DE483236C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes. It was found that binaphthylene dioxide provides a red-brown quinone with the gross formula ('' _ "H, 04. Its constitution is probably that of a 4. # 4'-binaphthone), which still contains the oxide bridges and can therefore be referred to as binaphthone dioxide for short were. This chition can be z. B. win very pure as follows (see. Patent 449 1:21). The action of benzoperoxide on dioxide produces a dibenzoate of total dioxide. When saponified, this produces a dioxy body, which is I) This name has already been introduced for the two-ring quinones of biriaphthyl. See Bünzly and Decker, Ber. 38, 3268. Pummerer and Frankfurter, Ber. 47, 472. is easily converted into the quinone by atmospheric oxygen. The formula of this quinone was ascertained by us through analysis, manufacture and analysis of its characteristic hydroquinone diacetate and various reactions. This acetyl derivative (CZ4Hl40a) crystallizes from chlorobenzene in yellow-green needles that do not melt at 29o °, but decompose earlier. Analysis C .., HixO, z found 72.35 ° @ o Cl 3.47 ° / "H. Ber. 72.39 °%"C; 3.54 ° @ o H. The binaphthone dioxide described above can also be obtained by oxidation of dioxide under certain conditions.

It has now been found that this quinone of the dioxide by nitration converts into a brown dinitroquinone of the formula C "" H.N20 $. The same thing can be said Nitrobenzene. recrystallize and form brown platelets delimited on six sides of green surface gloss.

Analysis: N found. 7, r9 ° (o; Ber. 6.97 ° b. This dinitro body is' sparingly soluble in most organic solvents. By reducing agents, e.g. hydrosulfite and caustic soda, zinc dust and glacial acetic acid, iron and hydrochloric acid or zinc and alkali, it changes into the corresponding diamino compound of dioxybinaphthylenedioxide. This oxy compound easily forms the diamino quinone of dioxide in air :, This diamino quinone is a blue-green vat dye of great abundance and luminosity. Recrystallized from pyridine on the Soxhlet, the dye forms purple needles with a metallic sheen. Analysis: N found. 7, g1%; 8,1g% / a.

The dye is insoluble i. Alcohol, benzene and petroleum ether, heavy soluble in glacial acetic acid and pyridine, moderately soluble in hot nitrobenzene.

Concentrated sulfuric acid dissolves red with a purple tinge. The leuco connection is light yellow. Its sodium salt is sparingly soluble in cold, slightly soluble in hot Water.

Mori can also conduct the nitration with aqueous nitric acid in such a way that that another nitroquinone is formed, the amino compound of which is a gray one Vat dye is. Also in organic solvents with concentrated nitric acid in the cold, as well as with nitrating acid in concentrated sulfuric acid as a solvent such gray coloring dyes are obtained.

Oxyderivate of Binaphthondioxy ds are obtained by oxidation of the same or by oxidation of the binaphthylene dioxide directly. . (See Patent 449 I21.) The oxyderivatives also yield in the case of titration with the usual means and reduction the ent -., similar nitro compounds blue-green coloring dyes. Example i 31 Parts by weight of quinone of the dioxide are 3 hours with .48o parts by weight of 5% Nitric acid refluxed. The solution turns dark red. One dilutes with water and sucks off the brown dinitro body.

Example e 31 parts by weight of quinone of the dioxide are suspended hot in 240 parts by weight of glacial acetic acid and 80 parts by weight of 6% strength nitric acid are gradually added. It is then refluxed for a further hour and falls with water. About 27 g of dinitroquinone are obtained. In this example, other organic solvents, e.g. B. nitrobenzene, use. According to this example, Oxy dinaphthöndioxyd can also be nitrated. Example 3 5 parts by weight of binaphthone dioxide are refluxed for 5 hours with zoo parts by weight of 2 percent strength nitric acid. The body is sucked off and boiled again with 100 parts by weight of 2% nitric acid for 5 hours. The red-brown nitro body is filtered off with suction and washed until it is free from acid. Purification can be done by dissolving in pyridine and precipitating the filtered solution with ether, alcohol or water. After reduction to the amino body, a cotton-gray vat dye is obtained. . EXAMPLE 3o parts by weight of oxyquinone of the dioxide are refluxed for 5 hours with 35o parts by weight of q.o percent nitric acid. It is precipitated with water, the red-brown nitro body is filtered off with suction and washed until it is free from acid. For purification, it can be recrystallized from nitrobenzene. Example s do parts by weight of dinitroquinone are reduced with zoo parts by weight of hydrosulfite, 8oo ccm of 2% sodium hydroxide solution and 7000 ccm of hot water. Complete dissolution occurs after a brief boil. The hot solution of the leuco compound is then filtered and left to cool in the absence of air. The yellow sodium salt of the leuco compound crystallizes out. Aspirated and treated with dilute sulfuric acid, it turns into the dye in the air. By blowing in air, some of the dye can be separated from the sodium salt filtrate.

Claims (1)

PATENT CLAIM: Process for the production of blue-green and gray Vat dyes, characterized in that the quinone is obtained from binaphthylene dioxide as well as its oxy compounds treated with nitrating agents and the nitro compounds possibly reduced.