The Manufacture and Production of New Derivatives of Alizarine or its Analogues.
Year: 1890

page_text: Date of Application, 4th Nov., 1890
Complete Specification Left, 4th Aug., 1891-Accepted, 19th Sept., 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarine or
its Analogues.
I, BENJAMIN WILLCOX of 47 Lincoln's 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 Farbenfabriken vormals Friedrich Bayer
& Company of Elberfeld in the Empire of Germany to be as follows
. I.
My foreign correspondents have discovered that in addition to the di- and tri-
oxyanthra-quinones described in the Provisional Specifications accompanying my
two applications for Patents Nos. 872) and 12715 of the present year quinizarine
and xantho purpurine can likewise be similarly converted into colouring matter
by treatment at a low temperature with fuming sulphuric acid of high percentage.
In this case also there results in the first place mordant dyeing intermediate
products (neutral sulphuric acid ether) which by solution in soda or potash and
subsequent boiling with acids or directly by heating with acids, can be converted
into the Bordeaux "product.
The product thus obtained from quinizarine appears to be identical with the
alizarine bordeaux obtained from alizarine itself.
From xantho purpurine there is obtained the purpurine bordeaux described in the
Specification No. 8725 of 1890 it being simultaneously oxidised into the purpurine.
The process for the production of this compound is similar to that described in
the Specification No. 8725 of 1890 the alizarine referred to in the examples given
in the said Specification being replaced by quinizarine or xantho purpurine.
II.
By oxidising alizarine bordeaux in a sulphuric acid solution there results as
stated in the Specification No. 12715 of 1890 a colouring matter dyeing chrome
mordanted wool a greenish blue and named alizarine cyanine. This oxidation
process is also therein described in its application to flavo and anthra purpurine
bordeaux.
My foreign correspondents have now discovered that the purpurine bordeaux
described in the Specification No. 8725 of 1890 can also by similar treatment be
converted into a cyanine which is probably identical with the alizarine cyanine
derived from alizarine itself as indicated by a treatment for the purpose of
comparison of products obtained from the two bordeaux originals and purified by
crystallization.
The process is precisely the same as that described in the Specification
No. 12715 of 1890; the purpurine bordeaux is allowed to remain in from 10 to 20
times the quantity of sulphuric acid at 66 degrees Baumé and finely pulverised
manganese is stirred in until a test portion diluted with concentrated sulphuric acid
displays the pure blue colour of alizarine cyanine.
III.
The oxidation of the hordeaux from alizarine (or quinizarine), purpurine (or
purpuroxanthine) flavo and anthra purpurine can, as my foreign correspondents
have now discovered, be effected not only by means of manganese or arsenic acid
but also by sulphuric acid alone and this under very different conditions. In
general the oxidation is caused to take place at a low temperature by the employ-
ment of fumming sulphuric acid of high percentage but with ordinary concentrated

page_text: acid it is necessary to heat to 200 degrees Centigrade and upwards in order to
obtain the cyanine.
In the first instance with the employment of fuming sulphuric acid of high
percentage the production of the bordeaux and its oxidation into cyanines may be
combined in one operation. With this object the process may be conducted as
follows for example:
About 10-parts by weight (10 kilos.) of dry purpurine are introduced into
150 parts by weight (150 kilos.) of oleum at 80 per cent. This mixture is allowed
to stand at a temperature not above 50 degrees until a test portion, after being
poured into water, filtered, dissolved in soda, decomposed with acids and dried
dissolves in alkali or concentrated sulphuric acid with the blue colour of alizarine
cyanine. The subsequent treatment of the reacting mixture is similar to that
described in the former Specification No. 8725 of 1890. By these means there is
obtained from the purpurine with fuming sulphuric acid not a purpurine bordeaux
but a cyanine direct from the product of its further oxidation.
When ordinary concentrated sulphuric acid is employed as the oxidising agent
the process is conducted as next hereinafter described in order to convert alizarine
bordeaux for example into cyanine.
About 10 parts by weight of alizarine bordeaux are heated to from about 200 to
230 degrees Centigrade with from about 50 to 100 parts of sulphuric acid at
66 degrees Baumé until a test portion being diluted with sulphuric acid shows the
blue colour and red fluorescence of alizarine cyanine.
It is evident that this second method of performing the oxidation can be
employed with like results when the bordeaux derived from alizarine, purpurine,
flavo and anthra purpurine is replaced by its sulpho acids described in the
Specification No. 12715 of 1890 the sulpho group being first split off at the
elevated temperature and the corresponding bordeaux being subsequently further
oxidised.
