to the material to be dyed with metal-releasing agents Funds are treated.

Passage I.

In U.S. Patent No. 3,098,096, inter alia. already similar water-soluble phenylazonaphthyl dyes described, the side chain on the naphthyl radical

—NH-CO

SO, - CH, - CH, - Cl

contain. However, these dyes do not contain a urea bridge between the naphthyl radical and the phenyl radical carrying the / 3-chloroethylsulfonyl group.

In FR-PS 1403 165 are water-soluble phenylazonaphthyl dyes discloses the one grouping of the formula bonded to the naphthyl radical

-NH-CO

N (CH ₃₎ -SO ₂ -CH ₂ -CH ₂ -C 1

exhibit. These dyes therefore also do not have a urea bridge.

DT-PS 10 86 368 relates to water-soluble phenylazonaphthyl dyes, which contain a / ^ - chlorinated propionylamino group on the phenyl radical. These dyes thus differ structurally from the dyes according to the invention described below to an even greater extent, in which there is between the / 3-chloroethyl group and the carbonamide bridge there is no phenyl radical.

In BE-'PS 6 19 785 azo dyes are described which have a side chain of the formula

- N (R ') - CO -CH ₂ -CH ₂ -XR

bound to the azo dye residue. Herein R 'denotes a hydrogen atom or an alkyl radical, R is a hydrocarbon radical and X is a sulfur or oxygen atom. These dyes thus have the reactive side chain characteristic of the dyes according to the invention, bound via the phenylurea radical not on.

In FR-PS 12 18 709, what structurally closest comparable dyes are concerned, water-soluble Phenylazonaphthyl dyes, which are the side chain

- SO ₂ - NH - CH ₂ - CH ₂ - Cl

contain bound to the naphthyl radical via the phenylurea radical, described. These dyes thus do not have the reactive group of the dyes according to the invention.

Passus Il

The dyes according to the invention are distinguished from these known dyes of the formulas

OH

SO ₃ H

SO, -CH ₉ -CH ₇ -Cl

OH

SO ₃ H

SO ₂ -CH ₂ -CH ₂ -Cl

SO ₃ H

OH

SO, H

- SO ₂ -CH ₂ -CH ₂ -Cl

CH,

NH-CO-NH ₂

NH-CO-NH,

13th

14th

when used in equimolar amounts by the formulas (1) and (2) given above by a

a stronger depth of color when dyeing cotton, better wash fastness and peroxide wash fastness

after the exhaust process. Cotton dyes.

The coloring agents according to the invention are also distinguished by the dyes according to the invention

substances compared to the known dyes of the previous 5 known dyes of the formulas

H (XS

HO

NH-CO-NH

HO ₃ S

Tn H C-O CH-i CHi Cl

HO ₃ S -N = N- HO
I. NH-CO-NH 1 NH-CO-NH [OJ HO ₃ S \ y HO ₃ S -N = N- HO Δ /
HO ₃ S \ /

X ₂ V ^ n ₂

H ₃ CN

SO ₂ -CH ₂ -CH ₂ -Cl
in the color strength when dyeing cotton fabric, and the known dyes of the formulas

HO ₃ S

HO ₃ S

HO NH — CO — NH

SO ₃ H

HO NH — CO

N-CH ₃
SO ₂ -CH ₂ -CH ₂ -Cl

N = N

HO, S

HO ₃ S

SO ₃ H NHCONH

N-SO ₂ -CH ₂ -CH ₂ -Cl
CH ₃

in the lightfastness of the cotton dyeings, the dye properties of the invention

think about it. contemporary dyes to be considered surprising

With regard to the structural similarity with and are mainly due to the new and unique

The advantageous reactive coupling components mentioned are determined for the known dyes.

