DE889338C - Process for the preparation of disazo dyes - Google Patents

Description

Process for the preparation of disazo dyes It has been found that new, valuable metallizable disazo dyes are obtained if diazotized amino monoazo dyes of the following formula are used: with oxynaphthalenes, 1-aryl-5-pyrazolones, acetoacetic arylamides or their substitution products, which, however, contain no carboxyl or sulfonic acid groups, to form o, o'-dioxydisazo dyes. In the above formula, A stands for the remainder of a diazo component which contains a sulfonic acid group. The benzene nucleus B contains a hydroxyl group adjacent to the amino group. The dyes obtained in this way can be converted into the corresponding chromium complex compounds both in substance and on the fiber with chromium-releasing agents.

The new dyes dye, either in substance or on the fiber converted into the chromium complex compounds, animal fibers and polyamide fibers in lightfast and dark brown to olive tones. Those produced in substance Chromium-containing dyes also have the advantage that they are based on animal Pull up fibers from neutral to weakly acidic baths.

EXAMPLE 1 i7.3 g of 1-aminobenzene-4-sulfonic acid are dianotized in the usual way and added at 0 to 5 ° to a solution which has been prepared from 15.1 9 of 2-acetylamino-1-oxybenzene, 1o ccm 3o ° / oiger sodium hydroxide solution and 25 g sodium carbonate in zoo ccm water. After half an hour of stirring, the batch is 1 / 1o of his; Volumeri's 30% sodium carbonate is added (and heated to 100 ° for 1 hour. After this time, the mixture is made slightly acidic with hydrochloric acid, the precipitation is completed by adding sodium chloride and filtered. Dissolved in water - with the addition of sodium hydroxide solution. - 7 g of sodium nitrite are added to the solution and slowly poured into dilute hydrochloric acid at 5 to 10 ° with thorough stirring. When the diazotization is complete, a solution of 14.4 g of 2 -Oxynaphthalene coupled. The disazo dye is separated by the addition of sodium chloride and filtered at pn io. Animal fibers can be dyed in red shades with the new dye. Post-treatment of such dyes with chromium-releasing agents turns the color shade towards black-brown The dyeings have good wet fastness and lightfastness, and conversion into the chromium complex compound by the single-bath chromium process gives dyeings with similar authenticity properties. "'Example 2 47g of the dioxydisazo dye described in Example i are dissolved in water with the addition of sodium hydroxide solution, at 20 ° it is made slightly acidic with acetic acid and a solution of 3o g of chromium fluoride (containing water of crystallization) is added." After that, will. several hours on the reflux condenser - boiled until a sample no longer shows any chromium-free dye. After adding sodium chloride, leaves. the chromium-containing dye can be filtered off thoroughly.

The conversion into a chromium complex compound can also be carried out in a shorter time - in the following ways: - -2oo g of a basic chromium sulphate solution ". Corresponding to 76 g of Cr, 03, - are mixed with 5 liters of water and, after adding - of -276 g salicylic acid heated to boiling: With 30% sodium hydroxide solution, the clear solution is slowly made up to a weakly alkaline reaction to 7 1. 47 g of the disazo dye shown in Example z are added to z 1 Water dissolved in hot water and mixed with 506 dcirider chromosalicylic acid solution described above: It - is - then - under "reflux", heated to boiling until the original color is no longer detectable. The resulting chromium-containing dye is deposited in a neutral reaction by adding salt. and 'dried, it is ground a black powder: .Animal fibers and also polyamide fibers can be dyed with it from acid to neutral bath in black-brown shades of good wet fastness and light fastness. - Example, 3 ".

