DES0036163MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration day: November 3rd, 1953 Announced on August 30, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 22b GROUP 3o3 INTERNAT. CLASS C 09b

S36163IVb / 22b

Dr. Albin Peter, Binningen and Dr. Wolfgang Frey, New World (Switzerland)

have been named as inventors

Sandoz A. G., Basel (Switzerland)

Representative: M. M. Wirth, Dr. W. Schalk and Dipl.-Ing. P. Wirth, patent attorneys, Frankfurt / M.

Process for the production of green substantive dyes of the anthraquinone series

The priority of the registration in Switzerland of November 7, 1952 has been claimed

It has been found that green anthraquinone series substantive dyes are obtained if 2 moles of an anthraquinone compound of the composition

SO ₃ H

O NH-R-NH ₂ wherein R is a phenyl or diphenyl radical, which

can be substituted by alkyl, alkoxy or halogen, and wherein the nucleus A in 5-, 6-, 7- or 8-position is a sulfonic acid group or in 6- and / or 7-position can carry halogen atoms, or 2 moles of any mixture of two or several different arthraquinone compounds of the same general composition or 2 moles of any mixture composed of one or more such anthraquinone compounds and one or more yellow, optionally metallized Aminoazo compounds, preferably in aqueous solution and in the presence of an acid-binding agent, with 1 mol of a Btltadien-i, 4-dicarboxylic acid halide or one of its

609 61: 6/436

S 36163 IVb / 22b

condensed by methyl or halogen substituted derivatives and optionally the dye obtained treated with a metal donor. A second embodiment of the process consists in that ι mol of butadiene-i, 4-dicar-

; ' , acid halide instead of 2 moles of a mixture from one or more anthraquinone compounds and one or more yellow, optionally metallized aminoazo compounds with 2 moles of a mixture of one or more anthraquinone compounds and one or more substituents which can be converted into a diazotizable amino group or having a carbon atom capable of coupling and optionally an azo group Amino compounds condensed, the condensation product after conversion of the 'into a diazotizable Amino group convertible substituents are diazotized into the amino group and the diazo compound with an azo component couples or the condensation product combined with a diazo compound and the dye obtained is optionally treated with a metal donor.

As anthraquinone compounds, for example, the condensation products of i-amino-4-bromoanthraquinone-2-sulfonic acid, i-Amino-4-bromoanthraquinone-2, 5- or -2, 6- or -2, 7- or -2, 8-disulfonic acid, i-Amino-4-bromo-6- or -7-fluoro- or -chloro- or -bromoanthraquinone-2-sulfonic acid and i-Amino-4-bromo-6, 7-dichloro- or -dibromoanthraquinone-2-sulfonic acid with 1,4-diaminobenzene, 1,4-D1-amino-2-chlorobenzene, 1,4-diamino-2-methyl- or ethylbenzene, 1,4-diamino-2-methoxy- or ethoxybenzene, 4, 4'-diamino-i, 1'-diphenyl and 4, 4'-diamino-3, 3'-dimethyl- or -dimethoxy-i, i'-diphenyl used. If only one of these starting materials is chosen, a uniform dye is obtained the composition

NH,

SCLH

NH-R —NH-CO —CH = CH-

in which R has the meaning given and in which the remainder of the 1,4-butadiene-1,4-dicarboxylic acid is replaced by methyl or halogen and the nuclei A can carry the abovementioned substituents.

Such dyes have compared to those from the German Auslegeschrift S 21 388 IVd / 22b (Patent 878 820) known, next comparable dyes, which instead of the muconic acid bridge a fumaric acid or maleic acid bridge, the advantage of a better affinity for vegetable fibers.

. If one takes different anthraquinone compounds, it does not matter in which molecular one Relationship they stand. Two different starting materials in a molecular ratio of 1: 1 generally result three end products, namely two symmetrical and one asymmetrical, which are both starting materials contains. The proportions of the three dyes in the final product? · are not known. Your "'relationship" "misses", if the starting materials are not in the molecular ratio of 1: 1 or if more than two starting materials are used. Through the choice of raw materials and the ratio of the molecules used the end products can have the best possible properties in terms of solubility in water, Solubility in the Fariebäd, Wascri- and ^ chweißelkheit to be brought. The best possible properties are advantageous in given starting materials a series of experiments with systematically changed molecular ratios. It has shown, that dye mixtures, which are obtained from a mixture of starting materials, are usually better are than the mixtures of uniform end products.