example 1

a) 23.9 parts by weight of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved in 200 parts of water with the addition of 33% by weight sodium hydroxide solution at pH 6-7. Is added under very intensive stirring a 40-50 ⁰ C warm solution of 35 parts by weight of 3 - (// - chloroethylsulfonyl) -phenyl-1-isocyanate (m.p .: 83 ° C) in 100 parts by weight of chlorobenzene and leaves at pH 6, Stir 5-7.0 until the starting product has reacted. It is diluted with 200 parts of water over the course of the first hour. The chlorobenzene is then distilled off in vacuo and the residue in the flask is made up to 500 parts by volume with water.

b) 30.3 parts by weight of 2-aminonaphthalene-1,5-disulfonic acid are completely diazotized in 200 parts of water and 30 parts by weight of 37% by weight hydrochloric acid at 0 to 5 ° C. with 20 parts by volume of 5N sodium nitrite solution. The excess acid is neutralized with saturated soda solution to Congo neutral and the solution from a) is added. Allowing the coupling without further cooling at pH 6.5-7.0 come to an end, diluted with water to 1700 parts by volume, clarified by the addition of 10 parts by weight of diatomaceous earth at 35-4O ⁰ C and the dyestuff is salted out by introducing sodium chloride. It is filtered, washed with dilute sodium chloride solution and drying the filter residue in a vacuum oven at 6O ⁰ C. The dyestuff, in the form of the free acid has the formula

HO, S

OH

HO ₃ S

N = N

HO ₃ S

NH-CO-NH

SO, -CH, -CH, -Cl

as a dark red powder.

When dyeing from aqueous alkaline solutions on cotton, the product gives strong, clear, yellow-tinged red Dyeings of good lightfastness and good wetfastness.

Example 2

a) 31.9 parts by weight of 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved in 200 parts of water with the addition of sodium hydroxide solution at pH 6.5-7.0. In this solution carries with good stirring at 0-10 ⁰ C 25 parts by weight of 4-vinylsulfonyl-phenyl-1-isocyanate (m.p .: 6I ⁰ C) as a powder, a, is stirred for 10 hours, diluted with 200 parts of water and clarifies in 40-50 ° C. 100 parts by weight of potassium chloride are added to the filtrate; the excreted product of the formula

KO, S

NH-CO-NH- ν

SO ₁ K

SO ₂ -CH = CH ₂

is separated from the mother liquor and washed with dilute potassium chloride solution.

b) 6.85 parts by weight of 1-aminobenzene-2-carboxylic acid are in 100 parts of water and 12 parts by weight of 37 weight percent hydrochloric acid at 0-5 ° C with an aqueous solution of 3.45 parts by weight

COOH

HO, S

SO, H

Sodium nitrite diazotized. Then one carries 30.2 parts by weight of the coupling component indicated under a) Formula and adjusts to pH 6.5-7.0 with sodium bicarbonate. After the coupling is completed Sodium chloride entered and the deposited dye, which in the form of the free acid has the formula

—CO — NH

// V SO ₂ -CH = CH,

comes, sharply suctioned and dried. A dark red powder is obtained.

c) 2 parts by weight of the dye powder obtained according to b) are dissolved in 15 parts of water and 5 parts by weight of urea, 1 part by weight Sodium bicarbonate and 27 parts by weight of a 4% by weight alginate thickener to form a printing paste stirred. This is printed on cotton, the print is dried at 60 ° C. and steamed for 5 minutes 98 to 103 ° C, washes with hot water and soap solution, rinses with water and dries. You get one strong, clear, red print with good to very good wet fastness properties.

Example 3

a) 31.9 parts by weight of 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 200 parts of water with the addition of sodium hydroxide solution. Is added under vigorous stirring, a solution of 35 parts by weight of 4 - (ß - chloroethylsulfonyl) - phenyl -1 - isocyanate (m.p .: 100 ⁰ C) in 90 parts by weight of benzene to

609 540/401

and let stir overnight at pH 6.5-7.0. then the benzene is distilled off.

