A New Class of Derivatives of Alizarine-blue..
Year: 1888

page_text: Pate of Application; 5th Oct., 188
Complete Specification Left, 5th July, 1889-Accepted, 10th Aug., 1889
PROVISIONAL SPECIFICATION.
A New Class of Derivatives of Alizarine-blue..
I, JAMES YATE JOHNSON, of 47 Lincolns Inn Fields, in the County of Middlesex,
Gentleman, do hereby declare the nature of this invention which has been com
municated to me from abroad by the Badisclie Anilin & Soda Fabrik of Ludwig-
shafen-on-the-Rhine, Germany, to be as follows:-
This Invention is based on the discovery that by the.action of sulphuric acid, or
of sulphuric anhydride upon Alizarine-Blue a new and peculiar class of derivatives is
formed some of which may be usefully employed as colouring, matters suitable for
Dyeing and Printing whilst others play the part of intermediate products in the
preparation of the said colouring matters.
The methods of producing the above named derivatives of Alizarine-Blue are
hereinafter described under the following divisions.
I. Alizarine-Blue-sulphuric acid
I. ALIZARINE-BLUE-SULPHURIO. AOID.
What. I name "Alizarine-blue-sulphuric acid "istas derivative of Alizarino-Blue
resulting from a limited or moderate action of sulphuric anhydride upon the said
colouring matter and possessing the general properties of a sulphuric ether of the
same, in as far as it is characterised by its tendency to undergo a decomposition* into
alizarine-blue and sulphuric acid under the influence of acids whilst in the presence of
alkalies it is-marked by its relative stability:
Upon the said property of regenerating Alizarine-blue depends the industrial
application of Alizarine-blue-sulphuric acid as a colouring matter and in this 'respect
it bears a certain analogy to the known Bisulphite-compounds of Alizarine-blue which
in a similar manner upon being employed for Dyeing or Printing in admixture with
acids or acid mordanis regenerate Alizarine-blue and are thus capable of fixing the
metallic lakes of the said colouring matter within.or upon fibre.
In order to produce Alizarine-blue-sulphuric acid from Alizarine-blue by the
action of sulphuric anhydride this agent may be employed in its free state or by
preference in the state of a. moderately concentrated funning sulphuric acid and in
a relative proportion corresponding to about one molecule (or somewhat more), for
each molecule of Alizarine-blue employed.
The following is an example of the manner in which Alizarine-blue-sulphuric acid
may be conveniently prepared in a mercantile condition.
About. ten parts by weight of dry and finely powdered Alizarine-blue are in
small portions at a time and under constant stirring added to about twenty parts
by weight of.fuming sulphuric acid containing about twenty three per cent. of free
anhydride. This operation: which generally requires about from four to six hours
being finished. the: mixture or solution thus obtained is to be kept agitated at a
temperature of about. fifty degrees centigrade during the space of about from four to
five hours in order to ensure a perfect dissolution of the alizarine-blue and then the
conversion of the latter into its sulphuric acid derivative is to be completed by
continuously agitating. the solution at an ordinary temperature during about twelve
hours.
Throughout this operation the access of moist air ought to be carefully, excluded.
The result of the process is then gradually poured into a mixture of ice and water

page_text: and the precipitate of alizarine-blue-sulphuric acid thus produced is to be filtered as
quickly as possible washed with ice-cold water and pressed.
In order to convert the free and unstable alizarine-blue-sulphuric acid into a
mercantile product soluble in water and possessing a sufficient degree of stability it
is advisable to prepare the alkaline salts of the same by the application of the known
methods for instance by mixing the free Alizarine-blue-sulphuric acid obtained as
above described in the state of a pressed pulp with as much of a diluted caustic soda
liquor as will be required for converting the same into a purple crystalline salt
presenting the appearance of pure indigotine. The sodium salt of the colouring
imatter thus prepared may then be obtained in a dry state by evaporation.
Alizarine-blue-sulphuric acid presents the following characteristic properties.
