DE933287C - Process for the preparation of metallizable disazo dyes - Google Patents

Description

Process for the preparation of metallizable disazo dyes Subject of the present patent is a process for the preparation of new disazo dyes, which attach to cotton and fibers made of regenerated cellulose and their Dyes can be treated with metal donating agents. The metallized Dyes are characterized by excellent fastness properties; so are for example those with a cation-active, optionally basic copper complex compound (e.g. available from Swiss patents 253-7a9 and 261 048 to 26I 052 treated dyeings are boil-proof and acid-proof and have excellent lightfastness. The dyeings treated with copper salts are also extremely lightfast and also alkaline.

The new dyes are made by adding i mole of 4, 4'-diamino-3, 3'-dioxydiphenyl-i, r'-urea-6, 6'-disulfonic acid tetrazotized and the tetrazo compound with 2 moles of a sulfonic acid group and carboxyl group-free oxynaphthalene in Coupling ortho position to its hydroxyl group.

Oxynaphthalenes that are suitable as azo components are, for example 2-Oxynaphthalene, 2-Oxynaphthalene-sulfonic acid amides and their nitrogen-substituted ones Derivatives, 2., 7-dioxynaphthalene, 2-oxy-6- or -7-methoxynaphthalene, 2-oxy-8-acylaminonaphthalenes, 2-oxy-8-carboalkoxyaminonaphthalenes, i-oxy-4-methylnaphthalene, 1-oxy-4-benzoylnaphthalene, i-oxy-5, 8-dichloronaphthalene and i, 5-dioxynaphthalene.

The coupling of the tetrazotized urea derivative with the azo component preferably takes place in a sodium or potassium hydroxide alkaline medium, if necessary in the presence of an organic tertiary base such as pyridine, quinoline or a crude Pyridine base mixture. After coupling has taken place, the disazo dye is customary Way worked up and dried. The new dyes have compared to the next comparable disazo dyes known from German patent 23i 448 the advantage of an improved affinity for cotton.

The following examples illustrate the invention. Included the parts mean parts by weight, the percentages mean percentages by weight.

Example 1 8.7 parts of 4, 4'-diamino, -3, 3'-dioxydiphenyli, i'-urea-6, 6'-disulfonic acid are in a solution of 3.2 parts of sodium hydroxide and 130 parts Dissolved water. 2.8 parts of sodium nitrite are added to the solution and then poured slowly at about 15 ° into a mixture of 18.5 parts of concentrated hydrochloric acid, 10 parts water and 10 parts ice. After the implementation is completed, the Tetrazo compound deposited by adding sodium chloride to the reaction solution and then filtered. The paste obtained is stirred at room temperature in a solution of 12.6 parts of 2-oxynaphthalene-6-carboxylic acid phenylamide, 10 parts concentrated ammonium hydroxide solution, 10 parts pyridine and zoo parts water. After the coupling has ended, the disazo dye formed is separated off by addition from sodium chloride to the reaction solution, filtered it, washed it with sodium chloride solution and dries it in a vacuum: it dyes cotton and fibers made from regenerated cellulose in red-violet tones, which, when coppered, are extremely washable and lightfast. example 2 8.7 parts 4,4'-diamino-3, 3'-dioxydiphenyli, i'-urea-6, 6'-disulfonic acid are dissolved in 130 parts of a 21% sodium hydroxide solution. After adding of 2.8 parts of sodium nitrite, the solution is left at about 15 ° with stirring slowly in a template of 18.5 parts of concentrated hydrochloric acid, io parts of water and io parts of ice pour in. When the tetrazotization is complete, 8.7 parts of 2-oxynaphthalene are obtained entered in the # suspension, and the reaction mass is added by adding of about 7 parts of a 30% sodium hydroxide solution to pH posed from 5 to 6. One adds. You now have ro parts of pyridine and 16 parts of one - 300 per cent. Sodium hydroxide solution and stir it until the coupling is completed The disazo dye formed is then precipitated with sodium chloride, filtered, washed with a 2oo% sodium chloride solution and dried in vacuo. He dyes cotton and regenerated cellulose fibers in red-violet tones, which When coppered, they are extremely wash-, light-, acid- and alkali-proof.

