DE1544505C3 - Reactive dyes and processes for their production and use - Google Patents

Description

F_ γ

where F is a radical of the azo, anthraquinones, phthalocyanine or nitro dye series, X represents an amino or amide group and Y represents a removable, reactive sulfonyl substituent stands and the remaining hydrogen atom of the thiazole residue by a low molecular weight alkyl or phenyl radical can be substituted.

2. Process for the preparation of reactive dyes by introducing an optionally by a low molecular weight alkyl or phenyl radical of the formula

-N

C-Y

in which Y denotes a radical which can be split off as a negative ion, in dyes containing amino or amide groups or dye precursors of the azo, anthraquinone, phthalocyanine or nitro dye series, which contain a reactive hydrogen atom on the amine or amide nitrogen, mediating Implementation of the dyes or dye precursors mentioned in a manner known per se with. Compounds of the general formula

Il

C-Y

in which Z denotes an anionically removable radical or a group containing such a radical, Y has the meaning given above, and converting any dye precursors used in a manner known per se into the desired reactive dyes, characterized in that that the reaction with such, if necessary, by a low molecular weight alkyl or phenyl radical-substituted thiazole compounds of the last-mentioned formula in which Y represents a removable, reactive sulfonyl substituent.

3. Process for dyeing and printing hydroxyl-containing materials, characterized in that that one or more dyes of the on these materials in any order Claim 1 applies and, if necessary, the material treated in this way increased the exposure Subjects to temperatures.

4. A method for dyeing nitrogen-containing materials, characterized in that they Materials with a dye of claim 1 from acidic to neutral liquor and optionally dyes then increase the pH range of the dye bath.

ίο where F is a radical of the azo, anthraquinone, phthalocyanine or nitro dye series, X represents an amino or amide group and Y represents one removable, reactive sulfonyl substituents and the remaining hydrogen atom of the thiazole radical can be substituted by a low molecular weight alkyl or phenyl radical, as well as processes for their Production and their use for dyeing and printing hydroxyl-containing or nitrogen-containing Materials.

The amino or amide groups can carry further substituents, such as lower alkyl (preferably Ci to C5), aralkyl, cycloalkyl or aryl groups, but are preferably in the form -NH- which is not further substituted. The amino groups are attached directly to an aromatic ring of the dye.
Y come as reactive sulfonyl substituents
lower alkyl sulfonates with preferred
1 - 5 carbon atoms, such as methylsulfonyl,
Ethylsulfonyl or propylsulfonyl radicals,
Arylsulfonyl radicals, such as phenylsulfonyl,

p-toluenesulfonyl, p-chlorophenylsulfonyl radicals,
Aralkylsulfonyl radicals, such as benzylsulfonyl and
p-Tolylmethylsulfonylreste, and also
Heterosulfonyl radicals, such as 2-benzothiazolesulfonyl,
in question.

Examples of suitable heterocyclic radicals are specifically as follows:

2-methylsulfonyl-4-phenyl-thiazol-yl-5,
4-methyl-2-methylsulfonyl-tiazolyl-5.
The new dyes can belong to the different classes, e.g. B. the series of azo, anthraquinone, phthalocyanine or nitro dyes.

These dye classes include dyes of the general compositions particularly valuable.

1. Azo dyes

B-N = N-D

wherein B and D represent aromatic, carbocyclic or heterocyclic radicals, for example B den Remainder of a carbocyclic diazo component of the benzene or naphthalene series and D the remainder of one enolic or phenolic coupling component,

z. B. a 5-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene, etc .; B and D can also be any in Azo dyes have customary substituents, including further azo groups; Ri stands for one Substituents or preferably for a hydrogen atom, Q for a direct connection or a group - CO— or - SO2— and Y stands for a reactive one Sulfonyl substituents.

Particularly valuable dyes of this series are those that are water-soluble, and especially those which have sulfonic acid and / or carboxylic acid groups. The azo dyes can be both metal-free and also contain metal, the copper, chromium and cobalt complexes being preferred among the metal complexes Have interest.

Important azo dyes are, for example, those of the benzene azo-naphthalene series, the
Benzene-azo-1-phenyl-5-pyrazolone series, the
Benzene-azo-aminonaphthalene series, the

Naphthalene-azo-naphthalene series, the

Naphthalene-azo-1-phenylpyrazolone-5 series

and the

Stilbene azo benzene series,

The dyes containing sulfonic acid groups are also preferred here. In the case of metal complex azo dyes the metal complex-bonded groups are preferably in the o-positions to Azo group, e.g. B. in the form of ο, ο'-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino and o-hydroxyo'-aminoazo groups.

2. Anthraquinone dyes O NH ₂

(III)

L denotes hydrogen or substituents, among these in particular the sulfonic acid group, ρ denotes the number 1, 2 or 3, Ri denotes a substituent or preferably hydrogen, Q denotes a direct bond or a —CO— or —SO2— group and Y denotes a reactive sulfonyl substituent.

The water-soluble products are also in the field of these dyes because of their excellent suitability for the dyeing and printing of cellulose-containing fibers are preferred, the sulfonic acid groups Substituted dyes prove to be particularly suitable.

3. Azaporphine dyes

Examples of suitable residues

-SO ₂ NH

(IV)

In this formula, Pc stands for the remainder of a phthalocyanine, e.g. B. a copper or nickel phthalocyanine or a tetraphenyl copper or nickel phthalocyanine, L represents hydrogen or a substituent, the sulfonic acid group being the substituent is preferred, r for the number 1 or 2, Ri for one Substituents or, preferably, hydrogen and Y for a reactive sulfonyl substituent. The phthalocyanine residue Pc can of course have further substituents, in particular sulfonic acid and sulfonamide groups.

Water-soluble phthalocyanine dyes of the formula (IV), which are suitable for application to cellulose-containing Materials are preferred, in particular, those in the remainder Pc and optionally additionally as a substituent L carry sulfonic acid groups.

-N

-Y

in dyes of the formulas (I), (II), (III) and (IV) are inter alia.

S SO ₂ CH ₃

SO ₂ CH ₃

The preceding compilation of a selection of suitable azo, anthraquinone and azaporphine dyes does not represent a restriction of the general formulas, neither with regard to the preparative possibilities for the preparation of such dyes in the context of the general formula (I), yet with regard to the valuable application properties of these products. The new dyes can also have any substituents customary in dyes, such as sulfonic acid, carboxylic acid, Alkylamino, arylamino, acylamino, aralkylamino, nitro, cyano, halogen, hydroxy, alkoxy, Thioether, azo moieties and the like. The dyes can moreover be further fixable Groupings like

Mono- or dihalotriazinylamino,

Mono-, di- or trihalopyrimidinylamino,

2,3-dihaloquinoxaline-6-carbonyl- or

-6-sulfonylamino-,

1 ^ -dihalophthalazine-ö-carbonyl- or

-6-sulfonylamino-, 2-halobenzthiazole-5-carbonyl- or

-5-sulfonylamino-,

esterified sulfonic acid oxalkylamide and

Oxalkylsulfongruppen, sulfofluorid-,

Haloalkylamino-acryloyamino,

Haloacylamino groups and the like

exhibit.

The new dyes of the formula (I) are obtained

if one uses dyes or dye precursors containing amino or amide groups according to known ones Process using compounds of the formula

converts, in which Z is an anionically removable radical, Y has the meaning given above and that remaining hydrogen atom optionally substituted by a low molecular weight alkyl or phenyl radical is, and in the case of the use of dye precursors these in a suitable manner into the desired Converts final dyes. Among the reactive substituents Y which can be split off as anionic radicals Cl, Br and sulfonyl substituents have preferred interest. Further suitable anionically cleavable Residues are, for example, F-, SO3M- (M = H or metal cation), quaternary ammonium groups, alkyl mercapto, Nitrile, alkoxy or aryloxy groups.

A heterocyclic 5-ring compound of the formula (V) which is suitable for the reaction is, for example

-i-methyl-1-methylsulfonylthiazole-S-carboxylic acid chloride

Cl-OC

SO ₂ CH ₃

The reaction amino- or amido-containing dyes or Farstoffvorprodukte with heterocyclic compounds of the formula (V) the starting materials used in organic, organic-aqueous or aqueous medium is depending on the type at temperatures from -10 ° C to 8O ⁰ C, preferably in the presence of alkaline condensing agent , such as pyridine, aqueous alkali carbonate or alkali hydroxide solutions performed

When using dye intermediates, the condensation products obtained are in conventionally converted into the desired final dyes. This method is of preferred interest for the preparation of azo dyes, for example by adding a diazo and / or coupling component, which has a reactive amino or amide group, initially with the reactive component (V) condensed and the intermediate product obtained then by diazotization and / or coupling and / or condensing into an azo dye.

In this, further conversion reactions can be carried out afterwards, as they are in Azo dyes are common, e.g. B. acylation, condensation, reduction, and metallization reactions. Also in the representation of other dyes, especially those of the phthalocyanine and anthraquinone series, the condensation of a reactive component (V) can first be carried out with an intermediate product, e.g. B. with m-phenylenediamine or a m-phenylenediaminesulfonic acid, and then the reaction product obtained with e.g. bromamic acid (l-amino-4-bromo-anthraquinone-2-sulfonic acid) to a reactive anthraquinone dye or with copper or nickel phthalocyanine sulfonic acid halide be further condensed to a reactive phthalocyanine dye.

The dyes obtainable by the various processes described can, as already for some Cases mentioned, are subjected to further reactions customary for the dyes, for example by one metallizable dyes with metal donating agents, in particular with chromium, cobalt, Copper or nickel salts, treated, dyes containing reducible groups, especially nitro groups have, reduced, dyes which have acylable groups, in particular acylable amino groups, acylated, or by subsequently treating dyes with sulfonating agents, such as chlorosulfonic acid, Thionyl chloride, oleum or SO3 in chlorinated hydrocarbons for additional sulfonic acid groups to introduce into the products. The last-mentioned procedure is sometimes of particular importance in the Range of anthraquinone and phthalocyanine dyes.

If the dyes represented according to the process contain metal complex-forming groups, they can be removed by the action of metal-donating agents, e.g. B. of copper, nickel, chromium or cobalt salts are converted into their metal complex compounds. Likewise, they can be subjected to other conventional conversion reactions such as diazotization, coupling, acylation and condensation reactions.
The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble compounds, they are of particular interest for dyeing textile materials containing hydoxyl groups and nitrogen, in particular textile materials made from native and regenerated cellulose, as well as from wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive sulfonyl substituent (s) in the heterocyclic ring A , the products are particularly suitable as reactive dyes for dyeing cellulose materials using the techniques that have recently become known for this purpose. The fastness properties obtained, especially wet fastness properties, are excellent.

For dyeing cellulose, the dyes are preferably used in an aqueous solution which with alkaline reacting substances, such as alkali hydroxide or alkali carbonate, or with alkaline reacting substances Substances passing over compounds, such as alkali bicarbonate, can be added. The solution can be further Auxiliaries are added which, however, do not react in an undesirable manner with the dyes should. Such additives are, for example, surface-active substances such as alkyl sulfates or migration substances preventing the dye or dyeing

Auxiliary products such as urea (to improve the solubility and fixation of the dyes), or Indifferent thickeners such as oil-water emulsions, tragacanth, starch, alginate or methyl cellulose.

The solutions or pastes thus prepared are applied to the material to be dyed, for example by padding in the padding or by printing and subsequently heated for some time at an elevated temperature, preferably 40 to 15O ⁰ C,. The heating can be carried out in the hot flue, in the steamer, on heated rollers or by penetrating into heated, concentrated alkaline salt baths, either on its own or in any order one after the other.

When using a padding or dye liquor without alkali, the dry goods are passed through a alkaline solution to which common salt or Glauber's salt is added. The salt addition this reduces the migration of the dye from the fiber.

The material to be colored can also be pretreated with one of the aforementioned acid-binding agents, then treat with the solution or paste of the dye and finally, as indicated, fix at elevated temperature.

For dyeing from a long liquor, one goes into an aqueous solution of the dye at room temperature and colors 40 to 90 minutes, if necessary with increasing the temperature up to 95 ° C, under partial addition of salt, e.g. B. sodium sulfate or sodium chloride, and then alkali, for example Sodium phosphates, sodium carbonate or alkali hydroxide. This is where the chemical reaction occurs Dye and fiber. After chemical fixation, the material to be dyed is rinsed with hot water and Finally soaped, removing any non-fixed residues of the dye. You get excellent real, especially water, sweat, rubbing, solvent and lightfast dyes.

In the so-called block cold dwell process can himself . save subsequent heating of the padded fabric by removing the fabric some time, e.g. B. 2 to 40 hours, stored at room temperature. In this process a stronger alkali is used than used in the dyeing process described above from a long liquor.

For printing on materials containing hydroxyl groups, a printing paste made from the dye solution, a thickener such as sodium alginate and an alkaline compound or a compound that splits off alkali when heated, such as sodium carbonate, sodium phosphate, Potassium carbonate, potassium acetate, or sodium and potassium bicarbonate, are used and the printed Material rinsed and soaped.

