The Manufacture of a New Preparation from "Saligenin."
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
The Manufacture of a New Preparation from "Saligenin."
I, LUDWIG SELL, of Villenkolonie Pasing, München, Bavaria, in the Empire
of Germany, Pharmaceutical Chemist, do hereby declare the nature of this inven-
tion to be as follows:-
This invention relates to a new preparation from saligenin capable of being
used for medicinal purposes, more especially in the treatment of uric-acid diathesis.
Experiments have shown that an effective product of this kind can be made
by the aid of saligenin if the latter is combined in a suitable manner with
physiological tanning materials or with tannic acid separated therefrom.
In these experiments it was established that physiological tanning materials
(that is to say, tanning materials which give no gallic acid on treatment with
dilute acids; tannin is consequently not applicable) when digested in alcoholic
aqueous solution with mineral acids, are partly hydrolysed and converted into
phlobaphenes, and that salicin, when digested in aqueous solution with dilute
mineral acid, is converted into saligenin, and that finally, for both transforma-
tions, a temperature of 90 degrees C. is necessary. It appears, moreover, that
if physiological tanning materials and salicin be allowed to act on each other
in the presence of dilute mineral acid, for example, a 5 per cent. solution of
hydrochloric acid, at 90 degrees C., a new condensation product is obtained which
has a greater medicinal effect than salicin, especially in cases of uric-acid
diathesis. Since the salicin, as stated, split up by dilute mineral acid at about
90 degrees C. giving saligenin, the same result is obtained if, instead of salicin,
ready prepared saligenin be employed. Of the physiological tanning materials,
oak-bark, cinchona-bark, and chestnut tanning material may here be mentioned
as examples, which, on heating with dilute mineral acid, give no gallic acid and
therefore are applicable for the purposes of this invention.
On the basis of these experiments, the desired product can be obtained in the
manner hereinafter described.
One part by weight of a physiological tanning material, that is to say, a
tanning material which gives no gallic acid with dilute acid, is heated with 20
parts by weight of 5 per cent. hydrochloric acid at 90 degrees C. until the tanning
material is split up into tannic acid and glucose. 38 parts by weight of salicin
are then added thereto, and the mixture further heated until the saligenin
reaction takes place. There then separates out a brown, resin-like substance which
has been formed from the tannic acid and saligenin, and in the residual colourless
solution, there is contained saligenin, glucose, hydrochloric acid, and undecom-
posed salicin. So long as free tannic acid can be detected in the mixture, no
saligenin reaction takes place; when, on the contrary, saligenin can be detected.
there no longer any free tannic acid reaction. It is necessary that salicin
or saligenin be employed in excess, and when employing 1 part by weight of
tanning material and 3.8 parts by weight of salicin, about 70 per cent. of the
new substance is obtained. This product is formed when employing any desired

page_text: physiological tanning material or the corresponding tannic acid. It is insoluble
in water, slightly soluble in benzol, ether, petroleum-benzine, petroleum-ether, or
dilute acids, partially soluble in acetone, easily soluble in alcohol (with a
Bordeaux-red colour) in wood spirit and 50 per cent. acetic acid, from which
solutions the substance can be re-precipitated by means of water unchanged. The
substance is also easily soluble in alkalis, from which solutions it is re-precipitated
on neutralisation with acids without change. Concentrated sulphuric acid dis-
solves the substance with a yellowish-brown colour, on the addition of concen-
trated nitric acid this colour is clearer. By adding bichromate of potassium, a
tinge of red is imparted to the solution. Concentrated nitric acid dissolves it only
with difficulty with a yellow colour, whilst concentrated hydrochloric acid is
almost without action thereon. The solution of the substance in concentrated
sulphuric acid gives, on dilution with water, a clear yellow solution which assumes
a clear brown colour on supersaturation with alkalies. The substance takes the
form of a snuff-coloured or chocolate-brown powder with an extremely slight
aromatic smell, calling to mind jalap-resin, with a not particularly characteristic,
weak, resin-like taste. It melts with decomposition and emission of acid-vapours
smelling like jalap-resin, which condense to an oily brown liquid On platinum
sheet, the substance burns without melting and without leaving behind any
residue. It is soluble in ammonia and caustic alkalies with a dark-brown colour.
