Improvements in the Manufacture of Perfumes.
Year: 1895

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Perfumes.
We MARIUS OTTO and ALBERT VERLEY both of 8 Passage Goudron
Boulevard St. Jacques Paris in the Republic of France Chemists do hereby declare
the nature of this invention to be as follows :-
We have discovered that ozone acts in an exceedingly advantageous manner upon
certain carbon compounds and in particular on the carbon compounds which have a
benzine nucleus, with a lateral chain C, H, so as to give aldehydes. The carbon
compounds to which we refer have this lateral chain in the form CH=CH-CH3
or its isomer CH₂ CH CH. We have applied this reaction to the industrial
preparation of substances capable of being employed in perfumery such as vanilline,
heliotropine, aubepine, and others.
-
==
Taking first those bodies in which the chain CH, exists as CH=CH-CH3
such as iso-eugenol, iso-safrol and anethol, the reaction takes place in the following
manner (taking iso eugenol as an example)

page_text: bodies which are to be oxydized in liquids in the manner hitherto used. This
advantage which arises from using a gaseous oxydizer instead of a liquid oxydizer
s of considerable importance. For example if the oxydation be made in the old
manner by sulphuric acid and bichromate of potass or chromic acid, it has to be
performed on masses of liquid which are in general fifty times as large as the
body that it is desired to oxydize, and this gives rise to difficulty in extracting
the product of the operation from the large quantity of liquid that has been used,
when the reaction is finished. Ozone on the other hand, being always diffused
among an excess of oxygen which is not ozonized, can act without danger of creating
any violent reaction on the hody without it being mixed with such liquids, so that
the vessels employed are required to be only of the size of the body to be operated
upon instead of say fifty times that size.
-
Taking next the bodies in which the chain C,H, exists in the form CH, CH
CH, such as eugenol, satrol and estragol, the ozone is applied in the same manner
and the action results in the same body; thus for eugenol
CH2-CH=CH,
CHO
CH-OCH3 +0,
=
2 CO2 + 2 H2O + CHOCH¸ (vanilline)
OH
and similarly for the other analogous bodies.
=
-
OH
It will be seen therefore that what is novel in our invention is (1) a method of
transforming the group C3H, in the form CH CH-CH3 into the aldehyde
group CIIO by means of ozone substantially as described (2) a method of trans-
forming by ozone the group C,H, in the form CH, CH: = CH₂ into the aldehyde
group CHO by means of ozone substantially as described (3) the application of this
method of oxydation to the carbon compounds with benzene nucleus or any other
nucleus in a closed ring which contains in a lateral chain C,H, in either of the
above forms so as to produce aldehydes and in particular to the transformation of
the following bodies into their aldehydes; eugenol or iso-eugenol into vanilline;
safrol or iso-safrol into heliotropine; estragol or anethol into aubepine; and
(4) effecting the change of iso-eugenol or eugenol into vanilline directly by means
of ozone without any preliminary operation to replace the hydrogen of the phenol
group by a radical.
Dated this 27th day of March 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture of Perfumes.
We, MARIUS OTTO and ALBERT VERLEY, both of 8 Passage Gourdon,
Boulevard St. Jacques Paris, in the Republic of France, Chemists, 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 :--
We have discovered that zone acts in an exceedingly advantageous manner
upon certain carbon compounds and in particular on the carbon compounds which
have a benzine nucleus, with a lateral chain C,H,, so as to give aldehydes. The
carbon compounds to which we refer have this lateral chain in the form
CH=CH-CH, or its isomer CH, CH=CH. We have applied this
reaction to the industrial preparation of substances capable of being employed in
perfumery such as vanilline, heliotropine, aubepine and others.
-

