DE1544499C3 - Reactive dyes - Google Patents

Description

The present invention relates to reactive dyes of the formula

F-X-A

where F = residue of a dye from the series of the azo, anthraquinone or phthalocyanine dyes, X = -N (R) -, where X is directly attached to the radical A and directly or is bound via a bridge member to an aromatic ring of the dye residue F, R = H or lower Alkyl, A = radical of a pyrimidine or 1,3,5-triazine ring of the at least one reactive sulfonyl substituent Contains bonded to a carbon atom of the heterocyclic ring, being in the series of pyrimidine dyes the binding arrangement

reactive sulfonyl substituent

F-X-

is present, with the exception of those manufactured according to the process of German Patent 12 58 993, as well as their Use for dyeing and printing hydroxyl groups and N-containing materials.

Preferred dyes are those with X = -NH-. Preferred alkyl groups R are those with 1-5 carbon atoms. The amino groups -N (R) - are on the one hand linked directly to the radical A and are on the other side either directly or via another bridge link, such as —SO2 “or —CO— (such as in the case of amide groups) or via an alkylene group, an arylene-, arylene-SCb-, arylene -CO-, Arylenamino or aralkylenamino group or a triazine or diazine ring, an arylenamidosulfonyl group or other types of members attached to an aromatic ring of the dye F. Contain such other bridge members heterocyclic ring systems as in the case of triazinyl or pyrimidinyl radicals, so these still reactive atoms or groups, such as halogen atoms or sulfonyl substituents, exhibit.

The reactive sulfonyl substituents in radical A are lower alkylsulfonyl radicals with preferably 1-5 C atoms, like

Methylsulfonyl, ethylsulfonyl or

Propylsulfonyl radicals,

Arylsulfonyl radicals, such as

Phenylsulfonyl, p-toluenesulfonyl,

p-chlorophenyl sulfonyl radicals,

Aralkylsulfonyl radicals, such as

Benzylsulfonyl and

p-Toluylmethylsulfonylreste, and also

Heterosulfonyl radicals, such as

2-benzothiazolesulfonyl,
in question.

As suitable heterocyclic rings A, which have at least one reactive sulfonyl substituent, include, for example:

2-carboxymethylsulfonyl-4-pyrimidinyl-,

2-methylsulfonyl-4-methyl-6-pyrimidinyl,

2-phenylsulfonyl-4-methyl-6-pyrimidinyl-,

2-phenylsulfonyl-4-methyl-5-crllor-

6-pyrimidinyl,

2,4-bis-methylsulfonyl-6-pyrimidinyl-,

2,4-bis-methylsulfonyl-4- or

-5-carbamidylpyrimidine,

2,4-bis-methylsulfonyl-5-sulfamidyl-

pyrimidine,

l-methylsulfonyl-3-triazinyl-,

l-methylsulfonyl-3- (3'-sulfophenylamino) -

5-triazinyl,

1-methylsulfonyl-3- (2'-hydroxyethylamino) -

5-triazinyl,

l-methylsulfonyl-S-amino-S-triazinyl-,

l-methylsulfonyl-S-methoxy-S-triazinyl-,

l-methylsulfonyl-3- (2'-benzthiazolyl) -

thio-5-triazinyl-,

l- (4'-methylphenyl-sulfonyl) -3-phenyl-

5-triazinyl-.

The reactive sulfonyl substituent or substituents in the core A can be further substituted by ionic or non-ionic groups, e.g. B. by carboxy (for example in the form of carboxymethyl), hydroxy, nitro or halogen (C1, Br) radicals. Among the large number of possible and preparatively useful radicals X, the following examples should be mentioned: -NH-, -N (CH ₃ ) -, -N (C ₂ H ₅ ) -, -N (C ₃ H;) -.

Within the framework of the dyes of the formula (I) are, among others, dyes of the following general compositions particularly valuable.

I. Azo dyes

Fb-N = N-D

■ Ν — Α

wherein B and D represent aromatic, carbocyclic or heterocyclic radicals, in particular 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, e.g. B. a 5-pyrazolone, an acetoacetic acid arylamide, an oxynaphthalene or an aminonaphthalene; Incidentally, B and D can be any in azo dyes Have customary substituents, including other azo groups; R and A have the in formula (I) meaning given, R preferably represents hydrogen.

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-l-phenyl-5-pyrazolone series, the benzene-azo-aminonaphthalene series, the naphthalene-azo-naphthalene series, the naphthalenazo-1-phenylpyrazolone-5 series and the stilbene-azobenzene series, here too the ones containing sulfonic acid groups Dyes are preferred. In the case of metal complex azo dyes are the metal complex-bound ones Groups preferably in the o-positions to the azo group, e.g. B. in the form of ο, ο'-dihydroxy-, o-hydroxy-o'-carboxy-, o-carboxy-o'-amino- and o-hydroxy-o'-amino-azo groups.

2. Anthraquinone dyes

O NH,

(III)

O NH-

Ν — Α

35

40

here L denotes hydrogen or substituents, among these in particular the sulfonic acid group, ρ denotes the number 1, 2 or 3; R and A have the meaning given in formula (I), R preferably represents hydrogen.

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 as particularly suitable

3. Azaporphine dyes

Pc-SO ₂ NH

(CH ₂

-N / A

(IV)

55

60

In this formula, Pc stands for the radical of a phthalocyanine, in particular a copper or nickel phthalocyanine or a tetraphenyl copper or nickel phthalocyanine, L for hydrogen or a substituent, the sulfonic acid group being preferred as the substituent, r for the number 1 or 2, q for the number 0, 1 or 2; R and A have the meaning given in formula (I), R preferably represents hydrogen. The phthalocyanine residue Pc can of course have further substituents, in particular sulfonic acid and sulfonamide groups, such as —SO2NH2, —SOjNH-alkyl, —SO ₂ N (alkyl) ₂ and SO ₂ NH (aryl) 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.

The new dyes of the formula I are obtained by converting into dyes or dye precursors by processes known per se introduces at least one group -X-A, in which X is a group

—N—

which directly with the remainder A and either directly or via another bridge element with the remainder F is linked, where R and A have the meaning given in formula (I).

If dye precursors are used, these are converted into the desired end dyes converted. The introduction of group - X - A in dyes or dye precursors can be followed realize various preparative methods. So you can use dyes containing amino or amide groups or dye precursors which have a reactive hydrogen atom on the amine or amide nitrogen have, with compounds of the general formula

A-Y

in which A has the meaning given in formula (I) and Y is an anionically removable radical, implement and in the case of the use of dye precursors these in a suitable manner in the convert desired end dyes. Among the reactive substituents which can be split off as anionic radicals Y have Cl, Br and sulfonyl substituents of preferred interest. Other suitable anionic residues that can be split off are, for example, F-, SO3M- (M = H or metal cation), quaternary ammonium groups, alkyl mercapto, nitrile, alkoxy or aryloxy groups.

Suitable heterocyclic compounds of the formula V for the reaction are, for example

2-carboxymethylsulfonyl-4-chloropyrimidine,

2-methylsulfonyl-6-methyl-

4-chloropyrimidine,

2,4-bis-methylsulfonyl-6-methyl-pyrimidine,

2,6-bis-phenylsulfonyl-4-methyl-

5-chloropyrimidine,

2,4,6-tris-methylsulfonyl-pyrimidine,

1,3-bis-methylsulfonyl-2,4,6-triazine,

1,3-bis-methylsulfonyl-

5- (3'-sulfophenylamino) -2,4,6-triazine and

numerous others in 5-position

substituted 1,3-bis-methyl-sulfonyl-

2,4,6-triazine or

2,4-bis-methylsulfonyl-pyrimidine

5-carboxylic acid chloride and the like.
The implementation of dyes or dye precursors containing amino or amide groups with heterocycle

see compounds of formula V, depending on the nature of the starting compounds used in an organic, organic-aqueous or aqueous medium at temperatures of - preferably 10 ° C to 80 ⁰ C in the presence of an alkaline condensing agent, such as pyridine. aqueous alkali carbonate or alkali hydroxide solutions.

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 representation of azo dyes. by, for example, a diazo and / or coupling component, which has a reactive amino or amide group, initially with reactive component V. condensed and the intermediate product obtained then by diazotization and / or coupling and / or condensing into an azo dye. Further conversion reactions can subsequently be carried out in this be made as they are customary in azo dyes, z. B. acylation, condensation, Reduction and metallization reactions. Also in the representation of other dyes, in particular those of the phthalocyanine and anthraquinone series, the condensation of a reactive component V first take place with an intermediate product, e.g. B. with m-phenylenediamine or a m-phenylenediaminesulfonic acid, and then the reaction product obtained with me z. B. 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.

Another variant of the preparation of the new dyes of the formula I is that one amino- or dyes containing amide groups or, in particular, dye intermediates which are attached to the amino or Amide group have an exchangeable hydrogen atom, with compounds of the general formula

40

A- (Z),

(VI)

wherein A has the meaning given in formula (I), Z is an anionically removable radical, excluding a sulfonyl radical, and t is the number 2 or a number greater than 2, replacing one of the anionically removable radicals Z, then converts the or the the remaining Z radicals are converted into sulfonyl substituents in a manner known per se and, when dye precursors are used, these are converted into the desired end dyes.

The exchange of one or more anionically removable substituents Z, z. B. of halogen atoms, against sulfonyl can be z. B. accomplish that the compounds with alkyl or arylsulfinates or, if X is, for example, an anionically cleavable alkyl mercapto or Aryl mercapto group, this with the help of suitable oxidizing agents, such as hydrogen peroxide, hypohalides or permanganates, into the corresponding sulfonyl radicals.

The dyes obtainable by the various processes described can, as already for some Cases mentioned, are subjected to further reactions customary for 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 post-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 prepared according to the process contain groups which form metal complexes, so can these by the action of metal-releasing agents, e.g. B. of copper, nickel, chromium or cobalt salts in their Metal complex compounds are transferred. They can also perform other common conversion reactions such as diazotization, coupling, acylation and condensation reactions.

The new dyes are extremely valuable products that can be used for various purposes suitable. As water-soluble compounds, they are of particular interest for dyeing hydroxyl-containing compounds and nitrogen-containing textile materials, in particular textile materials made from native and regenerated Cellulose, also made from wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the or the reactive sulfonyl in the heterocyclic ring A, the products are particularly suitable as Reactive dyes for dyeing cellulose materials according to those that have recently become known for this purpose Techniques. The? · Fastness properties obtained, in particular 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 metal hydroxide or alkali carbonate, or with alkaline reacting substances Substances passing over compounds, such as alkali bicarbonate, can be added. The solution can hurt 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 Dye-preventing substances or dyeing auxiliaries, 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 produced in this way are applied to the material to be colored, for example by padding in a padder (short liquor) or by printing, and then ^{heated to an elevated temperature, preferably from 40 to 150 °} C., for some time. The heating can be carried out in the hot flue, in the steamer, on heated rollers or by placing in heated concentrated salt baths, either individually 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 with the solution or paste of the

Treat the dye and finally, as indicated, fix at elevated temperature.

For dyeing from a long liquor it is in an aqueous solution of the dyestuff (liquor ratio of 1: 5 to 1: 40) at room temperature and stained 40 to 90 minutes, optionally while increasing the temperature up to 85 ^C C by portionwise addition of salt, z. B. sodium sulfate, and then alkali, such as sodium phosphates, sodium carbonate or alkalis. This is where the chemical reaction occurs between the dye and the fiber. After the chemical fixation has taken place, the dyed material is rinsed with hot water and then soaped, removing non-fixed residues of the dye. The dyeings obtained are extremely fast, in particular wetfast and lightfast.

In the so-called cold pad process can save a subsequent heating of the padded tissue by the fact that the tissue some time, e.g. B. 20 to 40 hours 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 is made from the dye solution, a thickening agent such as sodium alginate and an alkaline reacting agent or alkali upon heating separating compound, such as sodium carbonate, sodium phosphate, potassium carbonate, potassium acetate or sodium and potassium bicarbonate, and the printed material is rinsed and soaped.

If the dyes contain groups which form metal complexes, the dyeings and prints can be used often by aftertreatment with metal donating agents, such as copper salts, z. B. copper sulfate, chromium, Cobalt and nickel salts, such as chromium acetate, cobalt sulfate or nickel sulfate, have their fastness properties improved will.

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

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 aids include: Compounds that prevent the migration of the dye on the fiber, 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, furthermore Thickening agents such as starch, tragacanth, alginate thickening, gum arabic, etc.

The aftertreatment of the dyeings, impregnations and prints obtained on polyamide fiber fabrics takes place preferably at a temperature of 50-110 ° C. and for a duration of 5 to 60 minutes.

Here, too, the colorations can be used in the event that the dyes used have metal complex-forming groups contain, with metal donors such as copper salts, z. 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 will.

The colorations obtainable with the new dyes are generally characterized by good to very good

ίο good fastness properties, especially due to excellent Wet fastness properties.

Compared to the next comparable reactive dyes, the halopyrirriidinylamino groups as reactive radicals have, as for example from the French patent specification 11 82 006, the Belgian patents

5 72 994, 5 72 973 or 5 90 451, the latter table example 60, or from German Patent 7 22 906, there Example 9, are known, the Dyes according to the invention, which instead of a reactive halogen substituent in the heterocyclic 6-ring have a removable sulfonyl group, characterized by surprisingly higher reactivity. the different responsiveness corresponds to a factor of 100 and above. The application of the new Dyes for dyeing cellulosic materials thus enable a significant reduction in the time Manufacturing times in dyeing and printing.

