DE117587C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

The esterification of a hydroxyl group in gallocyanine dyes gives rise to new compounds obtained, which differ from the starting materials by their bluer and purer ones Distinguish nuances.

The substitution of a hydroxyl hydrogen by the Rest of an aromatic sulfonic acid proved. This gives dyes which Able to dye wool in an acid bath and at the same time, like the gallocyanins, the property to form true color lakes. In addition, these show new dyes the characteristic reactions of the oxazines; they can be turned into colorless leuco bodies which are easily re-oxidized by air in an alkaline solution. With They give aniline and its homologues even in the cold and with quinone aniline compounds Phenols or their sulphonic acids are formed by leuco bodies, which in turn are formed by oxidation can be converted into valuable dyes. They form with alkali bisulfites easily soluble sulfonic acids or leucosulfonic acids. The new compounds have a good ability to crystallize and are partly easily soluble in water as alkali salts, while others are insoluble; the latter can be done by treating with Sodium bisulfite can be converted into soluble sulfonic acids.

The fluorescence of their solutions, especially the one, is characteristic of the new dyes alcoholic.

Esterification occurs smoothly by the action of sulfochlorides of aromatic hydrocarbons to an aqueous alkaline solution or suspension of the relevant gallocyanin dye.

Example I. 10 kg of gallocyanine chlorohydrate in powder form are stirred into 100 l of water and then a solution of 7 kg of soda in 50 1 of water was added; one stirs so long until a uniform paste of the gallocyanine sodium salt has arisen and now runs within 6 hours 5.5 kg of benzenesulfonyl chloride with constant stirring and gradual heating to 70 to 8o °; stir until the smell of sulfochloride disappears, filtered off little insoluble matter and mixed with common salt; on cooling it crystallizes Dye in shiny green leaves-out. It dissolves easily in water with a pure blue color Color on; with dilute hydrochloric acid an insoluble crystalline hydrochloride is formed; the Solution in concentrated sulfuric acid is colored blue. The dye dyes wool in acetic acid or weak sulfuric acid bath blue; on chromed wool or with acetic acid Printed chrome on calico, it delivers blue colored lacquers.

In the above example, the benzenesulfonyl chloride can be used with the same success by the o- and ρ-Toluenesulfochloride or mixtures of these bodies and their homologues are replaced. Instead of gallocyanin, its bisulfite compound or its leuco derivative can be used will; in the latter case a subsequent oxidation by air is sufficient to remove the dye to obtain. By treating the dye obtained according to Example I with sodium bisulfite in aqueous solution a very easily soluble compound forms, which on

Addition of table salt precipitates oily and after drying and neutralization with ammonia represents a bronze colored powder that easily dissolves in water with a blue color. It stains wool a little more green than the base product.

Example II. Iokg Prune, i.e. the gallocyanin dye from nitroso dim ethy lan iline and gallic acid methyl ester are dissolved in iool water Dissolved cold and a solution of 7 kg of soda in 50 1 of water was added. To the as thick Paste excreted color base become gradually and with stirring and heating to 80 ° 5.5 kg of benzenesulfonyl chloride were added. After the sulfochloride disappears, the in insoluble bodies excreted from green leaflets are filtered off, and finally with diluted bodies Washed hydrochloric acid, which removes some unchanged prune. The received The pigment is insoluble in dilute hydrochloric acid and in soda solution, it dissolves in alcohol blue with red fluorescence and crystallized in green leaflets; the solution in benzene is red-blue and shows very strong red fluorescence.

To convert the dye into a form suitable for dyeing purposes, 1 part of which 3 parts gasoline and 0.3 parts sodium bisulfite and a little water are added, Let stand for 24 hours or warm gently for 2 to 3 hours; the resulting green crystal pulp consists of a mixture of water-soluble dye and its leuco derivative; the mass is poured into dilute saline solution, washed out, then with ammonia Made alkaline and bubbled with air until the leuco compound is completely in dye is converted. The dye is obtained pure by dissolving it in warm water, er crystallizes in green leaves and stains wool in an acid bath in a pure blue-green.

If in Examples I and II the benzenesulfonyl chloride is replaced by the o- and p-toluenesulfonyl chloride, in this way color bodies are obtained which have the properties of the bodies of benzene sulfochloride are very similar; they also have a good crystallization capacity and all show the characteristic strong red Fluorescence in alcoholic solution.

If you replace the dye Prune in Example II by the equivalent amounts of Gallamine Blue or Celestine Blue. d. H. Gallocyanin dyes from nitrosodimethyl or. Nitrosodiethylaniline and gallamic acid and otherwise proceed exactly as indicated, in this way one also obtains well-crystallized color bases which are insoluble in acids and alkalis, which, by treatment with bisulfite, give water-soluble crystallized dyes.

The dye from Celestine blue dyes wool in an acid bath in a very pure blue-green; the The shade of the dye obtained from gallamine blue is somewhat redder.

Claims (2)

Patent Claims: i .-- Process for the preparation of blue dyes by the action of aromatic sulfochlorides on dyes of the gallocyanin series in weakly alkaline solution. 2. Conversion of the dyes obtained according to claim 1 into soluble compounds, be it dyes or leuco bodies, by treatment with alkali bisulfites.