DE57452C - Process for the preparation of green to blue azo dyes of the tripbenylmethane series - Google Patents

Description

IMPERIAL

PATENT OFFICE.

The m- and p-amidotetrasubstituted diamidotriphenylmethanes can be diazotized with ease, and the resulting diazo compounds can be combined with dye components to form new azo bodies which, by oxidation, form a new series of lead green to blue coloring agents called azotriphenylmethane - dyes should be.

Depending on whether one starts from the m- or p-amido compounds, one obtains green or blue to deep blue-black coloring matter.

Of the triamidotriphenylmethane derivatives (hereinafter is diamidotriphenylmethane briefly referred to as "D.") so far, the following are considered usable in the present proceedings found:

m- and p-amidotetramethyl-D.,

m-Amidodimethyldiethyl-D.,

m-Amidotetraethyl-D.,

m-Amidodiethyldibenzyl-D.

Among the dye components to be used heretofore, the following have been found to be proven most useful:

Salicylic acid, m-cresol carboxylic acid (o-oxyp-toluic acid, COOHiOH: CH ₃ = 1: 2: 4);

α- and ß-naphtholecarboxylic acid, a-ß-dioxynaphthalene (ß-naphthohydroquinone), i-8-dioxynaphthalene.

Since the usual azo dyes of the components listed here have stain-coloring properties the latter are also peculiar to the products of this patent.

The dyes of the m-series with salicylic acid and cresol carboxylic acid dye wool pre-stained with chromium yellow-green, with naphthol carboxylic acids dark olive green; those of the ρ series with salicylic acid and cresol carboxylic acid green-blue to green-black, with a- and ß-naphtholcarboxylic acid, 1 · 8-dioxynaphthalene and α · ß-dioxynaphthalene, on the other hand, blue.

All of these dyes are more or less sparingly soluble in water and come from this best to use in the form of a fine paste.

Example I.

34.5 kg m-Amidotetramethyldiamidotriphenylmethan are dissolved with 33 kg of hydrochloric acid (33 per cent.) In 200 1 of water, cooled to 0 ⁰ C. and treated slowly with stirring with a solution of 7 kg of sodium nitrite. The resulting diazo compound is slowly introduced into a solution, cooled to 0 ° C., of 14 kg of salicylic acid in 120 kg of sodium hydroxide solution (33 pCt.) And 100 1 of water, while stirring, and the mixture is left to stand ^{at 0 to 4 ° C. for 24 hours.} Then one warms up gently and either the deposited yellow azotriphenylmethane leuco base is filtered off, dried and oxidized in acetic or hydrochloric acid solution with the calculated amount of lead peroxide, or better, the mixture obtained directly, after dilution with water, is supersaturated with 200 kg of hydrochloric acid, whereby the Azoleukobase easily goes into solution, filtered if necessary, and transmits at a temperature of 30 ⁰ C. 84 kg Bleisuperoxydpaste (28 procentig) with stirring a.

The liquid is then heated up to approx. 80 ^° C., which emerges in brown flakes.

The separated dye is filtered off hot and washed out with hot saline solution.

The dye thus obtained is dried and finely ground or, better, directly as a paste used. It is very heavy in cold water, and easy in hot water, especially with the addition of Acetic acid, soluble. Glacial acetic acid dissolves it easily.

On wool that has been pre-stained with chrome, it creates a beautiful yellowish-green color that is fast to light and milled.

Example II.

34.5 kg of p-amidotetramethyldiamidotriphenylmethane are diazotized exactly as in Example I. and the diazo solution in a solution of 20 kg of a-oxynaphthoic acid in 120 kg of sodium hydroxide solution (33 pct.). The brown precipitate is filtered off after a few hours, dried, dissolved in 200 l of strong acetic acid, 84 kg of lead peroxide (28 percent) added, mildly warmed; then the lead is precipitated with 20 kg of 50 percent sulfuric acid and filtered.

The dye precipitates as soon as the filtrate is diluted with water; completely happens this is due to the addition of table salt. It is filtered off and used directly as a paste. Chrome-stained wool stains the same blue.

If you replace the two components in the above examples with others, you get you get the following results:

Salicylic acid

m-cresol carboxylic acid

m-amidotetramethyl-D

p-amidotetramethyl-D

m-Amidodimethyl diethyl-D.

m-Amidotetraethyl-D

m-Amidodiethyldibenzyl-D ..

yellow-green
green Blue
yellow-green
yellow-green
green (weak)

α-naphtholecarboxylic acid

ß-naphtholecarboxylic acid

yellow-green
green Blue
yellow-green
•yellow-green
green (weak)

ß-naphtholecarboxylic acid

(from the melting point

216 ° C.)

m-amidotetramethyl-D.
p-amidotetramethyl-D.

dark olive green blue

dark olive green
blue

greenish black
greenish blue

p-amidotetramethyl-D. and α · ß-dioxynaphthalene green-blue

p-amidotetramethyl-D. And 1 ■ 8-dioxynaphthalene blue.

Claims (1)

Patent claim: green until in it Diazo compounds Procedure for the representation of
blue azotriphenylmefhan - dyes,
insisting that the
of the following leuco bases of the m- and p-amidotetrasubstituted diamidotriphenylmethanes:
a) m- and p-amidotetramethyl-D., m-Amidodimethyldiethyl-D., m-Amidotetraethyl-D., m-Amidodiethyldibenzyl-D. with salicylic acid or the m-cresol carboxylic acid [COOH: Oi ^ CÄ, = 1: 2: 4), b) m- and p-amidotetramethyl-D. with α-naphtholecarboxylic acid, ß-naphtholecarboxylic acid of patent No. 31240 or patent No. 50341 (Schm.-P. 216 ⁰ C), c) p-amidotetramethyl-D. with α · ß-dioxynaphthalene (ß-naphthohydroquinone) or 1 ■ 8-dioxynaphthalene combined and oxidized the azo dyes obtained.