DE77452C - Process for the preparation of blue dyes of the gallocyanine group - Google Patents

Description

IMPERIAL

PATENT OFFICE

Phenols, sulfonic acids and dialkyl-m-amido derivatives these enter into connections with the gallocyanine dyes when they are in brings together suitable solvents and the reaction, possibly by heating End leads. In the majority of cases, leuco bodies, weakly colored compounds, are formed which change into blue to blue-violet dyes by oxidation, from bluer shade than the starting product. As a result of this property, these condensation products can can be used in fabric printing by being oxidized on the fiber. To the coloring character of the oxidized The products of condensation can be better brought to gelation in sulphonic acids be transferred. This latter reiction is of course no longer necessary if nan assumed a phenol sulfonic acid instead of phenol. Finally it can do that too üondensationsproduct of the phenol with the jallocyanin dye first into a sulfonic acid and the latter are oxidized.

i. Example. Gallocyanin + resorcinol.

Add to a concentrated aqueous solution of 1 part resorcinol, which is mixed with

Parts of commercially available hydrochloric acid of 20 to ι ° B. is added, 2 parts of gallocyanin in Mold and stir the mixture, which thickens quickly anyway. To completion The reaction is warmed to water bath temperature for some time. The dark purple one The coloring of the gallocyanine has now completely disappeared and the new condensation product excreted in the form of a green crystal pulp. It is diluted with water and washed to remove the precipitate free hydrochloric acid and easily soluble by-products.

The newly formed body is somewhat soluble in water with a yellow-green color, much lighter in the presence of alkalis, and it then very quickly oxidizes to an intensely bluer color Coloring. These properties are used to convert it into its oxidation product, which is precipitated in blue-violet flakes by dilute acids.

This oxidized substance still has scarcely any coloring character; better for the same To bring them to bear, they are converted into a sulfonic acid. It is heated by precipitation with acid obtained from the oxidized product and dried precipitate with about 5 parts of sulfuric acid monohydrate a few hours at water bath temperature. The sulfonic acid thus obtained is insoluble in water and can be isolated in the usual way; it forms a dye that forms varnishes with metal oxides of great importance bluer shade than gallocyanin.

The same result is obtained when one uses the green condensation product just described first converted by resorcinol and gallocyanin into a sulphonic acid and then this oxidized to dye, or by using an oxidizing agent, e.g. B. Iron oxide, added, or finally by using a stronger sulfuric acid which at 100 ° has an oxidizing and sulphurizing effect at the same time.

2nd example. Gallocyanin -f- Schäffer'sche

ß-naphthol sulfonic acid.

The simplest way of carrying out this reaction is to first do the Schaffer's acid is produced in the usual way, then after sulfurization has taken place of the ß-naphthol and, after the mass has cooled, the gallocyanin in powder form, in the proportion of 300 parts of gallocyanine to 220 parts of that for formation Naphthol used by ß-naphthol sulfonic acid. It is warmed up weakly for some time to the disappearance of the original color of the gallocyanine, and then add the mixture in water. Since the compound formed is somewhat soluble in acidic and pure water it is best to wash off the excess sulfuric acid with salt water. In alkali dissolved, the leuco body is oxidized to dye by the oxygen in the air, and afterwards precipitated again with dilute acid. It dyes chrome-stained wool in a lively blue-violet shade.

3rd example. Gallocyanin - \ - pyrogallol.

200 parts of pyrogallol are dissolved cold in 1200 parts of 80 pCt sulfuric acid. Monohydrate and introduces 300 parts of gallocyanine into the solution, avoiding heating. Is a complete color change from blue If it turns brown-green, it is diluted with water and the procedure is continued as in the example ι specified. The dye dyes cotton, which is pre-stained with metal oxides, in blue tones of a less pure shade than the resorcinol derivative.

4th example. Gallocyanin -f- dimethyl-

m-amidophenol.

The aforementioned condensation is best achieved with 300 parts of gallocyanine and 200 parts of dimethyl-m-amidophenol in the presence of 900 parts of hydrochloric acid, as in Example 1 indicated, made. The reaction product is soluble in acidic water; in order to isolate it, the free acid must be blunted. Otherwise the procedure is same as given in Example 1.

