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

page_text: Date of Application, 5th June, 1890
Complete Specification Left, 5th Mar.. 1891-Accented, 11th Apr., 1891
PROVISIONAL SPECIFICATION.
The Manufacture of New Derivatives of Alizarin 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:-
By the action of sulphuric acid upon alizarine two mono sulpho acids have
heretofore been obtained and fully described namely the common alizarine sulpho
acid or the water soluble alizarine wool colouring matter of commerce (compare
Grache and Liebermann Annalen 160, 144) and the alizarine purple sulpho acid of
v. Perger (Journal für Praktische Chemie (2) 18 173).
My foreign correspondents have now discovered that by the action of fuming
sulphuric acid of different strengths upon alizarine, new well characterised
derivatives result of which the most important technically are obtained as described
in the following examples namely.
T. ALIZARINE DISULPHO ACID.
By allowing from 5 to 10 molecules of sulphuric acid anhydride in the form of
a 20 to 40 per cent. oleum to act upon one molecule of alizarine at a temperature of
130 to 170 degrees Centigrade there is obtained with the intermediate formation of
ordinary alizarine mono sulpho acid a substance which appears to be sulphuric acid
ether of an alizarine disulpho acid. It is characteristic of this substance that its
alkaline solution is scarcely coloured and is permanent even when boiled whilst its
acid solution merely by long standing and instantaneously on boiling changes into
alizarine disulpho acid which then on the addition of alkali is recognized by the
blue violet solution peculiar to the disulpho acid. The following is given as an
example of the manufacture of this alizarine disulpho acid the parts being by
weight.
20 parts of dry pulverized alizarine and 250 parts of oleum containing 24 per cent.
anhydride are slowly heated to from about 135 to 140 degrees Centigrade. A
sample of the sulphurating mixture is occasionally taken and poured into water
boiled up and supersaturated with soda lye. The formation of the disulpho acid is
terminated when the blue colour of this alkaline solution ceases to increase. This
takes place with the ingredients in the proportions hereinbefore specified in about
6 hours. The mixed product of the re-action is then poured out into 1000 parts
of water and boiled up. After cooling the disulpho acid is separated by the addition.
of chloride of lime filtered pressed and dried.
The alizarine disulpho acid thus obtained dissolves very easily in water with a
reddish yellow colour. Contrary to the usual result alizarine mono sulpho acid
cannot be salted out of this solution with common salt but can be easily and
quantitatively extracted with chloride of lime.
The ordinary alizarine mono sulpho acid dissolves with a violet colour in alkalies
but the colour of the alkaline solution of the disulpho acid is blue violet. In like
manner the colours obtained upon mordanted wool with the alizarine disulpho acid
are considerably bluer than the corresponding colours obtained with the ordinary
alizarine mono sulpho acid.

page_text: water to about 200 degrees Centigrade or preferably by heating it with sulphuric
acid of 60 degrees Baumé to about 180 degrees Centigrade one sulpho group is
easily and smoothly split off and an alizarine mono sulpho acid is obtained which is
identical with that which my foreign correspondents have described in their
Specification to their German Patent No. 50164 as alizarine mono sulpho acid (or
a mixture of two isomers) being obtained in the soda melt as an intermediate
product in the production of yellow tinged alizarine from anthora quinone di
sulpho acid.
The alizarine mono sulpho acid thus obtained from the aforesaid alizarine disulpho
acid readily produces in melting with caustic soda a mixture of flavo and anthra
purpurine whence it follows that the disulpho acid as well as the mono sulpho acid
obtained therefrom represent a mixture of two isomers.
To convert the alizarine disulpho acid into the corresponding alizarine mono
sulpho acid being a process of production possessing certain technical advantages
over that dealing with anthra quinone disulpho acid the process is conducted as
follows.
