Manufacture of a New Chemical Substance from Orris-root.
Year: 1893

page_text: Date of Application, 1st May, 1893
Complete Specification Left, 22nd Jan., 1894-Accepted, 10th Mar., 1894.
PROVISIONAL SPECIFICATION.
Manufacture of a New Chemical Substance from Orris-root.
I JOHANN CARL WILHELM FERDINAND TIEMANN, Member of the Firm of
Haarmann and Reimer, of Holzminden, residing at Berlin, Germany, do hereby
declare the nature of this invention to be as follows:-
In experimenting with the mixture of different bodies obtained in treating orris
root (the root of Iris florentina and Iris Pallida, &c.) with alcohol or ether and
distilling the extracts obtained in a current of steam, I have discovered a new
substance which is the aromatic principle of the orris root, and which I have found
to be a ketone of the composition C₁,HO, and I have given to this substance
the name of "Irone."
20
From the analysis which I have made of the mixture of the substances
accompanying the irone in the root and especially from the determination of the
chemical nature of the irone I have arrived at simple methods which allow of the
separation of the irone from the substances contained together with it in existing
commercial preparations of orris root, such as for instance, those known under the
names of orris butter, orris oil &c., and to prepare the pure irone on a commercial
scale.
The preparation of the irone may be carried out in the following way.
The alcoholic or ether extract of the orris root is subjected to distillation in a
current of steam. Organic acids, such as myristic and oleic acid &c., the methylic
ethers of these acids, alcohols of higher series and small quantities of aldehydes,
in particular oleic aldehyde &c. pass over together with the irone, into the distillate.
These combinations are dissolved in ether and the ether solution is agitated with
a dilute solution of an alkali for separating the free acids. The residue of the
ether solution is dissolved in alcohol and mixed at ordinary temperature with a
weak solution of alkaline hydrates which saponify the ethers of the organic acids.
After some minutes it is poured into water, the neutral oils are dissolved in ether,
the ether is evaporated and the residue is distilled in a current of steam. The
irone is one of the bodies distilling over at first. By repeating this operation
several times I obtain a product giving the characteristic reactions of the ketones,
but containing still small quantities of aldehydes (such as oleic aldehyde) and other
impurities. To eliminate the aldehydes, this product is treated with weak oxidizing
agents, such for instance as with water and silver oxide, under heating. The irone
is then converted into its phenylhydrazone or condensed with another substituted
ammonia to a ketone derivative also decomposable by dilute acids.
In using the phenylhydrazone the process may be carried out, for example, in
the following way :-
Nearly equimolecular parts of crude irone and of phenylhydrazine are allowed
to act upon one another during several days. The oily product is then distilled
in a current of steam.
The impurities and the surplus of hydrazine pass over and the phenylhydrazone
of the irone remains in the distilling apparatus.
After having added dilute sulphuric acid or another acid, the distillation is
continued in order to obtain the pure body.
It is evident from the above description, that the described process permits ¸ of

page_text: the separation from the irone not only the different substances contained with it in
the root, but also the impurities produced in the course of the different processes
employed for extracting the orris root.
The irone is a ketone of the formula C₁,H2O boiling under a pressure of
16 m.m. at a temperature of 144° C., having a specific weight of 0-939 and an
index of refraction n D = 1.50113.
The irone, like most of the ketones of the higher series, does not combine with
bisulphite of sodium and is decomposed by the simultaneous action of a heated
chloride of lime solution into chloroform and an organic acid.
At a high temperature hydro-iodic acid splits off water from the irone and
transforms it into a hydrocarbon of the formula C₁₂H₁ boiling at from 115°
to 120° C. under a pressure of 12 m.m. By means of strong oxidizing agents this
hydrocarbon is converted into an acid of the formula C₁₂H₁O. melting at
214° C.
The pure irone has the characteristic odour and flavour of the orris root, and its
use in a pure state in perfumery, confectionery, and distillery offers considerable
advantages.
It will be seen from the above description that hitherto the aromatic principle
of the orris root has never before been obtained by itself, either in a pure state or
otherwise, it having always been supplied to the different industries making use
thereof as compounds with other chemical bodies. There exist essential differences
between these compounds and the pure irone, both as regards their form and those
properties which are of value in their industrial application.
Dated this 1st day of May 1893.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of a New Chemical Substance from Orris-root.
I, JOHANN CARL WILHELM FERDINAND TIEMANN, Member of the Firm of
Haarmann and Reimer of Holzminden, residing at Berlin, 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 experimenting with the mixture of different bodies obtained in treating orris
root (the root of Iris florentina and Iris Pallida etc.) with alcohol or ether and
distilling the extracts obtained in a current of steam, I have discovered a new
substance, which is the aromatic principle of the orris root and which I have found
to be a ketone of the composition C₁HO, and I have given to this substance
the name of " Irone."
From the analysis which I have made of the mixture of the substances accom-
panying the irone in the root and especially from the determination of the chemical
nature of the irone, I have arrived at simple methods, which allow of the separation
of the irone from the substances contained together with it in the existing
commercial preparations of orris root, such as for instance, those known under the
names of orris butter, orris oil etc. and to prepare the pure irone on a commercial
scale.
The preparation of the irone may be carried out in the following way :-
The alcoholic or ether extract of the orris root is subjected to distillation in a
current of steam. Organic acids, such as myristic and oleic acid etc., the methylic
ethers of these acids, alcohols of higher series and small quantities of aldehydes,
in particular oleic aldehyde etc., pass over together with the irone, into the distillate.
These combinations are dissolved in ether and the ether solution is agitated with