Compared to the next comparable reactive dyes, the chloropyrimidine-5-carbonyl groups as reactive residues have as they are from the Belgian patent specification

6 44 495 are known, the dyes according to the invention show the surprising advantage of the better ones Over-dyeing fastness of the dyeings of cotton.

Compared to dyes with chlorobenzoxazole carbonyl or chlorobenzothiazole carbonyl groups as reactive residues, as they are known from Belgian patent 6 14 896, the claimed dyes show the surprising advantage of better wash fastness and higher reactivity.

Compared to reactive dyes with chlorotriazine groups as a reactive radical, such as those from the German Patent specification 1117 245, Belgian patent specification 6 09 054 and French patent specification 12 71 348 are known, the claimed dyes show the surprising advantage of higher reactivity.

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

B e i s ρ i e 1 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 ^[/ ₂ hour at 0-10 ⁰ C. After excess nitrous acid has been removed, 10.7 parts of 3-aminotoluene, dissolved in 10 parts by volume of concentrated hydrochloric acid and 150 parts of water, are added and the coupling is completed by blunting the mixture to pH 3-5. The resulting aminoazo dye 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 thereupon with 21 parts

(> 5 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine added and vigorously stirred. The temperature of the reaction mixture is kept at about 65 ° C. by heating; the fresh hydrochloric acid is blunted with soda solution

709 633/8

from until the reaction
Dye of the formula

is finished. The resulting

SO ₁ Na

N = N

SO ₁ Na

CH ₃

-NH

SO ₂ CH ₃

CH ₃

is salted out with 80 parts sodium chloride, pressed, washed and dried at about 5O ⁰ C in vacuo. 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, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kg thickening), 2 g Contains sodium hydroxide and 10 g of soda and which has been made up to 1 kg with water, dries, 8 Steam minutes at 105 ° C, rinse with hot water and Soap at the boil, a strong, reddish-yellow print of good wash and lightfastness is obtained.

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

NaO ₁ S

SO ₃ Na

NH,

OH

N = N-

NaO ₃ SO Cu O SO ₃ Na

(prepared according to the information in German patent specification 11 17 235) by coupling diazotized l-amino-8 (benzenesulfonyloxy) -naphthalene-disulfonic acid- (3.6) in a soda-alkaline medium with the equivalent amount of 2-AcetyIamino-5-hydroxynaphthalenedisulfonic acid- (4.8), conversion of the monoazo compound into the copper complex by oxidative coppering and hydrolysing the acetyl and the benzenesulfonyl) are dissolved in 2500 parts by volume of water of 60-65 ⁰ C at pH 6 - 6.5 and dissolved at this temperature with 0, 12 mol of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine were added.

During the condensation, a pH of 7-7.5 is maintained by adding sodium carbonate solution. When the reaction has ended, the dye is salted out and isolated. The dye adjusts when dry dark powder that dissolves in water with a blue color.

Abbreviations for the reactive components:

A = 2-methylsulfonyl-4-chloro-6-methylpyrimidine.
B = 1-4 -bis-methylsulfonyl-o-methylpyrimidine.

10

100 parts by weight of a cotton fabric are at room temperature with an aqueous solution containing 2% of the dye, contains 15 g / l sodium hydrogen carbonate and 150 g / l urea, fouladed, dried in between, Heated to 140 ° C for 10 minutes, then rinsed and soaped at the boil. The fabric comes in very clear blue Shades dyed wetfast.

Example 3

46 parts of the method similar to that in Example 1 by coupling diazotized 2-AminonaphthaIin-4,8-disulfonic acid, 3-methylamino-toluene obtained monoazo dye are dissolved in 400 parts of water at 60-65 ⁰ C at pH 7 - 8 and dissolved in the presence of of excess sodium acetate or calcium carbonate partially mixed with a total of 25 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine and stirred at this temperature until a sample no longer changes color when acidified. The resulting dye of the likely formula

SO ₂ CH ₃

N = N

is filtered off with suction, washed and dried. Cotton fabric is impregnated with a solution at 20.degree.-25.degree. C. which contains 20 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g of urea and 5 g of sodium bicarbonate 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 14O ⁰ 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 strong reddish yellow coloration of good wet, rub and lightfastness is obtained.

The table below shows the diazo components. Coupling components and the reactive components that can be linked to the amino group are listed, from which dyes can be built up analogously to the information in Examples 1-3, their color tones - obtained after one of the application methods described - also in the table are recorded.

Example!
No.

Diazo component

Coupling component

Reactive shade
component

4 2-aminonaphthalene-4,8-disulfonic acid 1-amino-1-methoxy-S-methyl-A

benzene

5 the same. The same. B

yellow
yellow

continuation

Example diazo component

Coupling component reactive color
component

6th l-aminonaphthane-3,6-disulfonic acid 1-amino-3-methylbenzene A. yellow 7th the same the same B. yellow 8th 2-aminonaphthalene-5,7-disulfonic acid the same A. yellow 9 the same the same B. yellow 10 2-aminonaphthalene-6,8-disulfonic acid the same A. yellow 11th the same the same B. yellow 12th 4-aminoazobenzene-3,4'-disulfonic acid the same A. Brownish yellow 13th 1-aminobenzene-4-sulfonic acid the same B. Brownish yellow -> l-aminonaphthalene-6-sulfonic acid 14th 2- (3'-sulfo-4'-aminophenyl) -6-methyl- the same A. yellow benzthiazole-7-sulfonic acid 15th 2-aminonaphthalene-4,8-disulfonic acid 1-methylamino-3-methoxybenzene B. yellow 16 the same l-amino-3-acetylaminobenzene A. yellow 17th the same aniline 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 ^{thorough stirring at 50-60 o,} C25 parts of 2,4-bis-methyl-sulfonyl-6-methyl-pyrimidine are added entered and stirred with constant blunting of the hydrochloric acid released to pH 6-7 until no more free amino groups 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 ₃ Na

SO ₂ CH ₃

NaO ₃ S SO ₃ 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 by the following method: 50 grams of cotton strand are dissolved in 1 liter of a dyeing liquor which contains 1.5 g of the above dye, colored, by raising the temperature within 30 minutes of 20 ⁰ C to about 80 ° C , adding a total of 50 g of table salt in several portions, then adding 20 g of soda and treating at this temperature for 60 minutes. After rinsing, boiling soaps and drying, a bluish red coloration with good wet, rub and dry properties is obtained

Lightfastness.

If, instead of the 25 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine, equivalent amounts of the following compounds are used in this example, the reaction temperature depending on the respective reactivities of the components, then red reactive dyes are also obtained, and cotton is obtained color the specified procedure in clear, bluish red tones:
4-chloro-2-methylsulfonylpyrimidine

4-chloro-2,6-bis-methysulfonylpyrimidine
4,5-dichloro-2,6-bis-methylsulfonylpyrimidine

4-chloro-2-methylsulfonylpyr'midine-6-carboxylic acid

4-Chloro-2-methylsulfonylpyrimidine-6-carboxylic acid methyl ester
4,6-dichloro-2-methylsulfonylpyrimidine
4-chloro-5-cyano-2-methylsulfonylpyrimidine.
The following table lists the hues of other dyestuffs which are built up from the diazo components, coupling components and reactive components that can be linked to the amino group in the latter analogously to the information in Example 18 - or by reacting the corresponding aminoazo dyestuffs with the reactive components - and are built up from the diazo components, coupling components also listed can be dyed or printed on cellulosic materials using one of the methods described above:

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

Example diazo component

Coupling component reactive color
component

1-aminobenzene-2-sulfonic acid

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

Red

Continue Tune

Example diazo component

Coupling component

Reactive shade

component

20 aminobenzene

21 the same.

22 1 -Amino ^ -carboxybenzene- ^ sulfonic acid

23 1-Amino-4-methylbenzene-2-sulfonic acid

24 l-Amino-3-acetylaminobenzene-6-sulfonic acid

25 1-Amino-3- (2 '- [4 "-sulfophenylamino] -4'-chlorotriazine-r, 3', 5'-yI-6 ') -aminobenzene-6-sulfonic acid

26 l-aminobenzene-2-sulfonic acid

26 a l-amino-3- (2 '- [4 "-sulfophenylamino] -

4'-methylamino-triazine-r, 3 ', 5'-yl-6') - aminobenzene-6-sulfonic acid

27 l-aminobenzene-2-sulfonic acid

28 1 -Amino ^ -acetylamino-o-sulfonic acid

29 the same

- (3 '-Aminobenzoylamino) -

S-hydroxynaphthalene ^ o-disulfone-

acid

the same

l-amino-8-hydroxynaphthalene-

3,6-disulfonic acid

the same

the same

the same

A.
B.

Red

Red
Red

Red
Red

Red

2-amino-5-hydroxynaphthalene A. orange 7-sulfonic acid the same A. orange

2-methylamino-5-hydroxy

naphthalene-7-sulfonic acid

the same

2-amino-5-hydroxynaphthalene

7-sulfonic acid A
A.

orange

Scarlet fever
Scarlet fever

Example 30

In the solution of 21 parts of the sodium salt of 1,3-diaminobenzene-6-sulfonic acid in 100 parts of water 25.0 parts of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine are added with thorough stirring registered and at 60-65 ° C with constant blunting of the released Stirring hydrochloric acid to pH 7-8 until a sample is diazotized and coupled to 1-hydroxynaphthalene-4-sulfonic acid gives a clear, yellowish red color. The resulting intermediate dye is after addition of ice directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid diazotized and then with a submitted solution of 47 parts of the sodium salt of 1-benzoylamino-8-hydroxy-naphthalene-3,6-disulphone; crazy and 12 parts of soda combined in 200 parts of water, coupling to the dye of the formula

CH ₃ O ₂ S

SO ₃ Na HO NH-OC-Q ₁ H ₅

N = N "
NaO ₃ S SO ₃ Na

CH ₃

takes place, which is salted out, filtered off with suction, washed and ^{dried at 30-40 0} C in a vacuum. The dye dissolves easily in water with a red color and, according to one of the processes described above, gives clear bluish red dyeings and prints on cellulose materials.

The following table shows the color tones and the pH of the coupling medium of dyes listed, the analogous to the information in Example 30 from

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

example Diazo component Coupling component Reactive pH des

component coupling medium

[• 'arbton

31 1,3-diaminobenzene

4-sulfonic acid c

2-aminonaphthalene-5,7-disulfonic acid A

4-5

orange

continuation

16

Example diazo component
No.

Coupling component

Reactive pH des

component coupling medium

hue

32 1,3-diaminobenzene
4-sulfonic acid 33
34 the same
the same 35 the same 36 the same 37 the same 38 the same 39 the same 40 the same 41 the same 42 the same 43 the same 44
45 1,4-diaminobenzene
3-sulfonic acid
the same 46 the same

2-aminonaphthalene-3,6-disulfonic acid A

2-aminonaphthalene-6-sulfonic acid B

2-N-methylamino-8-hydroxy-A

naphthalene-6-sulfonic acid

1 - (3 ', 5' -Dichloro-1 ', 2'-thiazole-A

4'-carbonamido) -8-hydroxynaphthalene-3,6-disulfonic acid 1- (2 ', 4'-dihydroxytriazine-1', 3 ', 5'-yl- B 6 '-amino) -8-hydroxynaphthalene-

3,6-disulfonic acid

1 - (3 ', 5' -Dichloro-1 ', 2'-thiazole-A

4'-carbonamido) -8-hydroxynaphthalene-3,6-disulfonic acid 2-hydroxynaphthalene-3,6-disulfone-A

acid 1-acetylamino-8-hydroxynaphthalin- B

3,6-disulfonic acid

1- (3'-sulfophenyl) -3-methyl-A

pyrazolone-5

1- (2 ', 5'-dichloro-4'-sulfophenyl) - A

3-methyl-pyrazolone-5

1- (5 ', 7'-disulfonaphthyl-2' -) - A

3-methyl-pyrazolone-5

1- (3'-sulfophenyl) -3-methyl-B

5-aminopyrazole

2-amino-8-hydroxynaphthalene-A

6-sulfonic acid 2-acetylamino-5-hydroxynaphthalene-A

7-sulfonic acid 1-acetylamino-S-hydroxynaphthalene- B

7-sulfonic acid 4-5

orange

4-5
4-5 orange
orange 7-8 Red 7-8 Red

7-8

Red

8th Scarlet fever 7-8 Red 6th yellow 6th yellow 6th yellow 6th yellow 4-4.5 Red 6-7 Scarlet fever 6-7 Red

B e i s ρ i e! 47 reactive dye of the formula

45

51.6 parts of that obtained by diazotizing 1-hydroxy-2-aminobenzoI-4-sulfonic acid and coupling on 2-amino-5-hydroxynaphthalene-7-sulfonic acid in water / pyridine in the presence of soda and subsequent treatment with a copper donating agent obtained dyes of the formula

NaO ₃ S

NH

SO ₃ Na

SO ₂ CH.,

NH,

are dissolved in 1500 parts of water at pH 7. Under thorough stirring 25.0 parts bears at 60-65 ⁰ C 2-methylsulfonyl-4-chloro-6-methylpyrimidine and blunts the hydrochloric acid liberated with sodium carbonate solution continuously to a pH of 7-8 at. If no free amino group is no longer detectable, the salted formed is pressed, gewasehen in vacuo at 30 -40 ⁰ C dried. Fabrics made of cellulosic materials can be treated with this dye by one of the processes mentioned above in wet, rub and lightfast

do ruby tones are dyed or printed.