It is capable of forming two series of alkaline salts soluble in water those containing
the minimum of alkali exhibit a yellow or brown appearance both in the dry state
and in the state of their concentrated aqueous solutions, whilst a larger proportion
of alkali effects a change of the said colours into purple or blue. The purple solution
of the potassium or sodium-salts assumes gradually the before named yellow or brown
tint upon the addition of water a similar change (owing to an abstraction of alkali)
takes place by carefully adding a small amount of a mineral or organic acid or by
passing a current of carbonic acid gas into the said purple solutions. This point being
reached a further addition of a mineral or organic acid causes the Alizarine-blue-
sulphuric acid thus set free to become precipitated in Alizarine-like yellow flocks
which quickly assume a crystalline appearance. By the simultaneous application of
heat the above named decomposition ensues alizarine-blue and sulphuric acid being the
result. This decomposition forms an especially striking experiment, if acetic acid he
employed for such purpose the solution becoming decolorized whilst Alizarine-blue
separates out in small glittering crystals closely resembling artificial indigo. By
employing sulphuric or hydrochloric acids in sufficient excess the well known red
solutions of the corresponding salts of alizarine-blue will form.
The alkaline solutions of Alizarine-blue sulphuric acid are precipitated by caustic
and carbonated alkalies as well as by common salt.
Alkaline reducing agents such for instance as zinc dust and caustic potash liquor
cause the purple colour of the alkaline solutions of alizarine-blue-sulphuric acid to
change into a yellow tint which upon the access of air changes back into the original
purple hue.
Alizarine-blue-sulphuric acid is chiefly useful for Dyeing wool or other animal
fibre with the aid of mordants used for the production of the variously coloured lakes
of alizarine-blue. On account of sulphuric acid becoming liberated during its
decomposition as above described it is less suitable for the Printing of cotton than are
the before-mentioned bisulphite compounds of alizarine-blue.
II. ALIZARINE-BLUE-SULPHOACID.
If the action of moderately strong fuming sulphuric acid upon alizarine-blue be
assisted by the application of heat exceeding a temperature of about one hundred
degrees centigrade a comparatively stable sulphoderivative of the said colouring matter
will be obtained possessing the percentage composition and general behaviour of a
monosulphoacid of alizarine-blue. The precise conditions of time and of temperature
required for the production of such sulphoderivative may be varied within wide limits
and are depending upon the relative proportion and strength of the fuming sulphuric
acid employed. The sulphonating process may for instance be carried on at a
temperature ranging from about one hundred degrees centigrade to about one hundred
and thirty degrees centigrade by employing about five parts by weight of a fuming
sulphuric acid containing about twenty three per cent. of free anhydride whilst a less
concentrated fuming acid requires a proportionate increase of temperature say to one
hundred and seventy degrees centigrade or higher.
The following is an example of the manner in which alizarine-blue sulphoacid may
be conveniently prepared.

page_text: About ten parts by weight of dry and finely powdered Alizarine-blue are gradually
mixed with about fifty parts by weight of fuming sulphuric acid containing about
twenty three per cent. of free anhydride and then the mixture or solution thus produced
is heated up to about from one hundred and twenty to about one hundred and thirty
degrees centigrade during the space of about from six to eight hours or until a sample
of the product when poured into water yields a precipitate which after being filtered
and washed forms a clear green solution upon the addition of caustic potash liquor in
excess and likewise dissolves in much boiling water.
The result of the operation is then poured into water and the precipitate of alizarino
blue sulphoacid thus obtained, after being heated up with the acid solution to about
one hundred degrees centigrade and then being allowed to cool down to about forty
degrees centigrade, is filtered washed with cold water, prossed and dried.
Free Alizarine-blue-sulphoacid, obtained as above described, is nearly insoluble in
cold water and dissolves as before mentioned, in much boiling water. The aqueous
solution possesses a characteristic blucish-green color. The alkaline salts of alizarine-
blue-sulphoacid are readily soluble in water with a blue colour which upon the addition
of caustic potash or soda liquor in excess changes into a bright green, no precipitation
of the alkaline salt of the colouring matter taking place. Common salt if added in
sufficient excess, precipitates the said alkaline salts, whilst soluble calcium or barium
salts cause a separation of the corresponding saline compounds of alizarine blue
sulphoacid.
