The Preparation of Derivatives (Nitro and Amido) of Alizarine-mono- sulpho-acid and of Dyestuffs therefrom.
Year: 1888

page_text: Date of Application, 23rd Oct., 1888
Complete Specification Left, 23rd July, 1889-Accepted, 24th Aug., 1889
PROVISIONAL SPECIFICATION.
The Preparation of Derivatives (Nitro and Amido) of Alizarine-mono-
sulpho-acid and of Dyestuffs therefrom.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been com-
municated to me from abroad by Farbenfabriken vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany to be as follows:-
This Invention relates to the production of alizarine blue mono sulpho acid. With
this object a mono nitro alizarine alpha mono sulpho acid is obtained by nitriting
dioxyanthraquinone alpha mono sulpho acid obtained from anthraquinone alpha
disulpho acid according to the known process with one molecule of nitric acid or the
corresponding quantity of a nitric acid salt. This nitro alizarine alpha mono sulpho
acid is treated with a reduction process in order to obtain an amido alizarino alpha
mono sulpho acid. The alizarine blue mono sulpho acid is obtained from these
products either (a) by heating the nitro alizarine alpha mono sulpho acid with
glycerine and sulphuric acid to from about 100 to 150 degrees centrigrade or (b) by
heating a mixture of the amido alizarine mono sulpho acid with the nitro alizarine
nono sulpho acid or other nitro substance with glycerine and sulphuric acid to from
about 100 to 150 degrees centigrade. The alizarine blue mono sulpho acid thus
obtained is converted into a bisulphite compound by treatment with alkaline bisulphites
as hereinafter described.
It is known that in the preparation of flavo and anthra purpurine by melting anthra
quinone alpha or beta disulpho acid with caustic soda in the presence of air or oxygen
yielding substances certain intermediate products are formed which dissolve in
alkalies with an intense blue colour. These products dye mordanted wool very
strongly and differ essentially in tone from those which are obtained with the alizarine
sulpho acids produced by sulphurising alizarine-The alizarine mono sulpho acids
derived from the anthra quinone alpha disulpho acids are obtained by decomposing
melted flavo purpurine with acids and filtering the heated product. The acid soda salt
of the sulpho acid mixed with from about 10 to 12 per cent. of flavo purpurine is
salted out from the filtrate after cooling.
In order to further purify the alizarine mono sulpho acid either the watery solution
thereof is treated with ether by a shaking out process or the dry mixture of the sulpho
acid and flavo purpurine is extracted with alcohol-The sulpho acids thus obtained can
be readily converted into a mono nitro product by treating them in a sulphuric acid
solution with the theoretical quantity of nitric acid or a nitric acid salt as hereinafter
described.
The manufacture of the new sulpho acid may be performed in practice as follows
for example:-
PRODUCTION OF MONO NITRO ALIZARENE ALPHA MONO SULPHO AOID.
About ten parts by weight of dry alizarine mono sulpho acid are dissolved in about
thirty parts of 66 per cent. sulphuric acid at a temperature of from about 20 to 30
degrees Centigrade and to the deep red solution are added from about 2 to 4 parts of
nitric acid-of 48° Baumé dissolved in about ten parts of 66 per cent. sulphuric acid-
After standing for a short time the yellowish red coloured mixture is poured into
water and precipitated by salting out the yellowish red coloured nitro compound.
This product may be purified by dissolving in heated water and mixing with an excess of
soda lye whereby the yellowish brown coloured solution is converted into fuchsine red-

page_text: On cooling the neutral salt of the compound separates in the form of a dark coloured
crystalline precipitate. This nitro substance can be readily reduced to the corre-
sponding amido-compound.
PRODUCTION OF MONO AMIDO ALIZARINE ALPHA MONO SULPHO ACID.
About ten parts of nitro alizarine alpha mono sulpho acid are dissolved in about
fifty parts of water and mixed with fifty parts of fuming hydrochloric acid... This
solution is heated and twenty parts of crystallized tin salt or proto chloride are
gradually introduced. The reduction is concluded when a sample dissolves in alkali
with a blue colour-On the addition of an acid the amido sulpho acid thus obtained
is precipitated from the alkaline solution in the form of a brownish yellow crystalline
precipitate soluble with difficulty, in water and almost wholly insoluble in diluted
acids. The mono nitro and mono amido compounds of the alizarine alpha mono
sulpho acid herein before described can be employed with advantage by the application
of Skraup's synthesis in the manufacture of an alizarine blue mono sulpho acid which
possesses the distinguishing peculiarity of being, capable of printing cotton oven
without the employment of bisulphite.
PRODUCTION OF ALIZARINE, BLUE MONO SULPHO ACID FROM NITRO ALIZARINE ALPHA
MONO-SULPHO-ACID AND AMIDO ALIZARINE ALPHA MONO-SULPHO ACID.
About twenty parts of the amido sulpho acid herein before described are mixed
with about ten parts of the nitro compound and the mixture is placed in about thirty
parts.of glycerine and about one hundred and fifty parts of 66 per cent. sulphuric acid.
The melt is heated to from 120 to 130 degrees Centigrade and this temperature is
maintained until a sample dissolves in alkali with a pure green colour. The melt is
poured into water the red deposit or precipitate is separated by filtration and washed
with water and purified by conversion into the soda salt.
The alizarine blue mono sulpho acid thus obtained is in the form of a precipitate
soluble with difficulty in water and of a changeable blueish red colour.
In alkalies the acid dissolves with a yellowish green colour and with a large excess
of alkali. The neutral soda salt separates in the form of a deep blue precipitate but
this soda salt dissolves much more readily than the corresponding salt of the alizarine
blue itself. The alizarine blue sulpho acid can be employed for printing cotton goods
as hereinbefore mentioned without the employment of bisulphite the shades obtained
with chromium mordants present a greener tinge than those obtained with alizarine
blue. The alizarine blue sulpho acid can be converted by treatment with bisulphite
into a readily soluble bisulphite compound.
TREATMENT OF ALIZARINE BLUE SULPHO ACID TO OBTAIN THE BISULPHITE
COMPOUND THEREOF.
About ten parts of 20 per cent. of alizarine blue sulpho acid paste are mixed with
ton naste of water and about si..
1 L
L 20 1.
D