10 parts of alizarine disulpho acid and 60 parts of sulphuric acid at 60 degrees
Baumé are heated to from about 180 to 190 degrees Centigrade. The conversion
is completed when a sample poured into water and supersaturated with soda lye
displays the clear blue colour of the alizarine mono sulpho acid or when the shade
of a sample shows no change compared to one previously taken this being the case
after about 6 hours. The whole is then poured into 500 parts of water salted out
with common salt, filtered pressed and dried.
Of course it is not necessary in this case to previously separate the alizarine
disulpho acid in the solid form but to the sulphurating mixture obtained according
to Example I. may be added the quantity of water or ice calculated for producing
sulphuric acid of 60 degrees Baumé and the conversion may then be proceeded with
in the manner hereinbefore described.
III. By causing a large excess of sulphuric acid anhydride in the form of an
oleum of high percentage to act at a low temperature not exceeding 50 degrees
Centigrade upon alizarine there results a good yield of an intermediate product
insoluble in water from which by several methods of treatment a new product totally
different from alizarine can be obtained. This conversion is most quickly and
conveniently performed by dissolving the product in boiling diluted soda lye and
decomposing it by boiling with hydrochloric acid.
The process may be conducted as follows for example.
10 parts of ground highly dried alizarine are introduced into 100 parts of oleun
containing 70 per cent. of anhydride with precautions to avoid great rise of
temperature.
The mixture is maintained at from about 35 to 40 degrees Centigrade for from
about 24 to 36 hours until a sample poured into icy water and immediately saturated
with soda lye gives a weak yellowisli red solution.
The mixed product of the reaction is then poured out into 200 parts of sulphuric
acid at 66 degrees Baumé or the mono-hydrate and this mixture is poured into
2000 parts of water. The materials are then boiled up filtered and the deposit is
dissolved by boiling with soda lyé in 2000 parts of water. The boiling solution is
precipitated with hydrochloric acid, the precipitate is filtered washed and employed
in the form of a paste.
The new colouring matter can be obtained being easily crystallised out of the
solvents usually employed for alizarine and melts with a dark colour at from 265
to 270 degrees Centigrade.
The colour of its solution in soda lye differs little from that of alizarine.
The latter dissolves with a reddish brown colour in concentrated sulphuric acid
but the solution obtained with the new substance in this solvent is a bright blue
violet. In like manner the new substance colours mordants in far bluer shades
totally different from alizarine with all mordants. With alumina mordants for
example a bordeaux red is obtained, with iron mordants violet blue and so on.

page_text: In addition to alizarine the process hereinbefore described is applicable in like
manner to purpurine, flavo purpurine anthra purpurine and anthra gallol.
The new colouring matters thus obtained differ with regard to their colour and
solution in concentrated sulphuric acid from the original products in the same way
as products obtained from alizarine differ from the latter.
My foreign correspondents have further discovered that the alizarine derivatives
described in Example III. and which they denominate alizarine-bordeaux afford a
number of technically important derivatives. Out of these the nitro derivative is
deserving of special mention being converted by a very smoothly conducted reaction
into a blue colouring matter in the same way as alizarine blue is produced from the
beta nitro alizarine (alizarine lye).
NITRO DERIVATIVE.
The alizarine-bordeaux can be nitrated by exactly the same method as is
employed for alizarine. The process may be conducted as follows for example.
16 parts of dry ground alizarine-bordeaux are suspended in 150 parts of glacial
acetic acid and 53 parts of nitric acid at 42 degrees Baumé are allowed to run
slowly and with stirring into this mixture which is carefully maintained at a
temperature of between 20 and 25 degrees Centigrade. The re-action is concluded
when a sample poured into water is almost completely precipitated by the addition
of soda lye in excess-the soda salt of the nitro substance being almost insoluble in
such lye.
The whole is then poured into water filtered off and washed neutral. The crude
product is very pure but may if desired be purified by producing the difficultly
soluble soda salt by treatment with diluted soda lye and decomposing this salt
with acids.