The colorations obtained with this dye are identical to those from Example 3 but a little more red-violet.

-5. Example. Resorcin + Prune (gallocyanin, obtained from gallic acid methyl ether and hydrochloric acid nitrosodimethylaniline) or GaIlam in blue (Gallocyanin, obtained from GaIlamic acid and hydrochloric acid nitrosodimethylaniline).

The way in which these connections can be made is similar to that in Example 1, only it is more advantageous to condense more resorcinol to be used: on 3 parts of Prune or GaIlaminblau 2 parts resorcinol and 9 parts commercially available Hydrochloric acid, the resorcinol previously dissolved in a little water. The further processing of the Condensationsproductes happens in the same way as indicated in Example 1, and the Coloring properties of the final products obtained are very similar, if not identical, to the obtained with the gallocyanine derivative.

In the examples described, the addition of concentrated hydrochloric acid or of sulfuric acid during condensation (the connection of gallocyanins with phenols) cited; in the same way one means can be replaced by the other without altering the result become, e.g. in example 1 the hydrochloric acid stay away completely or with sulfuric acid of 80 to 90 pCt. Monohydrate to be replaced.

Such changes, however, require the use of slightly different weight ratios between phenol and gallocyanin, and other temperatures as well; remains in principle but the reaction is the same. The specified proportions, condensation agent (such as hydrochloric acid or sulfuric acid) and temperatures should therefore not be the only ones to determine be.

On the characteristics of the condensation products shown and those obtained from them The essential reactions are compiled in two tables, one for the dyes Condensation products, the second for the dyes obtained from them.

re action
i. Example:
Gallocyanin
+ Resorcinol the Co η de
2nd example:
Gallocyanin
+ ß - naphthol-
sulfonic acid
(Schäffer) nsationpr
3rd example:
Gallocyanin
+ Pyrogallol 0 ducts:
4th example:
Gallocyanin
+ Dimethyl- '
m-amidophenol 5. Example:
Prune or
Gallamine blue
+ Resorcinol Solution in cold
water almost unsolvable
lich in pure zu
was difficult
soluble insoluble insoluble almost unsolvable
lich Solution in heifsem
water somewhat soluble
with dirty
greener yellow
coloring a little easier
soluble than in
cold water insoluble insoluble sparingly soluble
with dirty
greener yellow
coloring

i. Example:
Gallocyanin
+ Resorcinol 2nd example:
Gallocyanin
+ β - naphtol-
sulfonic acid
(Schäffer) 3rd example:
Gallocyanin
+ Pyrogallol 4th example:
Gallocyanin
-f- dimethyl-
m-amidophenol 5. Example:
Prune or
Gallamine blue
+ Resorcinol Behavior in a
Dissolution of vinegar
baking soda insoluble sparingly soluble
with dirty
yellow-greener
Color which
in the air
slowly blue
will somewhat soluble
when warming,
with yellow-green
Color on the
Air slowly
turning blue insoluble insoluble Behavior in iopro
centiger soda solution green-yellow color
exercise which
in the air very much
quickly in blue,
transforms green-yellow color
exercise at the
Air quickly in
Blue over
going green solution,
which in air
entry blue
turns purple insoluble green-yellow color
exercise which
in the air very much
quickly in blue
transforms Behavior in baking soda
lye same ver
hold like in
Soda solution same ver
hold like in
Soda solution same ver
hold like in
Soda solution soluble with
dirty
purple color same ver
hold like in
Soda solution Solubility in wine
ghost poorly soluble
with greenish
yellow color insoluble insoluble insoluble ■ poorly soluble
with greenish
yellow color Solubility in ice
vinegar almost unsolvable
lich insoluble insoluble very little sol
lich almost unsolvable
lich Coloring with concen-
treacherous sulfuric acid brownish lo
sung which
when heating
first green, then
greenish blue
and blue-gray
will brown solution;
when heating
it becomes direct
gray-blue brown solution with green
Color soluble brown solution,
when heating
first green, then
green blue and
blue-gray who
dend Addition of traces
Nitric acid for
above solution first brownish yellow,
then bläuroth
and last
red orange ge
colors the brown lo
sung is only
blue then
purple, last
colored red the brown one
Solution will
blue then
brown purple too
last brown the color goes
of green in
Blue, then in
Red brown across the brown one .
Solution will
first blue, then
red and last
red orange Nitric acid alone
.of 40 ⁰ B. Solution of
red violet
colour red violet
solution with red-brown
Color soluble with blue color
soluble red violet
Solution.

