Production of Substances suitable for Manufacture of Perfumery and Aromatics.
Year: 1893

page_text: Date of Application, 18th Sept., 1893
Complete Specification Left, 11th June, 1894-Accepted, 4th Aug., 1894
PROVISIONAL SPECIFICATION.
Production of Substances suitable for Manufacture of Perfumery
and Aromatics.
I, JOHANN CARL WILHELM FERDINAND TIEMANN, Member of the Firm of
Haarmann and Reimer of Holzminden, residing at 18 Beudlerstrasse Berlin, W.
Prussia, Germany, do hereby declare the nature of this invention to be as
follows:-
In my Provisional Specification No. 8736 of 1893 I have described the
production of substances suitable for perfumery from a body termed pseudoionone
obtained by shaking together citral and acetone with hydrate of barium. I have
now found that in this process may be used not only the citrals naturally occurring
in lemon oil, lemon grass oil &c., but also the artificial citrals obtained by the
oxidation of the alcohols having the formula CHO and present in many etherial
oils, such alcohols as geraniol, rhodinol, linalool, aurantiol, lavendol, likareol &c.
Also, in the same manner as natural citrals, may be employed citrals treated
with weak condensing agents which probably contain an isomer of the citral.
I bave also found that in the process described in my Specification No. 8736
of 1893 above referred to
1. For the acetone may be substituted its homologues and:
2. For the citral, citronellon (citronellal), an aldehyde richer by two atoms of
hydrogen, without changing essentially the technical effect, that is to say,
the properties of the final product in so far as regards its industrial
application.
EXAMPLE I.
Equal parts of citral and ethyl-methyl-ketone are shaken together with dilute
soda lye for several days. The product of reaction, taken up in ether, is freed from
ether by heating it on the water bath, and is separated by distillation in a current of
steam from the citral not attacked and from the unchanged ethyl-methyl-ketone
and the volatile products of its condensation. The oil remaining in the still is
distilled over in vacuo, the methyl pseudoionone passing over under a pressure
of 21-5 m.m. at a temperature of from 160° to 175° C.
This methyl-pseudoionone has a peculiar, but not very pronounced odour, it is
converted by digestion with dilute acids, such as sulphuric acid of 3 per cent., at
a temperature of about 102° C., into methyl ionone boiling under a pressure of
24 m.m. at a temperature of from 155° to 160° C. The odour of the methyl ionone
resembles that of the ionone.
The condensation of the ethyl-methyl ketone with citral takes place somewhat
more slowly than that of the acetone with citral. The higher homologues of acetone
may be condensed with citral in an analogous manner. But in these cases the
condensation requires still longer time.

