CH615693A5 - Process for preparing new trisazo dyes, the trisazo dyes and use thereof - Google Patents

Description

The present invention relates to a process for the preparation of new trisazo dyes in the form of the free acid of the formula I.

h2n oh

Kl- N «'N- - N« .N -

or or

N a N - D] _ (I)

(so3h) 2

correspond to what

R is an optionally substituted alkyl group with 1-6 carbon atoms,

Di denotes a radical of the benzene series which contains sulfonic acid groups and which optionally carries further substituents, and

Kj is the remainder of a hydroxydiphenylamine which may have further substituents

The new trisazo dyes of the formula I are generally used in the form of their salts, for example as alkali salts, in particular in the form of the sodium salts or potassium salts, for carrying out dyeing processes. They have good color properties and are particularly suitable for dyeing non-textile substrates, for example for dyeing paper or leather. However, they can also be used for dyeing textile fibers, in particular for dyeing vegetable textile fibers such as cotton or regenerated cellulose.

Some polyazo dyes have already been described in the literature. The closest prior art is German Patent No. 927 041, which describes dyes for dyeing leather fibers. Example 33 of this patent discloses a dye which, however, differs from the dyes according to the invention in that a fourth azo group is bonded in the group which corresponds to the grouping Kx of the dyes according to the invention.

According to one method according to the invention, the new trisazo dyes, which are in the form of the free acid

40

Correspond to formula I, prepared by using a diazotized amino-diazo compound of formula II as the starting material

NHo OH

H2tf - (/ \

45

di)

(SOjH).

55 •

in which

R has the meaning given in formula I, and uses it in any order with hydroxydiphenylamine of the formula IV

Kj-H (IV)

and also a diazotized amine of formula III

60

D! -NH2

(III)

couples.

When carrying out this process, the coupling of the hydroxydiphenylamine of the formula IV is preferably carried out in the o-position to the hydroxyl group.

Preferred new trisazo dyes of the formula I are those which are in the form of the free acid of the formula Ia

615 693

4th

h2n oh

N- "N 13 N -

-yjr \ jç

or or ho5S

n «n - di

(la)

SO ^ H '

correspond, being in this formula

R, D j and Kt have the same meaning as in formula I.

Of these preferred trisazo dyes, those are again particularly preferred which, in the form of the free acid of the formula Ib ki- '- n -

nhp oh n »n -

or or ho5S

n - n -d ^

SOjK

, (! *)

(S03H) m, in which

Dj 'denotes an unsubstituted phenyl radical or a phenyl radical substituted by alkyl groups having 1-4 carbon atoms, alkoxy groups having 1-4 carbon atoms, carboxy groups, nitro groups, chlorine atoms, alkylcarbonylamino groups having 1-4 carbon atoms or oxyalkylamino groups,

m is 1 or 2, and

R and K [have the same meaning as in formula I.

A preferred meaning which the radicals R have in the new azo dyes of the formula I and the preferably prepared azo dyes of the formulas Ia and Ib is that of optionally substituted methyl groups or ethyl groups. As already mentioned, however, the alkyl radicals in these trisazo dyes have the more general meaning of an optionally substituted alkyl radical having 1 to 6 carbon atoms inclusive, of the substituents hydroxyl groups, alkoxy groups, in particular having 1 to 4 carbon atoms, halogen atoms and in particular chlorine atoms, are preferred.

In the trisazo dyes of the formula I and the preferably prepared trisazo dyes of the formula Ia prepared by the process according to the invention, the sulfonic acid group-containing radicals of the benzene series Ü! optionally, in addition to the sulfonic acid groups, carry further substituents, such as, for example, halogen atoms, in particular chlorine atoms, alkyl groups, in particular alkyl groups with 1 to 4 carbon atoms, alkoxy groups, in particular alkoxy groups with 1 to 4 carbon atoms, hydroxyl groups, carboxy groups, carboxylic ester groups, in particular carboalkoxy - Groups, such as those in which the alkoxy group has 1 to 4 carbon atoms, acylamino groups, in particular alkylcarbonylamino groups and arylcarbonylamino groups, of which the optionally substituted phenylcarbonylamino groups are particularly preferred, oxaloyl groups, nitro groups and arylamino groups, in particular optionally substituted phenylamino groups.