The following table lists the heavy metal complexes of other aminoazo dyes and those with the Amino group linked reactive components as well as the color tones of these dyes on cellulose materials

65 listed. The manufacture of the aminoazo dyes. Their metal complexes and their conversion with the Rcaktivkoniponenten can be analogous to the information in Example 47 can be done.

703 Π33 / 3

17 18

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

Example aminoazo dye

Complex reactive shade

bound component heavy metal

48 l-Hydroxy-2-aminobenzene-4,6-disulfonic acid

- * i-Amino-S-hydroxynaphthalene-T-sulfonic acid

49 l-Hydroxy-2-aminobenzene-4-sulfonic acid - * 2-Ethylamino-5-hydroxynaphthalene-7-sulfonic acid

50 l-amino ^ -hydroxy-o-nitronaphthalene ^ -sulfonic acid - + 2-Amino-5-hydroxynaphthalene-7-sulfonic acid

51 the same.

52 1-Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid - ► 1-amino-S-hydroxynaphthalene-4-sulfonic acid

53 1-Amino-2-hydroxy-5-methylsulfonyl-benzene

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

54 the same.

55 the same.

56 l-Amino-2-methylbenzene-4-sulfonic acid - * 1-Amino-2-hydroxy-5-methylbenzene - ♦ 1-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

57 the same.

58 the same.

59 (l-amino-2-chlorobenzene-4-sulfonic acid - + 1-hydroxy-2-acetylaminobenzene), saponified, - * l-amino-8-hydroxynaphthalene-3,6-disulfonic acid

60 the same.

61 1 -Amino-S-hydroxynaphthalene ^ -sulphonic acid <- 1-hydroxy-2,6-diaminobenzene-4-sulphonic acid - * 1,3-dihydroxybenzene

62 1-Amino-S-hydroxynaphthalene ^ o-disulfonic acid <- 1-hydroxy-2,6-diaminobenzene-4-sulfonic acid - * 2-hydroxynaphthalene

63 1-Amino-S-hydroxynaphthalene ^ -sulfonic acid <- 1-hydroxy-2,6-diaminobenzene-4-sulfonic acid - * 3-methylpyrazolone- (5)

example

Cu Cu Cu Cr Co Cu

Co Cr

Cu

Co Cr

Cu

A A A A B A

A A

Co A. Co A. Co A. Co A.

Ruby ruby ruby

greenish

Gray

reddish

black

violet

Gray

greenish black blue

Gray

greenish black navy blue

Grey black

black Black

96 parts (based on 100% goods) of the usual Way freshly prepared by the action of chlorosulfonic acid and thionyl chloride on copper phthalocyanine Copper phthalocyanine tetrasulfochloride or the isomeric from 1 -sulfo-benzene-ß ^ -dicarboxylic acid via the corresponding copper phthalocyanine tetrasulfonic acid built up copper phthalocyanine tetrasulfochloride are in the form of the moist, well washed suction cake in 500 parts of water and 500 parts of ice suspended, the solution of 50 parts of the sodium salt of 1,3-diaminobenzene-4-sulfonic acid in 500 parts Added water and adjusted the pH to 8.5 with soda. The suspension is stirred for 24 hours Room temperature and keeps the pH always at 8.5 by continuously adding soda. The resulting Condensation product is precipitated at pH 1-2 by adding sodium chloride, filtered off with suction, washed and then dissolved again in 1000 parts of water until neutral. In the blue solution are 71 parts with vigorous stirring 2,4-bis-methyl-sulfonyl-6-methyl-pyrimidine entered and with constant blunting with soda solution pH 7-8 stirred at 60-65 ° C until no free Amino groups are more detectable. The reactive dye of the formula obtained in this way

SO ₂ CH ₃

Cu phthalocyanine

(SO ₃ Na) ,,

- (SO ₂ -

SO ₃ Na CH ₃

is salted out, washed and ^{dried at 30-40 0} C in a vacuum. He represents a dark blue, i

Powder soluble in water with a blue color and dyes cotton and regenerated cellulose according to one of the Above mentioned dyeing or printing processes in clear blue tones of good wet, rub and light fastness.

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'-diamino-stilbene-2,2'-disulfonic acid is used, reactive dyes are obtained which are cellulose materials dye in wet, rub and lightfast, clear blue tones using one of the above methods.

If one starts from 4 ', 4 ", 4'", 4 "" - tetraphenyl-Cu-phthalocyanine, one obtains after sulfochlorination and Conversion with 1,3-phenylenediamine-4-sulfonic acid and acylation with 2,4-bis-methylsulfonyl-6-methyl-pyrimidine a reactive dye, the cellulose materials in the presence of acid-binding agents in clear, wet and colors lightfast green tones.

IO

Example 65

71 parts of the 1-amino-4-bromo-anthraquinone-2-sulfonic acid are dissolved aminoanthraquinone dyes obtained with excess 4,4'-diaminodiphenyl-2,2'-disulfonic acid in 700 parts of water, carries 25 parts at 60-65 ° C with thorough stirring 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine and maintains a pH by continuously adding soda solution from 7 - 7.5 upright. When no more amino groups can be detected, the resulting dye becomes the formula

SO ₂ CH ₃

salted out, filtered off with suction, washed and dried at 30 - 40 ° C in a vacuum. It dyes cotton and regenerated cellulose according to one of the processes listed above in wet, rub 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 when used, similar dyes are obtained whose blue colorations are also similar in fastness to that of the one obtained above Have dye:

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

anthraquinone-2-sulfonic acid,

l-Amino-4- (4'-aminophenylamino) -anthraquinone-2,6-disulfonic acid,

Mixture of isomers

l-amino-4- (4'-aminophenylamino) -anthraquinone-2,5-

and 2,8-disulfonic acid,

Mixture of isomers

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

anthraquinone-2,5- and 2,8-disulfonic acid,

SO ₃ Na CH ₃

Mixture of isomers

l-Amino ^ -ß'-aminophenylaminoVanthraquinone-2,5-
and -2,8-disulfonic acid,

l-Amino-4- (3'-aminophenylamino) -anthraquinone-2,6-disulfonic acid,

1-Amino-4- (3'-amino-4'-sulfophenylamino) -anthraquinone-2-sulfonic acid.

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

Example f) 6

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-pheny 1-3-methyl-pyrazolone- (5) obtained aminoazo dye, a reactive dye is obtained which Cellulose materials according to one of the processes given above in good wet, rub and lightfast yellow-brown Tones colors.

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

HO ₃ S

SO ₃ Na

HO ₃ SO Cu O SO ₃ Na

are dissolved in 3000 parts by volume of water at pH 6 and with stirring at a temperature of about 6O ⁰ C with 21

Parts by weight (0.1 mol) of 2-methyl-sulfonyl-4-chloro-6-methyl-pyrimidine united. The mixture is stirred until the condensation has ended, the dye through Addition of a little sodium chloride deposited and isolated. The residue is washed with acetone and dried at room temperature under reduced pressure. A dark powder is obtained, which is in Water with a green color dissolves and cotton according to the procedures given in Examples 1-3 colors in green tones.

Impregnating cotton fabric with a solution of 20-25 ⁰ C, the per liter of liquor, 25 g of the above dyestuff and 0.5 g of a nonionic wetting agent (eg, a polyoxäthylierten oleyl alcohol), 150 g of urea and 20 g of sodium carbonate. The fabric is then squeezed between two rubber rollers to a moisture content of approx. 100%. After intermediate drying at 50 -60 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 according to one of the others, in Examples 1 to 3, 18 and 30 described dyeing or printing processes 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

HO ₃ SO

formula

H ₁ N

SO, H

N = N

HO ₁ SO 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 are obtained in 2000 parts by volume Dissolved water at pH 6.5 and combined with 25 parts by weight of 2,4-bis-methylsulfony! -6-methyl-pyrimidine. The reaction mixture is stirred at 60-65 ° C. until the condensation has ended, the pH of the reaction solution being adjusted to 7-7.5 by adding soda is held. After the reaction has ended, the dye is salted out, 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

H, N

SO ₂ H SO ₃ H

manufactured according to the information in German patent specification 10 61 460 or 10 85 988, is carried out in the usual way brought to reaction with 22 parts by weight of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine. One gets through Adding soda brings the pH to 7-7.5 and isolates the dye by salting out after the reaction has ended. He When dry, it is a dark powder that dissolves in water with a purple color. Cotton fabric is colored in light- and wet-fast violet tones.

Example 70

27.5 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid Sodium is dissolved in 150 parts of water, with 25 parts of 2,4-bis-methyl! Sulfonyl-6-methyl-pyrimidine added and at 50-55 ° C with constant blunting of the methanesulfinic acid formed with a total of 34 parts by volume of 16% soda solution stirred to pH 6-7. After a short time, the acylation takes place

NaO ₃ S

finished, the pH is 6 and no longer veins.

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

SO ₂ CH ₃

After stirring for another five hours, the above-mentioned processes are added in reddish-tinged orange.

80 parts of table salt completely separated, filtered off, with tones of very good and good wet fastness properties

diluted sodium chloride solution and washed at 35 ° C. for a period of time.

Vacuum dried. Rr stains the chemical substance used in this example instead of 25

Parts by weight of 2,4-bis-methylsulfonyl-6-methy 1-pyrimidine equivalent amounts of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine, in this way an orange reactive dye and its coloring behavior are obtained the reaction product of the bis-methylsulfonyl derivative is equivalent to.

In an analogous manner, acylation of the in 24

Column 3 of the following table listed aminonaphtholsulfonic acids with 2,4-bis-methylsulfonyl-6-methyl-pyrimidine and coupling the acylamino-naphtholsulfonic acids formed with those in column mentioned diazo components orange to red reactive dyes.

example Diazo component No. 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 the same 83 the same 84 2-aminonaphthalene 1,5,7-trisulfonic acid 85 the same 86 the same 87 2-aminobenzene sulfonic 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 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 c 103 l-amino-benzene- 2-carbonic acid-4-sulfone acid

Aminonaphtholsulfonic acid

Hue on cotton

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

2 - (^ - Hydroxyäthylamino) -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-methylamino-5-hydroxynaphthalene-7-sulfonic acid

2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid 2 - (/ i-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- (ß-Hydroxyäthylamino) -5-hydroxynaphthalene-

7-sulfonic acid 2-amino-8-hydroxynaphthalene-6-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-Amino-8-hydroxynaphthalene-4,6-disulfonic acid 1-Amino-8-hydroxynaphthalene-6-sulfonic acid

1-amino-8-hydroxynaphthalene-6-sulfonic acid

l-amino-8-hydroxynaphthalene-3,6-disulfonic acid l-amino-S-hydroxynaphthalene ^ o-disulfonic acid

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

Orange orange

orange

orange

Scarlet fever

Scarlet fever

orange

Orange orange

orange

orange

Scarlet fever

Scarlet fever

orange

orange

Scarlet fever

orange

orange

Scarlet scarlet orange bluish red

bluish red bluish red

bluish red bluish red bluish red

bluish red bluish red bluish red

bluish red bluish red

bluish red

continuation

Example diazo component

Aminonaphtholsulfonic acid shade on cotton

104 1-amino-4-acetylamino-1-amino-8-hydroxynaphthalene-3,6-disulfonic acid benzene-2-sulfonic acid

105 the same. L-amino-8-hydroxynaphthalene-4,6-disulfonic acid

example

Violet bluish red

56.8 parts of the l-amino-S-acetylaminobenzene-6-sulfonic acid which has been diazotized by coupling to 2-aminonaphthalene-5,7-disulfonic acid diaminoazo dye obtained in acetic acid medium and subsequent alkaline or acidic hydrolysis of the acetylamino group are dissolved in 450 parts of water at pH 7. After adding 25.0 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine is constantly dulling the released sulfinic acid with soda solution to pH 7 - 7.5 stirred for about one hour at 60 ° C. When the acylation is complete, the reactive dye formed becomes the formula

SO ₃ Na

CH ₃ O ₂ S

N = N

SO ₃ Na

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 real-life using one of the above-mentioned processes yellowish orange tones.

Example 107

For a neutral solution of 60 parts of the trisodium salt of 2-aminonaphthalene-3,6,8-trisulfonic acid diazotized by coupling with 3-acetylamino-aniline

SO ₃ Na

NaO ₃ S

The aminoazo dye obtained in an acetic acid medium in 500 parts of water is added to 22 parts of 2-methyl-sulfonyl-4-chloro-6-methyl-pyrimidine and stir for one hour at 65 ° C, with constant addition of sodium hydroxide solution a pH of 7 - 7.5 is maintained. The partially precipitated acylation product is at pH 7 completely separated out by adding 100 parts of sodium chloride and filtered off. Can be used for cleaning Reactive dye obtained redissolved in 2500 parts of water at 30 ° C., clarified and salted out of the filtrate with 350 parts of table salt are separated again. The dye has the formula

SO ₂ CH ₃

N = N

SO ₃ Na NH-COCH 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 a the above-mentioned dyeing process in the presence of acid-binding agents in very real reddish yellow Tones colors. Real yellow dyeings are also obtained on wool and polyamide fibers.

