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

page_text: Date of Application, 13th Aug., 1890
Complete Specification Left, 1st June, 1891-Accepted, 4th July, 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarine
and 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 com-
municated to me from abroad by The Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld in the Empire of Germany) to be as follows:-
I. In the Provisional Specification accompanying my application for a Patent
No. 87250 certain intermediate products are described as being obtained by the
action of fuming sulphuric acid upon alizarine or alizarine like colouring matters at
a low temperature. These products by successive treatment with soda lye and
boiling with acids are converted into new alizarine colouring matters termed
alizarine bordeaux which conversion may be brought about although less con-
veniently in other ways such as by prolonged boiling with diluted sulphuric acid
or by heating to from about 160 to 180 degrees Centigrade with sulphuric acid of
60 degrees Baumé.
By a careful examination of alizarine bordeaux my foreign correspondents have
now ascertained that the fuming sulphuric acid has an oxidising action on the
alizarine, two atoms of oxygen entering the dioxy anthraquinone molecule in the
reduction of the sulphuric acid anhydride to sulphurous acid and a tetra oxy
anthraquinone free from sulphur results. The sulphuric acid ether of this tetra
oxy anthraquinone is formed in the first place of course being the intermediate
product previously described which on boiling with acids is converted into the tetra
oxy anthraquinone with splitting off of sulphuric acid. The reaction that here
takes place is consequently of a peculiar and novel description the fuming sulphuric
acid having an oxidising action in place of acting as a sulphurising or sulphone
forming agent. By treating this intermediate product with ammonia in place of
with caustic soda new colouring matters which differ from but are similar to
alizarine bordeaux are immediately obtained without heat after treatment with
acids.
For their production the process is conducted as follows taking alizarine for
example.
The reaction mixture obtained as described in the Specification accompanying
the Application No. 87250 from 10 parts by weight of alizarine and 100 parts of
fuming sulphuric acid containing 70 per cent. of anhydride is mixed (precautions
being taken to prevent any rise of temperature) with twice the quantity of sulphuric
acid mono hydrate, this mixture is poured into 2000 parts of ice cold water and the
resulting precipitate is filtered as cold as possible. The intermediate product thus
obtained is thereupon introduced into 150 parts by weight of liquid ammonia and
allowed to stand with occasional stirring for say twelve hours. The materials are
then diluted with water and after treatment with acid the colouring matter is
obtained as a dark coloured precipitate.
The new product differs from alizarine bordeaux by the considerably bluer colour
of the solution in soda lye and by the bluer tone of the colours obtained therewith.
By boiling with soda lye it is converted into alizarine bordeaux with loss of
ammonia; continued boiling with diluted sulphuric acid has the same effect.
In place of employing the intermediate product of alizarine it is evident that
those of purpurine flavo purpurine anthra purpurine or anthra gallol or the inter-
mediate product hereinafter described in part II. as rufigallic acid may be employed
with the same effect.

page_text: II. Rufigallic acid bordeaux
-
In completing the process referred to in the
Specification accompanying the Application No. 8725 my foreign correspondents
have further discovered that the alizarine like products therein referred to can be
replaced by rufigallic acid with like results. By subjecting rufigallic acid to the
action of fuming sulphuric acid containing from 70 to 80 per cent. of anhydride at a
low temperature and proceeding in other respects as directed in the Specification
annexed to the Application No. 8725 a new colouring matter is obtained contrary
to the indications given by Klobukowski (Berichte IX. 1256) according to whom
rufigallic acid is not changed by sulphuric acid anhydride.
An important technical effect is hereby obtained the new product being a very
strong colouring matter producing bordeaux brown tones for example on chromated
wool whereas rufigallic acid is known to produce weak colours only and is valueless
as a dye. The solution of the new colouring matter in concentrated sulphuric acid
is violet whereas the solution of rufigallic acid in the same is red.
III. By subjecting alizarine bordeaux in sulphuric acid solution to the action of
oxidising agents such as manganese or arsenic acid that is to say by applying to
alizarine bordeaux tetra oxy anthraquinone the same reaction as is employed in
producing purpurine from alizarine a new colouring matter is obtained which is
entirely different from the product resulting from the action of fuming sulphuric
acid of high percentage upon purpurine according to the Specification annexed to
the Application No. 872500.
To produce this new colouring matter which is termed alizarine cyanine the
process may be conducted as follows for example.
10 parts by weight of dry pulverized alizarine bordeaux are dissolved in 100 parts
by weight of sulphuric acid at 66 degrees Beaumé and 10 parts by weight of finely
pulverised manganese are gradually introduced (with continual stirring) into this
solution. The reaction taking place under a rise of temperature is known by the
progressive change of the colour of the sulphuric acid solution from violet to blue
and is ended when the colour of this solution ceases to change under prolonged
action or heating to 100 degrees Centigrade. The mixture is poured into water,
boiled, filtered, and washed out, the precipitate being redissolved in a hot diluted
soda solution; this alkaline solution is filtered and the colouring matter precipitated
therefrom with acid.
