The Manufacture or Production of New Anthraquinone Dye-stuffs.
Year: 1898

page_text: [Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of New Anthraquinone Dye-stuffs.
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:-
In the Specifications of Letters Patent No's. 87250 and 12715%, my foreign
correspondents shewed that on heating oxyanthraquinones with fuming sul-
phuric acid of high percentage, sulphuric acid ethers of polyoxanthraquinones
were formed, which, by means of suitable saponifying agents, could be trans-
formed into the corresponding free polyoxyanthraquinones. Thus, for instance,
from alizarine (which is a dioxyanthraquinone) alizarine bordeaux (which is
a tetraoxyanthraquinone) was obtained, owing to the oxidizing action of the
fuming sulphuric acid.
My foreign correspondents have now found that if the said re-action is per-
formed in the presence of bromine, the process proceeds in an analogous manner,
that is to say, the oxyanthraquinones are transformed into sulphuric acid ethers
of polyoxanthraquinones, which are at the same time brominated. Thus, inter-
mediate products are obtained which represent sulphuric acid ethers of new
brominated polyoxyanthraquinones. These intermediate products can easily be
transformed by means of suitable saponifying agents into the free brominated
polyoxyanthraquinones, which represent valuable dye-stuffs.
In order to illustrate the new process, the following examples are given, the
parts being by weight.
EXAMPLE I.
14 parts of bromine are stirred at ordinary temperature into a mixture of
20 parts of alizarine with 200 parts of fuming sulphuric acid (containing
S0 per cent. of SO). The reaction proceeds under evolution of hydrobromic acid,
the mixture assuming a violet-blue color. After the re-action is finished, the
mixture is poured on ice, the new sulphuric acid ether being thus separated.
It can be easily isolated, owing to the fact that it is difficultly soluble in cold
water.
This intermediate product is soluble in concentrated sulphuric acid, with a
red color, and in a dilute caustic soda with dull red color. If it is dissolved
in hot dilute caustic soda lye, and the resulting solution is diluted by means of
a large quantity of water, the corresponding dye-stuff is obtained in the shape
of a dark-red precipitate.
The new dye stuff is soluble in a dilute soda lye with a blue color, in a sodium
carbonate solution with a blueish violet color, and in ammonia with a violet
blue color. By concentrated sulphuric acid, it is dissolved with a reddish
violet color, which changes into blueish-green on the addition of boric acid,
owing to the formation of a boric ether. The coloring matter dyes chrome-
mordanted wool blueish-violet shades.

page_text: EXAMPLE II.
To a mixture prepared from 400 parts of fuming sulphuric acid (containing
80 per cent. of SO) and 20 parts of purpurine, 13 parts of bromine are added,
with stirring at ordinary temperature.
When the mixture has assumed a blue color, the reaction is finished, and the
so-formed intermediate product can be isolated from the reaction mixture in
the manner described in the foregoing Example I.
The intermediate product is soluble in concentrated sulphuric acid with a red
color, in dilute caustic soda with a dull violet-red color. It can be transformed
into the corresponding dye stuff in the manner described in the preceding
example.
The resulting dye stuff is soluble in dilute caustic soda lye, and in ammonia
with a reddish-violet color. By concentrated sulphuric acid, it is dissolved with
a violet-red color, which changes into blue on the addition of boric acid. It dyes
chrome-mordanted wool blue shades.
EXAMPLE III.
20 parts of anthrachrysone are mixed with 400 parts of fuming sulphuric acid
containing 80 per cent. of SO. Subsequently 12 parts of bromine are added
with stirring. The reaction is performed very quickly under evolution of hydro-
bromic acid, a large quantity of the intermediate product being separated dur
ing the reaction. On pouring the whole greenish blue colored mixture on ice,
the new sulphuric acid ether is separated in the shape of a dark flaky precipitate.
It dissolves in dilute cold caustic soda-lye with a dull-blue color, and in con-
centrated sulphuric acid with a reddish-violet color. It can be transformed into
the corresponding dye-stuff in the manner described in the above Example I.
The new dye stuff is soluble in concentrated sulphuric acid with a blue color,
which changes into greenish-blue on the addition of boric acid. The solution in
concentrated sulphuric acid exhibits a spectrum which is different from that
of a sulphuric acid solution of hexaoxyanthraquinone. The dye-stuff is dis-
solved by dilute caustic soda with a greenish-blue color, by a sodium carbonate
solution with a reddish-violet color. On adding an excess of alkali to these
solutions, the dye stuff is precipitated. The coloring matter dissolves in hot
animonia with a blue color. It dyes chrome-mordanted wool pure blue shades.
It may be remarked that my foreign correspondents do not intend to limit
themselves to the particulars given in the foregoing specification, as these can
be varied within wide limits, without altering thereby the nature of the present
invention.
Thus, for instance, instead of the oxyanthraquinones used in the examples,
other oxyanthraquinones can be employed, such as anthrapurpurin, flavopur-
purin, anthrarufin, chryazin, or the like.
The saponification of the intermediate sulphuric acid ethers can be performed
in any other suitable manner, for instance, by boiling with dilute acids, or
heating with concentrated sulphuric acid of about 60 degrees Baumé, to from 60
to 180 degrees Centigrade.
Dated this 12th love of
1 1000
The Manufacture or Production of New Anthraquinone Dye-stuffs.
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