If hydrochloric acid be added to an alkaline solution of alizarine blue sulphoacid
a purple crystalline precipitate of the free acid will be produced, which dissolves in an
adequate excess of hydrochloric acid with a red colour, no regeneration of alizarine
blue thus taking place not even, at a boiling heat. Zinc dust reduces the colouring
matter in alkaline solution, the red solution thus produced quickly reassumes its
original blue or green hue upon the access of air.
Alizarine blne sulphoacid can be employed for dyeing and printing in a similar
manner as alizarine blue. The shades, which may be obtained upon chrome-
mordanted wool, are of a tint somewhat greener than that of the corresponding dyes
of alizarine blue.
Alizarine blue sulphoacid dissolves in solutions of the bisulphites of potash, soda or
ammonia, and may be regenerated from the bisulphite compounds thus formed in a
very pure condition by the addition of acids or acid salts especially at an elovated
temperature. The said bisulphite compounds may therefore be conveniently employed
for fixing alizarine blue sulphoacid, within or upon textile fibres or fabrics, with the
aid of the appropriate mordants in the manner practised in the dyeing or printing
with the analogous bisulphite compounds of alizarine blue.
III. INTERMEDIATE PRODUCT.
A derivative greatly differing from the above described alizarine blue sulphuric
acid, both in respect of its properties as well as of the transformations which it is
capable of undergoing, may be obtained by pushing the action of sulphuric
anhydride upon alizarine blue to its maximum extent essentially in the manner
hereafter described. For this purpose sulphuric anhydride is conveniently employed
in the state of a highly concentrated fuming sulphuric acid, (say of one containing
about seventy per cent. of free anhydride,) and a relatively very large proportion of
the agent (say about ten and more molecules for each molecule of the alizarine blue to
be operated upon) is to be used.
The following is an example of the manner in which the said derivative may be
produced.
About ten parts by weight of perfectly dry and finely powdered alizarine blue are-
in very small portions at a time-added to about one hundred parts by weight of
fuming sulphuric acid containing about seventy per cent. of free anhydride.
Throughout this operation the mixture is to be kept agitated and rise of temperature
ought to be carefully prevented by the application of external cooling. After the

page_text: By submitting the before-described alizarine-blue-green to the action of mono-
hydrated or rectified sulphuric acid at a temperature exceeding one hundred degrees
Centigrade, the red colour of the sulphuric acid solution of the said colouring matter
gradually changes into a purple, owing to the production of a new derivative, which I
term "Alizarine-Green."
The said conversion of alizarine-blue-green into .alizarine-green may, for instance,
be effected by heating about one part by weight of alizarine-blue-green with about
ten parts by weight of mono-hydrated sulphuric acid at a temperature ranging from
about one hundred and twenty degrees Centigrade to about one hundred and thirty
degrees Centigrade during the space of about from six to eight hours. By pouring
the result of the operation into water a precipitate of the new derivative will then be
obtained.
As however alizarine-blue-green in its turn results from the action of sulphuric acid
upon the intermediate product as hereinbefore described, it is practically advantageous
to omit the previous separation of alizarine-blue green from its sulphuric acid solution
and simply to continue the action of sulphuric acid until the desired production of
alizarine-green has been completed.
The following is an example of the manner in which alizarine-green may be
conveniently prepared from alizarine-blue by the successivo, action of sulphuric
anhydride and of mono-hydrated sulphuric acid without separating the "intermediato
product," formed at first (as above described under Division III) and by omitting the
previous separation of alizarine-blue-green (as above described under Division IV).
About ten parts by weight of perfectly dry and finely powdered alizarine-blue are
added in very small portions at a time to about one hundred parts by weight of
fuming, sulphuric acid containing about seventy per cent. of free anhydride.