17.39 i-Aniinobenzene-2-sulfonic acid are diazotized and, as in Example Z, coupled with 111 9 2-acetylamino-1-oxybenzene to form the monoazo dye. The “dye is separated with sodium chloride, filtered and saponified with dilute hydrochloric acid at 80 °. After cooling, the oxyaminomonoazo dye is isolated and dissolved in water with the addition of NätxonlauZe sl. The solution is added with 7 g Sodium nitrite is added and the mixture is added dropwise to dilute hydrochloric acid at 5 to 10 ° with stirring. Finally, the mixture is stirred for a further half an hour. and then the diazotization mixture was added to the sodium hydroxide alkaline solution of 14.4 g of 2-oxynaphthalene. The disazo dye formed is filtered off after addition of sodium chloride. He dyes wool in red tones. By converting the dye on the fiber into the chromium complex compound, a black-brown coloration with good wet and light fastness is obtained. By treating the dye in substance with chromium-releasing agents, as described in the example, a product is obtained which, when dry, gives a black powder and dyes wool or polyamide fibers in black-brown shades with good fastness properties. Example 4 The diazo compound prepared in the usual way from 22.3 g of i-aminonaphthalene-4-sulfonic acid is converted into a solution of 15 "g of 2-acetylamino-i-oxybenzene, 10 ccm of 30% sodium hydroxide solution; 25 g of soda and 100% After half an hour of stirring, the mixture is heated to 0 ° and 1/10 of the volume of 30% sodium hydroxide solution is added. The temperature is kept at 0 to 100 ° for one hour, the solution is then made slightly acidic and the aminooxymonoazo dye is precipitated by sodium chloride The substance is filtered off at 70 °, dissolved in water with the addition of sodium hydroxide solution and quickly poured into dilute hydrochloric acid at 0 ° to 5 ° with stirring nitrous acid remains positive. The diazotization mixture is added to a sodium-alkaline solution of 14.4 g of 2-oxynaphthane bfiltered and washed down with 511% sodium chloride solution. The dyestuff obtained in this way .. provides on animal fibers and polyamide fibers - a red dyeing which, treated in the usual way with chromium-releasing agents, gives a black-brown with good fastness properties.

"- 5z g of the dye described in this example are shown in 8oo cc water with 10 cc sodium hydroxide solution - hot - dissolved. For this. become 45o cc- the Chromosalicylic acid solution prepared according to examples. - It's stirring Heated until the original dye can no longer be detected. Then table salt is added. Only after further heating separates the chromium-containing, Dye in a readily filterable form: it is filtered off and dried. Of the The new dye is a black powder and dyes animal fibers or polyamide fibers from acidic or neutral bath in black-brown tones of good wet fastness and Lightfastness.

If, in this example, if the following is otherwise the same: working method, das 2-oxynaphthalene diireh 17.7 g.acetoacetylaminobenzene or through 21.5 g i - (. 3'-nitro - phenyl) -3 = methyl-5-pyrazolone, in this way one obtains disazo dyes which are on the fiber or in substance in their chromium complexes transferred, on. animal fibers and polyamide fibers are very reddish-tinged brown Shades of good wet fastness and light fastness result.

If in this example the 2-oxynaphthalene is replaced by i-acetylamino-7-oxynaphthalene, this results in the chromium complex compound produced on the fiber or in substance on, animal fibers and polyamide fibers an olive green of good wet fastness and Lightfastness. Example 5 22.39 i-Aminonaphthalene-4-sulfonic acid are used in customary Way diazotized and a solution of 16.59 2-acetylamino-q.-methyl-i-oxybenzene, 10 cc of 30% sodium hydroxide solution and 25 g of sodium carbonate are added to 150 cc of water. The resulting monoazo dye is precipitated with sodium chloride and filtered, then dissolved in 8oo ccm of 5% hot sodium hydroxide solution and heated to go ° for 1 hour. To this time the solution is made weakly acidic and by adding sodium chloride the precipitation completes. The aminooxyazo dye thus obtained is added with the addition of sodium hydroxide solution dissolved in water, mixed with 7 g of sodium nitrite and diluted in Hydrochloric acid added dropwise. When the diazotization is complete, a solution of 14.4 g 2-oxynaphthalene, 15 cc sodium hydroxide solution and 25 g sodium carbonate in 150 cc water given. After stirring for four hours, the disazo dye formed becomes without prior Filtered addition of sodium chloride and dried. He dyes animal fibers and polyamide fibers in red tones. By post-treatment in the usual way with chromium-releasing Medium or even in the single-bath chrome process, bluish-gray colorations are obtained of good wet and light fastness. 53.2 grams of the disazo dye described in this example are dissolved in water with the addition of sodium hydroxide solution and with 7o0 ccm that in example 2 mentioned chromosalicylic acid solution added. After several hours of heating, the original dye can no longer be detected. The chromium-containing dye will separated from the solution by sodium chloride and filtered. He dyes animal fibers and polyamide fibers from acidic or neutral bath in gray tones of good wet and Lightfastness.

Claims (1)

Claim: Process for the preparation of disazo dyes, characterized in that rdiazotized aminomonoazo dyes of the general formula where A stands for the remainder of a diazo component containing an SO, H group, and the benzene residue B adjacent to the N H2 group contains a hydroxyl group, with oxynaphthalenes, i-aryl-5-pyrazolones, acetoacetic arylamides or their substitution products, but none Containing carboxyl or sulfonic acid groups, couples to o, o'-dioxydisazo dyes and the resulting dyes, optionally in bulk or on the fiber, are converted into their chromium complex compounds.