As already mentioned further above, in the new trisazo compounds of the formula I and the corresponding compounds of the formulas Ia and Ib which are preferably prepared by the process according to the invention, the residues Kt) may also be the residues of a hydroxydiphenylamine and may carry further substituents. These

However, substituents must not be azo groups, because the corresponding dye substituted with a further azo group, as already mentioned above, is described in Example 33 of German patent specification 927 041. Examples of further substituents which can carry the hydroxydiphenyl amino radicals Kj are alkyl groups, in particular 10 alkyl groups with 1-4 carbon atoms, nitro groups, halogen atoms, in particular chlorine atoms, sulfo groups, hydroxyl groups, amino groups, alkylamino groups, dialkylamino groups, in particular corresponding groups in which the alkyl radical or each of the alkyl radicals has 1-4 carbon atoms, acylamino groups, in particular alkylcarbonylamino groups, in particular those in which the alkyl radical has 1-4 carbon atoms, and also aminocarbonylamino groups.

Particularly preferred substituents for the radical Kj in the 40 compounds of the formulas I, Ia and Ib are of the above-mentioned alkyl groups with 1 to 4 carbon atoms, nitro groups, hydroxyl groups, sulfo groups or chlorine atoms.

The processes according to the invention for the preparation of the 45 new trisazo dyes of the formula I proceed according to the reaction principles described in the book Houben-Weyl:

Methods of Organic Chemistry, Volume X / 3, page 226.

The synthesis processes explained above are illustrated using the following reaction scheme:

55

60

Coupling component

(KaH)

(1 mole)

1-amino-8-hydroxy-naphthalenedisulfonic acid (1 mol)

3. 4,4'-diamino-3,3'-dialkoxy diphenyl (1 mole)

1.

(angry)

2nd

Di-NH2 (1 mole)

In this reaction scheme, after the aminodiazo compound of the formula II has been prepared, it is first coupled to the amine of the formula III. This coupling can be carried out in neutral, alkaline or acidic medium. The subsequent coupling with the optionally substituted hydroxydiphenylamine of the formula IV

5

615 693

K ^ H

(IV)

in which the rest

K! represents the remainder of a hydroxydiphenylamine which may carry further substituents,

takes place predominantly in the o-position to the hydroxy group.

If necessary, however, a coupling in the p-position to the hydroxyl group or a partial coupling in the p-position can also take place.

However, the process according to the invention for the preparation of the new trisazo dyes of the formula I can, as already explained above, also be carried out according to the following reaction scheme:

[Coupling component 2. 4,4-diamino-3,3'-dialkoxy 1.

K ^ H (1 mole)

diphenyl (1 mole)

3rd

D! -NH2

(III)

and then the coupling with the optionally further substituted hydroxydiphenylamine of the formula IV

In the second reaction scheme explained, the order is reversed.

Coupling with the hydroxydiphenylamine of the formula IV and the diazotized amine of the formula III is also preferably carried out in an aqueous medium.

As examples of amines of formula III

D.-NH,

(III)

(angry)

l-amino-8-hydroxy-naphthalene

disulfonic acid J —s

(1 mole) D, -NH2

(1 mole)

In this process, too, the 4,4'-diamino-3,3'-dialkoxy-diphenyl is first bis-diazotized, and this is then coupled with the l-amino-8-hydroxy-naphthalene-disulfonic acid, whereby the aminodiazo compound of formula II is obtained. This process step is preferably carried out in an aqueous medium. The acidic NH2 coupling of the bis-diazotized diaminodialkoxy-diphenyl with l-amino-8-hydroxy-naphthalenedisulfonic acid takes place in an acidic medium, optionally in the presence of coupling accelerators such as urea formamide, dimethylformamide or (poly) glycol - or alkyl ethers. In this preparation of the starting materials of formula II, the procedure is expediently such that the coupling component, e.g. H-acid is dissolved in the presence of the coupling accelerator in an aqueous or anhydrous medium and the bis-diazotization solution is added at temperatures of 0 to 50 ° C., preferably 10 to 20 ° C.

Examples of l-amino-4-hydroxy-naphthalenedisulfonic acids that can be used to prepare the starting materials of formula II are the following: l-amino-8-hydroxy-naphthalenedisulfonic acid- (4,6) or - ( 3,5), but especially l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid. (H acid).

