DE118393C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- JVl 118393 - CLASS 22 c.

SHARED COMPANY

Patented in the German Empire on June 6, 1900.

The present invention relates to the preparation of leukogallocyaninsulfonic acids, as well as of Gallocyaninsulfonic acids, some of which provide valuable dyes.

As is known, the BEZW by condensation of nitrosodimethylaniline. of Nitrosodiethylaniline obtained with gallic acid, gallic acid ethers or gallamic acid Gallocyanine neither in the cold nor in the heat by the usual suI-furirmittel, such as sulfuric acid, sulfuric anhydride, etc., sulfonate. The only previously known means of representing this Bodies, which incidentally have technical disadvantages, are described in patent specification 80434 been.

The unexpected fact has now been discovered that the leuco derivatives of these same gallocyanines obtained by the process of Patent Specification 108550 can be sulfurized directly by the usual process if the sulfurization is carried out at a low temperature. Concentrated sulfuric acid and fuming sulfuric acid can be used for this purpose, but the reaction proceeds more smoothly if the sulfuric acid monochlorohydrin 5 O ₂ - OH - Cl is used. The leukogallocyaninsulfonic acids obtained in this way are in and of themselves dyes, of which those derived from gallamic acid have the valuable property of staining chrome-stained goods in much bluer tones than can be achieved with the original gallocyanins, that is, their starting products. The leukogallocyaninsulfonic acids have the ability to stain chrome-stained cotton, from which the chrome stain has been etched away in places, without staining the stain-free areas. In alkaline solutions these leucoallocyanine sulfonic acids oxidize very rapidly in air; If an acid and common salt are added to these oxidized solutions, the corresponding gallocyanine sulfonic acids are precipitated; Of course, this oxidation can also be carried out with other oxidizing agents than air.

The gallocyaninsulfonic acids easily prepared by the present process are partly valuable dyes which can be used in coloring or printing Provide color tones that match those obtainable with the corresponding leukogallocyanine sulfonic acids are similar, but show greater intensity and greater luster; like the latter, they have no affinity for unheated cotton, but are soapy on chrome-stained wool or cotton Nuances.

Example I.

Representation of the sulfonic acid of the leuco derivative of Corei'n 2R (which latter by the action of gallamic acid on hydrochloric acid nitrosodiethylaniline or hydrochloric acid diethylamidoazo-

benzene is obtained).
10 kg of the leukocore'in 2 R obtained by the process of patent specification 108550 are gradually introduced into 60 kg of 100 percent sulfuric acid with thorough stirring at normal temperature, so that no heating occurs; then the whole thing is left to itself until a sample, by adding water, separates a copious precipitate; the operation takes about 4 to 6 days. The product obtained is poured into 1000 liters of ice water, after a few hours filtered, pressed and brought to the dye content desired for use.

Example II.

Representation of the sulfonic acid of the leuco derivative of gallamine blue (which the latter due to the action of gallamic acid on hydrochloric acid nitrosodi

methylaniline is obtained).
ι ο kg of the leuco derivative of gallamine blue obtained according to the details of patent specification 108550 are, taking the same precautionary rules as in Example i, dissolved in 20 kg of 100% sulfuric acid and then gradually with vigorous stirring with 20 kg of sulfuric acid monochlorohydrin SOj. O H-Cl added. The end of the reaction, which lasts about 2 to 3 days, is recognized as under I, and the product is now added to 1000 liters of ice water and the rest of the procedure is as above.

Example III.

Representation of the sulfonic acid of the leuco derivative of Prune (which latter by handling the; Gallic acid methyl ether with nitrosodimethylaniline chlorohydrate is obtained).

ι ο kg of according to the specifications of the patent specification 108550 obtained leukoprune are gradually stirring vigorously and without Warming added to 40 kg of sulfuric acid monochlorohydrin; sets after 1 or 2 days gradually and with external cooling of the reaction vessel 2 kg of 50 percent sulfuric acid and then pour the whole thing into 800 l of ice water, add 22 kg of sodium hydrate and 100 kg Add common salt and the rest of the procedure as in the previous examples.

Example IV.

Conversion of a leukogallocyaninsulfonic acid into gallocyaninsulfonic acid.

The leukogallocyaninsulfonic acid obtained according to one of the preceding examples is in 500 liters of water are suspended in a vat of not too small a diameter and then passed through Dissolved addition of 20 kg of a 25 percent sodium hydrate solution. The solution is stirred vigorously in the air until you no longer notice any increase in the intensity of the color, salt out under event. Neutralization of the excess alkali by adding hydrochloric acid, filters, praises and brings the product thus obtained in the form of the sodium salt to the for the Use desired dye content.

The characteristic of the new leukogallocyaninsulfonic acids and gallocyaninsulfonic acids Reactions are compiled in the table below.

dye solution
in
Alkalis solution
in
Alkalis +
acetic acid solution
in
Alkalis +
hydrochloric acid solution
in
more concentrated
sulfuric acid Leukogallo cy aninsu.lf0 -
acid changes color on the
Air (immediately)
red-violet turns blue becomes reddish and
run one
weak down
shock arise pale purple
dichroic
Solution that through
ZuSaIZ ₁ one
Oxidizing agent
turns intense blue Gallocyanine sulfonic acid greyish red
violet turns grayish blue
without education
one
Precipitation becomes red and
run one
Precipitation ent
stand blue solution

dye solution
in
Alkalis solution
in
Alkalis +
acetic acid solution
in
Alkalis +
hydrochloric acid solution
in
more concentrated
sulfuric acid Leucoprunesulfonic acid stains
the air immediately
brown purple turns gray-blue becomes brownish red
forming a
Precipitation pale purple
dichroic
Solution that through
Addition of one
Oxidizing agent
turns intense blue Prunesulfonic acid brownish red
solution becomes bluish black,
without the
Formation of a
Precipitation too
cause becomes brownish red
under education
one
strong down
blow blue solution Leucogallamine blue
sulfonic acid changes color on the
Air immediately
violet turns blue turns purple and
forms
a weak one
Precipitation pale purple
dichroic
Solution that through
Addition of one
Oxidizing agent
turns intense blue Gallamine blue sulfonic acid purple solution turns blue without
education
one down
blow. becomes purple under
education
one down
blow blue solution Sulfonic acid des
Leuco derivative des
Core'in 2 R changes color on the
Air immediately
blue-violet turns vivid blue turns red-violet
under education
one
Precipitation pale purple
dichroic
Solution that through
Addition of one
Oxidizing agent
turns intense blue Sulfonic acid des
Core'in 2 R vivid blue-violet
solution turns vivid blue
without education
one
Precipitation turns red-violet
under education
one
Precipitation blue solution.

Claims (2)

Patent Claims: Process for the preparation of leukogallocyaninsulfonic acids, consisting in that the according to the information of the D. R. P. 108550 available leukogallocyanine at lower Temperature are treated with sulfurizing agents. 2. Conversion of the leukogallocyaninsulfonic acids obtained by the process of claim 1 in gallocyanine sulfonic acids by oxidizing them in an alkaline solution by means of air or some other suitable solution Oxidizing agent.