IV.
In the preparation of the alizarine cyanine, and its analogues my foreign corre-
spondents have ascertained that in this case also in the same way as in the
production of the bordeaux, mordant dyeing intermediate products are formed
which can be very readily decomposed but under certain conditions may be isolated
without difficulty. These products are of considerable technical importance as by
acting upon them with ammonia a very valuable dyestuff is obtained which is
totally different from alizarine cyanine and its analogues.
For the production of the intermediate product from alizarine bordeaux the
process is conducted as follows:--
About 10 parts by weight (10 kilos.) of alizarine bordeaux are dissolved in
about 200 parts by weight (200 kilos.) of sulphuric acid at 66 degrees Baumé and
oxidised with about 12 parts by weight (12 kilos.) of manganese care being taken
not to allow the temperature of the oxidising mixture to rise above about
30 degrees Centigrade as the intermediate product undergoes decomposition at
higher temperatures of reaction. The mixture is then poured out, with continued
precautions against rise of temperature, into icy water whereupon the intermediate
product separates in the form of dark violet coloured flakes which are separated
by filtration and washed as quickly as possible with icy water until the washing
water begins to show a violet colour as it runs off. The intermediate product thus
obtained forms a dark violet precipitate which dissolves in water with a violet
colour. On boiling this solution either alone or with the addition of sulphuric or
hydrochloric acid alizarine cyanine separates in reddish brown flakes.
The intermediate product dissolves readily in alcohol with a violet colour.
In the reacting mixture itself it can be easily recognised as a portion poured into
concentrated sulphuric acid does not display the cinnabar red fluorescence
characteristic of alizarine cyanine whilst the solutions show no essential difference
when held up to the light.

page_text: As hereinbefore stated the action of ammonia upon this intermediate product
affords a new and extremely valuable dyestuff.
The process for obtaining this product is conducted as follows:-
+
The intermediate product obtained as hereinbefore described from 10.parts.by
weight or 10 kilos. of alizarine bordeaux is dissolved in 50 parts by weight (50 kilos.)
of 20 per cent. ammonia; after solution it is diluted with water and filtered and the
dyestuff is then precipitated with acid.
The new product is thus obtained in the form of a violet black precipitate which
dissolves in ammonia and potash lye with considerably bluer or greener colour than
alizarine cyanine. A solution of this product in alcohol is blue violet, a solution
in concentrated sulphuric acid is red without fluorescence.
On aluminium mordants this new colouring matter produces very clear pure blue
shades the chromium lake is coloured a blue green.
Analogous intermediate products are obtained by the oxidation of the bordeaux
from anthra and flavo purpurine which on being treated with ammonia are converted
into similar new colouring matters.
V.
Colouring matters possessing similar properties to those resulting from the
process lastly hereinbefore described are also obtained by taking the colouring
matter described in the Specification No. 12715 of 1890 and resulting from the
action of ammonia upon the alizarine-purpurine-flavo and anthra purpurine bordeaux
intermediate product and treating it in a sulphuric acid solution with an oxidising
agent preferably manganese.
With this object the process may be conducted as follows for example.
About 10 parts (10 kilos.) by weight of the dry ammonia product (obtained from
alizarine-bordeaux-sulphuric-acid-ether and ammonia) are dissolved at a low
temperature in about 150 parts by weight (150 kilos.) of sulphuric acid at 66 degrees
Baumé and about 12 parts by weight (12 kilos.) of finely pulverised manganese
are introduced with continued stirring the temperature being maintained under
about 30 or 40 degrees Centigrade.
After stirring for about two hours the oxidising process is completed and the
mixture is then poured into water, the separating colouring matter is isolated by
filtration and purified by a dissolving process.
By these means the colouring matter is obtained in the form of a dark coloured
paste. Its solution, in ammonia is violet blue in soda lye it is indigo blue, and in
concentrated sulphuric acid it is blue. It dyes a blue violet on aluminium mordants
and on chromium mordants a blue colour tinged with green is obtained.
Dated this 4th day of Novembar 1800.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarinė or
its Analogues.
I, BENJAMIN WILLCOX of 47 Lincoln's 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

page_text: temperature with fuming sulphuric acid containing a high percentage of anhydride.
In this case also in the first place intermediate products (neutral sulphuric
ethers) result which are capable of dyeing with the aid of mordants. These
intermediate products may be converted into "Bordeaux either by dissolving
them in soda or potash and subsequently boiling the solutions with acids, or directly
by heating with acids.
