DE605938C - Process for the preparation of anthraquinone dyes - Google Patents

Description

According to the invention is an aminoanthraquinone or a. Derivative of the same with the acid halide of a dinitrodiaryldisulfiddicarboxylic acid in which the nitro groups ortho to the —S — S bond or with the acid itself in the presence of an acid halide forming agent aeylated and the resulting disulfide is reduced to the corresponding orthoaminomercaptan, which is then treated with a haloacetic acid, the orthoaminothioglycolic acid arises.

The new dyes thus obtained are applied to the fiber in the manner described in British patent specification 377 740 applied and then give real colorations. As examples of dinitrodiaryldisulfiddicarboxylic acids which according to the invention can be used, the following are mentioned: 2, 2 - Dinitro - 4, 4'-dicarboxydiphenyl disulfide, 2, 2'-Dinitro-5, S'-dicarboxydiphenyldisulnd, 2, 2'-dinitro-5, S'-diethoxy-4, 4'-dicarboxydiphenyl disulfide and 2,2'-dinitro-6, δ'-dicarboxydiphenyl disulfide.

Aminoanthraquinones, for example, those in the German patent 225 232 mentioned should be applied.

The following examples indicate embodiments of the method, whereupon the same but is not limited. The parts = are parts by weight.

example 1

22 parts of 2, 2'-dinitro-4, 4'-dicarboxydiphenyl disulfide, 15 parts of thionyl chloride and 200 parts of nitrobenzene are stirred at 100 to 100 ° on a reflux condenser for 20 hours; warmed up for a long time. After this time, the acid chloride formed has dissolved to a clear solution in the nitrobenzene. 22 parts of a-aminoanthraquinone now be added and the mixture ^2% j ₂ hours at 130 to 135 ⁰ stirred. Hydrochloric acid escapes and the mixture thickens. After cooling to 40 ^° , the yellow crystalline mass is filtered off and washed successively with nitrobenzene and alcohol.

The compound obtained in this way is treated with 2000 parts of water, 200 parts of a 33% caustic soda solution and 120 parts of sodium hydrosulphite ^{at 30 0 1} J for _{2 hours, resulting in a clear solution.} Then are added 80 parts of sodium chloroacetate, and then stirred for 1 hour at 60 to 70 ^0th Sufficient hydrogen peroxide is added to oxidize the leucoanthraquinone compound and common salt is added to precipitate the sodium salt of the thioglycollate formed. The precipitate is filtered off and. washed with saline solution. That

Product is an orange-yellow powder that, in warm water, turns into a clear yellow solution is soluble and which probably has the following constitutional formula:

NH ₉

CO

SCH ₉ CO ₉ Na

This dye is applied to the fiber in the manner indicated above. Wool is thereby colored orange-yellow, this shading in the lactamization turns into a pure yellow, which is excellent washfastness and durability against blocks.

Example 2

22 parts of 2, 2'-dinitro-4, 4'-dicarboxydiphenyl disulfide are treated in the manner indicated in Example ι to give a solution of the acid chloride. Thereafter, 25 parts of i-amino-4-methoxyanthraquinone are added and the mixture at 130 to ^{135/0 3} ₄ hours and finally stirred at 190 ^{0 for} a few minutes. On cooling, red crystals separate out, which are filtered and washed with alcohol. The product is converted into a water-soluble dye in the manner described in Example 1. This is a bluish red powder that dissolves in warm water to form an orange solution. Wool is dyed in orange shades which, when lactamized, turn into orange, laugh-colored shades.

Example 3

If in Example 2 instead of the i-amino-4 - methoxyanthraquinone an equivalent Amount of i-amino-4-oxyanthraquinone is applied and otherwise in the same If you work in the way indicated there, a product is created which, after lactamization on wool gives an orange-scarlet shade similar to that which is formed with the dye obtained according to Example 2.

Example 4

If in the procedure given in Example 1, the · i-aminoanthraquinone through an equivalent amount of i-amino-5-methoxyanthraquinone is replaced, a product is created which, when lactamized, gives a more reddish shade of yellow than the dye prepared according to Example 1.

Example 5

If in example 1 instead of 2, 2'-dinitro-4, 4'-dicarboxydiphenyl disulfide 22 parts of 2,2'-dinitro-6, ö'-dicarboxydiphenyl disulfide are applied and the rest of the same procedure is carried out, an orange-yellow powder is produced, which has the following constitutional formula:

CO-NH-CO

CH ₉ CO ₉ Na

When this dye is applied to the fiber and lactamized it gives Shades similar to those of the product of Example 1.

Example 6

If in the example S instead of -des i-aminoanthraquinones an equivalent amount of i-amino-4-methoxyanthraquinone is used, the result is a dye that, when applied to wool and after lactamization, becomes a brilliant scarlet shade of such excellent block fastness.

Example 7

If in example 1 the i-aminoanthraquinone by the equivalent amount of i-amino-5-chloroanthraquinone is replaced, the result is a dye which, when lactamized, has a more reddish shade than that prepared according to Example 1.

Example 8

If in example 1 the i-aminoanthraquinone by an equivalent amount of 1-amino-4-methylaminoanthraquinone is replaced, the result is a dye that gives a blue-violet shade on wool, which in the Lactamizing turns into a reddish blue.

B ei sρ i e, l 9

22 parts of a-aminoanthraquinone, 22 parts of 2, 2'-Dinitrodiphenyldisulfid-4, 4 '' - dicarboxylic acid, 15 parts of thionyl chloride and 200 parts of dry nitrobenzene are mixed together and heated gradually I ¹ J ₂ hours at 140 ^0th The mixture is heated to 135-140 ° until the evolution of hydrochloric acid has ceased. After cooling to 60 °, the product is filtered off and washed with nitrobenzene until the

Claims (1)

Wash liquid is colorless, and finally washed with alcohol. The thus obtained Product is converted into the soluble dye in the manner described in Example. The result is a dye which is identical to that obtained according to Example ι. Patjsntansi'kuch: Process for the production of anthraquinone dyes, characterized in that that an aminoanthraquinone or a derivative thereof with the acid halide a dinitrodiaryl disulfide dicarboxylic acid in which the nitro groups are in the ortho position to the —S — S bond, or with the acid itself in the presence an acid halide-forming agent are acylated to give the acylation product the corresponding o-aminomercaptan reduced and this with a haloacetic acid is converted into the o-aminothioglycolic acid derivative.