Manufacture of New Chemical Substances suitable for Perfumery, Confectionery, and the like.
Year: 1893

page_text: Date of Application, 1st May, 1893
Complete Specification Left, 22nd Jan., 1894-Accepted, 24th Feb., 1894
PROVISIONAL SPECIFICATION.
Manufacture of New Chemical Substances suitable for Perfumery,
Confectionery, and the like.
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:-
"
I have found that a mixture of citral and acetone, if it is subjected, in the
presence of water, for a sufficiently long time to the action of hydrates of alkaline
earths or of hydrates of alkali metals, or of other alkaline agents, is condensed to
"Pseudo-ionone
a ketone of the formula C₁,H,,O. This substance which I term
may be produced for instance in shaking together for several days equal parts
of citral and acetone with a solution of hydrate of barium and in dissolving the
products of this reaction in ether.
The residue of the ether solution is fractionally distilled under a reduced
pressure and the fraction is collected which boils under a pressure of 12 m.m. at a
temperature of from 138° to 155° C., and from it the unattacked citral and
unchanged acetone and volatile products of condensation are separated in a current
of steam, which readily carries off these bodies.
The product of condensation remaining in the distilling apparatus is purified by
the fractional distillation in vacuo. Under a pressure of 12 m.m. a liquid distils
off at a temperature of from 143 to 145° C. This product of condensation which
I term "Pseudo-ionone" is a ketone readily decomposable by the action of
alkalies. Its formula is C₁,HO, its index of refraction is n D = 1,527 and its
specific weight 0,904.
20
The pseudo-ionone has a peculiar but not very pronounced odour; it does not
combine with bisulphite of sodium as most of the ketones of the higher series, but,
in other respects, it possesses the ordinary characteristic properties of the ketones,
forming, in particular, products of condensation with phenylhydrazine, hydroxyl-
amine and other substituted ammonias.
Although the odour of the pseudo-ionone does not appear to render it of great
importance for its direct use in perfumery, it is capable of serving as raw material
for the production of perfumes, the pseudo-ionone being converted by the action of
dilute acids into an isomeric ketone which I term "Ionone" and which has most
valuable properties for perfumery purposes. This conversion may be effected for
example by heating for several hours in an oil bath 20 parts of "pseudo-ionone'
with 100 parts of water, 2.5 parts of sulphuric acid and 100 parts of glycerine, to
the boiling point of the mixture. The product resulting from this reaction is
dissolved in ether, the latter is evaporated and the residue subjected to the
fractional distillation in vacuo. The fraction distilling under a pressure of 12 m.m.
"
at a temperature of from 125° to 135° C. is collected. This product may be still
further purified by converting it by means of phenylhydrazine or other substituted
ammonias into a ketone condensation product decomposable under the action of
dilute acids.
-
The ketone derivatives of the pseudo-ionone are converted under similar
conditions into ketone-derivatives of the ionone. The pure ionone corresponds to
the formula C,H,O, it boils under a pressure of 12 m.m. at a temperature of
1,507.
about 128° C., its specific weight is 0,935 and its index of refraction n D
The ionone has a fresh flower-perfume recalling that of violets and vines, and is
peculiarly suitable for being used in perfumery, confectionery and distillery..
The ionone when subjected at a higher temperature to the action of hydroiodic

