DE1090799B - Process for the preparation of polyazo dyes - Google Patents

Description

Process for the production of polyazo dyes Addendum to patent 1056 7 59 The main patent relates to a process for the production of polyazo dyes of the constitution (in which the diphenylamine radical contains one or two sulfonic acid groups, A 'an aromatic radical, B' the radical of a benzene series dioxy compound capable of coupling twice and B "the radical of any azo component).

These dyes dye leather in lightfast brown tones.

As an extension of this inventive concept, it has now been found that particularly valuable polyazo dyes of similar constitution are obtained if a compound of the formula is used as component B 'for the preparation of these dyes (in which n is the number 1 or 2 and the benzene ring can contain further substituents [for example hydroxyl, carboxyl, sulfonic acid groups] or can also be dihydrogenated).

In the preparation of these dyes, the order of formation the azo groups can be varied, as described in the main patent. The azo group the component B 'can, for. B. are also only formed after the aminonaphthol compound of B 'has already reacted with a diazo group of component A'.

Optionally, the dye components or the finished dyes still be treated with metal donating agents. The dyes dye leather in deep brown tones of high color strength. In particular, they dye suede very well done. The solutions of the dyes show an excellent resistance to acids. Some of these dyes are also suitable for dyeing cotton.

Compared to those already known from German patent specification 842100 The products according to the invention are distinguished by polyazo dyes of similar constitution by significantly better solubility.

Example 1 One from 27.9 kg of 4,4'-diaminodiphenylamine-2-sulfonic acid Tetrazo solution prepared is with the aqueous solution of the sodium salt of 14.6 kg of 1-oxybenzene-2-carboxylic acid combined. An aqueous one is then left with cooling Solution of 32 kg of sodium carbonate and then a solution of 17.2 kg of sodium hydroxide come in. The formation of the diazo compound is complete after a short time. By acidification it is separated off with hydrochloric acid, filtered and stirred up again with water and ice. The slurry is poured into one with excess sodium carbonate or sodium hydroxide offset solution of the monoazo dye from the diazo compound of 31.9 kg of 1-amino-8-oxynaphthalene-3,6-disulfonic acid and running about 10.5 kg of 1,3-dioxybenzene. After the formation of the trisazo dye has ended a diazo solution prepared from 9.3 kg of aminobenzene is added and stirred, until the diazo compound has disappeared.

The tetrakisazo dye is made by looking and neutralizing with Hydrochloric acid deposited, filtered and dried. It forms a dark, water-soluble one Powder that remains in solution even when acids are added and colors suede in deep neutral dark browns. The solution paint in concentrated Sulfuric acid is olive green.

If you replace the aminobenzene with the equivalent in the above example Amount of 1 amino-2 methoxybenzene, you get a dye, the suede colors in deep, somewhat greenish brown tones (Havana brown). The solution color in concentrated sulfuric acid is blackish brown.

The corresponding dye with 1-amino-4-methoxybenzene gives almost the same shade, while 1-naphthylamine gives a dye, which dyes suede in reddish dark brown tones.

Instead of 4,4'-diaminodiphenylamine-2-sulfonic acid, the equivalent amount of 4,4'-diaminodiphenylamine-2,3'-disulfonic acid will be similar obtained brown tetrakisazo dyes.

