DE58868C - Process for the preparation of blue-black to green secondary disazo dyes - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

CLASS 22: dyes, varnishes, lacquers.

Patented in the German Empire on August 31, 1890.

The ß-naphthoxyacetic acid presented by Spika (Gaz. Chim., Vol. 16, pp. 438 ff.)

C ₁₀ H ₇ -OCHfCO ₂ H

gives by the action of nitric acid of 40 ⁰ B. at 15 to 20 ° C. a nitro product of mp. 190 to 192 ⁰ , which by treatment with the usual acidic reducing agents (tin and hydrochloric acid, tin chloride and hydrochloric acid or zinc and hydrochloric acid) in the Anhydride of a-amido-ß-naphthoxyacetic acid

, .NH-CO

transforms. The latter anhydride forms white needles in its pure form, which at 200 to Melting 205 °, hardly in water, difficult in ether or cold alcohol, easily in hot Are soluble in alcohol. By briefly boiling with caustic soda, hydration occurs Formation of the sodium salt of amido-ß-naphthoxyacetic acid

C H

H ₂ COONa '

which in slightly brownish colored, shiny, easily soluble in warm water Crystallized needles can be obtained. The mixed with mineral acid solution of the same converts back into the anhydride when standing for a long time or when warming up, while with careful acidification in the cold the amido - ß - naphthoxy acetic acid as such is obtained.

In the same way, sulfoderivatives of amido-ß-naphthoxyacetic acid are obtained if, instead of ß-naphthoxyacetic acid, sulfonic acids thereof, e.g. B. from the action of chloroacetic acid on Schäffer'sche ß-naphthol-ß-sulfonic acid is based on ß-naphthoxy acetic ß-sulfonic acid. The product obtained in the latter way, the α-amido-β-naphthoxyl acetic-β-sulfonic acid, has the composition in the form of its anhydride: ^N

SO, H

^ NH ~ CO

O ~

CH

the sodium salt

5 O, Na CO

'CH ₀

O ~

can be kept crystallized in beautiful, shiny leaves, which are little in the cold, Easily soluble in hot water and diluted by treating with boiling water Sodium hydroxide solution can be hydrated in the same way as the non-sulphurised compound.

The said a-amido-ß-naphthoxy acetic acid respectively. their sulfoderivative. unites with diazo compounds to azo dyes, which are converted back into diazo compounds and new ones can be combined with amines, phenols and their sulfo and carboxylic acids. the The dyes produced in this way dye pure black, black-green and black wool on wool green tones; in this way they differ significantly from the corresponding with a-naphthylamine produced dyes, and included the first green azo dyes, which are generated without the involvement of other chromogens (tetra-alkyl diamidotriphenylcarbinol).

(2nd edition, issued on August 19, 18/8)

The following combinations have so far been found to be particularly valuable wool dyes proven.

ι. From β-naphthylamine monosulfonic acid des Patent No. 20760 (first component) + a-amido-ß-naphthoxyacetic acid (second component) -f "(as third component):

a-naphtol. . . dyes wool greenish black; ß-naphthol · ... dyes wool bluish black;

β - naphthol sulfonic acid (Schäffer). . . dyes wool blue-black;

α - naphtol - α - sulfonic acid (Nevile and Winther) ... dyes wool green-black;

β - Naphthol disulfonic acid (R) ... dyes wool green-black.

2. From ß-naphthylamine sulfonic acid of the patent No. 20760 + a-amido-β-naphthoxyacetic sulfonic acid + β-naphthol sulfonic acid (Schäffer) ... dyes wool blue-black.

3. From naphthylamine disulfonic acids of patent no. 27346 + a-amido-ß-naphthoxyacetic acid +:

ß-naphtol. . . dyes wool blue-black;

β - naphthol sulfonic acid (Schäffer) ... dyes wool green-black;

β - Naphthol disulfonic acid (R) ... dyes wool green-black.

4. From ρ - amidosalicylic acid -f- a-amido-ßnaphthoxyacetic acid -f-

a-Naphtol ... dyes wool and chrome-plated Coal black wool;

ß-naphtol. . . also blue-black;

ß-naphthol sulfonic acid (Schäffer). . . likewise blackish green;

ß-Naphthalene disulfonic acid (R). . . colors chromed Wool green.

5. From o-amidosalicylic acid - + - ß-amido-ßnaphthoxy acetic acid +

a-naphtol. . . dyes chromed wool blackish blue;

β - naphthalene disulfonic acid (R). . . also gray-blue.

Of these combinations, that produced from the naphthylamine disulfonic acid of the patent No. 27346 a-Amido-ß-naphthoxy acetic acid and β - naphthol disulphonic acid (R) on wool, soap-resistant Colorings and show the dyes represented by means of amidosalicylic acids important property of being fixed completely mill-proof by chromed wool.