b) 22.2 parts by weight of 6-chloro-4-aminotoluene-3-sulfonic acid are diazotized in 100 parts of water and 20 parts by weight 37gewichtsprozentiger hydrochloric acid at 0 to 5 ⁰ C with 17.3 parts by weight 40gewichtsprozentiger sodium nitrite solution. Then you give that

To the reaction mixture from a) and make it neutral with saturated soda solution. The mixture is left at 0-10 ⁰ C and pH 6-7 until the end of the clutch stir up with water to 3000 parts by volume to, clears and the dyestuff is salted with sodium chloride. The precipitated dye, which in the form of the free acid has the formula

H, C

NH-CO-NH

SO ₃ H V-SO ₂ -CH ₂ -CH ₂ -Cl

corresponds, is suctioned off with dilute sodium chloride solution washed and dried.

It gives strong, clear, red dyeings and prints on cotton with good wet fastness properties.

Example 4

a) 23.9 parts by weight of 2-amino-8-hydroxynaphthalene-6-sulfonic acid are dissolved neutrally in 200 parts of water with the addition of sodium hydroxide solution. Under good Stirring is added to this solution at pH 6.5-7.0 and room temperature 40 parts by weight of 2 - (/ 3-chloroethylsulfonyl) phenyl-1-isocyanate (an oily compound). In the course of the next hour, it is diluted with 750 parts of water. After 10 hours you clear up and the filtrate is mixed with 250 parts by weight of sodium chloride. The excreted product will separated from the mother liquor and washed with dilute aqueous sodium chloride solution.

b) 17.3 parts by weight of l-aminobenzene-4-sulfonic acid are diazotized in 100 parts of water and 20 parts by weight of 37% by weight hydrochloric acid with the aqueous solution of 6.9 parts by weight of sodium nitrite at 0-5 ° C, the excess acid is blunted with soda solution and then the solution of the product obtained under a) was added in 1000 parts of water. The mixture is left at pH 6.5-7.0 and clutching 0-10 ⁰ C to an end and is salted with potassium chloride from. The precipitated dye, which in the form of the free acid has the formula

OH

HO ₃ S

NH-CO-NH

HO ₃ S

SO ₇ -CH ₂ -CH ₂ -CI

corresponds, is filtered off with suction, washed with dilute potassium chloride solution and ^{dried at 50 0} C in a vacuum drying cabinet. The dye gives a scarlet fade when printed on cotton.

In the following table there are more according to the invention available azo dyes explained, which are given according to those given in Examples 1 to 4 Methods by coupling the azo components given in column I with the diazonium salts of the amines listed in column II and the cotton by the direct dyeing method or by the pad dyeing process as well as the printing process in the nuances mentioned in column III to dye.

No. I.

Azo component

II
Diazo component

III.
Shade a. Bw.

NHCONH

SO ₂ CH = CH ₂

HO ₃ S

HO ₃ S

O-NH ₂
SO ₃ H

orange

HO ₃ S

NHCONH

SO ₂ -CH ₂ CH ₂ Cl

SO ₃ H

orange

19th

continuation

No. ι

Azo component

NHCONH

SO ₂ CH = CH,

OH

/ π

HO ₃ S

NHCONH

SO ₂ CH ₂ CH ₂ Cl

5 the same.

OH

HO ₃ S

NHCONH

SO ₂ CH ₂ CH ₂ Cl

7 the same.

8 the same.

HO

AV

NHCONH

HO ₃ S

10 the same.

11 the same.

12 the same.

SO ₂ CH ₂ CH ₂ CI 20

11th SO ₃ H
Λ> J Diazo component A. SO ₃ H Y HO ₃ S A. τ HO ₃ S

IH

Shade a. Bw.

Scarlet fever

orange

HO ₃ S

NH,

Scarlet fever

HO ₃ S
HO ₃ S

</ V- _N = _N _ <f V-NH ₂ ruby red

SO ₃ H

CH ₁

SO ₃ H

HO ₃ S

HO ₃ S

violet

violet

OCH ₃

NH ₂ violet

HO ₃ S

SO ₃ H CH ₃

NH ₂
SO ₃ H

Scarlet fever

-NH

HO ₃ S

SO ₃ H

NH ₂ violet

f V-MH - ^ / V-NH ₂ purple

21

continuation

No. I.