This ammoniacal solution gives, with silver nitrate, in the first place a greenish-
blue fluorescence, and, after warming and standing, a silver mirror. In the
acetic acid solution, silver nitrate produces a brown precipitate. The substance
reduces Fehling's solution very strongly. The alcoholic solution of the substance
is not acted upon by iron chloride, and consequently gives neither a tannic acid
nor a saligenin reaction. If however the alcoholic solution diluted with water
be warmed for a long time, a filtrate is obtained from the liquid (which becomes
cloudy on cooling), and this filtrate gives a greenish-black coloration or pre-
cipitate with iron chloride.
The product can be obtained pure, in the manner above described, for which
purpose it is entirely separated by decantation of the solution, which contains
glucose, hydrochloric acid, salicin and saligenin, and can be collected on a filter
and thus easily separated from the excess of the substances employed and the
other decomposition-products (for example, glucose, saligenin).
The new product can also be made in concentrated solution, for which purpose,
after the reaction is complete, the hot fairly-concentrated solution is placed on one
side to cool; a brownish amorphous-crystalline substance then separates out
which, for the greater part, contains the new product, but also various substances
crystallising out therewith, such as salicin, saligenin, etc., which were either
employed or formed in the process.
For the manufacture of the new preparation, those tanning materials which
give gallic acid on heating with acids, cannot be employed, such, for example, as
tannin (gallotannic acid). The latter product, when used as above mentioned,
gives a reaction-product which contains a great part of the tannin unaltered and
which, in contradistinction to the reaction-products obtained from the physiological
tanning-materials, is soluble to a considerable extent in hot water and in ether.
Dated the 18th dow of I
1808
D. YOUNG & Co.,
11 and 12, Southampton Buildings, London, W.C.,
Agents for the Applicant.

page_text: The Manufacture of a New Preparation from "Saligenin."
I, LUDWIG SELL, of Villenkolonie Pasing, München, Bavaria, in the Empire
of Germany, Pharmaceutical Chemist, do hereby declare the nature of this inven-
tion 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 a new preparation from saligenin capable of being
used for medicinal purposes, more especially in the treatment of uric-acid diathesis.
Experiments have shown that an effective product of this kind can be made
by the aid of saligenin if the latter is combined in a suitable manner with
physiological tanning materials or with tannic acid separated therefrom.
In these experiments it was established that physiological tanning materiais
(that is to say, tanning materials which give no gallic acid on treatment with
dilute acids; tannin is consequently not applicable) when digested in alcoholic
aqueous solution with mineral acids, are partly hydrolysed and converted into
phlobaphenes, and that salicin, when digested in aqueous solution with dilute
mineral acid, is converted into saligenin, and that finally, for both transforma-
tions, a temperature of 90 degrees C. is necessary. It appears, moreover, that
if physiological tanning materials and salicin be allowed to act on each other
in the presence of dilute mineral acid, for example, a 5 per cent. solution of
hydrochloric acid, at 90 degrees C., a new condensation product is obtained which
has a greater medicinal effect than salicin, especially in cases of uric-acid
diathesis. Since the salicin, as stated, is split up by dilute mineral acid at about
90 degrees C. giving saligenin, the same result is obtained if, instead of salicin,
ready prepared saligenin be employed. Of the physiological tanning materials,
oak-bark, cinchona-bark, and chestnut tanning material may here be mentioned
as examples, which, on heating with dilute mineral acid, give no gallic acid and
therefore are applicable for the purposes of this invention.
On the basis of these experiments, the desired product can be obtained in the
manner hereinafter described.
One part by weight of a physiological tanning material, that is to say, a
tanning material which gives no gallic acid with dilute acid, is heated with 20
parts by weight of 5 per cent. hydrochloric acid at 90 degrees C. until the tanning
material is split up into tannic acid and glucose. 38 parts by weight of salicin
are then added thereto and the mixture further heated until the saligenin
reaction takes place. There then separates out a brown, resin-like substance which
has been formed from the tannic acid and saligenin, and in the residual colourless
solution, there is contained saligenin, glucose, hydrochloric acid, and undecom-
posed salicin. So long as free tannic acid can be detected in the mixture, no
saligénin reaction takes place; when, on the contrary, saligenin can be detected,
there is no longer any free tannic acid reaction. It is necessary that salicin
or saligenin be employed in excess, and when employing 1 part by weight of
tanning material and 38 parts by weight of salicin, about 70 per cent. of the
new substance is obtained. This product is formed when employing any desired
physiological tanning material or the corresponding tannic acid. It is insoluble
in water, slightly soluble in benzol, ether, petroleum-benzine, petroleum-ether, or
dilute acids, partially soluble in acetone, easily soluble in alcohol (with a
Bordeaux-red colour) in wood spirit and 50 per cent. acetic acid, from which
solutions the substance can be re-precipitated by means of water unchanged. The
substance is also easily soluble in alkalies, from which solutions it is re-precipitated

page_text: on neutralisation with acids without change. Concentrated sulphuric acid dis-
solves the substance with a yellowish-brown colour, on the addition of concen-
trated nitric acid this colour is clearer. By adding bichromate of potassium, a
tinge of red is imparted to the solution. Concentrated nitric acid dissolves it only
with difficulty with a yellow colour, whilst concentrated hydrochloric acid is
almost without action thereon The solution of the substance in concentrated
sulphuric acid gives, on dilution with water, a clear yellow solution which assumes
a clear brown colour on supersaturation with alkalies. The substance takes the
form of a snuff-coloured or chocolate-brown powder with an extremely slight
aromatic smell, calling to mind jalap-resin, with a not particularly characteristic,
weak, resin-like taste. It melts with decomposition and emission of acid-vapours
smelling like jalap-resin, which condense to an oily brown liquid. On platinumi
sheet, the substance burns without melting and without leaving behind any
residue. It is soluble in ammonia and caustic alkalies with a dark-brown colour.
