The Manufacture of Derivatives of Alizarine-green, suitable for Dyeing and Printing.
Year: 1888

page_text: Date of Application, 20th Oct., 1888
Complete Specification Left, 20th July, 1889-Accepted, 24th Aug.. 1889
PROVISIONAL SPECIFICATION.
The Manufacture of Derivatives of Alizarine-green, suitable for
Dyeing and Printing.
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 Badische Anilin & Soda-Fabrick of Ludwig-
shafen-on-the-Rhine, in the Empire of Germany, to be as follows:-
This Invention relates to the production of derivatives of "Alizarine-Green," one
of the derivatives which can be obtained (according to a former Invention of my
Foreign Correspondents) from Alizarine-Blue by the successive action of sulphuric
anhydride and of monohydrated sulphuric acid either with or without separation of
the intermediate results of the said action.
Now this present Invention is based upon the discovery, that Alizarine-Green may
be converted into new derivatives, resulting from the action of either fuming or
concentrated sulphuric acid and possessing the properties of colouring matters suitable
for Dyeing and Printing.
In order to prepare the said new derivatives, Alizarinegreen may be employed in
its finished mercantile condition, or the process of producing the same from Alizarine-
Blue as before stated may be combined with the final action of fuming or of
concentrated sulphuric acid into one continued operation without the separation of the
intermediate results of the process.
I. ALIZARINEGREEN-SULPHOACID.
The following is an example of the manner in which Alizarine-Green may he
converted into its herein-before named sulphoderivative:
About ten parts by weight of dry and finely divided Alizarine-green are gradually
added to about two hundred parts by weight of fuming sulphuric acid, containing
about from eight to ten per cent. of free anhydride. Throughout this operation the
mixture or solution thus prepared should be well agitated and then its temperature is
to be raised to about from one hundred and thirty to about one hundred and thirty
five degrees Centigrade and maintained thereat for about four or five hours or until a
sample of the product has become practically soluble in water. This point being
arrived at, the result of the operation is then poured into water and the solution thus
obtained is filtered and precipitated by the addition of common salt. The precipitate
of the colouring matter may afterwards be collected upon a filter, pressed
and dried.
Alizarinegreen-sulphoacid, prepared in this manner presents the following charac-
teristic properties.
In its solid state it has the appearance of a crystalline powder consisting of small
needle-shaped crystals possessing a metallic lustre. It is readily soluble in water.
The aqueous solution has a blueish-green colour, which changes into Red upon the
addition of mineral acids. Alkaline carbonates produce blue saline compounds, whilst
caustic alkalies form green alkaline salts, which are not precipitated from their
aqueous solutions by adding thereto an excess of caustic alkali. Alizarinegreen-
sulpho-acid resembles Alizarinebluegreen in its general aspect, but it may be readily
distinguished therefrom by its greater solubility in water and by the dingy brown
colour of its solution in concentrated sulphuric acid, the corresponding solution of
Alizarinebluegreen exhibiting a bright purple colour. Fuming sulphuric acid con- .
taining about twenty three per cent. of free anhydride dissolves Alizarinegreen-sulpho-
acid with a grass green colour, whilst the solution of Alizarinebluegreen in the same
solvent possesses a blue green tint.

page_text: Alizarinegreen-sulphoacid is readily converted by
potash, soda or ammonia, into bisulphite-compounds, soluble in water and capable of
being employed in dyeing and printing in a manner similar to that in which the
known analogous bisulphite-compounds of Alizarine blue are employed.
Alizarinegreen-sulphoacid produces upon wool, which has received a chrome- 5
mordant, green shades similar to those of Alizarinegreen itself.
11. ALIZARINE-INDIGO-BLUE.
Alizarine-indigo-blue is produced whenever Alizarinegreen is heated with con-
centrated sulphuric acid at a temperature of about two hundred degrees Centigrade
until the purple colour of the acid solution has changed into a bright Indigo blue. 1
The conversion of Alizarinegreen into its new derivative may therefore be effected by
a continuation of the process herein before mentioned as of my foreign correspondents
prior Invention whereby Alizarinebluegreen is converted into Alizarinegreen by the
action of monohydrated or rectified sulphuric acid at a temperature of about one
hundred and thirty degrees centigrade.
