DE135563C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

By oxidizing together equimolecular amounts of alkylated p-phenylenediamine thiosulfonic acids and m-diamines with e.g. B. Potassium dichromate in acetic acid solution results in a good yield of previously unknown compounds of the character of the indamines, hereinafter referred to as ρ-dialkylamidoindaminothiosulfonic acids are designated.

As has been found, these compounds can now be converted into valuable dyes, when heated with sulfur and alkali sulfur. This takes place intermediate under the influence of the sulfur alkali initially the formation of the thiazine ring takes place. The thiazines can be detected by shaking the air-oxidized solutions with chloroform, in which they dissolve with red color. With further action of the sulfur and sulfur alkali then gradually disappear the thiazines, and sulfur dyes are formed from them, which cotton in the presence of suitable amounts of alkali sulfur dye directly in purple tones. When heated with alkaline sulfur and also through Sodium sulfhydrate or sodium hydrosulfite supply these coloring vats, which likewise can be used for dyeing.

The representation of the p-dialkylamidoindaminothiosulfonic acids can be carried out in the following way: 250 Th. Dimethyl-p-phenylenediamine thiosulfonic acid are in 10,000 Th. Water with the addition of 40 Th. Caustic soda dissolved and with a solution of 108 Th.

m-Phenylenediamine in 5000 Th. Water and 265 Th. Hydrochloric acid (19 ⁰ B.) mixed.

A solution of 200 Th. Is added to this with stirring and possibly with cooling. Potassium dichromate in 1000 th. Water, which 1000 th. 3oproc. Acetic acid are added.

After a short time, the p-dimethylamidoindaminothiosulfonic acid formed separates out in dark, shiny metal crystals. It is sucked off and pressed. The connection When heated, dissolves in ammonia and soda solution with a deep blue color, in hydrochloric acid with a red color which turns purple when cooked.

Instead of dimethyl-p-phenylenediamine thiosulfonic acid one can use the corresponding amount of the other alkylated p-diamine thiosulfonic acids use. The indamines obtained analogously to the example given are the ones described above quite similar.

For the preparation of the above-mentioned sulfur-containing dyes, the following procedure is used, for example: 300 parts of the dimethylamidoindaminothiosulphonic acid cake obtained according to the preceding example are converted at 10 ° in 700 th. molten sodium sulphide (Na ₂ S -j- 9H ₂ O) entered. After about half an hour stirring, the temperature is slowly increased to 120 ^0, then one carries gradually 100 Th. Sulfur and then heated under Rückflufskühlung approximately 24 hours BEZW. until a sample has been oxidized in air to chlorine

form no longer emits any red dye or emits only small amounts of it. That Reaction mixture is made with iooooTh. water boiled, one feeds and falls the dye, which z. Th. When it cools down, completely off by introducing air '. The dye stains unstained cotton in the presence of it of sulphurous sodium already in a cold bath in violet-blue tones of very good ones Authenticity properties. The shade is reddened by steaming the alkaline dye. Furthermore, the dyeings on the fiber can be carried out using the customary aftertreatment methods, e.g. B. the action of chromates, copper salts, zinc salts, hydrogen peroxide and so on, subject as well as treat with diazo compounds, where z. B. the nitrodiazobenzene a purple black supplies. Finally, the dye on the fiber can be diazotized and deal with the usual developers; then darker tones emerge.

Instead of 'dimethylamidoindaminothiosulfonic acid, one can also use that obtainable from it Use thiazine. This is obtained, among other things, by boiling the dimethylamidoindaminothiosulfonic acid with concentrated sodium sulphide solution and subsequent oxidation by air, whereby the dye precipitates, or by heating said indaminothiosulfonic acid with concentrated sulfuric acid. the in the latter case after pouring the sulfuric acid-containing solution into ice water Thiazine base deposited with sodium hydroxide solution dissolves in chloroform with a red color, stains turns blue when the chloroform solution is poured onto memorial paper and forms with acids blue water-soluble salts which stain tannin cotton blue.

For the purpose of converting it into the nouns sulfur dye, the thiazine is dissolved in 3 parts of molten crystallized sodium sulfur, whereupon, after adding Y ₂ parts of sulfur, the procedure is exactly as described in the above example. ■

The other abovementioned p-amidoindaminothiosulfonic acids can also be used analogously, and the procedure for converting these acids into the noun dyes is the same as that given when using the ρ-dimethylamidoindaminothiosulfonic acid. The products obtained in this way are very similar to ^{1 described above.} If you use z. B. the indaminthiosulphonic acid formed from the thiosulphonic acid of p-amidomonomethylo-toluidins and m-phenylenediamine, the result is a dye which hardly differs from that obtained from dimethylamidoindaminothiosulphonic acid in terms of both nuance and other properties.

Claims (1)

Patent claim:
Process for the preparation of violet substantive dyes, consisting in treating the indaminothiosulphonic acids obtainable from aromatic monoalkylated or asymmetrically dialkylated p-diamine thiosulphonic acids and m-diamines, or the thiazines which can be prepared from these, with alkali sulfur and sulfur or similarly acting agendas.