Similar dyes are obtained by proceeding as above, but instead of the 60 parts of 4'-amino-2'-acetylamino-phenyl- (1 ') -azonaphthalene- (2) -3,6,8-trisulfonic acid Sodium corresponding amounts of the amino compounds given in column 2 and the Coupling components indicated in column 3 in the usual way by diazotization and coupling in Acetic acid medium obtained aminoazo dyes used and with 2-MethyIsulfonyl-4-chloro-6-methyl-pyrimidine acylated.

Example diazo component

Coupling component

108 2-aminonaphthalene 1,5-disulfonic acid 109 the same 110 the same

1-amino-3-methyl-6-methoxybenzene

l-amino-3-methylbenzene l-aminonaphthalene-6-sulfonic acid Hue on cotton

strong reddish yellow

Yellow reddish yellow

27

continuation

28

Example diazo component

Coupling component color on
cotton

111 2-aminonaphthalene-1,5-disulfonic acid

112 the same.

113 the same.

114 2-aminonaphthalene-5,7-disulfonic acid

115 the same.

116 the same.

117 the same.

118 the same.

119 1-aminonaphthalene-3,7-disulfonic acid

120 the same.

121 1-aminonaphthalene-3,7-disulfonic acid

122 2-aminonaphthalene-3,6-disulfonic acid

123 the same

124 the same.

125 the same.

126 the same

127 the same.

128 2-aminonaphthalene-6,8-disulfonic acid

129 the same.

130 the same.

131 2-aminonaphthalene-4,8-disulfonic acid

132 the same.

133 the same.

134 the same.

135 2-aminonaphthalene-4; 8-disulfonic acid

136 the same.

137 the same.

138 the same.

139 the same.

140 2-aminonaphthalene-3,6,8-trisulfonic acid

141 the same.

142 the same.

143 the same.

144 the same.

145 the same.

146 the same

147 the same.

148 the same.

149 the same.

-Amino-3-acety laminobenzene

3-aminophenylurea l-amino-3-hydroxyacetylaminobenzene

1-amino-S-methyl-o-methoxybenzene

l-aminonaphthalene-7-sulforic acid
-Amino-3-acetylaminobenzene
3-aminophenylurea
l-amino-3-hydroxyacetylamino-benzene
1-amino-3-methyl-6-methoxybenzene

1-amino-3-methylbenzene-amino-naphthalene-6-sulfonic acid

-Amino-3-methylbenzene
1-amino-3-methyl-6-methoxybenzene

1-amino-3-acetylaminobenzene
3-aminophenylurea
l-amino-3-hydroxyacetylaminobenzene
1-aminonaphthalene-6-sulfonic acid
l-amino-3-acetylaminobenzene

1-amino-2-methoxynaphthalene-6-sulfonic acid

l-aminonaphthalene-6-sulfonic acid
-Aminonaphthalene-6-sulfonic acid

-Aminonaphthalene-7-sulfonic acid
1-amino-2-methoxynaphthalene-6-sulfonic acid

1-methylamino-3-methylbenzene
1-ethylamino-3-methylbenzene

N-methylaniline

N-ethylaniline

N - (/ i-hydroxyethyl) aniline

N-butylaniline

Aniline 1-amino-3-methylbenzene
3-aminophenylurea
l-amino-3-hydroxyacetylaminobenzene
l-amino-S-acetylamino-o-methoxybenzene

1-amino-3-acetylamino-6-methylbenzene

l-amino-3-methane-sulfonylaminobenzene

2,5-dimethoxyaniline

3-methyl-6-methoxyaniline N-methylaniline reddish yellow

red-tinged yellow red-tinged yellow strongly red-tinged yellow

reddish yellow reddish yellow reddish yellow reddish yellow strong reddish yellow

reddish yellow reddish yellow

reddish yellow

strong reddish yellow

reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow

strong reddish yellow

reddish yellow yellow

yellow

strongly reddish

Yellow .

yellow

yellow

yellow
Geib
yellow
yellow
reddish yellow

reddish yellow reddish yellow reddish yellow yellowish
orange

red-tinged yellow red-tinged yellow yellow-tinged
orange
yellowish
orange
reddish yellow

29 30th

continuation

Example diazo component

Coupling component

150 2-aminonaphthalene 3,6,8-trisulfonic acid 151 the same 152 the same 153 the same 154 the same 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-2,5-disulfonic acid

N-ethylaniline

N-butylaniline

N - (/ ^ - hydroxyethyl) aniline

3- (N-ethylamino) toluene

2-aminotoluene

1-amino-2,5-dimethylbenzene

1-amino-2-methoxybenzene

-Amino-3-methoxy benzene

-Ethylamino-3-methoxy benzene

l-aminonaphthalene-6-sulfonic acid

l-aminonaphthalene-7-sulfonic acid

1-amino-3-methylbenzene

l-amino-3-acetylaminobenzene
-Amino-3-methylbenzene

l-aminonaphthalene-6-sulfonic acid
l-amino-3-acetylaminobenzene

3-aminophenylurea

l-amino-3-hydroxyacetylaminobenzene

N-methylaniline

N-ethylaniline

N-butylanilaniline

N - (/ ^ - hydroxyethyl) aniline

1- (N-ethylamino) -3-methylbenzene

l-aminonaphthalene-6-sulfonic acid

l-aminonaphthalene-7-sulfonic acid

-Amino-3-methylbenzene

-Amino-S-acetylaminobenzene

1-amino-2-methoxy-5-methylbenzene

-Amino-2,5-dimethoxybenzene

1-amino-2-methoxy-5-methylbenzene

Hue on
cotton

reddish yellow

reddish yellow reddish yellow reddish yellow reddish yellow strong reddish yellow

strong reddish yellow

reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow

reddish yellow yellow

yellow
reddish yellow

reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow yellow
yellow

reddish yellow reddish yellow reddish yellow

65 parts of the dye of the formula Example 180

NaO ₃ S

NH,

(Prepared by coupling diazotized I-hydroxy-65 dissolved neutrally. 22 parts of 2-methylsulfonyl-4-

Add 2-amino-benzene-4,6-disulfonic acid to 2-amino-8-hydrochloro-6-methyl-pyrimidine and stir at 60-65 ° C

xynaphthalene-6-sulfonic acid and copper-plating of the obtained with constant blunting of the liberated acid

ncn azo dyes) are in 700 parts of water with soda solution to pH 7-7.5, until no free

31 32

Amino group is more detectable. The resulting reactive dye of the formula

O Cu O SO ₂ CH,

NaO ₁ S

SO ₁ Na

is salted out, filtered, washed and dried at 30-40 ⁰ C. It dyes cellulose materials in very real ruby tones using one of the methods given above.

Dyes with similar properties are obtained

analogous to the procedure described above from the copper complexes from the in the table below listed diazo and azo components produced azo dyes:

example Diazo component No. 181 l-hydroxy-2-amino- benzene-4-sulfonic acid 182 the same 183 the same 184 the same 185 1 -hydroxy-2-amino- benzene-4,6-disulfonic acid 186 the same 187 the same 188 the same 189 the same 190 1 -hydroxy-2-amino- benzene-4,6-disulfonic acid 191 the same 192 1 -hydroxy- 2-amino- benzene-5-sulfonic acid 193 the same 194 1 -H vdroxv-2-amino-

Coupling component shade on cotton

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid ruby

2-ethyl-amino-5-hydroxynaphthalene-7-sulfonic acid ruby

2 - (/ i-Hydroxyäthy! Amino) -5-hydroxynaphthalene-ruby 7-sulfonic acid

2-Amino-8-hydroxynaphthalene-3,6-disulfonic acid ruby

2-Amino-5-hydroxynaphthalene-l, 7-disulfonic acid ruby

2-Amino-8-hydroxynaphthalene-3,6-disulfonic acid ruby

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid ruby

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

2 - (/ y-Hydroxyethylamino) -5-hydroxynaphthalene-ruby 7-sulfonic acid

l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid purple

l-Amino-8-hydroxynaphthalene-4,6-disulfonic acid purple

l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid purple

l-Amino-S-hydroxynaphthalene ^ o-disulfonic acid violet

1-amino-S-hydroxynaphthaiine-S ^ -disulfonic acid with a bluish tinge

4-acetylaminobenzene violet

6-sulfonic acid

195 l-hydroxy-2-amino-l-ethoxy-8-hydroxynaphthalene-3,6-disulfonic acid with a bluish tinge 4-acetylaminobenzene violet 6-sulfonic acid

(4-position acetylamino group then saponified)

196 the same as l-amino-8-hydroxynaphthalene-2,4-disulfonic acid blue

197 the same. L-Amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid blue

198 l-Hydroxy-2-amino-1-amino-8-hydroxynaphlhalin-2,4-disulfonic acid blue 6-acetylaminobenzene

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

199 l-amino-2-hydroxy- like blue 6-nitronaphthaIin-

4-sulfonic acid

(6-position nitro group subsequently reduced to -NH ₂ )

200 l-amino-2-hydroxy-l-amino-8-hydroxynaphthalene-2,4,6-trisulfonic acid blue 6-nitronaphthalene

4-sulfonic acid

(6-position nitro group then reduced to - NH ₂ )

201 l-hydroxy-2-amino- like blue 6-acctyIaminoben / ol-

4-sulphonic acid (6-position acetylamine saponified) /li'lti.n.-il

Example 202

The procedure described in Example 30 is followed, but the diazotized intermediate product containing reactive groups is coupled in a soda-alkaline medium instead of 47 parts of the sodium salt of l-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid with 40 parts of the sodium salt of l-acetylamino-e-hydroxynaphthalene-a.edisulfonic acid and isolates the resulting dye of the formula

CH ₁ O ₂ S

H, C

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

SO ₁ Na HO NH-CO — CH,

SO _-1 Na

again partially crystallized solution of 26.2 parts of the potassium salt of l-amino-naphthalene-8-sulfonic acid in 250 parts of hot water and blunts the strongly acidic coupling mixture at 10 -20 ⁰ C. by cautious addition of sodium hydroxide solution to pH. 4 The coupling is completed quickly; the aminoazo dye formed is completely salted out with 100 parts of sodium chloride, filtered off with suction, washed and redissolved in 500 parts of water at 10 ° C. and pH 6-7. The aqueous solution is mixed with 25.0 parts of bis-methylsulfonyl-6-methyl-pyrimidine-2.4 and stirred for one hour at 55-60 ⁰ C under running blunting of the released acid with sodium carbonate solution to pH 7-7.5. When no more aminoazo dye can be detected, the partially precipitated reactive dye becomes of the formula

SO ₁ 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 according to one of the above Dyeing process in the presence of acid-binding agents dyes in very good wet-, light- and chlorine-fast yellow tones. True yellow colorations are also obtained on wool and polyamide fibers.

If one proceeds as indicated above, but instead of 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 2,4-bis-methylsulfonyI-6-methylpyrimidine likewise valuable yellow to brown reactive dyes.

Diazo component

1-aminobenzene-l ^ -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 c

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

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

4-Amino-2-acetylamino-azobenzene-2 ', 5'-di.sulfonic acid shade on cellulose fiber

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

Continue Tune

Diazo component

Color on cellulose fiber

NH,

reddish brown

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

SO ₃ Na

N = N- / V-NH,

reddish brown

(l-aminobenzene-2,5-disulfonic acid acidic on the technical mixture of 1-aminonaphthalene-6- and -7-sulfonic acid coupled)

SO ₃ Na

NaO ₃ S ^ y

N = N

SO ₃ Na

NH ₁ purple-tinged brown

SO ₃ Na

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

SO ₃ Na

reddish brown

NaO ₃ S

I.
SO ₃ Na

(l-Amino-naphthalene-2,5,7-trisulfonic acid acidic on l-amino-l-methoxy-S-methylbenzene coupled)

Example 204

If cellulose fabric is printed with a printing paste containing 30 g of the dye described in Example 18, 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 the 3rd nitrobenzene-sulphonic acid contains and which was filled with water to 1 kg, 30 seconds attenuates then between dry and then in a suitable steamer at 103-1 15 ⁰ C, is obtained after rinsing and soaping at the boil a strong bluish red print of good Wet, rub and light fastness.

Example 205

A mixture of the solutions of 65.5 parts each of the chromium 2: 1 complex and the cobalt 2: 1 complex of the dye of the formula

HO NH,

N = N-

NaO _-1 S SO ₁ Na

SO _-1 Na

in each 400 parts of water with 50 parts of finely powdered, 4-chloro-6-methyl-pyrimidine 2-Methyl-sulfonyl-about 2 hours at 60 -70 ⁰ C while maintaining a pH of 7 - stirred. 8 When the aminoazo dye (Co complex: blue; Cr complex: blue-green) can no longer be detected by chromatography, the resulting mixture of the two reactive dyes is salted out with potassium chloride, filtered off and dried.