Azo component 22

I!
Diazo component

IU

Shade a. Bw.

OH

HO ₃ S

NHCONH

SO ₃ H

NH ₂ reddish orange

SO ₃ H

14 the same

OH

NHCONH

SO, --CH = CH,

16 the same

OH

π ι i

HO, S NHCONH

OH

HO ₃ S SO ₃ H

NHCONH HO ₃ S, 1 V

SO ₂ -CH = CH ₂

SO ₂ CH ₂ CHXl

OH OH

SO ₃ H SO ₂ CH ₂ CH ₂ Cl

HO ₃ S

Ν — CO — NH

SO ₂ CH ₂ CHXl

OH

HO ₃ S

NH-CO-NH

SO ₂ -CH ₂ -CH ₂ -Cl

HO ₃ S SO ₃ H

SO ₃ H
\ ~ / - NH ₂

H ₃ CO

NH,

SO ₃ H

NH,

SO ₁ H

NH,

CH,
SO ₃ H

NH ₂

/ γν \ Ä /

NH,

HO ₃ S

Red

orange

Scarlet fever

orange

Scarlet fever

Red

orange

Red

Example 5

253 parts by weight of 1-aminobenzene-2,5-disulfonic acid are diazotized in 1000 parts of water and 240 parts by weight of 37 weight percent hydrochloric acid at 0 to 5 "C with 172.5 parts by weight of 40 weight percent sodium nitrite solution gives 281 parts by weight of 2-acetylamino - 5 - hydroxynaphthalene - 7 - sulfonic acid and 2000 parts of water and adjusts to pH 6.5 with soda 7.0 After the coupling has ended, 940 parts by weight of 33 percent strength by weight sodium hydroxide solution are added, boils under reflux for 4 hours, adjusts to pH 6 with 37 weight percent hydrochloric acid to 7 and allowed to cool to room temperature. A solution at 40 ° C. is added with vigorous stirring of 500 parts by weight of 3 - (/? - chloroethylsulfonyl) -phenyl-1-isocyanate in 1200 parts by weight of chlorobenzene and allowed to stir for 12 hours. One distills now the chlorobenzene is removed under vacuum, diluted with 15,000 parts of water, clears at 40-50 ° C and salts the dye, which in the form of the free acid has the formula

HO ₃ S

OH

HO ₃ S

N = N

HO ₃ S

NH-CO-NH

comes with sodium chloride. The precipitated dye is filtered off with suction with dilute sodium chloride solution washed and dried. The product gives when dyeing and printing on cotton brilliant, strong orange tones of very good lightfastness and good washfastness.

Example 6

a) 23.9 parts by weight of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are in 200 parts of water with the addition of 33 weight percent sodium hydroxide solution in a neutral solution transferred. One leaves under good

OH

SO ₂ CH ₂ CH ₂ Cl

Stir a solution of 30 parts by weight of 3-vinylsulfonyl-phenyl-1-isocyanate (Melting point: 46 ° C.) in 60 parts by weight of acetone and the mixture is stirred at pH 6.5 to 7.0 until the starting product is consumed.

It is heated to 70-75 ° C, at this temperature 26 parts by weight of sodium-30 containing water of crystallization. thiosulfate and holds by adding dropwise Acetic acid pH 5.8-6.3. The mixture is stirred for a further 3 hours at 70-75 ° C and pH 5.8-6.3, diluted with water to 1000 parts by volume and clears at 30-40 ° C. By adding sodium chloride, the coupling component becomes the formula

NaO ₃ S

NH-CO-NH

salted out. The precipitated product is filtered off with suction and washed with sodium chloride solution.

b) 17.3 parts by weight of 1-aminobenzene-3-sulfonic acid are at 0-5 ° C in 150 parts of water and 20 parts by weight 37 weight percent hydrochloric acid with 17.3 parts by weight 40 weight percent sodium