"
The product thus obtained from quinizarin is apparently identical with the
alizarin-bordeaux derived from alizarin and that obtained from xantho purpurin is
the purpurin-bordeaux described in the Specification No. 8725.
The process for the production of these compounds is the same as that described
in the Specification No. 87250 the alizarine referred to in the examples of the said
Specification being replaced by quinizarin or xantho purpurin.
II.
By oxidizing alizarin-bordeaux in a sulphuric acid solution as stated in the
Specification No. 12715 a colouring matter is obtained named alizarin-cyanin
capable of dyeing wool mordanted with chromium salts a greenish-blue. In the
same Specification the application of this oxidation process to flavo and anthra
purpurin-bordeaux is also described.
My foreign correspondents have now discovered that the purpurin-bordeaux
described in the Specification No. 872500 may also by similar treatment be converted
into a cyanin which by judging from a comparison of purified products obtained
from the two bordeaux apparently is identical with the alizarin cyanin derived
from alizarin.
The process is precisely the same as that described in the Specification
No. 127150
The purpurin bordeaux is dissolved in from 10 to 20 times its weight of sulphuric
acid at 66 degrees Baume and finely pulverized black oxide of manganese is stirred
in until a test portion diluted with concentrated sulphuric acid shews the pure
blue colour of alizarin cyanine.
III.
The oxidation of the bordeaux from alizarin or quinizarin purpurin or purpuro-
xanthin flavo- or anthra-purpurin can as my foreign correspondents have now
discovered be effected not only by means of oxide of manganese or arsenic acid
in sulphuric acid solution but also by sulphuric acid alone. The colouring matters
thus obtained however are different from the cyanins aforesaid though they have
on the other hand some resemblance to them. This oxidation takes place at a low
temperature when a fuming sulphuric acid containing a high percentage of anhy-
dride is employed whilst ordinary concentrated sulphuric acid yields the product of
oxidation only at a temperature of 200 degrees Centigrade or more.
When fuming sulphuric acid of high percentage is employed the production of
the Bordeaux and their oxidation into the new products may be combined in one
operation and may be carried out in the following manner.
About 10 parts by weight of dry purpurin are introduced into 150 parts by
weight of fuming acid containing about 80 per cent. of anhydride.
This mixture is allowed to stand for some time at a temperature not exceeding
50 degrees Centigrade until a test portion after having been poured into water
filtered off redissolved in soda decomposed with acids and dried dissolves in alkalies
or concentrated sulphuric acid with a violet colour and shews a strong fluorescence.
The subsequent treatment of the resulting mixture is similar to that described in
the Specification No. 87250. The product thus obtained has the composition of
an hexoxy anthra quinone and the same product results by the same treatment of
alizarin-Bordeaux.
When ordinary concentrated sulphuric acid is employed as an oxidising agent the
process is to be conducted as hereinafter described. In order to convert alizarin
Bordeaux, for example, into a new derivative;

page_text: About 10 parts, by weight, of alizarin Bordeaux are heated to from about
200 to 230 degrees Centigrade with from about 100 to 200 parts by weight of
sulphuric acid at 66 degrees Baumé until a test portion diluted with sulphuric acid
shows a violet colour and a strong fluorescence.
This second method of performing the oxidation can be employed with like
results if instead of the Bordeaux derived from alizarin, purpurin, flavo- and
anthrapurpurin their sulpho acids described in the Specification No. 12715% are
employed, the sulpho group being first split off at the high temperature and the
resulting Bordeaux being thereupon oxidised.
IV.
In preparing alizarin cyanin and its analogues my foreign correspondents find
that just as in the case of the Bordeaux intermediate products are formed which
will dye mordanted wool and that although very readily decomposed under certain
conditions these may be isolated without any difficulty. These products are of
considerable technical value as by acting on them with ammonia very valuable dye-
stuffs are obtained which are totally different from alizarin cyanin and its analogues.
To produce the intermediate product from alizarin Bordeaux the process is
performed as follows.
About 10 parts, by weight, of alizarin Bordeaux are dissolved in about 200 parts
by weight, of sulphuric acid at 66° Baumé and oxidised with about 12 parts by
weight of oxide of manganese taking care not to allow the temperature of the
mixture to rise above about 30 degrees Centigrade as the intermediate product
undergoes decomposition at a higher temperature. The mixture is then poured
into ice water carefully avoiding any rise of temperature whereupon the inter-
mediate product separates in the form of dark violet coloured flakes which are
filtered off and washed as quickly as possible with icy cold water until the escaping
water begins to show a violet colour. The intermediate product thus obtained is
in the form of a dark violet precipitate which dissolves in water with a violet
colour. On boiling the aqueous solution, either alone or with sulphuric or hydro-
chloric acid, alizarin-cyanin separates in reddish-brown flakes.
