The Manufacture or Production of New Anthraquinone Dye-stuffs.
Year: 1899

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:-
My foreign correspondents have found that, by causing halogens, such as
chlorine or bromine, to act on alphamonoamidoanthraquinone or its alphyl-
derivatives (such as alphaanilidoanthraquinone, alphatoluidoanthraquinone, or
the like), new halogen derivatives are obtained, which, when treated with
aromatic amines, yield from green to blue dye-stuffs, and that the latter can be
transformed into valuable dye-stuff sulphonic acids by the action of sulphonating
agents.
In order to illustrate the new process more fully, the following examples are
given, the parts being by weight.
EXAMPLE A.
10 parts of alphaamidoanthraquinone which are spread out in a suitable
vessel, are subjected to the action of bromine. When the product treated in
this manner has assumed a uniform loam-yellow color, it is washed with water,
then with a dilute sodium carbonate solution, and finally dried. The brominated
alphaamidoanthraquinone thus produced represents a garnet-red powder. When
recrystallized from glacial acetic acid, it is obtained in the shape of brick-red
needles.
The new body is readily soluble in nitrobenzene, aniline, and pyridine, with a
reddish-yellow color. By concentrated sulphuric acid, it is dissolved with a
yellow color, which is not changed by the addition of boric acid.
EXAMPLE B.
10 parts of alpha-para-toluidoanthraquinone, which can be produced by the
action of alphanitroanthraquinone on paratoluidine (see Römer, Berichte der
Deutschen Chemischen. Gesellschaft," Vol. 16, p. 363) are dissolved in 200 parts
of hot glacial acetic acid. To the solution thus obtained, after being cooled
down to 50 degrees Centigrade, 12 parts of bromine, which are mixed with
50 parts of glacial acetic acid, are added, with stirring. The reaction takes
place instantly, the temperature of the mixture rising in a considerable degree,
whilst the blueish-red color of the liquid turns into brownish-yellow.
The brominated product thus produced is then completely separated in the
shape of yellowish-red crystals by the addition of water. Finally, it is filtered
off. dried, and pulverized.
The brominated alphaparatoluidoanthraquinone thus obtained represents a
crystalline yellowish-red powder. When recrystallized from glacial acetic acid,

page_text: it is obtained in the shape of yellowish-red needles. It is dissolved by concen-
trated sulphuric acid, with a yellowish-green color.
In a manner analogous to that described in the foregoing Examples A and B,
other of the above-defined halogen derivatives can be produced.
The production of the above-defined new dye-stuffs from the said halogen
derivatives may be illustrated by the following Examples C & D.
EXAMPLE C.
A mixture of 10 parts of brominated alphamonoamidoanthraquinone, obtained
according to the foregoing Example A, and 100 parts of paratoluidine is boiled
until a test portion dissolves in chloroform with an intense blue color. After
the reaction mass has been allowed to cool down to about from 80 to 100 degrees
Centigrade, it is poured into diluted hydrochloric acid, and the precipitate thus
produced, which represents the new dye-stuff, is filtered off. It is soluble with
an intense blue color in aniline, pyridine, and chloroform, soluble with difficulty
in glacial acetic acid, and insoluble in ligroin. When recrystallized from glacial
acetic acid, it is obtained in the shape of large dark-violet leaves having a metallic
lustre.
EXAMPLE D.
Brominated alpha-paratoluidoanthraquinone obtained according to the fore-
going Example B is subjected to the action of paratoluidine in the manner
described in the foregoing Example C. The reaction product thus produced
dissolves in organic solvents with a green color. When recrystallized from
glacial acetic acid, it is obtained in the shape of glittering blue needles.
The process proceeds in an analogous manner if in the Examples C & D),
other of the above-defined halogen-containing compounds, or other aromatic
amines, are employed.
In order to illustrate the production of the above-mentioned dye-stuff sulphonic
acids, the following Example E is given.
EXAMPLE E.