OH

SO ₂ -CH ₂ -CH ₂ -S-SO ₃ Na

diazotized nitrite solution. The excess acid is neutralized with saturated soda solution, which is included a) The moist product obtained is added and the coupling is allowed to come to an end at 0-10 ° C. and pH 6.5-7.0. Of the resulting dye, which in the form of the free acid has the formula

SO ₃ H

N = N

HO ₃ S

NH-CO-NH

comes, is salted out with sodium chloride, suction filtered, washed with dilute sodium chloride solution and dried. The product gives on tree-SO ₂ -CH ₂ -CH ₂ -S-SO ₃ H

want clear, strong orange dyeings and prints of good lightfastness and good wet fastness properties.

009 540/401

Example 7

a) 60.4 parts by weight of the coupling component of the formula given under Example 2 a) are stirred

in 350 parts of water, adds 14 parts by weight of diethylamine and sodium hydroxide solution to pH 10.5-11.0 and stir for 4 hours. Salt with sodium chloride out, sucks the precipitated compound, which in the form of the free acid has the formula

NH-CO-NH - / "X-SO ₂ - CH ₂ -CH ₂ -N (C ₂ Hs) ₂

HCXS

SO ₃ H

corresponds, from and washes with dilute sodium nitrite solution 15 diazotized and then with the under a)

chloride solution after.

b) 17.3 parts by weight of 1-aminobenzene-4-sulfonic acid in 100 parts of water and 15 parts by weight of 37 weight percent hydrochloric acid are mixed with 17.3 parts by weight of 40 weight percent sodium obtained moist product at 0-5 ° C. It provides with saturated sodium carbonate solution to pH 6.5-7.0 and leaves at 0-10 ⁰ C coupling to an end. Then you salt the dye, which in the form of the free acid has the formula

HO ₃ S

NH-CO-NH SO ₂ CH ₂ CH ₂ -N (C ₂ H ₅ ) Ij

HO ₃ S

SO ₃ H

corresponds to, with sodium chloride, sucks off, washed with dilute sodium chloride solution and dries at 60 ° C in a vacuum drying cabinet.

In the presence of soda or caustic soda, the product produces clear, yellow-tinged red on cotton Prints of good washfastness.

Example 8

a) 31.9 parts by weight of 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 150 parts of water with the addition of sodium hydroxide solution. 45 parts by weight of 3 - (/ S-phenoxyethylsulfonyl) phenyl-1-isocyanate (melting point 87 ° C.) are sprinkled in as a powder and the mixture is stirred overnight at room temperature and pH 6-7. It is then diluted with 700 parts of water, filtered and the filtrate is treated with potassium chloride. The precipitated compound is filtered off with suction and washed with dilute potassium chloride solution.
b) 22.2 parts by weight of 6-chloro-4-aminotoluene-3-sulfonic acid are diazotized in 100 parts of water and 20 parts by weight of 37% by weight hydrochloric acid at 0 to 5 ° C. with 17.3 parts by weight of 40% by weight sodium nitrite solution. The moist product obtained under a) is added, neutralized with soda solution and allowed to couple to completion at pH 6.5-7.0. The dye that has the formula in the form of the free acid

SO ₃ H

OH

N = N

H ₃ CI HO ₃ S
Cl

NH-CO-NH

SO ₃ H

corresponds, is salted out with sodium chloride, filtered off with suction, washed with dilute sodium chloride solution and dried. On cotton it gives scarlet dyeings and prints of good quality Wet fastness properties.