Throughout this operation the mixture is to be kept agitated and every rise of
temperature ought to be carefully prevented by the application of external cooling.
After the entire amount of alizarine blue has thus been added (an operation which
generally requires about eight hours) the mixture or solution is to be agitated during
the space of another five or six hours at a temperature of about fifty degrees Centigrade
in order to complete the conversion of alizarine blue into its new derivative, and then
(without separating the intermediate product thus formed) about two hundred parts
by weight of concentrated or rectified sulphuric acid of about 1.84 specific gravity are
added, and the temperature of the solution is gradually raised to about from one
hundred and twenty degrees Centigrade to about one hundred and twenty five degrees
Centigrade. After maintaining the temperature at the said range for about eight
hours the result of the operation is poured into water and the precipitate of alizarine-
green thus obtained, after being heated up with the acid solution to about one hundred
degrees Centigrade and then being allowed to cool down to about forty degrees
Centigrade, is filtered, washed and pressed.
Alizarine-green, prepared as above described, presents the following characteristic
properties.
In its free or uncombined state it appears under the form of fine blueish-grey,
needle-shaped crystals, which are insoluble in cold water and possess only a slight
degree of solubility in boiling water and in alkaline solutions. Alizarine-green
forins .blue saline, compounds with alkaline carbonates and green compounds upon

page_text: being mixed with caustic potash or soda liquor in excess. The said compounds or
salts of alizarine-green are quite insoluble in excess of caustic alkaline solutions. It
combines with the bisulphites of potash, soda or ammonia, forming soluble compounds
analogous to those of alizarine blue and capable of being used in an analogous manner
in dyeing and printing with the aid of appropriate mordants. Alizarine-green can
likewise be employed as a dyestuff or colouring matter in a similar manner to that in
which alizarine blue is employed. The shades produced by alizarine-green are very
fast and are distinguished from the corresponding shades of alizarine blue, principally
from those obtained with the aid of chrome-mordants, by their tint more or less
approaching green.
Dated this 5th da
hon 1000
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
A New Class of Derivatives of Alizarine-blue.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been
communicated to me from abroad by The Badische Anilin & Soda Fabrik of
Ludwigshafen on the Rhine 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 is based upon the discovery that by the action of sulphuric acid or
of sulphuric anhydride upon Alizarine Blue a new and peculiar class of derivatives
is formed some of which may be usefully employed as colouring matters suitable for
dyeing and printing, whilst others play the part of intermediate products in the
preparation of such colouring matters.
The above named derivatives of Alizarine-Blue which my foreign correspondents
have found to yield practical results and the methods of producing the same are
hereinafter described under the following divisions :-
I. Alizarine Blue-sulphuric acid.
II. Alizarine Blue-sulpho acid.
III. Intermediate Product.
IV. Alizarine-Blue-green.
V. Alizarinė-Green.
I. ALIZARINE-BLUE-SULPHURIC ACID
The colouring matter which my foreign correspondents name "Alizarine-blue
sulphuric acid" is a derivative of Alizarine Blue, resulting from a limited or moderate
action of sulphuric anhydride upon the latter colouring matter and possessing the
general properties of a sulphuric ether of the same, in so far as it is characterised by
a tendency to undergo a decomposition into Alizarine Blue and sulphuric acid under
the influence of acids, whilst in the presence of alkalies it is marked by its relative
stability.
Upon the said property of regenerating Alizarine Blue depends the industrial
application of Alizarine Blue-sulphuric acid as a colouring matter, and in this
respect it bears a certain analogy to the known Bisulphite-compounds of Alizarine
Blue, which in a similar manner upon being employed for dyeing or printing in
admixture with acid mordants, regenerate Alizarine Blue and are thus capable of
fixing the metallic lakes of the said colouring matter within or upon the textile fibre
or fabric.