This ammoniacal solution gives, with silver nitrate, in the first place a greenish
blue fluorescence, and, after warming and standing, a silver mirror. In the
acetic acid solution, silver nitrate produces a brown precipitate. The substance
reduces Fehling's solution very strongly. The alcoholic solution of the substance
is not acted upon by iron chloride, and consequently gives neither a tannic acid
nor a saligenin reaction. If however the alcoholic solution diluted with water
be warmed for a long time, a filtrate is obtained from the liquid (which becomes
cloudy on cooling), and this filtrate gives a greenish-black coloration or pre-
cipitate with iron chloride.
The product can be obtained pure in the manner above described, for which
purpose it is entirely separated by decantation of the solution, which contains
glucose, hydrochloric acid, salicin and saligenin, and can be collected on a filter
and thus easily separated from the excess of the substances employed and the
other decomposition-products (for example, glucose, saligenin).
The new product can also be made by means of a concentrated solution (for
instance in alcohol), for which purpose, after the reaction (for which, in this case,
the described reagents are employed in alcoholic solutions instead of aqueous solu-
tions), is completed, the hot fairly-concentrated solution is placed on one side to
cool; a brownish amorphous-crystalline substance then separates out which, for
the greater part, contains the new product, but also various substances crystal-
lizing-out therewith, such as salicin, saligenin, etc., which were either employed
or formed in the process.
For the manufacture of the new preparation, those tanning materials which
give gallic acid on heating with acids, cannot be employed, such, for example, as
tannin (gallotannic acid). The latter product, when used as above mentioned,
gives a reaction-product which contains a great part of the tannin unaltered and
which, in contradistinction to the reaction-products obtained from the physiological
tanning-materials, is soluble to a considerable extent in hot water and in ether.
I find that the proper way to adminster the remedy is at the rate from six to
eight grams per day in individual doses of one gram each. In some cases, it
may be advantageous to adminster the remedy from one to four times per day in
doses of five-tenths of a gram each, continuing the same for about a week. In
practice the remedy has been given in the form of pills.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The manufacture of a new preparation from saligenin, by allowing salicin
to act on physiological tanning principle preferably in a five per cent. mineral
acid solution, at an elevated temperature (about 90 degrees C.) until free tanning
principle or free tannic acid can no longer be detected in the solution and the
saligenin reaction is set up, the salicin being replaced, if desired, by the inter-

page_text: mediately-formed decomposition-product saligenin and the physiological tanning
principle by the likewise intermediately-formed physiological tannic acid.
2. A new preparation from saligenin and by the action of tannic acid forming
a brownish solid substance, having a slightly aromatic smell, being insoluble in
water, slightly soluble in benzol, ether, petroleum-benzine, petroleum-ether, dilute
acids, partially soluble in acetone, easily soluble in alcohol (with a Bordeaux-red
colour), in wood spirit, 50 per cent. acetic acid, from which solution the product
can be precipitated by addition of water unchanged, further being easily soluble
in alkalies (from which solution it is precipitated without change on neutralisa-
tion with acid), which substance is influenced by the described reagents as
described and gives neither a tannic acid reaction nor a saligenin reaction, the
tannic acid reaction taking place after the product has been warmed for a long
time.
Dated the 0th are of Vouch 1000
D. YOUNG & Co.,
11 and 12, Southampton Buildings, London, W.C.,
Agents for the Applicant.