Year: 1895

page_text: Date of Application, 8th Nov., 1895
Complete Specification. Left, 7th Aug., 1896-Accepted, 26th Sept., 1896
1, Dr. ARTHUR EICHENGRÜN of No. 9 Rheinwerft Bonn in the Empire of
Germany, do hereby declare the nature of this invention to be as follows:-
My invention consists in combining iodoform with hexamethylenetetramine and
its combinations with alkylhalogen or iodine.
Iodoform contrary to its general behaviour combines readily with hexamethylene-
tetramine and not only with the free base itself, but also with compounds which this
base forms with other substances, in decomposing these compounds into their
components.
Such compounds are the combinations of hexamethyleneamine with phenols or
with aldehydes such as the combination of hexamethyleneamine and hydrate.of
chloral.
The action of iodoform (394 grms.) on hexamethyleneamine (140 grms.) or on
one of the above mentioned additional substances, produces iodoformhexamethylene-
tetramine CHI¸ — CH₁₂N, which I have named iodoformin.
-
Jodoformin is a white subtile powder, insoluble both in water and in alcohol, it
melts at 178° Celsius. In contact with acids or alkalies it decomposes and produces
iodoform.
By the action of halogenalkyles or iodine on iodoformin new additional products
are obtained containing both halogenalkyle or iodine and iodoform. Å better
method of obtaining these substances is to make iodoform act upon the compound
of hexamethyleneamine with halogenalkyles or with iodine.
Both methods produce:
1) lodethyliodoformin, which I have named iodoformal and which forms dark
yellow needles soluble in alcohol but not in water and melting at 128° C.
2) Icdmethyliodoformin, light yellow needles, easily soluble in alcohol and
melting at 179° C.
3) Todmethyleneiodoformin are small, yellow needles melting at 174° C.
4) Bromethyliodoformin, dark yellow needles, easily soluble in alcohol and
melting at 114° C.
5) lod-iodoformin, a light brown powder, melting above 200° C. All these
substances separate just as iodoformin does upon coming in contact with acids or
alkalies and produce iodoform.
Dated this Fourth day of November 1895.
COMPLETE SPECIFICATION.
New and Useful Bodies Derived from Iodoform.
I, Dr. ARTHUR EICHENGRÜN, of No. 9, Rheinwerft, Bonn, 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 :-
Whereas the alkyliodides usually can be easily combined with ammonia and fatty

page_text: bases, forming the iodine salts of amine- imide- nitrile-, and ammonium-bases,
iodoform, which differs entirely in its manner of. formation and its chemical
behaviour from the real alkyliodides, remains quite indifferent upon coming into
contact with these bases.
For this reason it is very peculiar that iodoform, as I have discovered, readily
enters into a combination with the nitrile-base, hexamethylentetramine producing a
substance of the composition
CH,,N, CHI,.
-
This compound is not only formed by the action of iodoform upon the free base,
but also upon the additive products which the latter forms with other substances,
in which case these compounds are decomposed into their components.
Of such additive combinations are principally to be considered the combinations
of hexamethylenamine with phenols, with chlorides of aromatic acids and with
aldehydes (for instance the combination of hexamethylenamine and hydrate of
chloral).
The action of iodoform on hexamethylenamine or on one of its derivatives
produces the above mentioned iodoform-hexamethylenamine C₂H₁N - CHI,.
This result is very strange for the following reasons:-
I. Because additive combinations of iodoform and free bases are entirely
unknown.
II. Because, according to the combinations of hexamethylentetramine with real
alkylbaloids (discovered by A. Wohl, Berichte der Deutschen Chem. Gesellsch.,
XIX 1840) one would have expected that iodoform, in case of its at all entering
into reaction with this base, would combine with three molecules of hexamethylen-
amine.
T

page_text: · Iodoformhexamethylenumine is a white subtile powder which melts at 178° and
cannot be dissolved either in water or in ether or alcohol. Upon coming in contact
with diluted acids or alkalies and even being agitated with water it decomposes
entirely into iodoform and hexamethylenamine.
By the action of silver nitrate no precipitate of silver iodide is formed but
iodoform is liberated and a double salt of silver nitrate and hexamethylenamine is
formed.
By the action of silver chloride and platinchloride the same decomposing effect
is produced.
On the other hand the compounds of Wohl have the characteristic properties of
iodine salts of ammonium bases. They are easily soluble in water and crystallize
unaltered on evaporating the aqueous solution.
The iodine is completely removed by treatment with silver nitrate.
When heated with silver chloride Wohl's compounds are converted into the
corresponding chlorine salts from which platinchloride-double salts can be prepared.
When heated in alcoholic solution Wohl's compounds become altered as for
instance the ethiodide-hexamethylenamine (melting at 144°) is converted into a
compound melting at 180° but never under any circumstances do they decompose
into their components as iodoform-hexamethylenamine does.
If one adds hydrate of potash to a concentrated watery solution the compounds
of Wohl are precipitated without being altered. This reaction doubtless shows that
they are salts of quaternary ammonium bases.
As such compounds they are not able to form a combination with another
haloid-alkyl but like hexamethylenamine itself they are also able to form additive
combinations with iodoform. These new compounds have the same chemical
properties as iodoformhexamethylenamine; they can not be dissolved in water and
are decomposed by acids and alkalies liberating iodoform.
Equally as well as by the action of iodoform on haloidalkylhexamethylenamine,
they can be obtained by the action of haloidalkyl on iodoform hexamethylenamine.
14 grs. of hexamethylenamine are dissolved in absolute alcohol, then 39.4 grs.
of iodoform are added and the mixture heated for a short time by means of a
water bath.
A white fine powder is then deposited consisting of iodoform-hexamethylen-
tetramine and having the above mentioned properties.
Instead of taking pure hexamethylentetramine one may mix the alcoholic solutions
of its components with a solution of iodoform.
EXAMPLE II.
23-4 gr. of monophenol hexamethylenamine are dissolved in alcohol; then 39.4 gr.
iodoform are added and the precipitated iodoformhexamethylenamine filtered. The
mother liquor contains all the phenol.

page_text: DR. ARTHUR EICHENGRÜN.