DE167805C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

Formaldehyde reacts with the gallocyanine dyes either in aqueous solution or in aqueous solution in the presence of organic acids or mineral acids. The reaction is generally promoted by the presence of acids, namely the more concentrated the latter are; in concentrated sulfuric acid z. B. takes place the reaction without any external information

ίο heat supply. Heating is also beneficial the reaction.

The various gallocyanin dyes do not all react with the same ease still at the same speed.

In the presence of acids, the formaldehyde can in any case in different ways To combine proportions with the gallocyanin dye, so that a certain Gallocyanine dye with formaldehyde provide various reaction products, the constitution of which has not yet been established can. Even if, to all appearances, equimolecular proportions are the most clearly definable reaction products give, one is not yet bound by a certain rule about the one to be applied Quantitative proportions bound.

The dyes obtainable by means of this reaction can be used both in the print shop as used in dyeing; on chrome stains they color in green-blue to yellowish-green, lightfast and whale-fast tones. When dry, they appear gray, more or less dark powders that are concentrated in sulfuric acid with greenish ones Dissolve until bluish in color. The products made from non-sulfonated gallocyanines have both acidic and basic character: with the acids they form salts, which are brownish in color in water dissolve and the water-insoluble color bases from their aqueous solutions by adding weak alkalis can be precipitated; these color bases give with caustic alkalis Solutions which more or less oxidize in air.

The connections between formaldehyde and gallocyanins change over time Exposure to water at more or less high temperatures, especially in Presence of acids; in this way they pass into new products, which in water are much more soluble, oxidize rapidly in the presence of alkalis in the air and their solutions in sulfuric acid with moderate addition of an oxidizing agent, such as. B. Brownstone, take on an intense green-blue color. Deliver these altered products when used in printing and dyeing, bluer shades than the formaldehyde-gallocyanin compounds, from which they are derived.

Of course, these modified dyes can be used directly by means of formaldehyde and the gallocyanins can be obtained by using the condensation of formaldehyde

the gallocyanines in the presence of water and an acid and the reaction mixture for a longer time or at higher temperatures heated. If the heating is interrupted - before the change is complete becomes mixtures of the primary compounds and the altered dyes obtained which mixtures, in certain cases, can be used technically advantageously.

Example I.

37 kg of the gallocyanine obtained from nitrosodiethylaniline and gallamic acid are dissolved in 500 l of warm water, 12 kg of 40 percent formaldehyde are added and ^{the mixture is then heated at 100 °} C. for 10 to 12 hours, ie until the liquid has become distinctly yellowish green. It is allowed to cool a little and then the dye is precipitated using 100 kg of sodium chloride. The same stains chrome-stained wool in blue tones.

Example'II.

To 70 1 of water, 100 kg of hydrochloric acid 21 ⁰ Be., 37 kg of the mentioned in Example I Gallocyanins (or the corresponding amount of another Gallocyanins) and 9 kg of 4oprozentiges formaldehyde added. After one to two hours of heating on the water bath, the transformation is complete; 50 kg of caustic soda of 38 ⁰ Be are then added. and then add 20 kg of table salt. Chrome-stained wool is colored yellow-green by the dye obtained.

Example III.

30 kg of oxalic acid are dissolved in 125 l of warm water, then with 37 kg of the in example I indicated Gallocyanins and then mixed with 12 kg of 40 percent formaldehyde. The mixture is heated at 100 ° C until the conversion is complete, i. H. while approximately 6 hours, after which the dye is precipitated with common salt. The latter colors chrome-stained wool in light blue tones.

Example IV.

37 kg of the gallocyanine mentioned in Example I (or the corresponding amount of a other Gallocyanins) become - without external heat supply - ■ more concentrated in 120 kg Dissolved sulfuric acid; then - with thorough stirring - 8 kg of 40% are gradually added Formaldehyde added. After 2 to 3 hours, the reaction mixture is poured into 600 l of water, the 150 kg of common salt contain; after cooling, the dye is filtered off. This dyes chrome-stained wool yellow-green.

