DE112115C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In the patent 87335 it is shown that when phenols are treated with formaldehyde and sulfurous acid salts, methylsulfonic acids of the phenols in question are formed.

An analogue to this reaction can now be found in the process of the French patent 268686, according to which basic dyes by the action of formaldehyde and ' Bisulfites - apparently also an entry of the methylsulfonic acid residue takes place here - in acidic dyes are transferred.

It has now been found that the amidoanthraquinones and their derivatives, such as e.g. B. the Amidooxyanthraquinones and their sulfonic acids, i.e. substances which, in contrast to the Products used in French patent 268686 do not have any basic properties, React easily with formaldehyde and sulphurous acid salts, in that the methylsulphonic acid residue enters the amido group. The products thus obtained are all vigorous Acid dyes which dye wool in red to green-blue shades in an acid bath. It is therefore possible by the new method, such substances, which on and for are not usable as dyes, such as the amidoanthraquinones, p-diamidoanthrarufin and so on, to be converted into strong acid dyes in an easy and elegant way. The reaction Probably takes place in such a way that in every amido group there is a methylsulfonic acid residue entry; so z. B. from the ι · 5-diamidoanthraquinone a sulfonic acid of the following constitution:

NH-CH ₂ SO ₃ H

CO-

CO NH

CH ₂ -SO ₃ H.

The procedure generally consists in using the amidoanthraquinone derivative in question in aqueous solution with formaldehyde and sulphites or bisulphites Addition of a little hydrochloric or sulfuric acid treated at ordinary or higher temperature. Bodies that are insoluble or sparingly soluble in water are expediently in Paste form used.

The following examples serve to explain the procedure:

Example I.

100 kg of a 10 proc. Paste of 1 x 5 diamido anthraquinone are with 300 1 Wasserj 10 kg 40 proc. Formaldehyde solution, 20 1 40 proc. Sodium bisulfite liquor and 40 1 fuming salt ^ acid (33 pCt.) heated to approx. 50 to 60 ° with thorough stirring until everything or almost everything Diamido anthraquinone with a red color in

solution has gone, which is the case after a comparatively short time.

It is then filtered, and the new dye is separated from the filtrate by means of sodium chloride or potassium chloride out, filter, praise and dry.

The product obtained in this way forms a brown-red powder which, in contrast to 1-5-diamidoanthraquinone Easily soluble in water with a red color and unheated wool stains in an acidic bath in beautiful bluish red ark-like nuances. The solution in concentrated sulfuric acid has an intense blue color, in contrast to 1 · 5-diamidoanthraquinone, which dissolves in sulfuric acid with a yellow color. When heated with strong mineral acids, the connection is split with reformation of 1 · 5-diamidoanthraquinone. An analysis gave the following result:

C = 37, ss pCt., H = 3.02 pCt.,
S = 13.31 pCt., Na = 9.2i pCt.

A water determination of 6.14 pCt. Accordingly, the following formula must be assigned to the body will:

/ NHCH ₂ SO ₃ Na (1)
C ₁₄ Zf ₆ O ₂ / ■ + 2H ₂ O,

^ NHCH ₂ SO ₃ Na (5)
for which the following values are calculated:

C = 37.91 pCt., H = z 3.18 pCt., S = 12.66 pCt.,
Na = 9, .o pCt., H ₂ O = 7.11 pCt.

Just like the 1 · 5-diamidoanthraquinone behave its isomers, the 1 · 8- and the ι · 7-derivative.

Example II.

In Example I, the 1 · 5-diamidoanthraquinone is replaced by the corresponding amount of p-diamidoanthrarufin in paste form and continues the reaction until a sample is in Sodium hydroxide solution with a green-blue color is clearly soluble, a dye is obtained which in cold Water is difficult to dissolve in hot water. Differs from p-diamidoanthrarufin The new compound is essentially characterized by the fact that, as mentioned above, it is present in alkalis of a splendid green-blue color, and that it dissolves in unheated wool in an acidic bath colors beautiful and strong pure blue nuances.