The following is an example of the manner in which Alizarinegreen may be converted
into Alizarine-indigoblue according to the present Invention.
About ten parts by weight of dry and finely powdered Alizarine-green are intimately
mixed with or dissolved in about two hundred parts by weight of concentrated or
rectified sulphuric acid of about 1.848 specific gravity and the mixture or solution
thus prepared is then whilst being agitated heated to about from two hundred to two
hundred and ten degrees Centigrade until it has assumed a pure indigo blue colour
which point will generally be arrived at after about five hours heating. The result of
the operation is then carefully poured into water and the precipitate thus formed is
collected upon a filter washed and pressed and may afterwards be dried or be used in
the state of a paste.
Alizarine-indigo blue prepared in this manner is insoluble in water even at the
boiling heat. It forms blue saline compounds upon treatment with caustic or
carbonated alkalies. These alkalino salts are quite insoluble in caustic alkaline
solutions. It dissolves with a bright indigo blue colour in concentrated sulphuric
acid and may thus be readily distinguished from alizarine-green the solution of which
in the said solvent is characterised by its red colour. It combines with the bisulphites
of potash soda or ammonia thus producing compounds soluble in water and capable
of being employed in Dyeing and Printing in a manner similar to that in which th
analogous bisulphite compounds of Alizarine-blue are employed.
Alizarine indigo-blue produces upon chrome-mordanted wool shades which ar
similar to those produced by indigo-blue.
Alizarine-indigo blue may likewise be prepared by heating Alizarine-green-sulpho
acid with concentrated sulphuric-acid,-say about one part by weight of the former
twenty parts by weight of the latter in the above described manner.
101 this 20th day of October 1888.
T □ JOHNSON & Co.,
H JOHNSON & Co.,
JH
Agents.
COMPLETE SPECIFICATION.
The Manufacture of Derivatives of Alizarine-green, suitable for
Dyeing and Printing.
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 Badische Anilin and Soda-Fabrik of Ludwig-
shafen-on-the-Rhine in the Empire of Germany) and in what manner the same is to
be performed to be particularly described and ascertained in and by the following
statement:
This Invention relates to the production of derivatives of "Alizarine-Green
"
one

page_text: Alizarine green-sulpho acid produces upon wool, which has received a chrome-
mordant, green shades similar to those of Alizarine green itself.
II. ALIZARINE-INDIGO BLUE.
Alizarine-indigo blue is produced by heating Alizarine-green with concentrated
sulphuric acid at a temperature of about two hundred degrees Centigrade until the
purple colour of the acid solution has changed into a bright Indigo blue colour. The
conversion of Alizarine-green into its new derivative may therefore not only be effected
by employing Alizarine-green in its isolated or separated condition, but, preferably,
by a continuation of the process (herein before mentioned as of my Foreign corre-
spondents prior Invention) whereby Alizarine-blue is converted into Alizarine-green
by the successive action of sulphuric anhydride and of monohydrated or rectified
sulphuric acid at a final temperature of about one hundred and thirty degrees
Centigrade.
The following is an example of the manner in which Alizarine-green, if employed
in its isolated or separated condition, may be converted into Alizarine-indigo blue
according to the present Invention.
About ten parts by weight of dry and finely powdered Alizarine-green are intimately
mixed with or dissolved in about two hundred parts by weight of concentrated or
rectified sulphuric acid of about 1'84 specific gravity, and the mixture or solution
thus prepared is then, agitated and heated to about from two hundred to two hundred
and ten degrees Centigrade, until it has assumed a pure indigo blue colour, which
point will generally be arrived at after about five hours heating. The result of the
operation is then carefully poured into water and the precipitate, thus formed, is
collected upon a filter, washed and pressed and may afterwards be dried or be used in
the state of a paste.