10 parts of the finely pulverized dye-stuff obtained according to the foregoing
Example C are stirred into 100 parts of sulphuric monohydrate. The resulting
mixture is then heated at about from 100 to 110 degrees Centigrade, until a
test portion, when poured into water, yields a clear solution. Subsequently,
the reaction mass is poured into ice water, and, from the mixture thus produced,
the dye-stuff is completely separated by the addition of common salt. Finally,
it is filtered off, dried, and pulverized.
The dry dye-stuff sulphonic acid so obtained represents a dark-green powder,
which is soluble with difficulty in water. It dyes unmordanted wool, in acid
baths, bright reddish-blue shades, and chrome-mordanted wool, bright blue
shades. My foreign correspondents proceed in an analogous manner in order
to produce other of the above mentioned dye-stuff sulphonic acids.
As a matter of course, my foreign correspondents do not intend to confine
themselves to the particulars given in the above examples, as these are merely
typical, and can be varied within wide limits.
Dated this 28th day of September 1899.
The manufacture or froduction of New Anthraquinone Dye-stuns.
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: 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:-
My foreign correspondents have found that, by causing halogens, such as
chlorine and bromine, to act on alphamonoamidoanthraquinone or its alphyl
derivatives (such as alphaanilidoanthraquinone, alphatoluidoanthraquinone, or
the like), new halogen derivatives are obtained, which, when treated with
aromatic amines, yield from green to blue dye-stuff's, and that the latter can be
transformed into valuable dye stuff sulphonic acids by the action of sulphonating
agents.
In order to illustrate the new process more fully, the following examples are
given, the parts being by weight.
EXAMPLE A.
10 parts of alphaamidoanthraquinone, which are spread out in a suitable
vessel, are subjected to the action of bromine. When the product treated in
this manner has assumed a uniform loam-yellow color, it is washed with water,
then with a dilute sodium carbonate solution, and finally dried. The brominated
alphaamido anthraquinone thus produced represents a garnet-red powder. When
recrystallized from glacial acetic acid, it is obtained in the shape of brick-red
needles.
The new body is readily soluble in nitrobenzene, aniline, and pyridine, with
a reddish-yellow color. By concentrated sulphuric acid, it is dissolved with a
yellow color, which is not changed by the addition of boric acid.
EXAMPLE B.
Into a mixture prepared from 10 parts of alphaamidoanthraquinone and 200
parts of acetic acid, a current of chlorine is introduced, whilst the mixture is
being continuously stirred, until, on testing, alphaamidoanthraquinone is no
longer found to be contained in the mixture. The reaction mixture is then
heated to about from 80 to 90 degrees Centigrade. Subsequently, it is allowed to
cool, and the yellowish-red chlorinated body which has been precipitated during
the reaction, is filtered off.
By a recrystallization from glacial acetic acid, the new chlorinated alpha-
amidoanthraquinone is obtained in the shape of brick-red needles, which are
insoluble in water, and readily soluble in hot nitrobenzene, aniline, and pyridine,
with a reddish-yellow color. It is also dissolved by concentrated sulphuric acid
with a yellow color.
EXAMPLE C.
10 parts of alpha-para-toluido-anthraquinone, which can be produced by the
action of alphanitroanthraquinone on paratoluidine, are dissolved in 200 parts
of hot glacial acetic acid. To the solution thus obtained, after being cooled
down to 50 degrees Centigrade, 20 parts of bromine, which are mixed with
50 parts of glacial acetic acid, are added, with stirring. The reaction takes place
instantly, the temperature of the mixture rising in a considerable degree, whilst
the blueish-red color of the liquid turns into brownish-yellow.
The brominated product thus produced is then completely separated in the
shape of yellowish-red crystals by the addition of water. Finally it is filtered
off, dried, and pulverised.
The brominated alphaparatoluidoanthraquinone thus obtained, represents a
crystalline yellowish-red powder. When recrystallized from glacial acetic acid,
it is obtained in the shape of yellowish-red needles. It is dissolved by concen-
trated sulphuric acid with a yellowish-green color.
In a manner analogous to that described in the foregoing Examples A, B, & C,
other of the above-defined halogen derivatives can be produced.
