The Manufacture or Production of New Anthraquinone Derivatives.
Year: 1899

page_text: Date of Application, 7th Mar., 1899
Complete Specification Left, 4th Dec, 1899-Accepted, 6th Jan., 1900
PROVISIONAL SPECIFICATION.
[Communicated from abroad by the FARBENFABRIKEN VORMALS FRIEDRICH BAYER
& Co., of Elberfeld, Germany.]
The Manufacture or Production of New Anthraquinone Derivatives.
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:-
My foreign correspondents have found that by causing halogens, such as chlorine
5 or bromine, to act on diamidoanthraquinones, new halogen derivatives are obtained
which, when treated with fuming sulphuric acid, with or without the presence of
boric acid or the like, yield valuable blue dyestuffs.
In order to produce the said halogen derivatives, any of the processes known or in
use for the purpose of producing halogen derivatives of the aromatic series, can be
employed.
The production of the halogen derivatives may be illustrated by the following
Examples A and B, the parts being by weight.
EXAMPLE A.
Into a mixture prepared from 20 parts of 1.5 diamidoanthraquinone and 100
parts of chloroform or glacial acetic acid, a current of dry chlorine is introduced,
until the reaction mixture, on testing, is no longer found to contain unchanged
diamido anthraquinone. Subsequently the mixture is filtered, and the residue
remaining on the filter, which is the new chlorinated derivative, is dried. When
rechrystallized from nitro-benzene or aniline, the pure compound is obtained in the
shape of yellowish-red needles, exhibiting a metallic lustre.
The new body melts above 360 degrees Centigrade, under decomposition. It is
soluble with difficulty, showing a yellowish-red color in organic solvents.
By concentrated sulphuric acid it is dissolved with a brownish-yellow color, which
is not changed by the addition of boric acid. The body dissolves in fuming
sulphuric acid (containing 40 per cent. of SO3) with a dirty violet color, which
changes into green on heating. When the body is dissolved in a forty per cent.
fuming sulphuric acid to which 10 per cent. of boric acid has been added, and the
resulting solution is heated to from 110 to 120 degrees Centigrade, a blue solution is
obtained which, when mixed with concentrated sulphuric acid, exhibits an absorption
spectrum characterized by two bands in its red part.
EXAMPLE B.
20 parts of 1.8 diamidoanthraquinone are spread out at the bottom of a closed
chamber, which contains at the same time 55 parts of dry bromine, in an open
vessel. After about two days, the whole bromine will have disappeared, being
absorbed by the diamido anthraquinone. The loam-yellow powder thus obtained,
which is a brominated derivative of 1.8 diamidoanthraquinone, is washed by means
of a dilute sodium bisulphite solution, and dried. When recrystallized from

page_text: pyridine or nitrobenzene, it is obtained in the shape of brownish-red needles
exhibiting a metallic lustre.
+
The new body is soluble with comparative readiness in organic solvents. By
heating the body with a 40 per cent. fuming sulphuric acid which contains boric
acid, a brownish red solution is obtained which, when mixed with concentrated
sulphuric acid, assumes a violet fluorescent color, and exhibits an absorption spectrum
characterized by two strong lines in its yellow and yellowish-green part, and by a
weak band in its blue part.
The process proceeds in an analogous manner on using other diamidoanthra-
quinones.
As above mentioned, the new halogen derivatives of the diamido-anthraquinones
yield very valuable dye-stuffs when treated with fuming sulphuric acid.
The dye-stuffs thus produced contain halogen and sulphur, and dye unmordanted
wool, in acid baths, from violet to blue shades. They yield, on chrome-mordanted
wool, fast blue shades. When the reaction is performed in the presence of boric
acid, colouring matters are obtained which are in general difficulty soluble in water,
and which yield, on chrome-mordanted wool, from greenish-blue to reddish blue
fast shades.
The production of these new dye stuffs may be illustrated by the following typical
A solution prepared from 50 parts of brominated 1.5 diamidoanthraquinone and
500 parts of fuming sulphuric acid containing about 40 per cent. of SO2, is heated
to from 110 to 120 degrees Centigrade. After a short heating, the re-action begins to
take place under evolution of bromine.
Heating is continued for about from 1 to 2 hours. The liquid is then cooled, and
poured into water to which a small quantity of sodium bisulphite may have been
profitably added. The resulting mixture is heated to boiling, and filtered. The
dark violet paste remaining on the filter, can directly be used for dyeing purposes.
It dissolves in hot water with a blue color, which changes into pure blue on the 3
addition of an alkali. If an excess of alkali, or if common salt, is added to the
watery solution, the sodium salt of the dye-stuff is precipitated in the shape of
brownish-violet flakes.
It dyes
The dye-stuffs yield, on chrome-mordanted wool, blue shades.
unmordanted wool beautiful violet-blue shades which are fast against the action of
alkalies. When dry and pulverized, the dye-stuff is a black powder, soluble in
concentrated sulphuric acid with a reddish-yellow color, which changes into blue on
the addition of boric acid.
EXAMPLE D.
To a cooled solution prepared from 50 parts of boric acid and 500 parts of a 40
per cent. fuming sulphuric acid, 50 parts of chlorinated 1.5 diamidoanthraquinone
are added with stirring. The dirty-yellow liquid thus obtained is heated to about
120 degrees Centigrade, by means of which operation it assumes by-and-by a pure
blue color. Heating is continued for a while, the temperature being slowly raised to
from 180 to 190 degrees Centigrade. The formation of the dye-stuff will be finished
when a test portion of the reaction liquid, mixed with concentrated sulphuric acid,
yields an absorption spectrum which consists of two lines in its yellow and green part.
When this stage is reached, the liquid is cooled and poured into water. The
resulting mixture is heated to boiling, and then filtered.
The pasty residue thus obtained is washed with water, and can directly be used for
dyeing purposes. It is soluble with difficulty in hot water. By dilute alkalies it is
dissolved, yielding a blue solution. On adding an excess of alkali, or common salt,
to this solution, the alkaline salts of the dyestuff are precipitated. The dry dyestuff
dissolves in concentrated sulphuric acid with a yellowish-red color, which changes

