DE1118379B - Process for the production of green dyes of the anthraquinone series - Google Patents

Description

It has been found that valuable green dyes are obtained by using a heterocyclic one Imide chloride, which contains at least two reactive halogen atoms, in a suitable order with at least 1 mol of an aminoanthraquinone compound of the general formula I.

Process for the production of green dyes of the anthraquinone series

O NH _a

SOoH

O NH-A-NH.

(I)

wherein A is at most a dinuclear radical of the benzene series, which is the primary amino group in a from ortho different position of the benzene ring linked with NH or in the second benzene ring contains, and wherein the ring I is substituted by 1 to 2 halogens or the sulfonic acid group can be, and converts at least 1 mole of an aminoazo dye of the formula II.

B-N = N-D

NH ₂

! -W

(Π)

In this formula, W denotes at least one water-solubilizing group, for example one Carboxyl group or, in particular, a sulfonic acid group, B an at most dinuclear radical of the Benzene series and D a 5-aminopyrazole group coupled in the 4-position, which is in the 1-position at most 2-ring radicals of the benzene series can be substituted, in particular a l-phenyl-5-aminopyrazole radical. The condensable amino group is preferably located in B or in the 1-aryl radical of D, and although in a position different from ortho of the azo- or pyrazole-bonded phenyl radical or in a second phenyl radical.

The sulfonic acid or carboxyl group W can also be present in B or in the 1-aryl radical of D. be. B and the 1-aryl radical of D can also be further substituted, for example one more Contain sulfonic acid or carboxyl group and halogen, alkyl, alkoxy or arylamino groups. B or D can in particular also include an m- or p-aminobenzoylammo group. The aryl residue of D can also contain a nitro, amino or acylamino group.

Applicant: J. R. Geigy A.-G., Basel (Switzerland)

Representative: Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and DipL-Chem. Dr. R. Koenigsberger,

Patent Attorneys, Munich 2, Bräuhausstr. 4th

Claimed priority: Switzerland of May 28, 1958

Dr. Peter Hindermann, Basel,

and Dr. Alfred Staub, Binningen, Basel (Switzerland), have been named as the inventor

Preferred dyes according to the invention contain an 1-aryl-3-methyl-5-aminopyrazoL radical. You get these from aminoazo dyes of the formula III

; _N = N - C = C:

C = N '
I CH ₃

; n- ε

-NH ₅

(III)

where W and E have the above meanings and E is a dinuclear radical of the benzene series at most means which, as indicated above, can be further substituted. In this formula III either B or E in particular also denote an m- or p-aminobenzoylaminophenyl radical.

109 747/471

3 4

In the anthraquinone compound of the formula I are then when a fixation of the dyes

A denotes an m- or preferably a p-phen with alkali according to known methods on one

ylene or a 4,4'-diphenylene radical. A can further- polyhydroxylated substrate, such as cellulose, is intended

be substituted, for example sulfonic acid or is. When well substantive dyes are made

Carboxyl groups, halogen, alkyl or alkoxy 5 should, then A is preferably a p-phenylene

groups included. A can also optionally be a radical or an optionally monosulfated 4,4'-di-

include m- or p-aminobenzoyl group. In the phenylene radical.

Halogens present in the core I preferably occupy aminoazo dyes which can be used according to the invention

the 6 or 7 position. Any one of the formulas II or III which may be present is obtained, for example

SuIfonsäuregruppe can be in the core I in any io by coupling of m- or p-nitro or acetyl

Position, or isomeric mixtures of aminobenzene-1-diazonium compounds or of

such disulfonic acids of the formula I can be used. m- or p-nitrobenzoylaminobenzoldiazoniumver-

As cyclic imide chlorides with at least two bonds with couplable 5-aminopyrazoles,

Mobile halogen atoms come through on the ring, in particular with l-phenyl-3-methyl-5-aminopyrazoles,

Bromine or chlorine substituted poly-N-heterocycles 15 in an acidic medium, the components being so

into consideration, primarily the 2,4,6-trihalogen selects that the azo dye has at least one water-

1,3,5-triazines, as well as the 2-aryl-4,6-dinalogen solubilizing group, especially sulfonic acid