The amino-diazo compound of the formula II is then diazotized both in the first reaction scheme and in the second reaction scheme, and in the reaction scheme explained first the coupling with the diazotized amine of the formula III then takes place

which are used for coupling in diazotized form 10 any aniline sulfonic acids may be mentioned, preferably those which have one or two sulfonic acid groups in the molecule. These aniline sulfonic acids can also carry further substituents, such as, for example, halogen atoms, in particular chlorine atoms, alkyl groups, in particular alkyl-1 groups with 1-4 carbon atoms, such as, for example, methyl groups, hydroxyl groups, alkoxy groups, in particular alk .oxy groups with 1-4 carbon atoms, such as, for example, methoxy groups or ethoxy groups, carboxy groups, carboxylic ester groups, in particular carbo-alkoxy groups having 20 1-4 carbon atoms in the alkoxy part, acylamino groups in which the acyl radical is preferably an alkylcarbonyl radical, for example a formyl radical, an acetyl radical or an oxalyl radical, or the acyl radical is an arylcarbonyl radical, for example that Benzoyl radical, nitro groups or arylamino groups, in particular optionally substituted phenylamino groups.

Specific examples of amines of formula III that can be used are as follows:

Aniline-2-, 3-, or 4-monosulfonic acid, aniline-2,4-, 2,5-or 3,5-disulfonic acid, 4-amino-anisole-2- or 3-sulfonic acid, 4-chloro- or methyl -aniline-2- or 3-sulfonic acid, 2-carboxy-aniline-4- or 5-sulfonic acid, 3- or 4-acetylamino-aniline-6-sulfonic acid, 4-oxalyIamino-aniline-3-sulfonic acid, 4-nitro ani-lin-2- or 3-sulfonic acid.

The hydroxydiphenylamines of the formula IV

K ^ H

(IV)

K! -H

Kl- N

(IV)

As mentioned above, the coupling components used may optionally have further substituents, but no further diazo group may appear as a substituent. Examples of possible substituents in the coupling component K, -H are alkyl groups, halogen atoms, amino groups, alkylamino groups, dialkylamino groups, sulfo groups, nitro groups, carboxy groups or acylamino groups, in particular alkylcarbonylamino groups or aminocarbonylamino groups. If alkyl groups appear as substituents, then these preferably have 1 to 4 carbon atoms and are optionally further substituted themselves.

Specific examples of coupling components of formula IV that can be used are as follows:

3-hydroxy-diphenylamine, 3-hydroxy-2'-methyl-diphenyl-amine, 3-hydroxy-4'-methyl-diphenylamine, 4-hydroxy-2 ', 4'-dinitrodiphenylamine, 2-hydroxy-2'-4 '-dinitrodiphenylamine, 2-hydroxy-4-chloro-2', 4'-dinitrodiphenylamine, 3-hydroxydiphe- "nylamin-sulfonic acid, 3-hydroxy-4'-nitro-2'-suIfo-diphenyl-amine, 3.3 '-Dihydroxy-diphenylamine.

Another object of the present invention is the use of the new trisazo dyes in the form of the free acid of the formula I.

- N «N -

N - Dx (I)

(so3h) 2

615 693

6

correspond to what

R is an optionally substituted alkyl group with 1-6 carbon atoms,

Ü! a residue of the benzene series which contains sulfonic acid groups and which optionally carries further substituents, and

Kj represents the remainder of a hydroxydiphenylamine which may have further substituents,

for dyeing non-textile substrates. These dyes are particularly suitable for dyeing paper or leather.

To carry out the dyeing process, the dyes, as already mentioned, are advantageously used not in the form of the free acids but in the form of their salts, for example as alkali salts.

The preparation of new trisazo dyes of the formula I and their use for dyeing leather are explained in more detail using the following two examples:

Example 1 :

24.4 parts (0.1 mol) of 4,4'-diamino-3,3'-dimethoxy-diphenyl (dianisidine) are good in 280 parts of water and 56 parts by volume of hydrochloric acid (d: 1.14) stirred and then slowly bis-diazotized in the usual manner at 10-15 ° C with 46 parts of 30% aqueous sodium nitrite solution. Stirring is continued for about 3 hours, clarifying any minor impurities and removing any excess nitrous acid with amidosulfonic acid. This bis-diazonium salt solution is added to a solution of 34.1 parts (0.1 mol) of l-amino-8-hydroxy-naphthalene-3,6-disulfonic acid monosodium salt (H-acid) in 280 parts of water (pH 7). and 280 parts of urea, which was adjusted to pH 3 with hydrochloric acid (d: 1.14). The mixture is stirred at 15-20 ° C. for about 4 hours, adjusted to pH 2 by dropwise addition of about 80 parts by volume of 20% sodium acetate solution and stirring is continued until the acidic H-acid coupling has ended. It is then adjusted to pH 9 by dropwise addition of 20% sodium carbonate solution at 0-5 ° C. and with the diazonium salt from 17.3 parts (0.1 mol) of aniline-4-sulfonic acid (diazo component) at pH 8.5-9 Adding soda solution combined.