The nitro substance thus obtained is in the form of a highly red precipitate
which dissolves in a small quantity of soda lye with a violet red colour, the addition
of a further quantity produces an almost complete precipitation as in the case
of beta nitro alizarine. The new product differs essentially from the latter never-
theless in respect of its solution in concentrated sulphuric acid which is of a
beautiful carmine red colour, whereas the alizarine orange produces a yellow solution,
as well as in respect of the colours produced in dyeing, a brick red being obtained
on alumina mordants for example.
AMIDO DERIVATIVE.
The nitro derivative can be easily and smoothly reduced and in this case also
precisely the same methods can be employed as with nitro alizarine. For example
the process may be conducted as follows."
13 parts of dry ground nitro derivative are heated to boiling with from about
300 to 600 parts of glacial acetic acid and a solution of 15 parts zinc chloride in
30 parts hydrochloric acid is added. The reduction is concluded when in a sample
no nitro substance can be detected as a difficulty soluble soda salt by means of
soda lyc.
After cooling the pure amido product is completely separated. It is neutrally
washed after diluting with a little water and filtering. The substance thus obtained
dissolves in concentrated sulphuric acid similarly to the corresponding nitro
derivative. With concentrated soda lye (at 34 degrees Baumé) it affords an indigo
blue solution which on being diluted with water turns to a red violet colour.
The nitro and amido derivative can he employed with advantage in Skraup's
quinoline syntheses and in this case also the reaction proceeds as smoothly as with
alizarine.
This process may be conducted as follows for example.
3 parts of nitro derivative and 4 parts of amido derivative are dissolved in
60 parts of sulphuric acid at 66 degrees Baumé and 10 parts of glycerine are added
to this solution.
The mixture is now cautiously heated taking care that the temperature does not

page_text: rise above 120 degrees Centigrade. The reaction is concluded when a sample
dissolves with a pure indigo blue colour in concentrated sulphuric acid and the
colour: thus obtained does not differ from that of the preceding sample.
"The materials are then poured into water filtered and neutrally washed.
The new colouring matter dissolves in concentrated sulphuric acid with a
beautiful blue colour whereas alizarine blue dissolves in the same with a red brown
colour. In other respects the properties of the new colouring matter resemble those
of alizarine blue and it can be purified by the same methods.
Evidently the colouring matter can also be obtained by heating the nitro
derivative alone with glycerine and sulphuric acid or in the foregoing example the
nitrated bordeaux can be replaced by any other nitro substance.
With bisulphite this new blue colouring product also gives a soluble combination
which can be used as such in dyeing.
Dated this 5th day of June 1800
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
The Manufacture of New Derivatives of Alizarin 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 vorm. Friedrich Bayer & Co., of
Elberfeld, in the Empire of Germany), and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement:-
By the action of sulphuric acid upon alizarin two mono-sulpho acids have here-
tofore been obtained and fully described, namely, the common alizarin sulpho-acid
or the alizarin wool colouring matter of commerce soluble in water (see Graebe and
Liebermann Annalen 160. 144) and the alizarin purple sulpho-acid of v. Perger
[Journal für Practische Chemie (2) 18. 173].
My foreign correspondents have discovered that by the action of fuming sulphuric
acid of different strengths upon alizarin new and well characterised derivatives result
of which the most important, technically, are obtained as described in the following
examples namely.
I. ALIZARIN DISULPHO-ACID.
By allowing from 5 to 10 molecular proportions of sulphuric anhydride in the
form of a 20 to 40 per cent. fuming sulphuric acid to act upon one molecular propor-
tion of alizarin at a temperature of 130 to 170 degrees Centigrade there is obtained
a substance which appears to be a sulphuric acid ether of an alizarin disulpho-acid,
ordinary alizarin mono-sulpho acid being an intermediate product. This substance
is characterised by affording a scarcely coloured and unchangeable alkaline solution.