Example 9

a) 319 parts by weight of 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid become neutral in 1500 parts of water with the addition of 33% strength by weight sodium hydroxide solution solved. A solution of 350 parts by weight at 40 ° C. is added with vigorous stirring 3 - (/? - Acetatoethylsulfonyl) -phenyl- 1-isocyanate (viscous Substance) in 650 parts by weight of chlorobenzene and leaves at pH 6-7 and room temperature Continue stirring until there is practically no starting product left. During the first hour a total of 1000 parts of water are gradually added. Finally, by vacuum distillation the chlorobenzene removed.

b) 303 parts by weight of 2-aminonaphthalene-1,5-disulfonic acid in 1000 parts of water, 1000 parts by weight Ice and 100 parts by weight of 37% by weight hydrochloric acid are diazotized at 0-5 ° C. with 173 parts by weight of 40% by weight sodium nitrite solution. The excess acid is truncated with soda, and the chlorobenzene-free solution from a) is added and adjusted to pH 6.5-7.0 with saturated soda solution and held. After the coupling is completed

27 28

diluted with 7000 parts of water and clarified, and sodium chloride is added to the filtrate. The retired Dye which, in the form of the free acid, has the formula

SO ₃ H

OH

N = N I NH-CO-NH

HO ₃ S

HO ₃ S

SO ₃ H

SO ₂ CH ₂ CH ₂ O-CO-CH ₃

comes, is filtered off, washed with dilute sodium chloride solution and dried.

The product gives clear red dyeings and prints with good wet fastness properties on cotton.

Example 10

a) 478 parts by weight of 4-aminophenyl - /? - sulfatoethyl sulfone are dissolved neutrally in 3400 parts of water with the addition of sodium bicarbonate. In this solution

H ₂ C-

CH ₂

OSO ₃ Na

and washes with sodium chloride solution.

b) 239 parts by weight of 2-amino-5-hydroxynaphthalene-7-sulfonic acid become neutral in 3000 parts of water with the addition of 33 percent strength by weight sodium hydroxide solution solved. The mixture is then carried at 50-60 ° C. with stirring the moist product obtained under a) within 3 hours while maintaining the mixture by dropping in saturated soda solution at pH 6.8-7.2. The mixture is left at pH 6.8-7.2 for a further 5 hours and stir 50-60 ° C and then to room temperature 340 parts by weight of phenyl chloroformate are left with stirring drop in and hold by simultaneously dropping in saturated soda solution pH 6.0-7.0 upright. If a sample of the reaction mixture after treatment with hydrochloric acid and sodium nitrite with an alkaline solution of 2-hydroxynaphthalene-3,6-disulfonic acid none There is more color reaction, the reaction is over.

The mixture is stirred for 2 hours, drawn at O -1O ⁰ C the precipitated compound of the formula

NH-CO — O-

cooling down.

c) 303 parts by weight of 2-aminonaphthalene-1,5-disulfonic acid are described as in Example 9 b) diazotized. Then you add the solution obtained in the present example under b) and put through Addition of saturated soda solution to pH 6.5-7.0.

When the coupling is complete, the mixture is made up to 12,000 parts by volume with water, and the filtrate is clarified mixed with potassium chloride. The precipitated dye, which in the form of the free acid has the formula

SO ₃ H

HO ₃ S

NH-CO-NH- -SO ₂ -CH ₉ -CH ₇ -O-SO ₁₁ H

comes, is filtered off, washed with potassium chloride solution and dried. He sums up on cotton strong, clear orange dyeings and prints with good wet fastness properties.

Example 11

a) 23.9 parts by weight of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are in 200 parts of water with the addition of sodium hydroxide solution in a neutral solution

OH

and the solution of 30 parts by weight of 3-O-chloroethylsulfonyl) phenyl-1-isocyanate in 60 parts by weight of chlorobenzene is added with vigorous stirring. The mixture is stirred for 5 hours at pH 6-7, diluted with 100 parts of water and then the chlorobenzene is removed by vacuum distillation. Now it is diluted with 500 parts of water, clarified at 25-30 ⁰ C and the filtrate is mixed with sodium chloride. The excreted compound of the formula

NaO ₃ S

NH-CO-NH

SO ₂ -CH ₂ -CH ₂ -Cl

is separated from the mother liquor by filtration or decantation and washed with sodium chloride solution washed.