page_text: COMPLETE SPECIFICATION.
The Preparation of Derivatives (Nitro and Amido) of Alizarine-
mono-sulpho-acid and of Dyestuffs therefrom..
."
1 BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County. of Middlesex Patent
Agent do hereby declare the nature of this Invention which has been communicated
to me from abroad by the Farbenfabriken vormals Friedrich Bayer & Co. of Elberfeld
in the Empire of Germany and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement:
:-
This Invention relates to the production of alizarine-blue-mono-sulpho-acid from
mononitro- and amido-alizarine mono-sulpho-acids. The mononitro alizarine mono
sulpho acids are obtained by nitriting dioxyanthraquinone-alpha and beta mono sulpho
acids, the corresponding amido compounds are prepared by reducing the above
mentioned nitro substances.
From these nitro- and amido-alizarine alpha and beta-monosulpho-acids the alizarine-
blue-mono-sulpho-acids are obtained as follows:-
By heating the nitro-alizarine alpha and beta-mono-sulpho-acids with glycerine and
sulphuric acid to from about 100 to 150 degrees centigrade or by heating a mixture
of the amido-alizarine-mono-sulpho acids or other like nitro-substances or compounds
with glycerine and sulphuric-acid to from about 100 to 150 degrees centigrade. The
alizarine-blue-mono-sulpho-acids thus obtained can be converted into bisulphite.com-
pounds by treatment with alkaline-bisulphite as hereinafter described.
It is known that in the preparation of flavo and anthra purpurine by melting anthra-
quinone alpha or beta-disulpho-acid with soda in the presence of oxidising substances
certain intermediate products are formed which dissolve in alkalies with an intense
blue colour. These products dye mordanted wool very strongly, and differ essentially.
in tone from those which are obtained with the alizarine sulpho acids produced by
sulphurating alizarine.
These alizarine-mono-sulpho-acids are obtained by decomposing imperfect melts of
flavo- or anthra-purpurine with mineral acids and filtering the heated products.
The soda salts of these sulpho acids mixed with from about 10 to 12 per cent. of
flavo-purpurine or anthra-purpurine are salted out from the filtrates after cooling.
In order to further purify the alizarine-mono-sulpho-acids either the watery solutions
thereof are treated with ether by a shaking-out process or the dry mixtures of the.
sulpho-acid and flavo-purpurine or anthra-purpurine are extracted with alcohol. The
sulpho-acids thus obtained can be readily converted into mono-nitro-products by
treating the same in a sulphuric acid solution with the theoretical quantity of nitric
acid or a nitric acid salt or in acetic acid solution with nitrous acid or the theoretical
quantity of a nitrous acid salt as herein after described.
The manufacture of these mono nitrocompounds is further explained by the
following examples.
PRODUCTION OF MONO-NITRO-ALIZARINE-ALPHA-MONO-SULPHO-ACID.
About 50 parts by weight of dry alizarine-mono-sulpho-acid are dissolved under
heating in 100 parts by weight of water. To this solution are added 200 parts by
weight of glacial acetic acid and then, at a temperature of 40° centigrade, under
continuous stirring, 25 parts by weight of sodium nitrite. The reaction is known to
be finished after standing for some time when .a sample does not dissolve clearly in
water on addition of a large proportion of soda-lye and a brown red coloured
precipitate results representing the new nitro-sulpho-acid. Then the mixture is
poured into water and precipitated by salting out the yellowish red coloured nitro-
compound. This product may be purified by dissolving in heated water and mixing
it with an excess of soda lye whereby the yellowish brown coloured solution is
converted into magenta red. On cooling the neutral salt of the nitro-compound
separates in the form of a dark coloured crystalline precipitate. If in the above