1,3,5-triazines and 2,4,6-trihalopyrimidines, in groups, contains. Then the nitro group becomes

if necessary also reduced dihaloquinoxalines or di-amino groups or the acetylamino group

halogen quinazoline. The cyclic 20 saponified are used. But you can also use suitable diazo

Imide chlorides in inert organic solvents, compounds of the benzene series in acidic agents with

especially in low molecular weight ketones, or a l-aryl-3-methyl-5-aminopyrazole compound

in a fine aqueous suspension in the presence of coupling, the 1-aryl radical of which is replaced by an amino, acetyl

inert organic solubilizers such as acetone, amino or nitro group or by an acetyl

Methyl ethyl ketone or dioxane. The 25 aminobenzoylamino or nitrobenzoylamino groups to be condensed

Amino compounds are used as an aqueous or an acetylaminophenyl or nitrostyryl group

Solutions of the alkali metal salts, for example as substituted and the optionally present

Solutions of the lithium, sodium or potassium salts, reducing the nitro group to the amino group or the

and saponify the acetylamino group released during the condensation.

Acid with alkali carbonate, alkali hydroxide, alkali 30 A modified process for the production of

bicarbonate or buffer salt mixtures of the o-phosphorus dyes according to the invention consists in that one

acids from. When using cyanuric chloride as the yellow aminoazo component in the dye association

cyclic imide chloride produces the first halogen atom. One can proceed as follows, for example,

preferably at low temperature, for example that one in the cyclic imide chloride, for example in

at 0 to 20 ° C, the second halogen atom at medium 35 cyanuric chloride, the first halogen atom against the

Temperature from 30 to 6O ⁰ C and the third halogen radical of a l-aminoaryl-3-methyl-5-aminopyrazole

atom exchanges at a higher temperature of 70 to 100 ° C and then the second and possibly

exchanged, whereby the solutions in one the third halogen atom with an aminoanthraquinone

Maintains pH value of 4 to 6 or 7 to 8. sulfonic acid component of. Formula I and with a

The sequence of the compo- 40 to be condensed allows organic nitrogen base to react. Which he-

nenten can be anything within certain limits. holding blue condensation compound will then

It depends on the condensation ability of the benzene series with a suitable diazo compound

Components and according to the solubility of the decoupled, either the 1-aminoaryl-

standing interconnections. 3-methyl-5-aminopyrazole or the diazo component is advantageous

first selects a salt of a sulfated amino compound 45 of the benzene series so that an acidic one is water-soluble

introduced. One may be present with the aminoazo dye making group. Another ver

or with the anthraquinone compound or with driving is that one in the heterocyclic

an optionally sulfated organic nitrogen imide chloride, for example in cyanuric chloride, the

base and then in any order a halogen atom with the blue aminoanthraquinone

proceed in stages, reacting 50 sulfonic acid component I, the second

If the preferred cyanuric chloride uses halogen atom against an optionally sulfated one

1 or 2 moles of anthraquinone, m- or p-diamino or m- or p-acetamino-

compound with in each case 2 or 1 mol of aminoazo dyestuff aminobenzene residue and the third halogen, if appropriate

or advantageously exchanges only 1 mole of these compounds for the aniline residue,

link together. The third halogen atom of 55 In the condensation compound thus obtained is

1,3,5-Triazinylrestes can then either be left, if appropriate, the acetamino group saponified, which

or diazotized by the residue of an organic nitrogen base, amino group and the diazo compound with

preferably by phenylamine. a 5-aminopyrazole coupling in the 4-position

Number, type and quantity of the components selects connection united.

With regard to the intended use, the following purpose of the end connections can be found in more detail. For example, the examples are to be taken.
Production of wool dyes is intended, then the dyes according to the invention preferably contain A preferably an m-phenylene radical, and two to four sulfonic acid groups, expediently also the dye II contains the amino group distributed over the anthraquinone and the azo dyestuff m- or p-position to the azo or pyrazole bond in the 65 component. Some of these sulfonic acid groups can be phenyl radicals corresponding to B or E. also be replaced by carboxyl groups.

