DE748916C - Process for the production of sulfur dyes - Google Patents

Description

Process for the production of sulfur dyes. Patent addition 745 336 The subject of patent 745 336 is a process for the production of sulfur dyes, that consists of 4, 5, g, 1O-dibenzo-3, 8-diazapyrene or its substitution products, optionally in the presence of metal salts, treated with sulphurizing agents and the raw melt is worked up in the usual way.

Upon further processing of this subject matter of the invention it was found that there are also 5, 6, 11, I2-dibenzo-4, Io-diazaperylene and its substitution products can be converted into valuable sulfur dyes in the same way. These too Dyes are characterized by good fastness properties. Example 1 In a Melt of 15 parts of sulfur in 15o parts of chlorosulfur will gradually become 50 Parts 5, 6, 11, I2-Dibenzo-4, Io-diazaperylen (prepared for example according to the Process of patent specification I26444) entered at 7o to 8o °. You heat slowly to 150 °, refluxed for 1 hour and then distilled to dryness away. The temperature is now increased to 270 ° and at this temperature for 6 hours held. After treatment with sodium sulphide and sodium hydroxide solution, the dye becomes digested in the usual way and from the aqueous solution by acidification or Blow out deposited. It is a blackish gray powder that contains the vegetable fiber from your sulphurous sodium bath turns olive.

Example 2 5o parts 5, 6, 11, 12-dibenzo-4, lo-diazaperylene are, as described in example i, fused with chlorosulfur and sulfur, dried and then with the addition of 8 parts copper sulfate for about 6 hours Baked 3oo °. After digestion with sodium sulphide and sodium hydroxide solution, the dye becomes deposited as an olive-brown powder, the vegetable from the sulfurous sodium bath Fiber olive dyes.

Example If the starting material is replaced by the in example i Dimethyl derivative prepared, for example, by the process of patent specification I26 444 from I, 5-di-p-toluidoanthraquinone), a product is obtained that has the vegetable Dyes fiber from the sulfur sodium bath olive.

Example 4 In a polysulfide melt of 56 parts of crystallized ' Sodium sulfur and 32 parts of sulfur are converted into 2o parts of dinitro- 5, 6, II, I2-dibenzo-4, iodiazaperylene (produced for example by nitration des 5, 6, II, I2-dibenzo-4, Io-diazaperylene in concentrated sulfuric acid with slightly more than the calculated amount of 10% nitric acid). At a temperature of 118 ° it is boiled in the reflux condenser for a few hours, then the melt is dried up. The temperature then gradually rises to 28o ° increased and held for 4 hours at 28o to 3oo °. After unlocking the rolled product With sodium sulphide and caustic soda, the dye is removed from its aqueous solution deposited by acidification. After drying it is a gray powder that comes out The sodium sulphide bath gives the vegetable fibers a brownish-olive color. Example 5 4o Parts 5, 6, II, I2-dibenzo-4, Io-diazaperylenemnonosulfonic acid, manufactured by Cleavage of a sulfo group from the dibenzodiazaperylenedisulfonic acid, which in turn when the 1,5-dianilidoanthraquinone is closed in the ring in 8% sulfuric acid (Slightly soluble in water, in hot soda solution with reddish-white color, in concentrated Sulfuric acid with a blue-red color soluble), are mixed with a polysulphide melt from 14o parts of crystallized sodium sulphide and 8o parts of sulfur at II8 ° boiled for several hours on the reflux cooler. After the melt has dried, the Temperature increased to 28o ° and the melt held at 28o to 29o ° for about 8 hours. After the crude product has been broken down with sodium sulphide and lye, the dye becomes separated from its aqueous solution by acidification. He's after drying a blackish powder that bathes the vegetable fibers from the sodium sulphide dyes in yellowish-gray-olive shades of excellent lightfastness.

Example 6 50 parts of dinaphtho-4, io-diazaperylene, made from r, 5-Di-2'-naphthylaminoanthraclhinone by heating in phosphoric acid, are with the four times the amount of sulfur gradually heated to 27o ° and a few hours at this Temperature held. Laugh at the smelting of the melt with sodium sulphide and caustic soda the dye is deposited in the form of a (ez blackish powder, which the vegetable Fiber olive dyes.

Example 7 6o parts of dinaphtho-4, Io-diazaperylenesulfonic acid (which by For heating the dinaphtho-4, Io-diazaperylene mentioned in Example 5 in a concentrated Sulfuric acid can be prepared to alkali solubility) wierden with a Polysulphide from 20 parts crystallized sodium sulfur and 120 parts sulfur cooked at II8 ° for several hours. Laughing drying of the melt is the temperature increased to 29o ° and the melt held at 29o to 3oo ° for about 8 hours. To The digestion of the crude product with sodium sulphide and lye becomes the dye separated from its aqueous solution by acidification. It's after drying a blackish powder that removes the vegetable fiber from the sodium sulphide bath dyes olive brown.

By adding copper sulfate to the melt, the hue of the obtained becomes Blackish brown dye. Example 8 In a polysulphide melt of 140 parts crystallized sodium sulphide and 801 parts of sulfur wierden at boiling temperature 40 parts of Dinitrodinaplhtho-4, Io-diazaperilen registered, produced for example by nitrating the dinaphtho-4, Io-diazaperylene (see Example 5) in concentrated Sulfuric acid finite a little more than the calculated amount of nitric acid. At a Temperature of 118 'is refluxed for a few hours, then the Melt dried up. The temperature is then gradually increased to 26o ° and Held for 6 hours at 26o to 270 °. 1 after digesting the crude product with Sulfur sodium and sodium hydroxide solution become the dye from its aqueous solution deposited by acidification. After trading it is a black powder that from your sodium sulphide bath the vegetable fibers in burnish olive hues colors of particular lightfastness. With the addition of 6 parts of copper vitriol an olive-brown dye is obtained in the melt.

Example 9 4o parts of tetramethyl-5, 6, II, I2-dibenzo-4, Io-diazaperylene, prepared from di- (2 ', 5'-dimethylanilido) -I, 5-anthraquinone, for example by Heating in phosphoric acid, I40 parts are crystallized with a polysulphide melt Sodium sulfur and 80 parts of sulfur at II8 ° for several hours on the reflux condenser cooked. After the melt has dried, the temperature is increased to 27o ° and the Melt held at 27o to 28o ° for about 8 hours. After the raw product has been broken down With sodium sulphide and lye, the dye is removed from its aqueous solution Acidification deposited. After drying it is a blackish powder that de vegetable fibers from the sulfur sodium bath in black-brown shades of colors with excellent lightfastness.

Claims (1)

PATENT CLAIM: Modification of the procedure of patent 745 336 for Production of sulfur dyes, characterized in that 5, 6, 1i, z2-dibenzo-4, zo-diazaperylene or its substitution products, optionally in the presence of metal salts, treated with sulphurizing agents and the crude melt in usual Way worked up.