DE492161C - Process for the preparation of azine dyes - Google Patents

Description

Process for the preparation of azine dyes Monosubstituted azine derivatives like Eurhodole and Eurhodine have so far been viewed as technically rather worthless (cf. F i e r z -David, Künstl. org. Dyes p.310), which is probably also for the So far known Oxy- and Aminoazines applies, as they usually do not have blank colorations show noteworthy authenticity properties.

As has been surprisingly found, one now arrives at one K.1 class of azine dyes, which the wool fiber in real yellow to red tones color if you put naphthophenazinesulfonic acids in the 8-position of the naphthatin nucleus substituted by hydroxyl or an amino or acidylamino group. The new dyes, Especially those with an aroylamino group stand out when dyeing wool through outstandingly beautiful and clear tints of unusual lightfastness. Example i 1o parts of i, 2-naphthophenazine-3, 8-disulfonic acid obtained from i, 2-naphthoquinone-3, 8-disulfonic acid and i, 2-diaminobenzene are rit 15 parts q.8% potassium hydroxide solution stirred, whereupon q.o parts of potassium hydroxide are added and the melt takes about an hour holds at 17o °. In this procedure, hydroxyl is formed in the 8-position, while the sulfo group is retained in the 3-position of the naphthalene nucleus. The melt is diluted with 20 parts of water. The potassium salt separates on cooling of 8-oxy-i, 2-naphthophenazine-3-sulfonic acid, while some of the lye does not reacted azine disulfonic acid remains. The 8-oxynaphthophenazine sulfonic acid obtained, one in concentrated sulfuric acid with a blue color, in water with a pure yellow color soluble compound, is a wool dye with good leveling properties and lightfastness. It delivers a clear yellow. Example e 33 parts of the potassium salt of 8-acetylamino-i, 2-naphthoquinone-5-sulfonic acid (e.g. obtained by treating the nitroso compound of 8-Acetylamino-i-oxynaphthalene-5-sulfonic acid in a known manner to form 8-acetylamino-2-amino-i-oxynaphthalene-5-sulfonic acid reduced and this oxidized) are in the usual way with i i parts of i, 2-diaminobenzene kon = -dense. The 8-acetylamino-i, 2-naphthophenazine-5-sulfonic acid obtained as the sodium salt is a compound that crystallizes in yellow, shiny brass needles in water with greenish yellow and in concentrated sulfuric acid with greenish yellow Color dissolves. When dyed on wool, it gives a clear, greenish yellow of excellent quality Leveling ability and unusually high lightfastness.

B_eispi_el, 3 38 parts of the acetyl compound obtained according to Example 2 (Sodium salt) are brought into solution with 800 parts of water; then will after Addition of 100 parts of concentrated sulfuric acid boiled for 6 hours, with .the 8-Amino-i, 2-naphthophenazine-5-sulfonic acid in free form than very difficult in water soluble compound which crystallizes in blue needles is obtained. It forms orange colored water-soluble alkali salts. Dyed on wool gives a red orange of good leveling ability.

Example d.

35 parts of the sodium salt of 8-amino-i, 2-naphthophenazine - 5 - sulfonic acid are dissolved in Soo parts of water, after the addition of i 6 parts of benzoyl chloride and i 2 parts of sodium carbonate is stirred for several hours at 6o to 70 °. It crystallizes 8-Benzoylamino-i, 2-naphthophenazine-5-sulfonic acid in yellow needles. The coloring on wool is a reddish yellow of good wash and milled fastness and excellent Lightfastness.

The compound obtained in a similar manner from 2-chlorobenzoyl chloride gives an orange that is noticeably equalizing, in addition to being wash and milled fast Has properties.

The dye made from 4-nitrobenzoyl chloride, which is presented in a similar manner , like the acetyl compound, delivers clear greenish-yellow tones. Despite noticeable The dye has a leveling capacity, the dye has an excellent washability and milled fastness as well as an unusually high light fastness. Similar to a clear shade of yellow supplies the dye prepared with 3-nitrobenzoyl chloride. Example s 65 parts of the potassium salt of 8-acetylamino-i, 2-naphthoquinone-5-sulfonic acid (Example 2) are in iooo parts of water with 40 parts of i, 2-diaminobenzene-q.-sulfonic acid Addition of 4.2 parts of sodium acetate condensed at 7o to 8o °. After the Reaction falls to the addition of table salt the azine compound, a mixture of 8-acetylamino-i, 2-naphthophenazine-q. ', 5- and -5', 5-disulfonic acid, from: Das in the dried state yellow powder dissolves in water with the same color. Dyed on wool is obtained a pure yellow of good wash and milled fastness and excellent light fastness.

This product can be saponified according to the example 3 win an 8-Aminoi, 2-naphthophenazindisulfoäure, which in turn again can be reacted with acid chlorides to form 8-arovlaminoazinedisulfonic acids. For example one obtains with q-nitrobenzoyl chloride a very clear yellow color of animal fibers Dye which has even better fastness properties than the acetyl compound. Example 6 According to Example 2, 8-acetylamino-i, 2-naphthoquinone-q-sulfonic acid (from 8-acetylamino-i-oxynaphthalene-q-sulfonic acid obtained) condensed with i, 2-diaminobenzene. The 8-acetylamino-i, 2-naphthophenazine- [sulfonic acid] obtained dyes wool in a similar shade and fastness to the 8-acetylamino-i described in Beispie12, 2-naphthophenazine-5-sulfonic acid.

An 8-aminonaphthophenazine-4-sulfonic acid can be obtained by saponification from which dyes are recovered by reaction with acid chlorides which are similar to those in Examples q. and 5 behavior described.

Claims (1)

PATENT CLAIM-: Process for the preparation of azine dyes, thereby characterized in that i, 2-naphthophenazine sulfonic acids are in the 8-position of the naphthalene nucleus substituted by hydroxyl or the amino or acidylamino group.