page_text: acid, splits off water and gives a hydrocarbon corresponding to the formula C₁₂Hi,
boiling under a pressure of 12 m.m. at a temperature of from 106° to 112° C.
hydrocarbon is converted by strong oxidising agents into an acid of the
formula C₁₂HO, melting at a temperature of 214° C.
12'
Dated this 1st day of May 1893.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Chemical Substances suitable for Perfumery,
Confectionery, and the like.
t
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:
I have found, that a mixture of citral and acetone, if it is subjected in the presence
of water for a sufficiently long time to the action of hydrates of alkaline earths or
of hydrates of alkali metals, or of other alkaline agents, is condensed to a ketone of
the formula CHO. This substance, which I term "Pseudo-ionone," may be
produced for instance in shaking together for several days equal parts of citral and
acetone with a solution of hydrate of barium and in dissolving the products of this
reaction in ether.
The residue of the ether solution is fractionally distilled under a reduced pressure
and the fraction is collected, which boils under a pressure of 12 m.m. at a temperature
of from 138° to 155° C., and from it the unattacked citral and unchanged acetone
and volatile products of condensation of acetone by itself are separated in a current
of steam, which readily carries off these bodies.
The product of condensation remaining in the distilling apparatus is purified by
the fractional distillation in vacuo. Under a pressure of 12 m.m. a liquid distills off
at a temperature of from 143° to 145° C. This product of condensation of citral
with acetone, which I term "Pseudo-ionone," is a ketone readily decomposable by
the action of alkalies. Its formula is C₁,HO, its index of refraction is n D =1,527
and its specific weight 0,904.
20
The pseudo-ionone has a peculiar, but not very pronounced odour; it does not
combine with bisulphite of sodium as most of the ketones of the higher series, but in
other respects it possesses the ordinary characteristic properties of the ketones,'
forming in particular, products of condensation with phenylhydrazine, hydroxyl-
amine and other substituted ammonias.
Although the odour of the pseudo-ionone does not appear to render it of great
importance for its direct use in perfumery, it is capable of serving as raw material
for the production of perfumes, the pseudo-ionone being converted by the action of
dilute acids into an isomeric ketone, which I term "Ionone" and which has most
valuable properties for perfumery purposes. This conversion may be effected for
example by heating for several hours in an oil bath 20 parts of "pseudo-ionone"
with 100 parts of water, 2-5 parts of sulphuric acid and 100 parts of glycerine, to
the boiling point of the mixture.
'"
The
The product resulting from this reaction is dissolved in ether, the latter is
evaporated and the residue subjected to the fractional distillation in vacuo.
fraction distilling under a pressure of 12 m.m. at a temperature of from 125° to
135° C. is collected. This product may be still further purified by converting it by
means of phenylhydrazine or other substituted ammonias into a ketone condensation
product decomposable under the action of dilute acids.'

page_text: The ketone derivatives of the pseudo-ionone are converted under similar con-
ditions into ketone-derivatives of the ionone. The pure ionone corresponds to the
formula Ci,HO, it boils under a pressure of 12 m.m. at a temperature of about
128° C., its specific weight is 0,935 and its index of refraction n D = 1,507.
The ionone has a fresh flower perfume recalling that of violets and wines, and is
peculiarly suitable for being used in perfumery, confectionery and distillery.
The ionone when subjected at a temperature surpassing 100° C. to the action of
hydroiodic acid, splits off water and gives a hydrocarbon corresponding to the
formula C,Hi, boiling under a pressure of 12 m.m. at a temperature of from 106°
to 112° C. This hydrocarbon is converted by strong oxidising agents into an acid
of the formula C₁,H₁,O, melting at a temperature of 214° C.
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. A new chemical product termed pseudo-ionone obtained by the reaction of
citral upon acetone in the presence of alkaline agents and subsequent treatment of
the products, substantially as described.
2. A new article of manufacture termed ionone suitable for perfumery and the
like and having the characteristics herein before set forth, obtained from pseudo-
ionone referred to in the preceding claim, substantially as described.
3. The process for the production of the pseudo-ionone referred to in the first
claim, consisting in the subjection of a mixture of citral and acetone to the action
of an alkaline agent, and in purifying the product of this reaction, extracted by
means of ether, by fractional distillation, substantially as described.
4. The process for the production of the ionone referred to in the second claim,
consisting in treating the pseudo-ionone referred to in the first claim or its ketone
condensation products with phenylhydrazine or other ammonia derivatives, finally
with acids, substantially as described.
Dated this 22nd day of January 1891
ABEL & IMRAY,
Agents for the Applicant.