The green dyes that can be metallized are preferably used for every 1 mole of amino containing the green dyes

compound I and II and leaves the third halogen atom structures, e.g. B. the salicylic acid group, so

the dye can be incorporated into the metal complex compound, e.g. B. the copper complex compound, transferred or the coloring can be metallized. The dye can also be made using metal-containing components being constructed.

The dyes are dark powders in the form of their alkali or ammonium salts that turn out to be hot Well dissolve water with green color, and depending on the composition wool, silk, leather, in particular but dye cellulose fibers in pure, lightfast green tones. Compared to known, comparable They are characterized by pure hue and, in particular, by increased durability of the dyes Stains against acids and alkalis.

In comparison with the dye described in Table Example 31 of German Patent 940 668, the dye of the formula obtainable according to the process

HCLS O NH

O NH

NH-C, C-NH N = C-CH ₃

C = C-N = N

NH ₂ / VCOOH

SOoH

differs in that it is a 5-pyrazolone radical. The following examples illustrate the

contains instead of the 5-aminopyrazole radical, the invention. Therein mean unless otherwise

the latter the advantage of better color fastness is noted, the parts are parts by weight. Parts by weight

compared to iron in the dye bath. are in the same proportion to parts of the volume as

Grams to cubic centimeters.

NH

example 1

NH-C ₆ H ₅

NH ₂ -C _x , N

SOoH

18.5 parts of cyanuric chloride are dissolved in 100 parts of acetone and poured onto 500 parts of ice and 300 parts of water in finely divided form.

At 0 to 5 ° C it becomes a solution of the sodium salt from 37.2 parts of 1- (p-sulfophenyl) -3-methyl-4- (p-aminophenylazo) -5-aminopyrazole in 500 parts of water. The hydrochloric acid released during the reaction is continuously blunted with 1 η sodium hydroxide solution and the pH is kept between 4 and 6. The reaction is complete in 30 minutes, and so is the reaction mixture is a gelatinous solution.

Then heated to 40 to 45 ⁰ C, adding the equimolecular amount, ie, 9.3 parts of aniline.

The split off hydrochloric acid is again truncated with 1 η sodium hydroxide solution and the pn value is increased 6 to 6.8 held. The second stage of condensation

finished in about 4 hours. It is heated to 40 to 45 ° C for about another hour.

The solution of the sodium salt from 40.9 parts of l-amino-4- (p-aminophenylaminoanthraquinone-2-sulfonic acid, made from l-amino-4-bromoanthraquinone-2-sulfonic acid and p-phenylenediamine, added in 1000 parts of water, holds the whole thing about Boil for 20 hours and neutralize the split off hydrochloric acid from time to time, so that the pH value 6.5 to 7.5.

To isolate the dye, a clearly brilliant alkaline reaction is produced by adding soda and salt out the dye.

The dye is a powder that is readily soluble in water. It dyes cotton in very pure green tones of good fastness properties.

1.5 parts of this dye are dissolved in 75 parts of hot water. One sets this solution a Dye liquor of 4000 parts by volume of water at 45 ° C. You go in with 100 parts of cotton yarn, drive to the Boil and leave to simmer for 45 minutes, during which time you gradually add up to 40 parts of Glauber's salt clogs.

A very pure green dyeing with good fastness properties, in particular good alkali fastness, is obtained.

The yellow aminoazo mentioned in the second section

dye is made by diazotizing p-nitroaniline and Coupling with l- (p-sulfophenyl) -3-methyl-5-aminopyrazole and subsequent reduction of the nitro to Amino group produced.

Is used in the first stage of the above example as a yellow component in place of l- (p-sulfophenyl) -3-methyl-4- (p-aminophenylazo) -5-aminopyr- azole 37.2 parts of 1-phenyl-3-methyl-4- (4'-amino-2'-sulfophenylazo) -5-aminopyrazole or 45.2 parts of 1- (p-sulfophenyl) -3-methyl-4 - (4'-amino-2'-sulfophenylazo) -5-aminopyrazole or 41.6 parts of l- (p-carboxyphenyl) -3-methyl-4- (4'-amino-2'-sulfophenylazo) -5-aminopyr- azole, dyes are also obtained which dye cotton in pure green tones.

