DE132424C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

CLASS 22d.

The inventor has succeeded in finding a method which allows some to be classified as 'the class' of the so-called. To manufacture products belonging to sulphine colors in pure crystalline form ¹ .

In contrast to the previously used process for the production of such dyes, which, according to the procedure of Vidal and others, consists in melting diphenylamine derivatives and other products with sodium sulphide and sulfur, with heterogeneous mixtures of the easily soluble alkali salts of the dyes with those in the reaction formed by-products are obtained, the inventor carries out the conversion in alcoholic solution with alkali polysulphides, preferably sodium tetrasulfide (Na ₂ S ₄ ), under pressure. Here the new color bodies are separated out directly in crystalline form and can easily be obtained in a pure state by filtering them off and washing them out with gasoline and cold water.

This method of producing sulfine colors has heretofore proven useful in such bodies proven, which deliver leucoindophenols during reduction, i.e. when using Nitro and amido-p-oxydialphylamine derivatives, as well as the corresponding indophenol derivatives and quinonimides themselves, d. H. the process is suitable to the production of such sulfine dyes, their origin and "their properties after than the sulfhydrates respectively. Disulphides of sulphurized phenols are to be understood.

These stains are in alcohol, dilute sulfuric acid ;: caustic soda and vinegar as well as insoluble, are only ausnahmst as direct as water-soluble alkali metal salts obtained, go against it when treated with sodium sulphide leaches into those over and color in this form unpickled cotton from kochsalzhaltigetn bath at ¹ .

As can be seen from the following examples, are made from one and the same starting product different colored bodies obtained depending on the choice of reaction conditions.

Example I.

10 parts of p-oxy-p ^ nitro-o'-amidodiphenylamine (melting point 196 to 197 ⁰ ) or p-oxy-0 'ρ' -dinifrodiphenylamine (melting point 187 to 188 °) or the brown sulphurized reduction products, which 'in the * heating alcoholic solutions of p-oxy-0 ¹ · p'-dinitrodipheriylämins arise with Alkalipölysulfiden be with '50 to 60 parts alcohol and r8 parts ¹ sodium tetrasulfide - that examples möglichstem Ausschlufs of water - in an iron or email liften Aufoclaven during ^3: heated to 13 5 to 145 ° for up to 4 hours. (The dye formation begins nicely at ι γό °.)

While the sodium tetrasulfide after the usual fusion acts explosively to p-oxy-0 ¹ · p 'dinitrodiphenylamine, the reaction proceeds in the present process quietly, the Diuck i'ili · Äutbcläven DAF gradually increases, - to ^date: Schlüfs ca 8 to 10 atmospheres to achieve

After cooling, they become crystalline Separated color bodies by suctioning off the brown to schmuiziggrürien mother liquor freed, event, up to a clear process with Fuel and then for the removal of added sulphurous acid "salts", which are included in resulting from the reaction, washed with cold water and dried. When sucking off

the color body becomes self-heating, probably as a result of a simultaneous oxidation process of the goods. The dye forms a shiny copper, dark blue powder and dissolves in sodium sulphide with a violet-blue color; it can be thickened by such Solutions can be converted into the form of the water-soluble alkali salts.

It dyes unheated cotton from baths containing sodium chloride in 2 perc. coloring deep dark violet blue, the color changes considerably due to oxidation on the fiber blue violet; in 5 proc. Coloring he delivers black-blue-violet tones, which with brown and green nuances provide a deep black.

The alcohol is distilled off from the alcoholic filtrate mentioned above. The received Product sets in water containing sulphurous sodium with a brown to greenish-black color Color-soluble powder, which turns unheated cotton from this solution into brown to greenish black, mixed with that. blue 'product in deep black tones.

Example II.