page_text: Taking first those bodies in which the chain C₂H, exists as CH=CH – CH,.
such as isoeugenol, iso safrol and anethol, the reaction takes place in the following.
manner (taking iso-eugenol as an example)
он
thus giving vanilline.
OH
It is well known that in the methods previously used for the preparation
of vanilline it has been indispensable to operate first on the phenol group OH
in order to secure that the oxydation should only affect the group C,H,, but we
have found that the action of ozone is so selective that the phenol group remains
unaffected, and the group C3H, only is oxydised. It is therefore not necessary
to replace by a preliminary operation the hydrogen of the phenol group by a
radical in order to obtain vanilline though our method is equally applicable to such
a process. For example, if iso-eugenate of potassium be treated with ozone we
obtain a potass salt of vanilline, and by treating this salt with an acid the vanilline
is set at liberty.
Similarly from iso-safrol we obtain heliotropine,
CHO
CH3-
CH,
and from anethol we obtain aubepine
CHO
CH
\OCH3
We prefer to effect these oxydations warm but it is unnecessary to dissolve_the-
bodies which are to be oxydized in liquids in the manner hitherto used. This
advantage which arises from using a gaseous oxydizer instead of a liquid oxydizer,.
is of considerable importance. For example, if the oxydation be made in the old
manner by sulphuric acid and bichromate of potass or chromic acid, it has to be
performed on masses of liquid which are in general fifty times as large as the body
that it desired to oxidize, and this gives rise to difficulty in extracting the product.
of the operation from the large quantity of liquid that has been used when the
reaction is finished. Ozone on the other hand, being always diffused among an
excess of oxygen which is not ozonized, can act without danger of creating any
violent reaction on the body without it being mixed with such liquids, so that the
vessels employed are required to be only of the size of the body to be operated upon
instead of say fifty times that size.
Taking next the bodies in which the chain CH, exists in the form CH, - CH
= CH, such as eugenol, safrol and estragol, the ozone is applied in the same manner
and the action results in the same body thus for eugenol
✓ OCH, +0, = 2 CO, + 2 H₂O + CH₁—OCH, (vanilline)
-
CH,

page_text: It will be seen therefore that what is novel in our invention is (1) a method of
transforming the group C3H, in the form CH=CH-CH, into the aldehyde
group CHO by means of ozone substantially as described; (2) a method of trans-
forming by ozone the group C,H, in the form CH, -CH=CH, into the aldehyde
group CHO by means of ozone substantially as described; (3) the application of
this method of oxydation to the carbon compounds with benzene nucleus or any
other nucleus in a closed ring which contain in a lateral chain C3H, in either of the
above forms so as to produce aldehydes, and in particular to the transformation of
the following bodies into their aldehydes; eugenol or iso-eugenol into vanilline;
safrol or iso-safrol into heliotropine; estragol or anethol into aubepine; and
(4) effecting the change of iso-eugenol or eugenol into vanilline directly by means
of ozone without any preliminary operation to replace the hydrogen of the phenol
group by a radical.
The ozone employed is preferably used as it is prepared which may be done in
any suitable form of ozonizer by subjecting dried and refrigerated oxygen to the
action of electricity of high tension in the usual way. The proportion of the oxygen
converted into ozone and the current requisite to form it will depend upon the shape
and capacity of the apparatus, employed. The ozone may be introduced by means
of a glass or earthenware tube passed into the compound to be treated and
terminating in a rose or perforated ball for effectually distributing the ozone.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed we declare that what we
claim is :-
1. The method of transforming by the action of ozone a group CH, whether
under the form CH=CH-CH, or under the form CH, -CH=CH, into the
aldehyde group as above described.
2. The herein described method of oxydizing a carbon compound as isoeugenol
having a benzene nucleus with a lateral chain CH, (in one or other of the forms
above mentioned) in order to produce its corresponding aldehyde, as vanilline which
method consists in first subjecting said carbon compound directly to the oxydizing
influence of ozone until the group C3H, has been transformed into the group CHO
substantially as set forth and then isolating the resulting aldehyde.
3. The application of the process claimed in the first claim to the transformation
of substances having a closed ring containing a lateral chain CH, in one or other
of the two forms above mentioned into their aldehyde derivatives and in particular
to the transformation of eugenol or isoeugenol into vanilline safrol or isosafrol into
heliotropine estragol or anethol into aubepine.
Dated this 28th day of January 1896.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.