DE97675C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

As is well known, indamines and indophenols are formed by co-oxidation of suitable paradiamines and amines respectively. Phenols. Also the sulfur derivatives of the p-diamines, which are derived therefrom through the entry of an S-SO ₃ H or SH etc. group, i.e. the pr-diamine thiosulfonic acids and the corresponding mercaptans and sulfides (see Patent No. 45839 and Annalen 251, 1 ff .), are able to form corresponding indamin- and indophenolthiosulphonic acids etc. (cf. ibidem p. 69 ff.), compounds of mostly green color, which are of great technical interest because of their convertibility into methylene blue substances.

It has now been shown that derivatives of U ₁ -amido - ß ₁ - naphtol, in particular Ci ₁ - amido -, S ₁ - naphthol-ß ₃ -sulfosa'ure with paradiamine thiosulfonic acids or with the corresponding mercaptans or sulfides by mutual oxidation to form dyes of indamine character. While, by analogy, from the amidonaphtholes mentioned, indamines of the type:.

NO

NH

should have expected the resulting compounds to have the composition of indophenols of the following type:

NO

These are hereinafter referred to as Oxynaphtindophenolthiosulfonsäuren (sulfonates, sulfides, etc.). There is therefore an exchange of the iVii group against an oxygen atom. The discovery of these compounds was made difficult by the fact that they were in opposition for the indamines, etc. discussed above, no green or blue, but in a neutral solution have a dirty purple-brown color, which is caused by acids (even acetic acid) after yellow-brown resp. turns yellow-red.

Instead of preparing the oxynaphtindophenolthiosulphonic acids etc. from the amidonaphtholsulphonic acid mentioned by oxidizing them together with the sulfur derivatives of the paradiamines, one can also proceed in such a way that the oxygen required for the oxidation is introduced into the reaction in the form of the nitroso group and accordingly Ct ₁ -

Nitroso-βj-naphtol-βg-sulipic acid directly on those Allows sulfur derivatives to act.

The sulfurized oxynaphthinedophenols so represented are both dyes Can be used directly as well as by treatment with concentrated sulfuric acid in blue thiazine dyes transferable.

In the following, the representation of those dyes is first described, which respectively from the p-amidodimethylanilinthiosulfonic acid of patent no. the associated mercaptan or sulfide on the one hand and Ci ₁ -amido- (nitroso) ßj- naphthol - ß ₃ - sulfonic acid on the other.

Example I.

Preparation of indophenolthiosulfonic _{acid from C 1} -amido-βj-naphthol-β ₃ -sulfonic acid.

24.8 parts of amidodimethylanilinthiosulphonic acid and 23.9 parts of amidonaphthol sulphonic acid are dissolved in 300.0 parts of water with the addition of the neutralizing agent or Dissolve just enough diluted ammonia and some ice solution. In this solution quickly läfst then with constant stirring at about 12 to 15 ⁰ 270 parts of a G. 24proc. Run in solution of ferric chloride. It is left to stand for some time, the indophenolthiosulphonic acid which has formed and which has separated out is filtered off, washed with a little hydrochloric acid-containing water, prefilled and dried at ordinary temperature.

In this way a red-brown, crystalline powder is obtained which dissolves in water, more easily in Alkalis, to form the salts described below. Bichromate is used instead of ferric chloride and acetic acid for oxidation and salting out with sodium chloride or potassium chloride, the corresponding alkali salt is obtained Oxyindonaphtolthiosulfonic acid. The same is a crystalline, dark blue, copper-shining one Link; it dissolves in water with a dirty wine-red to purple-brown color and becomes from it precipitated blue by table salt, while dilute hydrochloric acid forms the free acid separated by red-brown, shiny needles. In concentrated sulfuric acid or Hydrochloric acid dissolves - like the free acid - with a yellow color. When heated with diluted Hydrochloric acid will discolor and split.

Example II.

Representation of the dye from Ci ₁ -nitroso-βj-naphtol-βg-sulfonic acid.

12.4 parts thiosulfonic acid and 13.8 parts Nitroso-β-naphthol sulfonic acid (Schaeffer) is converted into ammonia with the addition of 9.0 parts (20 pCt.) Dissolved in 400 parts of cold water, the solution with 80 parts of acetic acid of 30 pct. acidified and a quarter of an hour respectively. Heated to a boil until the yellow-brown Color of the solution disappeared and an increase in the incoming dirty purple-red Color is no longer noticeable. Further processing is the same as in example L

The products obtained in this way, such as those obtained from Ct ₁ -amido-βj-naphthol-β ₃ -sulfonic acid according to Example I, are identical to those shown from dioxynaphthalene sulfonic acid and thus no longer contain the nitrogen of amidonaphthol. This also emerges with certainty from the analyzes carried out.

To represent the dyes from amidodimethylaniline mercaptan or bisulfide is carried out in an analogous manner by z. B.

10 parts of the zinc salt of the mercaptan mentioned (Patent No. 45839) in 400 parts Dissolve water and 9 parts hydrochloric acid, with sodium acetate until the onset of turbidity added, acidified with 200 parts of acetic acid and otherwise proceed as indicated above. The products thus obtained are extremely similar to those described above.

Claims (2)

Patent claims: ι. Process for the preparation of "indophenolthiosulfonic acids (sulfonates) or sulfides, consisting in using paradiamine thiosulfonic acids or the corresponding mercaptans or sulfides a) in a mixture with the molecular amount of aj-amido-ßj-naphthol-ßg-sulfonic acid of Subject to oxidation; b) _{heated with Ct 1} -nitroso-βj-naphtol-β ₃ -sulfonic acid in aqueous or acetic acid solution until the initially yellow-brown color has turned into a dirty violet-red. 2. The special embodiment of the method protected by claim 1 below Use of p-amidodimethylanilinthiosulfonic acid, ρ - amidodimethylaniline mercaptan or bisulfide.