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 the following Aminoazol'arb.stoffc use / t. you get also valuable black color pens:

Diazo component

1-hydroxy-2-amino-4-nitro-
^{! 0} benzene

1-hydroxy-2-amino-4-nitro- ₍ . Naphthalene-
^ sulfonic acid

Coupling component

i-hydroxy

8-amino-naph-

thalin-3,6-disul-

fonic acid

the same

Example 206

Coupling pM

To the neutral solution of 53.15 parts of the disodium salt of the diazotized by coupling 1-amino ^ -nitrobenzene ^ -sulfonic acid with 1 - (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, 25.0 Parts 2,4-ßis-methy! Sulfonyl-6-methyl-pyrimidine and The mixture is stirred for one hour at 55-60 ° C., the acid released being continuously added to soda solution a pH value of 6.5 - 7 becomes blunt. The departed one Dye of the formula

CH ₃ O ₂ S

N> -HN-;

is filtered off, warm in 3000 parts of water at pH 6-7 dissolved and precipitated again from the filtered solution by adding sodium chloride. After filtering, Drying and powdering gives a yellow, readily water-soluble powder that consists of cellulose materials long liquor at 60 ° C or according to the Klotz-Kaltwcrweil process colors with soda as an acid-binding agent in clear, wash-, rub- and lightfast yellow tones.

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

NaO _-1 S

If aminoazo dyes built up in the components listed in the table are used, valuable ones are also obtained new reactive dyes.

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, whereby the forms the desired aminoazo dye.

Example diazo component

Azo component

pH of the shade on cellulose

Clutch

mediums

l-Amino-4-nitrobenzene l- (4'-sulfophyl) -3-methyl-

2-sulfonic acid pyrazolone- (5)

(4-position nitro group then reduced)

the same. 1 - (4'-sulfophenyl) -3-carboxy-

pyrazolon- (5) like l- (3'-sulfoplicnyl) -3-methyl-

5-aminopyra / ol 5 6

yellow

5 6 red-tinged CJeIb

ή 7 (IeIb

continuation Diazo component 1544499 1 -amino-3-acetyl-aminobenzene- then saponified) 40 Shade on cellulose example 6-sulfonic acid l - (/ i-hydroxyethyl) -3-methyl- No. (3-position acetylamino group pyrazolone- (5) pH des 39 Azo component the same 1 mole of bis-pyrazolone from 4,4'-bis- Clutch yellow 210 hydrazinodibenzyl-2,2'-disulfone mediums 2 moles of l-amino-3-acetyl- acid and ethyl acetoacetate) 6-7 amino-benzene-6-sulfonic acid 1 - (4'-sulfophenyl) -3-carboxy- yellow 211 (saponified) pyrazolone- (5) 1 mole of l-amino-3-acetyl- 5-6 yellow 212 amino-benzene-6-sulfonic acid 5-6 yellow 213 5-6

(saponified)

214 1-Amino-5-acetyl-aminonaphthalene-3,7-disulfonic acid (saponified)

215 1-Amino-2-methylbenzene-4,6-disulfonic acid

216 the same.

217 1-Amino-2-methylbenzene-4,6-disulfonic acid

218 l-aminobenzene-2-sulfonic acid

219 2-aminonaphthalene-3,6-disulfonic acid

220 2-aminonaphthalene-3,7-disulfonic acid

221 2-aminonaphthalene-4,8-disulfonic acid

222 2-aminonaphthalene-3,6-disulfonic acid

223 2-aminonaphthalene-4,8-disulfonic acid

224 l-amino-4-methoxybenzene-2-sulfonic acid

225 the same.

226 l-aminobenzene-2-sulfonic acid

227 l-aminobenzene-3-sulfonic acid

228 l-aminobenzene-4-sulfonic acid

229 l-Amino-4-methylbenzene-2-sulfonic acid

230 l-Amino ^^ - dimethylbenzene-6-sulfonic acid

231 the same.

232 the same.

233 4-Aminoazobeny.ol-3.4'-disulfonsiiurc

1 - (4'-sulfophenyl) -3-carboxy- 5-6 reddish yellow pyrazolone- (5) 2-acetylamino-5-naphthol- 7-8 orange 7-sulfonic acid (saponified) 2-acetylamino-8-naphthol- 7-8 Red 6-sulfonic acid (saponified) 1 -Chlor-2-acetylamino- 7-8 orange 5-naphthol-7-sulfonic acid (saponified) 1 -acetylamino-8-hydroxy- 7-8 Red naphthalene-4,6-disulfonic acid (saponified) the same 7-8 bluish red the same 7-8 bluish red the same 7-8 bluish red 1 -acetylamino-8-hydroxy- 7-8 bluish red naphthalene-3,6-disulfonic acid (saponified) 1 -acetylamino-8-hydroxy- 7-8 bluish red naphthalene-3,6-disulfonic acid (saponified) 2- (N-acetyl-N-methylamino) - 7-8 yellowish red 5-hydroxynaphthalene-7-sulfone acid (saponified) 2- (N-acetyl-N-methylamino) - 7-8 Red S-hydroxynaphthalene-ö-sulfone- acid (saponified) the same 7-8 Red the same 7-8 Red the same 7-8 Red the same 7-8 Red

2- (N-Acetyl-N-methylamino) - 7-8 red

S-hydroxynaphthalene-o-sulfone-

acid (saponified)

2-acetylamino-8-hydroxy-7 8 red

naphthalene-6-sulfonic acid (saponified)

2-acctylamino-8-hydroxy-7 8 red

naphthalene-3,6-disulfonic acid

(saponified)

l-Amino-3-aeetyIaminoben / ol 5 ft yellow-brown

7O ¹ J Γιλ

42

continuation Diazo component Azo component pH des
Clutch
mediums Shade on cellulose example
No. 4-aminoazobenzene
3,4'-disulfonic acid
the same
the same
the same l-amino-3-hydroxyacetylamino-
benzene
l-amino-naphthalene-6-sulfonic acid
l-amino-naphthalene-7-sulfonic acid
l-amino-2- (4'-amino-2'-sulfo- 5-6
5-6
5-6
8th Yellow-brown
Yellow-brown
Yellow-brown
black 254
235
236
237

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

example

52.4 parts of the disodium salt of 4 - ([4 "-aminophenyl] -amino) -2'-nitro-dipheny! Amine-3,4'-disulfonic acid
are dissolved in 1000 parts of water and treated with 25.0 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine for one hour

NaO ₃ S

NH3 stirred at 55-65 ° C. The acid that is released is continuously mixed with soda to a pH value of 6.5 - 7.5 dulled. The formed reactive nitro dye of the formula

NH-

NO,

SO ₃ Na SO ₂ CH,

-NH

is salted out, filtered off, washed and dried. It dyes cellulose fibers from a long liquor or afterwards one of the usual Klotz processes in the presence of soda as an acid-binding agent! in wet and rubbing fastness, deep purple browns.

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 with 22.0 parts of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine stirred for one hour at 65 ° C. The hydrochloric acid released in the process is continuously increased with soda solution a pH value of 6.5 - 7.5 blunted. After the reaction has ended, the resulting reactive dye becomes the formula

O NH,

SO ₃ Na

NH

SO ₇ CH,

CH ₃

salted out, filtered off, washed and ^{dried at 30-40 0} C (, _0. It dyes cellulose materials in very good wet, rub and lightfast clear blue shades.

Blue dyes of similar properties are obtained. if you proceed as above, but instead of the there mentioned water-soluble aminoanthraquinones> 5 livaies equivalent amounts of the aminoanthraquinone sulfonic acid derivatives listed below with 2-Methylsilill'onyl-4-chloro-b-methyl-pyrimcline acylated:

Example no.

Water-soluble amino-anthraquinone derivative

240

241

242

243

244

245

50 247 248

249

250

251

252

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

l-Amino-4- (2'-chloro-3'-aminophenyl) -ammo-anthraquinone-2,5'-disulfonic acid

l-amino-4- (2'-methyl-3'-methylamino-

phenyl) -amino-anthraquinone-2,5'-disulfone-

acid

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

l-amino-4- (3'-aminophenyl) -amino-

anthraquinone-2,6,4'-trisulfonic acid

l-amino-4- (4'-aminophenyl) -amino-

anthraquinone-2,5,3'-trisulfonic acid

l-amino-4- (3'-aminophenyl) -amino-

anthraquinone-2,5,4'-trisulfonic acid

Mixture of l-amino-4- (3'-aminophenyl) -

amino-anthraquinone-2,4 ', 5- and

2,4 ', 8-trisulfonic acid

also those with 5% oleum at 20-30 "C post-sulfated derivatives:

l-Amino-4- [4 '- (4 "-aminobenzyl) -phenyl] -

amino-anthraquinone-2-sulfonic acid

l-amino-4- (4'-methylaminophenyl) -

amino-anthraquinone-2-sulfonic acid

l-amino-4- (3'-methylaminophynyl) -

amino-anthraquinone-2-sulfonic acid

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

amino-anthraquinone-2-sulfonic acid

l-amino-4- (7'-amino-naphthyl- [2 ']) -

amino-anthraquinone-2-sulfonic acid

continuation

example
No.

Water-soluble amino-anlhraquinone derivative

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), gives after acylation with 2,4-bismethylsulfonyl - 6 - methyl - pyrimidine a violet reactive dye

B e i s ρ i eI 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-amino-p-sulfophenyl) -amide is adjusted to 1.3 liters and pH 7; 40 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidine are added at 50-55 ° C. While stirring, the temperature is increased by 5 ° C per hour, and finally left for several hours at 65-70 ⁰ C. At the same time, 3N NaOH is added dropwise to maintain a pH of about 6.5 - 7.5 until an average of every dye molecule has at least one pyrimidine residue, which can be easily determined on the one hand by the consumption of the sodium hydroxide solution and on the other hand by determining the amino groups. 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. Unreacted 2,4-bis-methylsulfonyl-6-methyl-pyrimidine 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 suctioned off and dried in vacuo or at normal pressure at about 30.degree. 195-20Og of crude dye are obtained, which still contains about 30% sodium chloride. The common salt can be largely removed by stirring the crude dye with 250 ml and suctioning it off again.

The dye dyes cellulosic materials by the Klotz thermofixing process at 140 ° C and after Block-steaming process in wet, rubbing and lightfast Turquoise tones.

The dye mixture used as the starting material can be obtained by methods known per se, e.g. B. C by adding 3 moles of an aqueous suspension of sulfonsäuregruppenfreiem Kupferphthalocyanintrisulfonsäurechlorid at 0-20 ⁰ 2,4-diaminobenzene sulfonic acid at a pH of about 6.5 and catalyzes the same time with 3 moles of pyridine, the saponification, the above-mentioned mixture of Pc- Sulphonamides are formed.

A similar product is obtained if a mixture is used as the starting material that contains the mentioned components in a molar ratio of 4: 1. This mixture is made from the same copper phthalocyanine trisulfonic acid chloride and 2 moles of 2,4-diaminobenzenesulfonic acid were 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 arylenediaminesulfonic acids, how

Toluene-diamine- (2,4) -sulfonic acid- (5);
4,4'-diamino-dibenzyl-disulfonic acid- (2,2 '),
Naphthylenediamine- (1,5) -disulfonic acid- (3,7)
were manufactured. Such products and their manufacture have been described many times in the patent literature. Their reaction with 2,4-bis-methylsulfonyl-6-methylpyrimidine can always be carried out in the same way.

This also applies to the conversion of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine 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-tolyl-mercapto) copper phthalocyanine with chlorosulfonic acid, 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 in an analogous manner by acylation of their Amino groups converted into valuable green reactive dyes with 2,4-bis-methylsulfonyl-6-methyl-pyrimidine will.

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

SO ₁ Na

SO ₂ CH ₃

SO ₁ Na

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 2-methylsulfonyl-4-chloro-6-methyl-pynmidine and coupling the dyestuff intermediates formed with the specified diazo components with valuable reactive dyestuffs which cellulose materials in the listed shades - preferably in the presence of soda - dyed or can be printed:

45 Diazo component 15 44 499 46 hue l-amino-4-methoxybenzene Coupling pH violet example
No. 6-sulfonic acid Coupling component 7-8 256 the same 1 -amino-8-hydroxynaphthalene- reddish purple 3,6-disulfonic acid 7-8 257 the same l-amino-8-hydroxynaphthalene- Scarlet fever 4,6-disulfonic acid 7th 258 1 -amino-5-chloro-benzene- 2-amino-5-hydroxynaphthalene orange 2-sulfonic acid 1,7-disulfonic acid 7th 259 l-aminobenzene-3-sulfonic acid the same orange l-aminobenzene-4-sulfonic acid 7th orange 260 the same the same 7th Scarlet fever 261 the same 7-8 262 4-aminobenzoic acid 2-amino-8-hydroxynaphthalene Red (/ i-sulfoethyl) amide 3,6-disulfonic acid 7-8 263 l-amino-4-sulfoacetylamino- l-amino-8-hydroxynaphthalene- violet benzene-6-sulfonic acid 3,6-disulfonic acid 7-8 264 l-amino-3-sulfoacetyIamino- the same orange benzene-6-sulfonic acid 7th 265 l-amino-4-sulfoacetylamino- 2-amino-5-hydroxynaphthalene Scarlet fever benzene 1,7-disulfonic acid 7th 266 l-aminobenzene-2,4-disulfone the same yellow 'acid 6th 267 2-amino-naphthalene- l- (2'-methyl-3'-amino-5'-sulfo- yellow 4,8-disulfonic acid phenyl) -3-methyl-pyrazolone- (5) 6th 268 the same

Example 269

If you follow the instructions in Example 30 35 tion at 10 ° C and pH 7.5 to 6.5 with the solution of 40.5 proceeded, but that obtained from 1,3-diaminobenzoI-6-sulfonic acid and 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine Dye intermediate after the diazotism

SO ₃ H

Parts of the disodium salt of 2-sulfoacetylamino-5-hydroxy-naphthalene-7-sulfonic acid couples, a reactive dye of the formula is obtained

OH

CH ₁ O ₇ S

N = N

W.
HO ₃ S NH-CO-CH ₂ -SO ₃ H

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 aminoazo dye used there 53.15 parts of the disodium salt obtained by coupling diazotized 1-amino-4-nitrobenzene-2-sulfonic acid with l- (2'-chloro-5'-sulfophenyl) -3-methyl-pyrazolone- (5) and subsequent reduction of the nitro group

aminoazo dye obtained with sodium sulfide is acylated with 2,4-bis-methylsulfonyI-6-methyl-pyrimidine, so you also get a valuable reactive dye, with which cellulose materials after the usual dyeing and printing processes can be printed in real yellow tones.