The colouring matter thus produced forms a red brown deposit a solution of
which in soda lye is blue tinged with violet and is not altogether permanent when
exposed to the air. The solution in concentrated sulphuric acid is of a pure blue
with a red fluorescence. Mordants are coloured by the new product in tones which
are remarkable for their great purity and are totally different from those produced
with alizarine bordeaux. For example a splendid violet is obtained with alumina
mordants and a blue tinged with green on a chromium mordant.
In like manner as hereinbefore described with regard to the alizarine bordeaux
the bordeaux derived from the analogues of alizarine such for example as flavo
purpurine and anthra purpurine can also be converted into new colouring matters
by the action of oxidising agents in sulphuric acid solution and these colouring
matters produce with chromium mordants shades of a greener tinge than the corre-
sponding alizarine cyanine. According to analysis alizarine cyanine is found to
be a penta oxy anthraquinone.
IV. The alizarine bordeaux and the products of the oxidation thereof herein
before described can be readily converted by treatment with fuming sulphuric acid
into sulpho acids which are useful as water soluble wool dyes.
The process for the manufacture of the alizarine bordeaux sulpho acids may be
conducted as follows, for example.
10 parts by weight of dry alizarine bordeaux and 40 parts of fuming sulphuric
acid containing 20 per cent. of anhydride are heated to from about 100 to 120 degrees
Centigrade until a test portion dissolves clearly in water. The sulphurising mixture
is poured into water (500 parts) salted out filtered pressed and dried.
The sulpho acid thus obtained dissolves readily in water the solution being

page_text: coloured blue by the action of soda lye. The colours produced on mordanted wool
are bluer than the corresponding colours obtained with alizarine bordeaux.
In this process in place of starting with alizarine bordeaux the sulpho seid in
question can also be obtained directly from the reaction mixture obtained according
to the Specification accompanying my Application No. 8725 by the action of
fuming sulphuric acid of high percentage upon alizarine by mixing it with twice
the quantity of mono hydrate and heating to from about 100 to 120 degrees
Centigrade until it becomes soluble in water. The product is then poured into
water boiled to decompose the sulphuric acid ester of the sulpho acid that is formed
and salted out preferably with the aid of chloride of calcium on account of the
great excess of acid.
Alizarine bordeaux sulpho acid is also obtained by the action of fuming sulphuric
acid of high percentage upon ordinary alizarine sulpho acid. The process may be
conducted as follows:-10 parts by weight of ordinary alizarine mono sulpho acid
are introduced into about 100 parts of fuming sulphuric acid containing from 70
to 80 per cent. of anhydride and the mixture allowed to stand for a few days at
a temperature of from 20 to 50 degrees Centigrade. The product is then poured
into water heated to boiling to decompose the sulphuric acid ester that is formel
salted out, after cooling, with chloride of lime, filtered pressed and dried.
On
splitting off the sulpho group by the known methods alizarine bordeaux is obtamed
from the sulpho acids produced by either process.
In place of the alizarine bordeaux the other colouring matters obtained from
purpurine anthra purpurine, flavo purpurine, anthra gallol and rufi-gallic acid
described in the Specification accompanying the Application No. 8725 and in
part II. of the present Specification being thereby changed into sulpho acids.
The new products obtained by oxidation from the alizarine bordeaux and
analogous colouring matters can be readily converted in like manner to alizarine
bordeaux into sulpho acids. The process may be conducted as follows:-
10 parts by weight of the dry product of oxidation are heated with 35 parts by
weight of fuming sulphuric acid containing about 20 per cent. of anhydride to
from about 100 to 120 degrees Centigrade until a test portion of the mixture forms
a clear solution in water. The materials are then poured into water salted out
filtered pressed and dried. The sulpho acids thus obtained dissolve readily in
water with a splendid red or in soda lye with a blue colour. On wool previously
mordanted with alumina a beautiful violet colour is produced an equally beautiful
blue being obtained on chromated wool.
Dal 1941 d of
1000
J. H. JOHNSON & Co..
Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Derivatives of Alizarine
and 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 com-
municated to me from abroad by 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:—
In the Specification accompanying my application for the Patent No. 8725
of 1890 certain intermediate products are described as being obtained by the
action of fuming sulphuric acid on alizarine or alizarine-like colouring matters
at a low temperature. These products are converted by gradual treatment with
soda lye and by boiling with acids into new alizarine colouring matters termed
alizarine bordeaux" which conversion may be effected, although less conveniently,
::

page_text: in other ways such as by continuous boiling with dilute sulphuric acid or by
heating to from about 160 to 180 degrees Centigrade with sulphuric acid o
60 degrees Baumé.
