Improvements in the Treatment of Amorphous Alkaloids Obtained in the Preparation of Cocaine.
Year: 1888

page_text: Date of Application, 23rd Aug., 1888
Complete Specification Left, 29th Oct., 1888
Complete Specification Accepted, 30th Nov., 1888
PROVISIONAL SPECIFICATION.
Improvements in the Treatment of Amorphous Alkaloids Obtained
in the Preparation of Cocaine.
We D. CARL LIEBERMANN of 29 Mathaeikirchstrasse, Berlin and Dr. FRITZ
GINSEL Director of Chemical Works, of Brunswick, both in the Empire of Germany
do hereby declare the nature of this invention to be as follows:-
In the preparation of cocaine from Coca leaves, certain unpleasant bye products
are developed, in the form of amorphous alkaloids, and we have now found that these
alkaloids can easily be decomposed so as to produce ecgonine.
We have further discovered that ecgonine, contrary to the statement of Merck
(Berichte der chemischen Gesellschaft, Bd. XVIII, p. 2958), can be converted without
difficulty into benzoylecgonine;" and this invention consists in the mode of treating
these amorphous alkaloids for the purpose of obtaining ecgonine and benzoyl-
ecgonine.
The amorphous bye-alkaloids of Cocaine readily undergo a reaction, during which
they decompose into organic acids and ecgonine, in most cases with a simultaneous
formation of methylic alcohol. This decomposition may be effected by means of acids,
alkalies, or alkaline earths, or even (though but partially and insufficiently) by super-
heated steam.
The best method to be employed for the decomposition of the amorphous alkaloids,
is to boil them in the presence of hydrochloric acid. The degree of concentration,
and the quantity of this acid employed, are of little importance, but we prefer
hydrochloric acid of 1, 1-1, 2 sp. gr., which we employ in considerable excess. Upon
the degree of concentration of the acid, and its relative quantity, depends the time
within which the re-action is completed, which time will vary from 1 to 2 hours, or
oven a shorter time. The insoluble organic acids formed are, after cooling, filtered off,
and the filtered liquor, containing the hydrochlorate of ecgonine, is evaporated to
dryness. The remaining salt, when washed with a small quantity of alcohol, is
nearly pure hydrochlorate of ecgonine, from which the free base will be obtained
by adding alkali. The ecgonine thus obtained may, if necessary, be further purified
y crystallisation in alcohol.

page_text: The ecgonine is easily converted into benzoylecgonine in the following manner —
To this end, either chloride of benzoyl, or benzoic anhydride may be employed.
Either dry ecgonine may be used, or ecgonine in presence of a small quantity of
water.
The following is an illustration of a method which answers well for benzoylizing
ecgonine. We wish, however, to state that we do not confine ourselves either to the
use of the benzoic anhydride only (chloride of benzoyl, for instance, also giving good
results) nor to the exact quantities, and details of the mode of procedure hereafter
described, inasmuch as other quantities (for instance, larger quantities of benzoic
anhydride), and other conditions (for instance, the exclusion of water) have given
satisfactory results.
An aqueous solution of ecgonine (1 Mol.) saturated at boiling heat, is decomposed
by the addition of rather more than an equivalent quantity of benzoic anhydride
(1 Mol). To complete the reaction, we maintain the mixture for a short time
(1 hour) at boiling point.
For the removal of the benzoic acid produced, the product of the re-action is,
after cooling, shaken several times in the presence of ether. The remaining aqueous
solution begins to solidify to a crystalline mass either directly on shaking, or after
standing for some time.
The crystals are separated from the mother liquor by means of a pump, and
washed with a very small quantity of water. They are then in the form of
benzoylecgonine, identical, in all its properties, with that already known.
The mother liquor contains some ecgonine which has escaped benzoylizing. This
liquor may be used directly for new benzoylizing operations, or the ecgonine may be
recovered from it by known methods.
Dated this 23rd day of August 1888.

page_text: COMPLETE SPECIFICATION.
Improvements in the Treatment of Amorphous Alkaloids Obtained
in the Preparation of Cocaine.
We, Dr. CARL LIEBERMANN of 29 Mathacikirchstrasse, Berlin and Dr. FRITZ
GIESEL, Director of Chemical Works, of Brunswick both in the Empire of Germany
do hereby declare the nature of this invention and in what manner the same is
to be performed, to be particularly described and ascertained in and by the following
statement:—
In the preparation of cocaine from coca leaves, certain unpleasant bye-products
are developed in the form of amorphous alkaloids, and we have now found that theso
alkaloids can easily be decomposed so as to produce ecgonine.
We have further discovered that ecgonine, contrary to the statement of Merck
(Berichte der chemischen Gesellschaft Bd XVIII, p. 2053) can be converted without
difficulty into benzoylecgonine, and this invention consists in the mode of treating
these amorphous alkaloids for the purpose of obtaining ecgonine and benzoyl-
ecgonine.
The amorphous bye-alkaloids of Cocaine readily undergo a re-action, during
which they decompose into organic acids and ecgonine, in most cases with a
simultaneous formation of methylic alcohol.
This decomposition may be effected by means of acids, alkalis, or alkaline earths, or
even (though but partially and insufficiently) by superheated steam.
The best method to be employed for the decomposition of the amorphous alkaloids
is to boil them in the presence of hydrochloric acid. The degree of concentration,
and the quantity of this acid employed, are of little importance; but we prefer
hydrochloric acid of 1, 1-1, 2 sp. gr., which we employ in considerable excess. Upon
the degree of concentration of the acid, and its relative quantity, depends the time
within which the re-action is completed, which time will vary from 1 to 2 hours,
or even a shorter time. The insoluble organic acid formed are, after cooling, filtered
off, and the filtered liquor, containing the hydrochlorate of ecgonine, is evaporated to
dryness. The remaining salt, when washed with a small quantity of alcohol, is
nearly pure hydrochlorate of ecgonine, from which the free base will be obtained by
adding alkali. The ecgonine thus obtained may, if necessary, be further purified by
crystallisation in alcohol.
The ecgonine is easily converted into benzoylecgonine in the following manner,
that is to say, by the use of either chloride of benzoyl or benzoic anhydride.
Either dry ecgonine may be used, or ecgonine mixed with a small quantity of
water.
The following is an illustration of a method which answers well for benzoylizing
ecgonine:
-
The aqueous solution of ecgonine (1 Mol), saturated at boiling heat, is decomposed
by the addition of rather more than an equivalent quantity of benzoic anhydridə
(1 Mol.). To complete the reaction, we maintain the mixture for a short time
(1 hour) at boiling point.

page_text: For the removal of the benzoic acid produced, the product of the reaction is, after
cooling, shaken several times in the presence of ether. The remaining aqueous
solution begins to solidify to a crystalline mass, either directly on shaking, or after
standing for some time.
The crystals are separated from the mother liquor by means of a pump, and washed
with a small quantity of water. They are then in the form of benzoylecgonine,
identical in all its properties with that already known.
The mother liquor will generally contain some ecgonine which has escaped
benzoylizing. This liquor may be used directly for new benzoylizing operations,
or the ecgonine may be recovered from it by known methods.
Having now particularly described and ascertained the nature of our said
Invention and in what manner the same is to be performed we declare that what
we claim is :―
The production of ecgonine and benzoyleegonine from the amorphous alkaloids
obtained in the preparation of Cocaine in the manner above described."
בד
1 7-
1000
NEWTON & SON,
Agents for the Applicants.