Improvements in the Manufacture or Production of Azo Coloring Matters, and of an Intermediate Product for use therein
Year: 1899

page_text: 1
Date of Application, 5th May., 1899
Complete Specification Left, 31st Jan., 1900—Accepted, 10th Mar,,
1900
Improvements in the Manufacture or Production of Azo Coloring
Matters, and of an Intermediate Product for use therein
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings, Chancery
Lane, in the County of London, Patent Agent, do hereby declare the nature of this
invention to be as follows:-
I
The présent invention relates to the production of a new a1 az
a-nitronaphtylamine-
sulphonic acid, and to new azo coloring matters derived from a a₂-nitronaphtylamine
sulphonic acids.
My foreign correspondents have found that a₁-nitro-a-naphtylamine-a-sulphonic
acid, which was unknown, up to the present, can be easily obtained by nitrating
a-naphtylaminesulphonic acid, for instance, by treating the same with concentrated
nitric acid in the presence of concentrated, sulphuric acid. The production of the
said new acid may be illustrated by the following example, the parts being by
weight.
EXAMPLE A.
22: 3 parts of a₁ a naphtylaminesulphonic acid are dissolved, at the ordinary
temperature, in 450 parts of concentrated sulphuric acid of 66 degrees Baumé. The
resulting solution is then cooled down to zero. Subsequently, 8 parts of concentrated
nitric acid (of 45 degrees Baumé) are slowly added, with stirring, care being taken
that the temperature of the reaction mixture does not exceed 10 degrees Centigrade.
When the addition of the nitric acid is finished, the mixture is poured on ice, by
means of which operation the new a₁-nitro-a, naphtylamine-a4-monosulphonic acid is
separated. It can be transformed into its sodium salt by dissolving in a dilute
sodium carbonate solution. From the solution thus obtained, the pure sodium salt is
separated by the addition of common salt.
The new acid is soluble with difficulty in cold water. The sodium salt. crystallizes
from a hot watery solution, in the shape of small yellow leaves.
According to further researches of my foreign correspondents, very valuable
coloring matters, which dye. wool, in acid baths, from violet to blue shades, are
obtained, in the diazo derivatives of the above described new a₁ ag-nitronaphtylamine-
sulphonic acid are combined with alkylized or alphylized alpha-naphtylamines, or the
sulphonic acids of these substituted alpha-naphtylamines, or with a α-amido-
naphtol, or the ẞ, or ẞ,-sulphonic acids of a α-amidonaphtol. My foreign corre.
spondents have further found that the diazo derivatives of the other Ալ a₁-nitro-
naphtylaminesulphonic acids, such, for instance, as the B or B-monosulphonic
acids of a-nitro-a-naphtylamine. (which are described in the German Patent
No. 73502) are also capable of yielding valuable violet to blue coloring matters, if they
are combined with the above mentioned dye-stuff components.
In order to illustrate the production of the said new dye-stuffs, the following
examples are given. the parts being by weight.

page_text: Improvements in the Manufacture or Production of Azo Coloring
Matters, and of an Intermediate Product for use therein.
+
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
The present invention relates to the production of a new alpha,-alpha-nitro-
naphthylamine sulphonic acid, and to new azo coloring matters derived from
alpha-alpha-nitronaphthylamine sulphonic acids.
My foreign correspondents have found that alpha,-nitro-alpha,-naphthylamine-
alpha-sulphonic acid, which was unknown up to the present, can be, easily obtained
by nitrating alpha-alpha,-naphthylamine sulphonic acid, for instance, by treating the
same with concentrated nitric acid in the presence of concentrated sulphuric acid.
The production of the said new acid may be illustrated by the following example,-
the parts being by weight."
EXAMPLE A.
22.3 parts of alpha,-alpha-naphthylamine sulphonic acid are dissolved, at the
ordinary temperature, in 450 parts of concentrated sulphuric acid of 66 degrees
Baumé. The resulting solution is then cooled down to zero. Subsequently, 8 parts
of concentrated nitric acid (of 45 degrees Baumné) are slowly added with stirring,
care being taken that the temperature of the reaction mixture does not exceed
10 degrees Centigrade. When the addition of the nitric acid is finished, the mixture is
poured on ice, by means of which operation the new alpha,-nitro-alpha-naphthyl-
amine-alpha-monosulphonic acid is separated. It can be transformed into its
sodium salt by dissolving in a dilute sodium carbonate solution. From the solution
thus obtained, the pure sodium salt is separated by the addition of common
salt.
The new acid is soluble with difficulty in cold water. The sodium salt crystallizes
from a hot watery solution in the shape of small yellow leaves.
According to further researches of my foreign correspondents, very valuable
coloring matters, which dye wool, in acid baths, from violet to blue shades, are
obtained, if the diazo derivatives of the above-described new alpha,-alpha-nitro-
naphthylamine sulphonic acid are combined with alkylized, or alphylized, alpha-
naphthylamines, or the sulphonic acids of these substituted alphanaphthylamines, or
with alpha,-alpha,-amidonaphthol, or the beta,- or beta, sulphonic acids of alpha₁-
alpha-amidonaphthol. My foreign correspondents have further found that the
diazo derivatives of the other alpha-alpha-nitro-naphthylamine sulphonic acids, such,
for instance, as the beta,- or beta-monosulphonic acids of alpha-nitro-alphaż-
naphthylamine (which are described in the German Patent No. 73502) are also
capable of yielding valuable violet to blue coloring matters, if they are combined
with the above mentioned dye-stuff components.
In order to illustrate the production of the said new dye-stuffs, the following
.examples are given, the parts being by weight.