Its acid solution however changes either on long standing, or instantaneously on
boiling, into alizarin disulpho-acid, which on the addition of alkali, affords the blue-
violet solution peculiar to the disulpho-acid. The following is given as an example
of the manufacture of this alizarin disulpho-acid.
20 parts by weight of dry pulverised alizarin and 250 parts by weight of fuming
sulphuric acid containing 24 per cent. of anhydride, are slowly heated to from about
135 to 140 degrees Centigrade. A sample of the sulphonating mixture is taken and
poured into water and the liquid is then boiled and supersaturated with soda lye.
The formation of the disulpho-acid is terminated when the blue colour of this alkaline
solution ceases to increase in depth. This takes place when the ingredients are used
in the proportions hereinbefore specified in about six hours. The mixed product of
the reaction is then poured out into 1000 parts by weight of water and the liquid is

page_text: boiled. After cooling, the disulpho-acid is separated by the addition of chloride of
potassium filtered, pressed, and dried.
In the foregoing example in place of alizarin, the ordinary alizarin mono-sulpho
acid or its salts may be employed.
The alizarin disulpho-acid thus obtained dissolves very easily in water with a.
reddish yellow colour. Unlike the alizarin mono-sulpho-acid, alizarin disulpho-acid
cannot be salted out of this solution with common salt but can be easily and quanti-.
tatively precipitated with chloride of potassium.
The ordinary alizarin mono-sulpho-acid dissolves with a violet colour in alkalies
but the colour of the alkaline solution of the disulpho-acid is blue-violet. In like
manner the colours obtained upon mordanted wool with the alizarin disulpho-acid
are considerably bluer than the corresponding colours obtained with the ordinary
alizarin mono-sulpho-acid.
II. CONVERSION OF THE ALIZARIN DISULPHO-ACID INTO ALIZARIN
MONO-SULPHO-ACID.
By heating alizarin disulpho-acid obtained as hereinbefore described with water
to about 200 degrees Centigrade, or preferably by heating it with sulphuric acid of
60 degrees Baumé to about 180 degrees Centigrade, one sulpho group is easily split
off and an alizarine mono-sulpho-acid is obtained which is identical with the sulpho-
acid my foreign correspondents have described in the Specification to their German
Patent 50164 as alizarin mono-sulpho-acid (or a mixture of two isomers).
The alizarin mono-sulpho-acid thus obtained from the aforesaid alizarin disulpho-
acid readily produces, when melted with caustic soda, a mixture of flavo- and anthra-
purpurin. This proves that the described disulpho-acid and also the mono-sulpho-
acid obtained therefrom consists of a mixture of two isomers.
To convert the alizarin disulpho-acid into the corresponding alizarin mono-
sulpho-acid, the process is conducted as follows:
10 parts by weight of alizarin disulpho-acid and 60 parts by weight of sulphuric
acid at 60 degrees Baumé are heated to from about 180 to 190 degrees Centigrade..
The conversion is completed when a sample, poured into water and supersaturated
with soda lye, shows no change of the clear blue colour compared with a sample
previously taken. This is usually the case after about 6 hours. The whole is then
poured into 500 parts by weight of water, salted out with common salt, filtered,
pressed, and dried.
Of course it is not necessary in this case to separate the alizarin disulpho-acid in
the solid form but to the sulphurating mixture, obtained according to Example I., the
quantity of water or ice calculated for producing sulphuric acid of 60 degrees
Baumé may be added and the conversion may then be proceeded with in the manner
hereinbefore described.
III. ALIZARIN-BORDEAUX.
By causing a large excess of sulphuric acid anhydride in the form of fuming
sulphuric acid of high percentage to act, at a low temperature, not exceeding
60 degrees Centigrade, upon alizarin, there results a good yield of an intermediate
product insoluble in water from which by several methods of treatment a new pro-
duct which my foreign correspondents denominate alizarin-bordeaux, totally different
from alizarin, can be obtained. This conversion is most quickly and conveniently
performed by dissolving the product in boiling diluted soda lye and decomposing it
by boiling with hydrochloric acid.