In order to produce Alizarine Blue-sulphuric acid from Alizarine Blue by the
action of sulphuric anhydride, this agent may be employed in its free state or, by
preference, in the state of a moderately concentrated fuming sulphuric acid
The colouring matter which my foreign correspondents name "Alizarine-blue
sulphuric acid" is a derivative of Alizarine Blue, resulting from a limited or moderato
action of sulphuric anhydride upon the latter colouring matter and possessing the
general properties of a sulphuric ether of the same, in so far as it is characterised by
a tendency to undergo a decomposition into Alizarine Blue and sulphuric acid under
the influence of acids, whilst in the presence of alkalies it is marked by its relative
stability.
Upon the said property of regenerating Alizarine Blue depends the industrial
application of Alizarine Blue-sulphuric acid as a colouring matter, and in this
respect it bears a certain analogy to the known Bisulphite-compounds of Alizarine
Blue, which in a similar manner upon being employed for dyeing or printing in
admixture with acid mordants, regenerate Alizarine Blue and are thus capable of
fixing the metallic lakes of the said colouring matter within or upon the textile fibre
or fabric.
In order to produce Alizarine Blue-sulphuric acid from Alizarine Blue by the
action of sulphuric anhydride, this agent may be employed in its free state or, by
preference, in the state of a moderately concentrated fuming sulphuric acid

page_text: and in a relative proportion corresponding to about one molecule (or somewhat
more) of available sulphuric anhydride for each molecule of Alizarine Blue
employed.
The following is an example of the manner in which Alizarine-Blue-sulphuric acid
may be prepared and then conveniently transformed into the mercantile condition of
a stable saline compound.
About ten parts by weight of dry and finely powdered Alizarine Blue are, in small
portions at a time and whilst constantly stirred, added to about twenty parts by
weight of fuming sulphuric acid, containing about twenty-three per cent. of free
anhydride. This operation generally requires about from four to six hours and on
being finished, the mixture or solution thus obtained is kept agitated at a temperature
of about fifty degrees Centigrade during the space of about from four to five hours,
in order to ensure a perfect dissolution of the Alizarine Blue, and then the conversion
of the latter into its sulphuric acid derivative is completed by continuously
agitating the solution at an ordinary temperature during about another twelve
hours. Throughout these operations the access of moist air ought to be carefully
excluded.
The result of the process is then gradually poured into a mixture of ice and water
and the precipitate of Alizarine Blue-sulphuric acid thus produced is filtered as quickly
as possible, washed with ice cold water and pressed.
In order to convert the free, and unstable Alizarine Blue-sulphuric acid into a
mercantile product, soluble in water and possessing a sufficient degree of stability,
it is advisable to prepare its alkaline salts by the application of the known methods,
say for instance by mixing the free Alizarine Blue-sulphuric acid, obtained as above
described in the state of a pressed pulp, with as much of a diluted caustic soda liquor
as is required for converting the same into a purple crystalline salt, presenting the
appearance of pure indigotine. The sodium salt of the colouring matter thus
prepared may then be obtained in a dry state by evaporation, or it may be used in
the state of a paste.
Alizarine Blue-sulphuric acid presents the following characteristic properties.
It is capable of forming two series of alkaline salts, soluble in water, those
containing the smaller proportion of alkali exhibiting a yellow or brown appearance
both in the dry state and in the state of their concentrated aqueous solutions, whilst
a larger proportion of alkali effects a change of the said colours into purple or blue.
The purple solutions of the potassium or sodium-salts (containing the larger
proportion of alkali) assume gradually the before named yellow or brown tint upon
the addition of water, a similar change (owing to an abstraction of alkali) takes
place when a small amount of a mineral or organic acid is carefully added or a
current of carbonic anhydride is passed into the said purple solutions. This point
being reached, a further addition of a mineral or organic acid causes the Alizarine.
Blue-sulphuric acid, thus set free, to become precipitated in Alizarine-like yellow
flocks, which quickly assume a crystalline appearance. By the simultaneous
application of heat the above named decomposition of the Alizarine Blue sulphuric
acid into Alizarine Blue and sulphuric acid ensues. This decomposition forms an
especially striking experiment, if acetic acid be employed for such purpose; the
solution becoming decolorized whilst Alizarine Blue separates out in small glittering
crystals, closely resembling artificial indigo. By employing sulphuric or hydro-
chloric acids in sufficient excess the well known red solutions of the corresponding
salts of Alizarine Blue will be formed.