page_text: solution prepared from 31.3 parts of tolyl-alpha,-alpha-naphthylamine sulphonic
acid, 300 parts of water, and 16 parts of sodium acetate.
After being further stirred for about 12 hours, the mixture is heated to about
80 degrees Centigrade, and the separated dye-stuff is isolated therefrom by filtration.
In order to purify the dye-stuff, it is dissolved in water with the addition of sodium
carbonate, and again precipitated from the resulting solution, with the aid of common
salt. The coloring matter dyes wool, in acid baths, bright reddish-blue shades which
are fast to milling.
EXAMPLE C.
26.8 parts of alpha,-alpha-nitronaphthylamine-beta,-sulphonic acid are diazotized,
in the usual way, with the aid of 7 parts of sodium nitrite. The diazo compound
thus obtained is stirred into a solution prepared from 20.8 parts of the hydrochlorate
-of ethyl-alpha-naphthylamine and about 400 parts of water, to which solution 16 parts
of sodium acetate have been added. After being stirred for about 12 hours, the
resulting mixture is heated to about 80 degrees Centigrade, and then filtered..
-The dye-stuff thus obtained can be purified in the manner described in the fore-
going example. It dyes wool, in acid baths, bright blueish-violet shades which are
fast to milling..
EXAMPLE D.
The diazo compound which can be obtained in the usual manner from 26.8 parts of
alpha,-alpha-nitronaphthylamine-beta,-sulphonic acid and 7 parts of sodium nitrite,
is introduced, with stirring, into a solution which has been prepared from 29.9 parts
of phenyl-alpha,-alpha-naphthylamine sulphonic acid, 16 parts of sodium acetate, and
300 parts of water. After stirring the resulting mixture for about 12 hours, it is
heated to about 80 degrees Centigrade. Subsequently, the finished dye-stuff is
isolated therefrom by filtration. It can be purified in the manner described in the
above example B. The new coloring matter dyes wool, in acid baths, bright reddish-
blue shades which are fast to milling.
EXAMPLE E.
26.8. parts of alpha,-alpha,-nitronaphthylamine-beta,-sulphonic acid are diazotized
in the usual manner with the aid of 7 parts of sodium nitrite. The resulting diazo
_compound is stirred into a solution prepared from 15.9 parts of alpha,-alpha,-amido-
naphthol, 4 parts of caustic soda, and 300 parts of water. The reaction mixture is
then stirred for about 12 hours at the ordinary temperature. Subsequently it is
heated to about 80 degrees Centigrade. Finally, the finished dye-stuff is isolated
therefrom by filtration. The new coloring matter, which can be purified in the
_manner described in the above Example B, dyes wool, in acid baths, greenish-blue
.shades.
As a matter of course, my foreign correspondents do not intend to confine them-
.selves to the particulars given in the above examples, as these are merely typical, and
can be varied and modified within wide limits, without altering thereby the nature
of the present invention.
:
; .
Having now particularly described and ascertained the nature of the said invention
and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. The process for the production of alpha,-nitro-alpha,-naphthylamine-alpha,-
mono-sulphonic acid, by treating alpha,-alpha,-naphthylamine sulphonic acid with
suitable nitrating agents, substantially as herein before described.
2. The process for the production of new azo-coloring matters, which process con-
sists in combining the diazo derivatives prepared from alpha,-alpha,-nitronaphthyl-
amine sulphonic acids, such as alpha,-alpha,-nitronaphthylamine-alpha-sulphonic
acid, alpha-alpha-nitronaphthylamine beta-sulphonic acid, alpha,-alpha-nitro-

page_text: naphthylamine-beta-sulphonic acid, with the following compounds, viz., alkylized or
alphylized alpha-naphthylamines, sulphonic acids of these substituted alpha-naphthyl-
amines, alpha-alpha-amido-naphthol or beta.- or beta-sulphonic acids of alpha₁-
alpha-amidonaphthol, substantially as herein before described.
3. As new articles of manufacture, the new bodies obtainable according to the
processes, herein before described and claimed.
Dated this 20th
1000