Improvements in the Manufacture and Production of Perfumes.
Year: 1897

page_text: Date of Application, 16th June, 1897
Complete Specification Left, 16th Mar., 1898-Accepted, 16th July, 1898
Improvements in the Manufacture and Production of Perfumes.
I, ALBERT VERLEY, of 7, Quai de Seine, Courbevoie, near Paris, in the Republic of
France, Electrician, do hereby declare the nature of my invention to be as
follows:-
My invention consists in the manufacture and production of a new class of
bodies, viz., ketonic alcohols of the aromatic series obtained from cymene and
their ethers which having a very agreeable odour resembling that of violets, can
be employed as perfumes. These alcohols are represented by the general formula
where R¹¹ is a monovalent acid or alcoholic radical.
These new bodies may be prepared in various ways.
methods of preparing them.
I will describe two principal
1ST METHOD
I act upon cymene in the presence of aluminium chloride with an acid chloride
such as the chlorides of acetyle, propionyle butyryle isobutyryle, etc.
In this way I
obtain the corresponding acetones, most of which have already been described by
Clauss and which answer to the formula
I act upon cymene in the presence of aluminium chloride with an acid chloride
such as the chlorides of acetyle, propionyle butyryle isobutyryle, etc.
In this way I
obtain the corresponding acetones, most of which have already been described by
Clauss and which answer to the formula
These brom-acetones when treated at boiling point with a salt of an organic
acid readily exchange their bromine for the corresponding acid residue and I
obtain ethers of the ketonic alcohols.
For example-the cymyl methylketone treated with bromine and then with sodic
acetate gives acetate of cymo-ketol which boils at 160° centigrade at 23 millimeters
pressure and which has a very agreeable odour resembling that of violets.
CD 071

page_text: 2ND METHOD.
Cymene is treated with the chloride of an organic acid which itself contains chlorine
or bromine, and the corresponding chlor- or brom-acetone is produced.
For example by acting with the chloride of monochloracetyl I get the chlor-
acetone
which has an odour like that of violets but cannot be employed in perfumery because
it is very irritating to the eyes.
By acting upon this chlor-acetone with an alcoholic solution of sodic acetate I
obtain as before the acetate of cymo-ketol which boils at 166° Centigrade at a
pressure of 23 millimeters.
Improvements in the Manufacture and Production of Perfumes.
I, ALBERT VERLEY, of 7, Quai de Seine, Courbevoie, near Paris, in the Republic of
France, Electrician, 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 :-
My invention consists in the manufacture and production of a new class of bodies,
viz.ketonic alcohols of the aromatic series obtained from cymene and their ethers,
which having a very agreeable odour resembling that of violets, can be employed as
perfumes. These alcohols are represented by the general formula
CH, (C,H,) (CH) (CO.COH.RR¹)
where RR¹ may be either hydrogen or any monovalent radicals and the corresponding
ethers are represented by the general formula
CH, (C,H,) (CH) (CO.COR".R.R¹)
METHOD.
I act upon cymene in the presence of aluminium chloride with an acid chloride such
as the chlorides of acetyle, propionyle, butyryle, isobutyryle &c. In this way I obtain
the corresponding acetones (ketones) most of which have already been described by
Clauss and which answer to the formula
CH (CH) (CH₂) (CO.CH.R.R')

page_text: In this way I obtain the corresponding brom-acetones (ketones) answering to the
formula
These brom-acetones (ketones) when treated at boiling point with a salt of an
organic acid readily exchange their bromine for the corresponding acid residue and I
obtain ethers of the ketonic alcohols represented by the formula
One molecular proportion of aluminium chloride is added to 1 kilogram of paracy-
mene, and the vessel exhausted by means of the pump, when a molecular
proportion of propionic chloride is added drop by drop.
The influence of the vacuum causes action to take place immediately, and
hydrogen chloride is liberated at common temperatures. When all the chloride
has been added, and hydrochloric acid ceases to be evolved under the influence
of the vacuum, the operation is interrupted.
The product is washed with water, and then rectified in order to separate the
cymene from propionyl cymyl ketone, which is formed during the reaction.
Propionyl cymyl ketone boils at 149°-152° Centigrade under a pressure of
30 mm.,
it has the formula
This product cannot be distilled, and it is therefore treated in the crude state with
an alcoholic solution containing one molecular proportion of sodium acetate. The
liquid is then boiled in a reflux apparatus during forty hours. At the end of this
time, the alcohol is evaporated, and the residue treated with water the oil which is
thus obtained being rectified by distillation in a vacuum.
In this way there is produced the compound
CgH..CgHg (CHg).CO.CH (CH,).OCO.CH.
The second method consists in treating cymene with the chloride of an organic
acid already chlorinated, brominated, or iodated, in which case the corresponding
0 chlorinated brominated or iodated acetone (ketone) is produced.
This chlorinated, brominated, or iodated ketone is treated as before with a boiling
alcoholic solution of the salt of an organic acid the corresponding ether of a ketonic
alcohol being thus obtained.

page_text: One molecular proportion of aluminium chloride is added to 1 kilogram of cymene.
The apparatus is then exhausted with the pump, and a molecular proportion of
chloracetic chloride added drop by drop. When the action is at an end, and the
product washed with water as before, excess of cymene is separated by distillation
from the chlorinated ketone.
which boils at 158°-160°
specific gravity 1.101 at 0°.
CH,.CH (CH).CO.CH, Cl,
:
Centigrade under a pressure of 20 mm., and has the
This ketone has the odour of violets, but it cannot be
used in perfumery, because it violently irritates the mucous membrane.
One molecular proportion of this ketone is dissolved in two parts of alcohol, and
treated with rather more than one molecular proportion of sodium acetate. After
being boiled for forty hours the alcohol is distilled, the residue is washed with water
and the supernatant oil distilled in a vacuum.
This
In this way the acetate of cymoketol is produced boiling at 175°-180° Centigrade
under a pressure of 29 mm., and having the specific gravity of 1.0755 at 0°.
compound has a very agreeable odour of violets.
If sodium propionate be used instead of sodium acetate-the corresponding
propionic ether is formed, which boils at 185°-197° Centigrade under a pressure of
30 min. it also has the odour of violets, and in an equal degree to the foregoing
substance.
Sodium butyrate yields the corresponding butyric ether, which boils at 195°-
198° Centrigrade under a pressure of 30 mm., it has the odour of violets, but to a less
marked and permanent extent than the previous compound.
Hydrolysis of these ethers with alcoholic potash yields the ketonic alcohol
U13 U17) (CH3). (CO.COH KR²) and their ethers.
2. The two herein before described processes of preparing the ethers, and in con-
sequence, the alcohols obtained from the ethers on hydrolysis.
3. As new products the bodies which result from the processes hereinbefore
described and claimed and their analogues especially, (1) brominated propionyl
cymyl ketone, and the acetic ether obtained on treating it with sodium acetate, (2)
chlorinated acetyleymyl ketone and the acetic propionic and butyric ethers corre-
sponding to this ketone.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.