The alkaline solutions of Alizarine Blue-sulphuric acid are precipitated by caustic
and carbonated alkalies as well as by common salt.
Alkaline reducing agents, such for instance as zinc dust and caustic potash
liquor, cause the purple colour of the alkaline solutions of Alizarine Blue-sulphuric
acid to change into a yellow tint, which upon the access of air changes back into the
original purple bue.
Alizarine Blue-sulphuric acid is chiefly useful for dyeing wool or other animal
fibre with the aid of the mordants used for the production of the variously coloured

page_text: decomposition, as above described, it is less suitable for the printing of cotton (than
are the before mentioned bisulphite compounds of Alizarine Blue.
II. ALIZARINE BLUE-SULPHO ACID..
If the action of moderately strong fuming sulphuric acid upon Alizarine Blue be
assisted by the application of heat, exceeding a temperature of about one hundred
degrees Centigrade, a comparatively stable sulpho derivative of the said colouring.
matter will be obtained, possessing the percentage composition and general behaviour
of a mono sulpho acid of Alizarine Blue. The precise conditions of time and, of
temperature required for the production of such sulpho derivative may be varied
within wide limits and are dependant upon the relative proportion and strength of
the fuming sulphuric acid employed. The sulphonating process may, for instance,
be carried on at a temperature ranging from about one hundred degrees Centigrade
to about one hundred and thirty degrees Centigrade by employing about five parts
by weight of a fuming sulphuric acid containing about twenty three per cent..
of free anbydride, whilst a less concentrated fuming acid requires a proportionate
increase of temperature say to one hundred. and seventy degrees Centigrade or
higher.
The following is an example of the manner in which Alizarine Blue-sulpho acid'
may be conveniently prepared.
About ten parts by weight of dry and finely powdered' Alizarine Blue are
gradually mixed and agitated with about fifty parts by weight of fuming sulphuric
acid, containing about twenty three per cent. of free anhydride, and then the mixture
or solution thus produced is heated up to about from one hundred and twenty to
about one hundred and thirty degrees Centigrade and agitated for about from
six to eight hours, or until a sample of the product, when poured into water
yields a precipitate, which after being filtered and washed forms a clear green.
solution upon the addition of caustic potash liquor in excess and likewise dissolves in
much boiling water:
The result of the operation is then poured into water and the precipitate
of Alizarine Blue-sulpho acid: thus obtained, after being heated up with the
acid solution to about one hundred degrees Centigrade and then being allowed to
cool down to about forty degrees Centigrade, is filtered, washed with cold water,
pressed and dried.
Free Alizarine Blue-sulpho acid, obtained as above described, is nearly insoluble in
cold water and dissolves; as before mentioned, in much boiling water. The aqueous
solution possesses a characteristic blueish-green colour. The alkaline salts of Alizarine
Blue-sulpho acid are readily soluble in water with a blue colour, which upon the
addition of caustic potash-or sodá liquor in excess changes into a bright green, no
precipitation of the alkaline salt of the colouring matter taking place. Common salt,
if addedlin sufficient excess precipitates the said alkaline salts, whilst soluble calcium
or barium salts-cause a separation of 'the corresponding saline compounds of Alizarine-
Blue-sulpho acid.
If hydrochloric acid be added to an alkaline solution of Alizarine Blue-sulpho
acid a purple crystalline precipitate of the free acid will be produced, which
dissolves in an adequate excess of hydrochloric acid with a red colour, no
regeneration of Alizarine-Blue thus taking place, not even at a boiling heat.
Zinc dust reduces the colouring matter in alkaline. solution, the red solution
thus produced quickly reassumes its original blue or green hue upon the access
of air.
Alizarine Blue-sulpho acid can be employed for dyeing and printing. in a similar
manner to Alizarine Blue. The shades, which may be obtained upon chrome-
mordanted wool, are of a tint somewhat greener than that of the corresponding dyes
of Alizarine Blue.
