Improvements in the Preparation of Yellow Colouring Matters suitable for Dyeing and Printing from Tetra-methyl-diamido- benzo-phenone and Anglomana ham
Year: 1884

page_text: Improvements in the Preparation of Yellow Colouring Matters
suitable for Dyeing and Printing from Tetra-methyl-diamido-
benzo-phenone and Anglomana ham
[Communicated from abroad by Heinrich Caro, Chemist to the Badische Aniline
and Soda Fabrik, of Ludwigshafen on the Rhine, in the Empire of Germany.]
"
I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of said Invention for "IMPROVEMENTS IN
"
THE PREPARATION OF YELLOW COLOURING MATTERS SUITABLE FOR DYEING AND
PRINTING FROM TETRA-METHYL-DIAMIDO-BENZO-PIIENONE AND ANALOGOUS KETONE
BASES OR THEIR HALOGEN DERIVATIVES a communication to me from abroad by
Heinrich Caro, Chemist to the Badische Aniline and Soda Fabrik of Ludwigshafen-
on-the Rhine in the Empire of Germany to be as follows:-
This Invention relates to the preparation of a new class of yellow colouring
matters suitable for dyeing and printing which hereafter shall be termed
Auramines."
The said coloring matters are produced in a direct manner by the action of
Ammonia upon the Carbonyle group of Tetramethyldiamido benzophenone Tetra-
ethyl-diamido benzophenone and analogous ketone bases-They may likewise be
obtained in a less direct manner by causing ammonia to react upon the halogen-
derivatives of the before mentioned ketone bases the preparation of which
derivatives has formed the subject matter of a former application for Letters Patent
by me dated the thirteenth day of March 1884 and numbered 4850.
In order to produce the said colouring matters according to the first named
direct method from Tetramethyldiamido benzophenone and analogous ketone bases.
Ammonia is to be employed in the form of Ammoniacal Salts or compounds and
more particularly in the form of its bydrochlorate Acetate Tartrate, Benzoate
Rhodanate or of its double compound with Chloride of Zinc. The reaction of
Ammonia upon the Carbonyle-group of the above said ketone bases requires the
application of heat and is generally greatly assisted by the cooperation of Chloride,
of zinc or similar Dehydrating Agents,

page_text: The following is an example of the manner in which this Invention may be
practically carried out in order to convert Tetramethyl diamido benzophenone into
its corresponding Auramine by the before mentioned direct method. About equal
parts by weight of dry and finely powdered Tetramethyl diamido benzophenone,
Hydrochlorate of Ammonia (Sal-ammoniac) and chloride of Zinc are intimately
mixed and then introduced into a cast iron enamelled pan fitted up within an
oil-bath, the temperature of which has previously been raised to about two hundred
degrees Centigrade. The mixture is to be kept in constant agitation until it has
entered into fusion. This point being arrived at the "melt" thus produced is
stirred up from time to time and its inside temperature is maintained at about
One hundred and sixty degrees Centigrade during the space of about five or six
hours or until a sample of the intense yellow product thus obtained almost
completely dissolves in hot water. The result of the operation is then allowed to
cool, powdered and first quickly washed with cold water, slightly acidulated with
hydrochloric acid in order to remove the excess of Chloride of zinc and sal ammoniac
contained therein and also for the purpose of neutralizing any Dimethylaniline or
other basic compounds which may have formed during the process.
The washed residue is afterwards exhausted with hot water and the yellow
solutions thus obtained are filtered and precipitated with common salt. Upon
cooling the colouring matter separates out in a crystalline condition and may then
be separated by filtration pressed and dried or recrystallized from water, diluted
Alcohol or other suitable solvents. In a similar manner the corresponding auramines
may be prepared from Tetra-ethyl-diamido-benzophenone or analogous tertiary
alkyl-derivatives of Tetra-diamido-benzophenone. In order to produce the said
coloring matters according to the second named, less direct manner by the action of
Ammonia upon the halogen derivatives of Tetramethyl-diamido benzophenone and
analogous ketone-bases ammonia is to be employed in its free or uncombined state-
The said halogen derivatives may be used either in their crude or in their purified
condition such as described in my hereinbefore mentioned application for Letters
Patent (N° 4850) and by preference in the state of solution in water alcohol
Chloroform Nitro benzole or other suitable solvents. Upon the addition of a strong
excess of caustic ammonia an immediate change of the blue color of the said
halogen-derivatives or their solutions into a red or orange-red color will be observed
to take place at the ordinary temperature After some time the mixture will
assume a light yellow colour owing to the production of Auramine-The described
changes may be assisted by a gentle application of heat The coloring matter
thus produced may then be separated by diluting the mixture with hot water
neutralizing the excess of ammonia by means of diluted Acetic acid filtering the
yellow solution thus obtained and precipitating the same with common salt.