The dyes contain metal complexing agents Groupings, the dyeings and prints can often be done by post-treating with metal donors Agents such as copper salts, e.g. B. copper sulfate, chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, can be improved in their fastness properties.

Textile materials containing amide groups, such as wool, silk, synthetic polyamide and polyurethane fibers, are generally made according to those customary for this purpose Staining methods stained in the acidic to neutral range, sometimes with a final increase the pH of the dyebath, e.g. B. to pH 6.5 to pH 8.5 is advantageous. .

The dyes are, for example, on synthetic polyamide fabric as solutions or preferably in applied in dispersed form and then, optionally together with (preferably lower Amounts) of acid-binding agents, such as sodium carbonate, are aftertreated. Particularly favorable results are obtained with dyes that are insoluble or only sparingly soluble in water. These will be after conventional techniques and with the addition of the known auxiliaries processed into a dye dispersion and used as such in the dye and / or pad bath or in a printing paste. The one for this application Suitable auxiliaries include compounds that prevent the migration of the dye on the fiber prevent, such as cellulose ethers, alkali metal chlorides and sulfates, wetting agents such as condensation products from ethylene oxide and fatty alcohols or phenols, sulfonated fatty alcohols, solvents, such as Thiodiglycol, also thickeners such as starch, tragacanth, alginate thickener, gum arabic, etc.

The aftertreatment of the dyeings, impregnations and prints obtained on polyamide fiber fabrics is preferably carried out at a temperature of 50-HO ⁰ C and for a duration of 5 to 60 minutes. In this case, too, the dyeings, in the event that the dyes used contain groups forming metal complexes, can be carried out with metal donating agents such as copper salts, e.g. B. copper sulfate or chromium, cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, are sometimes improved in their fastness properties.

The colorations obtainable with the new dyes are generally characterized by good to very good good fastness properties, in particular due to excellent wet fastness properties.

The dyes according to the invention show up against the closest comparable dyes to the Belgian ones Patent 6 30 929 the surprising advantage of delivering deeper colors on cotton and compared to the next comparable dyes of the Belgian patent 6 24 259 the surprising The advantage of delivering deeper colors on cotton in a much shorter time.

In the following examples, parts stand for parts by weight, unless otherwise stated.

example 1

To a solution of 34.7 parts of 2-aminonaphthalene-4,8-disulfonsaurem sodium and 7 parts of sodium nitrite in 300 parts of water are added under cooling with ice 28 parts by volume of concentrated hydrochloric acid and the mixture is stirred for half an hour at 0 -10 ⁰ C. After excess nitrous Acid has been removed, are added 10.7 parts of 3-aminotoluene, dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water, and the coupling is completed by blunting the mixture to pH 3-5. The aminoazo dye formed is salted out, filtered off with suction, washed and then redissolved in 700 parts of water with the addition of sodium hydroxide solution at pH 7. The aqueous solution is then mixed with 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, which is made into a paste with a wetting agent and a little water, and stirred vigorously. The temperature of the reaction mixture is kept at about 20 ^° C .; the hydrochloric acid released is blunted with soda solution until no free amino group can be detected any longer. the

609535/412

resulting dye of the formula

SO ₃ Na

NaO ₃ S

SO ₃ Na

OH

N = N

NaO, SO Cu O SO ₁ Na

NH,

(produced according to the information in German Patent 1117 235) by coupling diazotized l-Amino-8 (benzenesulfonyloxy) -naphthalene-disulfonic acid- (3,6) in a soda-alkaline medium with the equivalent Amount of 2-acetylamino-5-hydroxynaphthalenedisulfonic acid (4.8), Conversion of the monoazo compound

NH-CO

SO ₂ CH ₃

S 0, Na

is salted out with 80 parts of sodium chloride, pressed off, washed and ^{dried at 30 to 40 0} C in a vacuum. It is a yellow powder that is soluble in water with a yellow color.

If you print cellulose fabric with a printing paste containing 15 grams of the dye per kilogram, 10 g of sodium m-nitrobenzenesulfonate, 100 g of urea, 300 ml of water, 500 g of alginate thickener (60 g Sodium alginate per kg of thickening), 2 g of sodium hydroxide and 10 g of soda and which are diluted with water to 1 Kilogram was topped up, dried, steamed for one minute at 105 ° C, rinsed with hot water and boiled soaps, the result is a strong, reddish-yellow print of good fastness to washing and light.

Example 2
0.1 mol of the copper complex compound of the formula

formation in the copper complex by oxidative coppering and hydrolysis of the acetyl and the benzenesulfonyl group) are dissolved in 2500 parts by volume of water at 20 ⁰ C at pH 6 - 6.5 and at this temperature with 0.1 mol of 4-methyl-2-methylsulfonyl thiazole-5-carboxylic acid chloride is added, which is made into a paste with a wetting agent and a little water. During the condensation, a pH of 6-6.5 is maintained by adding sodium carbonate solution. When the reaction has ended, the dye is salted out and isolated. When dried, the dye is a dark powder that dissolves in water with a blue color.

A cotton fabric is padded with an aqueous solution of 20 ⁰ C, 20 g / l of the dye, 10 g / l sodium m-nitrobenzenesulfonate, containing 15 g / l sodium bicarbonate and 150 g / l Harstoff, padded, at 60-70 ⁰ C Intermediate dried, heated to 140 ^° C. for 10 minutes, then rinsed and soaped at the boil. The fabric is dyed wetfast in very clear blue tones.

Example 3

46 parts of the method similar to that in Example 1 by coupling diazotized 2-aminonaphthalene-4,8-disulfonic acid, 3-methylamino-toluene obtained monoazo dye are dissolved in 400 parts of water of 20 ⁰ C at pH 7 in the presence of excess -8 Sodium acetate or calcium carbonate partially mixed with a total of 26.4 parts of 4-isopropyl-2-methylsulfonylthiazole-5-carboxylic acid chloride and stirred at this temperature until a sample no longer changes color when acidified. The resulting dye of the formula

SO ₃ Na

SO ₇ CH,

SO ₁ Na

is salted out, filtered off with suction, washed and dried.

(Eg. A polyoxäthylierten oleyl alcohol) is impregnated cotton fabric with an aqueous solution of 20-25 ⁰ C, the g per liter of liquor 20 of the above dye, 10 g of sodium m-nitrobenzenesulfonate, 0.5 of a nonionic wetting agent as well as 150 g urea and contains 15 grams of sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 80% of the weight of the fabric. After intermediate drying at 60-70 ⁰ C 1 -3 minutes is heated to 140 ⁰ C and purged the coloration thus obtained thoroughly with hot water and boiling for 20 minutes with a solution containing per liter 5 g of Marseilles soap and 2 g of sodium carbonate . After rinsing and drying, a strong reddish yellow coloration of good wet, rub and lightfastness is obtained.

The table below shows the diazo components, coupling components and those with the

Amino group linkable reactive components listed, from which analogously to the information in the Examples 1-3 dyes can be built up,

the color shades of which - obtained using one of the application methods described - are also listed in the table.

Abbreviations for the reactive components:

A = 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride. B = 4-isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride.

example
No. Diazo component Coupling component acid - * l-aminonaphthalene-6-sulfonic acid the same Reactive
component hue 4th 2-aminonaphthalene-4,8-disulfonic acid 1-amino-2-methoxy-5-methyl- 2- (3'-sulfo-4'-aminophenyl) -6-methyl- A " yellow benzene benzthiazole-7-sulfonic acid 1 -Methylamino-3-methoxy- 5 the same the same 2-aminonaphthalene-4,8-disulfonic acid benzene B. yellow 6th l-aminonaphthalene-3,6-disulfonic acid 1 - amino-3-ynethylbenzene 1 - Amino-3-acetyIamino- A. yellow 7th the same the same the same benzene B. yellow 8th 2-aminonaphthalene-5,7-disulfonic acid 1 - amino-3-methylbenzene 'Aniline A. yellow 9 the same the same the same B. yellow 10 2-aminonaphthalene-6,8-disulfonic acid 1-amino-3-methylbenzene A. yellow 11th the same the same B. yellow 12th 4-aminoazobenzene-3,4'-disulfonic acid 1-amino-3-methylbenzene A. brownish yellow 13th 1-aminobenzoI-4-sulfone- 1-amino-3-methylbenzene B. brownish yellow 14th A. yellow 15th B. yellow 16 A. yellow 17th A. yellow

Example 18

In the solution of 36.5 parts of the sodium salt of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts of water with good stirring at 20 ⁰ C 24 parts of 4-methyl-2-methylsulfonylthiazol-5-carboxylic acid chloride was added and the resulting hydrochloric acid is constantly blunted to pH 6-7 and stirred until no free amino group can be detected. The intermediate dye product obtained in this way is, after dilution with 600 parts of water and addition of 12 parts of soda , coupled at 5-10 ° C. with 17.5 parts of diazotized 2-aminobenzenesulfonic acid dissolved in 200 parts of water. The dye of the formula which is formed at a final pH of approx. 7

SO, well

HO NH-OC

SO ₂ CH ₃

NaO ₃ S

SO ₁ Na

is salted out with 100 parts of sodium chloride, filtered off with suction, washed and ^{dried at 30-40 0} C in a vacuum. The dye forms red needles with a metallic sheen, which easily dissolve in water with a red color.

If fabric made of cotton or regenerated cellulose is made according to one of the methods described in Examples 1-3 The process described dyed or printed with this dye gives clear bluish-red tones Dyeing and prints with good wet, rub and lightfastness.

Equally good results are obtained according to the following Proceedings:

50 grams of cotton strand are containing in 1 liter of heated to 5O ⁰ C dyeing liquor containing 1.5 g of the above dye, colored, by the temperature within 30 minutes of 50 ⁰ C to about 85 ⁰ C increases, adding a total of 100 g of table salt in several portions, then adding 20 g of soda and 60 Treated minutes at 85 ° C. After rinsing, boiling soaps and drying, one obtains a

bluish red dyeing of good wet, rub and light fastness.

The following table lists the color shades of other dyes that are also derived from listed diazo components, coupling components and with the amino group in the latter linkable reactive components analogous to the information in Example 18 - or by conversion of the corresponding aminoazo dyes with the reactive components - are built up and according to one of the The methods described above can be dyed or printed on cellulosic materials:

Abbreviations for the reactive components as in the table for example 3

Abbreviations for the reactive components as in the table for example 3

example
No. Diazo component Coupling component Reactive
component hue 19th 1-aminobenzene-2-sulfonic acid 1 -amino-8-hydroxynaphthalene- B. Red 3.6-disulfonic acid 20th ■ the same. 1 - (3'-aminobenzoylamino) - A. Red 8-hydroxynaphtha! In-3,6-di- sulfonic acid 21 the same the same B. Red 22nd 1 -amino-2-carboxybenzene- 1 - amino-8-hydroxynaphthalene- A. Red 4-sulfonic acid 3,6-disulfonic acid 23 1-amino-4-methylbenzene- the same A. Red 2-sulfonic acid 24 1 - Amino-3-acetylaminobenzene- the same B. Red 6-sulfonic acid 25th 1 - Amino-3- (2 '- [4 "-sulfophenyl- the same A. Red amino] -4'-cnlortriazin-1 ', 3', 5'-yl-6 ') - aminobenzene-6-sulfonic acid 26th 1-aminobenzene-2-sulfonic acid 2-amino-5-hydroxynaphthalene A. orange 7-sulfonic acid 26 a l-amino-3- (2 '- [4 "-sulfophenylammo] - 2-amino-5-hydroxynaphthalene A. orange .4'-methylamino-triazin-r, 3 ', 5'-yl-6') - 7-sulfonic acid aminobenzene-6-sulfonic acid 27 ' 1-aminobenzene-2-sulfonic acid 2-methylamino-5-hydroxy A. orange naphthalene-7-sulfonic acid 28 1-amino-4-acetylamino-6-sulfonic acid the same A. Scarlet fever 29 ' the same 2-amino-5-hydroxy A. Scarlet fever naphthalene-7-sulfonic acid

Example 30

In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 100 parts of water, 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are introduced with thorough stirring and at 20 ^° C. below Constant blunting of the hydrochloric acid released to pH 6-7, stirred until a sample of diazotization and coupling on 1-hydroxynaphthalene-4-sulfonic acid gives a clear, yellowish-red color. After ice has been added, the resulting dye-by-product is diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then with a initially charged solution of 47 parts of the sodium salt of 1-benzoylamino-e-hydroxy-naphthalene-S.ö-disulfonic acid and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula

SO, well

CH ₃ SO;

CO-HN

NaO ₃ S HO NH-OC-Cf ₁ H,

S 0, Na

takes place, which is salted out, filtered off with suction, washed and dried at 30-40 ° C in a vacuum. The dye dissolves easily in water with a red color and gives clear ones after one of the methods described above bluish-tinged red dyeings and prints on cellulose materials. .. ·. ■ ··

The following table shows the color shades and the pH value of the coupling medium of dyes listed, the analogous to the information in Example 30 from a diazo component which contains a further, preferably acylatable amino group, from a Coupling component and produced from a reactive component that can be linked to the diazo component will. For dyeing and printing cellulose materials with the dyes in the table the methods mentioned above can be used.

