DE146915C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

In the German patent specification 127361 is a method of producing a body similar to aniline black by oxidation a mixture of hydrochloric aniline with m-nitroaniline described. It was now found that not only aniline, but also its homologues, also naphthylamines, paraphenylenediamines, 1-, 2-, 4- and 1-, 2-, 5-To-. luylenediamines, amidophenols and their homologues, amidodiphenylamines, etc. with nitroanilines mixed subject to the action of oxidizing agents, give products in which the one containing the nitro group Core appears to enter the molecular complex of the oxidation product.

The oxidation products of the mixture of amines with nitroamines are thereby produced that z. B. ^,

6.96 parts by weight of p-phenylenediamine,

6.00 - m-nitroaniline,

20.00 - hydrochloric acid conc.,

2.50 - chlorammonium,

8.00 - sodium chloride,

2.00. - copper nitrate

(or a similarly acting salt) can act on each other.

The oxidation products are obtained from mixtures of other amines in an analogous manner and nitroamines are obtained by also depending on the number of amido groups present the amounts of hydrochloric acid and chlorate can be changed accordingly.

In the table below are the most important of these oxidative reactions. products described:

20th Oxidation product
of the mix
from Appearance Solubility of the body in Caustic soda
loproz. Soda solution
ioproz. alcohol
o, 6 percent sulfur
acid conc.
in the
cold sulfur
acid conc.
in the
Boiling heat Aniline + m-nitroaniline black
green
powder hot something
soluble
yellow Red · hot something
soluble
yellow Red hot low
solution
Red soluble
tan;
Water falls
black green soluble
black
green; much
Water dissolves
brownish o-toluidine +
m-nitroaniline
35 black
powder hot
yellow Red
soluble very hot
low lo
sung yellowish hot low
solution
Red soluble
Brown;
Water falls
Brown soluble
Brown
black ; much
Water dissolves
brownish red

Oxidation product
of the mix
₅ - from Appearance Solubility of the body in Caustic soda
ioproz. Soda solution
ioproz. alcohol
göproz. sulfur
acid conc.
in the
cold sulfur
acid conc.
in the
Boiling heat p-toluidine +
m-nitroaniline
10 red-brown
powder hot yellow-red
soluble very hot
low
solution
yellowish hot low
solution
Red soluble
Brown;
Water falls
Brown soluble
Brown; much
Water dissolves
brownish red p-phenylenediamine +
m-nitroaniline brown
powder cold
low
yellow-red
solution hot low
yellow-red
solution hot low
yellow-red
solution yellow-brown
soluble;
Water falls
Brown dirty
blue black
soluble; much
Water dissolves
brownish red p-phenylenediamine +
p-nitroaniline black
brown
powder hot low
solution
yellow Red hot low
solution
yellow Red hot low
solution
yellow Red yellow-brown
soluble;
Water falls
Brown violet
black
soluble; much
Water dissolves
purple α-naphthylamine +
m-nitroaniline Brown
purple
powder hot low
solution
yellow Red hot low
solution
yellow Red hot low
solution
yellow Red yellow-brown
soluble;
Water falls
Brown dark
brown lo
sung; much
Water dissolves
brown, however
not full
constant p-amidophenol +
m-nitroaniline yellow-brown
powder yellow-red
Solution,
However not
Completely hot
partially
• wine red
soluble hot
partially
soluble
brownish red green
Solution;
Water falls
Brown intensive
blue lo
sung; much
Water dissolves
purple p-amidophenol -f
p-nitroaniline
35 black
brown
powder totally hot
soluble
yellow Red hot un
Completely
soluble
yellow-brown hot
partially
soluble
brownish red green
Solution;
Water falls
Brown intensive
blue lo
sung; much
Water dissolves
purple p-amidodiphenylamine +
m-nitroaniline black
powder hot low
solution
brownish red hot low
solution
brownish red hot low
solution
violet tan
Solution;
Water falls
violet
black blue-green
Solution; much
Water dissolves
brown purple p-amidodiphenylamine +
, p-nitroaniline
45 black
Pieces hot low
solution
red-brown insoluble hot low
solution
dirty red soluble
brown purple;
Water falls
green dirty-
black
green lo
sung; much
Water dissolves
brown purple.

It has now been further found that these bodies fused with sulfur and alkali sulfur Provide dyes which dye cotton directly in brown, green and black tones, lightfast and washable.

Example.

ι Part of the oxidation product of the mixture of p-phenylenediamine and m-nitroaniline was crystallized with 1.5 parts of sulfur and 3 parts of sodium sulfur. triturated, entered into a melting vessel and ^{heated to 150 °} C .; then a further 2 parts of sodium sulfide were added and up to about 280 ⁰ C. increasing the temperature. It escapes in abundance

Gases (ammonia and hydrogen sulfide) and the reaction takes about 3 to 4 hours completed. A melt is obtained which dissolves in water with an olive-brown color and Cotton in a bath containing sodium sulphide and sodium chloride directly dyes olive-brown. In The dyes were prepared in a similar manner from the other oxidation products.

The amounts of sulfur and sodium sulphide as well as the working conditions can be changed.

The table below shows the reactions of the most important of these dyes cited.

dye
from the
Oxidation product
of the mix
⁵ of Solubility of the dye in sulfur
acid
conc. Saltpetre
acid
conc. Baking soda
lye
ioproz. soda
solution
ioproz. sulfur
sodium
solution
ioproz. alcohol
o, 6 percent colors
tree
wool Aniline + m-nitroaniline hot track
soluble
greenish soluble
- yellow Red insoluble insoluble soluble
olive brown insoluble Brown-
prickly
black o-toluidine + m-nitroaniline hot something
soluble
Brown hot
yellow Red
soluble soluble
Brown soluble
hraun soluble
Brown insoluble Brown p-toluidine 4-m-nitroaniline soluble
Brown cold
soluble
yellow-brown soluble
Brown hot something
soluble
Brown soluble
Brown insoluble Brown p-phenylenediamine +
m-nitroaniline insoluble hot
soluble
yellow Red soluble
olive brown , hot
soluble
Brown soluble
olive brown insoluble olive brown 20th
p-phenylenediamine +
p-nitroaniline little
soluble
dirty-
dark
violet cold'
soluble.
garnet red hot
soluble
red-violet nearly
insoluble soluble
red-violet insoluble reddish
black ₂ g of a-naphthylamine +
m-nitroaniline nearly
insoluble hot
yellow-brown
soluble hot
soluble
Brown insoluble hot
soluble
Brown insoluble Brown p-amidophenol +
m-nitroaniline
30th insoluble hot red
soluble dark
green
soluble hot
heavy
soluble
green soluble
green insoluble black
green p-amidophenol +
p-nitroaniline soluble
olive green soluble
Brown
violet hot
soluble
black
green insoluble soluble
bottles
green insoluble black 35
p-amidodiphenylamine +
m-nitroaniline hot something
soluble
Brown Green hot
red-brown
soluble, hot
olive brown
soluble soluble
Brown soluble
olive brown insoluble olive brown p-amidodiphenylamine +
■ ₀ p-nitroaniline . nearly
insoluble. hot
dark
red-brown
soluble hot
partially
soluble
Brown hot
track by track
soluble soluble
Brown insoluble olive
Brown.

Claims (1)

. Patent claim:
Process for the preparation of sulfur dyes, characterized in that the by the action of oxidizing agents on salt mixtures of mbezw. p-nitroaniline with amines (aniline and its homologues, naphthylamines, hydroxylated amines, diamines, amidodiphenylamines etc.) available products with sulfur and alkali sulfur or similar agents to higher Temperatures heated.