page_text: described example the alizarine-alpha-monosulpho acid is replaced by the alizarine-
beta-monosulphoacid mononitroalizarine-beta-monosulphoacid is obtained.
This product has the same qualities as the corresponding alpha compound and
differs therefrom only inasmuch as it is more easily soluble in water and dyes
mordanted wool a redder shade.
It is found that the same difference appears in all cases between the alpha and beta
compounds for example between in the following described amido compounds and the
alizarine-blue-sulpho-acids.
These above described nitro-substances can be readily reduced by the known
reducing processes to the corresponding amido-compounds.
The following is an example of this reduction.
PRODUCTION OF MONO-AMIDO-ALIZARINE-ALPHA-MONO-SULPHO ACID.
About ten parts by weight of nitro alizarine-alpha-mono-sulpho acid are dissolved
in about fifty parts of water and mixed with fifty parts of fuming hydrochloric acid.
This solution is heated and about 20 parts of crystallised tin salt are gradually added.
The reduction is known to be finished when a sample dissolves in alkali with a blue
colour. On the addition of mineral acid the amido sulpho acid thus obtained is
precipitated from the alkaline solution in the form of a brownish yellow crystalline
precipitate soluble with difficulty in water and insoluble in diluted acids. If in the
above described example mononitro alizarine-beta-monosulpho-acid is employed the
corresponding amido-compound results which has mostly the same qualities as the alpha
compound.
The mono-nitro and mono-amido-compounds of the alizarine alpha- and beta-mono-
sulpho-acids herein before described can be employed with advantage by the application
of Scraup's synthesis in the manufacture of alizarine-blue-monosulpho-acids, which
possess the distinguishing peculiarity of being capable of printing cotton even without
the employment of bisulphite.
PRODUCTION OF ALIZARINE-BLUE-MONO-SULPHO-ACID FROM NITRO-ALIZARINE-ALPHA-
MONO-SULPHO-ACID AND AMIDO-ALIZARINE-ALPHA-MONO-SULPHO ACID.
About 20 parts by weight of the amido-sulpho-acid hereinbefore described are mixed
with about ten parts of the nitro-compound and the mixture is placed in about
thirty parts of glycerine and about one hundred and fifty parts of 66 per cent.
sulphuric acid.
The melt is heated to from about 120 to 130 degrees centigrade and this temperature
is maintained until a sample dissolves in alkali with a puro green colour.
The melt is poured into water the red deposit or precipitate is separated by filtration
and washed with water and purified by conversion into the soda salt. The alizarine-
blue-mono-sulpho-acid thus obtained is soluble with difficulty in water and has a
changeable blueish red colour.
In alkalies the acid dissolves with a yellowish green colour and with a large excess
of alkali the neutral soda salt separates in the form of a deep blue precipitate but this
soda salt dissolves much more readily than the corresponding salt of the alizarine-blue
itself.
The alizarine-blue-sulpho-acid can be employed for printing cotton goods as herein-
before mentioned without the employment of bisulphite the shades obtained with
chromium mordants present a greener tinge than those obtained with alizarine-blue.
The corresponding alizarine-blue-beta monosulpho acid manufactured in the same
manner has quite the same qualities as the alpha compound; it differs only by a redder
shade.
These alizarine-blue-sulpho-acids can be converted by treatment with bisulphite
into readily soluble .bisulphite-compounds which are easily decomposed by mineral
acids.

page_text: TREATMENT OF ALIZARINE-BLUE-SULPHO-ACID TO OBTAIN THE BISULPHITE
COMPOUND THEREOF.
About ten parts by weight of 20 per cent. alizarine-blue-sulpho-acid paste are mixed
with about ten parts of water and about six parts of sodium bisulphite at 30 degrees
Baumé and the mixture is heated to a temperature not exceeding 50 degrees centigrade;
the solution thus obtained is diluted with water and the bisulphite compound is
precipitated in the form of a brown deposit by common salt.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of mononitrocompounds of alizarine-alpha- and beta-mono-
sulphoacid by treating alizarine alpha- and beta-monosulphoacid with the theoretical
quantity of nitric acid or nitrous acid or of a nitric acid salt or a nitrous acid salt in
presence of acids substantially as herein before described.
2. The manufacture of amido-alizarine alpha- and beta monosulpho acids by nitriting
the mono sulpho acids as hereinbefore described and claimed and reducing the nitro-
compounds substantially as hereinbefore described.
3. The manufacture of alizarine-blue-alpha- and beta-monosulpho-acid from the
nitro and amido compounds (prepared as hereinbefore set forth) by heating the nitro-
alizarine alpha and beta-monosulphoacid with glycerine and sulphuric acid to from
about 100 to 150 degrees centigrade or by heating a mixture of amido-alizarine-alpha-
or beta-monosulpho-acid and nitro-alizarine alpha- or beta-monosulphoacid or other
like nitro compound with glycerine and sulphuric acid to from about 100-150 degrees
centigrade substantially as hereinbefore described.
4. The manufacture of the bisulphite compounds of the alizarine-blue-alpha- and
beta-mono-sulpho-acids by treating the alizarine-blue-alpha- and beta-monosulpho
acids with an alkaline-bisulphite substantially as hereinbefore described.
5. As new articles of manufacture the dye stuffs hereinbefore described. .
uay
puty 1333.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
uzy
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.