page_text: EXAMPLE C.
A solution prepared from 50 parts of brominated 1.5-diamidoanthraquinone and
500 parts of fuming sulphuric acid, containing about 40 per cent. of SO2, is heated to
from 110 to 120 degrees Centigrade. After a short heating, the reaction begins to
take place with evolution of bromine.
Heating is continued for about from 1 to 2 hours. The liquid is then cooled and
poured into water, to which a small quantity of sodium bisulphite may have been
profitably added.
The resulting mixture is heated to boiling, and filtered. The dark-violet paste
remaining on the filter can directly be used for dying purposes. It dissolves in hot
water with a blue colour, which changes into pure blue on the addition of an alkali.
If an excess of alkali, or if common salt is added to the watery solution, the sodium
salt of the dye-stuff is precipitated in the shape of brownish-violet flakes.
The dye-stuff yields, on chrome-mordanted-wool, blue shades. It dyes un-
mordanted wool, beautiful violet-blue shades which are fast against the action of
alkalies.
When dry and pulverized, the dye-stuff is a black powder soluble in concentrated
sulphuric acid with a reddish-yellow color, which changes into blue on the addition of
boric acid.
EXAMPLE D.
To a cool solution prepared from 50 parts of boric acid and 500 parts of a 40 per
cent. fuming sulphuric acid, 50 parts of chlorinated 1.5-diainido-anthraquinone are
added with stirring. The dirty-yellow liquid thus obtained is heated to about
120 degrees Centigrade, by means of which operation it presently assumes a pure
blue color. Heating is continued, the temperature being slowly raised to from
180 degrees to 190 degrees Centigrade. The formation of the dye-stuff will be finished
when a test portion of the reaction liquid, mixed with concentrated sulphuric acid,
yields an absorption spectrum which consists of two lines in its yellow and green
parts.
When this stage is reached, the liquid is cooled and poured into water. The
resulting mixture is heated to boiling, and then filtered.