Yellow aminoazo compounds, which according to the invention are mixed with the anthraquinone compounds for condensation with the 1,4-butadiene-i, 4-dicarboxylic acid halide are for example those of the benzene series, such as 4-amino-i, i'-azobenzene-4'-sulfonic acid or 4-amino-2 ', 3-dimethyli, i'-azobenzene-4'-sulfonic acid, also more complex ones yellow aminoazo dyes of the stilbene, naphthalene, pyrazolone and acetoacetylaminoaryl series. The shades the final dyes are obtained by adding aminoazo compounds to the anthraquinone starting compounds a shift to yellow-green. It is clear that the yellow aminoazo compounds . At least partially mixed with the anthraquinone compounds. Dicarboxamides associate. If groups are introduced with the aminoazo compounds which lead to the formation of Metal complexes are capable, the end products can be treated with metal donors Agents in substance or on the fiber are converted into metal complex compounds, which usually have improved wet fastness properties compared to the unmetallized dyes. It is also possible, to use already metallized aminoazo compounds for condensation with the anthraquinone compounds.

To carry out the process, the starting materials are dissolved in the form, for. B. their alkali salts in water and adds the solutions, with advantage at temperatures between -10 and + 30 °, the butadiene-i, 4-di- 'carboxylic acid halide, which is in a solvent such as carbon tetrachloride, chloroform, methylbenzene, chlorobenzene or with good stirring, 1, 2-dichlorobenzene may be released so slowly that the p _H values can be kept from 6 bis.8 the hydrogen ion concentration preferably in the range. The amount of alkali required to regulate it is allowed to run in, for example in the form of a solution of sodium acetate, lithium carbonate, sodium carbonate, sodium borate or sodium hydroxide. But you can also the acid released by a buffer, z. B. sodium bicarbonate, intercept. The dyes are precipitated from the solution by salting out or acidifying, if necessary in the heat and after previous distilling off the organic solvent, filtered and - optionally after conversion into an alkali salt - dried. You are dark

.609.61 (5/43 «

S 36163 IVb / 22b

green powders that dissolve in water with a blue-green, green to yellow-green color. From these solutions they dye fibers and structures made of natural and regenerated cellulose in just such shades of excellent lightfastness and in some cases very good washfastness. The dye mixtures outlined above behave in each case, with or without azo components, in terms of color as uniform Dyes.

ίο The metallization in substance of those dyes, which contain groups capable of forming metal complexes, preferably with copper or nickel-releasing agents. The coppering, for example, can be achieved by heating the dyes with ' Copper salts in weakly acidic to weakly alkaline aqueous medium, if necessary with application from pressure and / or in the presence of ammonia or organic bases such as diethanolamine, Pyridine and quinoline, or in the melt of an alkali salt of a low molecular weight aliphatic Monocarboxylic acid happen. If the dye contains substituents which enable metal complexes to be formed an alkoxy group, the metallization is advantageously carried out with splitting of this alkoxy group.

Almost all dyeings with metallizable and metal-containing dyes can be done with cation-active, 65 optionally basic copper complex compounds (e.g. obtainable from Swiss patents 253 709 and 261 048 to 261 052), ·. whereby their wash and perspiration fastness is further improved. 70

The following examples illustrate the invention without restricting it. The parts mean, as a rule, parts by weight; if parts of the room were used, this is expressly mentioned. The percentages are percentages by weight and the temperatures are given in degrees Celsius. The intermediate products of the anthraquinone series used are compiled in Table 1 below; _: they are quoted with the associated Roman numeral.

NH,

SO ₃ H

(3)

NH-R

table

No. Meaning of R importance
X ' from
y Position of
χ y - (I) -SO ₃ H - 6th - (Π) - SO ₃ H
-SO ₃ H . 7th
7th -SO ₃ H - 5 - (III) - - - - (IV) - / "Vnh ₂ - - - - (V) '- (VI) -SO ₃ H '- 6th CH ₃ O - (VII) - / Vnh ₂ -Cl -Cl ■ 6 ■ 1
CH ₃ O - - - ■ 7th (VIII) - <()> - ^ΝΗ * - (IX) Cl ■ ■,.:.,

609 6W436

S 36163 IVb / 22b

No.

