New Formic Aldehyde Compounds and Processes of Preparing the same.
Year: 1897

page_text: Date of Application, 13th Mar., 1897
Complete Specification Left, 6th Dec., 1897-Accepted, 22nd Jan.,
1898
PROVISIONAL SPECIFICATION.
New Formic Aldehyde Compounds and Processes of Preparing the
same.
We, HEINRICH OPPERMANN, Doctor of Philosophy, and RICHARD GOEHDE,
Engineer, both of No. 12, Leipziger-Platz, in Berlin, German Empire, do hereby
declare the nature of this invention to be as follows:-
The present invention relates to the application of formic aldehyde for thera-
peutic and preservation or disinfection purposes to a greater extent than has
hitherto been practicable, and consists essentially in combining the formic aldehyde
chemically with sugars of the cane sugar group and to render this combination
stable.
When caused to react under suitable conditions, formic aldehyde is capable of
combining chemically with the sugars of the cane sugar group by substitution of
a hydroxyl group. The new combination which possesses the composition C₁ H21
010 CH, O+ water, is hygroscopic and forms in consequence thereof syrups with
water, which are of crystal clear quality and permanent even in the greatest con-
sistency, that is, they do not, as do for instance concentrated solutions of milk
sugar (lactose), congeal on cooling to an amorphous or crystalline opaque mass.
The syrup cannot be evaporated to complete dryness, and can only be brought into
the dry state by mixing with a sufficient quantity of powdered sugar, preferably
milk sugar; the particles of the powder so obtained, however, conglomerate easily
together. On exposing the new compound to a temperature of 50 to 60 degrees
centigrade, it decomposes back into formic aldehyde and sugar, and in the presence of
moist air it developes formic aldehyde. Now the new formaldehyde-sugar com-
pound may be rendered considerably more stable, that is to say so as to support
temperatures up to from 70-80° centigrade, and so without reducing its solu-
bility in water, by combination with haloid compounds of the alkalies and of
ammonium (chloride bromide and iodide of potassium, sodium or ammonium) by
the application of one equivalent of the haloid compound to every two equivalents
of the sugar and coupling thereby two equivalents of the formic aldehyde-sugar
compound with one equivalent of the haloid compound used, for instance 2/C₁₂ H₂
010 Ch, O, Na C, + 4 to 6 water. The product of this reaction which forms a
perfectly clear fluid, can be evaporated to dryness and then constitutes a mass
capable of being pulverised but which nevertheless is also hygroscopie, this mass as
well as the syrups can be heated without decomposition to about 80 degrees centi-
grade and are completely odourless in dry air. In the case of ammonium haloid
compounds 2 equivalents of the same instead of but one may be combined with
2 equivalents of the formic aldehyde-sugar compound. Of these ammonium com-
pounds that formed with one equivalent has a reddish colour whilst that prepared
with two equivalents is yellowish. The above mentioned haloid compounds may
be replaced with the like result by bitartrate of potassium or by a solution of agar-
agar prepared with potassic bitartrate, or a mixture of potassic bitartrate and one
or several of the said haloid compounds may be used.
10°

page_text: For instance the process may be carried out as follows:-
Taking milk sugar (lactose) by way of example:-Milk sugar is dissolved in
one half of its weight of water with the addition of a little formic aldehyde prefer-
ably in aqueous solution, and brought to boiling and kept at this temperature
until the milk sugar is completely dissolved. The requisite quantity of CH, O
corresponding to the above formula is then added, the mixture allowed to stand for
a few hours and finally the excess of water evaporated at below 70 degrees centi-
grade. The fluid then forms an aqueous solution of the compound C12, H2 010
CH₂O water. The same is concentrated by evaporation to the requisite con-
sistency which is preferably effected in a vacuum at a temperature below 70 degrees
centigrade. In place of the dissolved formic aldehyde use may be made of its
polymer namely trioxy-methylene, applying the sanie suspended in methyl-alcohol
or water.