The following components can also be used as first components: aniline and its homologues, sulfanilic acid, Aniline disulfonic acid, m-amidobenzoic acid, amidophenolsulfonic acid, α - naphthylamine, ß-naphthylamine - β - sulfonic acid, amidoazobenzene disulfonic acid, azo derivatives of ρ - phenylenediamines; also the tetrazo compounds: benzidine, benzidine disulfonic acid, diamidodiphenic acid and analogous diamines.

As a third component, besides those mentioned, for example, they have been found to be suitable been: α-naphthylamine, phenyl- and tolyla-naphthylamine, Dioxynaphthalene (i, 8), resorcinol, m-phenylenediamine and diphenyl-m-phenylenediamine.

The representation of the dyes listed is explained using the following example:

1. Representation of the intermediate product from ß-naphthylamine-a-sulfonic acid (Patent No. 20760) and α-amido-β-naphthoxyacetic acid.

12.3 kg of ß-naptylamine-a-sulfonic acid soda are dissolved in 150 l of water, the solution is cooled with 100 kg of ice, with 18 l of hydrochloric acid (1.19 sp. G.) are added and a solution diazotized by 3.5 kg of sodium nitrite in 15 liters of water.

On the other hand, 10 kg of a-amido-ß-naphtoxylessigsäureanhydrid cooked for the purpose of Hydratisirung with 50 1 sodium hydroxide solution (40 ⁰ B.) and 50 1 of water is frozen until the liquid to form a slurry. It is then diluted with 250 liters of hot water, allowed to cool, 400 kg of ice are added and acidified with 125 liters of acetic acid (30 percent).

This solution is mixed in the usual way with that shown as described above Diazo compound with stirring. The combination is completed within a short time. the The mixture obtained can be processed as described under 2., in the same way; The product, so far as it is still in solution, is isolated from this by adding hydrochloric acid and table salt like.

The formation of the intermediate product takes place in the same way when using for example benzidine, sulfanilic acid, naphthionic acid or amidosalicylic acid, while one when using the naphthylamine disulfonic acids of Patent No. 27346, the diazo compound the same on the amidonaphthoxyacetic acid expediently in hydrochloric acid instead of acetic acid Solution reacts. The solution must be warmed up after the combination has taken place Avoid, as anhydride formation within the finished intermediate product is also avoided Amidonaphtoxylessigsäurerest can take place, which prevents further diazotization will.

2. Representation of the combination from the according to i. obtained intermediate product with ß-naphthol sulfonic acid (S c hä f f e r).

The mixture obtained after the described under 1. manner, with 18 1 of concentrated hydrochloric acid (20 ⁰ B.) was added and further diazotirt with 3.5 to 4.2 kg of sodium nitrite in concentrated aqueous solution with stirring and if necessary with Eiszusatz. The yellow-brown mixture is then allowed to flow into a solution of 18 kg of ß-naphtholsulfonate of soda (Schäffer) in 600 l of water, which is cooled with 600 kg of ice and mixed with 100 to 150 kg of calcined soda. After the combination

the dye formed is salted out and purified by dissolving.

When using other dye components such as naphthylamine, phenylnaphthylamine etc. The place of β-naphthol sulfonic acid is combined under the conditions which are suitable for this Bodies are suitable for association with diazo compounds.

Claims (1)

Patent claim: Process for the preparation of blue-black to green azo dyes, consisting in, that the one by the action of diazo compounds to a- amido τ ß-naphtoxylessigsäure BEZW. a- Amido-ß-Naphthoxylessig-ß-sulfonic acid obtained amidoazo compounds. diazotized again and with the following phenols respectively. their sulfonic acids combined to form the following combinations: ι. β - naphthylamine monosulfonic acid (patent no. 20760) -f- α - amido - β - naphthoxyacetic acid + one of the following connections: a) β-naphthol sulfonic acid (Scha ff er), b) ß-naphthol disulfonic acid (R); β - Naphthylamine monosulfonic acid (Patent No. 20760) -f-a-Amido-ß-naphthoxy acetic-ß-sulfonic acid + ß-naphthol sulfonic acid (Schäffer); Naphthylamine Disulfonic Acids (Patent No. 27346) + a-amido-ß-naphthoxyacetic acid -f- one of the following compounds: a) ß-naphtol, b) ß-naphthol sulfonic acid (Schaffer), c) ß-naphthol disulfonic acid (R); p-amidosalicylic acid -f-α-amido-ß-naphthoxyacetic acid + one of the following compounds: a) a-naphtol, b) 8 - naphtol, c) ß-naphthol sulfonic acid (Schaffer), d) ß-naphthol disulfonic acid (R); ο-amidosalicylic acid + a-amido-ß-naphthoxyacetic acid + one of the following compounds: a) a-napthol, b) β - naphthol disulfonic acid (R).