Just like p-diamidoanthrarufin, p-diamidochrysazine behaves.

In the above example, if the p-diamidoanthrarufin is replaced by its almost insoluble in water Monosulfonic acid, you get one in cold water with a pure blue color Color easily soluble dye, which unheated wool in an acid bath in something colors more greenish nuances than the starting product. This is exactly how p-diamidochrysazine monosulfonic acid behaves.

Instead of the last-mentioned monosulfonic acid, it is of course also possible to use those sparingly soluble nitrogenous dyes respectively. Apply dye mixture, which by Heating of dinitroanthraquinone with sulfur and oleum from 10 to 30 pCt. Anhydride content, with or without the addition of boric acid, dyes, which are mainly mixtures of isomeric diamidodioxyanthraquinone monosulfonic acids and, for example the above-mentioned monosulfonic acids of p-diamidoanthrarufins respectively. ρ-diamidochrysazins included as essential ingredients.

Example III.

100 kg of a 20 proc. Paste of diamidoanthrarufindisulfonic acid (patent 96364) are 'with 15 kg 40 per cent. Formaldehyde solution and 20 kg 40 proc. Sodium bisulphite liquor mixed and ^{stirred at 50 0} until a sample poured into water gives a purely green-blue solution which, on the addition of hydrochloric acid, does not differ significantly according to Roth or. Turns purple, which is the case after a short time. The reaction mixture, which now represents a green-blue, perfectly clear solution, is mixed with further bisulphite liquor, the new dye soon separating itself for the most part in the form of fine, deep-blue needles, which are sucked off and dried.

The dye differs from diamidoanthrarufindisulfonic acid by its extraordinarily high solubility in cold water. The color of this solution is significant greener than that of the starting products and is not changed by the addition of a larger amount of hydrochloric acid. the Color of the solution of diamidoanthrarufindisulfonic acid suggests under the same conditions turns to violet, and finally the dye falls in the form of fine crystals the end. The solution of the new compound in concentrated sulfuric acid is yellow when added from boric acid it turns green-blue and now shows the same spectrum as the boric acid ether the diamidoanthrarufindisulfonic acid itself. By heating with strong hydrochloric acid the Substance split with deposition of diamidoanthrarufin disulfonic acid. The new Dye stains unheated wool in extremely clear shades, which are greener than that of the starting product.

Diamidochrysazine disulfonic acid behaves exactly like diamidoanthrarufine disulfonic acid of patent 100136.

The process proceeds in a completely analogous manner if one uses instead of the one used in the examples

Body uses other amidoanthraquinone derivatives.

The following table gives an overview of the characteristic properties of these products given.

Formaldehyde compound
applications from: water 'Lb "si
Caustic soda mg in
sulfur
acid, con-
centered sulfuric acid
after adding
Boric acid Color _;
chromge
pickled wool those on
unheated
Wool ι · 5 - Diamidoanthra-
chinone bluish
red bluish
red blue unchanged red red ι · 8 - Diamidoanthra-
chinone bluish red bluish red dirty
blue like bluish
red bluish
red p-diamido anthrarufine blue greenish
blue yellow-green blue green Blue blue Diamido anthrarufin
disulfonic acid greenish
blue greenish
blue yellow first green, then
greenish blue green Blue blue Diamidochrysazine
disulfonic acid blue blue yellow dirty
yellow-green green Blue blue Diamido anthrarufin
^; monosulfonic acid blue blue yellow-brown blue green Blue blue Diamido anthra
chrysondisulfonic acid blue
violet blue red-brown reddish brown blue violet blue.

Claims (1)

Patent claim: Process for the preparation of acid dyes of the anthracene series, consisting of that amidoanthraquinone derivatives formaldehyde in the presence of sulphurous acid respectively whose salts can act.