The following is an example of the manner in which Auramine may be prepared
by the above described action of Ammonia upon the Chlorinated derivative produced
from Tetra methyl diamido benzophenone according to the manner described in my
above recited application for Letters Patent.
About twenty parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone are intimately mixed with or dissolved in about fifteen parts by
weight of nitro benzole and then, at the ordinary temperature about ten parts by
weight of Oxychloride of Phosphorous are added--The halogenizing action is first
allowed spontaneously to proceed and is afterwards completed by heating the blue
product thus obtained at a temperature of about seventy degrees Centigrade during
the space of about fifteen minutes.
The result of the operation is then cooled down to the ordinary temperature and
gradually mixed with about seventy parts by weight of concentrated caustic
Ammonia liquor due care being taken to avoid any considerable development of
heat caused by the reaction. The dark orange-red Alkaline mixture thus obtained
is then strongly agitated during the space of about three hours and afterwards
allowed to stand all night. The semi-fluid yellow Crystalline deposit chiefly
consisting of Auramine, Nitrobenzole and unchanged ketone-base, if any is then

page_text: separated from the Alkaline solution and repeatedly exhausted with hot water
slightly acidulated with Acetic Acid. The yellow solutions thus obtained are then
filtered precipitated with common salt and the resulting precipitate after being
filtered and pressed may afterwards be recrystallized from hot water or from any
other suitable solvent.
Auramine produced by either of the above described direct or indirect methods
possesses the following characteristic properties which are to be observed in the
preparation of the same. They are basic coloring matters capable of being employed
for Dyeing and Printing in a similar manner as other known basic yellow-dye-
stuffs such for instance as Chrysaniline or Flavaniline From the reason hereafter,
stated they are conveniently employed in a state of neutral or nearly neutral.
solutions and at a temperature below One hundred degrees Centigrade, the coloring
matters not being able to resist either the action of strong Acids or of continued
steaming.
The free Auramine bases are colourless their saline compounds are yellow, and
partly well crystallized. The solutions of the Auramine-salts possess a lemon-
yellow-colour and exhibit no fluorescence.
Strong hydrochloric Acid when added in the cold to an Auramine-solution does
not at first effect any apparent change but at an elevated temperature the yellow
solution becomes gradually decolorized such change being caused by the regeneration
of ammonia and of the Ketone-bases originally employed in the preparation of the
coloring matters.
A similar decomposition takes place by the prolonged boiling of their neutral
solutions. An Alcoholic Auramine-solution is slowly decolorized by Sodium-
amalgam or similar reducing agents, the colourless compound thus produced
dissolves with little or no colour in Acetic Acid but the Acid solution, upon being
heated quickly assumes an intense purplish-blue colour owing to a decomposition
of the reduced Auramine into ammonia and into an Alkylized amido-derivative of
Benzhydrol.
Dated this 26th day of March 1881.
J. HENRY JOHNSON,
47, Lincoln's Inn Fields, London, W.C.

page_text: "
I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention for "IMPROVEMENTS
IN THE PREPARATION OF YELLOW COLOURING MATTERS SUITABLE FOR DYEING
AND PRINTING FROM TETRAMETHYLDIAMIDOBENZOPHENONE AND ANALOGOUS
KETONEBASES OR THEIR HALOGEN DERIVATIVES which Invention has been
communicated to me from abroad by Heinrich Caro, Chemist to the Badische
Aniline and Soda Fabrik Ludwigshafen on 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 relates to the preparation of a new class of yellow colouring
matters suitable for dyeing and printing which I will hereinafter terin "Auramines."