Alizarine Blue-sulpho acid'dissolves in solutions of the bisulphites of. potash,,soda.

page_text: or ammonia, and may be regenerateal from the bisulphite-compounds thus formed in
a very pure condition by the addition of acids or acid salts especially at an clevated
temperature. The said bisulphite-compounds may therefore be conveniently employed
for fixing Alizarine Blue-sulpho acid within or upon textile fibres or fabrics with the
aid of the appropriate mordants in the manner practised in dyeing or printing with
the analogous bisulphite-compounds of Alizarine Blue.
III. INTERMEDIATE PRODUCT:
A derivative greatly differing from the above described Alizarine Blue-sulphuric
acid, both in respect of its properties as well as of the transformations, which it is
capable of undergoing, may be obtained by pushing the action of sulphuric anhydride
upon Alizarine Blue in the cold or at a slightly elevated temperature to its maximum
extent, essentially in the manner hereinafter described. For this purpose sulphuric
anhydride is conveniently employed in the state of a highly concentrated
fuming sulphuric acid-(say of one containing about seventy per cent. of free-
anhydride) and a relatively very large proportion of the agent,-(say about
ten and more molecules for each molecule of the Alizarine Blue to be operated
upon)—is used.
The following is an example of the manner, in which the said derivative may be
produced.
About ten parts by weight of perfectly dry and finely powdered Alizarine Blue are
in very small portions at a time-added to about one hundred parts by weight of
funing sulphuric acid containing about seventy per cent. of free anhydride.
Throughout this operation the mixture is kept agitated and every rise of temperature
ought to be carefully prevented by the application of external cooling. After the
entire amount of Alizarine Blue has thus been added-an operation which generally
requires about eight hours the mixture or solution is agitated for another five or six
hours at a temperature of about fifty degrees Centigrade, in order to complete the
conversion of Alizarine Blue into its new derivative.
The product thus formed is an extremely unstable compound, which can hardly be
separated from its acid solvent without suffering some decomposition. If it be
desired to effect such separation, the result of the before-described operation ought
to be mixed as quickly as possible with strongly refrigerated monohydrated sulphuric
acid, in order to reduce the strength of the fuming acid in excess and then the
solution thus obtained should without delay be poured upon ice. In this manner a
yellowish-brown crystalline precipitate will be produced, whilst a portion of the
product forms a brown solution, from which it gradually separates out after standing
some time. The new derivative: thus: obtained.is.soluble in water, acids and alkalies.
As long as no decomposition has ensued, the acid solutions exhibit a brownish-yellow
colour, but gradually at ordinary temperature and rapidly upon being heated to
ebullition the said solutions assume a red colour owing to the production of
Alizarine-Blue green, the colouring matter immediately hereinafter to be described.
A similar production of the said Alizarine-Blue green takes place in the alkaline
solutions of the unstable derivative and manifests itself by a corresponding change
of colour. In the presence of au excess of caustic potash or soda the alkaline
solution of the derivative which is dingy brown at first, turns into a solution
of a bright green colour, whilst carbonated alkalies effect: a change of colour
into. blue.
IV. ALIZARINE BLUEGREEN.

page_text: The following is an example of the manner in which Alizarine Green may be
conveniently prepared from Alizarine Blue by the successive action of sulphuric
anhydride and of sulphuric acid without separating the "intermediate product,"
formed at first (as above described under Division III and omitting also
the previous separation of Alizarine Blue green (as above described under
Division IV).
About ten parts by weight of perfectly dry and finely powdered Alizarine Blue
are added in very small portions at a time to about one hundred parts by weight of
funing sulphuric acid containing about seventy per cent. of free anhydride.