The yellow aminoazo dyes mentioned can be prepared in an analogous manner by diazotizing p-nitroaniline-o-sulfonic acid and coupling with appropriately substituted 1-phenyl-S-methyl-S-aminopyrazoles and reduce the nitro to the amino group.

NH

CO

CO

Example 2

RR = Cl or - NH- C "H _e

NH-.

NH

SO, H

N = NC ■ C-CH ₃

I Il

NH ₂ -C,, N

SO ₃ H

18.5 parts of cyanuric chloride are dissolved in 100 parts of acetone and the solution is crushed into 500 parts Added ice and 300 parts of water, creating a fine dispersion.

The solution of the sodium salt from 37.2 parts of 1- (p-sulfophenyl) -3 is added with cooling to 0 to 5 ° C - methyl - 4 - (ρ - aminophenylazo) - 5 - aminopyr azole in 500 parts of water and blunted the Hydrochloric acid released from condensation with 2N soda solution, so that the pn value is 4 to 6 and at the end 6.5 amounts to.

The solution of the sodium salt from 48.9 parts of l-amino-4- (4'-aminophenylamino) anthraquinone-2,3'-disulfonic acid is then added in 1000 parts of water, heated to 40 to 45 ° C and neutralized the split off hydrochloric acid again with 2N soda solution. The second stage is completed in about 20 hours.

The reaction can be terminated at this stage and the dye isolated by salting out. He dyes cotton in very pure green tones. By post-treating the dyeing with a boiling solution which contains 20 parts of trisodium phosphate and 300 parts of Glauber's salt in 1000 parts and subsequent boiling with a solution which contains 1 part of a polyglycol ether of a higher molecular weight alkylphenol and 2 parts of soda in 1000 parts, the wet fastness properties of the direct dyeing are achieved still improved, as well as the lightfastness.
The replacement of the third chlorine atom in the dye described above by the aniline residue is carried out as follows: 25 parts of aniline are added to the solution described in section 3 of this example (second stage) and the mixture is heated to the boil for 24 hours. Then it is made clearly brilliantly alkaline by adding 10 parts of soda and the dye is isolated by salting out.

When dry, the dye is a dark powder that dissolves in water with a green color. He dyes cotton in pure green tones.

Used as the blue anthraquinone component instead of l-amino-4- (4'-aminophenylamino) -anthraquinone-2,3'-disulfonic acid in the second stage of the above example, the solution of the sodium salt

56.5 parts of l-amino-4- [4 '- (4''- aminophenyl) phenylamino] anthraquinone-2,3' disulfonic acid in 1200Teilen water of 50 ⁰ C or the solution of 60.9 parts of the disodium salt 1-Amino-4- (4'-aminophenylamino) -anthraquinone-2,5- or 2,8-disulfonic acid in 3000 parts of water at 50 ° C. and if the procedure is otherwise analogous to the above, green dyes are also obtained A technical mixture of 2,5- and 2,8-disulfonic acid can also be used.

The blue anthraquinone component used is 1-amino-4- [4 '- (4 "-aminophenyl) -phenylamino] -anthraquinone 2,6- or 2,7- or a mixture of 2,6- and 2,7-disulfonic acid or the corresponding 2,6,3 "-

Trisulfonic acid, similar green dyes are obtained.

The blue component used is 1-amino-4- [4 '- (4 "-aminobenzoylamino) -phenylamino] -anthraquinone-2-sulfonic acid and as the yellow component l- (p-sulfophenyl) -3-methyl-4- (4'-amino-2'-sulfophenylazo) -5-aminopyrazole, this gives a green dye with a slightly more bluish cast.

If the blue component used is 1-amino-4- (4'-amino-3'-sulfophenylamino) -6- or 7-chloro- or 6,7-dichloroanthraquinone-2-suh ° onic acid and as Yellow component the aminoazo dye mentioned in section 2, one also obtains one green dye.

Example 3

NH,

NH

NH

= N-C-C-CH.

SO, H

18.5 parts of cyanuric chloride are crushed by dissolving in 100 parts of acetone and pouring onto 500 parts Finely divided ice and 300 parts of water.