Meaning of R

meaning of
χ y

Position of

χ I y

(X)

(XI)

(XII).

NH,

CH ₃

CH,

NH ₉

NH,

example 1

In 600 parts of water 19.6 parts of (I) is dissolved 29 ° / ₀ sodium hydroxide solution with addition of 7 parts. After cooling the solution to 0 to 5 ° provides to their reaction to a _pH value of 6 to 8.5 and can with good stirring a solution of 3.95 parts of butadiene-i, 4-dicarbonsäurechlörid in 80 parts of carbon tetrachloride dropwise. The _pH value is kept constant within the limits stated above by simultaneous dropwise addition of a dilute sodium hydroxide solution. When the condensation is over, the carbon tetrachloride is distilled off. The solution is then made strongly acidic with hydrochloric acid and the precipitated dye acid is filtered off with suction. This is pasted with sodium carbonate until it has a neutral reaction and then dried. A black-green powder is obtained which dissolves easily in water and, from this solution, turns a beautiful green of high lightfastness onto cotton and fibers made from regenerated cellulose.

Example 2

In the above example, the 3.95 parts of 1,4-butadiene-1,4-dicarboxylic acid chloride are replaced by 4.3 parts 2-methylbutadiene-1,4-dicarboxylic acid chloride is obtained in this way one green dye of similar properties.

Example 3

In 600 parts of water 5.5 parts The mixture is stirred 29 ° / ₀ sodium hydroxide solution, 8.2 parts (V), 10 parts of (I) and 30 parts of chlorobenzene. In ο ⁰ to 5 and a _pH value of 6.5 to 8.5 is sprinkled within 30 minutes a total of 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride in the mass and neutralizes the hydrogen chloride formed with dilute sodium hydroxide solution. After the condensation has ended, the chlorobenzene is distilled off, the solution is strongly acidified with hydrochloric acid and the dye acid is suction filtered off at 65 °. This is converted into the sodium salt in the usual way and dried. The dye is a dark green powder; from aqueous solution .. he dyes cotton and fibers from regenerated cellulose in beautiful bluish green shades with very good fastness properties, especially good light fastness.

-SO ₃ H

-SO ₃ H

- SO.H

Example 4

With the addition of 5 parts Cleans 30 ° / _O strength sodium hydroxide solution are dissolved in 600 parts of water 9.8 parts (V) and 4.5 parts of 4-amino-i, i'-azobenzene-4'-sulfonic acid. The solution is cooled at 3 to 8 ° and added dropwise to her at a _pH value from 6.8 to 8.5 within 30 minutes with good stirring a solution of 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride in 75 Allocate trichlorethylene, the resulting hydrogen chloride being neutralized by dilute sodium hydroxide solution. When the condensation is completed, distilled from trichlorethylene, the solution is at 75 ⁰ 40 parts by volume of 30 ° / _O hydrochloric acid to and filtered off under suction, the dye acid. After pasting with the necessary amount of sodium carbonate for neutralization and drying, a dark green powder is obtained which dyes cotton and fibers made of regenerated cellulose from aqueous solution in pure green shades of very good washing and lightfastness.

Example 5

If in the above example instead of 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride 5.4 parts of 1,4-D1-chlorobutadiene-i, 4-dicarboxylic acid chloride is used, a similar dye is obtained.

Example 6

In 600 parts water 10 parts (V) and 10.8 parts of the trisodium salt of diazotized by coupling i-carboxy-2-aminobenzene-5-sulfonic acid is dissolved with the addition of 4 parts by volume of 30 ° / _o sodium hydroxide solution with i- [4 "-amino-i ', i" -stilbenyl- (4')] - 3-methyl-5-pyrazolone 2 ', 2 "-disulfonic acid available' Aminomonoazoverbindung In ο ⁰ to 5 and a _pH value between 6th , 5 and 8.5 is slowly added dropwise to the solution with vigorous stirring, a solution of 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride in chloroform, keeping the _pH value with diluted sodium hydroxide at the initial value. After completion of the condensation iao if 'the mass is weakly alkaline and the chloroform is distilled off.