The said colouring matters are produced in a direct manner by the action of
ammonia upon the Carbonyle-group of Tetramethyldiamidobenzophenone, Tetra-
ethyldiamidobenzophenone and Dimethyldiethyldiamidobenzophenone They may
likewise be obtained in a less direct (and therefore less convenient) manner by
causing ammonia to react upon the halogen derivatives of the before mentioned
Ketonebases the preparation of which derivatives has formed the subject matter of
a former application for Letters Patent by me dated the thirteenth day of March
One thousand eight hundred and eighty four and numbered 4850.
In order to produce the said colouring matters according to the first named
direct manner from Tetramethyldiamidobenzophenone and the before named
analogous Ketonebases, Ammonia cannot be employed in its free or uncombined
state, but it is found to react, upon being employed in the form of certain ammo-
niacal salts or compounds. A considerable production of colouring matter has so
far been obtained only by the application of ammonia in the form of its hydro-
chlorate, acetate, tartrate, benzoate, Sulphocyanate or of its double compound with
Chloride of Zinc-The reaction of Ammonia upon the Carbonyl group of the above
said Ketonebases requires the application of heat. It is considerably assisted by
the co-operation of dry chloride of zinc, and in the presence of the said dehydrating
agent, the carbonate and sulphate of ammonia have been found likewise to produce
a considerable yield of colouring matter.
In practice the best results have hitherto been obtained with the employment of
hydrochlorate of ammonia, and chloride of zinc-The following is an example of
the manner in which this Invention may be practically carried out in order to
convert Tetramethyldiamidobenzophenone into its corresponding Auramine by the
before mentioned direct action of ammonia upon the Carbonyle-group of the said
Ketone-base.
About ten parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone, about ten parts by weight of hydrochlorate of ammonia, (sal-
ammoniac) and about ten parts by weight of dry chloride of zinc, are intimately
mixed and then introduced into a cast iron enamelled pan fitted within an oil
bath, the temperature of which has previously been raised to about two hundred
degrees centrigrade.
The mixture is to be kept in constant agitation until it has assumed a homo-
geneous pasty condition-This point being arrived at the "melt" thus produced
ought to be aked up or turned over from time to time, and its inside temperature
maintained at about one hundred and sixty degrees centrigrade during the space of
about five or six hours, or until a sample of the product thus obtained almost

page_text: completely dissolves in hot water-The result of the operation is then allowed to
cool and when sufficiently cool it is to be powdered and well agitated with about
two hundred parts by weight of cold water, with the addition of about from one
to two parts by weight of hydrochloric acid of a specific gravity of about 1.18 in
order to dissolve the excess of chloride of zinc, and sal-ammoniac contained therein,
and to neutralize any free Dimethylaniline or other basic compounds which may
have formed during the process-The mixture is then allowed to settle, the super-
natant saline solution is removed by decantation, and the solid residue is pressed,
washed with cold water; and ground up into the state of a coarse powder-The
said powder is then digested during the space of about fifteen minutes with about
two hundred parts by weight of water, the temperature of which has been previously
raised to about eighty degrees Centrigrade. The yellow solution thus obtained is
filtered and precipitated with common salt.
•
Upon cooling, the colouring matter separates out in a crystalline condition, and
may then be filtered, pressed, and dried." A further purification of the Auramine
thus obtained may be effected by recrystallizing the same from water.
In a similar manner the corresponding auramines may be prepared from Tetra-
ethyl-diamidobenzophenone or from Dimethly-diethyldiamidobenzophenone.
From a point of economy the before described direct manner of producing the
auramines, is preferable to the second named, less direct, and therefore less con-
venient manner which is based upon the action of ammonia upon the above said
halogen derivatives of Tetramethyl-diamidobenzophenone and analogous Ketone-
bases, and which I now shall proceed to describe.
°
In order to produce Auramines in the said manner ammonia is to be employed
in its free or uncombined state-The said halogen derivatives may be used either
in their crude or in their purified condition, such as described in my before
mentioned application for Letters Patent (No 4850) and by preference in the
state of their solutions in water, alcohol, chloroforin, nitrobenzole, or other suitable
solvents. Upon the addition of a strong excess of caustic ammonia, an immediate
change of the blue colour of the said halogen derivatives, or their solutions, into a
red or orange red colour, will be observed to take place at the ordinary tem-
perature After sometime the mixture will assume a light yellow colour owing to
the production of Auramine.
The described changes may be assisted by the gentle application of heat-The
colouring matter thus produced may then be separated by diluting the mixture
with hot water, neutralizing the excess of ammonia by means of diluted acetic
acid, filtering the aqueous solution thus obtained, and precipitating the same with
common salt.