By a thorough examination of alizarine bordeaux my foreign correspondents
have now ascertained that the fuming sulphuric acid has an oxidising action on
the alizarine the sulphuric anhydride being reduced to sulphur dioxide two atoms
of oxygen entering into the dihydroxyanthraquinone molecule forming a tetrahy-
droxyanthraquinone free from sulphur. The sulphuric ether of this tetrahydroxy-
anthraquinone which is obtained in the first place and forms the above mentioned
intermediate product on boiling with acids easily changes into tetrahydroxy-
anthraquinone. Consequently a peculiar and new action takes place as the fuming
sulphuric acid exercises an oxidising action and neither sulphonates nor
any sulphone to be formed. By treating the intermediate derivative with ammonia
in place of with caustic soda, new colouring matters differing from alizarine-
bordeaux are obtained and they are separated by acidulating at ordinary
temperature.
causes
I. As to the conversion of alizarine itself the process can be carried out as
follows:-
The mixture which is obtained according to the Specification of the Application
No. 87250 and consists of 10 parts by weight of alizarine and 100 parts of fuming
sulphuric acid containing 70 per cent. of anhydride is very slowly added (in order
to prevent injurious rise of temperature) to twice the quantity of sulphuric acid.
This liquid is then poured into 2000 parts by weight of icy cold water. The
resulting precipitate is filtered off at a temperature as low as possible and is then
added to 150 parts by weight of liquid ammonia and allowed to stand, with
occasional stirring, for about twelve hours. By diluting with water and after
treatment with acid the colouring matter is obtained as a dark coloured precipitate.
The new product differs from alizarine bordeaux by the considerably bluer
colour of its solution in soda lye and by the much bluer shades of the colours
obtained therewith. By boiling with soda lye and also by continued heating with
dilute sulphuric acid it is changed into alizarine bordeaux with loss of ammonia.
In place of the intermediate product from alizarin the respective derivatives from
purpurin, flavo-purpurin, anthrapurpurin, anthragallol, or that which is described
hereinafter in part 11. as rufigallic acid may be employed with the same effect.
II. Rufigallic acid bordeaux. In completing the process described in the
Specification of the Application No. 87250 my foreign correspondents have further
discovered that instead of the alizarine-like products therein mentioned rufigallic
acid may be employed with like results. By treating at a low temperature rufigallic
acid with fuming sulphuric acid containing from 70 to 80 per cent. of anhydride
and proceeding in other respects according to the aforesaid Specification a new
colouring matter is obtained contrary to Klobukowski's account (Berichte IX. 1256)
according to whom rufigallic acid is not at all changed by sulphuric anhydride.
An important technical effect is hereby obtained as the new product forms a very
strong colouring matter and produces for example on chromated wool claret-brown
shades whereas rufigallic acid is known to be perfectly valueless as a dye owing to
its slight colouring power. The solution of the new colouring matter in concentrated
sulphuric acid is violet whereas that of rufigallic acid is red.
III. According to further researches alizarine bordeaux (tetrahydroxyanthra-
quinone) in sulphuric acid solution is changed by the action of oxidising agents
(such as oxide of manganese or arsenic acid that is to say by subjecting alizarine
bordeaux to the same treatment by which purpurin is obtained from alizarin (into
a new colouring matter which differs entirely from the product obtained by the
action of fuming sulphuric acid of high percentage on purpurins according to the
Specification of the Application No. 8725*0.
To produce this new colouring matter (which is termed by my foreign corre-
spondents "alizarin-cyanine ") the process may be performed as follows:-10 parts
by weight of dry pulverised alizarine bordeaux are dissolved in 200 parts by weight

page_text: of sulphuric acid at 66 degrees Baumé; and then 10 parts by weight of finely
pulverised oxide of manganese are gradually added to this solution whilst continually
stirred. Reaction takes place as the temperature rises and its progression is
indicated by the gradual change of the colour of the sulphuric acid solution from
violet to blue. The process is finished when the colour of the sulphuric acid
solution, after standing for some time, ceases to change. Afterwards the mixture
is poured into water and the whole liquid is boiled and the precipitate which
separates is filtered off, washed and redissolved in a hot diluted solution of sodium
carbonate. This alkaline solution is then filtered and the colouring matter
precipitated by means of acids. It forms a red-brown precipitate its solution in
soda lye is blue with a violet huc not very fast when exposed to the air, and its
solution in concentrated sulphuric acid is of a pure blue colour with red fluorescence.
Mordanted material is coloured by the new product in shades remarkable for
their great purity and totally different from those produced by alizarine bordeaux.