15 16

Abbreviations for the reactive components as in the table for example 3

example Diazo component Coupling component Reactive pH des hue No. component Clutch mediums 31 1,3-diaminobenzoI- - 2-aminonaphthalene-5.7-di- A. 4-5 ' orange 4-sulfonic acid sulfonic acid 32 the same 2-aminonaphthalene-3,6-disulfone A. 4-5 orange acid 33 the same 2-aminonaphthalene-6-sulfonic acid B. 4-5 orange 34 the same 2-N-methylamino-8-hydiOxy- A. 4-5 orange naphthalene-6-sulfonic acid 35 1,3-dieminobenzene 1- (3 ', 5'-dichloro-r, 2'-thiazole- A. 7-8 Red 4-sulfonic acid 4'-carbonamido) -8-hydroxy- naphthalene-3,6-disulfonic acid 36 the same 1 - (2 ', 4'-dihydroxytriazine B. 7-8 Red r, 3 ', 5'-yl-6'-amino) -8-hydroxy- naphthalene-3,6-disulfonic acid 37 the same l- (3'.5'-dichloro-l'.2'-thiazole- A. 7-8 Red 4'-carbonamido) -8-hydroxy- naphthalene-3,6-disulfonic acid c 38 the same 2-hydroxynaphthalene A. 8th Scarlet fever .. 3,6-disulfonic acid 39 the same .1 - Acetylamino-8-hydroxy- B. 7-8 Red naphthalene-3,6-disulfonic acid 40 the same l- (3'-sulfophenyl) -3-methyl- A / ' 6th yellow - pyrazolone-5 41 the same ■ l- (2 ', 5'-dichloro-4'-sulfophenyl) - A. 6th yellow 3-methylpyrazolone-5 42 the same l- (5 ', 7'-disulfonaphthyl-2' -) - A. 6th yellow 3-methyl-pyrazolone-5 43 the same 1 - (3'-sulfophenyl) -3-methyl- B. 6th yellow 5-aminopyrazole 44 1,4-diaminobenzene 2-amino-8-hydroxynaphthalene A. 4-4.5 Red 3-sulfonic acid 6-sulfonic acid 45 1,4-diaminobenzene 2-acetylamino-5-hydroxy A. .6-7 Scarlet fever 3-sulfonic acid naphthalene-7-sulfonic acid 46 the same 1 -acetylamino-5-hydroxy- B. 6-7 Red naphthalene-7-sulfonic acid

Example 47

51.6 parts of the by diazotizing l-hydroxy-2-aminobenzene-4-sulfonic acid and coupling to 2-amino

45

S-hydroxynaphthalhW-sulfonic acid in water / pyridine in The dye obtained in the presence of soda and subsequent treatment with a copper donating agent the formula

S 0-, Na

are dissolved in 1500 parts of water at pH 7. With thorough stirring, 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride ^{are introduced at 20 ° C. and the hydrochloric acid liberated is blunted with soda solution}

continuously to a pH of 5-7. If no free amino group can be detected any longer, the one formed is Reactive dye of the formula

CH ₃

NH-CO

SO ₂ CH ₃

SO ₃ Na

609535/412

salted out, pressed out, washed and dried in vacuo at 30-40 ° C. Fabrics made from cellulosic materials can with this dye according to one of the above-mentioned processes in wet, rub and lightfast Ruby tones can be colored or printed.

The following table lists the heavy metal complexes of other aminoazo dyes and those with the 18th

Amino group linked reactive components, as well as the color tones of these dyes on cellulose materials cited. The preparation of the aminoazo dyes, their metal complexes and their conversion with the Reactive components can be carried out analogously to the information in Example 47.

Abbreviations for the reactive components as in Table for Example 3

example Aminoazo dye complex Reactive- No. bound component c Heavy metal 48 l-hydroxy-2-aminobenzene-4,6-disulfone- Cu A. acid - »2-amino-5-hydroxynaphthalene- 7-sulfonic acid 49 i-Hydroxy ^ -aminobenzene ^ -sulfone- Cu A. acid -> 2-ethylamino-5-hydroxynaphthalene- 7-sulfonic acid 50 l-amino ^ -hydroxy-ö-nitronaphthalene- Cu A. 4-sulfonic acid -> 2-amino-5-hydroxy- naphthalene-7-sulfonic acid 51 the same Cr A. 52 l-amino ^ -hydroxy-ö-nitronaphthalene- Co B. 4-sulfonic acid - <■ 1 -amino-8-hydroxy- naphthalene-4-sulfonic acid 53 l-amino-2-hydroxy-5-methylsulfonyl- Cu A. benzene - «■ l-amino-8-hydroxynaphthalene- 3,6-disulfonic acid 54 the same Co A. 55 the same Cr A.

Color ion

56 1-Amino-2-methylbenzene-4-sulfonic acid -> ■ 1-amino ^ -hydroxy-S-methylbenzene - «· l-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

57 the same. Co

58 the same Cr

59 (l-amino-2-chlorobenzene-4-sulfonic acid - * l-hydroxy-2-acetyIaminobenzene), saponified - * l-amino-8-hydroxynaphthalene-3,6-disulfonic acid

60 the same. Co

61 l-Amino-8-hydroxynaphthalene-4-sulfonic acid "- l-Hydroxy-2,6-diaminobenzene-4-sulfonic acid" 1,3-dihydroxybenzene

62 l-amino-S-hydroxynaphthalene-S.ö-di-Co sulfonic acid ■> - 1-hydroxy-2,6-diaminobenzene-4-sulfonic acid -> · 2-hydroxynaphthalene

63 l-Amino-S-hydroxynaphthalene ^ -sulfone- Co acid - i-hydroxy ^ .ö-diaminobenzene-4-sulfonic acid -► 3-methylpyrazolone- (5)

A.
A.

ruby

ruby

ruby

greenish gray
reddish black

violet

Gray

greenish black
blue

Gray

greenish black
Navy blue

Gray
black

black
black

Example 64

96 parts (based on 100% goods) of the usual way by the action of chlorosulfonic acid and Thionyl chloride on copper phthalocyanine freshly prepared copper phthalocyanine tetrasulfochloride or des isomeric, from l-sulfobenzene-3,4-dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid built up copper phthalocyanine tetrasulfochlorids are in the form of the moist, well washed The suction cake is suspended in 500 parts of water and 500 parts of ice, the solution of 50 parts of the sodium salt the 1,3-diaminobenzene-4-sulfonic acid in 500 parts of water was added and the pH was adjusted to 8.5 with soda set. The suspension is stirred for 24 hours at room temperature and is kept constant Adding soda always keeps the pH at 8.5. The resulting condensation product is at pH 1-2 by adding precipitated from sodium chloride, filtered off with suction, washed and then redissolved in 1000 parts of water until neutral. In the blue solution becomes a slurry of 72 parts

Cu phthalocyanine

- (SO ₃ Na) _n
- (SO ₂ -NH-

^ Methyl ^ -methylsulfonyl-thiazole-S-carboxylic acid chloride was added in water with a wetting agent, and stirred with continuous dulling of the liberated hydrochloric acid with sodium carbonate solution to pH 5 -7 as long as at 20 ⁰ C until no more free amino groups can be detected. The reactive dye of the formula obtained in this way

NH-CO S
SO ₃ Na

S0, CH,

is salted out, washed and ^{dried at 30-40 0} C in a vacuum. It is a dark blue powder that is soluble in water with a blue color and dyes cotton and regenerated cellulose by one of the above-mentioned dyeing or printing processes in clear blue shades of good wet, rub and lightfastness.

Instead of the 96 parts of copper phthalocyanine tetrasulfonyl chloride you can - with otherwise the same procedure as in example 64 - also 87 parts (based on 100% strength goods) of the by the action of chlorosulfonic acid Copper or nickel phthalocyanine trisulfochloride available in the form of copper or nickel phthalocyanine moist suction cakes, washed well with ice water, can be used; one then also obtains a clear blue coloring reactive dyes.

Even if one works as indicated in Example 64, but from 87 parts of copper phthalocyanine trisulfochloride goes out and instead of the 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonic acid 90 Parts of the sodium salt of 4,4'-diamino-diphenyl-2,2'-disulfonic acid or 90 parts of the sodium salt of 4,4'-diaminostilbene-2,2'-disulfonic acid is used, gives 4-n n ~ 2-3

one reactive dyes, which cellulosic materials by one of the above methods in wet, rubbing and color lightfast, clear blue tones.

If one goes from the 4 ', 4 ", 4'", 4 "" -Tetraphenyl-Cu-phthalocyanine from, so obtained after sulfochlorination and conversion with 1,3-phenylenediamine-4-sulfonic acid and Acylation with 4-methyl-2-methylsulfonylthiazole-5-carboxylic acid chloride a reactive dye that converts cellulose materials in the presence of acid-binding agents in clear, colors wet and lightfast green tones.

Example 65

71 parts of the aminoanthraquinone dye obtained by reacting 1-amino-4-bromo-anthraquinone-2-sulfonic acid with excess 4,4'-diaminodiphenyl-2,2'-disulfonic acid are dissolved in 700 parts of water at 20 ^° C. with vigorous stirring, add 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and maintain a pH of 6-7 by continuously adding soda solution. When no more amino groups can be detected, the resulting dye is of the formula

O NH

SO, well

O NH <f

V-NH-CO S SO ₂ CH

SO ₃ Na

salted out, vacuumed, washed and at 30 - 40 ° C im Vacuum dried. It dyes cotton and regenerated cellulose using one of the methods listed above in wet, rubbing and lightfast blue tones.

If one proceeds as indicated in Example 65, but instead of the 71 parts of the one used there Starting dye-equivalent amounts of one of the following derivatives of l-amino-4- (aminoarylamino) -anthraquinone-2-sulfonic acid is used, similar dyes are obtained whose blue colorations are similar in fastness to that of the one obtained above Have dye:

l-amino-4- (4'-amino-2'-sulfophenylamino) -

anthraquinone-2-sulfonic acid,

1 - Amino-4- (4'-aminophenylamino) -

anthraquinone-2,6-disulfonic acid, mixture of isomers from

l-amino-4- (4'-aminophenylamino) -

anthraquinone-2,5- and 2,8-disulfonic acid, mixture of isomers from

l-Amino-4 (4'-amino-2'-sulfophenylamino) -anthraquinone-2,5- and 2,8-disulfonic acid, Mixture of isomers

l-Amino-4- (3'-aminophenylamino) -anthraquinone-2,5- and -2,8-disulfonic acid, l-amino-4- (3'-aminophenylamino) -anthraquinone-2,6-disulfonic acid, l-amino-4- (3'-amino-4'-sulfophenylamino) -anthraquinone-2-sulfonic acid.

With 1 - amino-4- (4 '- [4 "-amino-2" -sulfophenyl] aminophenyl) -anthraquinone-2,6-disulfonic acid one obtains reactive dyes with a bluish gray tint.

Example 66

If you proceed as indicated in Example 47, it works instead of the copper-containing amino monoazo dye used there by the equivalent amount

of the chromium complex obtained by coupling diazotized l-amino-2-hydroxy-3-chlorobenzene-5-sulfonic acid with

1- [3 '- (3 "-aminophenyl)] - sulfonylimido-sulfonyl-phenyl - 3-methyl-pyrazolone- (5) obtained aminoazo dye, so one obtains a reactive dye, which cellulosic materials according to one of the above

specified procedure in good wet,
lightfast yellow-brown tones.

friction and

Example 67
0.1 mol of the copper complex compound of the formula

HO ₃ S

SO, well

CH,

are dissolved in 3000 parts by volume of water at pH 6 and with stirring at a temperature of about 50 ° C with 24 Parts by weight (0.1 mol) of 4-methyl-2-methyl-sulfonylthiazole-5-carboxylic acid chloride united. The mixture is stirred until the condensation has ended and the dye is removed by adding a little sodium chloride secluded and isolated. The residue is washed with acetone and taken at room temperature dried under reduced pressure. A dark powder is obtained which dissolves in water with a green color and dyes cotton in green shades according to the procedures given in Examples 1-3.

Cotton fabric is impregnated with a solution at 20-25 ° C. which contains 25 g of the above dye and 0.5 g of a nonionic wetting agent (eg a polyoxyethylated oleyl alcohol), 150 g of urea and 20 g of sodium carbonate per liter of liquor. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50 -6O ⁰ C for 10 minutes at 140 ° C is heated and purged the coloration thus obtained thoroughly with hot water and boiling for 20 minutes with a solution containing per liter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, a green dyeing of good wet, rub and lightfastness is obtained.