Its
The intermediate product dissolves readily in alcohol, with a violet colour.
presence in the mixture in which it is produced may easily be recognised as a
portion poured into concentrated sulphuric acid does not display the vermilion-red
Huorescence characteristic of alizarin cyanin whilst the solutions show no essential
difference when held up to the light.
By the action of ammonia upon this intermediate product a new and extremely
valuable dye-stuff is formed. The process for obtaining this product may be
performed as follows:-
The intermediate product obtained as hereinbefore described from 10 parts by
weight of alizarin-Bordeaux is dissolved in 50 parts by weight of 20 per cent.
ammonia the solution is then diluted with water, filtered and the dye-stuff
precipitated with acids.
The new product is thus obtained in the form of a violet-black precipitate which
dissolves in ammonia and potash lye with considerably bluer or greener colour
than alizarin-cyanin. A solution of this product in alcohol is blue-violet, and a
solution of it in concentrated sulphuric acid is red and not fluorescent or only very
slightly fluorescent.
This colouring matter produces with alumina mordants blue shades whilst the
chromium lakes have a blueish-green colour.
Analogous intermediate products are likewise obtained by the oxidation of the
Bordeaux from anthra- and flavo-purpurin and by treatment with ammonia they
are converted into new colouring matters similar to that from alizarin-Bordeaux.
V.

page_text: which are produced by the interaction of ammonia and the alizarin-purpurin, flavo-
and anthra-purpurin Bordeaux intermediate products, and treating them in a
sulphuric acid solution with an oxidising agent, preferably manganese dioxide.
This process may be carried out in the following manner.
About 10 parts, by weight, of the dry ammonia product (obtained from alizarin
Bordeaux sulphuric ether and ammonia) are dissolved at a low temperature in
about 150 parts by weight of sulphuric acid at 66° Baumé and about 12 parts, by
weight, of finely pulverised oxide of manganese are introduced with continued
stirring, the temperature not being allowed to rise above about 30 or 40 degrees
Centigrade. After about two hours stirring the oxidation is completed and the
mixture is then poured into water, the dyestuff which separates is filtered off and
purified by redissolving it and reprecipitating.
By these means the colouring matter is obtained in the form of a dark coloured
paste. Its solution in ammonia is violet-blue, that in soda lye is indigo-blue and
that in concentrated sulphuric acid blue. It dyes a blueish-violet on wool mordanted
with alumina salts and on wool mordanted with chromium salts it dyes a blue with
a greenish hue.
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 conversion of quinizarin and xantho-purpurin into colouring matters
(quinizarin Bordeaux and xantho purpurin Bordeaux) by treatment with fuming
sulphuric acid containing a high percentage of anhydride at a low temperature by
boiling the alkaline solutions of the intermediate products formed in the first place
with acids or by boiling the mere solutions of these intermediate products with
acids.
2. The production of alizarin cyanin from the purpurin-Bordeaux described in
the Specification No. 872500 by treating the said purpurin-Bordeaux in sulphuric
acid solution with manganese dioxide or other suitable oxidising agent.
3. The oxidation of the Bordeaux of alizarin quinizarin, purpuroxanthin,
purpurin, Havopurpurin and anthra purpurin into cyanin-like products by employing
only sulphuric acid either that containing a high percentage of anhydride or
ordinary concentrated acid, the process taking place in the first case at low
temperature, in the latter case at temperatures of about 200 degrees Centigrade.
4. The conversion of the sulpho-acids of the Bordeaux and the analogous com-
pounds enumerated under III and described in. the Specification No. 1271500 into
cyanin-like oxidation products according to the same process which is employed for
the Bordeaux themselves as mentioned under III.
5. The isolation of intermediate products resulting when the Bordeaux and the
analogous compounds enumerated under III are oxidised into the corresponding
cyanine by means of oxidising agents in sulphuric acid solution at low temperature
as herein before described.
6. The conversion of the intermediate products mentioned under V into dye-
stuffs by the interaction of ammonia.
7. The manufacture of dye-stuffs by the action of ammonia on these inter-
mediate products which result when according to the Specification No. 1271590
alizarin, purpurin, flavo- and anthra purpurin are converted into their Bordeaux
derivatives and then oxidising the matters thus produced containing nitrogen by
means of manganese dioxide in sulphuric acid solution.
Dated this 4th day of August 1891.
J. H. JOHNSON & CO.,
47, Lincoln's Inn Fields, Agents.