page_text: To a mixture prepared from 400 parts of fuming sulphuric acid (containing
80 per cent. of S03) and 20 parts of purpurine, 13 parts of bromine are added,
while stirring, at ordinary temperature.
When the mixture has assumed a blue colour, the reaction is finished, and
the so-formed intermediate product can be isolated from the reaction mixture
in the manner described in Example I.
The intermediate product is soluble in concentrated sulphuric acid with a
red colour, and in dilute caustic soda with a dull violet-red colour. It can be
transformed into the corresponding dye-stuff in the manner described in the
preceding example.
The resulting dye-stuff is soluble in dilute caustic soda lye, and in ammonia,
with a reddish-violet color. By concentrated sulphuric acid, it, is dissolved with
a violet red colour, which changes into blue on the addition of boric acid. It
dyes chrome mordanted wool, blue shades.

page_text: EXAMPLE III.
20 parts of anthrachrysone are mixed with 400 parts of fuming sulphuric acid
containing 80 per cent. of SO. Subsequently 12 parts of bromine are added
while stirring. The reaction is performed very quickly with evolution of hydro-
bromic acid, a large quantity of the intermediate product being separated during
the reaction. On pouring the whole greenish-blue coloured mixture on ice, the
new sulphuric acid ether is separated in the shape of a dark flaky precipitate.
It dissolves in dilute cold caustic soda-lye with a dull-blue color, and in concen-
trated sulphuric acid with a reddish-violet color. It can be transformed into
the corresponding dye-stuff in the manner described in Example I.
The new dye stuff is soluble in concentrated sulphuric acid with a blue color,
which changes into greenish-blue on the addition of boric acid. The solution
in concentrated sulphuric acid exhibits a spectrum which is different from that
of a sulphuric acid solution of hexaoxyanthraquinone. The dye-stuff is dis-
solved by dilute caustic soda with a greenish-blue color, and by a sodium car-
bonate solution with a reddish-violet color. On adding an excess of alkali to
these solutions, the dye-stuff is precipitated. The coloring matter dissolves in
hot ammonia with a blue color. It dyes chrome-mordanted wool, pure blue
shades.
It may be remarked that my foreign correspondents do not intend to limit
themselves to the particulars given in the foregoing specification, as these can
be varied within wide limits, without altering thereby the nature of the present
invention.
Thus, for instance, instead of the oxyanthraquinones used in the examples,
other oxyanthraquinones can be employed, such as anthrapurpurin, flavopur-
purin, anthrarufin, chrysazin, or the like.
The saponification of the intermediate sulphuric acid ethers can be performed
in any other suitable manner, for instance, by boiling with dilute acids, or
heating with concentrated sulphuric acid of about 60 degrees Baumé, to from 60
to 80 degrees Centigrade.
Having now particularly described and ascertained the nature of the said in-
vention 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 producing brominated sulphuric-acid ethers of polyoxyan-
thraquinones, which process consists in treating oxyanthraquinones with fuming
sulphuric acid in the presence of bromine, substantially as hereinbefore described.
2. The process for producing brominated oxyanthraquinone dye-stuffs, by
saponifying the sulphuric acid ethers obtainable according to the foregoing
Claim 1, substantially as hereinbefore described.
3. As new articles of manufacture, the new products hereinbefore defined.
Dated this (ith day of January 1899
NEWTON & SON,
Agents for the Applicant.