For example a splendid violet is obtained with alumina mordants and a blue with
a tinge of green is obtained with chromium mordants.
In the manner herein before described with regard to the alizarine bordeaux the
bordeaux derived from the analogues of alizarin (such for example as flavopurpurin
and anthrapurpurin) may be converted into new colouring matters by the action
of oxidising agents in sulphuric acid solution, and these colouring matters produce
with chromium mordants shades of a greener tinge than do the corresponding
alizarin cyanine which according to analytical research chiefly represents a
pentahydroxyanthraquinone.
IV. The alizarine bordeaux and the product of the oxidation thereof herein-
before described may by treatment with fuming sulphuric acid be readily converted
into sulpho acids which are valuable as wool dyes soluble in water.
The process for the manufacture of the alizarine bordeaux sulpho acid may be
performed in practice as follows:-
10 parts by weight of dry alizarine bordeaux and 40 parts of fuming sulphuric
acid containing 20 per cent. of anhydride are heated to from about 100 to 120 degrees
Centigrade until a test portion dissolves clearly in water. The mixture is poured
into water (500 parts by weight) and the sulphonated product after having been
salted out is filtered off pressed and dried.
The alizarine bordeaux sulpho acid readily dissolves in water and the solution
becomes blue on the addition of soda lye. The shades it produces on mordanted
wool are bluer and clearer than are the corresponding colours obtained by means of
alizarine bordeaux.
Instead of employing alizarine bordeaux the sulpho acid in question may also be
produced directly from the mixture obtained according to the Specification accom-
panying my Application No. 8725 by the action of fuming sulphuric acid of high
percentage upon alizarine by mixing it with twice the quantity of mono hydrate
and heating to from about 100 to 120 degrees Centigrade until it becomes entirely
soluble in water. The mixture is then poured into water and this liquid is boiled
in order to decompose the sulphuric ether which is first formed. The alizarine
bordeaux sulpho acid thus obtained is salted out most conveniently with the aid of
potassium chloride.
Alizarine bordeaux sulpho acid is also obtained by the action of fuming sulphuric
acid of high percentage on ordinary alizarine sulpho acid and this process may be
performed as follows:-
10 parts by weight of ordinary alizarine mono sulpho acid are added to about
100 parts by weight of fuming sulphuric acid containing from 70 to 80 per cent. of
anhydride and the mixture after standing for a few days at a temperature of from
20 to 50 degrees Centigrade is poured into boiling water in order to decompose the
sulphuric ether that is formed in the first place. The alizarine bordeaux sulpho
acid which is easily separated by salting out with potassium chloride at the ordinary
temperature is then filtered off, pressed and dried. On separating the sulpho

page_text: group by the known methods alizarine bordeaux is obtained from the sulpho acids
produced by either process.
Other colouring matters similar to the alizarine bordeaux and obtained from
purpurin, anthrapurpurin, flavopurpurin, described in the Specification accompanying
the Application No. 872500 and in part II. of the present Specification can also be
changed into sulpho acids in the same manner as in the case of the alizarine
bordeaux.
The new products obtained by oxidation from alizarine bordeaux and the
analogous colouring matters can be readily converted in a similar manner into
sulpho acids. The process may be performed as follows.
10 parts by weight of the dry product of oxidation are heated with 35 parts by
weight of fuming sulphuric acid (containing about 20 per cent. of anhydride) to from
about 100 to 120 degrees Centigrade until a test portion of the mixture dissolves
clearly in water. The solution thus obtained is then poured into water and the
sulpho acid is salted out, filtered, pressed and dried. These sulpho acids readily
dissolve in water with a splendid red colour and in soda lye with a blue colour.
They produce on wool mordanted with alumina a pretty violet colour and on wool
mordanted with a chrome mordant exceedingly blue shades.
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
I. The production of new colouring matters by the action of ammonia on the
intermediate products obtained according to the third claim of the Specification of
the Patent No. 8725 from alizarine purpurin, flavopurpurin, anthrapurpurin, and
anthragallol.
11. The manufacture of a new dyestuff by the treatment of rufigallic acid with
fuming sulphuric acid containing a high percentage of anhydride and at a low
temperature.
III. The process for the manufacture of new colouring matters (termed "alizarine-
cyanines") by oxidising alizarine bordeaux or its analogues described in the
Specification No. 87250 in sulphuric acid solution by means of oxidising agents.
IV. The transformation both of alizarine bordeaux or its analogues described
in the Specification No. 8725 and of the products obtained by oxidation therefrom
according to the third claim of the said Specification into sulpho acids very
valuable as wool dyes by heating them to about 100 degrees Centigrade with
an excess of fuming sulphuric acid.
V. The new dyestuffs hereinbefore described.
Dated thi
ст
1001
J. H. JOHNSON & Co.,
Agents.