The solution of the sodium salt from 37.2 parts of l- (p-sulfophenyl) -3-methyl-4- (3'-aminophenylazo) -5-aminopyrazole is added, made from diazotized! 3-nitroaniline by coupling with l - (- p-sulfophenyl) -3-methyl-5-aminopyrazole, in 370 parts of water and neutralized the split off hydrochloric acid by dropwise addition of 100 parts by volume of 1 η-sodium hydroxide solution. The reaction is complete in 15 minutes, although temporarily Complete solution occurs, from which the yellow sodium salt slowly separates.

This sodium salt is brought into solution by heating to 40 to 45 ° C., 9.3 parts of the solution Aniline added and added dropwise by 100 parts by volume 1 η-sodium hydroxide solution kept at a pH of 6 to 6.5 according to consumption. The second The stage is completed in 1 to 2 hours and the compound is dissolved.

The solution of 40.9 parts of 1-amino-4- (p-aminophenylamino) -anthraquinone-2-sulfonic acid in 1000 parts of water and 100 parts by volume of 1N sodium hydroxide solution is then added and the whole is heated to the boil. From time to time the split off hydrochloric acid is neutralized to a pH of 6.5 to 7.5. The reaction has ended after 15 to 20 hours. By adding 100 parts by volume of concentrated sodium hydroxide solution, it is made strongly alkaline and the dye is salted out in the heat. It is then filtered off at about 40 ^° C. and washed with 10% sodium chloride solution.

The dye dyes wool from an acetic acid bath in blue-tinged green, pure shades with good fastness properties. Cotton is also dyed in bluish green tones.
If in the first reaction stage of the above example, 37.2 parts of 1-phenyl-3-methyl are used as the yellow component instead of 1 - (p - sulfophenyl) - 3 - methyl - 4 - (3 '- aminophenylazo) -5-aminopyrazole -4- (3'-amino-6'-sulfophenylazo) -5-aminopyrazole, an analogous dye is obtained which gives somewhat less bluish green colorations.

If 37.2 parts of 1 - phenyl - 3 - methyl - 4 - (3 '- amino - 4' - sulfophenylazo) -5-aminopyrazole are used as the yellow component, this also gives a green dye, the wool from an acetic acid bath in bluish green Colors tones.

If 45.2 parts of 1- (p-sulfophenyl) -3-methyl-4- (3'-amino-4'- or 6'-sulfophenylazo) -5-aminopyrazole are used as the yellow component, this also gives green dyes which dye cotton in more or less bluish green tones.

49.1 parts of 1 - (p - sulfophenyl) - 3 - methyl - 4 - [4 '- (ρ - aminobenzoylamino) phenylazo] -5-aminopyrazole can also be used as the yellow component or 4,4'-bis-

109 747/471

[3 "-Methyl-4" - (3 '"- amino-4'" - or 6 "'- sulfophenylazo) - 5" - aminopyrazolyl - (I ")] - diphenyl used will.

Leave the yellow aminoazo dyes mentioned

yourself ζ. B. analogously, as indicated in Example 1, by diazotizing m-nitroaniline or m-nitroaniline sulfonic acids and coupling with appropriately substituted 1-phenyl-3-methyl-5-aminopyrazoles.

NH ₂

CO

-SO _s H

Example 4

NHC ₆ H

NH

NH

C-CH ₃

SO ₃ H

18.5 parts of cyanuric chloride are, as described in the previous examples, in finely divided Dispersion transferred.

At 0 to 5 ° C it becomes a solution of the sodium salt from 44.1 parts of 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-4- (4 "-aminophenylazo) -5-aminopyrazole added in 500 parts of water and neutralized the liberated hydrochloric acid as usual.

Then are added at 40 to 50 ⁰ C, the solution of the sodium salt from 40.9 parts of l-amino-4- (4'-aminophenylamino) -anthraquinone-2-sulfonic acid in 1000 parts of water is added, keeping at 40 to 50 ° C and the split off hydrochloric acid blunted to a pH of 6 to 7.