page_text: into bluish-violet on the addition of boric acid. The coloring matter dyes chrome-
mordanted wool reddish-blue shades.
My foreign correspondents point out that they do not at all confine themselves; to
the particulars given in the foregoing examples, as these are merely typical, and can,;
be varied within wide limits, without altering thereby the nature of, the present:
invention.
Thus, for instance, instead of fuming, sulphuric acid containing 40 per cent. of
SO,, such fuming acids as contain a smaller or larger percentage of SO, can be.
employed. In this case, the resulting dyestuffs yield blue shades, which in general
are redder or greener according to the concentration of. the fuming acid..
Dated this 7th day of March 1899.
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 in tion and in what manner the same is to be performed, to be particularly
descri (and ascertained in and by the following statement :-
My oreign correspondents have found that, by causing halogens, such as chlorine
or b nine, to act on diamidoanthraquinones, now halogen derivatives are obtained,
wh
1, when treated with fuming sulphuric acid, with or, without the presence of boric
or the like, yield valuable blue dyestuffs.
ar
in order to produce the said halogen derivatives, any of the processes known or in
se for the purpose of producing halogen derivatives of the aromatie series can be
employed.
The production of the halogen derivatives may be illustrated by the following
examples A and B, the parts being by weight.
EXAMPLE A.
Into a mixture prepared from 20 parts of 1.5-diamidoanthraquinone and 100 parts
of chloroform or glacial acetic acid, a current of dry chlorine is introduced, until the
reaction mixture, on testing, is no longer found to contain unchanged diamidoanthra-.
quinone. Subsequently, the mixture is filtered, and the residue remaining on the
filter (which is the new chlorinated derivative), is dried. When recrystallized from
nitrobenzene or aniline, the pure compound is obtained in the shape of yellowish-red
needles exhibiting a metallic lustre.
The new body melts above 360 degrees Centigrade, under decomposition. It is
soluble with difficulty, showing a yellowish-red color in organic solvents.
By concentrated sulphuric acid, it is dissolved with a brownish-yellow-color, which
is not changed by the addition of boric acid. The body dissolves in fuming sulphuric
acid (containing 40 per cent. of SO3), with a dirty-violet color. When the body is
dissolved in a 40 per cent. fuming sulphuric acid, to which 10 per cent. of boric acid
has been added, and the resulting solution is heated to from 110 to 120 degrees
Centigrade, a blue solution is obtained, which, when mixed with concentrated
sulphuric acid, exhibits an absorption spectrum characterized by two bands in its red
part.

page_text: The pasty residue thus obtained is washed with water, and can directly be used for
dyeing purposes. It is soluble with difficulty in hot water. By dilute alkalies it is
dissolved, yielding a blue solution. On adding an excess of alkali, or common salt, to
this solution, the alkaline salts of the dyestuff are precipitated.
The dry dyestuff dissolves in concentrated sulphuric acid with a yellowish-red
color, which changes into blueish-violet on the addition of boric acid. The coloring
matter dyes chrome-mordanted-wool, reddish-blue shades.
My foreign correspondents point out that they do not at all confine themselves to
the particulars given in the foregoing examples, as these are merely typical, and can
be varied within wide limits, without altering thereby the nature of the present
invention.
Thus, for instance, instead of fuming sulphuric acid containing 40 per cent. of
SO, such fuming acids as contain a smaller or larger percentage of SO, can be
employed. In this case, the resulting dyestuffs yield blue shades, which in general
are redder or greener according to the concentration of the fuming acid. Naturally,
the production of the halogen-containing compounds, and their transformation into
the sulphonic acids, can also be combined into one operation, viz., by subjecting the
diamidoanthraquinones to the action of fuming sulphuric acid in the presence of the
halogens, and with or without the addition of boric acid. In order to illustrate this
method of proceeding, the following Example E is given.
EXAMPLE E.
60 parts of bromine are stirred into a solution prepared from 30 parts of 1.5-
diamidoanthraquinone, 50 parts of boric acid, and 500 parts of fuming sulphuric acid
(containing 40 per cent. of SO3), care being taken. that the temperature of the
reaction mixture does not rise above 50 degrees Centigrade. When the whole
bromine has been absorbed, the mixture is heated to about 180 degrees Centigrade,
and kept at this temperature for about 3 hours. Subsequently, the resulting dye-stuff
is isolated in the manner described in the foregoing Example D.
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 producing new halogen derivatives of diamidoanthraquinones,
by allowing halogens to act on the diamidoanthraquinones, substantially as herein-
above described.
2). The production of new dye-stuffs of the anthraquinone series, by allowing
fuming sulphuric acid to act, with or without the presence of boric acid, on the
halogen-containing compounds obtainable according to the foregoing Claim 1,
substantially as hereinbefore described.
3.). The process for producing new dye-stuffs of the anthraquinone series, which
process consists in first treating diamidoanthraquinones with halogens, and, secondly,
subjecting the halogen-containing compounds thus obtained, to the action of fuming
sulphuric acid, with or without the presence of boric acid, substantially as herein-
before described.
4.). The combination of the processes referred to in the above Claims 1 and 2 into
one operation, which process consists in subjecting the diamidoanthraquinones to the
action of fuming sulphuric acid in the presence of the halogens, and with or without
the addition of boric acid, substantially as hereinbefore described.
5.) As new articles of manufacture, the new products obtainable, according to the
processes herein before described and claimed.
Dated this 2nd day of December 1899.
NEWTON & SON
NEWTON & SON,
Agents for the Applicant.