Process for Separating Ionone into the two varieties a-
Year: 1899

page_text: Date of Application, 27th Jan., 1899
Complete Specification Left, 21st Oct., 1899-Accepted, 2nd Dec., 1899
and B-Ionone.
I, JOHANN CARL WILHELM FERDINAND TIEMANN, of No. 4, Brueckenallee, Berlin,
n the Empire of Germany, do hereby declare the nature of this invention to be as
follows:-
Process for Separating Ionone into the two varieties a-
I have shown in the "Berichte der Deutschen chemischen Gesellschaft" No. 31,
1898, page 851, that ionone can be purified by a process consisting in dissolving it by
boiling for several hours in a solution of sodium bisulphite, in eliminating the impurities
which are present by extraction with an extracting agent, such as ether, and then in
setting free the ionone from the aqueous solution thus purified by heating with
alkaline hydroxide.
I have found that in this process the solution of sodium bisulphite can be replaced
by a solution of sodium sulphite, to which a suitable agent is added which, at the
boiling temperature of the solution employed, combines the sodium hydroxide that is
disengaged in the reaction.
This purpose is attained for instance by means of an addition of a little more than
one molecular weight of glacial acetic acid to one molecular weight of sodium
sulphite, Na,SO3, or by an addition of ammonium sulphate from which the alkaline
hydroxide which is set free expels the ammonia at the boiling temperature of the
solution.
Moreover I have found firstly, that by evaporating the neutral or feebly alkaline.
solution obtained in heating ionone with a solution of alkali bisulphite, the alkali
salts of the derivatives of the hydrosulphonie acid of the a-ionone formed in this
reciprocal action are first separated by crystallisation, and secondly, that from
the neutral or feebly alkaline reacting solution of ionone obtained by boiling
ionone with alkali bisulphite, or with alkali sulphite and acetic acid, or with alkali
sulphite and ammonium sulphate there is liberated by distillation in a strong
current of steam essentially only ẞ-ionone which passes over into the distillate.
there is added alkaline lye in excess to the solution, (which when treated with a
current of steam no longer yields an oily distillate) mainly only a-ionone is eliminated
therefrom, and this can be obtained either from the rapidly cooled liquor by extraction
with a solvent, such as ether, or by distillation in a current of steam after having been
neutralized by an acid.
If
The separation described of the two varieties of ionone-a-and ẞ-ionone- from one
another, if carried out in a correct manner, is nearly quantitative."
B-ionone is characterised by the generally known semi carbazone the melting point
of which is 148° C.; B-ionone may be still further purified by converting it into the
crystallised semicarbazone melting at 148° C. and by resolving this by means of
sulphuric acid.
a-ionone is characterised by the known well crystallising oxime melting directly at
a temperature of 87° C., or at one or two degrees higher after repeated recrystallisation.
into the crystallised oxime
a-ionone may be still further purified by converting
and by the known decomposition of the latter by means of sulphuric acid.

page_text: EXAMPLE.
100 parts of ionone are boiled with a solution of 100 parts of sodium bisulphite or
the equivalent quantity of potassium bisulphite or the equivalent quantity of sodium
sulphite (Na,SO) to which is added per one molecular weight of sodium sulphite
a little more than one molecular weight of glacial acetic acid or of ammonium
sulphate in excess, in 300 parts of water, the boiling being continued until the oil
has dissolved to a clear solution. This ordinarily requires from 8 to 10 hours.
The solution, which reacts only feebly alkaline, is shaken for removing the
impurities with a suitable extracting medium such as ether.
The solution is then treated with a strong current of steam which carries over
B-ionone,
If required, this ß-ionone is still further purified by converting it into semicar-
bazone melting at 148° C. and by resolving the latter by means of sulphuric
acid.
When no more oil drops pass over, either sodium carbonate is added to the
solution freed from ẞ-ionone, and the a-ionone thus set free is distilled over directly
in a current of steam, or alkaline lye is added and after a short time the liquor is
rapidly cooled, whereupon a-ionone is obtained by shaking with ether, or the
solution is heated for a short time with alkaline lye for setting free a-ionone from its
hydro-sulphonic acid salts, rapidly cooled, neutralised with any suitable acid and
finally a-ionone is distilled over in a current of steam.
If required, a-ionone may be still further purified by converting it into the
crystallised oxime melting at 87° C. and by decomposing the latter by means of an
acid.
But if the ionone to be decomposed contains only very small quantities of the
variety, which however seldom occurs, the solution obtained by boiling ionone with
alkali bisulphites may be concentrated by evaporation and filtered off from the alkali
salts of the derivatives of the hydrosulphonic acid of the a-ionone which crystallise
on cooling, and the filtrate may be subjected to the treatment above described for
separation of the a- and ẞ-ionone.
Dated this 27th day of January 1899.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Process for separating Ionone into the two varieties a- and s-Ionone.
I, JOHANN CARL WILHELM FERDINAND TIEMANN, of No. 4, Brueckenallee, Berlin, 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 :-
I have shewn in the "Berichte der Deutschen chemischen Gesellschaft" No 31,
1898, page 85, that jonone can be purified by a process consisting in first dissolving
it by boiling for several hours in a solution of sodium bisulphite, then eliminating the
impurities which are present by extraction with an extracting agent, such as ether,
and finally setting free the ionone from the aqueous solution thus purified by heating
with alkaline hydroxide.
I have found that in this process for the solution of sodium bisulphite may be
substituted a solution of sodium sulphite, to which is added a suitable agent
capable at the boiling temperature of the solution employed of combining with
the sodium hydroxide that is disengaged in the reaction,