The following is an example of the manner in which Auramine may be prepared
by the above described action of ammonia upon the chlorinated derivative produced
from Tetramethyldiamidobenzophenone according to the manner described in my
above recited application for Letters Patent.
About twenty parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone are intimately mixed with, or dissolved in about fifteen parts by
weight of nitrobenzole, and then at the ordinary temperature, about ten parts by
weight of Oxychloride of Phosphorous are added.The balogenizing action is first
allowed spontaneously to proceed, and is afterwards completed by heating the blue
product thus obtained at a temperature of about seventy degrees centigrade during
the space of about fifteen minutes.-The result of the operation is then cooled down
to the ordinary temperature, and gradually mixed with about seventy parts by
weight of caustic ammonia liquor of about 0.95 specific gravity. Due care ought to
be taken to moderate the developement of heat caused by the reaction-The dark
orange red alkaline mixture thus obtained, is then strongly agitated during the
space of about three hours and afterwards allowed to stand for a period, say all
night. The semi-fluid yellow crystalline deposit, chiefly consisting of Auramine,
Nitrobenzole, and unchanged Ketone base, if any, is then separated from the
Alkaline solution and repeatedly exhausted with water previously heated up to

page_text: a temperature of about eighty degrees centigrade, and slightly acidulated with
acetic acid. The yellow solutions thus obtained are then filtered, precipitated with
common salt, and the resulting precipitate after being filtered and pressed, may he
finally purified by recrystallisation from water.
Auramines produced by either of the above described direct or indirect methods,
possess the the following characteristic properties which ought to be borne in mind in
the preparation of the same. They are basic colouring matters capable of being
employed for Dyeing and Printing, in a similar manner as other known basic
yellow dye stuffs, such for instance as Chrysaniline or Flavaniline-From the
reasons hereafter stated they are conveniently employed in a state of neutral or
nearly neutral solutions, and at temperatures below one hundred degrees Contigrade,
the colouring matters not being able to resist either the action of strong acids or of
long continued contact with boiling water or steam.
The free Auramine bases are colourless, their saline compounds are yellow, and
some of them, as for instance the hydrochlorate of the auramine produced as before
described from Tetramethyldiamidobenzophenone may be obtained in a well
crystallized condition. The hydrochlorates, sulphates, acetates and tartrates, of
the auramines, are readily soluble in water, their hydrojodates and sulpho cyanates
are almost insoluble in cold and sparingly soluble in hot water. The solutions of
the Auramine salts possess a lemon yellow colour and exhibit no fluorescence.
Strong hydrochloric acid when added in the cold to an Auramine solution,
does not immediately effect any apparent chemical change, but at an elevated
temperature the yellow solution becomes gradually decolourized, such change boing
caused by the regeneration of ammonia, and of the Ketone bases originally
employed in the preparation of the said colouring matters.
A similar decomposition takes place by the prolonged boiling of their neutral
aqueous solutions.
An alcoholic Auramine solution is slowly decolourized upon being treated in the
cold with sodium amalgam, or zinc dust, the colourless compound thus produced
dissolves with little or no colour, in cold acetic acid, but the acid solution when
heated quickly assumes a rich purplish blue colour owing to a decomposition thus
taking place, the chief products of which are ammonia and the correspondingly
alkalized paradiamidoderivative of Benzbydrol.
Having now particularly described and ascertained the nature of the said
Invention and in what manner the same is to be performed I declare that what
I claim is
First Producing the yellow colouring matters suitable for Dyeing and Printing,
or Auramines, hereinbefore described, in a direct manner from Tetramethyldiamido-
benzophenone, Tetraethyldiamidobenzophenone, or Dimethyldiethyldiamidobenzo-
phenone, by the action of ammonia upon the carbonyle group of the said
Ketone-bases, with or without the co-operation of dry chloride of zinc, the
ammonia being employed in the form of its hereinbefore defined salts or com-
pounds, substantially as hereinbefore described.
Second The preparation of the before named yellow colouring matters or
Auramines, by treating the halogen derivatives of the above said Ketone bases
(the preparation of which halogen derivatives is described in my former application
for Letters Patent dated the thirteenth day of March One thousand eight hundred
and eighty four and N° 4850) with ammonia, in its free or uncombined state
substantially as herein before described