To the transfer. of the resulting dye in its copper complex compound was added to the solution, 8 parts of crystallized sodium acetate and 28 parts of space 1 * 5 20 ° / _O strength copper sulfate solution is added and stirred to

61ι6 / 4ϊ6

S 36163IVbI'22b

for 15 minutes at 80 °. The copper-containing dye is precipitated by adding 60 parts of sodium chloride to the reaction solution, suction filtered while warm and dried. A dark green powder is obtained which is made from an aqueous solution of cotton and fibers regenerated cellulose in beautiful yellowish green tones with very good fastness properties, in particular good lightfastness, colors.

Example 7

The dye described in the above example can also be obtained by adding 10 parts (V) and 7.2 parts of i- [4 "-amino-i ', i" -stilbenyl- (4')] -3-methyl-5 -pyrazolon-2 ', 2 "sodium disulfonate in 600 parts water with the addition of 4 parts by volume of 3O ° / ₀ sodium hydroxide solution dissolves and carries out the condensation with the 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride by the procedure of this example. After condensation has taken place, the

ao reaction mass sodium carbonate alkaline, it cools to ο to 5 ° and mixed them with an ice-cold diazo suspension, which by direct diazotization of 3.2 parts of i-carboxy-2- aminobenzene-5-sulfonic acid is available in 12 parts of dilute hydrochloric acid.

After coupling is complete, the dye is converted into its copper complex compound as described in Example 6 convicted.

To prepare the nickel complex compound, 5 parts of the metal-free dye are dissolved in 200 parts of water, and 3 parts of crystallized sodium acetate are added to the solution. At 70 ⁰ to add it within 20 to 30 minutes so much of a io ° / ₀ aqueous nickel sulfate solution until consistent excess nickel (II) ions are detectable. The resulting nickel complex compound of the dye is precipitated from the metallizing solution by adding sodium chloride, filtered and dried. It has similar properties to the copper complex compound.

Example 8

In 600 parts of water is stirred 4 parts by volume of 3o ° / ₀ sodium hydroxide solution, 4.1 parts (V), 4.9 parts of (I) and 9.2 parts of the monosodium salt of diazotized by coupling i-carboxy-2-aminobenzene 5-sulfonic acid with i- (4'-amino) -phenyl-3-methyl-5-pyrazolone available aminomonoazo compound. The solution is cooled to 0 to 5 ⁰ and added dropwise with good stirring it at a _pH value of 8 was slowly added a solution of 3.9 parts of butadiene-i, 4-dicarboxylic acid chloride in 60 parts of chloroform to. With dilute sodium hydroxide solution the _pH value is maintained at the initial value. When the condensation is finished, the chloroform is distilled off, contributes 8o ° 8 parts of crystallized sodium acetate and 25 parts by volume of 20 ° / _O strength copper sulfate solution into the solution and stirring this still for 15 minutes at 8o °. The resulting copper corplex compound of the dye is precipitated by adding sodium chloride, filtered and dried. It dyes cotton and regenerated cellulose fibers from an aqueous solution yellow-green. The dyeings are very good wet and lightfast.

Example 9

5.1 parts (XII) and 7.4 parts of the trisodium salt of the copper complex are dissolved in 400 parts of water from the sulfonic acid obtained by coupling diazotized i-carboxy-2-aminobenzene-5-sulfonic acid with i- [4 "-aminoi ', i "-stilbenyl (4 ')] - 3-methyl-5-pyrazolone 2', 2" -disulfonic acid Aminomonoazoverbindung available with as much dilute sodium hydroxide solution, that the _pH value _is 8 beträgt.Bei 0 to 5 ⁰ is added dropwise to the mixture slowly under vigorous stirring, a solution of 2.7 parts of 1,4-dichlorobutadiene-i, 4-dicarboxylic acid chloride in carbon tetrachloride to and maintains the _pH value with diluted sodium hydroxide solution constant. After the completion of condensation is distilled from the carbon tetrachloride. the copper-containing dye is precipitated from the condensation solution by adding 50 parts of sodium chloride, filtered off with suction and dried to give a green powder which, from aqueous solution, dyes cotton and regenerated cellulose fibers in yellow-green shades with good fastness properties.