In the third reaction stage, 25 parts of aniline are added and the whole thing for 24 hours Boiling heated. A green dye, which is cotton in pure green tones, is isolated by salting out colors.

If the yellow component used is l- (3'-sulfophenyl) -3-methyl-4- (4 "-aminophenylazo) -5-aminopyr- azole or 1- (3'-chlorophenyl) -3-methyl-4- (4 "-amino-2" -sulfophenylazo) -5-aminopyrazole or 1- (- 3'-Carboxyphenyl) -3-methyl-4- (4 "-amino-2" -sulfophenylazo) -5-aminopyrazole or 1- (2'-Chlorophenyl) -3-methyl-4- (4 "-amino-2" -sulfophenylazo) -5-aminopyrazole or 1- (2'-chloro-6'-methylphenyl) -3-methyl-4- (4 "-amino-2" -sulfophenylazo) -5-aminopyrazole or 1- (4'-nitrophenyl) - 3 - methyl- 4 - (4 "- amino - 2" - sulfophenylazo) -5-aminopyrazole, this also gives green dyes.

In the latter case, the nitro group can subsequently be reduced to the amino group be transferred. The resulting dye also dyes cotton in green tones.

The yellow components used can be obtained by diazotizing acetyl-p-phenylenediamine or p-acetylaminoaniline-o-sulfonic acid, Coupling with the appropriately substituted l-aryl-S-methyl-S-aminopyrazoles and saponifying the acetylamino groups.

Example 5

NH

CO

CO '

- SO, H

NH

18.5 parts of cyanuric chloride are, as described in the preceding examples, in finely divided form brought. The solution of the sodium salt from 37.2 parts of 1- (4'-aminophenyl) -3-methyl-4- (4 "-sulfophenylazo) -5-aminopyrazole is then added at 0 to 5 ° C in 500 parts of water and neutralizes the released

Hydrochloric acid with 100 parts by volume of 1 η sodium hydroxide solution. When that amount of caustic soda is used up, the reaction is the first stage finished.

The mixture is then heated to 40 to 50 ° C., and the solution of 43.1 parts of the sodium salt of l-ammo-4- (4'-aminophenylamino) anthraquinone-2-sulfonic acid is added in 1000 parts of water and gradually blunt the liberated hydrochloric acid with 100 parts by volume of 1N sodium hydroxide solution so that the pn value is 6.5 to 6.8.

20 parts of aniline are then added, the mixture is kept at the boiling temperature for 24 hours and the pH value is maintained occasional addition of 1 η-sodium hydroxide solution between 7 and 8.

The dye, isolated by salting out, dyes cotton in green tones.

IO

The yellow aminoazo dye mentioned in the second section is obtained as follows: It is diazotized p-sulfamic acid and couples with 1- (4'-aminophenyl) -3-methyl-5-aminopyrazole.

Is used as the yellow component by diazotizing 5-amino-2-hydroxybenzoic acid and Coupling with 1- (4'-aminophenyl) -3-methyl-5-aminopyrazole obtained aminoazo dye gives also a green dye.

Likewise, the dye can be used as the yellow component, which is obtained by diazotizing 2-Amino-1-carboxybenzene-5-sulfonic acid and coupling with 1- (4'-ammophenyl) -3-methyl-5-aminopyrazole.

NH

SO ₃ H

Example 6

C.H «

NH-1 JL-NH-N

-N = NC C-CH ₃

I! Il

NH ₂ - C _s , N

SO "H

23.6 parts of 2-phenyl-4,6-dichloro-1,3,5-triazine are dissolved in 100 parts of warm acetone and converted into a fine dispersion by pouring into 800 parts of water. The solution of the sodium salt of 37.2 parts of 1- (p-sulfophenyl) -3-methyl-4- (4'-aniinophenylazo) -5-aminopyrazole in 800 parts of water is added to this dispersion at room temperature, heated to 40-5O ⁰ C and the released hydrochloric acid is blunted with 1η sodium hydroxide solution, so that the pn value is 4 to 6. When 100 parts by volume of 1N sodium hydroxide solution have been consumed, the first reaction stage is ended.