For the introduction of the haloid compounds of the alkalies or of ammonium
or their abovenamed equivalents it is preferable not to take the finished compound
but to proceed in the following manner:
The milk sugar or other sugars of the cane sugar group are treated with about
half their weight of water and the haloid compound to be made use of, as for
instance iodide of sodium, or bromide of potassium, or chloride of ammonium and
so forth, is added thereto in such proportion, as corresponds to one equivalent
thereof to every two equivalents of the sugar. The mixture is heated until com-
pletely dissolved, when formic aldehyde dissolved in water or methyl-alcohol is
added. Before evaporating the water in a vacuum it is preferable to let the pre-
paration stand for several hours. On the application of iodide of ammonium and
bromide of ammonium the same is preferably added after the solution of the sugar
and after the solution has been cooled to 60 degrees centigrade; the preparation
is then, after standing for several hours, concentrated 'under a vacuum!
For obtaining the product in the form of syrups or in the dry state, the evapora-
tion of the water is preferably conducted under a vacuum, whilst the heating is
kept below 70 degrees centigrade.
Experiment has proved that the haloid compounds of potassium are the most
suitable means for rendering stable the compound of formic aldehyde with
saccharose (cane sugar and beet sugar), whilst when lactose (milk sugar) is employed
the haloid compounds of sodium have given the best results. When the said haloid
compounds are replaced by bitartrate of potassium, the same is made use of in
the same proportion as the former, and the use thereof can also take place in form
of a solution of agar-agar prepared by means of potassic bitartrate or in the form
of a mixture with the said haloid compounds. The improvement obtained by the
present invention in the utilisation of formic aldehyde for therapeutic, pre-
servative, or disinfecting purposes is characterized by properties of the new
compound.
"AQT UŽNITY TO ÁRD
IGT STUD
New Formic Aldehyde Compounds and Processes of Preparing the
same.
We, HEINRICH OPPERMANN, Doctor of Philosophy, and RICHARD GOEHDE,
Engineer, both of No. 12, Leipziger-Platz, Berlin, German Empire, do hereby

page_text: 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:-
The present invention relates to the application of formic aldehyde for thera-
peutic and preservation or disinfection purposes to a greater extent than has
hitherto been practicable, and consists essentially in combining the formic aldehyde
chemically with sugars of the cane sugan group and to, render this combination
stable.
When caused to react under suitable conditions formic aldehyde is capable of
combining chemically with the sugars of the cane sugar group by substitution of
a hydroxyl group. The new combination which possesses the composition C₁₂ Ho
010 CH, O+ water, is hygroscopic and forms in consequence thereof syrups with
water, which are of crystal clear quality and permanent even in the greatest con-
sistency, that is, they do not, as do for instance concentrated solutions of milk
sugar (lactose), congeal on cooling to an amorphous or crystalline opaque mass.
The syrup cannot be evaporated to complete dryness, and can only be brought into
the dry state by mixing with a sufficient quantity of powdered sugar, preferably
milk sugar, the particles of the powder so obtained, however, conglomerate easily
together. On exposing this new compound to a temperature of 50 to 60 degrees
centigrade, it decomposes back into formic aldehyde and sugar, and in the presence
of moist air it developes formic aldehyde.
4 to 6 water.
The new formaldehyde-sugar compound may be rendered considerably more
stable, that is to say so as to support temperatures up to from 70-80° centigrade,
and so without reducing its solubility in water, by combination with haloid com-
pounds of sodium, potassium and ammonium (chloride, bromide and iodide of
potassium, sodium or ammonium) by the application of one equivalent of the haloid
compound to every two equivalents of the sugar and coupling thereby two equiva-
lents of the formic aldehyde-sugar compound with one equivalent of the haloid
compound used, for instance 2/C₁₂ Hat 010 CH₂ 0/, Na C₁
The product of this reaction which forms a perfectly clear fluid, can be evaporated
to dryness and then constitutes a mass capable of being pulverised but
which nevertheless is also hygroscopic. This mass as well as the syrups can
be heated without decomposition to about 80 degrees centigrade and they are
all completely odourless in dry air. In the case of ammonium haloid compounds
2 equivalents of the same instead of but one may be combined with 2 equivalents
of the formic aldehyde-sugar compound.