Example 10

In 400 parts of water and 7 parts by io ° / ₀ sodium hydroxide solution 4.1 parts (V) and 4.6 parts of the monosodium salt is dissolved from the diazotized by coupling i-carboxy-2-aminobenzene-5-sulfonic acid with i- ( 4'-amino) phenyl-3-methyl-5-pyrazolone available aminomonoazo compound. The mixture is cooled to 0 ° to 10 ° and 2.2 parts of 2-methylbutadiene-1,4-dicarboxylic acid chloride are slowly added dropwise at this temperature with thorough stirring. With dilute sodium hydroxide solution the _pH value is maintained of the mixture between 6.5 and 8.5. When the reaction is completed, the mixture is heated to 8o °, inflicting 5 parts of crystallized sodium acetate and 20 parts by volume of 20 ° / _O strength copper sulfate solution and it is stirred there for 15 minutes at 8o °. The copper-containing dye is precipitated at 70 ⁰ with 40 parts of sodium chloride from the plating solution and suction filtered. After drying, a dark green powder is obtained which dyes cotton and fibers made from regenerated cellulose from an aqueous solution in yellowish green shades. The dyeings show very good fastness to light and washing.

In the following table 2 there are recorded further dyes, which after one of the in the methods described in Examples 1 to 10 prepared can be. To identify the dyes, in column (b) the butadieni, 4-dicarboxylic acid halide of the composition

Cl-CO-C = C-CH = C-CO-Cl (4)

y ζ y

components to be linked are specified. In column (c) the number of parts of butadiene, 4-dicarboxylic acid chloride and in columns (d) and (e) the meaning of the symbols y and ζ in the formula (4) listed. The hue of the dyeings made by the new dyes on cotton and fibers regenerated cellulose is shown in column (f). ,

609 6116/456

S 36163 IVb / 22b

Table 2

(a)
example
No, (b) 19.5 parts (Π)
22.6 parts (III) (C) (d)
y (e)
Z (f) II
12th 23.8 parts (X) 3.9
3.9 H
H H
H green
bluish green 13th 22.6 parts of the technical mixture
(IV) and (XI) 3.9 H H the same 14th 10.0 parts (I),.
9.6 parts (VIII) 3.9 H H the same 15th 9.8 parts (V),
7.8 parts of the technical mixture
(IV) and (XI) 3.9 H H the same l6 10.6 parts (IX),
7.8 parts of the technical mixture
(IV) and (XI) 3.9 H H also: 17th 11.8 parts (VI),
7.0 parts (VII) 3.9 H H bluish green I8 7.4 parts (I),
1.5 parts (III),
1.1 parts (V) 3.9 H H green 19th 9.8 parts (I),
9.3 parts of monosodium salt from (i-Carb-
oxy-2-aminobenzene-5-sulfonic acid
-> - i- (4'-Ammo) -phenyl-3-niethyl-
5-pyrazolone). 2.4 H H the same 20th 9.8 parts (I),
9.3 parts of monosodium salt from (i-Carb-
oxy-2-aminobenzene-4-sulfonic acid
-> - i- (3'-Amino) -phenyl-3-methyl-
5-pyrazolone) 5.3 Cl H yellowish green 21 9.8 parts (I),
4.7 parts of monosodium salt from (i-Carb-
oxy-2-aminobenzene-4-sulfonic acid
-> ■ i- (3'-amino) -phenyl-3-methyl-
5-pyrazolone),
4.6 parts of monosodium salt from (i-Carb-
oxy-2-aminobenzene-5-sulfonic acid
- »- i- (4'-amino) -phenyl-3-methyl-
5-pyrazolone) 5.3 Cl H green 22nd 10 parts (I),
8.2 parts (V) 5.3 Cl H the same 23 14.7 parts (I),
4.1 parts (V) 4.3 H CH ₃ bluish green 24 12.3 parts (V),
4.9 parts (I) 4, o H H green 25th 4.9 parts (I),
4.1 parts (V) 4.0 H H - bluish green 26th 9.8 parts (I),
9.4 parts of monosodium salt from (i-Carb-
oxy-2-aminobenzene-5-sulfonic acid
-y i-acetoacetylamino-4-amino-
benzene) 3, o Cl H olive green 27 3.9 H H green .