Similar reactive dyes are obtained if, instead of the aminoazo dye mentioned above, one is used the aminoazo dyes built up from the components listed in the table below 2-Methy! Sulfonyl-4-chloro-6-methyl-pyrimidine acylated:

Example diazo component

Azokomponcntc

hue

271 l-Amino-4-nitrobenzene-2-sulfonic acid (reduced)

272 the same.

1- (2'-Methyl-4'-sulfophynyl) -3-methyl-yellow

pyrazolone- (5)

1- (2 ', 5'-Disulfophenyl) -3-methyl-OcIb

pyrazolone- (5)

47
tongue O 1544499 48 Azo component Color ion "ortsct Diazo component example l- (2'-methyl-4'-sulfo-6'-chlorophenyl) - yellow No. l-amino-4-nitrobenzene-2-sulfone 3-methyl-pyrazolone- (5) 273 acid (reduced) 1 - (2 ', 5' -Dichloro-4'-sulfophenyl) -3-methyl- yellow the same pyrazolone- (5) 274 l- (2'-methyl-4'-sulfophenyl) -3-methyl- greenish yellow 1 -amino-3-acetylaminobenzene- pyrazolone- (5) 275 6-sulfonic acid (saponified) l- (4'-sulfophenyl) -3-methyl-pyrazolone- (5) greenish yellow the same l- (2'-methyl-4'-sulfophenyl) -3-carboxy- greenish yellow 276 the same pyrazolone- (5) 277 l- (2'-chloro-4'-suIfophenyl) -3-carboxy- greenish yellow the same pyrazolone- (5) 278 Example 279 58 parts of the dye of the formula Cu O

NaO ₃ S

N = N

NaO ₃ S

NH-CH ₃

(made by coupling diazotized 1-hydroxy-2-amino-4-chloro-benzene-5-sulfonic acid to 2-methylamino-8-hydroxy-naphthalene-6-sulfonic acid and coppering of the azo dye obtained) are dissolved neutrally in 700 parts of water. 22.0 parts are finely added powdered 2-methylsulfonyl-4-chloro-6-methyl-pyrimi-

Add din and stir at 60-65 ° C with constant Blunt the released hydrochloric acid with soda solution to pH 7 - 7.5 until there are no more free amino groups is demonstrable. The reactive dye formed of the formula

SO ₇ CH,

NaO ₃ SI NaO ₃ S
Cl

is salted out, filtered, washed and dried at 30 -40 ⁰ C. It dyes cellulose materials in very real violet tones using one of the methods given above.

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

example
No. Diazo component Azo component Clutch 280 l-hydroxy-2-amino-4-chloro
benzene-5-sulfonic acid c I-amino-S-hydroxynaphthalene-
3,6-disulfonic acid 10 281 the same l-amino-8-hydroxynaphthalene
3,6-disulfonic acid 10 282 2-amino-naphthalene-
4,6,8-trisulfonic acid
(oxidizing copper-plated) 2-hydroxy-6-acetylamino
naphthalene-4-sulfonic acid c
(saponified) 8 - < 283 1 -amino ^ -hydroxy-o-nitro-
naphthalene-4-sulfonic acid c
(reduced) l-hydroxy-8-ethoxy-naphthalene-
3,6-disulfonic acid c K)

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

Coupling pH shade

reddish purple
bluish purple reddish blue

blue

7ci! I rat / n

Fortset / unu

Example diazo component
No.

Azo component

Coupling pH shade

284 1-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 3-Methoxy-4-amino-6-methyl-azobenzene-2 ', 4'-disulfonic acid
(demethylating coppered)

288 the same.

289 the same.

290 3-Methoxy-4-amino-6-methyl-azobenzene-2 ', 5'-disulfonic acid
(demethylating coppered)

291 the same.

292 the same.

2-hydroxy-3-aminonaphthalene

5,7-disulfonic acid

the same

2-hydroxy-3-aminonaphthalene-7-sulfonic acid

2-methylamino-5-hydroxynaphthalene-7-sulfonic acid

2-amino-8-hydroxynaphthalene

3,6-disulfonic acid

2-Amino-5-hydroxynaphtha! In-

1,7-disulfonic acid

2-methylamino-5-hydroxy

naphthalene-7-sulfonic acid

2-amino-8-hydroxynaphthalene-3,6-disulfonic acid 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid 10

3-9

3-9

Red
blue

blue

10 Navy blue 10 Navy blue 10 Navy blue 10 Navy blue 10 Navy blue 10 Navy blue

Example 293

If one proceeds according to the information in Example 239, however, instead of the 54.7 parts mentioned there, the Disodium salt of l-amino-4 - [(2'-methyI-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, the cellulose fibers by one of the customary dyeing processes dyes in very wet-fast, clear, red-tinged blue tones.

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 60-65 ° C heated and 20 parts of 2,4-bis-methyIsulfonyl-6-methyl-pyrimidine added. 40 parts of 15% soda solution are added over the course of an hour, so that the pH is between 6 and 7.5. The acylation product partially precipitates.

A freshly prepared diazonium salt solution from 13.6 Parts of p-aminobenzylsulfonic acid are 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 washed and dried at 30 ° C in a vacuum drying cabinet. The dye obtained corresponds to egg formula

NaO ₁ S-CH ₂

OH

NaO ₃ S SO ₁ Na

SO ₂ CH _-1

CH ₁

If you proceed 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-l, 7-disilfonic acid with 2-methylsulfonyl-4-chloro-6-diethylpvrimidine acylated and the coupling component containing reactive groups with dia / otierter p-aminobenzylsull'onic acid Coupling, you get an easily soluble reactive dye. of fabrics containing cellulose fibers colors in brilliant red-tinged orange tones.

Cotton or rayon fabric is impregnated on a padder at 2O-2T C with a solution that pro Liters of liquor 30g in this example. Paragraph I,

described dye, 100 g urea and 20 g soda contains, squeezes to a moisture content from approx. 100% and rolls up the damp tissue again. After standing at room temperature for 24 hours the fabric is rinsed, soaped at the boil in the usual way and dried. You get a brilliant one scarlet color with good wet and light fastness.

Impregnating cotton or rayon fabric on a foulard at 20-25 ⁰ C with a solution g per liter of liquor 30 of the in this example, paragraph 1, dye described, 100 g of urea and 20 g of sodium carbonate, squeezed to a moisture content of approx. 100% and steams for 30 seconds at 103 ° C. After rinsing, boiling soaps and drying, a brilliant scarlet dyeing with good wet and light fastness is also obtained.

Cotton fabric is impregnated with a solution of 20-25 ° C, the per liter of liquor 20 g of the dye available according to this example, paragraph 1, and 0.5 g of a nonionic wetting agent (z. B. a polyoxyethylated Oieylalkohols) and 150 g of urea and contains 15 grams of sodium bicarbonate. The fabric is then squeezed between two rubber rollers to a moisture content of 100%. After intermediate drying at 50 -60 ⁰ C for 10 minutes at HO ⁰ 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, Paragraph 1, described dye, 100 g urea, 300 g water, 500 g alginate thickening (60 g 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 dried in between and then in one

HO ₃ S

suitable damper dampens 30 seconds 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 part of a polyoxyethylated stearylamine derivative containing hydroxy groups contains. The dye bath is brought to a boil in 30 minutes, then one hour colored at the boil. After rinsing and drying, you get a brilliant, wash, squeeze and lightfast Scarlet coloration.

Example 295

28.9 parts of 2-amino-1-methylbenzene-3,5-disulfonic acid (monosodium salt) are diazotized and the diazo compound is coupled with 13.7 g of 1-amino-2-methoxy-5-methylbenzene in a weakly acidic medium. The monoazo dye obtained is isolated and then or immediately diazotized in solution without isolation and coupled under alkaline conditions with 25.3 parts of 2-methylamino-5-hydroxynaphthalene-7-sulfonic acid. The diazo dye is salted out by adding sodium chloride, suction filtered and the isolated product with about 50 parts of crystalline copper sulfate, 40 parts of diethanolamine, 50 parts of ammonia (D: 0.88) metallized in 5 hours at 95- 100 ⁰ C. The dye is isolated from the coppering solution by adding salt and carefully acidifying it.

The coppered amino-disazo dye is now in aqueous solution at pH 7-8 at a temperature of 60-65 ° C with 22.0 parts of 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine acylated, the pH through Soda addition is kept in the specified range. When the acylation is complete, the dye is with Sodium chloride isolated and dried at 35 ° C. The dye corresponds to in the form of the free sulfonic acid Formula:

SO ₂ CH ₃

SO ₃ H

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-methylbenzene-3,5-disulfonic acid and l-amino ^ -methoxy-S-niethylbenzene with those in the following table listed aminonaphtholsulfonic acids and 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine 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 thus obtained are blue in color.

Example 296

0.1 mol of 4-ureido-2-amino-1-hydroxybenzene-5-sulfonic acid are diazotized and coupled with 0.1 mol of 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid using alkaline soda. The coupling solution is adjusted to a content of 2 mol / liter with caustic soda and then refluxed for 3 hours to saponify the ureido group. After cooling, it is neutralized with hydrochloric acid. 2n by adding 25 parts of copper sulfate and 100 parts of sodium hydroxide is metallized dye at 45 ° C and a pH of 4-6, and after 30 minutes at pH 7-7.5 and temperatures of 60-70 ⁰ C with 0, 1 mole of 2-methylsulfonyl-4-chloro-6-me-

ethyl pyrimidine acylated. The obtained dye of the formula

O Cu

O NH,

SO ₃ H

SO ₃ H

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

Example 297

A neutral paste of copper phthalocyanine-3,3 ', 3 "-trisulfonic acid chloride made from 600 g of technical grade 96% copper phthalocyanine is stirred with a little water, adjusted to 4 l and at a pH of 3.5-6.0 with 216 g of N- methyl-N- (4'-amino-2'-sulfobenzyl) -amine initially at 0-3 ° C, last 20-35 ⁰ C, is reacted with addition of 300 ml (= 295 g) of pyridine, and then the pyridine at pH 9.0 is distilled off with steam from the resulting solution of copper phthalocyanine-disulfonic acid-monosulfonic acid- (3'-sulfo-4'-methyl-aminomethyl-anilide) -Bis-methyIsulfonyl-6-methyI-pyrimidine 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 is separated off from the excess acylating agent by addition of acetic acid to pH 7.0 and falls by stirring in 2.5 1 of concentrated sodium chloride solution.

After suction filtration and drying at 30 ⁰ C to obtain a clear turquoise blue dye, which is fixed from sodaalkalischer solution at 40-60 ⁰ C with very good yields and wash fastness 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-sulfobenzyI-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 is 8-oxynaphthalene-4,6-disulfonic acid lN-benzoyl-amino-at 30-35 ⁰ C to an aqueous solution of equimolar amount of sodium bicarbonate and 16 parts in 200 parts by volume of water is added dropwise.

The dye partially precipitates and is brought back into solution by adding 2000 parts by volume of water. At 55-60 ⁰ C then 20 parts of 2,4-bis-methylsulfonyl-6-methyl-pyrimidin added. A soda solution is added dropwise to keep the pH between 7 and 8. After completion of the acylation, such as soda consumption is detected at one deposits the dye with 10 percent sodium chloride from, sucked and pressed off and dried in a vacuum oven at 30 ⁰ C. The obtained bluish red dyestuff in the form of the free acid of the formula

CH ₃ O ₂ S

SO ₃ H

HO NH-OCQ ₁ H ₅

N-CH ₁

CH,

HO ₁ S SO ₃ H

Example 299

38.9 parts of 2-diazo-l-hydroxybenzoI-4-sulfonic acid 6-Nitro-by sodaalkalische clutch 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 composed of 4-chloro-2-diazo-1-hydroxybenzene-6-sulfonic acid and 1-amino-S-hydroxynaphthalene-5-disulfonic acid are carried into this suspension one. the pH being adjusted by the dropwise addition of

65 soda solution is held between 7 and 9. After 20 minutes at 70-80 ⁰ C., a dark blue solution has formed. The paper chromatogram shows that a uniform mixed complex has formed. The mixed complex is acylated within one hour at 65 ° C and pH 7-8 with 25.0 parts of 2-methylsulfonyl-4-chloro-6-methylpyrimidine, the pH being kept in the specified range by adding a soda solution dropwise. The acylic dye is salted out with 20% potassium chloride, removed and dried at 30 ° C. A dark powder is obtained which dissolves in water with a blue-gray color.