10 parts of p-oxy-0 ¹ · p'-dinitrodiphenylamine, in 70 parts of fuel released, or corresponding to this content alcoholic solution as obtained directly in the condensation of p-amidophenol with ο · p-dinitrochlorobenzene in the presence of anhydrous sodium acetate is heated with 18 parts Natriumtetrasiilfid for 5 hours in enamelled autoclave to 160 to 170 to ⁰ and the precipitated crystalline dye according to the previous example insulated. The color body, which is otherwise insoluble in all solvents, dissolves in sodium sulphide with a green-blue color and stains an acid-fast gray on unheated cotton from a salty bath, which does not undergo any noticeable change in shade on the fiber during post-oxidation. The reaction proceeds less smoothly if, instead of sodium tetrasulphide, the equivalent amount, that is, about 20 parts of crystallized sodium sulphide and 8 parts of sulfur, are used.

Analogously, the color bodies from the indophenols from p-amidophenol and Metadiaminen or from the Dinitrophenylchinonimid which is erhallen as yellowish, crystalline, insoluble in alkalis mass, when p-oxy-0 ¹ · ρ ^ dinitrodiphenylaminlösungen with hypochlorite salts (Eau de Javelle) are oxidized. Of those following the procedure of. French patent 284387 of m-pbenylenediamine or m-tolylenediamine derived indophenols respectively. according to the process of patent 103861 from p-oxy-p ¹ · o ¹ -dinitrodiphenylamine prepared sulfurized dyes differ from the present process from the same indophenols respectively. Dyes prepared from p-Oxyo ¹ · p ¹ -dinitrodiphenylamine simply because they are excreted in a solid crystalline form and obtained in a pure state by filtering off and washing out.

In the following, the dyestuff from p-Oxyo ¹ · p'-dinitrodiphenylamine, as well as the dyestuff prepared from the indophenol from p-amidophenol and m-tolylenediamine according to Example I, are the products obtainable from the same starting materials according to patent specification 103861 and French patent specification 284387 juxtaposed.

Dye from p-oxy-0 ¹ ·. p-dinitrodiphenylamine.

According to Example I, the present one
description Following the example of the patent specification
103861 (deposited with acetic acid
and cleaned) Solution in water at counter
wait for sodium sulphide violet blue green Blue Carbon dioxide separates from the
aqueous sulphurous sodium
containing solution a red-brown one in the air
dark blue violet
Precipitation from a green-gray, in the air
greenish-black becoming low
knock off Acetic acid separates from the
aqueous sulphurous sodium
containing solution as above as above Hydrochloric acid separates from the
aqueous sulphurous sodium
containing solution as above as above in caustic soda almost insoluble soluble (better in heat)
with green-blue color in ß-naphtol soluble with red-violet color soluble with green-blue color.

Claims (1)

Dye from the indophenol from p-amidophenol and m-toluylenediamine. According to example I present
description According to the French patent
font 284387 Solution in water at counter
waiting for sodium sulphide röthlichbiau greenish blue Carbon dioxide separates from the
aqueous sulphurous sodium
containing solution nothing off; the reddish blue
Color of the solution suggests in
red-violet around, on paper
it always dabs in color
getting stronger purple-black nothing off; the green-blue color
the solution turns brown
um, dabbed on paper
they turn green first and then
blue Acetic acid separates from the
aqueous sulphurous sodium
containing solution nothing off; the color of the
Solution turns reddish
blue in dirty reddish-
brown around a red-brown one in the air
blackening down
knock off Hydrochloric acid separates from the
aqueous sulfur nalrium-
containing solution a red-brown-black one
Precipitation from a brown, iron oxide
hydrate-like, looking
Precipitation from in caustic soda difficult, almost insoluble soluble with a greenish blue tinge
colour in ß-naphtol not soluble soluble with red, gradually
blackening color. Godfather ν τ-Α ν saying:
Process for the preparation of sulfur dyes in pure form, consisting in that ρ - oxydialphylamine derivatives in alcoholic Solution with alkali polysulfides respectively. Sulfur sodium and sulfur heated under pressure and the color bodies precipitated in the process are isolated.