Also by one of the other dyeing or printing processes described in Examples 1 to 3, 18 and 30 Clear green tones with good fastness properties are obtained on cellulose materials.

Example 68

0.1 mole of the paste of the aminoazo compound of the formula

SO ₁ H

N = N

HO, S O Cu O

SO ₃ H

SO ₃ H

by coupling the diazonium compound from 6-acetamino-2-amino-naphthalene-4,8-disulfonic acid with 2-oxynaphthalene-3,6-disulfonic acid and saponification and conversion of the monoazo compound into the copper complex is obtained are dissolved in 2000 parts by volume of water at pH 6.5 and with 24 parts by weight 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride united. The reaction mixture is stirred at 20 ° C. until the condensation has ended, the pH the reaction solution is kept at 6-7 by adding soda. After the reaction has ended, the Salted out dye, isolated and dried in vacuo.

The dried dye is a dark powder that dissolves in water with a purple color and Dyes cotton in the presence of alkali in bluish violet tones.

Example 69

The aqueous solution of 0.1 mol of the copper complex of the formula

HO ₃ SO

SO, H

SO ₁ H

55

60 prepared according to the information in German patent specification 10 61 460 or 10 85 988, is combined in the usual way with a solution of 24.0 parts by weight of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride in water. The pH is maintained at 6-7 by adding soda and the dye is isolated by salting out after the reaction has ended. When dry, it is a dark powder that dissolves in water with a purple color. Cotton fabric is dyed in lightfast and wetfast violet tones.

Example 70

27.5 parts of 2-methylamino-5-hydroxy-naphthalene-7-sulfonic acid Sodium is dissolved in 150 parts of water, with 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride added and at 20 ° C with constant blunting of the hydrochloric acid formed with a total of 34 parts by volume of 16% sodium carbonate solution to pH 4-6 stirred. After a short time, the acylation is complete, the pH is 6 and no longer changes.

24

Are then added to 30 parts of sodium bicarbonate and allowed at 20 ⁰ C within 15 minutes, the diazo suspension of 34 parts of the disodium salt of 2-aminonaphthalene-1,7-disulfonic acid in 200 parts of water are added dropwise. The orange-colored reactive dye of the formula which was formed immediately

SCXNa

NaO, S.

NaO ₃ S

is completely separated after stirring for one hour by adding 80 parts of sodium chloride, filtered off, with Washed dilute sodium chloride solution and dried at 35 ° C in a vacuum. He dyes cellulose materials the above processes in reddish orange tones with very good and good wet fastness properties Chlorine resistance.

In this example, 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride is used instead of 24 parts by weight equivalent amounts of 4-isopropyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, so N-CO

CH,

SO ₂ CH ₃

an orange reactive dye is obtained whose coloring behavior corresponds to that of the dye 4-methyl derivative is similar.

In an analogous manner, those listed in column 3 of the table below are obtained by acylation Aminonaphtholsulfonsäuren with 4-methyl-2-methylsul-20 fonyl-thiazole-S-carboxylic acid chloride and coupling the Acylamino-naphtholsulfonic acids formed with the diazo components mentioned in column 2 organge to red reactive dyes. .

example
No.

Diazo component

Aminonaphtholsulfonic acid

Hue on cotton

71 2-aminonaphthalene 1,7-disulfonic acid 72 the same 73 the same 74 the same 75 the same 76 the same 77 ' 2-aminonaphthalene 1,5-disulfonic acid 78 the same 79 the same 80 the same 81 the same 82 2-aminonaphthalene 1,5-disulfonic acid 83 the same 84 2-aminonaphthalene 1,5,7-trisulfonic acid 85 the same 86 the same 87 2-aminobenzenesulfonic acid 88 the same 89 the same 90 the same 91 the same 92 2-aminonaphthalene 1-sulfonic acid 93 the same 94 2-aminonaphthalene 1,5-disulfonic acid 95 the same 96 the same 97 2-aminonaphthalene 1,7-disulfonic acid 98 the same 99 the same

2-Ethylamino-5-hydroxynaphthalene-7-sulfonic acid Orange

2 - (/ i-Hydroxyäthylamino) -5-hydroxynaphthalene-

7-sulfonic acid '■. · · .- · ■' · ■: \ -

2-Amino-5-hydroxynaphthalene-7-sulfonic acid 2-Amino-5-hydroxynaphthalene-l, 7-disulfonic acid 2-amino-8-hydroxynaphthalene-6-sulfonic acid 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid

2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid 2 - (/ j-Hydroxyethylamino) -5-hydroxynaphthalene-7-sulfonic acid ■. '. -

2-Amino-5-hydroxynaphthalene-7-sulfonic acid 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid 2-amino-8-hydroxynaphthalene-6-sulfonic acid

2-amino-8-hydroxynaphthalene-3,6-disulfonic acid 2-amino-5-hydroxynaphthalene-7-sulfonic acid

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid 2-amino-8-hydroxynaphthalene-6-sulfonic acid 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid 2- (jS-hydroxyethylamino) -5-hydroxynaphthalene-

7-sulfonic acid ■. - ■■

2-Amino-8-hydroxynaphthalene-6-s-sulfonic acid 2-Amino-8-hydroxynaphthalene-3,6-disulfonic acid 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

1-Amino-8-hydroxynaphthalene-4,6-disulfonic acid 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

1 - Amino-8-hydroxynaphthalene-4,6-disulfonic acid 1-amino-8-hydroxynaphthalene-6-sulfonic acid 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

1 - Aniino-8-hydroxynaphthalene-4,6-disulfonic acid 1-amino-8-hydi "oxynaphthalene-6-sulfonic acid

the same

the same

likewise scarlet fever

also orange

. the same - ■■ ■■ '.; .. the same.

the same. the same. scarlet fever

also orange

the same. Scarlet Orange the same.

Scarlet fever

also orange, bluish red

like-like

like. like. like.

the same.

609 535

continuation

example
No.

Diazo component

Aminonaphtholsulfonic acid

Hue on
cotton

100 2-aminonaphthalene 1,5,7-trisulfonic acid 101 l-amino-4-chlorobenzene 2-sulfonic acid 102 1 - amino-2-methoxy- benzene-5-sulfonic acid 103 1-amino-benzene-2-carbon acid-4-sulfonic acid 104 1-amino-4-acetylamino- benzene-2-sulfonic acid 105 the same

1-amino-8-hydroxynaphthalene-6-sulfonic acid
l-Amino-8-hydiOxyruiphthalin.-3.6-disulfonsat.ire
l-amino-8-hydroxynaphth; iline-3,6-disulfonic acid
l-amino-8-hydroxyn; iphthalene-3,6-disulfonic acid

the same
i-Amino-S-hydroxyniiphthalene ^ .ö-disulfonic acid

bluish tint Red the same the same the same violet bluish tint Red

Example 106

56.8 parts of the diaminoazo dye obtained by coupling diazotized l-amino-S-acetylaminobenzene-δ-sulfonic acid to 2-aminonaphthalene-5,7-disulfonic acid in an acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are 450 parts at pH 7 Dissolved water. After adding 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, the resulting hydrochloric acid is stirred ^{with soda solution to pH 4-6 for about one hour at 50 ° C. while constantly blunting the liberated hydrochloric acid.} When the acylation has ended, the reactive dye formed is of the formula

CH,

SO ₁ Na

NH

CH ₃ SO ₂ S CO-HN N = N

salted out, filtered off, dissolved again in 4000 parts of water at 30 ° C, filtered and from the filtrate through Addition of 400 parts of table salt deposited in completely pure form. The dye is as usual at 35 ° C im Vacuum dried. It dyes cellulose materials in a true yellowish tinge using one of the above-mentioned processes Shades of orange.

Example 107

For a neutral solution of 60 parts of the trisodium salt of the coupling of diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid with 3-acetylamino-aniline The aminoazo dye obtained in an acetic acid medium in 500 parts of water is added to 24 parts of 4-methyl-2-methylsulfonyl-thiazole-S-carboxylic acid chloride and stir for one hour at 45.degree. C., a pH of approx. 6 being maintained by the constant addition of sodium hydroxide solution will. The partially precipitated acylation product is at pH 6.5 by adding 100 parts of sodium chloride completely separated and filtered off. The reactive dye obtained in this way can be cleaned again in 2500 Parts of water at 30 ° C dissolved, clarified and again by salting out the filtrate with 350 parts of common salt to be deposited. The dye has the formula

NaO ₃ S

- CO
SO ₃ Na NH-COCH ₃

SO ₂ CH ₃

and after filtering off, drying at 35 ° C and grinding it is a yellow powder that easily dissolves in water with yellow color dissolves and cellulose fibers after one of the above dyeing processes in the presence acid-binding agents in very real reddish yellow tones. Also on wool and polyamide fibers true yellow colorations are obtained.

Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4'-amino-2'-acetylamino-phenyl- (l ') - azo-naphthalene- (2) -3,6,8-trisul- Fonsaurem sodium corresponding amounts of the amino compounds given in column 2 and the Coupling components indicated in column 3 in the usual manner by diazotization and coupling in

acetic acid medium obtained carboxylic acid chloride acylated.

Aminoazo dyes used and with ^ methyl ^ -methylsulfonyl-thiazole-S-

example
No. Dia / .okoinponenle Coupling component Hue on
cotton 108 2- aminonaphthalene- 1,5-disulfone- 1-amino-3-methyl-6-methoxy benzene strong reddish yellow acid 109 the same 1-amino-3-methylbenzene yellow 110 the same 1-aminonaphthalene-6-sulfonic acid reddish yellow 111 the same I-amino-3-acetylaminobenzene the same 112 the same 3-aminopheny! Urea the same 113- the same i-amino-3-hydroxyacetylaminobenzene the same 114 2-aminonaphthalene 1 - Amino-3-methyl-6-methoxybenzene strong reddish yellow 5,7-disulfonic acid 115 the same 1-aminonaphthalene-7-sulfonic acid reddish yellow 116 the same 1-amino-3-acetylaminobenzene the same 117 the same 3-aminophenylurea the same 118 the same l-amino-3-hydroxyacetylamino-benzene the same 119 1 -aminonaphthalene- 1-amino-3-methyl-6-methoxybenzene strong reddish yellow 3,7-disulfonic acid 120 the same 1-amino-3-methylbenzene reddish yellow 121 1-aminonaphthalene 1-aminonaphthalene-6-sulfonic acid the same 3,7-disulfonic acid 122 2-aminonaphthalene 1-amino-3-methylbenzene the same 3,6-disulfonic acid 123 the same 1-Amino-3-methyl-6-methoxybenzoI strong reddish yellow 124 the same 1-amino-3-acetylaminobenzene reddish yellow 125 the same 3-aminophenylurea the same 126 the same l-amino-3-hydroxyacetylaminobenzene the same 127 the same 1-aminonaphthalene-6-sulfonic acid the same 128 2-aminonaphthalene 1-amino-3-acetylaminobenzene the same 6,8-disulfonic acid 129 the same 1-amino-2-methoxynaphthalene strong reddish yellow 6-sulfonic acid 130 the same 1-aminonaphthalene-6-sulfonic acid reddish yellow 131 2-aminonaphthalene-4,8-disulfone 1 - aminonaphthalene-6-sulfonic acid yellow acid 132 the same 1-aminonaphthalene-7-sulfonic acid the same 133 2-aminonaphthalene-4,8-disulfone 1 - amino-2-methoxynaphthalene- strong reddish yellow acid 6-sulfonic acid 134 the same 1-methylamino-3-methylbenzene yellow 135 2-aminonaphthalene-4,8-disulfone 1-ethylamino-3-methylbene: iol yellow acid 136 the same N-methylaniline the same 137 the same N-ethylaniline the same 138 the same N- (j3-hydroxyethyl) aniline the same 139 the same N-butylaniline the same 140 2-aminonaphthalene aniline reddish yellow 3,6,8-trisulfonic acid 141 the same 1-amino-3-methylbenzene the same 142 the same 3-aminophenylurea the same 143 the same l-amino-3-hydroxyacetylaminobenzene the same 144 the same 1 - amino-3-acetylamino- yellowish orange 6-methoxybenzoI 145. the same 1 - amino-3-acetylamino- reddish yellow 6-methylbenzene 146 the same 1 - Amino-3-methane-sulfonyl- the same aminobenzene 147 the same 2,5-dimethoxyaniline yellowish orange 148 the same 3-methyl-6-methoxyaniline the same 149 the same. N-methylaniline reddish yellow 150 2-aminonaphthalene 4-ethylaniline the same 3,6,8-trisulfonic acid 151 the same N-butylaniline the same 152 the same N- (j3-hydroxyethyl) aniline the same 153 the same 3- (N-ethylamino) toluene the same

29

continuation

example
No.