R e a c t i 0 the end product 3rd example: c t e: 5. Example: i. Example: 2nd example: Gallocyanin 4th example: Prune or
Gallamine blue Gallocyanin Gallocyanin
4- β - naphthol + Pyrogallol Gallocyanin
+ Dimethyl + Resorcinol + Resorcinol sulfonic acid
(Schäffer) insoluble ¹ y
m-amidophenol insoluble Solution in cold insoluble poorly soluble insoluble water with blue Colour , insoluble insoluble Solution in heifsem insoluble a little easier very difficult water soluble than in soluble with cold water blue purple insoluble coloring insoluble Behavior in solution insoluble with blue insoluble of acetic acid Color soluble Baking soda

ι. Example:
Gallocyanin
+ Resorcinol 2nd example:
Gallocyanin
+ β - naphtol-
sulfonic acid
(Schäffer) 3rd example:
Gallocyanin
+ Pyrogallol 4th example:
Gallocyanin
+ Dimethyl
m-amidopheno.l 5. Example:
Prune or
Gallamine blue
+ Resorcinol ioprocent soda
solution blue solution,
with excess
of soda
violet with little soda
blue, with over
made of soda
violet with dirty
blue color
soluble purple solution blue solution,
violet at.
Excess soda Addition of double
sulphurous
Baking soda to dissolve in
Soda. precipitation
from black-
purple
Flakes, which
soon black
go green Precipitation; the
Precipitation
goes from
black purple
in black green
above ■ greenish
black cases
lung Precipitation; Color
envelope from
Black purple
in black green precipitation
of black
purple
Flakes, which
soon black
go green Behavior in baking soda
lye with purple
brownier
Color soluble same ver
hold like in
Soda solution with brown
green color
soluble purple solution with purple
brownier
Color soluble Solubility in wine
ghost insoluble very difficult
soluble insoluble sparingly soluble
with blue
colour insoluble Solubility in ice
vinegar insoluble very little sol
lich with violet
colour insoluble quite soluble
with purple
colour insoluble Conduct against con-
centered sulfur
acid with green-blue
Color soluble blue-gray
coloring
the solution with blue color
soluble blue solution green-blue lo
sung Adding little
Nitric acid for lo
solution in sulfuric acid the color will
blue at first,
then red and
finally red
orange the color goes
through purple
brown in brown
above the color goes
of blue in
Brown purple,
then in brown
above the solution
becomes red-brown Transition from
Green blue in
Roth, then
Red orange Conduct against con-
centered saltpetre
acid red solution brown purple
coloring
the solution red coloring
the solution brown purple
coloring
the solution red solution.

Claims (6)

Patent Claims: 1. Process for the preparation of new dye formation suitable condensation products through the action of phenols, their sulfonic acids and their dialkyl amido derivatives on gallocyanin dyes. 2. Conversion of the condensation products obtained according to patent claim 1. in blue to blue-violet coloring matter by oxidation of the same and possible sulfurization. 3. Representation of a product suitable for printing purposes according to the process of patent claim 1. BEZW by condensation of resorcinol. Pyrogallol with gallocyanin, Gallamine blue or prune in the presence of suitable solvents. 4. Representation of blue to blue-violet dyes according to the method of the patent claim 2. by oxidation of the after Claim 3. Condensation products obtained and any subsequent sulfurization or by sulfurization of these condensation products, followed by their oxidation. 5. Representation of a blue-violet dye according to the method of patent claims 1. and 2. by condensation of Schä'ffer's ß-naphthol sulfonic acid with gallocyanin, Gallamine blue or prune and subsequent oxidation of the condensation product obtained. 6. Representation of a blue-violet dye according to the method of patent claims 1. and 2. by condensation of dialkylm-amidophenol with gallocyanin, gallamine blue or prune, oxidation of the product of condensation obtained, and any preceding or subsequent sulfurization.