The following table shows a number of other tetrakisazo dyes which were prepared from 4,4'-diaminodiphenylamine-2-sulfonic acid and are built up according to the above scheme: n 13 hue D (dioxy compound + A suede Aminooxynaphthalenesulfonic acid) 2-oxybenzoic acid 1,3-dioxybenzene 1-amino-8-oxynaphtha- 1-amino-4-nitrobenzene reddish- lin-3,6-disulfonic acid dark brown 4-methyl2-oxy- like. Like 1-amino-2-methoxy- dark brown benzoic acid benzene like. like. like. 1-aminonaphthalene- like. 4-sulfonic acid 6-methyl-2-oxy- like. Like. Like. Like. benzoic acid like. like. like. aminobenzene like. 2-oxybenzoic acid the same. The same. 1-aminobenzene- reddish- 2-sulfonic acid dark brown the same. the same. the same 1-aminobenzene-like. 3-sulfonic acid the same. the same. the same 1-aminobenzene-like. 4-sulfonic acid the same. the same. the same. 1-aminobenzene dark brown 2,4-disulfonic acid like. like. like. 1-amino-2-methyl- like. benzene-5-sulfonic acid the same. the same. the same 1-amino-4-methoxy-Havana brown benzene-3-sulfonic acid the same. the same. the same 1-amino-4-nitrobenzene- red-tinged- 2-sulfonic acid dark brown the same. the same. the same 1-aminonaphthalene green tint 4-sulfonic acid dark brown like. like. like. 1-aminonaphthalene- like. 5-sulfonic acid like. like. like. 1-amino-2-methoxy- like. benzene-5-sulfonic acid the same. the same. the same 2-aminonaphthalene dark brown 4,8-disulfonic acid like. like. like. 2-aminonaphthahn- like. 3,6-disulfonic acid the same. the same. the same. 2 Amino-naphthalene dark brown 6,8-disulfonic acid the same. the same. 1 Amino-8-oxynaphtha- aminobenzene red-tinged- lin-4,6-disulfonic acid dark brown Phenylmethyl- like 1-amino-8-oxynaphtha- 1-aminonaphthalene- violet-tinged- Pyrazolon lin-3,6-disulfonic acid 4-sulfonic acid dark brown Acetessiganilid like. dark brown p-cresol the same. the same. the same dark brown 2-oxybenzoic acid dihydro-1,3-dioxy- like aminobenzene reddish- benzene dark brown Diox binding color (yv g -f- A suede Aminooxynaphthalenesulfonic acid) 2-oxybenzoic acid 1,3-dioxybenzene 2 amino-8-oxynaphtha- 1-aminonaphthalene-Bordo brown ] yn-6-sulfonic acid 4-sulfonic acid like. like. 2-amino-5-oxynaphtha- like. like. ] yn-7-sulfonic acid the same. the same. 1-Amino-7-oxynaph- 1-aminonaphthalene- yellowish- thalin-3-sulfonic acid 4-sulfonic acid dark brown The same. The same. 2-Anino-5-oxynaph-1-amino-2-methoxy-Bordobraun thalin-7-sulfonic acid benzene-5-sulfonic acid the same. the same. the same. 1-Amino-2-methoxy-dark bordo brown naphthalene-6-sulfone acid same. Same. 1-Amino-7-oxynaph-1-Amino-2-methoxy- Medium brown thalin-3-sulfonic acid benzene-5-sulfonic acid the same. the same. 1-Amino-8-oxynaphtha- 1-Amino-2-methoxy- yellowish- lin-4,6-disulfonic acid benzene medium brown the same the same the same aminobenzene red-tinged medium brown the same. The same. 1-Amino-8-oxynaphtha-2-aminobenzoic acid dark brown lin-3,6-disulfonic acid the same. the same. the same 5-nitro-2-aminobenzoe- the same. acid the same. the same. the same. 1-Amino-2-methoxy- greenish- 5-methylbenzene dark brown. the same. the same. the same 1-amino-2-chlorobenzene red nitrogen . dark brown the same. the same. the same 1,4-diaminobenzene dark brown the same. the same. the same. 1 Acetylamino-3-amino-dark brown benzene Same. Same. Same. 1-Acetylamino-4-amino-deep dark brown benzene like. like. like. 1-amino-2-methoxy- like. 4-nitrobenzene like. like. like. 1-amino-2-methylbenzene like. like. like. like. 1-amino-4-methylbenzene like. Example 2 22.3 kg of 1-aminonaphthalene-4-sulfonic acid are diazotized and the diazo suspension is combined with about 30 kg of 1-amino-8-oxynaphthalene-3,6-disulfonic acid. The violet monoazo dye obtained is further diazotized in the presence of hydrochloric acid with 6.9 kg of sodium nitrite and the diazoazo compound is combined in the presence of excess sodium carbonate or sodium hydroxide with an aqueous solution of about 10.5 kg of 1,3-dioxybenzene.