Throughout this operation the mixture is kept agitated and every rise of temperature
ought to be carefully prevented by the application of external cooling. After the
entire amount of Alizarine Blue has thus been added (an operation which generally
requires about eight hours) the mixture or solution is agitated during the space of
another five or six hours at a temperature of about fifty degrees Centigrade in order
to complete the conversion of Alizarine Blue into the "intermediate product" as
above described under Division III) and then without separating this body about two
two hundred parts by weight of concentrated or rectified sulphuric acid of about
1.84 specific gravity are added and the temperature of the solution is gradually raised
to about from one hundred and twenty degrees Centigrade to about one hundred and
twenty five degrees Centigrade. After maintaining the temperature at the said
range for about eight hours the result of the operation is poured into water and
heated up to about one hundred degrees Centigrade. It is then allowed to cool down
to about forty degrees Centigrade, and the precipitate of Alizarine Green thus
obtained is filtered washed and pressed.
Alizarine Green, prepared as above described, presents the following characteristic
properties:-
It
In its free or uncombined state it appears in the form of fine blueish grey, needle
shaped crystals, which are insoluble in cold water and possess only a slight degree of
solubility in boiling water, and in alkaline solutions. Alizarine Green forms blue
saline compounds with alkaline carbonates and green compounds upon being mixed
with caustic potash or soda liquor in excess. The said compounds or salts of
Alizarine Green are quite insoluble in excess of caustic alkaline solutions.
combines with the bisulphites of potash soda or ammonia, forming soluble compounds
analagous to those of Alizarine Blue and capable of being used in an analogous
manner in dyeing and printing with the aid of appropriate mordants Alizarine
Green can likewise be employed as a dyestuff or colouring matter in a similar
manner to that in which Alizarine Blue is employed. The shades produced by
Alizarine Green are very fast and are distinguished from the corresponding shades
of Alizarine Blue (principally from those obtained with the aid of chrome mordants)
by their tint more or less approaching Green.
Having now particularly described and ascertained the nature of the said Inven-
tion and the manner in which the same is or may be used or carried into effect I
would observe in conclusion that I wish it to be understood that I do not confine
myself to the exact details as above described, as the proportions, weights,
temperatures, concentration of acids and so forth may be varied, as hereinbefore
indicated, without materially changing the result of the above described processes,
but I declare that what I claim is :-
First. The preparation of a new class of derivatives of alizarine-blue by causing
sulphuric acid or sulphuric anhydride to act upon alízarine-blue substantially as
herein before described.
Second. The process of preparing Alizarine-blue-sulphuric acid by the limited
or moderate action of sulphuric anhydride upon Alizarine-blue, substantially in the
manner herein before described under Division I.
Third. The process of preparing Alizarine-blue-sulphoacid by the action of fuming
sulphuric acid at an elevated temperature upon Alizarine-blue, substantially in the
manner bereinbefore described under Division II.

page_text: Fourth. The process of preparing the "intermediate product" herein before described,
under Division III by the energetic action of sulphuric anhydride upon Alizarine-blue
substantially in the manner herein before described under the said 'Division:
Fifth. The process of preparing Alizarine-bluegreen by the decomposition in acid'
or alkaline solution of the "intermediate product" named in the fourth claiming
clause, preferably, (without previous separation of the said intermediate product)
by the successive action of sulphuric anhydride and of sulphuric acid upon
Alizarine-blue, all substantially in the manner hereinbefore described under the
Divisions II and III.
Sixth. The process of preparing Alizarine-green by the action of monohydrated or
rectified sulphuric acid at an elevated temperature upon the Alizarine-blue green
named in the fifth claiming clause; preferably (without previous separation of the
said Alizarine-blue-green) by the successive action of sulphuric anhydride and of
sulphuric acid upon Alizarine-blue, all substantially in the manner herein before
described under the Division V.
Seventh. As a new manufacture the derivatives of Alizarine-blue named in
the preceding claiming clauses and the bisulphite-compounds of Alizarine-blue
sulphoacid, Alizarine-bluegreen and Alizarine-green, all substantially as herein
before described' and characterised under the Divisions. I, II, III, IV and V.
Dated this day or JULY 1889.
J. H. JOHNSON & Co.,
Agents.
J. H. JOHNSON & Co.,
Agents.