b) 18.9 parts by weight of 2-amino-1-hydroxybenzoI-4-sulfonic acid are in 200 parts of water, 200 parts by weight of ice and 25 parts by weight of 37 weight percent Hydrochloric acid at 0-5 ° C with 17.3 parts by weight of 40 weight percent sodium nitrite solution diazotized. The moist product obtained under a) is entered, mixed with 20 parts by weight of pyridine,

adjusts to pH 6.5-7.0 with saturated soda solution and lets ^{stir at 35-40 0} C for about 20 hours. Sodium chloride is then added, the precipitated product is sharply suctioned off and the filter residue is mixed with 1000 parts of water. 25 parts by weight are one containing water of crystallization of copper sulfate to, represents with sodium carbonate solution to pH 5.0-5.5 and stirred for 4 hours at 50-60 ⁰ C. Then, it is salted out with sodium chloride. The dye that is used in

ίο the free acid form the formula

NH-CO-NH

SO ₃ H

CHt CHt Cl

corresponds, is filtered off, washed with sodium chloride solution and dried. He dyes on cotton a real and lightfast bluish red.

Example 12

13.7 parts by weight of l-aminobenzene-2-carboxylic acid are diazotized in 200 parts of water and 25 parts by weight of 37% by weight hydrochloric acid at 0-5 ° C. with 17.3 parts by weight of 40% by weight sodium nitrite solution and then with 50.7 parts by weight of the coupling component given in Example 11 a) Formula offset. It is washed with saturated sodium carbonate solution to pH 6.5-7.0 and the mixture is stirred at 0-10 ⁰ C until the end of the coupling. 25 parts by weight of chrome alum are then added and the mixture is kept for 8 hours at pH 5-6 and 95 ° C. with stirring. It is clarified hot and the chromium complex dye is salted, which gives the formula in a metal-free acidic form

NH-CO-NH

SO ₂ -CH ₂ -CH ₂ -Cl

corresponds to, with sodium chloride. It is filtered off with suction, washed with sodium chloride solution and dried.

The product provides brown dyeings and prints on cotton.

Example 13

18.9 parts by weight of 2 - amino - 1 - hydroxybenzene-4-sulfonic acid are diazotized 37gewichtsprozentiger hydrochloric acid at 0 to 5 ⁰ C with 17.3 parts by weight 40prozentiger solution of sodium nitrite in 150 parts of water and 25 parts by weight. The excess acid is truncated with saturated sodium carbonate solution until the reaction is congone-neutral and the diazonium salt is then added, with stirring, to a cold solution of 23.9 parts by weight of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in 150 parts of water and 30 parts by weight of 33% by weight sodium hydroxide solution. When the coupling has ended, the pH is adjusted using hydrochloric acid. 4-5 and salted out with sodium chloride. The precipitated dye is sharply suctioned off and mixed with 500 parts of water. 14 parts by weight of cobalt sulfate containing water of crystallization are added, the pH is adjusted to 5.5-6.0 with soda solution and the mixture is stirred at room temperature for 3 hours. A clear solution forms. The solution of 30 parts by weight of 3- (β -chloroethylsulfonyl) -phenyl-1-isocyanate in 70 parts by weight of chlorobenzene is added with thorough stirring and the mixture is stirred overnight. The chlorobenzene will

distilled off under vacuum and the residue on the flask made up to 800 parts by volume with water. One clarifies at 40 ° C and salts the cobalt complex dye, which in metal-free acidic form has the formula

OH OH

N = N

HO, S

SO ₃ H

corresponds to, with sodium chloride. The precipitated product is filtered off with suction with sodium chloride solution washed and dried. On cotton it provides prints with a bluish brown tinge of good lightfastness.