Then the aqueous alkaline solution of 19.9 parts of 3-hydroxy-2'-methyl-diphenylamine (as coupling component) is added and coupled at pH 9.5 with soda solution. After the coupling has ended, the dye obtained is precipitated in 5 customary manner with hydrochloric acid, isolated and dried. After crushing the dry substance, a dark powder is obtained which dissolves in water with a black color. Leather is dyed in black tones using the usual dyeing process. The colorations show good coloristic Grundigen-io shade.

Example 2:

24.4 parts (0.1 mol) of dianisidine are bis-diazotized as described in Example 1 and acid-coupled with 34.1 parts (0.1 mol) of H-ij acid monosodium salt. After the acid coupling has ended, 19.9 parts (0.1 mol) of 3-hydroxy-2'-methyl-diphenylamine are added as a sodium alkaline solution and coupling is carried out by adding sodium carbonate solution dropwise to pH 9.5. The disazo dye obtained is isolated in a customary manner and optionally dried. The shredded dye is a dark powder that dissolves in water with red-violet color and dyes cotton in red-violet tones.

To prepare the trisazo dye, the resulting paste of the above disazo dye is dissolved in about 1,200 parts of 25 alkaline water and coupled with 0.1 mol of a diazonium salt from 17.3 parts (0.1 mol) of aniline-4-sulfonic acid at pH 9 , 5 on. The dye obtained is isolated as in Example 1. After drying, a dark powder is obtained which dyes leather in black tones.

3o Is used as the diazo component instead of aniline-4-sulfonic acid, aniline-2 or 3-sulfonic acid, or aniline-2,4-, 2,5-disulfonic acid, or 4-aminoanisole-3-sulfonic acid, or 3- or 4- Acetylaminoaniline-6-sulfonic acid, or 4-nitraniline-2-sulfonic acid, similar black dyes are obtained. 35 If the coupling components used instead of 3-hydroxy-2'-methyldiphenylamine, 3-hydroxy-diphenylamine or 3,3'-dihydroxy-diphenylamine or 3-hydroxy-4'-methyl-diphenylamine, dyes of black shades are obtained.

C.

Claims (4)

615 693 2nd PATENT CLAIMS 1. Process for the preparation of new trisazo dyes which are in the form of the free acid of the formula I h2n oh Kl- N = i N »N - or or N = N - D-l (I) correspond to what R is an optionally substituted alkyl group with 1-6 carbon atoms, Dj is a residue of the benzene series containing sulfonic acid groups, which may also carry further substituents, and Kj is the remainder of a hydroxydiphenylamine which may have further substituents, characterized in that a diazotized amino-diazo compound of the formula II is used as the starting material det, and this in any order with hydroxydiphenylamine of the formula IV 3 "Kj-H (IV) nho oh h2îi - rva- n - x - or or and also a diazotized amine of formula III Dj-NHJ (III) (so, h> 3 2 (II) in which R has the meaning given in formula I, use 3u couples. 2. The method according to claim 1, characterized in that the coupling of the hydroxydiphenylamine of the formula IV takes place in the o-position to the hydroxyl group. 3. The method according to claim 1, characterized in that one produces trisazo dyes of the formula I, which in the form of the free acid of the formula Ia H 11 N = N " 0R 'OR N «H - D- (la) correspond, being in this formula R, Dj and Kj have the same meaning as in formula I. 4. The method according to claim 3, characterized in that one produces trisazo dyes of the formula I which in the form of the free acid of the formula Ib nhp oh ki- n N - n «n -d-j | '<S03H) b (Ib) ho3s so3h, in which fi5 chlorine atoms alkylcarbonylamino groups with 1-4 carbon di 'denotes an unsubstituted phenyl radical or a phenyl radical substituted by atoms or oxyalkylamino groups means alkyl groups with 1-4 carbon atoms, alkoxy groups, 1-4 carbon atoms, carboxy groups, nitro groups, m is 1 or 2, and 3rd 615 693 R and Kx have the same meaning as in formula I. 5. Trisazo dyes produced by the process according to claim 1, which have the formula I in the form of the free acid. 6. Use of new trisazo dyes in the form of the free acid of the formula I Kl- N «n- ^ 3'C = ^ ~ N »N - or OR N »N - D2 (I) where is 7. Use according to claim 6, for dyeing R is an optionally substituted alkyl group with 1-6 paper. Carbon atoms, use according to claim 6, for coloring Dj a residue of the benzene series containing sulfonic acid groups, leather. which optionally carries further substituents means and 20 K! represents the remainder of a hydroxydiphenylamine optionally bearing further substituents, for dyeing non-textile substrates.