The process may be conducted for example as follows:
10 parts by weight of ground highly dried alizarin are introduced into 100 parts
by weight of funing sulphuric acid containing 70 per cent. of anhydride with pre-
cautions to avoid great rise of temperature.
The mixture is maintained at from about 35 to 40 degrees Centigrade for from
about 24 to 48 hours or until a sample poured into ice and immediately saturated
with soda lye gives a weak yellowish red solution.

page_text: The mass is then poured out into 200 parts by weight of sulphuric acid at
66 degrees Baumé, or the mono-hydrate, and this mixture is poured into 2000 parts
by weight of water. The materials are then boiled up, filtered and the deposit is
dissolved by boiling with soda lye in 2000 parts by weight of water.
The boiling
solution is precipitated with hydrochloric acid, the precipitated alizarin-bordeaux
filtered, washed, and employed in the form of a paste.
I do not confine myself exactly to the above details such as proportions, weights,
temperatures, and concentration of the fuming sulphuric acid, as they may be varied
without materially changing the results.
The alizarin-bordeaux easily crystallizes from the solvents usually employed for
alizarin as, for example, glacial acetic acid, or nitrobenzene. The colour of its
solution in soda lye differs but little from that of alizarin. The latter dissolves
with a reddish brown colour in concentrated sulphuric acid but the solution obtained
with alizarin-bordeaux in this solvent is a bright blue-violet. In like manner the
alizarin bordeaux colours mordants far bluer shades and totally different from
alizarin. With alumina mordants for example a claret red is obtained, and with
chromium mordants a violet-blue.
In addition to alizarin the process hereinbefore described is applicable in like
manner to purpurin, flavopurpurin, anthrapurpurin and anthra gallol. The new
colouring matters (bordeaux) thus obtained differ with regard to the colour of their
solution in concentrated sulphuric acid from the original products in the same way
as the alizarin-bordeaux obtained from alizarin, differs from the latter.
My foreign correspondents have further discovered that the alizarin-bordeaux
affords a number of technically important derivatives. Of these the nitro
derivative may be without difficulty converted into a blue colouring matter by a
reaction similar to that by which alizarin-blue is produced from beta-nitro-
alizarin (alizarin-orange).
IV. NITRO-ALIZARIN-BORDEAUX,
The alizarin-bordeaux can be nitrated by the same method as that employed for
alizarin.
The process may be conducted as follows for example.
16 parts by weight of dry ground alizarin-bordeaux are suspended in 150 parts by
weight of glacial acetic acid and 54 parts by weight of nitric acid at 42 degrees
Baumé are allowed to run slowly into this mixture which is kept stirred and is
carefully maintained at a temperature of between 20 and 25 degrees Centigrade.
The reaction is concluded when a sample poured into water is almost completely
precipitated by the addition of soda lyc in excess, the soda salt of the nitro
compound being almost insoluble in an excess of soda-lyc.
The whole is then poured into water, filtered off, and washed. The crude product
is very pure but may if desired be purified by preparing the difficultly soluble
soda salt by treatment with diluted soda lye and decomposing this salt with acids.
The nitro compound thus obtained forms a deep red precipitate which dissolves
in a small quantity of diluted soda lye with a violet-red colour; the addition of a
further quantity of soda lyes produces an almost complete precipitation as in the
case of beta-nitro-alizarin. The new product differs essentially from the latter in
respect of its solution in concentrated sulphuric acid (which is of a beautiful carmine-
red colour, whereas alizarin-orange produces a yellow solution), as well as in
respect of the shades produced in dyeing, with alumina mordants for example.