page_text: a dilute solution of an alkali for separating the free acids. The residue of the
ether solution is dissolved in alcohol and mixed at ordinary temperature with a
weak solution of alkaline hydrates, which saponify the ethers of the organic acids..
After some minutes it is. poured into water, the neutral oils are dissolved in
ether, the ether is evaporated and the residue is distilled in a current of steam..
The irone is one of the bodies distilling over at first.
By repeating this operation several times I obtain a product giving the
characteristic reactions of the ketones, but containing still small quantities of
To eliminate the-
aldehydes (such as oleic aldehyde) and other impurities.
aldehydes this product is treated with weak oxidizing agents, such for instance as
with water and silver oxide under heating. The irone is then converted into its
phenyl-hydrazone or condensed with another substituted ammonia to a ketone-
derivative also decomposable by dilute acids.
In using the phenylhydrazone the process may be carried out for example in the
following way:-
Nearly equimolecular parts of crude irone and of phenylhydrazine are allowed
to act upon one another during several days. The oily product is then distilled in
a current of steam: The impurities and the surplus of phenylhydrazine pass over
and the phenylhydrazone of the irone remains in the distilling apparatus.
After having added dilute sulphuric acid or another acid, the distillation is.
continued in order to obtain the pure body.
It is evident from the above description, that the described process permits of
the separation from the irone not only the different substances contained with it in °
the orris root, but also the impurities produced in the course of the different
processes employed for extracting the orris root.
The irone is a ketone of the formula CHO boiling under a pressure of
16 m.m. at a temperature of 144° C., having a specific weight of 0.939 and an index
of refraction n D = 1.50113.
The irone, like most of the ketones of the higher series, does not combine with
bisulphite of sodium and is decomposed by the action of a heated chloride of lime
solution into chloroform and an organic acid.
18
At a temperature surpassing 100° C. hydro-iodic acid splits off water from the
irone and transforms it into a hydrocarbon of the formula C₁₁, boiling at from.
115° to 120° C., under a pressure of 12 m.m. By means of strong oxidizing agents
this hydrocarbon is converted into an acid of the formula CH₁₂O, melting
at 214° C.
The pure irone has the characteristic odour and flavour of the orris root, and its
use in a pure state in perfumery, confectionery and distillery offers considerable
advantages.
It will be seen from the above description, that hitherto the aromatic principle
of the orris root has never before been obtained by itself in a pure state, it having
always been supplied to the different industries, making use thereof naturally mixed
with other chemical bodies.
There exist essential differences between these mixtures and the pure irone, both.
as regards their form and those properties, which are of value in their industrial
application.
Having now particularly described and ascertained the nature of this inven--
tion and in what manner the same is to be performed I declare that what
I claim is
"
1. Process for the production of the aromatic principle of orris root herein
termed Irone" consisting in separating the volatile constituents of the orris root
by means of steam etc., in the manner herein described and converting the crude
orris ketone (irone) thus isolated by means of phenylhydrazine or of another
substituted ammonia into a ketone condensation product, which is decomposed by
acids and from which the irone is then obtained by distillation, substantially as.
described.

page_text: 2. As a new manufacture, the product termed "Irone" obtained by the process.
referred to in the first claim.
1
11
Ր T
1004
ABEL & IMRAY,
Agents for the Applicant.