Example 14

30.3 parts by weight of 2-aminonaphthalene-6,8-disulfonic acid are added to 200 parts of water and 30 parts by weight of 37% by weight hydrochloric acid at 0-5 ° C 17.3 parts by weight of 40 weight percent sodium nitrite solution diazotized. Then 50.7 parts by weight of the coupling component of the example lla) given formula and represents with saturated

Cu

HO, S

NH-CO-NH

HO ₁ S

HO ₃ S

corresponds, is suctioned off with dilute sodium chloride solution washed and dried.

The product gives strong violet dyeings and prints of good lightfastness on cotton and good wet fastness properties.

At game 15

a) 47.8 parts by weight of 1-amino-5-hydroxynaphthalene-7-sulfonic acid are dissolved in 400 parts of water with the addition of sodium hydroxide solution at pH 6-7. Is added, with rapid stirring a 40-45 ⁰ C warm

OH

NaO ₃ S

SO ₂ -CH ₂ -CH ₂ -Cl

aqueous soda solution to pH 6.5-7.0. Keeping this pH range at 0-10 ⁰ C until the end of the coupling. Sodium chloride is then added, the dye which has separated out is filtered off with suction and the moist filter residue is stirred with 2000 parts of water. Now is added to 45 parts by weight copper sulfate containing water of crystallization as well as 75 parts by weight of crystal-water-containing sodium acetate, is stirred for 30 minutes and then added dropwise 5.0-5.2 35gewichtsprozentiger within 2 hours 50 parts by weight hydrogen peroxide solution at 20-25 ⁰ C and pH. The mixture is left to stir overnight and salted out with sodium chloride. The precipitated dye,, 25 which in the form of the free acid has the formula

NH-CO-NH

SO ₂ CH ₂ CH ₂ Cl

Solution of 60 parts by weight of 3 - (/ S-chloroethylsulfonyl) phenyl-1-isocyanate in 135 parts by weight of chlorobenzene. After 30 minutes, the mixture is diluted with 500 parts of water and allowed to stir overnight. The chlorobenzene is then distilled off in vacuo and the residue in the flask is made up to 8000 parts by volume with water. Add 10 parts by weight of activated carbon to, heated to 80-90 ⁰ C and filtered hot. The filtrate is mixed with 2000 parts by weight of sodium chloride and, after cooling to room temperature, the precipitated coupling component of the formula

suctioned off and washed with dilute sodium chloride solution.

b) 40.6 parts by weight of 2-aminoanisole-5-sulfonic acid in 300 parts of water and 40 parts by weight SO, -CH, -CH, -Cl

37 weight percent hydrochloric acid at 0-5 ° C with 34.6 parts by weight of 40 weight percent sodium nitrite solution diazotized. 114 parts by weight are added the coupling component specified under a)

609 540/401

Formula added, the with saturated aqueous sodium carbonate solution and neutral pH 6.5-7.0 and 0-10 leaves at ⁰ C, the clutch come to an end. It is salted out with sodium chloride and the precipitated dye of the formula is filtered off with suction

OCH,

OH

NaO ₃ S

NH-CO-NH

off, washed with dilute sodium chloride solution and dried at 6O ⁰ C in a vacuum drying cabinet.

The product gives strong red dyeings and prints with good wet fastness properties on cotton.

c) 74.3 parts by weight of the fiber-reactive azo color substance of the formula given under b) are in 400 parts of water were stirred. 32 parts by weight of glacial acetic acid and 48.5 parts by weight of water of crystallization are added Sodium acetate and 43 parts by weight of copper sulfate containing water of crystallization and heated for about 5 hours under reflux to boiling until no more non-metallized dye is contained in the chromatogram. The mixture is then allowed to cool to room temperature and potassium chloride is added. The retired Dye which, in the form of the free acid, has the formula

HO ₃ S

NH-CO-NH

SO ₂ -CH ₂ -CH ₂ -Cl

corresponds, is filtered off, washed with aqueous potassium chloride solution and dried.

The product provides violet dyeings and prints on cotton which have good or very good fastness properties.

Claims (1)

Patent claims: 1. Azo dyes, which in their acidic form of the general formula HO H D-N = N (1)