Diazo component

Coupling component

Hue on
cotton

154 2-aminonaphthalene 3,6,8-trisulfonic acid 155 the same 156 the same 157 the same 158 the same 159 the same. 160 the same. 161 2-aminonaphthalene 4,6,8-trisulfonic acid 162 . the same 163 1-aminonaphthalene 2,4,7-trisulfonic acid 164 the same 165 4-nitro-4'-aminostilbene 2,2'-disulfonic acid 166 the same 167 the same 168 the same 169 the same 170 the same 171 the same 172 the same 173 Aniline-2,5-disulfonic acid 174 the same 175 the same 176 the same 177 the same. 178 the same 179 ■ aniline-2,4-disulfonic acid

2-aminotoluene reddish yellow 1-amino-2.5-dimet hy! benzene strong reddish yellow 1-amino-2-methoxybenzene the same . 1-amino-3-methoxybenzene reddish yellow i-ethylamino-3-methoxybenzene the same l-aminonaphthalene-6-sulfonic acid the same l-aminonaphlhalin-7-sulphonic acid the same I - Amino-3-methylbenzene the same -Amino ^ -acetylaminobenzene the same 1-amino-3-ynethylbenzene yellow i-aminonaphthalene-6-sulfonic acid c the same i-amino-3-acetylaminobenzene reddish yellow 3-aminopheny! Urea the same l-amino-3-hydroxyacetylaminobenzene the same M-methyliiniline the same N-ethylaniline the same N-butylanilaniline the same N - (/ J-Hydroxyethyl) aniline the same 1- (N-ethylamino) -3-methylbenzene the same 1-aminonaphthalene-6-sulfonic acid the same 1 - aminonaphthalene-7-sulfonic acid the same 1-amino-3-methylbenzene yellow 1 - Amino-3-acetylaminobenzene the same 1-amino-2-methoxy-5-methylbenzene reddish yellow 1-amino-2,5-dimethoxybenzene the same 1-Amino-2-methoxy-5-methylbenzoI the same

Example 180

65 parts of the dye of the formula

O- - Cu O

NaCXS

NH, (prepared by coupling diazotized 1-hydroxy-2-aminobenzene-4,6-disulfonic acid, 2-amino-8-hydro xynaphthalin-6-sulphonic acid and coppering the receive NEN azo dyes) are dissolved in 700 parts of water until neutral. 24.0 parts of 4-methyl-2-methylsulfonylthiazole -S-carboxylic acid chloride are added and the mixture is stirred at 20 ° C., while the hydrochloric acid released is constantly blunted with soda solution to pH 5-6, until no free amino group can be detected. The resulting reactive dye of the formula

NaO ₁ S

O Cu

N = N

NaO ₃ S

SO ₁ Na CH

ΝΗ - CO S SO ₂ CH ₃

is salted out, filtered off, washed and analogous to the above-described operation from 30-40 ⁰ C dried. According to one of the above 65 copper complexes of the ruby shades produced from the processes given in the table below, cellulose materials are produced in very detailed diazo and azo components. . ten azo dyes: dyes with similar properties are obtained

31 32

Example no.

Diazo component

Coupling component shade on cotton

181 182 183 184 185 186 187 188 189 190 191 192 193 194 195

1-hydroxy-2-aminobenzene-4-sulfonic acid c the same

the same.

1-hydroxy-2-aminobenzene-4,6-disulfonic acid the same

like. like. like. like.

1-hydroxy-2-aminobenzene-5-sulfonic acid the same. 2-methylamino-5-hydroxynaphthalene

7-sulfonic acid 2-ethyl-amin.o-5-hydroxynaphth.alin-

7-sulfonic acid 2- (ß-Hydroxyäthyiamino) -5-hydroxy-

naphthalene-7-sulfonic acid

2-amino-8-hydroxynaphthalene

3,6-disulfonic acid 2-amino-5-hydroxynaphthalene

1,7-disulfonic acid 2-amino-8-hydroxynaphthalene-

3,6-disulfonic acid 2-methylamino-5-hydroxynaphthalene

7-sulfonic acid 2-ethylamino-5-hydroxynaphthalene-

7-sulfonic acid 2 - (/? - Hydroxyäthylamino) -5-hydroxy-

naphthalene-7-sulfonic acid

-Amino-8-hydroxynaphthalene-

3,6-disulfonic acid i-amino-S-hydroxynaphthalene ^ .e-di-

sulfonic acid - amino-8-hydroxynaphthalene-

3,6-disulfonic acid -amino-8-hydroxynaphthalene-

4,6-disulfonic acid -amino-8-hydroxynaphthaIin-

3,6-disulfonic acid -ethoxy-8-hydroxynaphthalene-

3,6-disulfonic acid

1 -hydroxy ^ -amino ^ -acetyl-

aminobenzene-6-sulfonic acid

1 -hydroxy ^ -amino ^ -acetyl-

aminobenzene-6-sulfonic acid

(4-position acetylamino group then saponified)

the same. l-amino-8-hydroxynaphthalene-

2,4-disulfonic acid

the same. 1 - Amino-8-hydroxynaphthalene-

2,4,6-trisulfonic acid

1 -hydroxy ^ -amino-e-acetyl- 1 -amino-8-hydroxynaphthalene-

aminobenzene-4-sulfonic acid 2,4-disulfonic acid

(6-position acetylamino group saponified) 1 - amino-2-hydroxy-6-nitro- like.

naphthalene-4-sulfonic acid

(6-position nitro group then reduced to - NH2)
i -Amino ^ -hydroxy-fS-nitro- 1 - Amino-8-hydroxynaphthalene-

naphthalene-4-sulfonic acid 2,4,6-trisulfonic acid

(6-position nitro group then reduced to - NH2) 1 -hydroxy ^ -amino-ö-acetyl- desgl.

aminobenzene-4-sulfonic acid (6-position acetylamino group saponified) ruby

ruby

ruby

ruby

ruby

ruby

ruby

ruby

ruby

violet

violet

violet

violet

bluish purple

bluish purple

Blue blue blue

Blue blue blue

example

Proceed as indicated in Example 30, couple however, the diazotized, reactive group-containing intermediate in a soda-alkaline medium instead of with Parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid with 40 parts of the sodium salt of l-acetylamino-S-hydroxynaphthalene-S.e- disulfonic acid and isolates the resulting dye of the formula

CH,

SO ₃ Na HO NH-CO-CH ₃ CH ₃ SO ₂ S CO -NH

NaO, S. SO ₃ Na

in the manner indicated in Example 30. The water-soluble dye stains cellulose materials after

609 535M12

Pad steaming or pad thermosetting process (for 140 ° C) in white-etchable, wet, rubbing and lightfast bluish red tones.

Example 203

The solution of 19.5 parts of the sodium salt of l-aminobenzene-4-sulfonic acid and 6.9 parts of sodium nitrite in 200 parts of water is concentrated in a mixture of 100 parts of ice and 28 parts by volume. Let in hydrochloric acid; then the mixture is stirred for half an hour at 0-10 ° C., and then excess nitrous acid is removed. To the thus obtained diazo suspension at 0-10 ⁰ C., the cooled and thereby again partially crystallized solution of 26.2

Divide the potassium salt of 1-amino-naphthalene-8-sulfonic acid in 250 parts of hot water and blunt the strongly acidic coupling mixture at 10-20 ° C. by carefully adding sodium hydroxide solution to pH 4. The coupling is completed quickly; the aminoazo dyestuff formed is completely salted out with 100 parts sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 1O ⁰ C and pH 6-7. The aqueous solution is mixed with 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and ^{stirred at 10 °} C. for one hour with soda solution to pH 5 while the hydrochloric acid liberated is continuously blunted. When the aminoazo dye is no longer detectable, the partially precipitated reactive dye becomes of the formula

NaO,

SO ₇ CH ₁

Salted out with 40 parts of table salt, filtered off and again in 800 parts of warm water for cleaning solved. After the solution has been clarified, the filtrate becomes pure by adding 80 to 100 parts of common salt Dye deposited. After filtering off, drying at 35 ° C and grinding, a yellow powder is obtained, which dissolves easily in water with a yellow color and the cellulose fibers after one of the above-mentioned dyeing processes dyes in the presence of acid-binding agents in very good wet, light and chlorinefast yellow tones. Also True yellow colorations are obtained on wool and polyamide fibers.

If you proceed as indicated above, but instead of the 19.5 parts of the sodium salt of 1-aminobenzene-4-sulfonic acid equivalent amounts of the diazo components listed in the table below to the Coupling l-amino-naphthalene-8-sulfonic acid is obtained after acylation with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride also valuable, yellow to brown reactive dyes.

Diazo component

Color on cellulose fiber

1-aminobenzene ^ S-disulfonic acid

2-amino-naphthalene-4,8-disulfonic acid

2-amino-naphthalene-5,7-disulfonic acid

2-amino-naphthalene-6,8-disulfonic acid

2-amino-naphthalene-3,6,8-trisulfonic acid

2-amino-naphthalene-4,6,8-trisulfonic acid

4-amino-azobenzene-3,4'-disulfonic acid

4-Amino-2-acetylamino-azobenzene-2 ', 5'-disulfonic acid

SO ₃ Na

NH,

(l-aminobenzene-2,5-disulfonic acid acidic on l-amino-naphthalene-6-sulfonic acid coupled)

reddish yellow
strong reddish yellow
strong reddish yellow
strong reddish yellow
strong reddish yellow
strong reddish yellow
yellowish brown
Orange brown

reddish brown

continuation

Diazo component

SO ₁ Na

SO ₃ Na

N = N

Colored ion on cellulose film

reddish brown

U-aminobenzene ^ S-disulfonic acid acidic on the technical mixture of l-aminonaphthalene-6- and -7-sulfonic acid coupled)

NH,

SO ₁ Na

(l-Amino-naphthalene-2,5,7-trisulphonic acid acidic to l-amino-naphthalene-6-sulphonic acid coupled)

purple-tinged brown

SO ₃ Na

OCH,

NaO ₃ S

NH,

reddish brown

SO ₃ Na

(l-Amino-naphthalene ^ SJ-trisulfonic acid acidic on l-Amino-I-methoxy-S-methylbenzene coupled)

Example 204

then intermediate drying and then in a suitable steamer for 30 seconds at 103 to 115 ° C steams so you get after rinsing and boiling

If one soaps cellulose fabric with a printing paste, a strong blue-tinged red print of good quality printed, which in the kilogram 30 g of the in Example 18 45 wet, rub and light fastness described dye, 100g urea, 300g Was- BeisDiel 205

ser, 500 g alginate thickening (60 g sodium alginate per

Kilograms of thickening), 10 g of soda and 10 g of a mixture of the solutions of 65.5 parts each

The sodium salt of 3-nitrobenzene sulfonic acid contains chromium 2: 1 complex and cobalt 2: 1 complex and which was made up to 1 kilogram with water, 50 plexes of the dye of the formula

OH

HO NH,

N = N

NaO ₁ S

SO ₃ Na

in 400 parts of water each is stirred with 48 parts of finely powdered 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride for about 2 hours at 20 ^° C. while maintaining pH 4.5-5.5 -Complex: blue; Cr complex: blue-green) is more detectable, the resulting mixture of the two reactive dyes is salted out with potassium chloride, filtered off and dried.

SO ₃ Na

The dye delivers on cellulosic materials by the pad dyeing process or in the presence of print acid-binding agents strong, very good wet and lightfast black tones.

If one proceeds accordingly, however, the mixture of the chromium 2: 1 and cobalt 2: 1 complex If the following aminoazo dyes are used, valuable black dyes are also obtained:

Diazo component Clutch
component Coupling
pH 1-hydroxy
2-amino-4-nitro-
benzene l-hydroxy
8-amino-naph-
thalin-3.6-disuifon- 9 acid 1-hydroxy
2-amino-4-nitro-
naphthalene-
7-sulfonic acid the same 9

CH, SO, S

CH ₃

CO-HN

Example 206

To the neutral solution of 53.15 parts of the disodium salt is added by coupling diazotized l-amino ^ -nitrobenzene ^ -sulfonic acid with l- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone- (5) and subsequent reduction of the nitro group with sodium sulfide obtained aminoazo dye in 300 parts of water 24.0 parts of 4-methyl-2-methylsulfoπyl-thiazoI-5-carboxylic acid chloride and the mixture is stirred for one hour at 25 ⁰ C, the hydrochloric acid liberated continuously on a soda solution pH value of 4 - 6 becomes blunt.

The deposited dye of the formula

SO ₁ Na

is filtered off, dissolved in 3000 parts of warm water at pH 6-7 and reprecipitated from the filtered solution by adding sodium chloride. After filtering off, drying and powdering, a yellow, readily water-soluble powder is obtained, the cellulose materials from a long liquor at 85 ⁰ C or with soda (in the cold-pad-dwell process) as an acid-binding agent in clear, washing, rubbing and colors in lightfast yellow tones.

If one proceeds as indicated above, but instead of the aminoazo dye used there equivalent amounts of those in the following

N = NC C-CH ₃

Ii Il

HO-C N

NaO ₃ S

Table listed components composed aminoazo dyes used, valuable new reactive dyes are also obtained.