In the solution of the disazo dye thus obtained, that according to Example 1 obtained diazoazo compound from the tetrazo compound of 27.9 kg of 4,4'-diaminodiphenylamine-2-sulfonic acid and 14.7 kg of 2-oxybenzoic acid entered, the reaction mass being clearly alkaline should react. After the coupling is complete, the dye is removed by warming, looking deposited and neutralized with hydrochloric acid. It forms a dark water-soluble one Powder that dyes leather in dark brown tones. The dyeing is good. the Solution color in concentrated sulfuric acid is dark olive green. Example 3 One from 27.9 kg of 4,4'-diaminodiphenylamine-2-sulfonic acid and 14.7 parts of 2-oxybenzoic acid produced diazoazo compound is in the presence of excess sodium carbonate combined with 31.9 kg of 1-amino-8-oxynaphthalene-3,6-disulfonic acid. The thus obtained Disazo dye dissolves in water and concentrated sulfuric acid with gray to black color. The aqueous solution of the dye is 6.9 kg of sodium nitrite offset. This mixture is run into ice and excess hydrochloric acid. the Diazodisazo compound is mixed with an alkaline solution of about 10.5 kg of 1,3-dioxybenzene united. The obtained trisazo dye can be deposited by sight. It dissolves in concentrated sulfuric acid with a black-brown color, while the Diazodisazo compound had dissolved with a greenish blue-black color. To the Solution of the trisazo dye in excess sodium carbonate is now left run diazo solution prepared from 12.3 kg of 1-amino-2-methoxybenzene. Of the The resulting tetrakisazo dye forms a dark color after it has been deposited and dried Powder that dissolves in concentrated sulfuric acid with a dark purple brown color and dyes leather in greenish dark brown tones.

Example 4 A trisazo dye prepared as described in Example 1 from 31.9 kg of 1-amino-8-oxynaphthalene-3,6-disulfonic acid, about 10.5 kg of 1,3-dioxybenzene, 27.9 kg of 4,4'-diaminodiphenylamine 2-sulfonic acid and 14.6 kg of 2-oxybenzoic acid dissolved in water and in the presence of excess sodium carbonate with an off 20.3 kg of 1 amino 2-methoxybenzene-5-sulfenoic acid produced diazo solution combined. The tetrakisazo dye obtained is dark, in water with dark brown and powder soluble in concentrated sulfuric acid with a black-brown color. He colors suede in full dark brown tones.

For the purpose of converting it into a copper complex compound, the dye dissolved in water and treated with a solution of about 100 liters of ammonia water (26% density 0.905]) and about 23.5 kg of crystallized copper sulfate for about 15 hours at 90 to 92 ° C stirred. The dye solution becomes by-product of small amounts if necessary filtered. The dye is made from the filtrate by adding rock salt and neutralizing it deposited with hydrochloric acid. After drying it looks like a dark powder, which is in water with dark brown, in concentrated sulfuric acid with yellowish black brown Color dissolves and stains leather in slightly more reddish brown tones than the uncoppered one Dye. The colorations are lightfast. The dyeing is good.

If one leads in a corresponding manner according to the information in the example 1, para. 2, produced dye, which as a diazo component, however, 1-amino-2-methoxybenzene contains, into the copper compound, a dye is obtained, the suede in full dark brown, lightfast tones that are only a little redder than the color of the starting dye, dyes. The dyeing is also very good.

On the other hand, the copper compound of the azo dye in which 2-aminobenzoic acid is used as the diazo component, leather with a slightly more yellowish tinge Brown tones compared to the original dye.

Claims (1)

PATENT CLAIM: Modification of the process of the main patent 1056 759 for the production of polyazo dyes of the constitution (in which the diphenylamine radical contains one or two sulfonic acid groups, A 'an aromatic radical, B' the radical of a dioxy compound of the benzene series which can be coupled twice and B "the radical of any azo component), characterized in that component B 'is used to synthesize such dyes a compound of the formula (in which n is the number 1 or 2 and the benzene ring can contain further substituents or can also be dihydrogenated). Considered publications: German Patent Specifications No. 639 669, 842100. When the application was announced, a coloring table was laid out.