Example V. ■>

37 kg of the gallocyanine given in Example I are placed in 70 l of warm water and the mass with 100 kg of hydrochloric acid of 21 ° Be. and then 16 kg of 40 percent formaldehyde were added. The mixture is heated to 90 ^° C. and after some time 500 1 of salt water are added. After cooling, the dye is filtered off. The same dyes chrome-stained wool green.

Example VI.

To 37 kg given in Example I and 501 Gallocyahins warm water, 100 kg of hydrochloric acid 21 ⁰ Be. and then added 4 kg of 40 percent formaldehyde. The mixture is heated at 100 ^° C. until the conversion is complete, and the dye is precipitated by pouring the reaction mass into 500 1 of salt water. Chrome-stained wool is dyed indigo blue by the same.

Example VII.

33 kg of from nitrosodimethylaniline and Gallamic acid obtained gallocyanins are in 110 kg sulfuric acid of 66 ° Be. dissolved and the resulting solution gradually, with good stirring, with 9 kg of 40 percent Formaldehyde added. After some time, the reaction mixture is in 600 l of salt water poured and, after cooling, the deposited dye filtered off and washed. Same creates a bluish green on chrome-stained wool.

Example VIII.

37 kg of one of the dyes obtained according to the preceding examples are converted into 400 l of water and 40 kg of hydrochloric acid of 21 ^° Be. added and then the mass boiled for 20 hours or heated ^{under pressure at 125 ° C. for 6 hours.} After cooling, the dye is precipitated by adding sodium chloride and then filtered off. It dyes chrome-stained wool blue.

Of course, the same dye is obtained if 37 kg of the one used in the examples Gallocyanins are dissolved in 400 l of warm water, the resulting solution with 40 kg of hydrochloric acid and 9 kg of 40 percent Formaldehyde, added, then heated at 100 ° C. for more than 20 hours and finally heated the dye is precipitated with common salt.

Example IX.

The same dye as in Example VIII can be obtained by using the hydrochloric acid leaves out, on the other hand longer or heated to higher temperatures, or by the

Hydrochloric acid with other acids (including organic acids) or with organic salts, such as aniline chlorohydrate, hydrochloric acid dimethylaniline, etc., or by mineral salts, such as Zinc Chloride, Zinc Sulphate, Calcium Chloride, Magnesium Chloride, Sodium Sulphate, etc., replaced.

Characteristic reactions of the dyes of Examples I to VII.

Aqueous solution yellowish.

Aqueous solution with the addition of:

a) soda acetic acid greenish precipitate;

b) caustic soda. brownish precipitate;

c) hydrochloric acid turns pink;

d) Hydrochloric acid and sodium nitrite intensely fuchsin red.

Sulfuric acid solution pale blue-green.

Sulfuric acid solution with the addition of:

an oxidizing agent, e.g. B. Mangandiox) ^ .. turns into gray.

Characteristic reactions of the dyes of Examples VIII and IX.

Aqueous solution. brownish.

Aqueous solution with the addition of:

a) soda acetic acid greenish precipitate;

b) Sodium hydroxide brownish precipitate, the 70

oxidizes in air;

, c) hydrochloric acid pink color;

d) Hydrochloric acid and sodium nitrite intensely fuchsin red.

Sulfuric acid solution. . . pale purple;

with the addition of an oxidizing agent,
z. B. Mang-andioxvd intense blue.

Claims (2)

Patent Claims:
I. Process for the preparation of new dyes which color from blue to yellowish green, consisting in that gallocyanin dyes are treated with formaldehyde in a suitable neutral or acidic medium. at temperatures of
be treated. If the dyes of Examples VIII and IX still contain traces of the original ones 35 dyes, the reactions are somewhat impaired and are not quite as clear. 2. Conversion of the products obtained according to claim 1 in more water-soluble and blue (from blue to green) coloring agents by mixing these products with water possibly in the presence of acids 100 to 200 ° C.