In the table, the term "saponified" means that an acylamino group contained in the aminoazo dye has been subsequently saponified, during the The expression "reduced" means that a nitro group contained in the diazo component after the coupling is reduced to the amino group, the desired aminoazo dye being formed.

40

example
No.

Diazo component

Azo component pH

of the coupling medium

Hue on
Cellulose

207 i-Amino-4-nitrobenzoI- l- (4'-sulfophenyl) -3-methyl-

2-sulfonic acid pyrazoIon- (5)

(4-position nitro group then reduced) 5-6

yellow

208 the same 1 - (4'-sulfophenyl) -3-carboxy- 5-6 reddish pyrazolone- (5) 209 the same 1 - (3'-sulfophenyl) -3-methyl- 6-7 yellow 5-aminopyrazole 210 1 -amino-3-acetylamino- the same 6-7 yellow benzene-6-sulfonic acid (3-position acetylamino group then saponified) 211 the same l - (/? - hydroxyethyl) -3-methyI- 5-6 yellow pyrazolone- (5) 212 2 moles of l-amino-3-acetyl- 1 mole of bis-pyrazolone from 4,4'-bis- 5-6 yellow amino-benzoI-6-sulfonic acid hydrazinodibenzyl-2,2'-disulfone (saponified) acid and acetoacetic ethyl ester) 213 1 mole of l-amino-3-acetyl- 1 - (4'-sulfophenyl) -3-carboxy- 5-6 yellow amino-benzene-6-sulfonic acid pyrazolone- (5) 214 (saponified)
1 - amino-5-acetyl-amino- 1 - ^ '- sulfophenyOO-carboxy- 5-6 reddish naphthalene-3,7-disulfonic acid pyrazolone- (5) yellow 215 ^ verseiitj -
1-amino-2-methylbenzene- 2-acetylamino-5-naphthol- 7-8 orange 4,6-disulfonic acid 7-sulfonsiiurc (saponified)

Example 239

The neutral solution of 54.7 parts of the disodium salt of l-amino-4- (2'-methyl-3'-aminophenyl) -amino-anthraquinone-2,5'-disulfonic acid in 1000 parts of water is mixed with 24.0 parts of 4 -Methyl-2-methylsulfonyi-thiazole-5-carboxylic acid chloride was ^{stirred at 20 °} C. for one hour. The hydrochloric acid released in the process is continuously blunted with soda solution to a pH value of 6.5-7. After the reaction has ended, the resulting reactive dye is of the formula

jl

NH,

SO ₃ Na

SO., Well

O NH

CH ₃ NH-CO

salted out, filtered, washed and dried at 30-40 ⁰ C. It dyes cellulose materials in very good wet, rub and lightfast clear blue tones.

Blue dyes with similar properties are obtained by proceeding as above, but instead of the there mentioned water-soluble aminoanthraquinone derivatives equivalent amounts of those listed below Aminoanthraquinone sulfonic acid derivatives with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated:

example

Water-soluble amino-anthraquinone derivative

240 1 - Amino-4- (3'-aminophenyl) -amino-anthraquinone-2,5'-disulfonic acid '

241 1-Amino-4- (2'-chloro-3'-aminophenyl) -aminoanthraquinone-2,5'-disulfonic acid

242 1 -amino-4- (2'-methyl-3'-methylaminophenyl) -amino-anthraquinone-2.5'-disulfone- acid

243 1-Amino-4- (4'-aminophenyl) -aminoanthraquinone-2,6,3'-trisulfonic acid

244 1-Amino-4- (3'-aminophenyl) -aminoanthraquinone-2,6,4'-trisulfonic acid

245 l-Amino-4- (4'-aminophenyl) -aminoanthraquinone-2,5,3'-trisulfonic acid

246 1-Amino-4- (3'-aminophenyl) -aminoanthraquinone-2,5,4'-trisulfonic acid

247 Mixture of l-amino-4- (3'-aminophenyl) -amino-anthraquinone-2,4 ', 5- and 2.4 ', 8-trisulfonic acid

further with 5% oleum at 20-30 ⁰ C nachsulfierten derivatives:

248 1-Amino-4- [4 '- (4 "-aminobenzyl) -phenyl] -amino-anthraquinone-2-sulfonic acid

249 1 - Amino-4- (4'-methylaminophenyl) -aminoanthraquinone-2-sulfonic acid

250 1 -Amino ^ -P'-methylaminophenyO-aminoanthraquinone-2-sulfonic acid

251 l-Amino-4- (2'-methylaminophenyl) -aminoanthraquinone-2-sulfonic acid

252 1 - Amino-4- (7'-amino-naphthyl- [2 ']) -amino-anthraquinone-2-sulfonic acid

253 condensation product of 1 mole of cyanuric chloride with 1 mole of 1,4-diamino-anthraquinone-2-sulfonic acid, 1 mole of aniline-2,5-disulfonic acid and 1 mole of ethylenediamine (one side), after acylation with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride a purple reactive dye.

SO ₂ CH ₃

Example 254

A solution of 107 g of a mixture of equal molar proportions of copper phthalocyanine trisulfonic acid (3.3 ', 3 ") mono- (m-amino-p-sulfophenyl) amide and copper phthalocyanine trisulfonic acid (3.3', 3") ") -di (m-aminop-sulfophenyl) -amide is adjusted to 1.3 liters and pH 6; at 1O ⁰ C 37.1 g of 4-methyl-2-methylsulfonyl-thiazol-5-carboxylic acid chloride are added. While stirring, the temperature is increased by 5 ° C per hour, and finally left for several hours at 20-25 ⁰ C. At the same time, 3N NaOH is added dropwise to maintain a pH of about 6.1-6.9 until, on average, every dye molecule has at least one 4-methyl-2-methylsulfonyl-thiazole-5-carbonamido radical, which is partly due to the consumption of the sodium hydroxide solution and, on the other hand, can be easily ascertained by an amino group determination. The 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride can also be added dissolved in Acton. For work-up, the dye solution can also be warmed up slightly at the stated pH without the reactivity of the dye with the cellulose being significantly reduced. The unreacted thiazole carboxylic acid chloride and the saponification products formed therefrom are separated off by filtration or in a separator. The reaction product is precipitated by adding 150 g of table salt per liter of dye solution. It is filtered off with suction and dried ^{in vacuo or at about 30 ° C. under normal pressure.} 195-20Og of crude dye are obtained, which still contains about 30% sodium chloride. The sodium chloride can largely be removed by stirring the raw dye with 250 ml of water and again suctioning it off.

The dyestuff dyes cellulose materials by the pad-thermofix at 140 ⁰ C and after the pad-steam method in wet-, frictional and lightfast turquoise shades.

The dye mixture used as the starting material can be obtained by methods known per se be e.g. B. by adding an aqueous suspension of sulfonic acid group-free copper phthalocyanine trisul-

Fonsäurechlorid at 0-20 ⁰ C 3 mol of 2,4-diaminobenzenesulfonic acid at a pH of about 6.5 is added and at the same time with 3 mol of pyridine catalyzes the saponification, the above-mentioned mixture of Pc-sulfonamides being formed.

A similar product is obtained if a mixture is used as the starting material that contains the contains mentioned components in a molar ratio of 4: 1. This mixture is made from the same copper phthalate

39

continuation

example
No.

Diazo component

Λ / o component

pH shade up

des Kuppkings cellulose
mediums

216 1-amino-2-methylbenzene 2-acctyluinino-o-naphthol- 7-8 Red 4.6-disull'on.saure 6-suiron.säui "C (saponified) 217 l-amino-2-methylbenzene l-chloro ^ -acetykiminoo-naphthol- 7-8 orange 4,6-disulfonic acid 7-suironic acid (saponified) 218 1-aminobenzene-2-sulfonic acid l-aeetvlamino-8-hydroxynaphthalene- 7-8 Red 4.6-disullons; uire (saponified) 219 2-aminonaphthalene.-3.6-di- the same 7-8 bluish tint sulfonic acid Red 220 2-aminonaphthalene-3.7-di- the same 7-8 bluish tint sulfonic acid Red 221 2-aminonaphthalene-4,8-di- the same 7-8 bluish tint sulfonic acid Red 222 2-aminonaphthalene-3.6-di- l-acctylamino-8-hydroxynaphthalene- 7-8 bluish tint sulfonic acid 3.6-disulfonic acid (saponified) Red 223 2-aminonaphthalene-4.8-di- 1 - acetylamino-8-hydroxy- 7-8 bluish tint sulfonic acid imphthalin-3,6-disulfonic acid Red (saponified) 224 ] -Amino-4-methoxybenzene- 2- (N-acetyl-N-methylamino) - 7-8 yellowish 2-sulfonic acid 5-hydroxynaphthalene-7-sulfonic acid Red (saponified) 225 the same 2- (N-acetyl-N-methylamino) - 7-8 Red 8-hydroxynaphthalene-6-sulfonic acid (saponified) 226 1 - aminobenzene-2-sulfonic acid the same 7-8 Red 227 1-aminobenzene-3-sulfonic acid the same 7-8 Red 228 1-aminobenzene-4-sulfonic acid the same 7-8 Red 229 l-amino-4-methyl- the same 7-8 Red benzene-2-sulfonic acid 230 1 - Amino-2,4-dimethylbenzene 2- (N-Acetyl-N-meihy! Amino) - 7-8 Red 6-sulfonic acid 8-hydroxynaphthalene-6-sulfonic acid (saponified) 231 the same 2-acetylamino-8-hydroxy 7-8 Red naphthalene-6-sulfonic acid (saponified) 232 '1 -Amino ^^ - dimethylbenzene- 2-acetylamino-8-hydroxy 7-8 Red 6-sulfonic acid naphthalene-3,6-disulfonic acid (saponified) 233 4-aminoazobenzene-3,4'-di- 1-amino-3-acetylaminobenzene 5-6 Yellow-brown sulfonic acid 234 the same 1 - Amino-3-hydroxyacetylamino- 5-6 Yellow-brown benzene 235 the same l-amino-naphthalene-6-sulfonic acid 5-6 Yellow-brown 236 the same l-amino-naphthalene-7-sulfonic acid 5-6 Yellow-brown 237 the same 1-amino-2- (4'-amino-2'-sulfo- 8th black

phenyl- (1 ') -azo) -8-hydroxynaphthalene-3,6-disulfonic acid

Example 238

52.4 parts of the disodium salt of 4 - ([4 "-aminophenyl] -amino) -2'-nitrodiphenylamine-3,4'-disulfonic acid verden dissolved in 1000 parts of water and with 24.0 parts

4-Methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride was ^{stirred at 20 °} C. for one hour. The hydrochloric acid released is continuously blunted with soda to a pH value of 4 - 6. The formed reactive nitro dye of the formula

NaO ₃ S

y ν

NH

NO ₁

NH-CO

SO ₇ CH,

SO ₃ Na

/ is salted out, filtered off, washed and dried. It dyes cellulose fibers from a long liquor or afterwards in the usual Klotz method in the presence of soda as an acid-binding agent in wet and rub-resistant, dark purple-brown tones.

609 535/412

cyanine trisulfonic acid chloride and 2 mol 2,4-diaminobenzenesulfonic acid obtained by the same procedure.

Instead of the starting materials mentioned, it is also possible to use those which act as the central atom Containing nickel instead of copper or those made from copper phthalocyanine trisulfonic acid chloride (4,4 ', 4 ") or from phthalocyanine tetrasulfonic acid chloride (3,4 ', 4 ", 4'") or - (4,4 ', 4 ", 4'") or using other arylenediamine sulfonic acids, such as toluene-diamine- (2,4) -sulphonic acid- (5); 4,4'-diamino-dibenzyl-disulphonic acid- (2,2 '), Naphthylenediamine- (1,5) disulfonic acid- (3,7). Such products and their manufacture have been described many times in the patent literature. Your implementation with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride can always be done in the same way.

This also applies to the conversion of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride with the copper and nickel phthalocyanine intermediates leading to green reactive dyes how they z. B. by polysulfochlorination of tetra- (3,3 ', 3 ", 3'") - (p-tolylmercapto) copper phthalocyanine with chlorosulfonic acid,

SO ₃ Na HO NH-CO S

SO ₃ Na

Condensation of 1 to 2 sulfochloride groups per molecule with 1,3-phenylenediamine-4-sulfonic acid or 1,4-phenylenediamine-3-sulfonic acid and saponification of the remaining sulfochloride groups are available; also the uniform or mixed amino and sulfo group-containing arylation and alkylation products of tri- and tetramercapto-copper (or nickel) phthalocyanine can be carried out in an analogous manner Acylation of their amino group with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride be converted into valuable green reactive dyes.

Example! 255

If one proceeds according to the instructions in Example 18, but the dye intermediate obtained not with the diazo compound from 17.5 parts of 2-aminobenzenesulfonic acid, but with the diazo compound from 20.8 parts of 3-chloroaniline-6-sulfonic acid in

In the presence of 12 parts of soda at a final pH of 7, a reactive dye of the formula is obtained
CH ₃

SO ₂ CH ₃

Cl NaO ₃ S

can be colored or with the cellulosic materials from a long liquor at 40 ⁰ C, or after a customary for reactive dyes padding or printing processes with soda as acid-binding agent in wet-fast, brilliant red colors printed.