The following is an example of the method, which in practice it is preferred to
employ in order to obtain Alizarine-indigo blue according to the present Invention,
without previously isolating or separating Alizarine-green from the results of the herein
before mentioned process for its production.
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 rise of temperature
ought to be carefully prevented by the application of external cooling. After the
entiro amount of Alizarino-blue has thus been added,-an operation which
requires generally about eight hours-the mixture or solution is agitated for another
five or six hours at a temperature of about fifty degrees Centigrade and then about
two hundred parts by weight of concentrated or rectified sulphuric acid of about
1-84 specific gravity are added. If now the temperature of the solution be gradually
raised to about one hundred and thirty degrees Centigrade, the production of
Alizarine-green (passing through the intermediate state of Alizarine-blue-green) takes
place, according to the hereinbefore mentioned former Invention of my Foreign
correspondents. In consequence of these changes the solution first assumes a red
colour (indicative of Alizarine-blue green) and subsequently it assumes the above
mentioned purple colour, by which the solution of Alizarine-green in sulphuric acid is
characterised.
This process is then continued by gradually raising the temperature of the said
acid solution to about from two hundred to two hundred and ten degrees Centigrade,
and this temperature is maintained for about five hours or until the purple colour of
the acid solution has changed into a bright Indigo blue, as herein before described.
The result of the operation is afterwards carefully poured into water and the
precipitate of Alizarine-indigo blue thus formed, is collected upon a filter, washed
and pressed and may then be dried or be used in the state of a paste.
In order to obtain Alizarine-indigo blue in a crystalline condition, it is convenient

page_text: to heat its hereinbefore named precipitato along with the acid liquor, in which it has
been formed, to the boiling point and then to filter the same after it has cooled down
to about forty degrees Centigrade.
Alizarine-indigo blue may likewise be prepared, although less economically, by
heating the herein before described Alizarine-green sulpho acid with concentrated
sulphuric acid say about one part by weight of the former to about twenty parts
by weight of the latter-in the above described manner.
Alizarine-indigo blue, prepared by any of the methods hereinbefore described, is
insoluble in water, even at the boiling beat.
It forms blue saline compounds upon treatment with caustic or carbonated alkalies.
These alkaline salts are quite insoluble in caustic alkaline solutions. It dissolves
with a bright indigo blue colour in concentrated sulphuric acid and may thus be
readily distinguished from Alizarine-green, the solution of which in the said solvent is
characterised by its purple colour. It combines with the bisulphites of potash, soda or
ammonia upon being digested with aqueous solutions of the said bisulphites, thus
producing compounds soluble in water and capable of being employed in Dyeing and
Printing in a manner similar to that in which the analogous bisulphite compounds of
Alizarine-blue are employed.
Alizarine-indigo blue produces, upon chrome-mordanted wool, shades which are
similar to those produced by Indigo blue.
I do not confine myself to the exact details as above described, as the proportions,
weights temperatures, concentration of acids, processes of purification and separation,
and so forth, may be varied to a large extent, without materially changing the above
described results.
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. As a new manufacture, the production of the hereinbefore described Alizarine-
green-sulpho acid by the action of fuming sulphuric acid at an elevated temperature
upon Alizarine-green, substantially in the manner herinbefore described.
Second. As a new manufacture, the production of the herein before described
Alizarine-indigo blue by the action of concentrated sulphuric acid at an elevated
temperature upon Alizarine-green, the latter being employed either in its isolated or
separated condition or in the state of its solution in sulphuric acid, such as results
from the successive treatment of Alizarine-blue with sulphuric anhydride and concen-
trated sulphuric acid all substantially as hereinbefore described.
Third. The preparation of Alizarine-indigo blue by heating Alizarine-green-sulpho
acid with concentrated sulphuric acid substantially as hereinbefore described under the
Division II.
Fourth. As a new manufacture, the production of the Bisulphite-compounds of
Alizarine-green-sulpho acid and of Alizarine-indigo blue by treating these colouring
matters with the bisulphites of potash, soda, or ammonia, substantially as hereinbefore
described.
A T
1000
J. H. JOHNSON & Co.,
Agents.