Example 3 8.7 parts 4, 4'-diamino-3, 3'-dioxydiphenyli, i'-urea-6, 6'-disulfonic acid are tetrazotized as described in the previous example; the tetrazo compound is coupled with 7 parts of 2,7-dioxynaphthalene. The received Disazo dye is deposited from the reaction solution by adding acetic acid, then filtered and dried in vacuo. It dyes cotton and fibers from regenerated Cellulose in burgundy red tones, which are copper-plated, washable and lightfast. example 4 8.7 parts 4,4'-diamino-3, 3'-dioxydiphenyli, i'-urea-6, 6'-disulfonic acid are tetrazotized according to the instructions in Example 2. After the tetrazotization is complete io, 2 parts of i-oxy-5, 8-dichloronaphthalene are entered into the suspension, and the coupling is then carried out according to the information in the example mentioned. Of the -formed disazo dye dyes cotton and fibers from-regenerated cellulose in violet tones, which: copper-plated, excellently wash, light, acid and alkali are. Example 5. If in the previous example the io, 2 parts of i.-Oxy-5; 8-dichloronaphthalene by 12.6 parts of 2-oxy-5-benzoylaminonaphthalene is obtained also a valuable disazo dye, which cotton and fibers from regenerated .Cellulose in red-violet. Tones colors. These have coppered, exquisite ones Authenticity properties.

Example 6-8; 7 parts of 4, 4'-diamino-3, 3'-dioxydiphenyli, i'-urea-6, 6 '= disulfonic acid are tetrazotized in the same way as was described in Example 2. 9.8 parts of 2-oxy-6-methylsulfonylnaphthalene are introduced into the tetrazo suspension, whereupon the coupling to the disazo dye takes place. This is then separated from the alkaline coupling solution by adding hydrochloric acid at a pH of approximately -9. The dye is filtered, washed with ro% sodium chloride solution and dried at 70 °. It dyes cotton and fibers - from regenerated cellulose - in burgundy shades; Which. coppered excellent =. washing-, light = ,. are acid and alkali-proof. In the table below there are other dyes marked by the color of their coppered color on cotton, those dyed by coupling, of: 1 mol of tetrazotized -4, 4-diamino-3, 3'- dioxydiphenyl-i, i'-urea @ 6, 6 '= disulfonic acid with 2 moles of an oxynaphthalene free from sulfonic acid groups and carboxyl groups. Tabel At-hue game 0xynaphthalene the copper No coloring on cotton 7 2-oxy-7-methoxynaphthalene .... burgundy red 8 2-oxy-5- (4'-methyl) -benzoyl- aminonaphthalene ............ red-violet g of 2-oxynaphthalene-3-carboxylic acid phenylamide ............... red-violet io 2-oxynaphthalene-3-carboxylic acid (4'-methyl) -phenylamide ..... red-violet 1i 2-oxynaphthalene-6-carboxylic acid (2'-methyl-4'-chloro) -phenyl- amide .................... red-violet 12 2-oxynaphthalene-3-carboxylic acid amide .................... red-violet 13 2-oxynaphthalene-3-carboxylic acid (2'-oxy) -äthylanüd ......... red-violet 14 2-Oxy-6-methylnaphthalene ..... red-violet 15 2-Oxy-6-tert-amylnaphthalene ... red-violet 16 2-oxynaphthalene-6-sulfonic acid amide .................... purple 17 2-Oxy-8-formylaminonaphthalene reddish blue At-hue game oxynaphthalene the copper No coloring on # Cotton 18 2-Oxy-8-acetylaminonaphthalene reddish blue 19 2-oxy-8-carbomethoxyamino naphthalene ............... blue 2o 2-oxy-8-carboethoxyamino naphthalene .......... *** '** blue 21 2-oxy-8-carbopropoxyamino naphthalene ............... blue 22 2-oxy-8-carbo- (2'-methoxy) - ethoxyaminonaphthalene ..... blue 23 1-Oxy-4-chloronaphthalene ...... brown

Claims (1)

Claim: Process for the preparation of metallizable disazo dyes, characterized in that one mole of 4,4'-diamino-3, 3'-dioxydiphenyl, i'-urea-6, 6'-disazo-acid is tetrazotized and the tetrazo compound is tetrazotized with 2 moles of a sulfonic acid group - and carboxyl group-free oxynaphthalene in the ortho position to its hydroxyl group. Referred publications: 'German Patent No. 231 448.