The solution of 43.1 parts of the sodium salt of l-ammo-4- (4'-ammophenylamino) anthraquinone-2-sulf is then added on acid in 800 parts of water and heated to boiling. By neutralizing with The pH value is kept at 6 to 8 with 1 N sodium hydroxide solution. When the reaction is over, the obtained Salt out the dye in the heat.

When dry, it is a dark powder that dissolves green in water and cotton colors in green tones.

Example 7

NH ₂

NHCH, COOH

NH-I ^ J- NH-

SOoH

N = C

CH ₃

18.5 parts of cyanuric chloride in 100 parts of acetone are added and the one which is split off is neutralized Acetone and dissolved by pouring into 100 parts of ice 65 hydrochloric acid by slowly adding 100 vol- and 100 parts of water divided into a fine dispersion of 1N sodium hydroxide solution.

leads. At 0 to 5 ^° C., 18.8 parts of 1- (4-amino) are then added to the solution of 48.9 parts

phenyl) -3-methyl-5-aminopyrazole, dissolved in 100 parts of 1 - amino - 4 - (4 '- aminophenylamino) - anthraquinone

2,5-disulfonic acid in 2000 parts of water and 100 parts 1 N sodium hydroxide solution is added, heated to 40 to 50 ° C. and the hydrochloric acid which is split off again gradually becomes blunt by 100 parts by volume of 1 N sodium hydroxide solution, so that the pn value is about 6 to 7.

20 parts of aniline are then added, the mixture is brought to the boil and the acetone is allowed to distill off until the Boiling temperature of 98 to 100 ° C is reached, from time to time the pH by adding 1 N sodium hydroxide solution adjusts to 6.8 to 7, and finally drives off excess aniline with steam.

It is then adjusted to a volume of 3000 parts by volume by dilution with water, and the mixture is cooled to 0 to 5 ° C and sets a solution of 21.7 parts of diazotized 2-amino-1-carboxybenzene-5-sulfonic acid in

250 parts of water are added, which had previously been brought to a pH of 6.5 by blunting is. The pH is kept at 7 by adding 2N sodium acetate solution and kept at .0 to Stirred at 5 ° C. until no more diazo components can be detected and a green solution originated. The resulting dye is salted out as usual. He dyes cotton in green Tones.

If the diazo solution of 2-amino-1-carboxybenzene-5-sulfonic acid is replaced in the last section of this example by a diazo solution of 15.3 parts of 5-amino-2-hydroxybenzoic acid, this also gives a green dye, the color of which can be copied onto cotton.

NH

Example 8

NHC _R H _B SO ₃ H

¹ N

NH

NH

NH ₂ → CH-C-CH ₃

Il Il

NH ₂ -C. , N

SOoH

32.1 parts of the primary condensation compound of 1 mol of cyanuric chloride and 1 mole of p-phenylenediamine-sulf o-oic acid are dissolved in 500 parts of water at 40 ⁰ C with the addition of lOOTeilen 1 N sodium hydroxide until neutral and with the solution of 43.1 parts of of the sodium salt of l-amino-4- (4'-aminophenylamino) -anthraquinone-2-sulfonic acid combined in 1000 parts of water. The hydrochloric acid which splits off at 40 to 50 ° C. is gradually neutralized with 100 parts by volume of 1N sodium hydroxide solution.

Now 20 parts of aniline are added and the mixture is heated to the boil for a long time, the pH value being reduced over time at time is set to 7 by adding 1 N sodium hydroxide solution. Then you do with 20 parts by volume concentrated sodium hydroxide solution strongly alkaline, the excess aniline is distilled off with steam and adjusts the resulting blue dye solution to a final volume of 4000 parts by volume.

The mixture is cooled to 0 ° to 5 ° C., 50 parts by volume of 2N sodium nitrite solution are added and the mixture is diazotized by adding 50 parts by volume of concentrated hydrochloric acid (36.5 percent by weight). Stirring is continued for 2 hours at 0 to 5 ° C, a suspension is of 25.3 parts of l- (4'-sulfophenyl) -3-methyl-5-aminopyrazole in 250 parts of water at 0 ⁰ C added and coupling is by blunting of the pH value to 3.5 to 4 (acetic acid) using sodium acetate. It is kept at 0 to 5 ° C. for several hours and gradually a green solution in which no more diazo components can be detected is obtained. This is then heated to 40 to 45 ° C, made clearly brilliantly alkaline with sodium hydroxide solution and salted out the dye. He dyes cotton in pure green tones.