In an analogous manner, the coupling components listed in the table below are obtained through Acylation of their amino group with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride and coupling of the dye intermediates formed with the specified diazo components valuable reactive dyes, with which cellulose materials in the listed shades - preferably in the presence of soda - can be colored or printed:

example
No. Diazo component Coupling component Coupling pH hue 256 1 - amino-4-methoxybenzene 1 -amino-8-hydroxynaphthalene- 7-8 violet 6-sulfonic acid 3,6-disulfonic acid 257 the same 1 -amino-8-hydroxynaphthalene- 7-8 reddish 4,6-disulfonic acid violet 258 the same 2-amino-5-hydroxynaphthalene 7 ■ Scarlet fever 1.7-disulfonic acid 259 1 -amino-5-chloro-benzene- the same 7th orange 2-sulfonic acid 260 1-aminobenzene-3-sulfonic acid the same 7th orange 261 1-aminobenzene-4-sulfonic acid the same 7th orange 262 the same 2-amino-8-hydroxynaphthalene 7-8 Scarlet fever 3,6-disulfonic acid 263 4-aminobenzoic acid - (/? - sulfo- 1 - amino-8-hydroxynaphthalene- 7-8 Red ethyl) amide 3,6-disulfonic acid 264 1-amino-4-sulfoacetylamino- the same 7-8 violet benzene-6-sulfonic acid 265 1 - Amino-3-sulfoacetylamino- 2-amino-5-hydroxynaphthalene 7th orange benzene-6-sulfonic acid 1,7-disulfonic acid 266 1-amino-4-sulfoacetylamino- 2-amino-5-hydroxynaphthalene 7th Scarlet fever benzene 1,7-disulfonic acid 267 1-aminobenzene-2,4-disulfone- 1 - ^ '- methyl ^' - amino-S'-sulfo- 6th yellow acid phenyl) -3-methyl-pyrazolone- (5) 268 2-amino-naphthalene-4,8-di- the same 6th yellow sulfonic acid

Example 269

If you proceed according to the instructions in Example 30, but that from 1,3-diaminobenzene-6-sulfonic acid and i-methyl ^ -methylsulfonylthiazole-S-carboxylic acid

CH ₁ SO

CH ₃

CO-NH

SO ₃ H

N = N

HO ₃ S

the cellulose materials according to the usual application process with soda as an acid-binding agent in real shades of orange.

Example 270

If one proceeds as indicated in Example 206, but instead of the Aminoazofarb substance used there 53.15 parts of the disodium salt obtained by coupling diazotized l-amino-l-nitrobenzene ^ -sulfonic acid with l- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone- (5) and subsequent reduction of the nitro group

rechlorid obtained dye intermediate after the diazotization at 1O ⁰ C and pH 7.5 to 6.5 with the solution of 40.5 parts of the disodium salt of 2-Sulfoacetylamino-5-hydroxynaphthalene-7-sulfonic acid coupling, to obtain a reactive dye of the formula

NH-CO-CH ₂ -SO ₃ H

aminoazo dye obtained with sodium sulfide with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated, a valuable reactive dye is also obtained, with which cellulose materials can be printed in real yellow tones using the usual dyeing and printing processes.

Similar reactive dyes are obtained if, instead of the aminoazo dye mentioned above, one of the aminoazo dyes built up from the components listed in the table below with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated:

example
No.

Diazo component

A / .okoinpoiienie

hue

271 1 -amino ^ -nitrobenzene ^ -sulfone- l- (2'-methyl-4'-sulfophenyl) -3-methyl- acid (reduced) pyrazolone- (5) 272 the same 1 '(2', 5'-disulfophenyl) -3-methyl- pyrazolone- (S) 273 the same l- (2'-methyl-4'-sulfo-6'-chlorophenyl) - 3-methylpyrazolone- (5) 274 1 -amino ^ -nitrobenzene ^ -sulfone- l- (2'.5'-dichloro-4'-sulfophenyl) - acid (reduced) 3-methylpyr; izolon- (5) 275 1 - Amino-3-acetylaminobenzene- l- (2'-methyl-4'-sulfophenyl) -3-methyl- 6-sulfonic acid (saponified) pyrazolone- (5) 276 the same 1 - (4'-sulfophenyl) -3-methyl- pyrazolone- (5) 277 the same l- (2'-methyl-4'-sulfophenyl) -3-carboxy- pyrazolone- (S) 278 the same l- (2'-chloro-4'-sulfophenyl) -3-carboxy- pyrazolone- (S)

yellow

yellow

yellow

yellow

greenish yellow greenish yellow greenish yellow greenish yellow

Example 279
58 parts of the dye of the formula

NaO ₃ S

(produced by coupling diazotized 1-hydroxy

2-amino-4-chloro-benzene-5-sulfonic acid on 2-methylami-

no-8-hydroxy-naphthalene-6-sulfonic acid and copper plating

of the obtained azo dye) are in 700 parts

Water dissolved neutrally. 24.0 parts are finely added

NH - CH ₃ powdered 4-methyl-2-methylsulfonyl-thiazole-5-car-

to bonsäurechlorid and stirred at 20 ⁰ C with constant

Blunt the released hydrochloric acid with soda oil

sung to pH 5 - 6, until there are no more free amino groups

is demonstrable. The reactive dye formed the

formula

O Cu

N = N

NaO ₃ SI NaO ₃ S
Cl

CH ₃

N-CO S SO ₂ CH ₃

is salted out, filtered off, washed and dried at 30-40 ° C. He colors according to one of the above specified method cellulose materials in very real violet tones.

Dyes with similar properties are obtained analogously to the procedure described above from the -

obtained by simple, demethylating or oxidizing copper plating - copper complexes of the in the following table listed diazo and azo components produced mono- and disazo dyes:

example
No. Diazo component A / .okomponenie Coupling pH hue 280 l-hydroxy-2-amino-4-chloro 2-amino-8-hydroxynaphthalene 10 reddish benzene-5-sulfonic acid 3.6-disulfonic acid violet 281 the same 1 -amino-8-hydroxynaphthalene- 10 bluish tint 3,6-disulfonic acid violet 282 2-amino-naphthalene-4,6,8-tri- 2-hydroxy-6-acetylamino- 8-9 reddish sulfonic acid (oxidizing naphthalene-4-sulfonic acid (saponified) blue

coppered)

283 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid
(reduced)

284 i-Hydroxy-2-aminobenzene-4,6-disulfonic acid

285 2-amino-naphthalene-4,8-disulfonic acid
(oxidizing copper)

286 2-aminonaphthalene-4,6,8-trisulfonic acid
(oxidizing copper)

287 S-methoxy ^ -amino-ö-methylazobenzene-2 ', 4'-disulfonic acid
(demethylating coppered)

288 the same.

289 the same.

290 S-methoxy ^ -amino-ö-methylazobenzene-2 ', 5'-disulfonic acid
(demethylating coppered)

291 3-Methoxy-4-amino-6-methylazobenzene-2 ', 5'-disulfonic acid
(demethylating coppered)

292 the same.

1-Hydroxy-8-ethoxy-naphthalene-3,6-disulfonic acid

blue

2-hydroxy-3-aminonaphthalene
5,7-disulfonic acid
the same 10
8-9 Red
blue 2-Hydroxy-3-aminonaphtha! In-
7-sulfonic acid 8-9 blue 2-methylamino-5-hydroxy
naphtha, haline-7-sulfonic acid 10 Navy blue 2-amino-8-hydroxynaphthalene
3,6-disulfonic acid
2-amino-5-hydroxynaphthalene
1,7-disulfonic acid
2-methylamino-5-hydroxy
naphthalene-7-sulfonic acid 10
10
10 Navy blue
Navy blue
Navy blue 2-amino-8-hydroxynaphthalene
3,6-disulfonic acid 10 Navy blue 2-amino-5-hvdroxvnarjhthalin- 10 Navy blue

1,7-disulfonic acid

example

If one proceeds according to the information in Example 239, however, instead of the 54.7 parts mentioned there, the Disodium salt of 1-amino-4 - ((2'-methyl-3'-aminophenyl) -amino) -anthraquinone-2,5-disulfonic acid 63.5 parts of the trisodium salt of l-amino-4 - ((3'-aminophenyl) -amino) -anthraquinone-2,4 ', 6' - (or. 2,2 ', 6') - trisulfonic acid, a reactive dye is obtained which Cellulose fibers after one of the usual dyeing processes in very good wetfast, clear, reddish cast Shades of blue.

When using equivalent amounts of l-amino-4 (3'-aminophenyl-amino) -anthraquinone-2,5,8-trisulfonic acid you also get a valuable reactive dye, cotton, in real grayish blue tones colors.

example

30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid are dissolved neutrally in 300 parts of water and 18.6 Part 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride added. In the course of an hour, 30 parts of 15% soda solution are added so that the pH value is between 4 - 6. The acylation product partially precipitates.

A freshly prepared diazonium salt solution from 13.6 parts of p-aminobenzylsulfonic acid is at 0-5 ° C in the suspension of the acylation product mixed with 12.5 parts of soda was added dropwise. After five hours Stirring at ice bath temperature is then salted out with common salt, filtered off with suction, with dilute common salt solution rewashed and at 30 ° C in a vacuum drying

609 535/412

cupboard dried. The dye obtained corresponds to the formula

NaO ₃ S -CH ₂ - / ~ \ -N = N

NaO ₃ S

NH

SO ₃ Na

SO ₂ CH ₃

If one proceeds as indicated above, but instead of 30.4 parts of 2-amino-8-oxynaphthalene-3,6-disulfonic acid 30.4 parts of 2-amino-5-oxynaphthalene-1,7-disulfonic acid with 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acrylated and the coupling component containing reactive groups with diazotized p-aminobenzylsulfonic acid couples, a readily soluble reactive dye containing cellulose fibers is obtained Dyes fabric in brilliant red-tinged orange tones.

You impregnate cotton or rayon fabric on a padder with a solution of 20-25 ° C, the pro Liters of liquor 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g Contains soda, presses to a moisture content of approx. 80% and rolls up the moist tissue again. After 24 hours of storage at room temperature, the fabric is rinsed and soaped at the boil in the usual way and dried. A brilliant, scarlet dyeing of good wet and light fastness is obtained.

You impregnate cotton or rayon fabric on a padder at 20-25 ° C with a solution that pro Liters of liquor 30 g of the dye described in this example, paragraph 1, 100 g of urea and 20 g Soda contains, squeezes to a moisture content of approx. 100% and steams for 10-120 seconds 103 ° C. After rinsing, boiling soaps and Drying also gives a brilliant scarlet dyeing with good wet and light fastness.

Cotton fabric is impregnated with a solution at 20-25 ° C containing 20 g of the dye obtainable according to this example, paragraph 1, 100 g of sodium m-nitrobenzenesulfonate and 0.5 g of a nonionic wetting agent (e.g. one polyoxyethylated oleyl alcohol) as well as 150 g urea and 15 g sodium bicarbonate. The fabric is then squeezed between two rollers to a moisture content of approx. 100%. After intermediate drying at 50 -6O ⁰ C for 10 minutes at 140 ° C is heated and purged the coloration thus obtained thoroughly with hot water and boiling for 10 minutes with a solution containing per liter 5 g of Marseilles soap and 2 g sodium carbonate. After rinsing and drying, a strong, scarlet coloration with good wet and light fastness is obtained.

If you print cellulose fabric with a printing paste containing 30 g of the kilogram in this example,

HO ₁ S

Paragraph 1, described dye, 100 g of urea, 300 g of water, 500 g of alginate thickening (60 g of sodium alginate per kilogram of thickening), 10 g of soda and 10 g of the sodium salt of 3-nitrobenzenesulfonic acid and which was made up to 1 kilogram with water, then 30 seconds attenuates between dry and then in a suitable steamer at 103-115 ⁰ C, then, after rinsing and soaping at the boil to obtain a strong scarlet dyeing having good fastness properties.

100 parts of wool are placed in a bath at 40 ° C. in which 1.5 parts of the in this example, paragraph 1, described dye and 6 parts of 30% acetic acid and 0.5 parts of a contains polyoxyethylated hydroxyl-containing stearylamine derivatives. The dye bath is in 30 Bring to a boil for minutes, then boil dyeing for an hour. Preserves after rinsing and drying you get a brilliant, washable, millfast and lightfast scarlet coloration.

Example 295

28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid are diazotized (Monosodium salt) and couples the diazo compound with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in weakly acidic medium. The monoazo dye obtained is isolated and then or immediately diazotized in solution even without isolation and treated with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid alkaline coupled. The disazo dye obtained is salted out by adding sodium chloride, suctioned off and the isolated product with about 50 parts of crystallized copper sulfate, 40 parts Diethanolamine, 50 parts of ammonia (D: 0.88) metallized in 5 hours at 95-100 ° C. From the copper plating solution the dye is isolated by adding salt and carefully acidifying.

