DE118392C - - Google Patents

Description

IMPERIAL Jk

PATENT OFFICE

The purpose of the method is to present a new class of azo dyes, which due to the presence of strongly basic groups are capable of pickling cotton with tannins to dye, but not the acid sensitivity of most basic azo dyes demonstrate.

In order to produce acid-insensitive basic azo dyes, the following have hitherto been used Taken paths.

Substances were chosen as components that were not in one of the basic groups aromatic nuclei, but contained in a side chain (see patent specifications 70678 and 105202), or diazo compounds of the amidoammonium bases were used one combined with amines and phenols (patents 87257, 87584, 95530, etc.). Man has also combined diazo compounds of dialkyl-ρ diamines with phenols and then the azo dyes converted into the corresponding ammonium dyes by means of haloalkyl (Patent 87585). Finally, there are oxyammonium bases of the naphthalene series with diazo compounds combined (patents 90310 and 97244).

The present process, a heretofore unknown class of ammonium azo dyes To represent, consists in that the dimethyl - m - toluylenediamine is the following Constitution:

CH,

NH ₂

N (CH,),

combined with diazo compounds and the resulting azo dyes by treatment with Halal.kylen or similarly acting agents converted into ammonium azo dyes. Here the surprising fact has been shown that at first only the dimethylamido group is converted to the ammonium group while the amido group remains intact; first when using a considerable excess of the alkylating agent and supported an alkylation in the amido group then takes place at higher temperatures. the In most cases, the formation of the ammonium compound is very easy with ordinary Temperature in front of you; if dimethyl sulphate is used as the alkylating agent, it takes place the formation of the ammonium compound even almost instantaneously and under heating, so that it is advantageous when used this alkylating agent to carry out the reaction with cooling.

The dyes prepared by this process dye tannin cotton in strong colors Tones that go from clear yellow to orange and red to purple. The colorations are excellent Authenticity. As explained above, the dyes also receive a free diazotizable one Amido group in the same nucleus as the ammonium group and can therefore can be converted into other dyes by diazotizing and further combining.

The starting material used is dimethylm-toluenediamine is formed by nitriding of dimethyl-ρ-toluidine and reducing the Nitro compound in the usual way

obtain. Dimethyl-m-toluenediamine is easily soluble in most organic solvents, and crystallizes from ligroin in needles of the scribe that are united in tufts. 52 ⁰ C

Example I. 25.4 kg of the by combining diazobenzene with the equimolecular Amount of dimethyl-m-toluenediamine and treatment with soda obtained color base are dissolved in 100 kg of nitrobenzene and at Ordinary temperature - with moderate cooling to avoid any substitution of the amido group to exclude - 13 kg of dimethyl sulfate - added. The liquid heats up itself and the ammonium methyl sulfate formed separates out as a crystal pulp. After short Time is the end of the reaction, which is evident from the solubility of the dye in soda solution can convince. The nitrobenzene is distilled off with steam, and the moderately warm solution is made weak with soda alkaline and filter it to separate any unconverted dye. To on cooling, the benzene-azo amidotoluylene trimethylammonium carbonate separates in orange crystals.

The dye is very easily soluble in water with a yellow color; he dyes tannin cotton yellow.

Azo base of Example II. 3 kg, of a- Diazonaphtalin and dimethyl-m-toluylenediamine be digested at gewöhnlicher.Temperatur with 5 kg of ethyl bromide. When the addition is complete, the excess ethyl bromide is distilled off and the dye, dissolved in dilute hydrochloric acid, is precipitated with common salt or zinc chloride. It dyes tannin cotton orange.

Example III. 53.5 kg of diazo base made from tetrazoditolyl and dimethyl - m - toluylenediamine dissolved in 250 kg of nitrobenzene in the heat, added after cooling 26 kg of dimethyl sulfate and nitrobenzene by means of steam from the crystalline pulp, which soon arises removed. The sulfate formed by the dye separates in small crystals the end; it can be converted into chloride by hydrochloric acid and common salt. The dye forms a reddish brown powder; he dyes tannin cotton brick-red.

Example IV. Benzene-azo-α-naphthylamine is diazotized and with dimethyl-m-tolylenediamine combined. 42 kg of the base, which has been deposited with soda and has been dried well, is dissolved in 200 kg of nitrobenzene and mixed with it 13 kg of dimethyl sulfate are methylated. After blowing off the nitrobenzene, the dye becomes completely salted out of its red solution with table salt. The dye forms a dark powder; it dyes tannic cotton garnet red.

In the table below we present the properties of a number according to our method representable amidophenyltrimethylammonium azo dyes together:

Diazotized base

Appearance

of the dry dye color

the watery
solution

colour

the solution in
cone. sulfuric acid

coloring
on tannin
cotton

aniline

o-tiuidin

p-toluidine

m - xylidine

p-xylidine

ψ-cümidin

ο - anisidine

p-anisidine

ρ - phenetidine

p-amidodiphenyl ether ..

ο - chloraniline

m - chloraniline

ρ - chloroaniline

m - nitroaniline

ρ - nitroaniline

Acetyl-ρ-phenylenediamine

orange crystals orange powder

brown powder orange needles

orange-brown powder

orange-colored crystals

green-brown powder

brown powder light brown crystal powder

red-brown powder

Brick-red crystal powder

red-brown powder

red-brown powder

yellow-brown powder

purple needles

yellow-brown crystal powder orange
yellow

yellow
»

η
orange

red

Brown

bluish-red

cherry red.
red orange
yellow

j?

orange

bluish-tinted red
orange

yellow
golden yellow

yellow-orange

golden yellow

reddish yellow

golden yellow

j;

orange

orange yellow

brownish yellow

reddish yellow

orange yellow

orange
orange yellow

Appearance colour colour yy coloring Diazotized base of the watery the solution in
cone. sulfur on tannin dry dye solution acid yy cotton a. - naphthylamine brownish red powder yellow blue blue orange β - naphthylamine red-brown powder yy purple brown yellow-orange Acetyl- ι · 4- naphthylene- , diamine shiny green black yellow-brown violet brown orange 2 ■ 7 - Naphthylenediamine ... powder
greenish black bronze bordeaux yy orange brown shiny powder Benzidine dark green, bronze red-violet brownish red shiny crystalline
powder j) orange Tolidine brownish red powder same red violet ziegelioth Dianisidine black crystalline
powder &
brownish red blue-violet dull red Amidoazobenzene purple brown powder orange blue brau η orange Aniline - azo - m - amido - p- cresol methyl ether brown-black powder red yy Scarlet fever Aniline - azo, - a. - naphthyl - amine dark purple powder green garnet red 0 - toluidine - azo - α - naph- yy & tvlamin. . ... purple powder red ρ - toluidine - azo - a - naph yy tylamine purple brown powder ρ - phenylenediamine azo - yy yy a - naphthylamine greenish black, bronze violet red cloudy purple shiny crystalline powder ρ - phenylenediamine - azo -
m - amido - ρ - cresol - methyl ether greenish black, bronze dirty red dirty shiny crystalline violet. powder

Claims (1)

Patent claim: Process for the preparation of amido-ammonium azo dyes, consisting in that diazo compounds are mixed with dimethyl-mloluenediamine (CH ₃ : NH ₂ : N (CH ₃ ) ₂ = 1: 2: 4 ^ combined and the resulting azo dyes treated with molecular quantities of methyl halogen or dimethyl sulfate at ordinary temperature or at moderate heat.