DE74690C - Process for the preparation of blue basic dyes from nitrosodialkyl-m-amidophenol and m-diamines of the benzene series - Google Patents

Description

IMPERIAL

PATENT OFFICE.

m-diamines of the benzene series.

In patent specification No. 62367 and its additives it was shown that salts of Nitroso derivatives of aromatic amines or from chlorimides in combination with dialkyl mamidocresol or phenol new green-blue basic dyes can be obtained.

It was now natural to try whether these dyes are not also the other way around Nitrosodialkyl-m-amidophenols and monamines of the benzene series.

On the basis of the usual theoretical ideas, for example the blue dye from nitrosodimethylaniline and dimethyl-m-amidophenol is identical be with the dye from nitrosodimethyl-mamidophenol and dimethylaniline. It has it has been shown, however, that the monamines of the benzene series (aniline, dimethylaniline, ethyl-otoluidine) either not reacting at all or only reacting in traces in the desired sense.

On the other hand, the interesting result has been found that m-amido-substituted aniline or m-amido-substituted dimethylaniline, generally m-diamines of the benzene series, again of formation blue dyes are capable.

To represent the dyes after this In the process, the respective components are heated, expediently using the same components Molecule, in a suitable solvent, such as alcohol, glacial acetic acid, etc. From the reaction product The easiest way to isolate the dye is to take it from the aqueous or weakly acidified solution impurities due to fractionated additive of sodium acetate, soda and the like separated and the filtrate with table salt and Chlorine zinc falls. The cleaning is repeated if necessary.

Examples:

1. 2 kg of hydrochloric acid nitrosodiethyl-m-amidophenol are mixed with 1 kg of m-toluenediamine and 5 l of alcohol until the dye has formed warmed up. It is then boiled well with water, filtered, and the filtrate falls with it Table salt and zinc chloride and cleans the dye by dissolving it.

2. 3 kg of hydrochloric acid nitrosodimethyl-m-amidophenol are mixed with 2 kg of m-amidodimethylaniline and ι ο 1 glacial acetic acid warmed on the water bath until the end of the reaction. Man boil the mass with water, filter it, clean the solution with sodium acetate, and precipitate it Then dye it with table salt and zinc chloride.

The dyes obtained are of a basic, in part even strongly basic, nature, so that their solutions are not, or only partially, precipitated by sodium acetate or soda. Your chlorine hydrates respectively. Chlorine zinc double salts dissolve easily in water. Both properties distinguish the dyes characteristically from the nile blue of Patent No. 45268 prepared from a- naphthylamine and nitrosodiethyl-m-amidophenol; minor

Solubility of both the chlorohydrate and the sulfate is technically worthless and therefore worthless at all is not the subject of the patent claim. From the aqueous solution of the Nile blue falls Soda instantly eliminates the free base in red flakes; furthermore the Nile blue dissolves in

concentrated sulfuric acid with an orange-yellow color, and from the aqueous solution of the Sulphate precipitates the insoluble hydrochloric acid with concentrated hydrochloric acid.

In contrast, our new dyes behave as follows:

Dye from: Solution in
more concentrated
sulfur
acid: At the
Dilute
with
Water: Chlorohydrate
respectively
Zinc chloride
double salt
dissolves
in water: From the
water
solution
falls lye: precipitation
dissolves in
Ether: The watery
solution
will with
more concentrated
Hydrochloric acid: Nitrosodimethyl-m-amido-
phenol and m-toluylene
diamine green ) tepid solution easy with
pale color tan
Flakes yellow with
more yellowish
Fluorescence gray-blue Nitrosodiethyl - m - amido-
phenol and m-toluylene
diamine reddish green ilaue solution easy with
blue color blueness
Flakes, in
noticeable. light
brownish yellow-red with
redder
Fluorescence gray, little
intensive Nitrosodimethyl-m-amido-
phenol and m-amido
dimethylaniline blackish
violet > tepid solution easy with
blue color purple
Flakes yellow with
redder
Fluorescence a little grayer Nitrosodiethyl-m-amido-
phenol and m-amido
dimethylaniline blackish
violet ilaue solution easy with
blue color blue
Precipitation yellow-red with
redder
Fluorescence grayer Nitrosodimethyl-m-amido-
phenol and m-amido
diethylaniline green ) tepid solution easy with
blue color blue
Precipitation yellow with
more yellowish
Fluorescence grayer Nitrosodiethyl-m-amido-
phenol and m - amido
diethylaniline blackish purple, then
blue solution easy with
blue color bluish
Precipitation yellow with
redder
Fluorescence reddish gray Nitrosodimethyl-m-amido-
phenol and m-ethyl
amidodimethylaniline blackish blue solution easy with
blue color purple
Precipitation yellow with
more yellowish
Fluorescence grayer Nitrosodiethyl - m-amido-
phenol and m - ethyl
amidodimethylaniline violet blue solution easy with
blue color blueness
Flakes yellow with
redder
Fluorescence : Gray Nitrosodimethyl-m-amido-
phenol and m-benzyl
amidodimethylaniline greenish red blue solution easy with
blue color purple
Flakes yellow-red with
rother
Fluorescence greenish Nitrosodiethyl - m-amido-
phenol and m-benzyl
amidodimethylaniline greenish
violet blue solution easy with
blue color purple
Flakes yellow-red with
redder
Fluorescence greenish Nitrosodimethyl-m-amido-
phenol and m - ethyl
amidodiethylaniline greenish
black blue solution easy with
blue color purple
Flakes yellow with
more yellowish
Fluorescence greenish gray Nitrosodiethyl - m-amido-
phenol and m-ethyl
amidodiethylaniline reddish gray blue solution easy with
blue color purple
Flakes yellow-red with
yellow-other
Fluorescence violet gray Nitrosodimethyl-m-amido-
phenol and m - benzyl
amidodiethylaniline green blue solution easy with
blue color purple
Flakes yellow-red with
redder
Fluorescence -blue gray,
little
intensive Nitrosodiethyl - m-amido-
phenol and m-benzyl
amidodiethylaniline reddish
violet blue solution easy with
blue color blueness
Flakes yellow-red with
rother
Fluorescence greenish,
little
intensive

Dye from: Solution in
more concentrated
sulfur
acid: At the
Dilute
with
Water: Chlorohydrate
respectively
Zinc chloride
double salt,
dissolves
in water: From the
water
solution
falls lye: precipitation
dissolves in
Ether: The watery one
solution
will with
more concentrated
Hydrochloric acid: Nitrosodimethyl-m-amido-
phenol and m-amidodi-
methyl-p-toluidine ■ green purple, then
blue solution easy with
blue color red-brown
Flakes yellow-red with
weak
yellower
Fluorescence a little grayer Nitrosodiethyl - m-amido-
phenol and m-amidodi-
methyl-p-toluidine greenish
violet purple, then
blue solution easy with
blue color red-brown
Flakes yellow-red,
almost without
Fluorescence Gray Nitrosodimethyl-m-amido-
phenol and m-benzyl
amidodimethyl-p-toluidine greenish red blue solution easy with
blue color red-brown
Flakes yellow-red,
almost without
Fluorescence greener Nitrosodiethyl - m-amido-
phenol and m-benzyl
amidodimethyl-p-toluidine greenish red blue solution easy with
blue color rothe
Flakes red,
almost without
Fluorescence greenish gray Nitrosodimethyl-m-amido-
phenol and tetramethyl
m-phenylenediamine greenish
violet blue solution easy with
blue color blueness
Flakes yellow-red with
rother
Fluorescence grayer Nitrosodiethyl-m-amido-
phenol and tetramethyl
m-phenylenediamine greenish
red - purple blue solution easy with
blue color blueness
Flakes yellow-red with
rother
Fluorescence reddish gray Nitrosodimethyl-m-amido-
phenol and tetramethyl
m-tolylenediamine greenish red blue solution easy with
blue color purple
Flakes yellow-red with
rother
Fluorescence Gray Nitrosodiethyl - m-amido-
phenol and tetramethyl
m-tolylenediamine greenish red blue solution easy with
blue color purple
Flakes yellow-red with
rother
Fluorescence Gray Nitrosodiethyl - m-amido-
phenol and dibenzyl-m-
toluenediamine greenish red blue solution easy with
blue color purple
Flakes red with
rother
Fluorescence greenish gray.

Claims (1)

Patent claim: Process for the preparation of blue basic dyes, their chlorohydrates respectively. Chlorine zinc double salts are readily soluble in water, consisting in the fact that salts of nitrosodimethyl-m-amido.phenol or nitrosodiethylm-amidophenol with m-diamines of the benzene series in the presence of a suitable solvent condenses and for the removal of contaminating by-products either the Reaetionsproduct systematically dissolves in water and precipitates again, or from its aqueous solution neutral or weakly acidified solution through the weaker basic components fractionated additive "of sodium acetate, soda and the like is separated and from the filtrate the blue dye precipitates.