55 56

The pentasodium salt of the dye corresponds to the formula

SO ₂ CH ₃

SO ₁

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 Obtained dyes in the manner indicated in this example. For the production of these dyes was the azo dye that carries the reactive group in the 2: 1 mixed complex is always used as a 1: 1 chromium complex.

example I: l-chromium complex Metal-free dye Hue on No. cotton 300 4-nitro-2-amino-1-hydroxybenzene 4-nitro-2-amino-1-hydroxybenzene black 6-sulfonic acid - * l-amino-8-hydroxy- - * 2-hydroxynaphthalene naphthalene-3,6-disulfonic acid 301 the same the same black 302 the same the same black 303 the same 4-nitro-2-amino-1-hydroxybenzene black

304 the same.

305 the same.

306 the same.

307 the same.

308 the same.

309 4-nitro-2-amino-1-hydroxybenzene-6-sulfonic acid - »l-Amino-8-hydroxynaphthalene-4,6-disulfonic acid

310 4-chloro-2-amino-1-hydroxy benzene-6-sulfonic acid - »l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

311 the same.

312 the same.

313 the same.

314 the same.

-> 2-HydroxynaphthaIin-6-sulfonic acid like black

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

- »1-Hydroxynaphthalene-4-sulfonic acid

6-nitro-2-amino-1-hydroxybenzene black

4-sulfonic acid - * 2-hydroxynaphthalene

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

-> l-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

the same blue-black /.

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

-> 2-hydroxynaphthalene-6-sulfonic acid 4-chloro-2-amino-1-hydroxybenzene navy blue

♦ 2-hydroxynaphthalene 4-nitro-2-amino-1-hydroxybenzene blue

> l-Acctylamino-8-hydroxynaphllialin-3,6-disulfonic acid

70 «! Ü33 / B

57 continuation 1: 1 chromium complex 5 44 499 58 Metal-free dye Hue on example cotton 1 No. ^ Chlorine-I-amino-l-hydroxybenzene- 4-nitro-2-amino-1-hydroxy benzene Navy blue 315 6-sulfonic acid - ► l-amino-8-hydroxy- - * l-Amino-8-hydroxynaphthaIin- naphthalene-3,6-disulfonic acid 2,4-disulfonic acid the same o-nitro-l-amino ^ -hydroxynaphthalene- Blue black 316 4-sulfonic acid -> 2-hydroxynaphthalene the same 2-aminobenzene-l-carboxylic acid Gray-green 317 5-sulfonic acid - * l-phenyl-3-methyl- 5-pyrazolone 4-nitro-2-amino-1-hydroxy benzene- o-nitro-l-amino ^ -hydroxynaphthalene- black 318 6-sulfonic acid - ♦ l-amino-8-hydroxy- 4-sulfonic acid -> 2-hydroxynaphthalene

naphthalene-3,6-disulfonic acid

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

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

321 4-Nitro-2-amino-1-hydroxybenzene-6-sulfonic acid - »l-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

322 the same.

323 the same.

324 the same.

4-chloro-2-amino-1-hydroxybenzene

- - l- (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

- * l-Hydroxynaphthalene-5-sulfonic acid 6-nitro-4-chloro-1-hydroxybenzene

-> l-hydroxynaphthalene-5-sulfonic acid

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 alkaline soda 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 ö-NitiO-l-diazo ^ -hydroxynaphthalene ^ -. sulfonic acid and 2-hydroxynaphthalene added. After 10 minutes a deep blue solution has formed.

The mixed complex is acylated with 25 parts of 40 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine at 60-65 ° C. and a pH of 6.5-7.5 in about one hour. The pH is kept constant by adding soda solution. The acylated dyestuff is precipitated, filtered off with suction and dried at 30 ⁰ C with 20% sodium chloride.

O, N

C) ₁ p

5 Well

SO ₂ CH,

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

Example 325

6 g of 1-amino-4- (4'-aminophenylamino) anthraquinone-2,5,8-trisulfonic acid are dissolved as Na salt in 180 ml of water at 40.degree. C., and the solution is adjusted to pH 8 and at 65-70 ° C 2.5 g of 2-methyl-sulfonyl-4-chloro-6-me-

NaO ₃ S

NH,

SO ₃ Na

NaO ₁ SO NH

added thyl-pyrimidine in small portions. Simultaneously dilute sodium hydroxide solution is added dropwise in such a way that a pH of 7.5-8.5 is obtained during the reaction is adhered to. The mixture is then stirred at 65-70 ° C. until all of the starting material has disappeared, and sucks off excess pyrimidine derivative and salt at 10 ° C with so much solid sodium chloride that there is about a 10% sodium chloride solution. One sucks off washes with a little saline solution and dries the resulting dye of the formula

NH

SO ₂ CH ₃

below 4O ⁰ C in vacuo. 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 using processes customary for reactive dyes Shades of good wet and light fastness.

The 1-amino-4- (4'-aminophenylamino) anthraquinone-2,5,8-trisulfonic acid used as starting material was obtained as follows: 31.2 g of p-phenylenediamine are dissolved in a solution of 62 g under nitrogen L-amino-4-bromo-anthraquinone-2,5,8-trisulfonic acid sodium and 12 g of soda registered and with the addition of CuCl paste stirred at 40 ° C until no more disulphated bromamic acid can be detected. so dilute hydrochloric acid is added to the solution, and the dyestuff which precipitates out is filtered off with suction and dilute Washed hydrochloric acid, mixed with so much dilute sodium hydroxide solution in 300 ml of water that just Solution enters and the dye is precipitated in the heat as sodium salt; the product is then washed and dried.

In the above examples, the used Reactive components are exchanged with one another under the same or similar reaction conditions will. Likewise, those on page 11, paragraph !, indicated reactive components in the reactions according to the previous examples instead use the reactive components specified there.

Example 326

An ice-cold aqueous-methanolic suspension of 50.1 parts by weight of 2,4,6-trisphenylsulfonyltriazine- (1,3,5), which contains 2 parts by weight of the condensation product of oleyl alcohol with 20 moles of ethylene oxide, is added dropwise with constant blunting of the acid liberated pH 5 to 6 at about 0 "C 1500 parts by volume of an aqueous solution of 56.8 parts of the trisodium salt of an aminoazo compound, which was obtained by coupling diazotized 1-aiiiinobenzene-2-sulfonic acid with 1-acetylamino-S-hydroxynaphthalene ^ .ödisulfon .siiurc in the presence of sodium carbonate and cleavage of the acetyl group by heating in an aqueous solution containing about 4% caustic soda to 80 to 85 ° C. The solution is stirred for a few minutes at 0 to 5 " and pH 5 to 6, then with 100 parts by volume of a solution of 185
Na ₂ HPO ₄ · 12 H ₂ O
pH adjusted to 6.5.

The resulting dye of the formula

Parts of KH ₂ PO ₄ and 262 parts in 1000 parts of water to about

SO ₇ C _n

HO ₃ S

SO ₃ H

is salted out with 200 parts by weight of sodium chloride, filtered off with suction and washed with acetone. The dark powder is then mixed with 10 parts by weight of a mixture of 42 parts of Na ₂ HPO ₄ and 75 parts of KH ₂ PO ₄ and dried at 20 to 30 ° C. in a vacuum. It dissolves in water with a red color.

The same dye is obtained when 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is acylated with trisphenylsulfonyltriazine with diazotized 2-aminobenzenesulfonic acid at pH 5 to 6 and a temperature of 0 to 5 ° C.

The dye obtained according to one of the specified regulations provides when printed on Cellulose fabric with soda as an acid-binding agent a strong bluish red print of good wet and light fastness. The same dyeings on cotton fabric are obtained from a long liquor after Thermosetting process or according to the block-cold dwell process.

Example 327

To an ice-cold aqueous-methanolic suspension of I8. ¹ ) Parts by weight of 2.4.6-TrisphonvlMilfonyl-triazin- (1.5, ")), which contains I part by weight of the Koitdensatiunspioduktes of oleyl alcohol and 20 mol of ethylene oxide, one drips with constant blunting of the acid liberated to pH 5 to 6, the solution neutralized with soda 19.2 parts by weight of the dye

formula

O NH

SO ₁ H

CH ₂ -NH-CH ₃

SO ₃ H

in 1000 parts of water. The mixture is stirred for a few minutes at 0 to 5 ⁰ C and pH 5 to 6, then with 50 parts by volume of a solution of 185 parts of KH ₂ PO ₄ and 262 parts of Na ₂ HPO ₄ · 12 H ₂ O in 1000 parts of water to about pH 6.5 set. The resulting dye of the formula

O NH ₂

SO ₃ H

O NH- <f> -CH ₂ -N-CH ₃

he »u / r \

^bUiH NN

a printing paste containing urea and soda is applied. The colorations are characterized by high wash and lightfastness.

By converting 2.4.b-Trisphcn> Isulfonyl-Iriazin- ( 1.3.5) with other amino groups containing Anthraquinone dyes are also valuable reactive dyes that correspond to the following formulas:

O NH ₂

SO ₃ H

O NH- <f> -SO ₃ H, ^S ° 2C "H

NH ^ N

N <

sacjH,

0 NH

C ₆ H ₅ -O ₂ SN SO ₂ C ₍₁ H ₅

is salted out with 50 parts by weight of sodium chloride, squeezed with 5 g of the mentioned in Example 326 phosphate mixture blended and dried at 20 to 30 ⁰ C in vacuo. It is a dark powder that dissolves in water with a blue color, gives a blue color on cellulose fibers when it is made from alkaline soda solution at room temperature or from aqueous solution by padding and post-treatment of the padding material, if necessary after drying, with a sodium hydroxide solution and Aqueous solution containing sodium chloride, or by pressure in

SO ₁ H SaC ₁ H,

SO ₂ Q ₁ H ₅
These also dye cellulose fibers blue.

Example 328

If, analogously to the procedure in Example 326, 54.4 parts by weight of 2,4,6-tris- (o-methy! Phenyl) -sulfonyltriazine- ( 1,3,5) with 49.7 parts of the disodium salt of the deacetylated aminoazo compound from diazotized 4-AminoanisoIsulfonic Acid- (3) and 2-Acetylamino-5-oxynaphthalene-7-sulfonic acid in order to obtain the dye of the formula

SO ₃ H

CH ₃ O

It is a reddish-brown powder, soluble in water with a red color, which cellulose materials in real scarlet tones.

If 2,4,6-tris-phenylsulfonyl-triazine- (1,3,5) is used with others analogously to the information in Example 326 Aminoazo compounds in order to obtain the dyes indicated in the table below, the cellulose materials color in the listed colors:

SO ₃ H

OH

SO ₂ C ₁₁ H ₅

orange

HO ₃ S

NH

SO, H

63

SO ₃ H OH

SN = N-HO ₃ S ⁷

SOX ₁₁ H ₅

NI
NH -i N

N <

SO ₂ Q ₁ H ₅

HO ₃ S

NH, SO ₃ H

N = N-

NH

N =

SO ₂ Q ₁ H ₅

SO ₃ H

SO ₂ Q ₁ H ₅

SO ₃ H

HO ₁ SN = N-

HO ₃ S

OH NH

SO ₂ Q ₁ H ₅

SO ₂ Q ₁ H ₅

HO ₃ S

-N = N
HO ₃ S

OH

SO ₂ Q ₁ H ₅

SO ₃ HN = <

SO ₂ Q ₁ H ₅

SO ₂ Q ₁ H ₅

SO ₂ Q ₁ H ₅

OH

OH

-N = N

HO ₃ S
SO ₃ H

SO, II

CII ₃ CO NH ^{y /} y NN

IK) ₁ p

SO ₂ Q ₁ H ₅

^S NH ■ - / 'N

. N <

OH

SO ₁ CJI ₅

SOX ₁₁ H,

Nile / 'N

N = -

64

orange

orange

orange

orange

orange

orange

Sdiarkich

65

OH SOjH

N = N-

SO ₂ CH ₅

SO ₁ H

NH- <N
N <

HO ₁ S-CH ₂

SO ₂ Q ₁ H ₅

SO ₂ Q ₁ H ₃

SO ₂ CH ₅

S0., H

OH

-N = N-

SO ₁ H

SO ₂ C ₁₁ H ₃

NH- <N

N <

SO ₂ C ₁ H ₅ 66

Scarlet fever

Scarlet fever

Scarlet fever

OH

SOjH

SO ₂ C ₁₁ H ₅

N-i.