page_text: This purpose is attained, for instance, by adding a little more than one
molecular proportion of glacial acetic acid to one molecular proportion of sodium
sulphite, NSO. or by adding ammonium sulphate from which the alkaline
hydroxide which is set free expels the ammonia at the boiling temperature of
the solution.
Moreover I have found firstly, that by evaporating the neutral or feebly
alkaline solution obtained in heating ionone with a solution of alkali bisulphite,
the alkali salts of the hydrosulphonic acid derivatives of a-ionone (compounds of
q-ionone with one or more molecular proportions of sulphurous acid) formed in
this reciprocal action are first separated by crystallization, and secondly, that from
the neutral or feebly alkaline reacting solution of ionone obtained by boiling ionone
with alkali bisulphite, or with alkali sulphite and acetic acid, or with alkali sulphite
and ammonium sulphate there is liberated by distillation in a strong current of
steam essentially only ẞ-ionone which passes over into the distillate. If there is
added alkaline lye in excess to the solution from which no more or only a very
little oily distillate is obtained by treatment with a current of steam, mainly
only a-ionone is eliminated therefrom, and this can be obtained either from the
rapidly cooled liquor by extraction with a solvent, such as ether, or by
distilling the liquor in a current of steam after it has been neutralized by an
acid.
The separation described of the two varieties of ionone-a-and B-ionone- from one
another, if carried out in a correct manner, is sufficiently nearly quantitative for
technical purposes.
B-ionone is characterised by the generally known semi-carbazone the melting
point of which is 148° C; B-ionone may be still further purified by converting it into
the crystallised semi-carbazone melting at 148° C. and by resolving this by means of
sulphuric acid.
a-ionone is characterised by the known well crystallising oxime melting directly at
a temperature of 87° C., or at one or two degrees higher after repeated re-
crystallisation.
u-ionone may be still further purified by converting it into the crystallised oxime
100 parts of ionone are boiled with a solution of 100 parts of sodium bisulphite or
the equivalent quantity of potassium bisulphite or the equivalent quantity of sodium
sulphite (Na, SO) to which is added per one molecular proportion of sodium sulphite
a little more than one molecular proportion of glacial acetic acid or ammonium
sulphate in excess, in 300 parts of water, the boiling being continued until the oil
has dissolved to a clear solution. This ordinarily requires from 8 to 10 hours.
The solution, which reacts only feebly alkaline, is shaken for removing the
impurities with a suitable extracting medium such as ether.
The solution is then treated with a strong current of steam which carries over
ẞ-ionone.
If required, this ẞ-ionone is still further purified by converting it into semi-
carbazone melting at 148° C and by resolving the latter by means of sulphuric
acid.
When virtually no more oil passes over, either sodium carbonate is added to the
solution freed from B-ionone, and the a-icnone thus set free is distilled over directly
in a current of steam, or alkaline lye is added and after a short time the liquor is
rapidly cooled, after which a-ionone is obtained by shaking with ether; a third
method is to heat the solution for a short time with alkaline lye for setting free
-ionone from its hydro-sulphonic acid salts, then to rapidly cool it, then to neutralise
it with any suitable acid and finally to distil over the a-ionone in a current of
steam,

page_text: If required, a-ionone may be still further purified by converting it into the
crystallised oxime melting at 87° C and decomposing the latter by means of an
acid.
But if the ionone to be decomposed contains only very small quantities of the
B-variety, which however seldom occurs, the solution obtained by boiling ionone with
alkali bisulphites may be concentrated by evaporation and filtered off from the alkali
salts of the hydrosulphonic acid derivatives of the azionone which crystallise on cooling,
and the filtrate may be subjected to the treatment above described for separation of
the C- and ß-ionone. The crystals of the hydrosulphonic acid derivatives of a-ionone
may be heated with alkali, as described above, for liberating the a-ionone.
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 :-
The herein described process for separating ionone into the two varieties a- and ß-
ionone by first hoiling ionone with alkali bisulphite solution, or with alkali sulphite
solution, to which has been added an agent which will combine with alkali hydroxide,
then distilling the B-ionone from the solution in a current of steam, either directly or
after crystallising by evaporation the greater part of the alkali hydrosulphonates of
a-ionone, and finally heating the solution from which the B-ionone has been separated
in this manner, or the crystals of the alkali hydrosulphonates of a-ionone obtained by
the evaporation, with alkali lye in excess to separate the a-ionone.
Autoha 1900
ABEL & IMRAY,
Agents for the Applicant.