The above mentioned haloid compounds may be replaced with the like result
by bitartrate of potassium or by a solution of agar-agar prepared with potassic
bitartrate, or a mixture of potassic bitartrate and one or several of the said haloid
compounds may be used.
For instance the process may be carried out as follows:-
Taking milk sugar (lactose) by way of example.-Milk sugar is dissolved in
one half of its weight of water with the addition of a little formic aldehyde prefer-
ably in aqueous solution, and brought to boiling and kept at this temperature
until the milk sugar is completely dissolved. The requisite quantity of formic
aldehyde corresponding to the above formula is then added, the mixture allowed
to stand for a few hours and finally the excess of water evaporated at below
50 degrees centigrade. The fluid then forms an aqueous solution of the compound
C12H2O10 CH2 O + water. The same is concentrated by evaporation to the
requisite consistency which is preferably effected in a vacuum at a temperature
below 50 degrees centrigrade. In place of the dissolved formic aldehyde use may
be made or its polymer namely trioxy-methylene, applying the same: suspended
in methyl-alcohol or water.
For the introduction of the haloid compounds of the alkalies or of ammonium or
their above named equivalents it is preferable not to take the finished compound
but to proceed in the following manner:-
The milk sugar or other sugars of the cane sugar group are treated with about
half their weight of water and the haloid compound to be made use of, as for

page_text: instance iodide of sodium, or bromide of potassium, or chloride of ammonium and
so forth, is added thereto in such proportion, as corresponds to one equivalent
thereof to every two equivalents of the sugar. The mixture is heated until com-
pletely dissolved, when formic aldehyde dissolved in water or methyl-alcohol is
added. Before evaporating the water in a vacuum it is preferable to let the pre-
paration stand for several hours. On the application of iodide of ammonium and
bromide of ammonium the same is preferably added after the solution of the sugar
and after the solution has been cooled to 60 degrees centigrade, the preparation is
then, after standing for several hours, concentrated under a vacuum.
For obtaining the product in the form of syrups or in the dry state, the evapora-
tion of the water is preferably conducted under a vacuum, whilst the heat is kept
below 70 degrees centigrade.
Experiment has proved that the haloid compounds of potassium are the most
suitable means for rendering stable the compound of formic aldehyde with
saccharose (cane sugar and beet sugar), whilst when lactose (milk sugar) is
When the
employed the haloid compounds of sodium have given the best results.
said haloid compounds are replaced by bitartrate of potassium, the same is made
use of in the same proportion as the former, and the use thereof can also take place
in form of a solution of agar-agar prepared by means of potassic bitartrate or in
the form of a mixture with the said haloid compounds. The improvement
obtained by the present invention in the utilisation of formic aldehyde for thera-
peutic, preservative, or disinfecting purposes is characterized by properties of the
new compound.
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:
-
1. The process for preparing new formic aldehyde compounds for therapeutic and
preservative purposes by treating sugars of the cane sugar group with formic aldehyde
or its polymer trioxymethylene, substantially as described.
2. The process for preparing new formie aldehyde compounds for therapeutic
and preservative purposes by treating compound solutions of sugars of the cane
group and haloid salts of sodium potassium or ammonium with formic aldehyde,
substantially as described.
3. The process for preparing new formic aldehyde compounds for therapeutic
and preservative purposes by treating compound solutions of sugars of the cane
sugar group and potassium bitartrate or agar-agar containing potassium bitartrate
with formic aldehyde substantially as described.
4. As new products the new compounds manufactured according to the process
claimed in the First Claim.
5. As new products the new compounds manufactured according to the process
claimed in the Second Claim.
6. As new products the new compounds manufactured according to the process
claimed in the Third Claim.
Dated this 6th day of December 1897.
W. P. THOMPSON & Co.,
Patent Agents for the Applicants,
Of London, Liverpool, Manchester, and Birmingham.