V. AMIDO-ALIZARIN-BORDEAUX.
The nitro derivative can be easily reduced and in this case also the same
methods can be employed as with nitro-alizarin. For example the process may be
conducted as follows:
13 parts by weight of dry ground nitro-alizarin-bordeaux are heated to boiling
with from about 300 to 640 parts by weight of glacial acetic acid and a solution
of 30 parts by weight of stannous chloride in 60 parts of hydrochloric acid is added.

page_text: The reduction is concluded when by adding soda lye to a sample, no nitro substance
can be detected as a difficultly soluble soda salt.
After cooling the pure amido product separates completely. It is filtered after
diluting with a little water and washed neutral. The substance thus obtained
dissolves in concentrated sulphuric acid similarly to the corresponding nitro
derivative. It dissolves in concentrated soda lye (at 34 degrees Baume) affording
an indigo blue solution which on being diluted with water turns to a red-violet
colour.
colour.
VI. QUINOLINE-DERIVATIVE OF ALIZARIN-BORDEAUX.
The nitro- and amido-alizarin-bordeaux can be employed with advantage in
Skraup's quinoline syntheses and in this case also the reaction proceeds as
smoothly as with alizarin.
This process may be conducted as follows for example.
20 parts by weight of the nitro product and 32 parts by weight of the amido
derivative are dissolved in 300 parts by weight of sulphuric acid at 66 degrees
Baumé and 50 parts by weight of glycerine are added to this solution.
The mixture is then cautiously heated, taking care that the temperature does not
rise above 150 degrees Centigrade. The reaction is concluded when a sample
dissolves with a pure indigo-blue colour in concentrated sulphuric acid and the
colour thus obtained does not differ from that of the preceding sample. The materials
are then poured into water filtered and washed neutral.
The new colouring matter dissolves in concentrated sulphuric acid with a
beautiful blue colour whereas alizarin-blue dissolves in this liquid with a red-brown
colour. In other respects the properties of the new colouring matter resemble
those of alizarin-blue and the said new colouring matter can be purified by the
same methods.
The colouring matter can also be obtained by heating the nitro-derivative alone
with glycerine and sulphuric acid or in the foregoing example the nitrated bordeaux
can be replaced by any other nitro substance.
This new blue colouring matter also forms a soluble combination with bisulphite
which can be used as such in dyeing or printing.
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 :-
First. The process for the manufacture of alizarin-disulpho-acid by heating
alizarin or the ordinary alizarin mono-sulpho-acid or its salts with fuming sulphuric
acid as above described.
Second. The process for the manufacture of alizarin mono-sulpho-acid by
heating the alizarin disulpho-acid herein specified in the preceding claiming
clause with water or diluted acids at a temperature of 200 degrees Centigrade
or with sulphuric acid of 60° Baumé at a temperature of 160 to 200 degrees
Centigrade.
Third. The process of producing intermediate products by acting with a large
excess of sulphuric acid anhydride or with funing sulphuric acid of high percentage
upon alizarin, purpurin, flavo-purpurin, anthrapurpurin, or anthragallol, at a low
temperature not exceeding 60 degrees Centigrade.
Fourth. The production from the intermediate products of Claim 3 of colouring
matters herein before called alizarin-bordeaux, by dissolving the said intermediat
products in alkali and adding acids to the boiling solutions.
Fifth. The process for producing nitro derivatives from the alizarin-bordeaux by
treating the same with nitric acid.
Sixth. The process for producing amidoproducts of alizarin-bordeaux by reducing
the nitroalizarin-bordeaux with reducing agents.
Seventh. The manufacture of quinoline derivatives of alizarin-bordeaux by
heating nitro-alizarin-bordeaux and amido-alizarin-bordeaux with glycerine and

page_text: sulphuric acid with, or without, the employment of nitro products such as nitro-
benzene, nitrotoluene, nitrophenol, nitronaphthalene and the like.
Eighth. The new products herein before described.
T
1
.
J. H. JOHNSON & Co.,
Agents.