Claims (6)

Claims: 1. A process for the preparation of green dyes of the anthraquinone series, characterized in that a heterocyclic imide chloride which contains at least two reactive halogen atoms is mixed in a suitable sequence with at least 1 mol of an anthraquinone compound of the general formula I, O NH ₂ SO, H O NH-A - (I) in which A denotes an at most dinuclear radical of the benzene series, which is the primary amino group in the benzene ring linked with NH in a position different from ortho or in the second Benzene ring contains and in which the ring I still with 1 to 2 halogens or with the sulfonic acid group may be substituted, and at least 1 mole of one B-N = N-D Aminoazo dye of the general formula II converts, W ~ "Tt -W
-J-NH ₁ <">, where B is an at most dinuclear radical of the benzene series and D is one coupled in the 4-position 5-aminopyrazole residue, which is in the 1-position at most binuclear residues of the benzene series sub- ίο may be substituted, and W means at least one acidic, water-solubilizing group and wherein the primary amino group in B is in a position other than ortho of the azo-bonded Benzene ring or in an optionally present second benzene ring or in the 1-aryl radical the 5-aminopyrazole component is, and optionally further mobile halogen des heterocyclic imide chloride reacts with reactive nitrogen bases. 2. The method according to claim 1, characterized by the use of an anthraquinone compound of the formula I, in which A is an optionally sulfated p-phenylene or 4,4'-diphenylene radical means. 3. The method according to claim 1 and 2, characterized by the use of an aminoazo dye III of the formula -N = N-C = C = N ' CH ₃ .NH ₉ : n —E -SOoH (III) 35 where B and E denote at most binuclear radicals of the benzene series, which are the primary amino group in a position different from ortho with respect to the azo or pyrazole bond of the corresponding Benzene ring or contained in a second benzene ring. 4. The method according to claim 1 to 3, characterized by the use of cyanuric chloride as heterocyclic imide chloride. 5. Modification of the method according to claim 1 to 4, characterized in that one is a heterocyclic Imide chloride, which contains at least two reactive halogen atoms, is suitable Sequence with at least 1 mol of an anthraquinone compound of the general formula I, O NHo SO ₃ H O NH-A —NH " (D 55 60 Benzene series means which the primary amino group in the benzene ring linked with NH in one of ortho different position or contains in the second benzene ring, and in which the ring I still with 1 to 2 halogens or can be substituted with the sulfonic acid group, and with at least 1 mol an 1-aryl-5-aminopyrazole compound of the general Formula IV implements, H ₂ N, H ₂ N- ε — n: ; c = ch approx. (IV) where E is a dinuclear radical of the benzene series and the condensation compound with an IV corresponding amount of a benzene series diazo compound, wherein one chooses the components so that either the diazo component or E at least one acidic, Contains water-solubilizing group. 6. Further modification of the method according to claim 1 to 4, characterized in that one is a heterocyclic imide chloride which contains at least two reactive halogen atoms contains, in suitable order with at least 1 mole of an anthraquinone compound of the general Formula I, O NH ₂ SO, H O NH-A-NH ₂ (I) in which A denotes an at most dinuclear radical of the benzene series, which is the primary amino group in the benzene ring linked with NH in a position different from ortho or in the second Benzene ring contains and in which the ring I still with 1 to 2 halogens or with the sulfonic acid group may be substituted, and with at least 1 mole of a diamino compound with a maximum of two atoms or acylaminoamino compound of the benzene series, which contains the optionally acylated amino groups contains in a position different from ortho, converts the condensation compound, if appropriate diazotized after saponification of acylammo groups and the diazo compound in a weakly acidic agent combined with a 5-aminopyrazole compound coupling in the 4-position. Considered publications: where A is at most a binuclear residue from German Patent No. 940 668. When the application was announced, a coloring table with an explanation was displayed. © 109 747/471 11.61