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

page_text: Date of Application; 5th Jan., 1899
Complete Specification Left, 30th Sept., 1899-Accepted, 18th Nov., 1899
[Communicated from abroad by the FARBENFABRIKEN VORMALS FRIEDRICH BAYER
& Co., of Elberfeld, Germany.]
The Manufacture or Production of New Anthraquinone
Derivatives.
1
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 Specification of Letters Patent No. 12011 of 1897, my foreign correspon-
dents have described the production of disulphonic acids of anthrarufin and
chrysazine.
They have now found that, by heating the said acids with caustic alkalies, the said
two disulphonic acids can be transformed into new trioxyanthraquinonemonosulphonię
acids which, when further heated with caustic alkalies, yield tetraoxyanthraquinones.
Thus, for instance, from anthrarufiue disulphonic acid, a monosulphonic acid having
the formula:-

page_text: & Choynacki (see "Annalen der Chemie-und Pharmacie, Vol. 163, p. 221), and termed
by these authors as "rufiopine."
Chrysazinedisulphonic acid, when treated in the above manner, first yields a mono-
sulphonic acid having the formula:-
A solution prepared from 5 parts of the sodium salt of anthrarufinedisulphonic
acid, 25 parts of potassium hydroxide, and 25 parts of water, is heated at from 180 to
210° Centigrade, until the liquid is suddenly transformed into a thick crystalline
mass. When this stage is reached, the reaction mixture is allowed to cool, and is
then acidulated by means of dilute hydrochloric acid.
Thus, the acid potassium salt of the oxyanthrarufinemonosulphonic acid is obtained
in the shape of a crystalline precipitate. When re-crystallized from hot weak
acidulated water, it is obtained in the shape of gold-yellow glittering crystals.
The pure oxyanthrarufinemonosulphonic acid dissolves in concentrated sulphurio
acid with a red color, which, on the addition of boric acid, changes into greenish blue.
By alkalies it is dissolved with a blue color. It dyes chrome mordanted wool, blue
shades, and yields on alumina mordanted wool, violet-red shades.
If, instead of anthrarufine disulphonic acid, chrysazine disulphonic acid is used,
similar effects will be produced. In this case, the formation of the trioxyanthra-
quinonemonosulphoacid is finished when a test portion of the reaction mixture is
found to be soluble in water with a violet color. The resulting trioxyanthra-quinone-
(oxyorysazine-) monosulphonic acid dissolves in concentrated sulphuric acid with a
red color, which changes into violet on the addition of boric acid. The new acid is
dissolved by alkalies with a viclet-red color. It dyes chrome-mordanted wool reddish-
violet shades, and yields on alumina-mordanted wool, claret shades.
If the above described trioxyanthraquinonemonosulphonic acid are further treated
with caustic alkalies at more elevated temperatures, the corresponding tetraoxyanthra-
quinones are obtained.

page_text: above example, but it 18 more prontable to start directly from the anthrarufine and
the chrysazinedisulphonic acids.
This method of proceeding may be illustrated by the following example, the parts
being by weight.
EXAMPLE B.
5 parts of chrysazinedisulphonate of potassium are heated, at from 210 to 280
degrees Centigrade, with a solution prepared-from 30 parts of potassium hydroxide
and 30 parts of water, until a test portion of the liquid dissolves in water with a blue
color. When this stage is reached, the liquid is allowed to cool, and then dissolved
in water. From the resulting solution, the free 1, 2, 7, 8-tetraoxyanthraquinone is
precipitated in the shape of orange flakes by the addition of an excess of dilute
hydrochloric acid.
When dried and pulverized, this precipitate forms a brownish powder, soluble with
difficulty in alcohol, glacial acetic acid, toluene, and nitrobenzene, but easily soluble
in pyridine. It can be purified by a recrystallization from glacial acetic acid. When
pure, it is soluble in concentrated sulphuric acid with a violet-red color, which
changes into blue on the addition of boric acid. By a sodium carbonate solution,
and by ammonia liquor, it is dissolved with a violet color, and by a caustic soda lye
with a blue color. It dyes chrome mordanted wool, crimson shades, and yields on
alumina-mordanted wool, red shades.
The process proceeds in an analogous manner if, instead of chrysazinedisulphonic
acid, anthrarufinedisulphonic acid is employed. The tetraoxyanthraquinone obtained
from the latter acid has the following properties: It is soluble in concentrated
sulphuric acid with a violet color, which changes into blueish-violet on the addition of
boric acid.
By a sodium carbonate solution, and by ammonia liquor, it is dissolved with a red
color, and by caustic soda lye with a reddish-violet color. It dyes chrome-mordanted
wool, violet shades, and yields on alumina-mordanted wool, red shades.
It may be pointed out that it is not the intention of my foreign correspondents
to confine 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.
Dated this 5th day of Tom100
The Manufacture or Production of New Anthraquinoņe
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 and in wuat manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
In the Specification of Letters Patent No. 12011 of 1897, my foreign correspondents
have described the production of disulphonic acids of anthrarufine and chrysazine.
They have now found that, by heating the said acids with caustic alkalies, the said
two disulphonic acids can be transformed into new trioxyanthraquininemonosulphonic
acids, which, when further heated with caustic alkalies, yield tetraoxyanthraquinones.

page_text: Thus, for instance, from the anthrarufine-disulphonic acid, a monosulphonic acid
having the formula;
can be obtained, which, when further treated with caustic alkalies at more elevated
temperatures, is transformed into a tetraoxyanthraquinone having the formula:
The latter compound is probably identical with a body described by Liebermann &
Choynacki (see "Annalen der Chemie und Pharmacie," vol. 163, p. 221), and terined
by these authors "rufiopine."
Chrysazine disulphonic acid, when treated in the above manner, first yields a mono- 1
sulphonic acid, having the formula.

page_text: like, the above mentioned tetraoxyanthraquinones can be transformed into hexaoxy-
anthraquinones.
The production of the trioxyanthraquinone monosulphonic acids may be illustrated
by the following example A, the parts being by weight :-

page_text: trated sulphuric acid with a violet color, which changes into blueish-violet on the
addition of boric acid.
By a sodium carbonate solution, and by ammonia liquor, it is dissolved with a red
color; by caustic soda lye with a reddish-violet color. It dyes chrome-mordanted
wool, violet shades, and yields on alumina-mordanted wool, red shades.
It may be pointed out that it is not the intention of my foreign correspondents to
confine 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.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed (as communicated to me
froin abroad), I declare that what I claim is:
1. The process. for. producing trioxyanthraquinone monosulphonic acids and tetra-
oxyanthraquinones, which consists in. treating anthrarufine disulphonic acid and
chrysazinedisulphonio. aoid with caustic alkalies, substantially as hereinbefore
described.
2. The production of; two. trioxyanthraquinone monosulphonic acids. by heating
antararufine disulphonic acid and chrysazinedisulphonic acid with caustic alkalies,
substantially as herein before described.
3. The manufacture of two tetraoxyanthraquinones by heating the trioxyanthra-
quinonemonosulphonic acids hereinbefore described, or the anthrarufine disulphonic
acid, and the chrygazine disulphonic acid, with, caustic alkalies, at elevated tempera-
tures, substantially as hereinbefore described.
4. As new articles of manufacture, the new compounds herein before described:
24
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