SO ₁ C ₁₁ H ₅

SO ₂ C ₁₁ H ₅

N
HO NH- ^ f N

N = <

SO ₂ C ₁₁ H ₅

HO ₁ S

SO ₁ H

SO ₁ H

HO NH

SO ₁ C ₁₁ H ₃

SO ₂ C ₁₁ H ₃

HO ₁ S

SUN, 11

SO ₂ C ₁₁ H ₃

SO ₁ H

N ■
HO NH "N

N = -

N N

SO ₂ C ₁₁ II ₃ red

Red

bluish red

ugly red

IK) ₁ p

SO ₁ II

67

SO ₃ H OCH,

_X- N = N
SO ₃ H CH, HO ₃ S

OH

Λ,

\ N

68

SO ₂ C ₁₁ H ₃

violet

NH - <N

SO, H

SO ₂ C ₁₁ H ₅

Further red or orange dyes are obtained if one uses such dyes from the components listed in Examples 19 to 29 arise and are not mentioned here.

example

If, in Example 326, 3-aminotoluene is used instead of the listed and 3-aminotoluene and the procedure is otherwise as _{indicated there, the aminoazo dye O 1} IMoI of the coupling product is obtained, the dye of the formula is obtained
from diazotized 2-aminonaphthalene-4,8-disulfonic acid

SO ₃ H

J = N- ^

N N

SO., H

CH,

SO ₂ Q ₁ H ₅

It provides a yellow, in water with a yellow color. Yellow colorations on cellulose materials are obtained soluble powder, the cellulose materials in real also with the similarly accessible dye yellow tones colors. '■ fender formulas:

O, N-

CH ^ = CH -J VN = N

SO, H

SO ₁ H

SO ₁ C ₁₁ H ₅ -N- <N ^CHl SO ₂ C ₁₁ H ₅

SO ₂ C ₁₁ H ₅

N- <

O ₁ N-

-CH = CH- - ''> - N - N - <( "V- NH - <N

SO., H

SO, H

SO, H

SO ₂ C ₁₁ H ₅

CH (OC-NH

SO ₁ II

! j

K), S.

S (), C "H,

/.- - N ■■ ··

, -NN " ; -— NII -4 N ■) WN = N.

NH -COCII, SO ₂ C ₁₁ H ₅

SO ₂ CH ₅

N ■ NN '' NII 'N

SO ₁ II Nil COCH ₁ SO ₂ C ₁₁ Hs

SO, Il

Because yellow l'iirbstolTe ilis l> |> s can be made at enlspreeheinler Verueiiduiiy ilcr l'arbslolle from the lieispicleii 4 to 17 hot in condensation mil 2.4.h TrisphctivlsiiliOml iria / in (1.5. ")) w ill be raised.

69

ΊΟ

Example 330

If one sets according to the instructions in Example 326

45.4 parts by weight 2,4,6-tris- (p-methylphenyl) -sulfonyl-

tri; izin- (1.3.5) with 48.3 parts by weight of the deacctylated th aminoazo compound from diazotized 4- (N-acetylamino) -2-aminobenzenesulfonic acid and 1- (4'-SuIfOpHcnyl) -pyrazolon-5-carboxylic acid- (3) um, this creates the dye of the formula

, SO ₂ C ₁ H ₄ -CH ₁ (P)

HOOC-

-N = N

N-

N =

SO ₂ C "H ₄ —CH, (p)

SO., H

SO ₁ H

can.

It represents a yellow, in water with a yellow color
soluble powder, with which cotton is dyed in greenish analogue produced dyes with similar yellow shades with good fastness properties 25 ton on cotton are:

SO ₂ C ₁₁ H ₅

SO ₂ C ₁₁ H ₅

Cl

SO ₁ H

HOOC

SO ₂ CH ₅

SO ₂ CH ₅

SO ₁ H.

Example 331
0.1 mol of the copper complex compound of the formula

- Cu O

NaO ₁ S

NaO ₁ S

(to

NH,

uirrl dissolved in I 100 I rilcn water at pllh and iiiiii-r vigorous stirring at 0 to 5 ° C while blunting with .Soda solution with a methanolic-aqueous suspension of 0.1 mol of 2,4,6-tris-phenylsulfonyl-triazine- (1,3,5), which contains 2 parts by weight of an emulsifier, condensed. The reactive dye obtained in this way dyes Cellulose materials in wet, rub and lightfast Riibintöncn.

The metal complex compounds indicated in Examples 48 to 63 can be used under analogous conditions to reactive dyes !! implemented the stilfonyltriazine series will.

Very brilliant blue dyeings on cotton are built up in a corresponding way

Dye of the formula

NaO ₁ SO Cu O SO ₃ Na

receive.

NaO ₃ S

Example 332

In the solution of 21 parts of the sodium salt of 1,3-diaminobenzo-6-sulfonic acid in 100 parts of water 50.1 parts by weight of 2,4,6-tris-phenylsulfonyl-triazine- (l, 3.5) given in aqueous-methanolic solution and at 0 - 5 ° C under constant Blunt the released acid to pH 5-6 so

SO ₃ H

Q ₁ H ₅ O ₂ S

SO ₂ Q ₁ H ₅

SO ₂ Q ₁ H ₅

stirred for a long time until a sample is diazotized and coupled to l-hydroxynaphthalene-4-sulfonic acid gives a clear, yellowish red color. The resulting intermediate dye product becomes after adding ice diazotized directly with 7 parts of sodium nitrite and 28 parts of concentrated hydrochloric acid and then with a submitted solution of 47 parts of the sodium salt of 1 -Benzoylamino-S-hydroxynaphthalene-S.ö-disulfonic acid and 12 parts of soda combined in 200 parts of water, wherein coupling to the dye of the formula

HO NH-CO-QH ₅

NH

N = N

NaO ₃ S SO ₃ Na

SO ₂ Q ₁ H ₅

takes place, which is salted out, filtered off with suction, washed and ^{dried at 20-3O 0} C in a vacuum. The dye dissolves in water with a red color and provides clear, bluish red dyeings and prints with high fastness properties on cellulose materials.

In an analogous manner, dyes can be obtained from the combinations given in Examples 31 to 46 specified nuances can be obtained.

Example 333

By condensation of the reaction products described in Example 64 of Kupferphthalocyaninsulfochloriden and l, 3-Diaminobcnzol-4-sulfonic acid with 2,4,6-tris-phenylsulfonyl-triazine (l, 3,5) at 5- 10 ⁰ C and a pH With a value of 6-7, dyes are obtained which dye cotton and regenerated cellulose in clear turquoise shades of good wet, rub and lightfastness by one of the dyeing or printing processes mentioned above.

A particularly valuable type of dye is obtained when the condensation product of copper phthalocyanine trasulfochloride and 1,3-diaminobenzene-4-sulphonic acid with an ammonium hydroxide solution as above is implemented that a compound of the following composition will result:

(SO ₃ H) ,, ⁽ '°

The condensations with the reactive components, for example 2-methylsulfonyl-4-chloro-6-methylpyrimidine, 2,4,6-tris-phenylsulfonyl-trioxin- (1,3,5), 2-methylsulfonyl-4-chloro-5-bromo-6-methylpyrimidine, 2-methylsulfonyl-4-chloro-5-cyanopyrimidine, etc., take place under the respective customary conditions.

Example 334

40.9 g of l-amino-4- (3'-amino-anilino) anthraquinone-2-sulfonic acid are dissolved in 300 ml of water until neutral. 26.5 g of 2-methylsulfonyl-4,5-dichloro-6-methylpyrimidine are added, the mixture is heated to 50.degree. C. and the hydrochloric acid liberated is neutralized with 20% sodium carbonate solution at pH 6. After the reaction has ended, it is suctioned off and at 50 ° C. in vacuo ⁰ C. The finely pulverized intermediate product is introduced into 220 ml of 15% oleum, the internal temperature being kept below 30 ° C. with external cooling. When the sulfonation has ended, which is followed by chromatography, it is decomposed on 500 g of ice and the deposited dye is filtered off with suction. It is dissolved in 200 ml of water, neutralized with sodium hydroxide solution, heated to 75 ° C. and mixed with 10% sodium chloride. Stirring cold will separate the dye of the likely formula
O NH,

SO ₂ CH ₃

CuPc (SO ₂ NII ₂ ) ,,
SO, NH

uubei.72.7 2 imil /) (). 5 I.

SO ₃ Na

NH

SO ₃ H

O NU

NII,

Cl

SO ₁ Na

CH,

from: i-r becomes; ι! ψΐΛ; ιιιμΐ mill Ικ 10 (in a vacuum

dried. The dye dyes cotton fabrics and regenerated cellulose fibers blue and has excellent properties Wet fastness properties.

Used instead of l-amino-4- (3'-aminoanilino) anthraquinone-2-sulfonic acid the l-amino-4- (3'-amino-anilino) -anthraquinone-2,6-disulfonic acid, one comes to a greenish blue of comparable Authenticity properties.

Example 335

5 parts of l-amino-4- (2 ', 6'-dimethyl-3'-aminomethyl) -anilino-anthraquinone-2,4'-disulfonic acid are stirred in 80 parts of water and 0.4 part of 50 percent sodium hydroxide solution is added, whereby a neutral solution is created. 2.7 parts of 4-methyl-5,6-dichloro-2-methylsulfonylpyrimidine are added at 55 ^° C. and the pH is kept between 5 and 5.5 at the specified temperature by adding dropwise sodium carbonate solution. After 2-3 hours the reaction has almost come to a standstill. Another 0.5 part of the pyrimidine derivative is added and the procedure continues as indicated until the reaction has ended. Residues are filtered off, 10 parts of a 25 percent NaCl solution are added to the filtrate at 50.degree. C. and the dye, which has crystallized in the form of flakes, is filtered off with suction at 25.degree. After washing with 5 percent NaCl solution and drying, 6.5 parts of a dark blue powder are obtained which gives very light and wet fast, clear reddish blue reactive prints on cellulose materials.

O NH ₁

NaO ₁ S

The dye has the formula:

O NH ₃

SO ₃ Na

SO ₂ CH ₃

SO ₃ Na

Example 336

20 parts of l-amino-4- (4'-methylaminomethyl) -anilinoanthraquinone-2,6,2'-trisulfonic acid sodium are in 200 parts of water at 60 ⁰ C with 12 parts of 4-methyl-5,6-dichloro-2- methylsull'onyl-pyrimidine acylated, the pH of the solution being kept at 5 - 5.5 by adding dropwise soda solution. The reaction has ended after 5-6 hours. After filtering off gray residues, the dye is deposited at 20 ° C. by adding 50 parts of a saturated NaCl solution, filtered off, washed with 10 percent NaCl solution and dried. Clear, greenish blue reactive prints with very good light and wet fastness properties are obtained on cotton. The dye corresponds to the formula:

Example 317

20 parts of I-amino-4- [2'.6'-dimethy 1-3 '- (3 "-amino-ben- / \ l) -aminomethyl] -ani! Ino-aMthraquinone-2.6.4" -trisulfonic acid sodium are acylated in 160 parts of water at 55 ^{° C. with 1} ) .l parts of 4-methyl-5,6-diehloi-2-methylsulfonylpyrimidine. The pH value is kept at 5 - 5.5 by adding In Sodalösiing. After about

O NH,

, ι '-SO ₁ Na 2 hours, the reaction has ended. The light-colored residues are filtered off and the dye is salted out with a little NaCl, filtered off and dried. The product gives very clear blue prints on cellulose media according to the above-mentioned process, which reach their full depth particularly quickly and are especially wet, rubbing and lightfast.

The dye has the formula:

Na (), S ',

ϊ Ϊ ο

ο! CH ₁ Il

HN IC ¹ II, C.

NH SO ₁ CH ₁

irc

NH SO ₁ Na

Cl

76

Example 338

10 parts of 1 - amino-4- (2 ', 6'-dimethyl-3'-methylaminomethyl) anilino-anthraquinone-2,6-sulfonic acid disu be 50prozentiger in 100 parts of water at 7O ⁰ C and 0.4 parts of sodium hydroxide solution neutralized and resolved. 5.5 parts of 3-methyl-4,5-dichloro-2-methyl-sulfonyl-pyrimidine are added and ^{soda solution is added dropwise at 70 °} C. in such a way that a pH of 5-5.5 is maintained. After 6 hours, 2.6 parts of the pyrimidine derivative are added and the reaction is allowed to proceed for a further 6 hours. Then it is diluted with 100 parts of water, gray residues are filtered off with suction and ^{15 parts of a saturated NaCl solution are added at 70 °} C., as a result of which the dye precipitates in small crystals. After washing with 10 percent NaCl solution and drying, a dark blue powder is obtained which, according to the process described, dyes cellulose fibers in clear blue shades. The dye has the formula:

NH

S O, CH,

NaO ₃ S

Claims (2)

Patent claims: 1. Reactive dyes of the formula F-X-A where F = residue of a dye from the series of azo, anthraquinone or phthalocyanine dyes, X = -N (R) -, where X is directly attached to the radical A and bound directly or via a bridge member to an aromatic ring of the dye residue F. is, R = H or lower alkyl, A = radical of a pyrimidine or 1,3,5-triazine ring of the at least a reactive sulfonyl substituent attached to a carbon atom of the heterocyclic ring contains, the bond arrangement in the series of pyrimidine dyes reactive sulfonyl substituent F-X is present, with the exception of those produced by the process of German Patent 12 58 993. 2. Use of the dyestuffs of claim 1 for dyeing and printing hydroxyl-containing groups and N-containing materials. 30th