The coppered amino-disazo dye is now in aqueous solution at pH 4-6 at a temperature of 20 ° C with 24 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride acylated, the pH being kept in the specified range by adding soda. When the acylation has ended, the dye is isolated using sodium chloride and dried at 35.degree. the In the form of the free sulfonic acid, the dye corresponds to the formula:

SO ₃ H

SO, CH ₄

he dyes cellulose fabric using the methods known for reactive dyes in wet and lightfast navy blue Tones.

In a similar way, further inventive Dyes can be produced by using the above-mentioned monoazo dye from 2-amino-1-methyI-benzene-3,5-disulfonic acid and 1-amino-2-methoxy-5-methylbenzene with the aminonaphtholsulphonic acids and 4-methyl-Z-methylsulphonyl-thiazole-S-carboxylic acid chloride listed in the table below combined according to the regulation given above.

Coupling component:

2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 2-amino-8-hydroxynaphthalene-3,6-disulfonic acid. The dyes obtained are blue in color.

52
Example 296

CH ₁ SO

is salted out. A blue coloration is obtained on cotton.

Example 297

A neutral paste of copper phthalocyanine-3,3 ', 3 "-trisulfonic acid chloride produced from 600 g of technical grade 96% copper phthalocyanine is stirred with a little water, adjusted to 4 liters and at a pH of 3.5-6.0 with 216 g of N -Methyl-N- (4'-amino-2'-suifobenzyl) -amine reacted at initially 0-3 ⁰ C, last 20-35 ⁰ C, with the addition of 300 ml (295 g) pyridine and then the pyridine at pH 9.0 distilled off with steam from the resulting solution of copper phthalocyanine disulfonic acid monosulfonsäure- (3'-sulfo-4'-methyl-aminomethyl-anilide). portionwise 305 g of finely powdered 4-methyl Add the cooled to 10 ⁰ C solution -2-methylsulfonyl-thiazole-5-carboxylic acid chloride sprinkled in over the course of 1 to 2 hours and a pH of 7.5-8.5 is maintained by adding dilute sodium hydroxide solution Dye always remains dissolved.

101 dye solution is obtained, which one from Remove excess acylating agent, adjust to pH 7.0 by adding acetic acid and stir in of 2.5 1 concentrated saline solution falls.

After suctioning off and drying at 3O ⁰ C, a clear turquoise-blue dye is obtained, which is made from soda-alkali

CH ₃ s— ^ HN ο-
ί NH ₂ HO ₃ / ⁷ X- co - T - Cu - -N = N- - O
I. Til Λ /

0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid are diazotized and soda-alkaline with 0.1 mol

l-amino-8-hydroxynaphthalene-2,4-disulfonic acid coupled. The coupling solution is applied with caustic soda to a Set content of 2 mol / liter and then reflux for 3 hours to saponify the ureido group cooked. After cooling, it is mixed with hydrochloric acid

ίο neutralized. By adding 25 parts of copper sulfate and 100 parts of 2N sodium hydroxide solution of the dye at 45 ⁰ C and a pH of 4 - 6 metallized and after 30 minutes at pH 4-6 and temperatures of 2O ⁰ C with 0.1 mol of 4- Methyl-2-methylsulfonyl-thiazole-5-

acylated carboxylic acid chloride. The obtained dye of the formula

SO ₃ H

SO ₃ H

shear solution at 40 - 60 ° C with very good yield and Washfastness is fixed on cotton.

If the NiPc-3,3 ', 3 "-trisulfonic acid chloride is used as the starting material, only a little is obtained Greener turquoise blue with equally valuable properties.

Example 298

12.5 parts of 3-amino-4-suIfobenzyl-N-methylamine are

dissolved in 150 parts by volume of concentrated hydrochloric acid. 4 parts of sodium nitrite in 20 parts by volume of water are added dropwise to the solution. The resulting clear diazonium salt solution becomes at 30-35 ° C an aqueous solution of the equimolar amount of 1 -N-benzoyl-amino-S-oxynaphthalene ^ .ö-disulfonic acid and 16 parts of sodium bicarbonate in 200 parts by volume of water.

The dye partially precipitates and is redissolved by adding 2000 parts by volume of water

brought. At 20 ^° C., 17.6 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride are then added. A soda solution is added dropwise to keep the pH between 6 and 7. After completion of the acylation, as is recognized in the soda consumption, it separates the dye with 10 percent sodium chloride from sucks and compresses, and pressed and dried in a vacuum oven at 30 ⁰ C. The bluish-red dye obtained conforms in the form of the free acid of the formula

SO, H

HO NH-OCC ₆ H ₅

CH ₂ HO ₃ S

CH ₃ SO ₂ S CO -N-CH ₃ SO ₃ H

299

example

38.9 parts by sodaalkalische coupling of 5-nitro-2-diazo-l-hydroxybenzene-4-sulphonic acid and 2-hydroxynaphthalene dye obtained are stirred in 200 parts of water at pH 8 at a temperature of 70-80 ⁰ C. 67.9 parts of the chromium complex compound of the azo dye from 4-chloro-2-diazo-1-hydroxybenzene-6-sulfone- containing 1 chromium atom per molecule of dye are carried into this suspension.

54

acid and l-amino-S-hydroxynaphthalene-S.ö-disulfonic acid, the pH being kept between 7 and 9 by adding soda solution. After 20 minutes at 70-80 ° C a dark blue solution has formed. The paper chromatogram shows that a uniform mixed complex has formed. The mixed complex is acylated within 30 minutes at 3 ° C. and pH 4-6 with 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride, the pH being kept in the specified range by adding a soda solution dropwise. The acylated dyestuff is salted out with 20% potassium chloride, filtered off and dried at 30 ⁰ C. A dark powder is obtained which dissolves in water with a blue-gray color.

The pentasodium salt of the dye corresponds to the formula

SO ₂ CH ₃

5 Na®

It dyes cotton in gray to black shades using the method given in Examples 1-3.

Valuable starting components can also be obtained from the following table Dyes in the manner indicated in this example

SO, received. For the production of these dyes was the azo dye, which carries the reactive group in the 2: 1 mixed complex, is always used as a 1: 1 chromium complex.

35

example

1: 1 chromium complex

Metal-free dye hue on cotton

300 4-nitro-2-amino-l-hydroxybenzene

6-sulfonic acid -> i-amino-8-hydroxynaphthalene-3,6-disulfonic acid

301
302
303 the same
the same
the same 304
305 the same
the same 306 the same 307 the same 308 the same 309 4 nitro

4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid - »l-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

310 4-ChloΓ-2-amino-1-hydroxybenzene-6-sulfonic acid - 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

311 the same.

312 the same.

313 the same.

4-nitro-2-amino-1-hydroxybenzene black

-> ■ 2-hydroxynaphthalene

also black

also black

4-nitro-2-amino-l-hydroxybenzene black

- ■ 2-hydroxynaphthalene-6-sulfonic acid

also black

4-nitro-2-amino-l-hydroxybenzene navy blue

- * 1 -Hydroxynaphthalene-4-sulfonic acid 6-nitro-2-amino-1-hydroxybenzene-4-sulfone black acid - 2-hydroxynaphthalene

4-nitro-2-amino-l-hydroxybenzene black

- «■ 1 -acetylamino-7-hydroxynaphthalene

6-nitro-1 -amino-2-hydroxynaphthalene- black

4-sulfonic acid - 2-hydroxynaphthalene

4-nitro-2-amino-1-hydroxynaphthalene black

6-sulfonic acid - 2-hydroxynaphthalene

4-nitro-2-amino-l-hydroxybenzene blue-black

- 2-hydroxynaphthalene

also blue-black

4-nitro-2-amino-1-hydroxybenzene blue-black

- »2-Hydroxynaphthalene-6-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene, navy blue

- 2-hydroxynaphthalene

56

continuation

example
No.

1: 1 chromium complex

Metiilll'reier Fnrbsloli

Hue; on cotton

314 4-chloro-2-amino-1-hydroxyben / ol-6-sulfonic acid -► l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

315 the same.

316 desg!

317 the same.

318 ^ Nitro ^ -amino-i-hydroxybenzene-6-sulfonic acid -► l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

319 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid - »■ 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

320 4-Methyl-2-amino-1-hydroxybenzene-6-sulfonic acid -> ■ l-amino-8-hydroxynaphthalene-3,6-disulfonic acid

321 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid ■ -> · 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid

322 the same.

323 the same.

324 the same.

4-nitro-2-amino-1-hydroxybenzene

- 1-Acetylamino-S-hydroxynaphthalene-3,6-disulfonic acid
4-NitiO-2-amino-1-hydroxybenzene

- 1-Amino-8-hydroxy-oxynaphthalene-2,4-disulfonic acid

ö -nitro-1-amino ^ -hydroxynaphthalene-4-s-sulfonic acid - * 2-hydroxynaphthalene

acid - · l-phenyl ^ -methyl-S-pyrazolone 6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid -► 2-hydroxynaphthalene

4-chloro-2-amino-1-hydroxybenzene - »· 1 - (4'-sulfophenyl) -3-methyl-5-pyrazolone

4-chloro-2-amino-1-hydroxybenzene - »2-hydroxynaphthalene-6-sulfonic acid

5-nitro-2-amino-1-hydroxybenzene - + 2-hydroxynaphthalene-6-sulfonic acid

4-nitro-2-amino-1-hydroxybenzene - ♦ 2-hydroxynaphthalene-8-sulfonic acid 4-nitro-2-amino-1-hydroxybenzene - * 1 -hydroxynaphthalene-5-sulfonic acid 6-nitro-4-chloro-l-hydroxybenzene -> ■ l-hydroxynaphthalene-5-sulfonic acid

blue navy blue

blue black

gray-green

black

violet

reddish blue black

black black black

62.0 parts of the trisodium salt of 4-chloro-2-amino-1-hydroxybenzene-6-sulfonic acid diazotized by soda-alkaline coupling and l-amino-8-hydroxynaphthalene-3,6-disulfonic acid obtained in 300 parts of water at 70-80 ° C and a pH of 8-9 with 54.2 parts of the 1: 1 chromium complex of the dye from e-nitro-l-diazo ^ -hydroxynaphthalene ^ -sulfonic acid and 2-hydroxynaphthalene added. After 10 minutes a deep blue solution has formed.

The mixed complex is mixed with 24.0 parts of 4-methyl-2-methylsulfonyl-thiazole-5-carboxylic acid chloride in about 15 minutes at 0-5 ° C. and a pH of 4-6 acrylated. The pH value is kept constant by adding soda solution. The acylated dye is precipitated with 20% sodium chloride, filtered off with suction and dried at 30.degree.

SO ₂ CH ₃

O ₃ S

SO ₃ 5 Na®

The process given in Example 3 gives a blue-black print of on cotton excellent light and wash fastness.

609 535/412

Example 325

6 g of l-amino-4- (4'-aminophenylamino) anthraquinone-2,5,8-trisulfonic acid are dissolved as Na salt in 180 ml of water at 40 ° C., the solution is adjusted to pH 8 and at 5-10 ⁰ C 2.4 g of 4-methyl-2-methyl-sulfonyl-thiazole-5-carboxylic acid chloride entered in small portions. At the same time, one leaves dilute sodium hydroxide solution

NaO ₁

NH,

S 0., Na

NaO ₃ S

below 40 ⁰ C in a vacuum. About 8.5 g of the dye are obtained in the form of blue-green needles.

The dye dyes cotton in a strong blue-green according to the methods customary for reactive dyes Shades of good wet and light fastness.

The l-amino-4- (4'-

Amino-phenylamino) anthraquinone-2,5,8-trisulfonic acid was obtained as follows: 31.2 g of p-phenylenediamine are under nitrogen in a solution of 62 g of 1 -amino ^ -bromo-anthraquinone ^ .S.S-trisulfonic acid Na-

add dropwise in such a way that a pH of 6 to 7 is maintained during the reaction. The mixture is stirred as long as claimed at 20 ⁰ C until all the starting material disappeared, filtered off excess Thiazolcarbonsäurechlorid and salted out at 10 ⁰ C with so much solid sodium chloride, so that about a 10% sodium chloride solution. It is filtered off with suction, washed with a little sodium chloride solution and the resulting dye of the formula is dried

NH

SO ₂ CH ₃

Trium and 12 g of soda and stirred with the addition of CuCl paste at 40 ⁰ C until no more disulphated bromamic acid can be detected. Dilute hydrochloric acid is then added to the solution, the dyestuff which precipitates out is filtered off with suction, washed with dilute hydrochloric acid, and so much dilute sodium hydroxide solution is added to 300 ml of water that solution occurs and the dyestuff is precipitated as Na salt when heated; the product is then washed and dried.

Claims (1)

Patent claims: 1. Reactive dye of the general formula -N F-X- C-Y The present invention relates to valuable new reactive dyes of the general formula