S 36163 IVb / 22b

Table 2

(a)
example
No. (b) ■ ro, 2 parts (XII), (C) y (e)
Z ( ^f ) the same 28 9, o parts of monosodium salts from (i-meth- 3.9 H H oxy-2-amino-5-nitrobenzene -> - i-Ace- toacetylaminobenzene-4-sulfonic acid and reduction) 9.8 parts (I), yellowish green 29 io, 3 parts of disodium salt from (2-amino- 3.9 H H naphthalene-6,8-disulfonic acid -> - i-Amino-3-methylbenzene) 9.8 parts (I), the same 30th 11.3 parts of the disodium salt from (2-amino- 4.3 H CH ₃ naphthalene-4, 8-disulfonic acid -> - i-Amino-3-acetylammobenzene) 5.1 parts (XII), the same 3i 7.5 parts of trisodium salt from (i-Oxy- 2.2 H CH ₃ 2-amino-6-chlorobenzene-4-sulfonic acid -> i- [4 "-amino-i ', i" -stilbenyl- (4')] - 3-methyl-5-pyrazolone-2 ', 2 "-disulfone- acid) 9.8 parts (I), green 32 4.6 parts of the monosodium salt of 4-amino 4.0 H H 4'-oxy-i, i'-azobenzene-3'-carboxylic acid 12.3 parts (I), olive green 33 6.0 parts (4-amino-i, i'-azobenzene- 4.0 H H 3, 4'-disulfonic acid -> - i-] 4'-amino] - benzoylamino-3-methylbenzene) 10.4 parts (V), olive green 34 8.4 parts (4-amino-i, i'-azobenzene- 4.0 H H 3, 4'-disulfonic acid -> - i-amino-3-ace- tylaminobenzene) 5.1 parts (XII), yellowish green 35 7.3 parts of trisodium salt from (i-methoxy- 2.0 H H 2-aminobenzene-4-sulfonic acid -> - i- [4 "-amino-i ', i" -stilbenyl- (4')] - 3-methyl-5-pyrazolone-2 ', 2 "-disulfone- acid)

Example 36

If in Example 3 instead of 8.2 parts (V) 9.8 parts of the technical mixture of i-amino-4- (4'-amino) -phenylamino-6-bromoanthraquinone-2-sulfonic acid and i-amino-4- (4'-amino) -phenylamino-7-bromoanthraquinone-2-sulfonic acid used, a similar dye is obtained, which also has excellent properties.

Example 37

If, in Example 4, 10.3 parts of i-amino-4- (4'-amino) -phenylamino-6-fluoroanthraquinone-2-sulfonic acid are used instead of 9.8 parts (V), thus a dye with similar properties is obtained.

Claims (2)

Claims: i. Method of manufacture stantiver dyes the green sub-anthraquinone series, characterized in that 2 moles of one Anthraquinone compound of the composition O NH, SO, H O NH-R-NH ₂ wherein R is a phenyl or diphenyl radical which is substituted by alkyl, alkoxy or halogen iao can be, and wherein the nucleus A in the 5-, 6-, 7- or 8-position is a sulfonic acid group or can carry halogen atoms in the 6- and / or 7-position, or 2 moles of any combination Mixture of two or more different anthrachmone compounds 609 616/436 S 36163 IVb / 22 b the same general composition or 2 moles of a mixture of any composition of one or more such anthraquinoric compounds and one or more yellow, optionally metallized aminoazo compounds, preferably in aqueous solution and'in the presence of an acid-binding agent, with ι mol of a butadiene-1,4-dicarboxylic acid halide or one of its derivatives substituted by methyl or Halqgen condensed and the obtained dye optionally with. treated with a metal donor. 2. Modification of the method according to claim i, characterized in that one ι mol of the butadiene-i, 4-dicarboxylic acid halide instead of 2 mol of a mixture of one or several anthraquinone compounds and one or more yellow, optionally metallized Aminoazo compounds with 2 mol of a mixture of one or more anthraquinone compounds and one or more substituents which can be converted into a diazotizable amino group or having a carbon atom capable of coupling and optionally an azo group Amino compounds condensed, the condensation product after conversion of the in a diazotizable amino group convertible substituents into the amino group and diazotized the diazo compound couples with an azo component or the condensation product with a Diazo compound combined and the dye obtained, optionally with a metal donor Means treated. Considered publications:
German patent application S 21388 IVd / 22b (patent 878 820). . 609 616 / 4-36 8. 56