page_text: This represents the product of condensation of citronellone (citronellal) with
acetone, which I term "dihydropseudoionone."
By digesting with dilute sulphuric acid, at about 3 per cent., at a temperature of
at least 102° C. the dihydropseudoionone is converted into dihydroionone which
boils under a pressure of 23-5 m.m. at a temperature of about 136° C. and has an
odour of fresh flowers.
Considerable quantities of by products are formed during this operation.
The methyl-ethyl &c. ionones and the bydrided ionone as well as ionone itself
are applicable as odorous substances in the manufacture of perfumery and as
aromatics for food.
Dated this 18th day of September 1893.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Production of Substances suitable for Manufacture of Perfumery
and Aromatics.
I, JOHANN CARL WILHELM FERDINAND TIEMANN, Member of the Firm of
Haarmann and Reimer of Holzminden, residing at 18 Beudlerstrasse, Berlin W.
Prussia, 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 2
and by the following statement :—
In my Specification to Patent No. 8736 of 1893 I have described the production
of substances suitable for perfumery from a body termed pseudoionone obtained
by shaking together citral and acetone with hydrate of barium. In the meantime
I have especially stated that in this process may be used not only the citrals 2
naturally occurring in lemon oil, lemon grass oil etc., but also the artificial citrals
obtained by the oxidation of the alcohols having the formula CHO and present.
in many etherial oils, such alcohols as geraniol, rhodinol, linalool, aurantiol, lavendol,.
likareol &c.
10 18
Also, in the same manner as natural citrals, may be employed citrals treated with 3
weak condensing agents which probably contain an isomer of the citral.
I have now found that in the process described in my Specification No. 8736
of 1893 above referred to
1. For the acetone may be substituted its homologues and:
2. For the citral, citronellone (citronellal), an aldehyde richer by two atoms 3
of hydrogen, without changing essentially the technical effect, that is to say,
the properties of the final product in so far as regards its industrial
application.
EXAMPLE I.
Equal parts of citral and ethyl-methyl-ketone are shaken together with dilute 4
soda lye for several days. The product of reaction, taken up in ether, is freed
from ether by heating it on the water bath, and is separated by distillation in
a current of steam from the citral not attacked and from the unchanged ethyl-
methyl-ketone and the volatile products of its condensation. The oil remaining in
the still is distilled over in vacuo, the methyl-pseudoionone passing over under a 4
pressure of 21-5 m.m. at a temperature of from 160° to 175° C.
This methyl-pseudoionone has a peculiar, but not very pronounced odour, it is
converted by digestion with dilute acids, such as sulphuric acid of 3 per cent., at a
temperature about 102° C. into methyl ionone boiling under a pressure of 24 m.m.
at a temperature of from 155° to 160° C. The odour of the methyl ionone resembles 5
that of the ionone.
The condensation of the ethyl-methyl-ketone with citral takes place somewhat

page_text: more slowly than that of the acetone with citral. The higher homologues of acetone
may be condensed with citral in an analogous manner. But in these cases the
condensation requires still longer time.
EXAMPLE II.
Equal parts of citronellone (citronellal) and acetone are shaken together with.
dilute alkaline lye for several days. The product of reaction is extracted by means
of ether and the ether residue of the distillation is subjected to a strong steam current.
The oil which passes over is collected.
By repeated fractional distillation in vacuo, a fraction, boiling under a pressure of
21 m.m. at a temperature of from 153° to 156° C., is obtained.
This represents the product of condensation of citronellone (citronellal) with
acetone, which I term "dihydropseudoionone." By digesting with dilute sulphuric
acid, at about 3 per cent., at a temperature of at least 102° C. the dihydro-
pseudoionone is converted into dihydroionone which boils under a pressure of
23-5 m.m. at a temperature of about 136° C. and has an odour of fresh flowers.
Considerable quantities of by-products are formed during this operation.
The methyl ethyl etc. ionones and the hydrided ionone may be still further
purified by converting them by means of phenylhydrazine or other substituted
ammonias into ketone-condensation products decomposable under the action of
dilute acids.
The products of condensation of the methylised ethylised &c. or hydrided
pseudoionones with phenylhydrazine, hydroxylamine or other substituted ammonias
are at first transformed by acids into the corresponding derivatives of the methylised
ethylised &c. or hydrided ionones and then split off into methylised ethylised &c. or
hydrided ionones and substituted ammonias.
The methyl-ethyl &c. ionones and the hydrided ionone as well as ionone itself are
applicable as odorous substances in the manufacture of perfumery and as aromatics
for food.
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 :-
A new manufacture of substances suitable for perfumery and aromatics from.
citral and the homologues of acetone, and also from citronellone (citronellal) and
acetone or its homologues by condensing the said compounds by means of alkaline
agents to new ketones (methylised, ethylised &c. or hydrided pseudoionones) and
converting these ketones or their products of condensation with phenylhydrazine,.
hydroxylamine &c. by means of acids into ketones isomeric with the methylised,.
ethylised &c. or hydrided pseudoionones, namely into the methylised, ethylised &c..
or hydrided ionones, substantially as set forth.
Dated this 11th day of June 1894.
ABEL & IMRAY,
Agents for the Applicant.