The production of the above defined new products from the said halogen
derivatives may be illustrated by the following Examples D and E,

page_text: EXAMPLE D.
A mixture of 10 parts of brominated alphamonoamidoanthraquinone, obtained
according to the foregoing Example A, and 100 parts of paratoluidine, is boiled
until a test portion dissolves in chloroform with an intense blue color. After
the reaction mass has been allowed to cool down to about from 80 to 100 degrees
Centigrade, it is poured into diluted hydrochloric acid, and the precipitate thus
produced, which represents the new condensation product, is filtered off. It is
soluble with an intense blue color in aniline, pyridine, and chloroform, and is
less soluble in glacial acetic acid and in ligroine. When recrystallized from
glacial acetic acid, it is obtained in the shape of large dark-violet leaves, having
a metallic lustre.
The process proceeds in an analogous manner if, in the above example, instead
of the brominated monoamidoanthraquinone, the chlorinated derivative thereof,
the preparation of which is described in Example B, is employed. The conden-
sation product obtained from the latter compound differs but little from that
which is obtained from the brominated monoamidoanthraquinone.
EXAMPLE E.
Brominated alphaparatoluidoanthraquinone, obtained according to the fore-
going Example C, is subjected to the action of paratoluidine in the manner
described in the foregoing Example D. The, reaction product thus produced
dissolves in organic solvents with a green color. When recrystallized from
glacial acetic acid, it is obtained in the shape of glittering blue needles.
The process proceeds in an analogous manner, if, in the Examples D and E,
other of the above defined. halogen-containing compounds, or other aromatic
amines, are employed.
In order to illustrate the production of the above mentioned dye-stuff sulphonic
acids, the following Examples F and G, are given:
EXAMPLE F.
10 parts of the finely pulverized product obtained according to the above
Example Dare stirred into a mixture of 100 parts of sulphuric monohydrate and
20 parts of fuming sulphuric acid (containing 20 per cent. of SO3). The resulting
mixture is then heated at about from 50 to 60 degrees Centigrade, until a test
portion, when poured into water and filtered off, yields a clear solution with
much hot water. Subsequently, the reaction mass is poured into ice-water.
By means of this operation, the dye-stuff, which is but slightly soluble in diluted
mineral acids, is completely precipitated. Subsequently it is filtered off, dried,
and pulverized.
The dry dye-stuff sulphonic acid so obtained represents a dark green powder,
which is soluble with difficulty in water. It dyes unmordanted wool, in acid
baths, bright blue shades, and chrome-mordanted wool, likewise bright blue
shades.
EXAMPLE G.
10 parts of the condensation product of brominated alphaparatoluidoanthra-
quinone with paratoluidine (the preparation of which is described in the
Example E) are stirred into 100 parts of sulphuric monohydrate. The resulting
mixture is then heated to about 100 degrees Centigrade, until a test portion, when
poured into a large quantity of water, yields a clear solution. The reaction
mixture is then further treated in the same manner as described in the foregoing
Example F.
The dry dye-stuff sulphonic acid thus obtained represents a dark-green powder
soluble in water with a blueish-green color.
It dyes unmordanted wool, in acid baths, bright green shades, and chrome-
mordanted wool, green shades, which are distinguished by their fastness against
washing and against light.

page_text: My foreign correspondents proceed in an analogous manner in order to produce
other of the above mentioned dyestuff sulphonic acids.
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 within wide limits.
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 halogen derivatives of alpha-amido-
anthraquinone, or of alphylated alpha amido-anthraquinones, which process con-
sists in treating these bodies with halogens substantially as herein before
described.
.
2. The process for the production of new products of the anthraquinone series,
which process consists in condensing the above mentioned halogen derivatives
of alpha-amido-anthraquinone, or of alphylated alpha amido anthraquinones,
with aromatic amines, substantially as described.
3. The process for the production of new dye stuff sulphonic acids, which
process consists in treating the condensation products obtainable by the process
claimed under Claim 2, with sulphonating agents substantially as described.
4. As new articles of manufacture, the new products obtainable by the processes
herein before described and claimed.
Dotal 1941 1 T 1000